(Ronald S. Bauer (Eds.) ) Epoxy Resin Chemistry

Publication Date: December 3, 1979 | doi: 10.1021/bk-1979-0114.
fw001
Epoxy Resin Chemistry

Publication Date: December 3, 1979 | doi: 10.1021/bk-1979-0114.fw001
Epoxy Resin Chemistry
Ronald S. Bauer, EDITOR
Shell Development Company

Based on a symposium sponsored
by the Division of
Organic Coatings and Plastics
at the 176th Meeting of the
American Chemical Society,
Miami Beach, Florida,
September 11-15, 1978.
ACS SYMPOSIUM SERIES 114
AMERICAN CHEMICAL SOCIETY

WASHINGTON, D.C. 1979
Library of Congress CIP Data

Epoxy resin chemistry.
(ACS symposium series; 114 ISSN 0097-6156)
Includes bibliographies and index.
1. Epoxy resins—Congresses.
I. Bauer, Ronald S., 1932- . II. American Chemi-
cal Society. Division of Organic Coatings and Plastics
Chemistry. III. Series: American Chemical Society.
ACS symposium series; 114.
TP1180.E6E59 668'.374 79-21858
ISBN 0-8412-0525-6 ASCMC8 114 1-271 1979
Copyright © 1979
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format of the Series parallels that of the continuing ADVANCES
IN CHEMISTRY SERIES except that in order to save time the
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PREFACE
înce their commercial introduction into the United States in the late
^ 1940's, epoxy resins have established themselves as unique building
blocks for high performance coatings, adhesives, and reinforced plastics.
Over the past five years epoxy resin sales have experienced an annual
growth rate of about 8%. In 1978, production in this country exceeded
310 million pounds, and domestic sales were greater than 280 million
Publication Date: December 3, 1979 | doi: 10.1021/bk-1979-0114.pr001
pounds. This sustained growth of epoxy resins is a result of the wide

range of properties that can be achieved with these versatile materials;
uses range from coatings for the ubiquitous beverage can to high per-
formance adhesions in spacecraft as well as for encapsulating their
sophisticated electronic components.
Work still continues as pressures for more environmentally acceptable
and energy efficient systems, and demands for even higher performance,
challenge the polymer chemist. This volume covers some of the new
resins, curing agents, and application techniques along with new ideas
about the chemistry and properties of existing epoxy resin systems.
Although comprehensive coverage of this field is not possible in our
symposium, it is hoped the papers presented here will help stimulate
polymer chemists to answer the challenges facing them.
Shell Development Company RONALD S. BAUER

Houston, Texas 77001
May 21, 1979
ix
1
The Photoinitiated Cationic Polymerization of Epoxy
Resins
J. V. CRIVELLO and J. H . W. L A M
General Electric Corporate Research and Development Center, Schenectady, NY 12301
Publication Date: December 3, 1979 | doi: 10.1021/bk-1979-0114.ch001
The importance of epoxy resins in the fabrication of surface

coatings is well recognized in the coatings and plastics industry.
In fact, the chief use of epoxy resins, amounting to over 100
million pounds last year, was for coating applications (1). Tra-
ditionally, these coatings have been applied from solvents and
cured by a baking process. Current efforts to reduce the amount
of energy required to carry out coating processes as well as an
increasing concern for the environment have provided the impetus
to begin the search for new curing chemistry and coating applica-
tion techniques which circumvent these problems.
Ultraviolet curing has emerged as a rapidly growing method
for the fabrication of essentially pollution-free coatings, having
only a fraction of the energy requirements of traditional ther-
mally cured materials. At the same time, the generally excellent
properties of the coatings which are obtained using uv curing
resins together with their high application and cure speeds have
made it attractive for many industries to install uv-cure lines.
While the bulk o f the work i n uv c u r i n g to date has i n v o l v e d
the r a d i c a l p o l y m e r i z a t i o n o f v i n y l compounds, during the past
f i v e years discovery of several new p h o t o i n i t i a t o r compounds now
makes i t p o s s i b l e to e f f e c t the uv-cure o f epoxy r e s i n s by a
c a t i o n i c process. With such systems, s o l v e n t l e s s l i q u i d epoxy
r e s i n s can be cured c o n t i n u o u s l y a t very high l i n e speeds using
approximately one tenth the energy which would be consumed by a
comparable thermal process. The f i r s t o f these new p h o t o i n i t i
ators are the a r y l d i a z o n i u m s a l t s ( I ) (2_>3.»4,5j. when these com-
pounds are i r r a d i a t e d using uv l i g h t , a fluoroaromatic compound,
n i t r o g e n and the strong Lewis a c i d , boron t r i f l u o r i d e , are pro-
duced (equation 1 ) .
+
Ar-N EN B F " 4 — > Ar-F + N 2 + BF^ (1)
I
I f the p h o t o l y s i s o f an a r y l d i a z o n i u m s a l t i s conducted i n the
0-8412-0525-6/79/47-114-001$05.00/0
© 1979 American Chemical Society
2 EPOXY RESIN CHEMISTRY
presence o f an epoxy r e s i n , boron t r i f l u o r i d e c a t a l y z e s the

c a t i o n i c p o l y m e r i z a t i o n o f the r e s i n . Due to the production o f
nitrogen as a byproduct o f the p h o t o l y s i s o f a r y l d i a z o n i u m s a l t s ,
the major uses o f c o a t i n g systems employing these p h o t o i n i t i a t o r s
l i e s p r i m a r i l y i n t h i n f i l m a p p l i c a t i o n s such as c o n t a i n e r c o a t -
ings [6) and p h o t o r e s i s t s ( 7 J .
R e c e n t l y , we have reported t h a t d i a r y l i o d o n i u m s a l t s ( I I )
are a second c l a s s o f h i g h l y e f f i c i e n t p h o t o i n i t i a t o r s f o r the
Ar-I-Ar'
X" = B F " , A s F 4 6 , PF 6 , SbCl 6 , etc.

II
c a t i o n i c r i n g opening p o l y m e r i z a t i o n o f epoxy r e s i n s ( 8 , 9 J .
P a r a l l e l work i n two other l a b o r a t o r i e s has l e d to the same con-
c l u s i o n (10, ]V). M e c h a n i s t i c s t u d i e s have shown t h a t on p h o t o l -
y s i s , d i a r y l i o d o n i u m s a l t s l i b e r a t e strong Br0nsted acids of the
type, HX, which subsequently i n i t i a t e c a t i o n i c p o l y m e r i z a t i o n .
In t h i s paper, we would l i k e to r e p o r t some recent work
which has l e d to the development o f t r i a r y l s u l f o n i u m s a l t s ( I I I )
as a t h i r d c l a s s o f useful p h o t o i n i t i a t o r s f o r c a t i o n i c polymeri-
z a t i o n and i n p a r t i c u l a r , describe t h e i r a p p l i c a t i o n to the
p o l y m e r i z a t i o n o f epoxides.
1
^r
+
Ar-S X"
Ar"
III
Results and D i s c u s s i o n
In our l a b o r a t o r y , we have found t h a t t r i a r y l s u l f o n i u m

s a l t s ( I I I ) i n which the anions are o f the type BF " A s F " , P F " , 6 6
SbF ~ e t c . , are e x c e l l e n t p h o t o i n i t i a t o r s f o r the p o l y m e r i z a t i o n

of epoxy r e s i n s as w e l l as a v a r i e t y o f other monomers (12, 13).
S i m i l a r r e s u l t s have a l s o been reported by another group o f
investigators (14).
T r i a r y l s u l f o n i u m s a l t s may be c o n v e n i e n t l y prepared v i a a
number o f s y n t h e t i c r o u t e s . In equations 2 , 3 and 4 are shown
three o f the most d i r e c t p r e p a r a t i v e methods.
A 1 C 1 +
6ArH + S C12 2 + 3C1 2 3 ^ 2(Ar) S Cl"3 + 6HC1 (2)
Ar Ar
+
^S-* 0 + Ar'-MgBr benzene > ^ .
s A r - x " + M gBrOH (3)
Ar' r e f 1 ux Ar
1. CRIVELLO AND LAM Photoinitiated Cationic Polymerization 3
1 1
Cu (cat)
(Ar) S2 + (Ar') I 2
+
X" > Ar Ar»S
2
+
X" + Ar'I (4)
Although the r e a c t i o n shown i n equation 2 i s simple and d i r e c t ,

the products which are obtained are g e n e r a l l y impure ( 1 5 ) . The
condensation o f d i a r y l s u l f o x i d e s w i t h Grignard reagents (equation
3 ) gives pure t r i a r y l s u l f o n i u m s a l t s ; however, the o v e r a l l y i e l d s
are g e n e r a l l y o f the order o f 2 0 - 3 0 % ( 1 6 ) . In a very recent
p u b l i c a t i o n from t h i s laboratory,we d e s c r i b e d a general s y n t h e s i s
which affords these compounds i n high y i e l d s ( 1 7 _ ) . This new
route i n v o l v e s the copper ( I I ) c a t a l y z e d a r y l a t i o n o f d i a r y l -
iodonium s a l t s with d i a r y l s u l f i d e s (equation 4 ) .
Both o f the methods shown i n equations 2 and 3 give r i s e to
t r i a r y l s u l f o n i u m h a l i d e s which are i n a c t i v e as p h o t o i n i t i a t o r s
for c a t i o n i c p o l y m e r i z a t i o n . These s a l t s must, t h e r e f o r e , be
converted to the corresponding s a l t s i n which the anion i s o f
the type X" = BF4", ASF5", P F c " , e t c . Th is conversion may be
accomplished using e i t h e r o f the two methods shown i n equation 5 .
Ag o +
?
_> Ar S3 OH" + AgCl
(5)
Using the above s y n t h e s i s , a wide v a r i e t y o f t r i a r y l s u l f o n -

ium s a l t p h o t o i n i t i a t o r s can be prepared. In Table 1 are shown
some r e p r e s e n t a t i v e t r i a r y l s u l f o n i u m s a l t p h o t o i n i t i a t o r s which
were prepared during the course of t h i s r e s e a r c h . A l l the com-
pounds i n t h i s t a b l e are w e l l c h a r a c t e r i z e d c r y s t a l l i n e com-
pounds w i t h w e l l defined m e l t i n g p o i n t s , elemental a n a l y s e s ,
u l t r a v i o l e t , p r o t o n , and 1
C nmr s p e c t r a (1_7).
3
The a b i l i t y
of t r i a r y l s u l f o n i u m s a l t s bearing n o n - n u c l e o p h i l i e counterions to
serve as p h o t o i n i t i a t o r s i s completely general and i n c l u d e s a l l
the s y m m e t r i c a l , unsymmetrical, s u b s t i t u t e d and u n s u b s t i t u t e d
as w e l l as p o l y n u c l e a r and h e t e r o c y c l i c s a l t s shown i n Table 1 .
In c o n t r a s t to r a d i c a l p h o t o i n i t i a t o r s which are a l s o gen-
e r a l l y thermally unstable, t r i a r y l s u l f o n i u m s a l t s display a sur-
p r i s i n g l e v e l o f thermal s t a b i l i t y . Figure 1 shows the thermo-
g r a v i m e t r i c a n a l y s i s curves for t r i p h e n y l s u l f o n i u r n h e x a f l u o r o -
arsenate performed i n a i r and n i t r o g e n at a heating r a t e o f
10°C/minute. In both c a s e s , thermal decomposition i s not ob-
served below 3 5 0 ° C . This high l e v e l o f thermal s t a b i l i t y i s
r e f l e c t e d i n the extremely long s h e l f l i f e s o f epoxy r e s i n s
s e n s i t i z e d with t r i a r y l s u l f o n i u m s a l t p h o t o i n i t i a t o r s . Figure 2
shows the p l o t s o f the increase i n s o l u t i o n v i s c o s i t y v e r s u s +
time i n months f o r various concentrations of ( C s ^ J q S ASF5" i n

the h i g h l y r e a c t i v e b i s e p o x i d e , 4 - v i n y l c y c l o h e x e n e d i o x i d e . Only
a s l i g h t increase i n the o v e r a l l s o l u t i o n v i s c o s i t y was noted
Table 1
Preparation of Triarvlsulfonium Salts
Elemental Analysis
Anion Mp (°C) Xm a x (e)
BF/ 191-193 227(21,000) calc. 61.71 4.28 9.14

4
298(10,000) fnd. 62.00 4.31 9.33
AsF " 6 195-197 227(21,000) calc. 47.63 3.31 7.06

298(10,000) fnd. 47.78 3.41 7.06
133-136 237(20,400) calc. 56.90 4.96 6.90

P F
6
249(19,700) fnd- 57.05 5.03 7.09
AsFg" - 225(21,740) calc. 46.49 3.88 5.90

280(10,100) fnd. 46.70 3.98 6.00
BF/ 162-165 243(24,700) calc. 64.28 5.35 8.16 g

278(4,900) fnd. 64.32 5.41 7.91 *
5
s
AsF " 6 111-112 275(42,100) g
287(36,800) calc. 50.00 3.95 6.67 w
307(24,000) fnd. 50.10 4.01 7.23 §
ι. CRivELLO AND L A M Photoinitiated Cationic Polymerization 5
oo ir> ο ·—
oo cr> *t CO
in LO cô oo
«3- ο ο to
CVI CVJ
i— "O
«Ο C
Ο ο
O Ο '—. ο ^ ο ο ο
ο ο ο Ο Ο νο
Ο Ο νο Ο
Ν 'ί Ο
in CM *
CNJ CVI Γ*»
CO CD KO 00 CVI
KO 00 ·— cô ex»
CVI CVI CO CVI CVI
κο
«Λ
• • - ο
100 A
φ (0 OU
§3
οΗ
—ι 1 ι 1 1 1 ι
100 200 300 400 500 600 700
Figure 1. Thermogravimetric analysis of (C H ) S AsF ~ in nitrogen and air at

6 5 S
+
6
a programmed heating rate of 10°C/min
3 4 5 6
TIME ( M O N T H S )
Figure 2. Solution stability study with various concentrations of (C H ) S AsF 6 5 s

+
6
in 4-vinylcyclohexene dioxide at55°C

1. CRivELLO AND L A M Photoinitiated Cationic Polymerization 7
a f t e r one year storage o f these s o l u t i o n s i n the dark at 55°C.

Although t r i a r y l s u l f o n i u m s a l t s are h i g h l y t h e r m a l l y s t a b l e ,
they undergo r a p i d p h o t o l y s i s when i r r a d i a t e d at wavelengths from
=
200-300nm. Under these c o n d i t i o n s , e f f i c i e n t (Φ3]3,360 0.17-
0.19) homolytic rupture o f one o f the carbon s u l f u r ' b o n d s r e s u l t s .
The f o l l o w i n g mechanism has been proposed f o r t h i s p h o t o l y s i s (12)
+ +
Ar S 3 X" ^ > [Ar S 3 χ"]* a
[Ar S 3
+
χ"]* > Ar st 2 + Ar- + X~ b
+
Ar S"!"
2 + YH > Ar S -H 2 + Y- c
+ +
Ar S -H 2 > Ar S 2 + H d
2Ar- > Ar-Ar e
Ar- + YH > ArH + Y· f (6)
I n t e r a c t i o n o f the r a d i c a l - c a t i o n , A r S - , w i t h the s o l v e n t or
2
monomer, YH, i n step c r e s u l t s i n the r e l e a s e o f a proton i n

step d and the r e s u l t a n t formation o f the strong a c i d , HX. Br0n-
sted a c i d s such as H B F 4 , HAsFs, and HSbF are w e l l known very 6
r e a c t i v e i n i t i a t o r s t o r the r i n g opening p o l y m e r i z a t i o n o f
epoxides (18). Although i t i s improbable t h a t acids such as those
mentioned above e x i s t i n the anhydrous s t a t e , when they are gen
erated by p h o t o l y s i s i n s o l u t i o n , i t i s l i k e l y t h a t immediate
p r o t o n a t i o n o f the monomer or the s o l v e n t occurs to produce
+
species such as HM X " . Subsequent a d d i t i o n o f monomer molecules
r e s u l t s i n propagation and chain growth. The o v e r a l l process i s
shown i n equation 7.
+
AroS X" !™ > Ar S 0 + Ar- + Y- + HX
0 2
YH
+
M + HX > HM X"
+ +
nM + HM X" > H(M) M n X" (7)
T r i a r y l s u l f o n i u m s a l t p h o t o i n i t i a t o r s are capable o f p o l y
m e r i z i n g almost a l l known types of mono and p o l y f u n c t i o n a l epox
ide c o n t a i n i n g monomers. The r e a c t i v i t y o f these systems depends
on a number o f f a c t o r s . The r e a c t i v i t y and number o f epoxide
groups present play a major r o l e i n determining the o v e r a l l r a t e
and extent o f p h o t o p o l y m e r i z a t i o n . Monomers most a c t i v e using
d i a r y l i o d o n i u m s a l t p h o t o i n i t i a t o r s are those possessing no
f u n c t i o n a l i t y other than the epoxide groups, i . e . , e p o x i d i z e d
o l e f i n s (19). I n t r o d u c t i o n o f f u n c t i o n a l groups such as e t h e r s ,
a c e t a l s or e s t e r s was found to a p p r e c i a b l y attenuate the r e a c t i v

i t y o f these monomers toward strong p r o t o n i c a c i d c a t a l y z e d p o l y
m e r i z a t i o n . Analogous r e s u l t s were observed using t r i a r y l s u l f o n
ium s a l t p h o t o i n i t i a t o r s .
While the photochemistry o f t r i a r y l s u l f o n i u m s a l t s i s domi
nated by the s t r u c t u r e o f the t r i a r y l s u l f o n i u m c a t i o n which i s
the l i g h t absorbing s p e c i e s , the p o l y m e r i z a t i o n chemistry i s domi
nated by the nature o f the a n i o n . The reason f o r t h i s derives
from the f a c t t h a t the type of anion present determines what p r o -
t o n i c a c i d i s produced on p h o t o l y s i s . As we have already shown,
t h i s a c i d i s the species r e s p o n s i b l e f o r the p o l y m e r i z a t i o n o f
the epoxide monomer. In Figure 3 i s shown p l o t s of the percent
conversion to polymer versus time f o r the uv induced photopoly-
m e r i z a t i o n of cyclohexene oxide using 0.02 moles o f t r i p h e n y l s u l -
fonium s a l t s having d i f f e r e n t a n i o n s . Since i t has been shown

t h a t the quantum e f f i c i e n c i e s f o r p h o t o l y s i s o f t r i p h e n y l s u l f o n -
ium s a l t s are independent o f t h e i r anions ( 1 2 ) , the d i f f e r e n c e s
observed i n the curves shown i n Figure 3 are due to the r e l a t i v e
r e a c t i v i t y o f the a c i d s i n p o l y m e r i z a t i o n . The curve f o r the
SbF5 s a l t was omitted from t h i s f i g u r e s i n c e p o l y m e r i z a t i o n
occurred at too f a s t a r a t e to be a c c u r a t e l y measured. Triaryl
sulfonium s a l t s may thus be ranked on the b a s i s o f t h e i r r e a c t i v
i t y i n the f o l l o w i n g order w i t h respect to t h e i r a n i o n s : SbF5~>
AsF5~>PF6~>BF4~. S i m i l a r l y , Figure 4 compares the r e a c t i v i t y o f
these same s a l t s i n the photopolymerization of another monomer,
styrene o x i d e . Even on a weight b a s i s , the order o f r e a c t i v i t y i s
the same as noted before although the molecular weight of_the t r i
a r y l s u l f o n i u m s a l t decreases i n the order SbFg">AsF ">PFg">BF^". 6
The above model s t u d i e s w i t h monofunctional epoxy compounds

give c o n s i d e r a b l e i n s i g h t i n t o the r e a c t i v i t y o f various t r i a r y l
sulfonium s a l t p h o t o i n i t i a t o r s . However, i n terms o f c o a t i n g s ,
one i s p r i m a r i l y i n t e r e s t e d i n the r e a c t i v i t y o f these photo-
i n i t i a t o r s i n d i - and m u l t i f u n c t i o n a l epoxy systems. Determina
t i o n o f the cure r a t e s r e q u i r e d to produce t a c k - f r e e coatings i s
a g e n e r a l l y accepted i n d u s t r y standard f o r the r e a c t i v i t y o f uv
cured c o a t i n g s . In Table 2 are given the cure r a t e s i n f t / m i η
which were determined f o r the c y c l o a l i p h a t i c b i s e p o x i d e , 3,4-
e p o x y c y c l o h e x y l m e t h y l - 3 ' , 4 ' - e p o x y c y c l o h e x a n e c a r b o x y l a t e (ERL
4221) using 1 mole % o f t r i phenylsulfoniurn BF ~ P F " , A s F / and C
SbF ' s a l t s . 4 6 b
A more q u a n t i t a t i v e measure o f the degree o f cure as w e l l as
the cure r a t e i n uv cure systems can be obtained w i t h the a i d
of a s p e c i a l l y designed d i f f e r e n t i a l scanning c a l o r i m e t e r . This
device was developed at General E l e c t r i c (20) and described by
the present authors i n previous p u b l i c a t i o n s ( 1 9 , 2 1 ) . Figure 5
shows the type of data which can be obtained using t h i s d e v i c e .
When the s h u t t e r i s opened a l l o w i n g uv l i g h t to s t r i k e the sam
p l e , immediate exothermic r e a c t i o n ensues which i s recorded as
a peak by the s t r i p c h a r t r e c o r d e r . The time i n t e r v a l from when
the s h u t t e r i s opened to the peak o f the exothermic curve i s one
CRTVELLO AND L A M Photoinitiated Cationic Polymerization
80
Ε ι ι ι I
0 1 2 5 10
UV CURE(MIN)
Figure 4. Photopolymerization of styrene oxide using 10% (C H ) S* X' salts

6 5 S
Table 2
UV Cure o f ERL 4221 Using Various T r i p h e n y l s u l f o n i u m S a l t s
Photoinitiator Cure Rate (ft/miη)*

+
(C H ) S
6 5 3 BF " 4 195
+
(C H ) S
6 5 3 PF " 6 228
+
(C H ) S
6 5 3 AsF " 6 248
( 6 5 3
C H } S + S B F
6~ 2 8 0
*1.0 mil f i l m s cured using three 200W/in. Hanovia Hg arc

lamps a l i g n e d p a r a l l e l to d i r e c t i o n o f t r a v e l o f the
conveyor.
measure o f the r e a c t i v i t y o f the p o l y m e r i z a t i o n system under

study: the s h o r t e r the time i n t e r v a l between these two p o i n t s ,
the more r e a c t i v e the system. In a d d i t i o n , the heat o f r e a c t i o n ,
ΔΗ, can be c a l c u l a t e d from the area under the curve. The ΔΗ v a l
ues are a q u a n t i t a t i v e measure o f the extent o f p o l y m e r i z a t i o n .
Comparing the various curves i n Figure 5 leads to the c o n c l u s i o n
t h a t the c h a r a c t e r o f the anion present i n the p h o t o i n i t i a t o r has
a marked e f f e c t on both the r a t e and extent o f p o l y m e r i z a t i o n .
Other important r a t e determining f a c t o r s i n the p h o t o i n i t i -
ated p o l y m e r i z a t i o n of epoxies are the c o n c e n t r a t i o n of the
p h o t o i n i t i a t o r , the wavelength o f the i r r a d i a t i n g l i g h t and i t s
i n t e n s i t y and the temperature. The i n f l u e n c e o f these f a c t o r s
can be c o n v e n i e n t l y determined using the modified d i f f e r e n t i a l
scanning c a l o r i m e t e r (DSC). Figure 6 shows a p l o t o f the e f f e c t
+
of c o n c e n t r a t i o n o f (C5H5)oS A s F " on the r a t e o f cure o f ERL
6
4221. The optimum cure rates are obtained at concentrations o f

2-3% o f t h i s p h o t o i n i t i a t o r . Further increase i n the photo
i n i t i a t o r l e v e l does not produce a corresponding increase i n the
cure r a t e , p o s s i b l y due to l i g h t screening e f f e c t s by the t r i a r y l
sulfonium s a l t i t s e l f or i t s p h o t o l y s i s p r o d u c t s .
A DSC study o f the e f f e c t o f l i g h t i n t e n s i t y on the cure
r a t e of ERL 4221 c o n t a i n i n g 2% by weight ( C H ) 3 S As Fβ" i s d i s 6 5
played i n Figure 7. In t h i s f i g u r e , I i s the i n c i d e n t l i g h t

0
i n t e n s i t y d e l i v e r e d by a GE H3T7 medium pressure mercury arc

lamp b a l l a s t e d at 200 W a t t s / i n c h of arc length and p o s i t i o n e d at
20 cm from the samples. As the curve shows, the cure times
approach l i m i t i n g values at both high and low l i g h t l e v e l s . At
high l i g h t i n t e n s i t i e s , the system i s l i m i t e d by the absorption
c h a r a c t e r i s t i c s o f p h o t o i n i t i a t o r , w h i l e a t very low i n t e n s i t i e s ,
there appears to be some type o f t h r e s h o l d or i n h i b i t i o n e f f e c t .
CRivELLO AND L A M Photoinitiated Cationic Polymerization
4r
t IRRAD. TIME (MIN.)

SHUTTER
OPEN
Figure 5. Photopolymerization of ERL 4221 using 1.5 mol % (C H )sS* X" salts: 6 5
(—; 4>ss&F- (
s
+
6 ; ; 4> s A5F - (—)
3
+
6 ; <^sPF- (
5
+
E; ; ^S BF -+
4
CONCENTRATION (%)
Figure 6. Concentration dependency of the cure rate of ERL 4221 on %

(C H ) S+AsF - 6 5 s 6
EPOXY RESIN CHEMISTRY
100 Γ
80 h
6 0
îS *
Ζ
g
ί 40 (-
20
0 ' 60 1120 180 240

TIME (SEC) TO REACH MAXIMUM CURE RATE
Figure 7. Effect of light intensity on the cure rate of ERL 4221 with 2%
(C H ) S+AsF -6 5 3 6
LU
g 35
LU
*~ ιο« 1
ι ι · 1 1 1 1 1
20 30 40 50 60 70 80 90 100 110
(TEMP.) (°C)
Figure 8. Effect of temperature on the cure rate of ERL 4221 with 2%

(C H ) S+PF - 6 5 3 6
Figure 8 shows the e f f e c t o f temperature i n the p o l y m e r i z a -

t i o n o f ERL 4221 using 2% ( C Ô H C ^ S * PFç' as the p h o t o i n i t i a t o r .
By i n c r e a s i n g the temperature from 25°C to 85°C, the time r e q u i r e d
to reach the maximum cure r a t e has been decreased by o n e - h a l f . In
a l l p h o t o i n i t i a t e d c a t i o n i c p o l y m e r i z a t i o n s employing e i t h e r d i -
aryliodonium or t r i a r y l s u l f o n i u m s a l t p h o t o i n i t i a t o r s , cure at the
highest temperature the s u b s t r a t e w i l l a l l o w w i l l give the highest
cure r a t e s . O b v i o u s l y , c e r t a i n trade o f f s must be made between
the cure temperature and l o s s o f the monomer through v o l a t i l i z a -
tion.
P h o t o i n i t i a t e d c a t i o n i c p o l y m e r i z a t i o n s o f epoxides are un-
affected by the presence of atmospheric oxygen. There i s , t h e r e -
f o r e , no need to blanket them w i t h n i t r o g e n . Water and other hy-
droxyl c o n t a i n i n g i m p u r i t i e s can be t o l e r a t e d i n amounts o f 1-2%
i n most epoxy monomers w i t h o u t s e r i o u s l y a f f e c t i n g t h e i r p o l y m e r i z -

ability. However, the presence o f water does change c o n s i d e r a b l y
both the r a t e and extent of p o l y m e r i z a t i o n of epoxy monomers. Fig-
ure 9 shows the DSC curves f o r the photopolymerization o f both dry
ERL 4221 and the same epoxy r e s i n c o n t a i n i n g 1-2% by weight water
1
using (Cs^)^" " SbF5~ as the p h o t o i n i t i a t o r . The presence o f a
second peak i n the DSC curve o f the wet ERL 4221 i n d i c a t e s the
presence o f another competing chemical process t a k i n g p l a c e . Ba-
s i c m a t e r i a l s present i n uv curable epoxy formulations as e i t h e r
i m p u r i t i e s , a d d i t i v e s or f i l l e r s can i n h i b i t the p o l y m e r i z a t i o n
and should g e n e r a l l y be avoided. UV-opaque f i l l e r s can be
t o l e r a t e d to s u r p r i s i n g l e v e l s . In Figure 10 i s shown a p l o t of
the heat o f r e a c t i o n , ΔΗ, on the l e v e l of TiÛ2 (anatase) i n a
formulation c o n t a i n i n g ERL 4221. The higher the TiÛ2 concentra-
t i o n p r e s e n t , the lower the extent o f p o l y m e r i z a t i o n which takes
place due to the screening e f f e c t of the pigment. Nevertheless,
even at TiO^ l e v e l s o f 12%, hard, t a c k - f r e e coatings can be ob-
t a i n e d provided t h a t the coatings are reasonably t h i n (<1 m i l ) .
In summary, t r i a r y l s u l f o n i u m s a l t s are a new c l a s s o f very
r e a c t i v e p h o t o i n i t i a t o r s f o r the r i n g opening p o l y m e r i z a t i o n of
epoxy monomers. By manipulating the various parameters of i n i t i a -
t o r c o n c e n t r a t i o n , i n i t i a t o r t y p e , temperature, and l i g h t i n t e n s i -
t y , one can e x e r c i s e considerable c o n t r o l over the r a t e and extent
of p o l y m e r i z a t i o n o f these compounds. F u r t h e r , the ready commer-
c i a l a v a i l a b i l i t y o f epoxy r e s i n s o f d i f f e r e n t s t r u c t u r a l types
gives the formulator c o n s i d e r a b l e l a t i t u d e i n the design of uv
cured coatings f o r a wide v a r i e t y o f s p e c i a l i z e d a p p l i c a t i o n s .
Experimental
M a t e r i a l s . Cyclohexene oxide and styrene oxide were d r i e d

over c a l c i u m h y d r i d e , then p u r i f i e d by f r a c t i o n a l d i s t i l l a t i o n .
S ^ - E p o x y c y c l o h e x y l m e t h y l - S ' ,4'-epoxycyclohexane c a r b o x y l a t e (ERL
4221) was obtained from the Union Carbide Company and p u r i f i e d as
described above. T r i a r y l s u l f o n i u m s a l t s used as p h o t o i n i t i a t o r s
15r
_J L_
0 2 4 6 8 10 12 14
% Ti02
Figure 10. Effect of Ti0 on the polymerization of ERL 4221 with 2%

2
(C H ) S+ SbFf
6 5 S
i n t h i s work were prepared as p r e v i o u s l y described ( 1 2 , 1 3 ) .
P h o t o p o l y m e r i z a t i o n s . 5 ml A l i q u o t s o f a 0.02 m o l / l i t e r
s o l u t i o n o f the appropriate t r i p h e n y l s u l f o n i u m s a l t p h o t o i n i t i a -
t o r i n cyclohexene oxide were placed i n sealed pyrex tubes. The
tubes were then placed i n a "merry-go-round" holder and i r r a d i -
ated using a Hanovia 450W medium pressure mercury a r c lamp. The
e n t i r e apparatus was immersed i n a waterbath a t 25°C. A t approp-
r i a t e t i m e s , the tubes were removed and poured i n t o methanol con-
t a i n i n g a small amount o f N H 4 O H . The p r e c i p i t a t e d polymers were
i s o l a t e d by f i l t r a t i o n followed by washing w i t h methanol and
d r y i n g i n vacuo a t 60°C o v e r n i g h t .
D i f f e r e n t i a l Scanning C a l o r i m e t e r S t u d i e s . A P e r k i n Elmer
DSC 2 d i f f e r e n t i a l scanning c a l o r i m e t e r modified w i t h a GE H3T7

medium pressure mercury a r c lamp and a f i l t e r system was used i n
these s t u d i e s . The apparatus i s s i m i l a r to t h a t described by
previous workers from t h i s l a b o r a t o r y ( 2 0 ) . Approximately 10 mg
samples o f the monomer-catalyst s o l u t i o n s were placed i n the
usual aluminum cups. Except where noted, i r r a d i a t i o n s were
c a r r i e d out i n an isothermal mode a t 30°C.
Literature Cited
1. Chemical Economics Handbook, Stanford Research Institute,

1978, 1, 580.0632.
2. Licari, J . J.; Crepeau, W. and Crepeau, P. C . , U.S. Patent

3,705,157, Sept. 7, 1965.
3. Schlessinger, S. I., U.S. Patents 3,708,296, Jan. 2, 1973;

3,826,650, July 30, 1974.
4. Watt, W. R., U.S. Patent 3,794,576, Feb. 26, 1974.
5. Feinberg, J . H . , U.S. Patents 3,711,390, Jan. 16, 1973;

3,816,281, June 11, 1974; 3,817,845, June 18, 1974; 3,829,369,
Aug. 13, 1974.
6. Ludwigsen, R. J., Soc. Mech. Eng., Technical Paper FC 74-533

(1974); J . Rad. Curing, 1975, 2 (1), 10.
7. Schlessinger, S.I., Photogr. Sci. and Eng., 1974, 18(4), 387.
8. Crivello, J . V. and Lam, J . H. W., J . Polym. S c i . , Symposium

No. 56, 1976, 1-11.
9. Crivello, J . V. and Lam, J. H. W., Macromolecules, 1977,

10(6), 1307.
10. Smith, G. H., Belg. Patent 828,841, Nov. 7, 1975.

11. Belg. Patent 837,782, June 22, 1976, to Imperial Chemical
Industries.
12. Crivello, J . V. and Lam, J . H. W., J . Polym. S c i . , in press.
13. Crivello, J . V., U.S. Patents 4,058,400 and 4,058,401, Nov.

15, 1977.
14. Belg. Patent 833,472, Mar. 16, 1976, to Imperial Chemical

Industries.
15. Pitt, H. M., U.S. Patent 2,807,648, Sept. 24, 1957.

16. Wildi, D.S.; Taylor, S. W. and Potratz, Η. Α., J . Am. Chem.

Soc., 1951, 73, 1965.
17. Crivello, J . V. and Lam, J . H. W., J . Org. Chem., 1978, 43

(15), 3055.
18. May, C. B. and Tanaka, Y . , "Epoxy Resin Chemistry and Tech

nology", Marcel Dekker, Inc., New York, 1975, 199-205; B i l l -
meyer, F. W., J r . , "Textbook of Polymer Science", Inter-
science Pub., New York, 1964, 294.
19. Crivello, J . V.; Lam, J . H. W. and Volante, C. N., J . Rad.

Curing, 1977, 4 (3), 2.
20. Moore, J . E . ; Schroeter, S. H.; Shultz, A. R. and Stang, L.

D., ACS Symposium Series No. 25, 1976, 9.
21. Crivello, J . V.; Lam, J . H. W. and Volante, C. N., Ctgs. and

Plast. Preprints, 1977, 37 (2), 4.
RECEIVED May 21, 1979.

2
Photosensitized Epoxides as a Basis for Light-Curable
Coatings
WILLIAM R. WATT
Princeton Research Center, American Can Company, Princeton, ΝJ 08540
Coatings which harden or "cure" by photoinduced polymeriza

tion offer a way to reduce air pollution and to conserve energy.
With such coatings, the change from liquid to solid is accom
plished by an increase in molecular weight rather than by removal
of solvent.
Although there has been increasing interest in light-curable
coatings over the past decade, most published investigations deal
with coatings based on free-radical polymerization. Much less has
been written about light-curable coatings based on ionic polymeri
zation; and what has been written is of relatively recent origin.
One of the earliest descriptions of this subject was a paper pre
sented by the author in 1974 describing photosensitized epoxide
coatings which cure by cationic polymerization on exposure to
ultraviolet radiation (1). Since that time, several technical
papers concerned with coatings based on photoinduced cationic
polymerization have appeared (2-11).
Photoinitiators for Cationic Polymerization of Epoxides
The development of light-curable epoxide coatings depends on

the availablility of a suitable photoinitiator. Several compounds
are known (see Table I) which w i l l i n i t i a t e c a t i o n i c p o l y m e r i z a
t i o n on exposure to l i g h t , but not a l l o f these are s u i t a b l e f o r
use i n commercial c o a t i n g o p e r a t i o n s . Some are c o s t l y , and t h e i r
use i n coatings a p p l i c a t i o n s would be uneconomical. With o t h e r s ,
the rates o f p o l y m e r i z a t i o n are too slow to be o f i n t e r e s t i n
high-speed c o a t i n g o p e r a t i o n s . These p h o t o i n i t i a t o r s have gener
a l l y not been a v a i l a b l e as o f f - t h e - s h e l f items from chemical
s u p p l i e r s . The n e c e s s i t y to s y n t h e s i z e them, together with the
f a c t that t h e i r use as p h o t o i n i t i a t o r s i s p r o t e c t e d by p a t e n t s ,
has been a hindrance to t h e i r widespread use. From such informa
t i o n as i s a v a i l a b l e , i t appears t h a t among the compounds l i s t e d
in Table I , the onium s a l t s show the g r e a t e s t promise o f meeting
0-8412-0525-6/79/47-114-017$07.00/0
Table I. Photoinitiators for Cross-Linking of Epoxides
Type Reference
1) Unsaturated nitrosamines (54)

( a c t i v a t e d by l i g h t and heat)
2) Diazonium Fluoroborates (14)
3) Diazonium P e r c h l o r a t e s ; P e r f l u o r o c a r b o x y l a t e s (15)
4) F l u o r i n a t e d alkane s u l f o n i c a c i d s a l t s o f (55)
s i l v e r and t h a l l i u m ; or a metal s a l t o f a
polyboron a c i d and a s i l v e r h a l i d e or
aromatic h a l i d e .
5) Cyclopentadienylmanganese t r i c a r b o n y l compounds (56)
6) B i s ( p e r f l u o r o a l k y l s u l f o n y l ) methane s i l v e r s a l t (57)
7) Diazonium s a l t s other than t e t r a f l u o r o b o r a t e s (18)
8) Aryliodonium s a l t s (35)
(36)
(37)
9) Aryliodonium s a l t s plus a c a t i o n i c dye (40)
10) Diazonium d i f l u o r o p h o s p h a t e , phosphotungstate, (58)

phosphomolybdate, tungstogermanate,
s i l i c o t u n g s t a t e and m o l y b d o s i l i c a t e
11) Group V i a Aromatic onium s a l t s (47)
12) Group Va Aromatic onium s a l t s (44)
13) T h i o p y r y l l i u m s a l t s (9)
2. WATT Photosensitized Epoxides 19
the requirements o f commercial c o a t i n g s . On p h o t o l y s i s , they w i l l

i n i t i a t e p o l y m e r i z a t i o n o f some epoxides, and they have the capa-
c i t y to promote the r a p i d cure required i n high-speed c o a t i n g
operations.
Three types o f onium s a l t s most often mentioned i n the l i t e r -
ature as p h o t o i n i t i a t o r s f o r epoxide p o l y m e r i z a t i o n are diazonium
s a l t s , aryliodonium s a l t s and onium s a l t s of the elements o f
Groups Va and V i a . Representative examples o f each type are shown
i n Table I I .
Diazonium S a l t s . The f i r s t use o f a diazonium s a l t as an

i n i t i a t o r f o r c a t i o n i c p o l y m e r i z a t i o n o f c y c l i c ethers was r e -
ported i n 1965 by Dreyfuss and Dreyfuss ( 1 2 ) , who announced the
p o l y m e r i z a t i o n o f tetrahydrofuran i n i t i a t e d by thermal decompo-
s i t i o n o f a "new c a t a l y s t " which they i d e n t i f i e d as benzene-

diazonium hexafluorophosphate. (In a l a t e r p u b l i c a t i o n (13) t h i s
material was c o r r e c t l y i d e n t i f i e d as p-chlorobenzenediazomum
hexaf1uorophosphate).
In the same y e a r , a patent was issued to L i c a r i and Crepeau
(14) f o r the photoinduced p o l y m e r i z a t i o n o f epoxide r e s i n s by
diazonium t e t r a f l u o r o b o r a t e s f o r use i n the encapsulation o f
e l e c t r o n i c components and the preparation o f c i r c u i t boards.
In 1966, E. F i s c h e r was granted a U . S . patent (15) c l a i m i n g
a method f o r p o l y m e r i z i n g c y c l i c ethers by means o f diazonium
s a l t s o f p e r c h l o r i c a c i d and p e r f l u o r o c a r b o x y l i c a c i d s decomposed
by heat and/or u l t r a v i o l e t r a d i a t i o n . The storage s t a b i l i t y o f
mixtures o f these s a l t s w i t h c y c l i c ethers was poor, and the
handling o f diazonium p e r c h l o r a t e s would r e q u i r e s p e c i a l c o n s i d e r -
a t i o n before i n t r o d u c t i o n i n t o l a r g e - s c a l e c o a t i n g o p e r a t i o n s .
Dreyfuss and Dreyfuss (13) reported t h a t p-chlorobenzene-
diazonium hexafluorophosphate was not a very e f f e c t i v e i n i t i a t o r
f o r p o l y m e r i z a t i o n o f epoxides, based on an observation t h a t
thermal decomposition of the diazonium s a l t i n the presence of
propylene oxide d i d not y i e l d a high molecular weight polymer.
However, S. I . S c h l e s i n g e r found t h a t epoxides could be p o l y -
merized by a wide v a r i e t y o f diazonium s a l t s , i n c l u d i n g p - c h l o r o -
benzenediazonium hexafluorophosphate, on exposure to u l t r a v i o l e t
r a d i a t i o n (16, 17). He d e l i n e a t e d d i f f e r e n c e s i n behavior between
various s a l t s and i d e n t i f i e d those which are most e f f e c t i v e i n
promoting r a p i d p o l y m e r i z a t i o n to high molecular weight. In par-
t i c u l a r , he showed t h a t the hexafluorophosphates are much more
e f f e c t i v e as p h o t o i n i t i a t o r s than the t e t r a f l u o r o b o r a t e s (18).
More than one mechanism has been proposed to e x p l a i n the
c a t a l y t i c a c t i v i t y o f diazonium s a l t s i n i n i t i a t i n g p o l y m e r i z a t i o n
of c y c l i c e t h e r s . Dreyfuss and Dreyfuss (13) postulated t h a t
i n i t i a t i o n i n v o l v e s hydrogen a b s t r a c t i o n from the c y c l i c e t h e r by
a carbenium ion formed v i a decomposition o f the diazonium s a l t ,
followed by p o l y m e r i z a t i o n v i a t e r t i a r y oxonium ions a s s o c i a t e d
with P F ' c o u n t e r i o n s .
6 The p o l y m e r i z a t i o n r e a c t i o n s s t u d i e d by
Dreyfuss and Dreyfuss were i n i t i a t e d by thermal decomposition o f
Table II. Representative Onium Salt Photoinitiators
® Θ
N =N P F 6
I® P F ®
9
ùOCH3
p-METHOXYBENZENEDIAZONIUM DIPHENYLIODONIUM
é
TRIPHENYLSULFONIUM
STRUCTURE
HEXAFLUOROPHOSPHATE HEXAFLUOROPHOSPHATE HEXAFLUOROPHOSPHATE
PM DPI TPS
A) SCHLESINGER, S. 1., A) CRIVELLO,J.V. 8 J.H.W. L A M , A) KNAPCZYK,J.W.,W.E.MC EWEN,

US PATENT 3 , 7 0 8 , 2 0 6 J. POLY. SCI., SYMPOSIUM * 5 6 , J A C S , 91 , 145 ( 1969)
3 8 3 - 3 9 5 ( 1976)
B) F E I N B E R G , J . H.
US P A T E N T 3 , 8 2 9 , 3 6 9 B) CRIVELLO,J.V. a J.H.W. L A M , B) C R I V E L L O , J.V. E T A L ,
C) W A T T , W.R. M A C R O M O L E C U L E S , 10,4*6, J. RADIATION CURING 5(1)
1307-1315 ( 1977 ) J A N . 1978
REFERENCES
US P A T E N T 3 , 7 9 4 , 5 7 6
the s a l t r a t h e r than p h o t o l y s i s . T h e i r mechanism would account

f o r a "dark r e a c t i o n " , e x p l a i n i n g the l i m i t e d storage s t a b i l i t y o f
some p h o t o s e n s i t i z e d epoxides i n the absence o f l i g h t .
The Schieman r e a c t i o n (19) was c i t e d by S c h l e s i n g e r (16) and
by L i c a r i and Crepeau (14) as the probable mechanism by which
i n i t i a t o r s f o r c a t i o n i c p o l y m e r i z a t i o n are released by diazonium
salts. Rutherford et a l (20) showed s i d e r e a c t i o n s to be m i n i
mized when the diazonium s a l t i s a hexafluorophosphate.
Although heat i s g e n e r a l l y used to promote decomposition o f
diazonium s a l t s by the Schieman r e a c t i o n , the r e a c t i o n has been
shown to occur a l s o under the i n f l u e n c e o f u l t r a v i o l e t r a d i a t i o n
(21, 2 2 ) :
Phosphorous p e n t a f l u o r i d e was shown by M u e t t e r t i e s (23, 24)

to i n i t i a t e p o l y m e r i z a t i o n o f c y c l i c ethers to h i g h - m o l e c u l a r -
weight polymers.
The r e l e a s e o f a Lewis a c i d such as B F or P F i n the pre
3 5
sence o f a m a t e r i a l capable o f undergoing c a t i o n i c p o l y m e r i z a t i o n

would be expected to y i e l d polymeric products, and the photo-
induced p o l y m e r i z a t i o n o f epoxides can be e x p l a i n e d according to
the mechanism f o r c a t i o n i c p o l y m e r i z a t i o n proposed by Rose (25)
and others (26, 27, 2 8 ) .
^ - Λ 4- P F 5 +H 0
2
PF 5 ΟΗΘ
,0® P F 5 O HΘ
5
The length o f time r e q u i r e d f o r a c o a t i n g to go from the

l i q u i d s t a t e i n which i t i s l a i d down on the s u b s t r a t e to a s o l i d
nontacky s t a t e i s dependent upon the c o n c e n t r a t i o n o f photo-
initiator. Coatings c o n t a i n i n g v a r i o u s amounts o f p-methoxy-
benzenediazonium hexafluorophosphate (PM) were a p p l i e d at a t h i c k -
ness o f 0 . 2 - 0 . 3 m i l to aluminum, and the time to become t a c k - f r e e
f o l l o w i n g two seconds' exposure to a General E l e c t r i c UA-3 mercury
arc (60 watts per inch) was determined. Coatings c o n t a i n i n g 1.0
to 1.2 parts o f PM per 100 parts o f epoxide cured r a p i d l y . Tack-
free times o f l e s s than one second could not be measured a c c u r -
a t e l y , and there appeared l i t t l e advantage i n using l a r g e r amounts
of p h o t o i n i t i a t o r . . At lower concentrations o f p h o t o i n i t i a t o r
there was a d r a s t i c increase i n the time r e q u i r e d f o r the c o a t i n g
to become nontacky, p a r t i c u l a r l y at concentrations below 0.6 parts
of p h o t o i n i t i a t o r per 100 parts of epoxide.
Table III. Effect of Photoinitiator Concentration on Rate of Cure
Amount o f P h o t o i n i t i a t o r ^ Tack-Free l m e ( 2 )
per 100 grams o f ECC* (seconds)

Grams Moles
0.2 0.0007 60+

0.4 0.0014 60+
0.6 0.0021 4
1.0 0.0035 3
1.2 0.0043 1
1.4 0.0050 1
(1) p-Methoxybenzenediazonium hexafluorophosphate (PM)
(2) Time following two seconds' exposure to G.E. UA-3

mercury arc at a distance of 4.5 inches for 0.2-
0.3 mil coating on aluminum to become tack free.
* ECC = 3,4-Epoxy cyclohexylmethyl-3 34-epoxy cyclo-

hexane carboxylate.
The amount o f r a d i a t i o n r e q u i r e d to decompose the PM photo-

i n i t i a t o r i n a c o a t i n g 0 . 2 - 0 . 3 mil t h i c k on aluminum was d e t e r -
mined s p e c t r o p h o t o m e t r i c a l l y by changes i n the u l t r a v i o l e t
absorbance f o l l o w i n g exposure to a mercury arc (29). By t h i s
method i t was determined t h a t more than 90% o f the PM was photo-
l y z e d during two seconds' exposure to the UA-3 arc at a d i s t a n c e
of 4.5 inches (see Figure 1 ) . The r a d i a t i o n dose r e c e i v e d by the
2
sample under these c o n d i t i o n s was 0.70 j o u l e / c m .
In mixtures o f epoxides and diazonium s a l t s , there i s
g e n e r a l l y a "dark r e a c t i o n " which takes place even i n the absence
of u l t r a v i o l e t r a d i a t i o n . Mixtures stored i n the dark at average
room temperatures w i l l g r a d u a l l y become more v i s c o u s and eventu-
ally solidify. The r a t e at which t h i s occurs i s i n f l u e n c e d by
WATT Photosensitized Epoxides
Figure 1. Change in UV absorbance of a photosensitized coating on exposure to

the mercury arc (Photosensitizer = PM)
several f a c t o r s , i n c l u d i n g storage temperature and sample s i z e .

I t i s s t r o n g l y dependent upon the epoxides which are present.
Some epoxides react very s h o r t l y a f t e r mixing w i t h a d i a -
zonium s a l t . Epoxides such as a l l y l g l y c i d y l e t h e r , v i n y l
cyclohexene d i o x i d e and butanediol d i g l y c i d y l ether react v i g o r -
o u s l y when mixed with p-chlorobenzenediazonium hexafluorophos-
phate, e v o l v i n g heat and forming s o l i d products. Diglycidyl
ethers o f bisphenol "A" (DGEBA) gel slowly over a p e r i o d o f
several hours. Other epoxy r e s i n s show a very gradual increase
i n v i s c o s i t y over a p e r i o d o f days or weeks (see Table I V ) .
Another f a c t o r i n f l u e n c i n g storage s t a b i l i t y o f photosensi-
t i z e d epoxides i s the s t r u c t u r e o f the aromatic diazonium s a l t .
The nature and p o s i t i o n o f s u b s t i t u e n t s on the benzene r i n g o f
the diazonium s a l t s i q n i f i c a n t l y i n f l u e n c e s r e a c t i v i t y toward
epoxides (see Table V ) .

Storage s t a b i l i t y can be f u r t h e r improved by a d d i t i o n o f
" s t a b i l i z e r s " which i n h i b i t the dark r e a c t i o n without r e t a r d i n g
r a t e o f cure. M a t e r i a l s f i t t i n g the d e s c r i p t i o n o f Lewis Bases
or e l e c t r o n - d o n o r compounds are g e n e r a l l y e f f e c t i v e i n i n h i b i t i n g
the dark r e a c t i o n . Many compounds o f t h i s t y p e , however, tend to
quench the c a t i o n i c r e a c t i o n c o m p l e t e l y , so t h a t c u r i n g does not
occur even on exposure to u l t r a v i o l e t r a d i a t i o n .
There are some donor compounds which, w h i l e not completely
preventing the dark r e a c t i o n , w i l l i n h i b i t i t and, at the same
t i m e , not i n t e r f e r e with the c u r i n g r e a c t i o n . C y c l i c amides ( 3 0 ) ,
n i t r i l e s ( 3 1 ) , s u b s t i t u t e d ureas (32) and s u l f o x i d e s (33) have
been shown to promote storage s t a b i l i t y o f p h o t o s e n s i t i z e d
epoxides without preventing r a p i d cure when exposed to u l t r a v i o l e t
radiation.
Figure 2 i l l u s t r a t e s the e f f e c t o f an added s t a b i l i z e r
(N-methylpyrrolidone) on storage s t a b i l i t y o f a mixture o f epoxy
resins.
S t a b i l i z a t i o n o f p h o t o s e n s i t i v e epoxides by e l e c t r o n donor
compounds i s probably due to formation o f a complex with the Lewis
a c i d which i s s l o w l y l i b e r a t e d by decomposition o f the diazonium
s a l t on storage (23, 3 4 ) .
Diary!iodonium S a l t s . The use o f d i a r y l i o d o n i u m s a l t s as

p h o t o i n i t i a t o r s f o r epoxide p o l y m e r i z a t i o n was f i r s t described i n
Belgian Patents issued i n 1975 and 1976 (35, 36, 37_). D i a r y l -
iodonium s a l t s had been used e a r l i e r i n photoinduced p o l y m e r i z a -
t i o n ( 3 8 ) , but they were used f o r f r e e - r a d i c a l p o l y m e r i z a t i o n s .
Diaryliodonium s a l t s are not strong absorbers o f l i g h t at
wavelengths above 300 nanometers ( 4 , 3 9 ) . They do not make
e f f i c i e n t use of the output o f the high-pressure mercury arc and,
as a r e s u l t , cure i n i t i a t e d by d i a r y l i o d o n i u m s a l t s i s apt to be
slow and to r e q u i r e longer exposure than i s the case with d i a -
zonium s a l t s . Rates o f cure can be increased by adding to the
d i a r y l i o d o n i u m s a l t a p h o t o s e n s i t i z e r which absorbs longer wave-
length r a d i a t i o n and permits c u r i n g under sources o f v i s i b l e
Table IV. Reactivity of Epoxides Toward Diazonium Salt
Epoxy Result when mixed with

E P O X I D E Value p - e h l o v o b e n z e n e d i a z o n i u m * PFe
V i n y l cyclohexene d i o x i d e 1.39 Vigorous exothermal reaction
Allyl glycidyl ether 0.87
Butanediol d i g l y c i d y l ether 0.75
3,4-Epoxy c y c l o h e x y l m e t h y l - 3 , 4 -
epoxy cyclohexane c a r b o x y l a t e 0.74 V i s c o s i t y goes from 470 to
2600 cps i n 5 days
DGEBA ( V i s . @25°C 4000-6000 cps) 0.57 Gels i n 20 hours
Epoxy phenol novolak ( V i s . @52°C

1400-2000 cps) 0.56
Bis(3,4-Epoxy-6-methyl cyclohexyl
methyl) adipate 0.47 928 to 1885 cps i n 5 days
Ci2-ii» alkyl glycidyl ether 0.35 8 to 30 cps i n 5 days

Table V . Benzenediazonium Hexafluorophosphates

Influence of Substituents
Melting Ultraviolet
2
Photoinitiator Point Absorption Cure Time 1
Potlife
(°C) Maxima (nm) (seconds) (hours)
N PF
2 6
162-164 273 Gelled within

24 hours
N PF
2 6
149-151 313 1 28
OCH3
N PF
2 6
230
132 300 1 96
335
OCH3
Gel led.within
24 hours
1
Time for ECC containing one pph photoinitiator to become tack-free
following two seconds' exposure to GE UA-3 mercury arc at 4.5 inches.
Sample temperature = 20°C.
1
Length of time in storage at 40°C for doubling of viscosity of formulation
consisting of 55 parts DGEBA, 30 parts ECC, 15 parts Cu-ih alkyl glycidyl
ether and 1 part photoinitiator.
0 1 2 3 4 5 6
STORAGE TIME, DAYS
Figure 2. Effect of electron donor compound on storage stability of photosensi-

tized epoxide mixture stored at 40°C (Photosensitizer = PM): (A) without N-
methylpyrrolidone; (B) 0.005% N-methylpyrrolidone added; (C) 0.02% N-methyl-
pyrrolidone added; (D)0.06% N-methylpyrrolidone added
light (40).
The mechanism by which d i a r y l i o d o n i u m s a l t s i n i t i a t e p o l y -
m e r i z a t i o n o f epoxides has been e x p l a i n e d as i n v o l v i n g a c i d s
produced from p h o t o l y s i s o f the d i a r y l i o d o n i u m s a l t (2^ 3^ 4 ) :
Ar IPF
2 6 — ^ A r l + Ar- + Y- + HPF 6
YH ( s o l v e n t )
T h i s i s followed by c a t i o n i c p o l y m e r i z a t i o n o f the epoxide i n i t i -
ated by the proton from H P F . 6
The d i a r y l i o d o n i u m metal h a l i d e complex s a l t s are not

commercially a v a i l a b l e at t h i s w r i t i n g . Methods f o r t h e i r pre-
p a r a t i o n are reviewed i n a paper by C r i v e l l o and Lam ( 4 ) .
Sulfonium S a l t s . Other onium s a l t s beside the diazonium and

halonium s a l t s w i l l , on exposure to l i g h t , i n i t i a t e polymerization
of epoxides and other monomers capable of undergoing c a t i o n i c
p o l y m e r i z a t i o n . The use o f onium s a l t s o f the elements of Groups
Va and V i a was f i r s t described i n 1975 ( 4 1 , 42) and 1976 (43).
More r e c e n t l y , U . S . patents have been granted c o v e r i n g the use o f
onium s a l t s o f the elements o f Groups Va (44, 45J and V i a (46,
47) w i t h epoxides and with other monomers which are known t o
polymerize c a t i o n i c a l l y .
There seems to be some confusion concerning the n e c e s s i t y to
add p h o t o s e n s i t i z e r s to increase s p e c t r a l absorbance i n order to
o b t a i n r a p i d cure o f epoxides c o n t a i n i n g t r i a r y l s u l f o n i u m s a l t s .
The aromatic sulfonium complex s a l t s are claimed to be photosen-
s i t i v e o n l y to the s h o r t e r wavelength r a d i a t i o n (_5, 3 9 ) , and they
have been reported to be s l i g h t l y l e s s p h o t o r e a c t i v e than d i a r y l -
iodonium s a l t s ( 6 ) . The l i m i t e d s p e c t r a l response has been c i t e d
as a s e r i o u s inherent l i m i t a t i o n w i t h respect to t h e i r use as
p h o t o i n i t i a t o r s i n p h o t o s e n s i t i v e compositions ( 4 8 ) . I t was
shown t h a t a c o a t i n g made up o f 4 parts t r i phenylsulfonium hexa-
fluorophosphate (TPS) i n 100 parts o f an epoxy r e s i n (DER 331)
f a i l e d to cure i n 5 minutes' exposure to a G . E . H3T7 mercury a r c ;
but f o l l o w i n g a d d i t i o n o f .02 parts o f 2 - e t h y l - 9 , 1 0 - d i m e t h o x y -
anthracene, c u r i n g occurred i n f i f t e e n seconds.
On the other hand, i t has been reported t h a t t r i a r y l s u l f o r r i u m
s a l t s are very r e a c t i v e p h o t o i n i t i a t o r s for the r i n g opening of
epoxy monomers (_7). I t was a l s o reported (49) t h a t a c o a t i n g com-
posed o f 4% by weight o f t r i p h e n y l s u l f o n i u m hexafluorophosphate i n
3 , 4 - ë p o x y c y c l o h e x y l m e t h y l - 3 , 4 - e p o x y cyclohexane c a r b o x y l a t e cured
i n 20 seconds' exposure.
I t has been p o s t u l a t e d (6) t h a t p h o t o l y s i s o f Group Va and
Via onium s a l t s proceeds as shown below, and that the a c i d HPF 6
then i n i t i a t e s r i n g opening and p o l y m e r i z a t i o n o f the epoxide.

This i s s i m i l a r to the mechanism proposed by Dreyfuss and Dreyfuss
(13). The n o n n u c l e o p h i l i c counterion PF ~does not react w i t h the
6
growing c a t i o n i c species
AR SPF
3 6 ^ • A r S + ArH +
2 Y- + HPF 6
The a r y l s u l f o n i u m metal h a l i d e complex s a l t s are not r e a d i l y

a v a i l a b l e . T r i p h e n y l s u l f o n i u m hexafluorophosphate can be pre-
pared from diphenyliodonium hexafluorophosphate by heating w i t h
phenyl s u l f i d e , as described by Knapczyk and McEwen ( 5 9 ) , or by
r e a c t i o n o f phenyl magnesium bromide w i t h d i p h e n y l s u l f o x i d e
followed by r e a c t i o n w i t h hexafluorophosphoric a c i d according to
the procedure o f W i l d i , T a y l o r and P o t r a t z (60).
Comparison o f P h o t o i n i t i a t o r s
Two p r o p e r t i e s of fundamental importance to the successful

f u n c t i o n i n g o f a p h o t o i n i t i a t o r f o r l i g h t - c u r a b l e coatings are
cure r a t e and storage s t a b i l i t y o f the p h o t o s e n s i t i z e d formu-
lations. In high-speed c o a t i n g o p e r a t i o n s , the i n t e r v a l between
a p p l i c a t i o n o f the c o a t i n g and r o l l i n g up or s t a c k i n g o f the
coated s u b s t r a t e i s often no more than a few seconds. In t h i s
b r i e f i n t e r v a l the c o a t i n g must be converted from a f r e e - f l o w i n g
l i q u i d to a nontacky s o l i d .
While capable o f r a p i d c u r e , the c o a t i n g must be s u f f i c i e n t l y

s t a b l e t h a t i t does not undergo a p p r e c i a b l e change i n the period
between a d d i t i o n o f the p h o t o i n i t i a t o r and a p p l i c a t i o n to the
object being coated. T h i s i n t e r v a l may be a few hours ( o n - s i t e
mixing) or several months, as would be the case w i t h coatings
prepared at a c e n t r a l l o c a t i o n and stored f o r extended periods
p r i o r to d i s t r i b u t i o n and use.
Comparison o f Rates of Cure. The r a t e a t which coatings

cure i s g e n e r a l l y based on personal judgment o f the time r e q u i r e d
to become nontacky to the touch. The t e s t i s simple and w i d e l y
used, but i t i s h i g h l y s u b j e c t i v e .
We have developed an instrument which e l i m i n a t e s much of the
s u b j e c t i v i t y o f the touch t e s t . T h i s instrument, which i s i l l u s -
t r a t e d i n Figure 3, c o n s i s t s o f an o s c i l l a t i n g stage which carries
a coated metal coupon i n t o an enclosure c o n t a i n i n g a shuttered
mercury arc ( G . E . UA-3, 60 watts per inch) i n a p a r a b o l i c r e f l e c -
tor. When the o s c i l l a t i n g stage enters the e n c l o s u r e , a s h u t t e r
opens, exposing the coated coupon to the u l t r a v i o l e t r a d i a t i o n
from the mercury a r c . At the end o f a measured i n t e r v a l , the
s h u t t e r c l o s e s , and the o s c i l l a t i n g stage r e t r a c t s .
The s h u t t e r operates on a t i m e r , p e r m i t t i n g v a r i a t i o n s i n
exposure time from one second to f i f t e e n minutes.
Figure 3. Device for measuring tack-free time: (1) probe (absorbent cotton);
(2) timer controlling interval between exposure and activation of probe; (3) oscil-
lating stage; (4) exposure timer; (5) constant temperature bath and circulator;
(6) air pressure regulator controlling pressure on probe; (7) General Electric UA-3
mercury arc, reflector, and shutter (inside enclosure)
210 235 260 285 310 335 360

WAVELENGTH^ NANOMETERS )
Figure 4. UV absorbance spectra of onium salt photoinitiators

When the s h u t t e r c l o s e s and the stage r e t r a c t s , a second

timer i s a c t i v a t e d which c o n t r o l s the i n t e r v a l between exposure
and a d m i n i s t r a t i o n o f the tack t e s t . This i n t e r v a l can a l s o be
v a r i e d from one second to 15 raiautes i n increments o f one second.
The tack t e s t i s administered by a small a i r - d r i v e n p i s t o n ,
to one end o f which i s attached a probe c o n s i s t i n g o f a b a l l of
absorbent c o t t o n . Pressure on the probe i s c o n t r o l l e d by a i r
pressure d r i v i n g the p i s t o n . A tacky c o a t i n g i s r e a d i l y recog-
nized by the tendency o f cotton 1 i n t e r s to adhere to i t . The
number of seconds f o l l o w i n g exposure f o r a c o a t i n g to become hard
enough t h a t i t does not p u l l c o t t o n 1 i n t e r s from the probe i s
defined as the " t a c k - f r e e t i m e " .
An advantage o f measuring independently both the exposure
time and the i n t e r v a l between exposure and the disappearance o f
tack i s that i t allows a separation o f the e f f e c t s o f u l t r a v i o l e t

r a d i a t i o n and the e f f e c t s of heat.
The photoinduced c u r i n g of epoxides i n v o l v e s two s t e p s :
1. Photodecomposition o f the i n i t i a t o r
2. P o l y m e r i z a t i o n o f the epoxide
U l t r a v i o l e t r a d i a t i o n i s r e q u i r e d only f o r the f i r s t s t e p . The

second s t e p , w h i l e independent o f UV r a d i a t i o n , i s influenced by
heat. Continuous exposure to a mercury arc to determine t a c k -
free time can i n f l u e n c e the course o f the p o l y m e r i z a t i o n because
of an increase i n temperature of c o a t i n g and s u b s t r a t e caused by
the intense heat o f the mercury a r c . To avoid t h i s c o m p l i c a t i o n
and to maintain c o n t r o l o f the temperature o f the c o a t i n g during
c u r e , exposure to the mercury arc was g e n e r a l l y l i m i t e d to two
seconds. This proved adequate to g i v e a t a c k - f r e e c o n d i t i o n
w i t h i n one second f o l l o w i n g exposure f o r the most r e a c t i v e
epoxides.
The PM and TPS p h o t o i n i t i a t o r s g e n e r a l l y gave s h o r t e r t a c k -
free times than DPI; and at the lower c o n c e n t r a t i o n l e v e l , PM
was somewhat more e f f e c t i v e than TPS. T h i s can be a t t r i b u t e d to
the more e f f i c i e n t use o f the mercury arc r a d i a t i o n by the PM
p h o t o i n i t i a t o r , which has an a b s o r p t i o n peak a t 313 nanometers
(Figure 4 ) , corresponding to a peak i n the emission spectrum o f
the mercury a r c . Absorption maxima f o r DPI and TPS are at the
lower end o f the spectrum, f a r removed from the peak output o f the
high pressure mercury a r c .
An e x p l a n a t i o n o f the d i f f e r e n c e s i n cure r a t e between DPI
and TPS i s l e s s o b v i o u s , as the absorption spectra o f these two
compounds are s i m i l a r . Depending on the method of p r e p a r a t i o n ,
however, the TPS p h o t o i n i t i a t o r frequently shows some absorbance
i n the s p e c t r a l region between 290 and 340 nm, o v e r l a p p i n g the
band at 310 i n the mercury lamp emission spectrum. This may be
the r e s u l t o f a f o r t u i t o u s contaminant not completely removed i n
s y n t h e s i s and p u r i f i c a t i o n o f the TPS p h o t o i n i t i a t o r .
Differences i n c a t a l y t i c a c t i v i t y o f the three p h o t o i n i t i a -

t o r s are most obvious when the coatings are exposed t o a source
of predominantly v i s i b l e l i g h t , such as s u n l i g h t , or to a source
of shortwave r a d i a t i o n , such as a g e r m i c i d a l lamp. Table VI
shows the time r e q u i r e d f o r 3,4-epoxycyclohexylmethyl-3,4-epoxy-
cyclohexane c a r b o x y l a t e (ECC) p h o t o s e n s i t i z e d w i t h the three
p h o t o i n i t i a t o r s to become t a c k - f r e e when exposed to v a r i o u s
sources o f l i g h t .
Table VI. Comparison of Photoinitiators
E f f e c t o f R a d i a t i o n Source on Rate of Cure o f

3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate
P h o t o s e n s i t i z e d w i t h PM, DPI or TPS
TACK-FREE TIME, seconds

R a d i a t i o n Source, Exposure Time PM DPI TPS
UA-3 (60W/in), 2 seconds 2 60 5

II II ^ II
1 5 1
S u n l i g h t (continuous exposure) 25-30 NC* NC*
Germicidal lamp (continuous 75 35 15
exposure)
*Did not cure in 30 minutes continuous exposure
I t can be seen t h a t under the i n f l u e n c e o f s u n l i g h t , PM w i l l

i n i t i a t e p o l y m e r i z a t i o n r e a d i l y , w h i l e n e i t h e r DPI nor TPS pro-
duces a cure. Under the germicidal lamp, which emits 254 nm
r a d i a t i o n almost e x c l u s i v e l y , the s i t u a t i o n i s r e v e r s e d , w i t h DPI
and TPS which are strong absorbers o f the s h o r t e r wavelength
r a d i a t i o n , being somewhat more e f f e c t i v e than PM.
Storage S t a b i l i t y o f P h o t o s e n s i t i z e d Epoxides. Storage

s t a b i l i t y o f p h o t o s e n s i t i z e d formulations i s dependent upon many
f a c t o r s , such as temperature, sample s i z e , s t r u c t u r e and concen-
t r a t i o n o f the p h o t o i n i t i a t o r , e x c l u s i o n o f l i g h t and the pre-
sence o f i m p u r i t i e s . Tests were run under p a r a l l e l c o n d i t i o n s
using a mixture o f epoxides known to give a short p o t l i f e w i t h
the PM p h o t o i n i t i a t o r to compare storage s t a b i l i t y o f the same
formulation p h o t o s e n s i t i z e d w i t h DPI or TPS.
Storage s t a b i l i t y was determined by p e r i o d i c measurement o f
v i s c o s i t y . Results are summarized i n Table V I I .
Table VII. Comparison of PM, DPI, and TPS: Potlife of

an Unstabilized Formulation @ 4 0 ° C
Time f o r V i s c o s i t y
Photoinitiator to Double
PM < 12 hours
DPI 13 days
TPS No change a f t e r 6 months
C h a r a c t e r i s t i c s o f the Curing Process
Dreyfuss and Dreyfuss (13) showed t h a t the c a t i o n i c polymer-

i z a t i o n o f c y c l i c ethers has the c h a r a c t e r i s t i c s of a " l i v i n g "

p o l y m e r i z a t i o n , i n t h a t there appears to be a l a c k o f t e r m i n a t i o n
except through r e a c t i o n o f the c a t i o n i c growing chain end with
i m p u r i t i e s ; and t h a t e v e n t u a l l y a steady s t a t e i s a t t a i n e d where
the l i v i n g polymer i s i n e q u i l i b r i u m w i t h i t s monomer.
In the p h o t o i n i t i a t e d c a t i o n i c p o l y m e r i z a t i o n o f epoxides,
UV energy i s r e q u i r e d o n l y to cause decomposition of the photo-
s e n s i t i v e s a l t r e l e a s i n g the m a t e r i a l s which i n i t i a t e p o l y m e r i -
z a t i o n . Once t h i s has been done, the propagation o f p o l y m e r i z a -
t i o n continues without f u r t h e r input o f UV energy. Crosslinking
continues long a f t e r exposure t o u l t r a v i o l e t r a d i a t i o n has been
stopped. The p r a c t i c a l consequence o f t h i s i s t h a t the coated
s u b s t r a t e can be r o l l e d up or stacked as soon as the surface
becomes nontacky. Curing w i l l continue i n s t o r a g e .
Evidence o f t h i s c o n t i n u i n g r e a c t i o n can be obtained spectro-
p h o t o m e t r i c a l l y . The i n f r a r e d spectrum o f a p h o t o s e n s i t i z e d
c o a t i n g on an aluminum s u b s t r a t e showed an a b s o r p t i o n band a t
1
910 c m " , as shown i n Figure 5. Immediately a f t e r c u r i n g t o a
1
t a c k - f r e e s u r f a c e , the i n f r a r e d absorbance at 910 cm- had
d i m i n i s h e d . A f t e r standing 20 hours longer i n the absence of
l i g h t , i t had a l l but disappeared, i n d i c a t i n g disappearance o f
n e a r l y a l l unreacted epoxide groups.
Evidence o f a c o n t i n u i n g r e a c t i o n was a l s o obtained by S. I .
S c h l e s i n g e r (17) who noted an increase i n the number o f steps on
a photographic step t a b l e t p r o p o r t i o n a l to the delay between ex-
posure and development.
Changes i n the s o l v e n t and abrasion r e s i s t a n c e o f cured coat-
ings w i t h age f o l l o w i n g exposure a l s o gave evidence o f a " l i v i n g "
p o l y m e r i z a t i o n . Resistance o f coatings to methyl e t h y l ketone
immediately a f t e r exposure i s g e n e r a l l y poor, even though the
c o a t i n g s are nontacky. These same coatings an hour or more l a t e r
e x h i b i t e x c e l l e n t r e s i s t a n c e to MEK.
Before After After standing

Exposure Exposure 20 Hrs. in dark
Figure 5. IR spectrum showing disappearance of epoxide band at 910 cm' fol-

1
lowing exposure of photosensitized coating to mercury arc

E f f e c t o f Epoxide S t r u c t u r e on Rate of Cure. The r a t e at

which p h o t o s e n s i t i z e d epoxides are converted from the l i q u i d to
the s o l i d s t a t e i s i n f l u e n c e d by the epoxide s t r u c t u r e . Some
p h o t o s e n s i t i z e d epoxides remain l i q u i d even a f t e r prolonged expo-
sure to the output o f a mercury a r c , w h i l e others s o l i d i f y i n
l e s s than one second. Rates a t which various epoxides become
t a c k - f r e e are shown i n Table V I I I .
Epoxidized o l e f i n s show the highest r a t e s o f c u r e . In the
formulation o f c o a t i n g s , i t i s g e n e r a l l y necessary to use a mix-
t u r e o f epoxy r e s i n s i n order to o b t a i n the rheology needed f o r
a p p l i c a t i o n or to o b t a i n the p a r t i c u l a r p r o p e r t i e s r e q u i r e d by
the end use o f the object being coated. Coatings to be cured at
ambient c o n d i t i o n s g e n e r a l l y r e q u i r e some a l i p h a t i c epoxide f o r
r a p i d cure ( 5 0 ) . The data i n Table IX i l l u s t r a t e s the e f f e c t o f
i n c l u d i n g a c y c l o a l i p h a t i c epoxide i n c o a t i n g formulations which

are to be cured under ambient c o n d i t i o n s .
Epoxides which cure r e l a t i v e l y s l o w l y or not a t a l l at
o r d i n a r y temperatures can be used as components o f mixtures con-
t a i n i ng 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate
(ECC), i n which case the r a t e o f cure i s dependent upon the amount
o f ECC i n the m i x t u r e .
Mixtures o f epoxides which are slow to cure at o r d i n a r y tem-
peratures w i l l cure more r a p i d l y at e l e v a t e d temperatures ( 3 ) .
The e f f e c t s o f temperature on r a t e o f cure o f mixtures o f a c y c l o -
a l i p h a t i c epoxide and a DGEBA r e s i n are shown i n Table X.
E f f e c t o f Humidity on Rate o f Cure
C a t i o n i c p o l y m e r i z a t i o n i s terminated by the presence of

contaminants, i n c l u d i n g water. In experiments to note the com-
bined e f f e c t s o f temperature and humidity on t a c k - f r e e t i m e ,
temperature o f the s u b s t r a t e was c o n t r o l l e d by means o f the
o s c i l l a t i n g s t a g e , as described above, and humidity was c o n t r o l l e d
by conducting the experiments i n an environmental chamber. Re-
s u l t s are shown i n Table X I .
At r e l a t i v e h u m i d i t i e s o f 65% or l e s s the e f f e c t on t a c k -
free time ranged from n e g l i g i b l e to s l i g h t w i t h epoxides c o n t a i n -
ing the PM or TPS p h o t o i n i t i a t o r s . With DPI, r e s u l t s were
s t r o n g l y dependent upon the epoxide. The 3:1 mixture o f c y c l o -
a l i p h a t i c diepoxide and DGEBA r e s i n showed no change i n t a c k - f r e e
time when humidity was r a i s e d from 45% t o 65%; but the t a c k - f r e e
time of the 3:1 mixture o f c y c l o a l i p h a t i c d i e p o x i d e and butane-
d i o l d i g l y c i d y l ether increased s i g n i f i c a n t l y .
High humidity (85%) caused a d r a s t i c increase i n t a c k - f r e e
time when the s u b s t r a t e was maintained at 35°C or l e s s . When the
s u b s t r a t e temperature was r a i s e d to 45°C, the e f f e c t of high
humidity on t a c k - f r e e time was overcome and r a p i d cure was ob-
served. Under commercial UV c u r i n g c o n d i t i o n s ( i . e . , m u l t i p l e
200 watt per inch lamps and no c o n t r o l o f s u b s t r a t e temperature),
coatings would o r d i n a r i l y reach or exceed 45°C on exposure to the
mercury arcs and t h i s would tend to obscure the e f f e c t s o f high
humidity.
Table VIII. Tack-Free Time of Various Epoxides Photosensitized

with PM, DPI, or TPS
TACK -FREE TIME, SECONDS**

EPOXIDES PM DPI TPS
0.005* | 0.01 * 0.005*| 0.01 * 0.005*1 0.01*
1 1 3 1 1 1
o
1 1 15 2 1 1
0 Q r 0 ^ C H 2 ) 4 - % ^ Q . 0 6 4 60+ 17 7 4
60+ 10 60+ 60 60+ 10

A
^ C H 3 C H ^
60+ 40 60+ 60+ 60+ 60+
60+ 30 60+ 40 60+ 60+

( EEWI75 Î
60+ 30 60 35 60+ 60+
(EEWI89Î
* CONCENTRATION IN MOLES OF PHOTOINITIATOR PER GRAM EQUIVALENT WEIGHT OF EPOXIDE
* * T I M E TO BECOME TACK-FREE FOLLOWING TWO SECONDS EXPOSURE TO GENERAL ELECTRIC U A - 3

( 6 0 WATTS /INCH ) MERCURY ARC AT 4.5 INCHES. TEMPERATURE OF S U B S T R A T E 3 0 ° C .
Table IX. Correlation of Viscosity, Epoxy Value, and Cure Time of Epoxide
Coating Showing Dependence of Rapid Cure on Cycloaliphatic Epoxide
EPOXIDE COATING COMPOSITION

Parts by Weight
Resin Resin Resin Resin Vis @ 25°C Epoxy Cure
1 2 3 4 (ops) Value ( seeoi
20 50 — 10 0.54 NC
20 80 -- -- 13 0.67 NC
20 -- 80 -- 100 0.64 4
— 80 — 20 31 0.69 NC
— -- 80 20 841 0.67 2
— 50 ~ 50 110 0.64 NC
-- — 50 50 2253 0.62 5
10 10 -- 80 622 0.53 NC
10 — 10 80 1504 0.53 9
10 40 — 50 94 0.60 NC
10 ~ 40 50 518 0.59 5
10 70 — 20 28 0.66 NC
10 — 70 20 314 0.63 3
5 80 — 15 24 0.67 NC
l
Each composition contained 1 pph PM
2
No. seconds continuous exposure to UA-3 Eg Arc @ 4.5 inches for
coating to become tack-free
*NC = No cure after 60 seconds exposure
*0.2-0. Ζ mil coating on aluminum
Resin 1 = Cxz-m alkyl glycidyl ether
Resin 2 = Butanediol diglycidyl ether
Resin 3 = 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane
carboxylate
Resin 4 = DGEBA (vis.ê25°C = 4000-6000 cps; EEW = 172-178)

Table X. Rate of Cure of DGEBA Resin
R e l a t i o n s h i p between amount of c y c l o a l i p h a t i c epoxide

added and cure r a t e at v a r i o u s temperatures
ECC ADDED Tack-free Time (seconds)

(pph) @23° @30° @40° @50° @60°
None 60+ 60+ 20 5 1
2 60+ 60+ 17 4 1
5 60+ 60+ 17 2 1
10 60+ 55 13 1 1
15 60+ 45 4 1 1
25 25 3 1 1 1
35 4 2 1 1 1
0.2-0.3 mil coatings on aluminum exposed to G.E. UA-3 for

4 sees, at 4.5 inches.
Photoinitiator: PM (1.3 parts per 100 parts epoxide)

Table XI· Comparison of Photoinitiators (PM, DPI, TPS)—Influence

of Temperature and Humidity on Tack-Free Time
2
TACK-FREE TIME, SECONDS
PHOTOINITIATOR
EPOXIDE 45%RH 65% RH 85%RH
e e e
TYPE CONC.' 25° 35 4 5 ° 2 5 35° 45° 25° 35 4 5 °
0 0 0 5 1 1 1 1 1 1 60+ 2 1
ΡM
P M
0.01 1 1 1 1 1 1 60+ 1 1
0 0 0 5
30 10 4 60+ 60+ 60+ 60+ 60+ 60+
DPI
0.01 2 1 1 35 2 1 60+ 60+ 1
EPOXY EQ.WT.= 140 0 0 0 5 1 1 1 1 1 1 60+ 2 1

TPS , K b
VIS. AT 25°C=550CPS 0.01 1 1 1 1 1 1 60+ 1 1
3 PARTS
2 1 1 5 1 1 60+ 13 1
1 1 1 4 1 1 60+ 7 1
4-1 PART 20 14 9 60+ 35 15 60+ 60+ 25

Ô-tCHglcO-^ «" °oT 18 6 2 60+ 15 3 60+ 60+ 5
EPOXY EQ. WT.= 138 5

4 2 1 13 3 1 60+ 45 2
TPS °°°
VIS. A T 2 5 ° C = 8 0 C P S 1 1 1 5 1 1 60+ 10 1
0.01
3 PARTS
60+ 1 1
™ °o°o? 60+ 1 1
+1 PART 60+ 1 1
60+ 1 1
E P O X Y EQ.WT.= 149 1 1 1 60+ 2 1

VIS. A T 2 5 ° C = 8 6 5 C P S ™ IT 60+ 1 1
1
M O L E S PHOTOINITIATOR P E R GRAM E Q . WT. O F EPOXIDE.
2
T I M E FOLLOWING E X P O S U R E TO UV FOR COATING T O B E C O M E T A C K - F R E E ( C O T T O N B A L L T E S T ).
M a i n t a i n i n g the s u b s t r a t e at lower temperatures i n a humid

atmosphere undoubtedly causes condensation o f moisture on the
s u b s t r a t e and c o a t i n g . Excess water w i l l complex w i t h the a c i d i c
i n i t i a t o r promoting p r e f e r e n t i a l l y the h y d r o l y s i s o f epoxy groups.
The net e f f e c t i s to consume epoxy groups which do not c o n t r i b u t e
to c r o s s l i n k i n g (53).
V o l a t i l i t y o f P h o t o s e n s i t i z e d Epoxy Coatings
A p r i n c i p a l m o t i v a t i n g f a c t o r i n the development o f l i g h t -
curable coatings i s the reduction i n v a p o r i z a t i o n o f m a t e r i a l s
which would c o n t r i b u t e to a i r p o l l u t i o n . I t i s therefore d e s i r -
able to minimize the amount o f low-molecular-weight m a t e r i a l i n
a c o a t i n g f o r m u l a t i o n . However, v i s c o s i t y l i m i t a t i o n s imposed by
the method o f a p p l y i n g the c o a t i n g to the s u b s t r a t e r e q u i r e the
i n c l u s i o n o f some low-molecular-weight m a t e r i a l .
L o w - v i s c o s i t y epoxide monomers are a v a i l a b l e which have high

b o i l i n g points and low vapor pressures. However, the nature o f
the c u r i n g process i n v o l v e s c o n d i t i o n s conducive to e v a p o r a t i o n .
The c o a t i n g i s a p p l i e d i n the form o f a t h i n f i l m w i t h a very
large surface. I t i s subjected to r a d i a t i o n from a h i g h - i n t e n s i t y
mercury arc which i n c l u d e s s i g n i f i c a n t i n f r a r e d r a d i a t i o n .
F u r t h e r , the coated surface i s g e n e r a l l y moving at a high v e l o c -
i t y , c r e a t i n g a strong flow o f a i r over the s u r f a c e .
The v o l a t i l i t y o f l i g h t - c u r a b l e epoxy formulations was
determined by observing changes i n weight at three stages:
- A f t e r c o a t i n g but before exposure

- A f t e r exposure
- A f t e r baking a t 110°C f o r 2 hours a t 1 mm pressure
Coatings were a p p l i e d a t a thickness o f approximately 0 . 3 m i l

to weighed aluminum sheets. The t o t a l weight o f c o a t i n g was
between 50 and 60 m i l l i g r a m s . Sheets coated w i t h uncured formu-
l a t i o n s were allowed to stand on the platform o f an a n a l y t i c a l
balance f o r ten minutes at ambient c o n d i t i o n s . T h i s i s c o n s i d e r -
ably longer than the normal i n t e r v a l between c o a t i n g and exposure
i n a standard c o a t i n g o p e r a t i o n , but i t was d e s i r e d to provide
exaggerated t e s t c o n d i t i o n s .
Coated p l a t e s were then exposed to the mercury arc u n t i l the
c o a t i n g was t a c k - f r e e . A f t e r being returned to e q u i l i b r i u m w i t h
room temperature, the coated p l a t e s were weighed a g a i n . The
aluminum p l a t e s w i t h cured coatings were then placed i n a vacuum
oven and baked as described above.
The method i s s e n s i t i v e to changes o f 0.1 m i l l i g r a m or 0.2%
o f the o r i g i n a l c o a t i n g weight.
I t was found t h a t the wet coatings could stand f o r more than
ten minutes w i t h no measurable change i n weight, i n d i c a t i n g no
s i g n i f i c a n t evaporation would be l i k e l y t o occur i n the b r i e f
i n t e r v a l between a p p l i c a t i o n o f the c o a t i n g and i r r a d i a t i o n .
S u r p r i s i n g l y , f o l l o w i n g exposure to the mercury a r c , the

coatings do not l o s e weight, but a c t u a l l y increase i n weight.
This gain i n weight on exposure to the mercury arc has been ob
served c o n s i s t e n t l y over several hundred samples. I t i s a very
r e a l e f f e c t and can be r a t i o n a l i z e d on the basis o f t e r m i n a t i o n
of the p o l y m e r i z a t i o n by water, probably absorbed from the humid
i t y i n the atmosphere.
F i n a l l y , the cured coatings were baked two hours at 110°C
under vacuum ( l e s s than 1 mm Hg), to remove any r e s i d u a l v o l a t i l e s
i n the cured c o a t i n g . The r e s u l t s shown i n Table XII i n d i c a t e
weight l o s s e s ranging from 0.28 to n e a r l y 7%, depending on compo
s i t i o n o f the c o a t i n g .
P r e p a r a t i o n of ρ-Methoxybenzenediazonium Hexafluorophosphate
S i x t y m i l l i l i t e r s (0.30 mole) of 5M h y d r o c h l o r i c a c i d was

added to 12.3 grams (0.10 mole) o f ρ - a n i s i d i n e , and the mixture
was s t i r r e d w i t h heating u n t i l a l l s o l i d s d i s s o l v e d . The s o l u
t i o n was d i l u t e d with 100 m l . o f d i s t i l l e d water and cooled on an
i c e - s a l t bath. A t about 0°C, c r y s t a l s began to form.
S e p a r a t e l y , a s o l u t i o n o f 6.9 grams (0.10 mole) of sodium
n i t r i t e i n 50 m l . o f d i s t i l l e d water was prepared and cooled t o
50C.
The n i t r i t e s o l u t i o n was added s l o w l y to the s t i r r e d a c i d
s o l u t i o n , dropping the n i t r i t e d i r e c t l y i n t o the a c i d , not along
the w a l l s o f the c o n t a i n e r . Rate o f a d d i t i o n was regulated so
t h a t the temperature o f the r e a c t i o n mixture d i d not exceed 8°C.
S t i r r i n g at 0°C was continued f o r 10-15 minutes, then 15 m l .
o f 65% aqueous hexafluorophosphoric a c i d was s l o w l y added,
keeping the temperature of the r e a c t i o n mixture below 8°C.
( C a u t i o n : HPF a t t a c k s g l a s s . A l l p l a s t i c containers and labware
6
should be used f o r handling and t r a n s f e r r i n g t h i s a c i d . )

S t i r r i n g and c o o l i n g were continued f o r 10-15 minutes a f t e r
a l l the HPF had been added.
6
The p r e c i p i t a t e d product was recovered by f i l t r a t i o n , washed

w i t h c o l d water u n t i l free o f c h l o r i n e (AgN0 t e s t ) and a i r d r i e d
3
on the f i l t e r .
The crude product was r e c r y s t a l l i z e d from methanol. Nineteen
grams (68% y i e l d ) o f a white c r y s t a l l i n e product (m.p. 150-151°C)
was o b t a i n e d .
1
Table XII. Changes in Weight of Light Curable Epoxide Coatings
During Various Stages of Processing
PERCENT CHANGE IN WEIGHT

Coating On standing On exposure to During
Formula 10 mins & 23°C mercury arc 2
bake 3
A Nil +2.24 -0.28

Β Nil +2.33 -6.88
C Nil +2.72 -2.40
D Nil +1.37 -1.21
Coating 0.2-0. δ mil thick on aluminum

2
200 watts per inch
3
2 hours at 110°C under vacuum (less than 1 mm Eg)
Conclusions
The c r o s s l i n k i n g o f epoxides i n i t i a t e d by a c i d i c products o f

p h o t o l y s i s i s a promising concept f o r the development o f non-
p o l l u t i n g , energy-conserving c o a t i n g s . I t i s p o s s i b l e t o formu
l a t e compositions from r e a d i l y a v a i l a b l e epoxy r e s i n s and mono
mers which can be a p p l i e d by conventional c o a t i n g machinery and
which cure r a p i d l y enough f o r high speed c o a t i n g o p e r a t i o n s .
Onium s a l t s have many o f the c h a r a c t e r i s t i c s r e q u i r e d o f
photosensitive i n i t i a t o r s f o r light-curable coatings. Aryl-
diazonium, aryliodonium and a r y l s u l f o n i u m s a l t s a l l i n i t i a t e
r a p i d c u r e . Storage l i f e o f p h o t o s e n s i t i z e d formulations ranges
from a few hours t o more than s i x months, depending upon s t r u c t u r e
of the p h o t o i n i t i a t o r , composition o f t h e c o a t i n g and storage
conditions.
The c a t i o n i c process i s not i n h i b i t e d by oxygen. Curing can
be i n i t i a t e d i n a i r under n a t u r a l s u n l i g h t o r l o w - i n t e n s i t y
mercury arcs whose useful l i f e t i m e i s several times t h a t o f the
h i g h - i n t e n s i t y arcs used i n f r e e - r a d i c a l c u r i n g processes.
T y p i c a l o f c a t i o n i c p o l y m e r i z a t i o n , the r a t e o f cure i s
i n f l u e n c e d by temperature and the presence o f moisture. By a
j u d i c i o u s choice o f epoxides, i t i s p o s s i b l e t o formulate
coatings which cure r a p i d l y under ambient c o n d i t i o n s .
The combination o f arylonium s a l t s w i t h s e l e c t e d epoxy
r e s i n s provides the e s s e n t i a l s f o r a v i a b l e system o f l i g h t -
curable coatings and should i n v i t e f u r t h e r i n v e s t i g a t i o n .
Literature Cited
1. Watt, W. R., "Light Curable Coatings from Photosensitized

Epoxides", 14th Annual Coatings Symposium, North Dakota State
University. (1974)
2. Crivello, J . V.; Lam, J. H. W., J. Polymer S c i . , 1976,

Symposium No. 56, 383-395
3. Crivello, J . V.; Lam, J . H. W.; Volante, C. N. J . Radiation

Curing, July 1977, 2-16
4. Crivello, J . V.; Lam, J . H. W. Macromolecules, 1977, 10, 6,

1307-1315
5. Crivello, J . V. "UV Curing: Science and Technology", (S. P.

Pappas, Ed.), Technology Marketing Corp., Stamford, Conn.,1978
6. Crivello, J . V.; Lam, J . H. W.; Moore, J . E . ; Schroeter, S.H.

J . Radiation Curing, 1978, 5, (1), 2-16
7. Crivello, J . V.; Lam, J. H. W.; Organic Coatings and Plastics

Preprints, 1978, Am. Chem. Soc., 39, 31-35
8. Watt, W. R., Organic Coatings and Plastics Preprints, 1978

Am. Chem. Soc., 39, 36-41
9. Ketley, A. D.; Tsao, J . H. Polymer Preprints, 1978, Am. Chem.

Soc. 19 (2), 656-661
10. Ludwigsen, R. J., Radiation Curing, February 1975, 10-14
11. Tarwid, W. Α.; Kester, D. E. Organic Coatings and Plastics

Preprints, 1977, Am. Chem. Soc. 37, (2), 67-72
12. Dreyfuss, M.P.; Dreyfuss, P. Polymer, 1965, 6, 93
13. Dreyfuss, M.P.; Dreyfuss, P. J . Polymer S c i . , 1966, A-1, 4

2179-2200
14. Licari, J . J.; Crepeau, P. C. US 3,205,157 (North American
Aviation, Inc.), September 7, 1965
15. Fischer, E. US 3,236,784 (Farbwerke Hoechst AG), February 22,

1966
16. Schlesinger, S. I . , Polymer Sci. and Eng. 1974, 14 (7),513-515
17. Schlesinger, S. I . , Photographic Sci. and Eng. 1974, 18 (4),

387-393
18. Schlesinger, S. I., US 3,708,296 (American Can Co.),

January 2, 1973
19. Roe, A. Organic Reactions 1949, 5, 193
20. Rutherford, K. G.; Redmond, W.; Rigamonti, J . J . Organic

Chem. 1961, 26, 5149-52
21. Lee, W. E . ; Calvert, J . G.; Malmberg, E. W. JACS 1961, 83,

1928-34
22. Lewis, E. S.; Halliday, R. E . ; Hartung, L. D. JACS 1969, 91

430
23. Muetterties, E. L. US 2,856,370 (Ε. I. DuPont de Nemours,Inc)

Oct. 14, 1958
24. Muetterties, E. L.; Bither, T. Α.; Farlow, M. W.; Coffman,

D. D. J . Inorg. and Nucl. Chem. 1960, 16, 52-59
25. Rose, J . B. "Chemistry of Cationic Polymerization" (P. H.

Plesch, Ed.), The MacMillan Co., 1963.
26. Flory, P. J. "Principles of Polymer Chemistry", Cornell

Univ. Press, 1953, p. 219.
27. Billmeyer, F. W., Jr. "Textbook of Polymer Science", J.

Wiley, 1962, p. 293.
28. Eastham, A. M. Encyclopedia of Polymer Sci. and Tech., 1965,

3, 35
29. Pobiner, H. Analytica Chim. Acta, 1978, 96, 153-163
30. Watt, W. R. US 3,721,617 (American Can Co.) March 20, 1973
31. Watt, W. R. US 3,721,616 (American Can Co.) March 20, 1973
32. Feinberg, J . H. US 3,771,390 (American Can Co.) Jan. 16, 1973
33. Feinberg, J . H. US 3,771,391 (American Can Co.) Jan. 16, 1973
34. Laubengayer, A. W.; Sears, D. S. JACS 1945, 67, 164-166
35. Belgian Patent 828,669 (General Electric Co.) Sept. 1, 1975
36. Belgian Patent 828,841 (3 M Company) November 7, 1975
37. Belgian Patent 837,782 (Imperial Chemical Industries, Ltd)

July 22, 1976
38. Smith, G. H. US 3,741,769 (3 M Company) June 26, 1973

39. Barton, R. W. US 4,090,936 (3 M Company) May 23, 1978
40. Crivello, J . V.; Schroeter, S. H. US 4,026,705 (General

Electric Co.) May 31, 1977

March 16, 1976
44. Crivello, J . V. US 4,069,055 (General Electric Co.)

January 17, 1978

January 17, 1978
46 Crivello, J . V. US 4,058,400 (General Electric Co.)

November 15, 1978

November 15, 1978
48. Smith, G. H. US 4,069, 054 (3 M Company) January 17, 1978

March 16, 1976
50. Watt, W. R. US 3,936,557 (American Can Co.) February 3, 1976
51. Sims, I. D. J . Chem. Soc. 1964, 864-865
52. Dreyfuss, M. P.; Dreyfuss, P. Macromolecules 1968, 1, (5),

437-441
53. Lee, H.; Neville, K. "Handbook of Epoxy Resins", McGraw-Hill

1967, 11-2.
54. British Patent 912,022 (3 M Company), December 5, 1962
55. Cripps, H. N. US 3,347,676 (Ε. I. DuPont de Nemours, Inc.)

October 17, 1967
56. Anderson, W. S. US 3,709,861 (Shell Oil Co.) Dec. 14, 1970
57. Kropp, J . E. US 3,586,616 (3 M Company) June 22, 1971

58. deMoira, P. P.; Murphy, J . P. US 3,930,858 (Ozalid Co.,Inc.),

January 6, 1976
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1965-1967
RECEIVED July 19, 1979.

3
Quaternary Phosphonium Compound Latent Accelerators
for Anhydride-Cured Epoxy Resins
JAMES D. B. SMITH
Westinghouse Research and Development Center, Pittsburgh, PA 15235
Epoxy resins are used extensively in the electrical industry

as insulation materials. In particular, they are used in conjunc-
tion with mica to insulate sophisticated rotating electrical
equipment, such as turbine generators, A.C. motors, and traction
motors. They also find widespread use in transformer and power
circuit breaker insulation applications. It can be stated that,
at the present time, epoxy resins would appear to be the material
of choice for the abovementioned applications because of their
overall superior properties compared to other thermoset polymeric
resins such as polyesters, polyurethanes and acrylics. Among
these superior properties exhibited by epoxy resins are higher
bond strengths, higher mechanical properties, lower shrinkage,
higher resistance to hydrolytic and chemical degradation, good
electrical properties and ease of processing and fabrication.(1,2)
Many of the above cited applications utilize solventless
epoxy resins containing "latent" catalysts which are designed to
be unreactive at room temperature but will give rapid cure of
resin with the application of heat.
A considerable amount of effort has been devoted i n recent
years, mainly i n industrial laboratories, to develop improved
"latent" catalysts for curing epoxy resins. This has been partic-
ularly the case i n the manufacture of e l e c t r i c a l equipment, such
as motors, transformers and generators where epoxy resins are
u t i l i z e d i n such diverse processes as casting, potting, encapsu-
lation, and vacuum pressure impregnation (vpi). For reasons of
economy and convenience, i t i s normal practice to store "one-
package" epoxy resins (i.e., catalyzed resins) in large storage
tanks (typically 2,000 to 10,000 gallons) i n close proximity to
the processing area. Thus, adequate catalyzed storage s t a b i l i t y
at ambient combined with efficient reactivity and cure at
elevated temperatures are necessary prerequisites.
Properties Required of Latent Catalysts. The specific

properties required by an ideal "latent"catalyst would be the
following:
0-841ê-CT/Bî?i8lSAo5:00/0
© 1979 SOOtetyLnLilSFatâl Society
1155 16th St. N. W.
(a) It should give rapid cure of epoxy resins at moderately

elevated temperatures (i.e., 120°-180°C).
(b) It should be completely miscible with the resins at a l l
temperatures. This i s particularly true of impregnating resins.
(c) The storage l i f e of the catalyzed resin should be
indefinite. In practice, the viscosity of the resin should not
change appreciably at room temperature over periods ranging from
several months to years.
(d) It should not adversely affect the properties of the
cured resin (e.g., tensile and e l e c t r i c a l properties).
The need for fast gel times in this application i s because of
the tendency for the impregnating resin to drain out during cure,
thereby leaving voids in the insulation. In practice, i t has been
found that, to avoid excessive void formation, the gel times of
the impregnating resins should be less than 30 min at the cure

temperature.
Experience in the e l e c t r i c a l industry has also shown that
thorough impregnation of the "groundwall" insulation materials
(e.g., mica flake paper) becomes d i f f i c u l t i f the viscosity of the
resin increases above 1,000 cps (as measured at 25°C). The
impregnation process, however, with more viscous resins, can be
made more effective by using higher pressures and elevated temper
atures, but this i s not always desirable or possible in production.
Previous Work on Latent Catalysts for Epoxy Resins. Numerous

patents (3^4_,3) have been issued i n recent years on the develop
ment of latent catalysts for DGEBA (i.e., diglycidylether of b i s -
1
phenol Ά ) resins, but most f u l f i l l only a few of the conditions
outlined above. One of the most successful of these has been the
boron trifluoride-monoethylamine complex (6) . However, one of the
serious disadvantages of this particular latent catalyst i s the
poor e l e c t r i c a l properties at elevated temperatures of the epoxy
resin i n the cured state (7).
To improve high temperature s t a b i l i t y over amine cured systems
and to give better physical and e l e c t r i c a l properties above their
heat distortion temperatures, i t has been general practice in
epoxy resin systems to use anhydride curing agents with DGEBA
epoxy resins (S) . Most anhydride formulations require elevated-
temperature cures with the ultimate properties dependent on post-
cures at temperatures of 150°C or higher.
For most commercial applications, i t i s necessary to add some
form of accelerator to the formulation to speed the rate of cure.
Both acidic and basic accelerators can be used. Consequently,
several latent accelerators have appeared on the commercial scene
in recent years. Included among these are quaternary ammonium
halides such as benzyltrimethylammonium chloride (9), stannous
1
octoate (5), zinc stéarate (10),'extra-coordinate siliconate
salts(11), triethanolamine borate (12) , triethanolamine titanate
(13), and various other metal chelates (14). However, a l l of
these materials have been rejected for one reason or another and
3. SMITH Anhydride-Cured Epoxy Resins 49
the quest for improved latent accelerators for anhydride cured

epoxy resins has continued.
Quaternary Phosphonium Compounds. Recent work (15,16) at our

laboratories has revealed a new family of latent accelerators.
This new family of compounds i s derived from the salts of tertiary
organo-phosphines and aryl or alkyl halides which have the general
structural formula:
X
where R]_, R2» R3 and R4 are alkyl or aryl groups and X i s

halogen, acetate, or dimethylphosphate anion.
Most of the data reported here w i l l be concerned with b i s -
f f
phenol A epoxy resin systems cured with the liquid anhydride,
1-methyltetrahydrophthalic anhydride (the Union Carbide commercial
designation for this material i s ZZLA-0334). However, these
quaternary phosphonium compounds have also been shown to be
effective with other anhydrides such as hexahydrophthalic anhy
dride (HHPA) .
Experimental
Different Quaternary Phosphonium Compounds Evaluated. Seven

different quaternary phosphonium salts were evaluated i n this
work:
i) Methyltrioctylphosphonium dimethylphosphate (MTOP-DMP),
i i ) Tetrabutylphosphonium acetate (TBPA) ,
i i i ) Methyltributylphosphonium dimethylphosphate (MTBP-DMP),
iv) Benzyltriphenylphosphonium chloride (BTPPC),
v) Tetrabutylphosphonium chloride (TBPC),
vi) Methyltriphenylphosphonium dimethylphosphate (MTPP-DMP),
v i i ) Triphenylethylphosphonium iodide (TPEPI).
With the exception of TPEPI, supplied by Arapahoe Chemical
Company, Boulder, CO, a l l of the phosphonium compounds were
supplied by Cincinnati Milacron, Reading, OH. The chemical
structures of the various quaternary phosphonium compounds are
shown i n Table I.
Most of the evaluation studies were made using a 1:1
stoichiometric bisphenol Ά ' epoxy-anhydride formulation. The
various quaternary phosphonium compounds were added at a 0.01 to
0.25% level (based on the combined anhydride and epoxy resin
weights). With the exception of MTPP-DMP, which showed p a r t i a l
insolubility i n the resin formulation, excellent s o l u b i l i t i e s at
ambient temperature were found.
Table I. The Structures of the Various

Quaternary Phosphonium Compounds
Phosphonium
Compound R
l R
2 R
3 R
4 X
0
MTOP-DMP CH C H
"0 P(0CH )
3 C
8 17H C
8 17H
8 17 3 2
0
TBPA C H C H C H
C H
4 9 4 9
4 9 4 9 ~0 H CH :CH
3 3
0
MTBP-DMP CH C H C H
"0 ^(OCH )
3 C
4 9 H 4 9
4 9 3 2
BTPPC C H C H "CI
6 5 2 C
6 5 H
°6 5 H C
6 5 H
TBPC 0,Η Λ
0,Η Λ 0,Η Λ "ci
4 9 4 9 4 9 4 9 fl
MTPP-DMP CH 3 C H
0 P(OCH ) 3 2
C
6 5 H C
6 5 H
6 5
TPEPI C H C H C H "i
C
2 5 H
6 5 6 5 6 5
Gel Time Data. I n i t i a l l y , gel times were recorded on 10 g

samples of resin i n 2 i n . diameter aluminum dishes over the
temperature range 135°C to 170°C Later, to give improved
accuracy, the gel time measurements were made in 19 χ 150 mm test
tubes in a constant temperature silicone o i l bath using a Sunshine
Gel Meter.
Storage Stability Data. Storage s t a b i l i t y characteristics of

e
the formulations were followed at room temperature (i.e., 25 C)
using a Gardner-Holdt bubble viscometer (ASTM //D154-56) . Termi
nation of a sample's catalyzed lifetime ( i . e . , storage l i f e ) was
taken to be when the viscosity reached a value of 1,000 cps at
25°C
E l e c t r i c a l Data. The e l e c t r i c a l properties of cured speci

mens of the epoxy resin, containing various quaternary phosphonium
compounds, were obtained on 2 i n . diameter discs (0.125 i n . to
0.25 i n . thick) using standard procedures (ASTM //D150-65T). In
these tests, the power factor (100 χ tan 6) and dielectric con
stant ( ε ' ) data were usually measured at 150°C (and a frequency of
60 Hz) on resin samples which had been cured for 16 h at 135°C
+ 5 h at 150°C
Results
The data shown in Tables II and III indicate the effective

ness of two of the phosphonium compounds as accelerators for
epoxy-anhydride resins. From the data i n Table I I , i t i s noted
Table I I . Gel Time Data for Quaternary

Phosphonium Latent Accelerators
in Epoxy-Anhydride Resins
Concentration
(% w/w) i n
EDOxv-Anhvdride Gel Time Data (min)
Latent Accelerator Resin 135°C 150°C 170°C
Methyltrioctylphosphonium 0.02 90 35
dimethylphosphate
0.04 115 55 25
(MTOP-DMP)
0.06 75 45 15
0.10 50 15 10
Tetrabutylphosphonium 0.02 120 65 30

acetate (TBPA)
0.04 75 40 15
0.06 60 30 10
0.08 50 25 —
Methyltributylphosphonium 0.02 — 85 35
dimethylphosphate
0.04 110 50 25
(MTBP-DMP)
0.06 75 40 13
Benzyltriphenylphosphonium 0.02 60 —
chloride (BTPPC)
0.10 — 15 —
Tetrabutylphosphonium 0.02 60 —
chloride (TBPC)
0.10 — 15 —
Methyltriphenylphosphonium 0.02 — — 90
dimethylphosphate (MTPP-DMP)
Triphenylethylphosphonium 0.02 125 65 30

iodide (TPEPI)
None >1000 >600 >450

Table III. Viscosity (Storage) Data for Quaternary

Phosphonium Latent Accelerators i n
Epoxy-Anhydride Resins
Storage
Stability Time
e
Concentration (Days at 25 C)
(% w/w) in for Resin
Epoxy-Anhydr ide Viscosity to Reach
Latent Accelerator Resin 500 cps 1000 cps
Methyltrioctylphosphonium 0.02 90 130

dimethylphosphate
0.04 60 85
(MTOP-DMP)
0.06 33 56
0.10 25 45
Tetrabutylphosphonium 0.02 70 112

acetate (TBPA)
0.04 45 80
0.06 30 42
0.10 15 21
Methyltributylphôsphonium 0.01 120 160

dimethylphosphate
0.02 70 115
(MTBP-DMP)
0.04 50 85
Benzyltriphenylphosphonium 0.02 60 90
chloride (BTPPC)
0.10 20 28
Tetrabutylphosphonium 0.02 65 90
chloride (TBPC)
0.10 18 30
Methyltriphenylphosphonium 0.02 115 150

dimethylphosphate
(MTPP-DMP)
Triphenylethylphosphonium 0.02 60 85
iodide (TPEPI)
None 150 300

that fast gel times (i.e., < 60 minutes) can be obtained with
small amounts of accelerator (e.g., 0.06%), particularly at
temperatures above 150°C. In the absence of accelerator, the
epoxy-anhydride resin showed very sluggish curing properties, the
gel time at 150°C being i n excess of 10 hours.
Appreciable latency i s shown by these phosphonium compounds
as demonstrated by the storage data shown in Table I I I . Using
1,000 cps (at 25°C) as being the limiting viscosity, "storage
lifetime" values can be assigned to each of the phosphonium com
pounds as indicated i n Table I I I . It would appear that the non-
halide phosphonium compounds (e.g., MTOP-DMP and MTBP-DMP) exhibit
higher latency than those containing halides. These differences
may be linked to the presence of impurities or hydrolyzed by
products in the halide compounds. In this respect, i t was noted
that two of the materials investigated (i.e., BTPPC and TBPC) had
pungent odors, suggesting the presence of free organo-phosphine;
presumably resulting from sample degradation or hydrolysis. The
three phosphonium compounds showing the best compromise between
storage lifetime and catalytic effectiveness were MTOP-DMP, MTBP-
DMP and TBPA.
The e l e c t r i c a l properties of the cured resins, containing
various quaternary phosphonium additives are shown in Table IV.
The data indicate that the lowest power factor (100 χ tan 6) and
f
d i e l e c t r i c constant (e ) values, as measured at 150°C, are shown
by the samples containing MTOP-DMP and MTBP-DMP. There would
appear to be a trend in these e l e c t r i c a l data i n that the samples
containing halide anionic species (e.g., chloride and iodide)
apparently exhibit higher power factor and d i e l e c t r i c constant
values than the non-halide phosphonium additives. This i s not too
surprising because of the more polar nature of the halide ions
compared to anions such as dimettriphosphate.
In the highest voltage e l e c t r i c a l applications ( i . e . , >15 kV)
in which these epoxy resins would be used, the insulation require
ments are such that a power factor value of <15% and a d i e l e c t r i c
constant of <6.0 (as measured at 150°C) are desirable. This
would then imply that epoxy resins containing MTOP-DMP and MTBP-
DMP would be acceptable for this application, whereas TBPA would
be marginal and TBPC and TPEPI would be unsuitable·
Discussion
Comparison with Other Latent Accelerators. To i l l u s t r a t e the

effectiveness of these quaternary phosphonium salts as acceler
ators for anhydride cured epoxy resins, a comparison of MTOP-DMP
and TBPA with other well-known accelerators i s given in Table V.
The data were obtained from work done in this laboratory using the
same resin systems. To make the comparison v a l i d , the concentra
tion given for each of these materials has been converted from
"phr" to "moles/200 g resin". Thus, the comparison i s made on a
molecular concentration basis instead of weight. Gel times were
Table IV. E l e c t r i c a l Properties of Cured Epoxy-Anhydride

Resins Containing Various Quaternary
Phosphonium Compounds*
E l e c t r i c a l Properties**
at 150°C, 60 Hz
Quaternary % Power Factor Dielectric
Phosphonium Compound* (100 χ tan 6) Constant ( ε ' )
Methyltrioctylphosphonium 8.8 4.1

dimethylphosphate
Methyltributylphosphonium 8.3 5.9

dimethylphosphate
Tetrabutylphosphonium 17.0 4.7

acetate
Tetrabutylphosphonium 29.6 6.2

chloride
Triphenylethylphosphonium 39.4 6.4

iodide
*Phosphonium compound added at *v* 0.05% (w/w) on resin.

**Resin samples cured 16 h at 135°C + 5 h at 150°C.
Table V. Relative Reactivities of Different

Accelerators i n Epoxy-Anhydride Resins
Relative Reactivity (R)
Accelerator (R χ 10~** j moles)
m n
MTOP-DMP 187.3
TBPA 190.1
Benzyltriethylammonium iodide 216.0
1-Methylimidazole 350.0
2-Methyllmidazole 259.0
Zinc stéarate 3165.0
Zinc oleate 1592.0
N,N-diethylethanolamine 213.5
(R) • Gel t i m e ^ o χ accelerator concentration (moles/200 g),

1 5 c
recorded at 135°C as shown in Table I I , and the measure of

relative reactivity (R) of each of the accelerators i s given by
the expression
(R) • [Time to reach gel point, minutes] χ [Molar concentration

of accelerator, (moles/200 g resin)]
Examination of the above equation shows that the more reactive

the accelerator, the lower the product (R) w i l l be. Data have
thus been calculated at 135°C for these accelerators as shown in
Table V.
Comparison of these data (Table V) show, quite clearly, how
much more reactive the phosphonium salts are i n the resin system
than compounds such as substituted imidazoles and organo-zinc
salts (e.g., zinc stéarate and octoate). The only accelerator

that shows substantially more potency than the quaternary phos-
phonium salts i s uranyl nitrate. However, this compound i s not a
latent accelerator in the sense that storage lifetimes are only
of the order of a few days.
The I n i t i a t i o n Mechanism with Phosphonium Compounds. Although

further experimental data are needed to give a f u l l e r under-
standing of the reaction mechanisms involved in the latent accel-
eration effect of these quaternary phosphonium compounds i n epoxy-
anhydride resins, there i s definite indication, at this stage,
that the mechanism does not involve the decomposition of the
phosphonium compound to the free phosphine species (16) . The
i n i t i a t i o n mechanism probably involves the formation of hydrogen-
bonded phosphonium-epoxy or phosphonium-anhydride complexes which
rearrange on the application of heat to form activated species
resulting i n polymerization of the epoxy-anhydride components
<έΖ)·
Quaternary Arsonium and Stibonium Compounds. More recently,
experimental work in this laboratory has revealed that quaternary
arsonium compounds (18) are extremely effective as latent accel
erators for epoxy-anhydride resins. Surprisingly, i t has also
been found that quaternary stibonium compounds are very much less
effective as accelerators than quaternary arsonium, phosphonium
or ammonium compounds. In fact, the order of gelation reactivity
of these compounds with epoxy-anhydride resins would appear to be
as follows:
Arsonium > Phosphonium > Ammonium > Stibonium
Since a l l these elements are i n the same group of the

Periodic Table (i.e., Group VA), one might expect the reactivity
trend to continue going from arsonium compounds to stibonium ones.
The fact that stibonium compounds are the least effective i n this
group suggests that steric hindrance effects, caused by the larger
stibonium (antimony) cation, may be playing a role.
Summary
Quaternary phosphonium compounds have been found to be

extremely effective latent accelerators for anhydride-cured epoxy
resins employed i n e l e c t r i c a l insulation applications. Used at
very low concentrations (0.01 to 0.25% level) i n these resins,
they have been found to give very fast gel times at elevated
temperatures combined with very good storage s t a b i l i t y properties
at room temperature. Results show that the quaternary phosphonium
compounds having non-halide anions give the best compromise of gel
reactivity, storage s t a b i l i t y and e l e c t r i c a l properties. Compari
son with other types of latent accelerators reveal that the
quaternary phosphonium compounds are among the most effective

additives yet discovered for epoxy-anhydride resin systems.
Literature Cited
1. Kohn, L. S., in "Epoxy Resin Technology," Edited by

Paul F. Bruins, Interscience Publishers, New York, 1968,
Chapter 11, 219-228.
2. Sillars, R. W., in "Electrical Insulating Materials and Their
Application," Institution of Electrical Engineers Monograph
Series 14, Peter Peregrinus Ltd., Stevenage, England, 1973,
192-198.
3. German Patent 1,162,439 to Westinghouse (Nov. 1958).
4. British Patent 869,969 to Shell (June 1961).
5. British Patent 966,917 to Union Carbide (Feb. 1965).
6. Launder, A. J., A.C.S. Div. Org. Coatings Plast. Chem.,
Preprints, 24, No. 2 (Sept. 1964).
7. Feuchtbaum, R. B., Insulation, 47 (Sept. 1962).
8. Lee, H. and Neville, K., "Handbook of Epoxy Resins," McGraw
- H i l l Book Company, 1967, Chapter 5, p. 20.
9. U.S. Patent 2,928,807 to Devoe & Raynolds Co. (March 1960).
10. Rogers, D. A. and Kauffman, R. Ν., Westinghouse R&D
Unpublished Work.
11. Vincent, H. L., Frye, C. L. and Oppliger, P. E . , in"Epoxy
Resins," Advan. Chem. Ser., 92, R. F. Gould, Ed.,
American Chemical Society, Washington, D.C., 1970,
Chapter 14.
12. Langer, S. H. and Elbling, I. Ν., Ind. Eng. Chem., 49, 1113
(1957).
13. Langer, S. H . , Elbling, I. Ν., Finestone, A. B. and
Thomas, W. R., J . Appl. Polym. Sci., V, No. 15, 370 (1961).
14. Belgian Patent 633,330 to CIBA (1963).
15. U.S. Patent 3,759,866 to Westinghouse (Sept. 1973).
16. U.S. Patent 3,784,583 to Westinghouse (Jan. 1974).
17. Smith, J . D. B., J . Appl. Poly. Sci., in Press.
18. U.S. Patent 3,979,355 to Westinghouse (Sept. 1976).

4
Development of Epoxy Resin-Based Binders for
Electrodeposition Coatings with High Corrosion
Resistance
W. RAUDENBUSCH
Koninklijke/Shell-Laboratorium, Amsterdam (Shell Research B.V.),
Badhuisweg 3, 1031 CM Amsterdam-Noord, The Netherlands
Electrodeposition (ΕD) has proved to be a most attractive

process for industrial coating, in particular for the priming of
automobile bodies. Epoxy resins play a leading role in this field,
nearly 6 % of a l l epoxy resins sold for coatings being used in ED
systems.
Until the early 1970s, a l l ED binders used industrially were
based on maleinised natural oils, acidic alkyd resins or epoxy
resin esters. Later, binders based on maleinised polybutadiene
oils (LMPBs = low-molecular-weight polybutadienes) also came into
industrial use, particularly in Western Europe. A l l these systems
were of the anionic type, i.e. their water solubility and their
deposition at the anode were due to the presence of carboxylate
groups in the binder molecules. More recently, cathodic ED, with
binders carrying cationic groups (e.g. -N+R H), has proved to be an
2
interesting alternative. This paper describes development work

directed towards improving the corrosion resistance of anionic, and
more briefly, cationic ED binders.
The p r o p e r t i e s , described i n broad terms, o f the d i f f e r e n t
c l a s s e s o f a n i o n i c binders are shown i n Table I. The systems i n i t i
a l l y used (epoxy e s t e r s , m a l e i n i s e d o i l s and a c i d i c alkyds) general
l y performed q u i t e w e l l and the r a p i d r i s e o f t h e LMPBs, notwith
standing t h e i r bath s t a b i l i t y problems, was t h e r e f o r e r a t h e r
surprising.
In f a c t , the advance o f LMPB-based binders was due t o one key
advantage: t h e i r superior c o r r o s i o n r e s i s t a n c e when a p p l i e d t o non-
phosphated s t e e l substrates. This property i s important i n modern
automotive a p p l i c a t i o n s s i n c e most cars now used i n Western Europe
are o f the i n t e g r a l body type on which spray-phosphating always
leaves some p o o r l y phosphated or even bare areas. Primers o f f e r i n g
good c o r r o s i o n p r o t e c t i o n on p o o r l y phosphated s t e e l are thus quite
e s s e n t i a l f o r ensuring a long l i f e t i m e o f modern c a r s . The s u p e r i o r
performance o f LMPBs i n t h i s respect was a s c r i b e d t o the low water
p e r m e a b i l i t y o f polybutadiene f i l m s Our more recent work,
however, has thrown a d i f f e r e n t l i g h t on t h i s theory.
0-8412-0525-6/79/47-114-057$05.00/0
TABLE I
PERFORMANCE OF ANIONIC ED BINDERS
Maleinised o i l s , Epoxy r e s i n M a l e i n i s e d LMPBs

a c i d i c alkyds esters
Bath stability adequate t o very good occasional

very good difficulties
ED p r o p e r t i e s good t o very good good t o

very good very good
Mechanical c o a t i n g good t o very good adequate t o

properties very good very good
Corrosion r e s i s t a n c e
- on phosphated s t e e l good very good very good
- on hare s t e e l poor poor very good
4. RAUDENBUSCH Epoxy Resin-Based Binders 59
Fundamental Studies on the Factors Governing Corrosion Resistance
When comparing two t y p i c a l ED b i n d e r s , a commercial LMPB

system and a l o n g - o i l epoxy e s t e r , i n the standard ASTM s a l t - s p r a y
t e s t (25 yrn c l e a r coatings on bare s t e e l , stoved at 180 C f o r
30 min), we f i r s t observed that the r a t i n g s (good with LMPB, poor
with the epoxy e s t e r ) d i d not depend on the method o f a p p l i c a t i o n
used (ED or spraying from solvent s o l u t i o n ) . Therefore, we subse-
quently a p p l i e d a l l binders simply from organic solvent s o l u t i o n s ,
which g r e a t l y speeded up our f u r t h e r work.
Our second observation was that the epoxy e s t e r coatings
f a i l e d by l o s s o f adhesion r a t h e r than by f i l m degradation. We
assumed that o f the d i f f e r e n t p o l a r groups present (carboxyl, ester,
ether) the carboxyls play the major r o l e i n adhesion promotion, and
l o s e t h i s f u n c t i o n upon s a l t formation with the aqueous a l k a l i

formed during s a l t - s p r a y t e s t i n g . Consequently, we i n q u i r e d which
other, more a l k a l i - r e s i s t a n t , adhesion-promoting groups might be
present i n LMPB b i n d e r s . By i n f r a r e d spectroscopy we discovered
that during c u r i n g o f LMPB f i l m s at 180 °C f o r 30 min about h0% o f
the carbon double bonds i n i t i a l l y present disappear and s u b s t a n t i a l
amounts o f hydroxyl and (ketonic) carbonyl groups are formed. The
assumption that these groups are p r i m a r i l y r e s p o n s i b l e f o r the high
c o r r o s i o n r e s i s t a n c e on bare s t e e l was supported by the f a c t that
LMPB coatings cured only by a i r - d r y i n g (20 °C/T d) contained much
l e s s OH and l e s s C=0 and showed poor s a l t - s p r a y r a t i n g s .
E l a b o r a t i n g on the hypothesis that hydroxyl groups may be
important a l k a l i - r e s i s t a n t adhesion promotors, we i n v e s t i g a t e d the
s a l t - s p r a y performance o f c e r t a i n epoxy-resin-based coatings which
a f t e r c u r i n g contain reasonably w e l l - d e f i n e d l e v e l s o f unreacted
hydroxyl groups. One such system c o n s i s t e d o f t h e s o l i d epoxy r e s i n
EPIKOTE 1007 (E-1007) cured with various amounts o f hexamethoxy-
methylmelamine (HMMM). When the hydroxyl content o f the r e s i n i s
known, and the equivalent weight o f HMMM i s taken as 130 (assuming
for s t e r i c reasons that only three o f t h e s i x a v a i l a b l e methoxy-
methyl groups are r e a c t i v e ) , i t i s p o s s i b l e t o c a l c u l a t e the amount
of r e s i d u a l OH groups i n cured coatings quite a c c u r a t e l y . These
experiments (see Table I I ) showed that good s a l t - s p r a y r e s i s t a n c e
on bare s t e e l may be expected i f t h e coating contains between 200
and kOO meq hydroxyl groups per 100 g. I t i s i n t e r e s t i n g t o note
that good s a l t - s p r a y r e s i s t a n c e appeared t o be u n r e l a t e d t o t h e
degree o f c r o s s l i n k i n g achieved i n t h i s system.
The strong b e n e f i c i a l i n f l u e n c e o f high hydroxyl l e v e l s on
c o r r o s i o n r e s i s t a n c e was a l s o seen i n other model experiments, at
l e a s t where epoxy r e s i n s formed the major coating i n g r e d i e n t s .
Some systems, however, most o f which were based on alkyds r a t h e r
than on epoxies, f a i l e d t o give s i m i l a r l y good s a l t - s p r a y r a t i n g s
even though t h e i r r e s i d u a l OH l e v e l was high (300toU00 meq/100g).
Thus other f a c t o r s c e r t a i n l y a l s o p l a y a r o l e . From our subsequent
work, some o f these f a c t o r s appear t o be:
TABLE I I
a
PROPERTIES OF "EPIKOTE" 1007/HMMM COATINGS ON BARE STEEL
Exp. E-1007/ Mechanical properties Methyl ASTM B117-6U Residual

no. HMMM ethyl salt-spray OH content
weight Buchholζ BS impact, ketone resistance^* of cured
ratio hardness direct, resistance films,
in. lb 1 day 8 days meq/100 g
1 99/1 95 < 5 poor 10 9 350

2 95/5 111 >100 good 10 9 305
3 90/10 115 >100 good 9i 7 250
h 85/15 133 < 5 very good 2 0 190
5 67/33 15^ < 5 very good 0 0 ^0
a. Clear 25 pm coatings a p p l i e d by spraying from organic solvent s o l u t i o n

and stoved at 180 °C f o r 30 min. Systems contained 0.5 %vr o f p - t o l u o l s u l -
f o n i c a c i d as c a t a l y s t .
b. Ratings: 10 = unaffected, 9 = 5 mm l o s s o f adhesion from s c r a t c h , 8= 10 mm
l o s s o f adhesion, 7= 15 mm l o s s o f adhesion, e t c . , 0 = t o t a l l o s s
of adhesion.
- S u s c e p t i b i l i t y o f cured coatings t o a l k a l i n e h y d r o l y s i s .
- H y d r o p h i l i c i t y o f cured f i l m s . Poor s a l t - s p r a y r a t i n g s were found
t o r e s u l t from the presence of too many p o l a r groups i n the coatings.
- S t e r i c (?) f a c t o r s . Generally we observed that the use o f even
modest amounts o f f a t t y acids or t h e i r e s t e r s i n OH-rich binders
s u b s t a n t i a l l y decreases the c o r r o s i o n r e s i s t a n c e . A p o s s i b l e
explanation would be s t e r i c a l s h i e l d i n g of the adhesion-promoting
groups by the long f a t t y a c i d t a i l s .
Development o f Anionic ED Binders with High Corrosion Resistance
The "high-hydroxyl" p r i n c i p l e was discovered i n experiments i n

which the coatings were c o n v e n t i o n a l l y a p p l i e d from organic solvent
s o l u t i o n s . We then set out t o develop ED binders conforming t o t h i s
p r i n c i p l e . Apart from o f f e r i n g good c o r r o s i o n r e s i s t a n c e , such

binders must o f course meet a number of f u r t h e r requirements, such as
- s o l u b i l i t y or d i s p e r s i b i l i t y i n water,
- good bath s t a b i l i t y ,
- good ED behaviour,
- c r o s s l i n k a b i l i t y on s t o v i n g ,
- good mechanical and chemical f i l m p r o p e r t i e s ,
- acceptable p r e p a r a t i o n methods and c o s t s .
Note: The formulations described i n t h i s s e c t i o n are covered by the
German Patent A p p l i c a t i o n OLS 2700537 and other a p p l i c a t i o n s
5
i n a number o f c o u n t r i e s .
Much of our work was based on the f o l l o w i n g approach: Into a
s o l i d epoxy r e s i n (EPIKOTE type 1001 or 100U) t e r m i n a l hydroxyl
groups were introduced by r e a c t i n g the epoxy groups with s t o i c h i o -
metric q u a n t i t i e s o f hydroxy acids such as l a c t i c o r , p r e f e r a b l y ,
d i m e t h y l o l p r o p i o n i c a c i d (DMPA). The r e s u l t i n g h y d r o x y l - r i c h "back-
bones" (8-12 OH groups/molecule) were then reacted with a c y c l i c
anhydride such as s u c c i n i c anhydride (SA) t o introduce the carboxyl
groups necessary f o r s o l u b i l i s a t i o n i n water:
CH -0H CH -0C0-CH -CH -C00H

o o o
t
o
2 ,2 2 2
CH^-0C0-C-CH o CH-0C0-C-CH-
CH -0H
o
2 I 3 2 , 3
^0 -OH CH -0C0-CH -CH -C00H
— OH CH -0H CH -C0
t
2 o
2 HOOC-C-CH3
OH
OH
— OH
CH2OH ^ — OH
I 2
> -OH
-OH
CH2-CO ^
Ë
OH — OH 0H
OH —OH OH
(DMPA) (SA)
—OH CH„-0H OH CH -0C0-CH -CH -C00H
2 2 2
CH -0C0 - C-CH
o 0
CH -0C0-C-CH o
2 , 3 2• , 3
EPIKOTE CH -0C0-CH -CH -C00H
CH -0H 2 2 2
100U
2
OH-RICH WATER-SOLUBLE
BACKBONE RESIN
I t soon became c l e a r that these o i l - f r e e binders were t o o

"hard", i . e . when a p p l i e d by ED they flowed p o o r l y during the
a c t u a l d e p o s i t i o n step and consequently formed rough coatings (nos.
1 and 2 i n Table I I I ) . B e t t e r - f l o w i n g binders were obtained when
the s u c c i n i c anhydride was r e p l a c e d by a s u b s t i t u t e d m a t e r i a l , v i z .
a premaleinised f a t t y a c i d (no. 3, Table I I I ) . U n f o r t u n a t e l y , how
ever, t h i s approach always l e d t o a d e t e r i o r a t i o n i n s a l t - s p r a y
r e s i s t a n c e , an e f f e c t t y p i c a l f o r m o d i f i c a t i o n s with n a t u r a l f a t t y
acids (see above).
We then discovered that we could improve the softness and the
flow o f the binders by i n c o r p o r a t i n g a d e r i v a t i v e o f a s y n t h e t i c
f a t t y a c i d . T h i s d e r i v a t i v e i s the g l y c i d y l e s t e r o f an α-branched
monocarboxylic a c i d with 10 carbon atoms and i s commercially a v a i l
able under the trade-name CARDURA. E10 (CE 10). Being a monoepoxy
compound, CE 10 could be e a s i l y i n c o r p o r a t e d by r e a c t i o n with part

o f the carboxyl groups present i n the b i n d e r s :
CH -0C0-CH -CH -C00H

I 2
o o o
2 2
CH -0-C0-C-CH
o o
2 I 3
-OH CH -0C0-CH -CH -C00H
d d d ^
Q
I—OH
-OH 2 CH -CH-CH -0C0-C H
-OH ±-Σ±-
-0H (CE 10)
-OH
I 2
o o o
2 2
CH -0-C0-C-CH
o o
ά
I 3

2 2 2
WATER-SOLUBLE
RESIN
OH
I
CH -0C0-CH -CH -C00-CH -CH-CH -C00-C H
o o o o o n Λ n
J d d d d d y I y
CH -0-C0-C-CH o
OH CH -0C0-CH -CH -C00H

ά
OH
-OH
0 H
' OH H
}-0H ?
.OH CH -0C0-CH -CH -C00-CH -CH-CH -0C0-C H ^
2 2 2 2 2 9 1
CH -0-C0-C-CH o
2 , 3
2 2 2
OH-RICH ED BINDER
(No. h i n Table I I I )
TABLE I I I
a
HYDROXYL-RICH ANIONIC ED BINDERS
No. Binder composition^ Hydroxyl ED Bath Mechanical Salt-

Molar r a t i o s content , 0
behaviour^ stability d
coating spray
properties rating
meq/100 g ( T d A o °C) (10 d)
1 E-100U/LA/SA hok poor fair good 9 e

1/2/1.5
2 h!9
e
E-IOOU/DMPA/SA poor fair good 9i
1/ 2 / 1 . 5
3 E-1001/DMPA/MAFA 358 good very good good 5 - 6e

1/ 2 /2
h E-1OOU/DMPA/SA/CE 10 3U1 good fair good 9 f
1/ 2 /I* /2
f
5 E-1001/AA/DMPA/TMA/CE 10 good very good good 9
2/1/2 /2.3/2.U
6 Commercial LMPB binder - good good fair 9 f
(comparison)
a. A l l binders (except no. 6) combined with HMMM (weight r a t i o 9 5 / 5 ) ; 25 ym t h i c k

c l e a r coatings a p p l i e d t o bare s t e e l by spraying or by ED, followed by s t o v i n g
at 180 °C f o r 30 min.
b. E-1001, E-100U: s o l i d ΕΡΙΚ0ΤΕ epoxy r e s i n s ; LA: l a c t i c a c i d ; DMPA: d i m e t h y l o l -
p r o p i o n i c a c i d ; SA: s u c c i n i c anhydride; TMA: t r i m e l l i t i c anhydride; MAFA: p r e -
maleinised f a t t y a c i d ; CE 10: CARDURA E10; AA: a d i p i c a c i d .
c. C a l c u l a t e d .
d. 10 % aqueous s o l u t i o n s c o n t a i n i n g ethylene g l y c o l mono-n-butyl ether (30 % on
b i n d e r s ) , and t r i e t h y l a m i n e f o r n e u t r a l i s a t i o n .
e. Spray-applied c o a t i n g s ; i r a t i n e s see Table I I
f. Both ED- and spray-applied c o a t i n g s ; f f
° rs a l t s
- P r a v
r a t i n g s see Table I I .
A binder of t h i s type (no. k i n Table I I I ) , i n combination

with small amounts o f melamine or phenolic r e s i n s as c r o s s l i n k e r s ,
showed good ED behaviour and good mechanical f i l m p r o p e r t i e s . I t s
s a l t - s p r a y r e s i s t a n c e was only s l i g h t l y lower than that of a
CARDURA-free analogue (no. 2 i n Table I I I ) . CE 10 seems t o have a
l e s s e r detrimental e f f e c t on the s a l t - s p r a y r e s i s t a n c e than n a t u r a l
f a t t y a c i d s , p o s s i b l y because i t s hydrocarbon chain i s much s h o r t e r .
The h y d r o l y t i c a l s t a b i l i t y o f binder no. k was not very good
and our next task was t o improve t h i s aspect.
Binders rendered water-soluble by the a c i d i c h a l f e s t e r p r i n
c i p l e contain a h y d r o l y t i c a l l y weak s i t e , v i z . the h a l f e s t e r l i n k a g e .
OH-RICH OH-RICH
J— OH + 0* C= 0 • 0-CO C00E
BACKBONE BACKBONE
CYCLIC
ANHYDRIDE ACIDIC HALFESTER
The reason i s probably that the s a p o n i f i c a t i o n o f the h a l f e s t e r i s

a s s i s t e d by the neighbouring carboxyl f u n c t i o n . We screened the
h y d r o l y t i c s t a b i l i t y o f binders c o n t a i n i n g d i f f e r e n t types of h a l f -
e s t e r s by s t o r i n g aqueous s o l u t i o n s (10 % s o l i d s content) at ko C
and p e r i o d i c a l l y checking the pH, the c o n d u c t i v i t y and the ED
behaviour. In t h i s way we found that binders c o n t a i n i n g h a l f e s t e r s
of maleic o r p h t h a l i c a c i d are quite unstable. The s t a b i l i t y of
binders with s u c c i n i c h a l f e s t e r s i s b e t t e r but probably s t i l l
i n s u f f i c i e n t f o r most i n d u s t r i a l a p p l i c a t i o n s . H a l f e s t e r s o f t r i -
m e l l i t i c anhydride (TMA) are considerably more s t a b l e than those
of s u c c i n i c a c i d . To our s u r p r i s e we found that m o d i f i c a t i o n of the
t r i m e l l i t i c h a l f e s t e r s with the above-mentioned monoepoxide CE 10
enhanced the s t a b i l i t y even f u r t h e r . I f about equimolar amounts o f
TMA and CE 10 are used there are s u f f i c i e n t c a r b o x y l i c functions
l e f t t o guarantee a good s o l u b i l i t y o f the binders i n water:
0
/C^/^V^COOH / \
OH-RICH
I- OH + 0 I (\ Τ + CH^-CH-CH -0-C0-C H
o n
BACKBONE
Η
0 TMA CE 10
OH
I
OH-RICH C00-CH -CH-CH - •0-CO-C H 9 15
BACKBONE
C00H'
CARDURA E10-TMA MODIFIED ED BINDER
From our l a b o r a t o r y experience we b e l i e v e that such systems are

about as s t a b l e as the i n d u s t r i a l l y well-known binders which are
rendered water-soluble with premaleinised f a t t y a c i d s .
A t y p i c a l h y d r o x y l - r i c h binder which i s modified with TMA and
and CE 10 i s no. 5 i n Table I I I . In t h i s binder the backbone i s
s l i g h t l y d i f f e r e n t from that o f the preceding b i n d e r s , i . e . ,
EPIKOTE 100U i s r e p l a c e d by a combination o f EPIKOTE 1001 (two
moles) and a d i p i c a c i d (one mole). T h i s was done t o f u r t h e r improve
the mechanical p r o p e r t i e s o f the c o a t i n g s .
With melamine or phenolic r e s i n s as c r o s s l i n k e r s binder no. 5
shows an a t t r a c t i v e combination o f good ED behaviour, good mecha-
n i c a l f i l m p r o p e r t i e s and high bath s t a b i l i t y . I t s s a l t - s p r a y
r e s i s t a n c e i s comparable t o that o f a commercial LMPB system (no.
6 i n Table I I I ) . Binder no. 5 a l s o shows s e l f - c r o s s l i n k i n g
behaviour, i . e . i t gives coatings with an i n t e r e s t i n g l e v e l o f

performance when stoved i n the absence o f e x t e r n a l c r o s s l i n k e r s .
In view o f these encouraging r e s u l t s , we decided t o submit
binder no. 5 t o customers under the code LR-2052. Customer
r e a c t i o n s so f a r have been quite p o s i t i v e and our views regarding
the high s a l t - s p r a y r e s i s t a n c e o f t h i s binder on non-phosphated
s t e e l were f u l l y confirmed.
With a view t o lowering raw m a t e r i a l costs (the DMPA used i n
binder LR-2052 i s r a t h e r expensive), we l a t e r developed another
OH-rich b i n d e r , designated LR-2053. This system i s based on a l i n e a r
backbone c o n t a i n i n g a l i q u i d epoxy r e s i n , EPIKOTE 828, d i p h e n y l o l -
propane, a d i p i c a c i d and CE 10 (molar r a t i o 3 / 2 / 2 / 2 ) and again i s
rendered water-soluble with a TMA/CE 10 combination (2.5 moles TMA
and 2.6 moles CE 10 per mole o f backbone). This binder performs as
w e l l as LR-2052, with an only m a r g i n a l l y lower s a l t - s p r a y r e s i s t a n c e .
With both b i n d e r s , LR-2052 and LR-2053, we have prepared
pigmented ED p a i n t s . We used a simple T1O2 based pigmentation with-
out a c t i v e i n g r e d i e n t s . T y p i c a l data f o r these p a i n t s are shown i n
Table IV. The general performance o f both pigmented systems was
very s a t i s f a c t o r y and the s a l t - s p r a y r a t i n g s were comparable t o
those o f unpigmented coatings.
In c o n c l u s i o n , we can say that i t i s p o s s i b l e t o design
anionic ED binders based on epoxy r e s i n s which give coatings with
a much b e t t e r s a l t - s p r a y r e s i s t a n c e on bare s t e e l than that o f
coatings based on conventional anionic b i n d e r s . The main design
features o f the epoxy r e s i n based binders are (1) the presence of a
s u f f i c i e n t l y high l e v e l o f hydroxyl groups i n the c r o s s l i n k e d
coatings, and (2) the omission o f n a t u r a l f a t t y a c i d s . In l a t e r
work we a p p l i e d the same p r i n c i p l e s t o c a t i o n i c ED b i n d e r s .
C a t i o n i c ED Binders
A c h i e f advantage claimed f o r coatings a p p l i e d by the cathodic

ED i s t h e i r s u p e r i o r c o r r o s i o n r e s i s t a n c e , and t h i s has been the
main i n c e n t i v e f o r our work i n t h i s area. I n i t i a l l y , we t r i e d t o
e s t a b l i s h whether the cathodic d e p o s i t i o n process as such would
l e a d t o improved c o r r o s i o n r e s i s t a n c e o f the c o a t i n g s . To t h i s end
TABLE IV
PIGMENTED ED PAINTS
Binder LR-2052 LR-2053
Paint composition
a a
Crosslinkin'g r e s i n Setaliet 100 Setaliet 100
B i n d e r / c r o s s l i n k e r weight r a t i o 85/15 85/15
13
Pigment /binder weight r a t i o 0.28 0.28
0
B i n d e r / s o l v e n t s weight r a t i o 100/1+0.5 100/U0.5
Degree o f n e u t r a l i s a t i o n ( t r i e t h y l a m i n e ) 0.83 0.80
Paint s o l i d s content, #w 1U.8 1U.8
Paint properties
PH ( 2 5 °C) 7.1 7.5

Specific resistance ( 2 5 C), Q.cm 1260 1280
Deposition temperature, C 30 30
Deposition time, min 2 2
Deposition v o l t a g e , V 150-175 150-200
Rupture v o l t a g e , V 220 250
Throwing power (Ford t e s t ) , cm/V 15/175 16/200
d
S t a b i l i t y o f p a i n t at 2 8 °C, weeks >k >k
6
Cured f i l m p r o p e r t i e s ( S t o v i n g : 1 8 0 °C/30 minutes)
Film thickness, um 22-28 22-28

F i l m appearance very good good
Pendulum hardness (Konig), s 195 170
Adhesion ( c r o s s h a t c h , DIN 5 3 1 5 1 ) Gt 0 Gt 0
E r i c h s e n impact, r e v e r s e , mm >3 >3
C o n i c a l mandrel bend (ASTM D 5 2 2 - 6 0 ) f passed passed
S a l t - s p r a y r e s i s t a n c e (ASTM B 1 1 7 - 6 U ; 10 d) 9-9-2 8^
a. Thermoreactive p h e n o l i c r e s i n (Synthèse B.V., H o l l a n d ) .

b. Titanium dioxide/carbon b l a c k / c l a y (weight r a t i o 3 6 / 2 / 2 ) .
c. Diethylene g l y c o l monobutyl ether/isophorone (weight r a t i o 2 / 1 ) .
d. C i r c u l a t i o n i n open c o n t a i n e r s , no u l t r a f i l t r a t i o n .
e. A l l c o a t i n g s a p p l i e d t o bare steel.
f . For r a t i n g s see Table I I .
we modified a given a n i o n i c ED b i n d e r , LR-38 ( a m a l e i n i s e d l o n g - o i l

epoxy r e s i n e s t e r modified with a styrene/methacrylic a c i d copo-
lymer), so that i t could be e l e c t r o d e p o s i t e d a n o d i c a l l y or catho-
d i c a l l y depending on the pH. Such "amphoteric" behaviour was
achieved by converting t h e ( s u b s t i t u t e d s u c c i n i c ) anhydride r i n g s
present i n LR-38 with 2-dimethylaminoethanol i n t o amino a c i d
f u n c t i o n s , e.g. |LR-38 -I— CH-COOH
CH2-COO-CH2-CH2-N(CH3) 2
S a l t - s p r a y data ( f o r nos. 1 and 2 i n Table V) i n d i c a t e d t h a t ,

on zinc-phosphated s t e e l , cathodic ED indeed l e d t o c o n s i d e r a b l y
b e t t e r c o r r o s i o n r e s i s t a n c e . On bare s t e e l , however, both cathodic
and anodic coatings f a i l e d completely. F u r t h e r , we prepared a
number o f d i f f e r e n t , amine-modified epoxy r e s i n e s t e r s c o n t a i n i n g

between 30 and 50 %w of d r y i n g f a t t y acids (e.g. no. 3 i n Table V).
These could a l l be deposited c a t h o d i c a l l y and again a t t a i n e d e x c e l -
l e n t s a l t - s p r a y r a t i n g s on phosphated s t e e l but performed p o o r l y
on bare s t e e l . We concluded that cathodic ED prevents phosphate
l a y e r degradation (a well-known phenomenon with anodic ED) and thus
leads t o s u p e r i o r c o r r o s i o n r e s i s t a n c e on p r e t r e a t e d s t e e l . On bare
s t e e l the binders performed too p o o r l y t o allow comparison between
cathodic and anodic ED.
In the l i g h t o f our more recent d i s c o v e r y o f the "high-
h y d r o x y l " p r i n c i p l e , the poor performance o f our e a r l y c a t i o n i c
systems on bare s t e e l can now be explained by t h e i r l a c k o f s u f f i -
c i e n t hydroxyl groups (<100 meq/100 g) and t h e i r high f a t t y a c i d
l e v e l s (30-50 %w). To optimise the c o r r o s i o n r e s i s t a n c e t h e t r e n d
should be towards e s s e n t i a l l y o i l - f r e e c a t i o n i c binders p r e f e r a b l y
based on epoxy r e s i n s and c o n t a i n i n g high l e v e l s o f r e s i d u a l OH
groups. I t i s i n t e r e s t i n g t o note t h a t a l l these f e a t u r e s are
r e a l i s e d i n a number o f c a t i o n i c systems proposed i n the patent
literature.
In our own work towards cathodic systems with high bare s t e e l
c o r r o s i o n r e s i s t a n c e we f i r s t prepared a number o f epoxy r e s i n /
amine adducts o f the formal composition:
Secondary Primary Secondary

Epoxy r e s i n Epoxy r e s i n
amine amine amine
Upon n e u t r a l i s a t i o n (with l a c t i c or a c e t i c a c i d ) these adducts
became water-soluble but showed q u i t e poor ED behaviour, probably
again owing t o the absence o f flow-promoting e n t i t i e s (no. U,
Table V). The ED behaviour was much improved by chemical i n c o r p o -
r a t i o n o f the monoepoxide, CARDURA E10 (no. 5, Table V). Unfortu-
n a t e l y , i n s p i t e o f the many hydroxyl groups present the cure o f
these binders with e x t e r n a l c r o s s l i n k e r s (melamine or phenolic
r e s i n s ) was marginal. T h i s undoubtedly i s due t o the l a c k o f c a t a -
l y s i n g a c i d i c f u n c t i o n s and t o the r e t a r d i n g i n f l u e n c e of the amino
groups.
We then attempted t o i n c o r p o r a t e c a t a l y s i n g a c i d i c moieties
i n t o such binders and found that s u l f a n i l i c a c i d (p-NH2-C5Hl|-S03H)
co-reacts with epoxy r e s i n s i n the presence o f other amines,
TABLE V
CATIONIC ED BINDERS
No. Binder type Hydroxyl ED Bath Crosslink- S a l t - s p r a y rating*'

0 d 8
or content , behaviour^ stability ability (10 days)
molar composition^
Phosph. Bare
steel steel
meq/100 g (11+ d / 2 3 °C) (Bonder 9 7 )
1 Amphoteric LR-38 0 good fair good 8 0

(anodic ED)
2 Amphoteric LR-38 0 fair fair good 9\ 0

(cathodic ED)
3 Amine-modified epoxy r e s i n e s t e r 90 good fair good 9l 0
1* E-1001/Deola/Eola 690 poor good marginal - -

2/ 2 /1
5δ E-1001/Deola/Eola/HD/CE 10 590 good good marginal - -

3 / 2 / 1 / 1 / 2
βδ E-1001/Deola/Eola/Sulfa/HD/CE 10 550 good good good 9\ 9\

3/ 2 /0.75/0.25 / 1 /2.75
a. 25 ym t h i c k c l e a r c o a t i n g s a p p l i e d by ED, followed by s t o v i n g at 180 °C f o r 30 min; binders nos. U-6

cured with HMMM (weight r a t i o 80/20).
b. E-1001: s o l i d EPIKOTE epoxy r e s i n ; Deola: diethanolamine; E o l a : ethanolamine; HD: h e x a n e d i a m i n e - 1 , 6 ;
CE 10: CARDURA E10; S u l f a : s u l f a n i l i c a c i d . For binders nos. 1-3 see t e x t .
c. C a l c u l a t e d .
d. 10 % aqueous s o l u t i o n s c o n t a i n i n g ethylene g l y c o l mono-n-butyl ether (30 $w on b i n d e r s ) and l a c t i c a c i d
f o r n e u t r a l i s a t i o n ( t r i e t h y l a m i n e with system no. 1 ) .
e. S t o v i n g at 180 C f o r 30 min i n the presence o f 20 % HMMM. Degree o f c r o s s l i n k i n g assessed from s o l v e n t
r e s i s t a n c e and mechanical c o a t i n g p r o p e r t i e s .
f . For r a t i n g s see Table I I .
g. Formulations nos. 5 and 6 i n Table V are covered by recent patent a p p l i c a t i o n s .
l e a v i n g the - S O 3 H group i n t a c t . An optimised binder o f t h i s type

(no. 6 , Table VJ c r o s s l i n k s v e i l and leads t o coatings with e x c e l -
l e n t s a l t - s p r a y r e s i s t a n c e on both phosphated and bare s t e e l . A
drawback o f t h i s binder i s the r a t h e r low pH o f the aqueous s o l u -
t i o n s {k.5-5.0), and work on cathodic systems with higher pH i s
t h e r e f o r e being c a r r i e d out.
From t h i s work we can conclude that the s a l t - s p r a y r e s i s t a n c e
of c a t i o n i c ED coatings a l s o appears t o b e n e f i t from a high l e v e l
of hydroxyl groups i n the cured f i l m s .
Abstract
Primer coatings f o r automobile bodies are g e n e r a l l y a p p l i e d

by e l e c t r o d e p o s i t i o n (ED) and binders based on epoxy r e s i n s p l a y a
l e a d i n g r o l e i n t h i s f i e l d . During recent years car manufacturers

have become more s t r i n g e n t regarding the c o r r o s i o n p r o t e c t i o n
demanded o f ED primers, not only on phosphated but a l s o on non-
p r e t r e a t e d s t e e l . T r a d i t i o n a l epoxy r e s i n b i n d e r s , modified with
d r y i n g f a t t y a c i d s , cannot meet these requirements. In a search f o r
f a c t o r s which i n f l u e n c e the s a l t - s p r a y r e s i s t a n c e o f t h i n (25 ym)
model coatings on bare s t e e l i t was found that a high l e v e l o f
r e s i d u a l hydroxyl groups i n the cured coatings (200-UOO m i l l i e q u i -
valents/100 grams) has a s t r o n g l y b e n e f i c i a l e f f e c t . T h i s discovery
l e d t o the development of epoxy-resin-based a n i o n i c ED binders
having very good s a l t - s p r a y r e s i s t a n c e on non-pretreated s t e e l .
E s s e n t i a l l y , these binders are o i l - f r e e , h y d r o x y l - r i c h epoxy r e s i n
e s t e r s which are modified with t r i m e l l i t i c anhydride and a flow-
promoting monoepoxy e s t e r (CARDURA E10). The "high-hydroxyl" p r i n -
c i p l e a l s o appears t o h o l d f o r cathodic ED, the a p p l i c a t i o n a l
v a r i a n t i n c r e a s i n g l y p r e f e r r e d by the i n d u s t r y . The development o f
epoxy-resin-based c a t i o n i c ED binders with high c o r r o s i o n r e s i s -
tance i s discussed.
Acknowledgement
The f o l l o w i n g colleagues have c o n t r i b u t e d t o t h i s work:

B.G. D i j k h u i s , P. Kooijmans, K. R u i j t e r , G. Schreurs, J.M.E. Seelen,
P.Y. S e y r o l , A.M.C. van Steenis' and J.J.M.H. Wintraecken.
Literature Cited
1. Heidel, K. Chemische Werke Hüls, A . G . , 1967, lecture: "Air-

-drying resins on the basis of liquid cis-polybutadiene".

5
Water-Borne Coatings Prepared from High Molecular
Weight Epoxy Resins
EDWARD G. BOZZI and CAMILLA Y. ZENDIG

Epoxy Resins Laboratory, CIBA-GEIGY Corporation, Ardsley, NY 10502
As air pollution controls tighten, as fuel reserves dwindle

and as industrial hazards are explored, solvents become increas-
ingly unattractive as diluents for coatings.
Industry has formulated several alternative coating technol-
ogies, probably the most advanced and easily substituted being
water-borne.
Our water-borne investigations led us recently to the discov-
ery of techniques for preparing oil-in-water emulsions of our
highest molecular weight epoxy resins. Known commercially as
ARALDITE ® 488, these resins have weight average molecular weights
of 15,000-20,000 and are ideal for applications requiring excel-
lent adhesion and formability.
Emulsions of these resins with relatively high solids content
can be prepared while the corresponding solvent cuts have viscosi-
ties too high for use in coatings. For example, at 40% solids in
Cellosolve acetate, ARALDITE 488 has a viscosity of 6000 cP. while
the water-borne emulsion at the same solids level is only 1000 cP.
For most methods of application the solids content of the solvent
cut would have to be dropped below 40% to give a workable viscos-
ity and this would exclude the resin from some important end uses
such as can end and 3-piece can body coatings. The resin i n i t s
emulsified form, however, has the proper solids/viscosity rela-
tionship for this particular end use.
In the emulsified state, the high molecular weight epoxy res-
in exists as small spherical droplets surrounded by a surfactant
which forms a "skin" over the droplets and thus prevents coales-
cence. While the viscosity within these particles may be great
due to the high viscosity of the solvent cut of resin, the overall
emulsion viscosity w i l l only be dependent on the total solids con-
tent and any water-soluble additives. Therefore, coatings with a
high non-volatiles content can be made from a very high molecular
weight epoxy resin i n i t s emulsified form but cannot be made from
the same resin at an equivalent solids level i n a solvent cut.
0-8412-0525-6/79/47-114-071$05.00/0
APPLICATIONS
Can End Coatings. In most cases, a two-step process i s used

when r o l l e r coating the interior ends of beer and beverage cans.
After the f i r s t resinous coating i s applied, the pull-tab i s form-
ed and a second coating follows to cover any cracks i n the o r i g i -
nal coating due to rivet and scribing operations. If the f i r s t
coating were, however, flexible enough to withstand the rivet and
scribing operations, the second repair coating could be elimina-
ted. We have evaluated our high molecular weight epoxy resin
emulsion for this end use and have found that the f l e x i b i l i t y i n -
herent i n the solvent-borne resin has not been lost during emulsi-
fication. At high resin/ hardener ratios we found excellent flex-
i b i l i t y and pasteurization resistance and good formulation s t a b i l -
i t y . Table I compares the properties of the high molecular weight

epoxy emulsion to a "7" type epoxy resin emulsion formulated with
melamine and urea-formaldehyde hardeners.
TABLE I
FORMULATIONS AND PHYSICAL PROPERTIES
FORMULATION NO. I II HI
ARALDITE 488 Emul- 245 237.5

sion, 40% Solids
"7" Type Epoxy Emul- - - 196

sion, 50% Solids
Melamine Hardener 2 - 2
(Cymel 303)
Urea Formaldehyde 10
Hardener (Beetle 65,
50% i n H 0)
2
Resin Crosslinker 98/2 95/5 98/2
Wedge Bend (mm) 10 0-1 15-20
Beer Pasteurization No Change/Ex- Slight Blush/ Slight Blush/

(160°F/45 m) cellent Adhe- Excellent Ad- Excellent Ad-
sion hesion hesion
Stability 14 58+ Weeks (Separation

at 15 Weeks)
Poor flow and leveling, particularly during r o l l e r coating,

and the need for an external catalyst, are, however, problems with
5. Bozzi AND ZENDIG Water-Bome Coatings 73
the high molecular weight epoxy emulsion. To solve these two

problems, we formulated the epoxy emulsion with 15-20% of various
water-base alkyds, polyesters and acrylics. After much experimen-
tation we found only a few systems with good film properties and
s t a b i l i t y and found in particular one alkyd, Kelsol 3900 from
Spencer-Kellogg, to perform very well with our epoxy resin emul-
sion. Table II shows the formulation evaluated and the properties
of the coating.
TABLE II
FORMULATION FOR CAN END COATING
Epoxy Resin Emulsion (40% Solids) - 73.4

Alkyd (Kelsol 3900) (48.6% Solids) - 15.1

Melamine Hardener (Cymel 303) - 4.1
Water - 7.4
100.0
Resins/Crosslinking Agent - 90/10

Epoxy/Alkyd - 4/1
Solids, % - 40.8
Viscosity, (#4 Ford Cup), sec. - 45
PERFORMANCE PROPERTIES
Substrate Treated Aluminum

Application Method Roller Coated
Cure Schedule (min./°F) 3/400
Appearance Good Flow and Leveling
209 Can End Immersed in C a S 0 4 , min. Pass, 6
Beer Pasteurization, 45 m/160°F
(Closed Container)
Appearance: No Change
Adhesion: Excellent
Water Pasteurization, 45 m/160°F
(Closed Container)
Appearance: No Change
Adhesion: Excellent
Wedge Bend, mm 22
Automotive Primer Coatings. To those working in the f i e l d

i t i s generally known that water-borne versions of "7" and "9"
type epoxy resins do not meet the high corrosion resistance re-
quirements for an automotive primer. However, the high crosslink-
ing density and excellent adhesion properties afforded by the high
molecular weight of our epoxy resin should make i t ideal for such
end uses.
Table III shows the formulation and performance properties
of our epoxy resin emulsion and appropriate primer coating f i l l e r s

cured with a proprietary water-borne phenolic hardener. The best
property of this coating i s i t s outstanding salt spray resistance.
We obtained over 1500 hours salt spray resistance on Bonderite
P-60 steel, with less than 1 mm creep. Even on cold rolled steel,
the coatings displayed 300 hours resistance (< 3 mm creepage)
while those of a commercial water-borne coating failed after only
24 hours exposure.
TABLE III
FORMULATION FOR AUTOMOTIVE PRIMER COATINGS
Epoxy 1Resin Emulsion (40% Solids) 38.3

Alkyd (Kelsol 3900) (48.6% Solids) 13.0

•Borne Phenolic Hardener (32% Solids)
Water-! 18.0
Water 8.6
Clay 6.5
BaS04 13.0
Lampblack 1.0
Ti02 1.6
100.0
Resins/Crosslinking Agent 88/12

Epoxy/Alkyd 70/30
Solids % 48.5
Viscosity, (//4 Ford Cup), sec. 50
PERFORMANCE PROPERTIES
Substrate Bonderite P60 Steel

Application Method 0.003 mil Doctor Blade
Cure Schedule (min./°F) 30/325
Appearance Good Flow and Leveling
Salt Spray Resistance 1500 Hours, < 1 mm
Creep
Other Applications. We have evaluated our epoxy resin emul*

sion with various thermoplastics. Results are shown graphically
in Table IV.
5. BOZZI AND ZENDIG Water-Borne Coatings
TABLE IV
THERMOPLASTIC MODIFIED EPOXY RESIN EMULSION
THERMOPLASTIC
Polyvinyl Acetate (Gelva Improved Impact and Acid

S55H, Monsanto) Resistance
Vinyl Acetate/Acrylic Co« Improved Adhesion and Acid

Polymer (Polyco 2151, Resistance
(Borden)
Alkyd (Kelsol 3906, Improved F l e x i b i l i t y and

Spencer-Kellogg) Dry Time
Acrylic (WS32, Rohm and Improved Hardness and Dry

Haas) Time
Adhesion i s usually improved while f l e x i b i l i t y i s main-

tained when using the high molecular weight epoxy emul-
sion as an upgrader i n water-borne thermoplastic systems.
CONCLUSION
Our investigations of very high molecular weight epoxy resin

emulsions as evaluated i n can end, automotive primer and thermo-
plastic-type maintenance coating systems have yielded some very
exciting and useful data. The largest technological challenge
that remains i s i n obtaining proper rheology. This problem i s
helped by the addition of very specific water-soluble resins.
Commercial success of the high molecular weight epoxy resin emul-
sion w i l l depend, therefore, on how well we can solve these Theo-
logical problems.

6
Aqueous Epoxy Resins for Electrical Reinforced Plastics
Industry
TERRY L. ANDERSON, JAMES H . M E L L O A N , K A T H L E E N L. POWELL,

ROLAND R. McCLAIN, J. BRANDON SIMONS, ROBIN L. CONWAY,
and DAVID A. SHIMP
Celanese Polymer Specialties Co., 9800 E. Bluegrass Parkway, Jeffersontown, KY 40299
The electrical reinforced plastics industry is undergoing

changes as the requirements of printed circuit boards become more
complex. This complexity is compounded by the requirements that
the processes be more environmentally acceptable. EPA acceptable
resins will ultimately be required of the resin producers.
The purpose of this paper is to present a new water based
epoxy resin system which will meet the current requirements of the
industry. In addition, an experimental system will be presented
which will approach the emerging requirements of the industry.
GENERAL TECHNOLOGY AND RESIN REQUIREMENTS
Prior to discussing the new water based system, let us review

the basic processes used in making the laminate.
Figure I gives a flow diagram of the typical laminate process.
Figure II gives a typical resin and curing agent varnish for-
mula which would be used to make the finished laminate.
0-8412-0525-6/79/47-114-077$05.00/0
Figure I I
TYPICAL ORGANIC SOLVENT VARNISH FORMULA
Epoxy r e s i n @ 80% NVM 125 parts

i n organic s o l v e n t
Dicyandiamide 4 parts
Organic Solvent 45 parts
Cure A c c e l e r a t o r 0.2 parts
As can be seen in Figures I and II, the processing involves

impregnating the fiberglass with the uncured epoxy resin solution,

and finally fully curing layers of the prepreg with copper foil
into a finished laminate. From this point the laminate is fabri-
cated into a finished printed circuit board.
The epoxy r e s i n s o l u t i o n i s t y p i c a l l y a halogenated epoxy
r e s i n d i s s o l v e d i n a v o l a t i l e s o l v e n t such as acetone. Various
p r o p r i e t a r y r e s i n parameters c o n t r o l such p r o p e r t i e s as cure speed,
w e t t i n g o f the g l a s s , and cured s t a t e T g .
NEW WATER BASED SYSTEM (ED-24574)
The above b r i e f d i s c u s s i o n i s not intended to be a comprehen-
s i v e review o f the processes used but i s intended as an overview.
Figure I I I shows the v a r n i s h formula f o r the new water based
system. The key feature o f t h i s v a r n i s h system i s t h a t no organic
s o l v e n t e x i s t s i n the e n t i r e formula.
Figure I I I
WATER BASED VARNISH FORMULA
Water Based Epoxy @ 167 parts

60% NVM
Dicyandiamide 3.2 parts
Water 22 parts
Accelerator 0.3 parts
Several basic problems can e x i s t w i t h a water based r e s i n

when manufacturing prepreg m a t e r i a l .
The f i r s t problem i s a r e a c t i v i t y problem. E a r l y attempts at
preparing water based systems encountered very slow r e a c t i v i t y o f
the dicyandiamide w i t h the epoxy r e s i n . This caused very slow
l i n e speeds f o r the l a m i n a t o r . This problem has been resolved
w i t h ED24574 and the cure response o f the system i s equal to
organic s o l v e n t based standards.
The second problem which can plague a water based system i s
one o f foaming o f the r e s i n . The foaming tendency i s considered
common t o a l l water based d i s p e r s i o n s and i s a t t r i b u t e d to the
6. ANDERSON ET AL. Aqueous Epoxy Resins 79
decrease i n s u r f a c e t e n s i o n caused by the d i s p e r s a n t . Foaming

manifests i t s e l f when the g l a s s c l o t h i s p u l l e d c o n t i n u o u s l y
through the r e s i n d i s p e r s i o n . S i n c e l a r g e volumes o f a i r a r e
introduced i n t o the g l a s s / r e s i n i n t e r f a c e a s u b s t a n t i a l amount o f
foaming can occur. Wetting problems a r e then introduced i n t o the
prepreg and u l t i m a t e l y i n t o the f i n i s h e d laminate. Unique a t t e n -
t i o n t o r e s i n composition has s o l v e d the foaming problem f o r ED-
24574. I t does not generate foam and the subsequent wetting pro-
blems i n the f i n i s h e d laminate.
The t h i r d problem a s s o c i a t e d with water based varnishes i s
poor e l e c t r i c a l i n s u l a t i o n p r o p e r t i e s o f the laminate a f t e r mois-
ture c o n d i t i o n i n g . T h i s problem i s probably the most c r i t i c a l
problem because i n s u l a t i o n f a i l u r e s o f the laminate can l e a d t o
e l e c t r i c a l f a i l u r e o f the f i n i s h e d p r i n t e d c i r c u i t board. T h i s
property i s measured by c o n d i t i o n i n g t h e f i n i s h e d laminate i n a
high moisture environment and then t e s t i n g the d i e l e c t r i c break-
down s t r e n g t h . ED24574 has e x c e l l e n t i n s u l a t i o n r e s i s t a n c e . T h i s
was achieved by a p r o p r i e t a r y r e s i n composition.
S o l u t i o n o f the above problems has allowed the ED24574 system
to run on commercial t r e a t e r l i n e s t o produce laminates which
w i l l pass NEMA FR4 requirements.
PROPERTIES OF ED24574
Figure IV gives the general p r o p e r t i e s o f the new water based
r e s i n ED24574. The key p r o p e r t i e s t o note a r e the e l e c t r i c pro-
p e r t i e s . S p e c i f i c a l l y , t h e d i e l e c t r i c breakdown v o l t a g e i s a s a f e
margin above the minimum requirements. The remainder o f the e l e c -
t r i c a l p r o p e r t i e s a r e a l s o well above the requirements.
Recently i n the i n d u s t r y , requirements on cured s t a t e Tg and
r e l a t e d phenomena have begun t o be requested o f the r e s i n sup-
p l i e r s . One o f two types o f t e s t s has been added over t h e NEMA
FR4 requirements l i s t e d i n F i g u r e IV. T h i s t e s t i s e i t h e r a
measurement o f the cured s t a t e Tg o r a pressure cooker J e s t .
The Tg requirement has i n c r e a s e d from about 115-120 C. t o a
l e v e l o f 120-130 C. f o r the cured laminate. The pressure cooker
t e s t i s run by s u b j e c t i n g the t e s t laminate t o 15 p s i steam i n a
conventional pressure cooker f o r 20-40 minutes. The t e s t l a m i -
nate i s removed from the pressure cooker, c o n d i t i o n e d one hour a t
room temperature and immediately placed i n a hot s o l d e r bath
(about 500 F . ) . The laminate i s then t e s t e d f o r water b l i s t e r i n g
between the laminate p l i e s . Any v i s i b l e b l i s t e r i n g i s considered
a failure.
Figure V presents data which compares the ED24574 system with
a standard o r g a n i c s o l v e n t based r e s i n system. As can be seen i n
F i g u r e V the ED24574 f o r m u l a t i o n does not pass t h e emerging Tg o r
pressure cooker requirements o f the i n d u s t r y .
Figure IV
PROPERTI ES OF LAMINATES PREPARED FROM ED24574
Laminate P r o p e r t i e s
Laminates cgnstructed from 12 pi ies of S t y l e 7628, 1-399 f i n i s h g l a s s c l o t h prepreg press cured
one hour at 350 F. and 150 psi were t e s t e d versus NEMA FR-4 s p e c i f i c a t i o n l i m i t s . Resul ts are l i s t e d
below: NEMA FR-4 Test
Laminate Property Conditioning Requirements Results
Resin Content (wt. %) - 34
F l e x u r a l Strength ( p s i )
Lengthwise 2 3 „ C , 50% RH 60,000 min. 84,000
Crosswise 2 3 ° C . , 50% RH 50,000 min. 64,000
Lengthwise 150°C - 8500
Izod Impact ( f t . - l b s . / i n . notch)
Lengthwise 48 h r s . @ 5 0 " C 7.0 min. 17.6
Crosswise 48 h r s . θ 50°C. 5.5 min. 10.3
Peel Strength ( l b . inch width)
1 o z . copper 20 sec. s o l d e r d i p 8 min. 11.4
Water Absorption (%) 24 h r s . @ 23°C. 0.20 max. 0.06
1 hr. @ B o i l , - 0.21
Volume R e s i s t i v i t y (megohm-cm) 96 h r s . @ 35°C.
6 9
& 90% RH 10 min. 10
Surface R e s i s t i v i t y (megohms) 96 h r s . 0 35°C.
7
& 90% RH 10 min. 10
D i e l e c t r i c Constant @ 1 megacycle 2 3 ° C , 50% RH 5.2 max. 5.0
24 h r s . θ 23°C. i n water 5.4 max. 5.1
D i s s i p a t i o n Factor @ 1 megacycle 2 3 ° C , 50% RH 0.025 max. 0.016
24^hrs. @ 23°C. in water 0.035 0.017
D i e l e c t r i c Breakdown (KV) 23°C. 50% Ry 45 min. > 60
V
p a r a l l e l to lamination 48 h r s . @ 50 C. i n water 40 min. 52
F l a m m a b i l i t y , per UL94V Burning
_ 7
Time (seconds)
6. ANDERSON ET AL. Aqueous Epoxy Resins 81
Figure V
COMPARISON OF LAMINATE Tg AND PRESSURE COOKER TEST RESULTS
Standard Acetone
S o l u t i o n Based
Resin ED24574
Tg (cured laminate) 125°C 100°C.
20 minutes pressure
cooker b l i s t e r i n g Pass Fail
30 minutes pressure
cooker b l i s t e r i n g Pass Fail

EXPERIMENTAL SYSTEMS
At present i t i s not c l e a r whether Tg or pressure cooker r e -
s u l t s w i l l be required o f the epoxy r e s i n s i n the e l e c t r i c a l l a m i -
nate i n d u s t r y . We have developed an experimental r e s i n i n the
l a b o r a t o r y which w i l l pass the new Tg or pressure cooker r e q u i r e -
ments. The r e s u l t s of t h i s experimental system are depicted i n
Figure VI and i n Figure V I I .
Figure VI
LAMINATE TEST RESULTS FOR EXPERIMENTAL RESIN
Experimental Resin
Tg 119°c.
20 minutes pressure cooker

blistering Pass
30 minutes pressure cooker

blistering Pass
As can be seen from t h i s data i n Figure VI s u b s t a n t i a l improve-

ment over the c u r r e n t ED24574 system has o c c u r r e d . Both Tg and
e l e c t r i c a l data are acceptable for t h i s i n d u s t r y .
CONCLUSION
A new water based epoxy r e s i n system has been developed f o r
the e l e c t r i c a l r e i n f o r c e d p l a s t i c s i n d u s t r y .
Key features o f the ED24574 system are i t s a b i l i t y to run on
commercial t r e a t e r l i n e s without cure speed problems, no foaming
or w e t t i n g problems, and f i n a l l y no i n s u l a t i o n r e s i s t a n c e pro-
blems a f t e r moisture c o n d i t i o n i n g .
The ED24574 system does not pass the emerging Tg or pressure
cooker requirements. However, an experimental r e s i n does pass
these requirements. I t i s a n t i c i p a t e d t h a t t h i s higher Tg r e s i n
w i l l a l l o w laminates to be made which w i l l pass the emerging r e -
quirements of the p r i n t e d c i r c u i t board i n d u s t r y .
Figure VII
PROPERTIES OF LAMINATES PREPARED FROM EXPERIMENTAL RESIN

Laminate P r o p e r t i e s
Laminates cgnstructed from 8 p l i e s of S t y l e 7628, 1-399 f i n i s h g l a s s c l o t h pre-preg press cured
one hour at 350 F . and 150 p s i were tested versus NEMA FR-4 s p e c i f i c a t i o n l i m i t s . R e s u l t s are l i s t e d
below:
NEMA FR-4 Test
Laminate Property Conditioning Requirements Results
Volume R e s i s t i v i t y (megohm-cm) 96 h r s . @ 3 5 T .
6 1 5
& 90% RH 10 min. 10
Surface R e s i s t i v i t y (megohms) 96 h r s . 9 35°C.
1 3
& 90% RH 10 mm. io
D i e l e c t r i c Constant @ 1 megacycle 2 3 ° C , 50% RH 5.2 max. 5.2
24 h r s . @ 23°C. 5.4 max. 5.3
i n water
D i s s i p a t i o n Factor @ 1 megacycle 2 3 ° C , 50% RH 0.025 max. .006
24 h r s . 9 23°C. 0.035 max. .007
D i e l e c t r i c Breakdown (KV) 2 3 ° C , 50% RH 45 min. 60
U
p a r a l l e l to laminations 48 h r s . @ 50 C. 40 min. 56
i n water
F l a m m a b i l i t y , per UL94V
Burning Time (seconds 7
38
Resin Content (%)
7
Epoxide Equivalent Weight Determination by Carbon-13
Nuclear Magnetic Resonance
W. Β. MONIZ and C. F. PORANSKI, JR.

Chemistry Division, Naval Research Laboratory, Washington, D C 20375
We have been involved f o r some time i n the development and

a p p l i c a t i o n of nuclear magnetic resonance (nmr) techniques f o r
the c h a r a c t e r i z a t i o n of thermosetting polymers. The e f f o r t has
been d i r e c t e d toward a n a l y s i s of both prepolymers and cured
r e s i n systems. We have p r e v i o u s l y described how carbon-13 nmr
can a i d the a n a l y s t d i s t i n g u i s h v a r i o u s types of epoxy r e s i n s
and i d e n t i f y r e a c t i v e d i l u e n t s which may be present (1), and have
published a comprehensive c a t a l o g of proton and carbon-13 nmr
spectra of epoxy r e s i n s and curing agents ( 2 ) . We have a p p l i e d
the r e l a t i v e l y new technique of proton-enhanced carbon-13 nmr
to the a n a l y s i s of s o l i d , cured epoxy systems ( 3 ) . I t appears
that t h i s technique w i l l be u s e f u l not only i n c h e m i c a l l y charac
t e r i z i n g cured systems, but a l s o i n probing t h e i r molecular
dynamics.
In t h i s paper we d i s c u s s the use of carbon-13 nmr to measure
epoxide equivalent weights of epoxy r e s i n s based on the d i g l y c i d y l
ether of bisphenol A (DGEBA). The r e s u l t s obtained to date i n d i
cate that the carbon-13 technique could be an a t t r a c t i v e a l t e r n a
t i v e to current methods.
Epoxy r e s i n s based on DGEBA are represented by the general
formula shown below. Commercial r e s i n s are mixtures of such
s t r u c t u r e s (oligomers) with v a r i o u s values of n. The epoxide
equivalent weight (EEW) measures the number of epoxide groups
a v a i l a b l e f o r r e a c t i o n during cure. In a r e s i n composed of o l i g o
mers, the EEW i s an average f o r the mixture.
The r e s i n system processing parameters which are of p r a c t i c a l
importance i n c l u d e EEW, v i s c o s i t y , and i n some cases, the r e l a t i v e
\ r ? " -τ
J*
J n
This chapter not subject to U.S. copyright.

Published 1979 American Chemical Society
proportions of the v a r i o u s n-oligomers. Zucconi (A)> f ° example, r
has reported that problems i n manufacture and performance of epoxy

p r i n t e d - c i r c u i t boards were traced to d i f f e r e n c e s i n the oligomer
d i s t r i b u t i o n of epoxy r e s i n batches which had met v i s c o s i t y and
EEW s p e c i f i c a t i o n s . He has developed a q u a l i t y c o n t r o l procedure
based on l i q u i d chromatography f o r monitoring oligomer d i s t r i b u
t i o n . The carbon-13 nmr technique described here measures EEW, but
not oligomer d i s t r i b u t i o n .
Dorsey, et a l . , have d e s c r i b e d a proton nmr method f o r EEW
determination which uses a measured amount of sym-tetrachlorοeth
ane as an i n t e r n a l standard ( 5 ) . They r e p o r t r e s u l t s on f i v e r e s
ins with EEW's below 300. Hammerich and Willeboordse have analyzed
the p r e c i s i o n of proton nmr EEW determinations (6). Some of the
problems i n accurate area measurement they p o i n t out, such as c a r

bon-13 s a t e l l i t e s and i n s u f f i c i e n t s e p a r a t i o n of main peaks, are
not of concern i n the carbon-13 nmr EEW determination.
While proton nmr i s s a t i s f a c t o r y f o r determinations on low
and medium EEW epoxy r e s i n s , the method l o s e s accuracy as the EEW
i n c r e a s e s . As shown i n F i g u r e 1, the proton nmr spectrum of DER
332LC (EEW=175) has sharp m u l t i p l e t s and i n t e g r a t i o n of the
r e l a t i v e areas i s s t r a i g h t f o r w a r d . But, as the spectrum of EPON
1004 (EEW^950) shows, when the EEW i n c r e a s e s , the m u l t i p l e t s
broaden due to overlap with the l i n e s of the a l i p h a t i c protons i n
the b r i d g i n g groups of the oligomers.
For carbon-13 nmr, the l a r g e chemical s h i f t d i s p e r s i o n and
the use of proton decoupling o b v i a t e such problems. F i g u r e 2 shows
carbon-13 nmr s p e c t r a of the r e g i o n of i n t e r e s t f o r two epoxy
r e s i n systems.
The three l i n e s at 44, 50, and 70 ppm form the b a s i s f o r the
carbon-13 nmr method of EEW determination. As η i n the general
oligomer s t r u c t u r e i n c r e a s e s , the number of b r i d g i n g carbons i n
creases, but the number of t e r m i n a l epoxide groups remains the
same, two per oligomer molecule. For the i d e a l i z e d n-oligomer,
the r a t i o of t e r m i n a l g l y c i d y l ether carbons of types c,d, or e,
to b r i d g i n g carbons (type b) i s 2/3n. Now, the i n t e n s i t y of the
carbon-13 l i n e at 70 ppm i s the sum of the i n t e n s i t i e s of the l i n e
due to the t e r m i n a l ether methylene carbon, I , and those due to
the b r i d g i n g carbons, 1^. Although Ι cannot §e measured d i r e c t l y ,
λ
b
OH
Δ
c d I Y
e
i t s value can be obtained by measuring the intensity of either the

line at 44 ppm (I ) or 50 ppm (1^), or their average value, I'.
Thus the ratio, 2?3n, can be expressed by - I') and
η = 2(I - I')/3I\
b
7. MONiz AND PORANSKI Epoxide Equivalent Weight Determination 85
Figure 1. Proton NMR spectra (100 MHz) of DER 332LC (upperj and Epon
1004 (lowerj.
EPON 828
EEW ~ 190
EPON 1002
EEW ~ 650
70 40
ppm
Figure 2. The 40-70 ppm region of the carbon-13 Ν MR spectra (15 MHz) of
two epoxy resins
T h i s a n a l y s i s assumes that a p a r t i c u l a r epoxy r e s i n c o n s i s t s

of only one n-oligomer, which of course i s not the t r u e p i c t u r e .
In order to i l l u s t r a t e that the η d e r i v e d by the above equation
y i e l d s the average η that would be found by chemical a n a l y s i s , we
generated a set of h y p o t h e t i c a l oligomer mixtures and c a l c u l a t e d
t h e i r EEW's based on carbon-13 nmr and chemical a n a l y s i s . As
shown i n Table I, the two methods g i v e e q u i v a l e n t r e s u l t s .
Table I. Epoxide E q u i v a l e n t Weights C a l c u l a t e d

f o r Four H y p o t h e t i c a l Epoxy Formulations
. mole percent of n-oligomer i n formulation

Λ
n-oligomer ,
a b c d
0 5 3 63 3
3 8 5 10 2
5 6 2 8 75
8 10 8 5 9
10 15 72 8 5
15 56 10 6 6
fchemical 1766 1532 568 1012

EEW
(carbon-13 1760 1533 568 1008
Q u a n t i t a t i v e aspects
Carbon-13 nmr became an important experimental technique

only w i t h the development of F o u r i e r transform (FT) nmr. But
the FT nmr experiment r e q u i r e s a t t e n t i o n to a number of f a c t o r s
i n order f o r the measurements to be q u a n t i t a t i v e l y meaningful
(]_,8^9). These may be d i v i d e d i n t o two c a t a g o r i e s : i n s t r u m e n t a l ,
which a f f e c t FT nmr of any nucleus; and those r e l a t e d to s p i n
dynamics, which f o r some n u c l e i , i n c l u d i n g carbon-13, demand
greater a t t e n t i o n .
Among the instrumental f a c t o r s i s the power envelope
of the r f i n t e r r o g a t i n g p u l s e . I t must cover the s p e c t r a l r e
gion of i n t e r e s t u n i f o r m l y so that a l l n u c l e i being studied are
a f f e c t e d to the same degree. The f i l t e r used i n the d e t e c t i o n
system must a l s o have uniform response across the spectrum.
Other instrumental c o n s i d e r a t i o n s are computer r e l a t e d and i n
clude f a c t o r s such as memory s i z e , word l e n g t h and ADC r e s o l u
t i o n ( 9 ) . Most modern FT nmr spectrometer systems are designed
to s a t i s f y the above requirements, but one must always v e r i f y
proper o p e r a t i n g parameters f o r the a n a l y s i s being run.
With regard to s p i n dynamics, two areas of concern i n c a r
bon-13 nmr are the s p i n - l a t t i c e r e l a x a t i o n time, T , and the
n
nuclear Overhauser effect,NOE. The r e l a x a t i o n time, Τ-, i s a mea

sure of the recovery of nuclear magnetization to e q u i l i b r i u m a f
f
t e r the r f p u l s e . In a given molecule, T- s of the v a r i o u s c a r
bons may vary widely. Since the accumulation of adequate s i g n a l
to n o i s e r a t i o i n carbon-13 FT nmr i s obtained by r e p e t i t i v e l y
p u l s i n g the nuclear system, one must assure that a l l n u c l e i
have returned to e q u i l i b r i u m between p u l s e s . The NOE i s a r e
s u l t of the proton decoupling used to e l i m i n a t e proton-carbon
s p i n c o u p l i n g . The carbon nmr s i g n a l s a r e enhanced v i a the proton
system, but the enhancement may not be the same f o r a l l carbons
i n a molecule.
Both r e l a x a t i o n e f f e c t s and NOE can be d e a l t w i t h i n sev
e r a l ways f o r q u a n t i t a t i v e carbon-13 measurements (7,8). The
approach we used i n v o l v e d gated decoupling to surpress NOE,
and a s u f f i c i e n t l y long delay time between pulses to assure

complete recovery of carbon magnetization.
f
The delay time was determined by measuring the T , s of the
carbons of i n t e r e s t i n s e v e r a l of the epoxy r e s i n systems. The
r e s u l t s , given i n Table I I , show that a delay time between pulses
of 16sec (5 times the longest T- (8)) would be adequate f o r these
m a t e r i a l s . In our EEW determinations, we used a pulse delay of
35sec.
Table I I . T 1 Values f o r Carbons of I n t e r e s t
Resin Τ (sec)
χ
44ppm 50ppm 70ppm
EPON 828 1.2 3.2 1.3

EPON 1001 1.2 2.9 0.4
EPON 1002 1.0 2.7 0.3
Results
Table I I I g i v e s the EEW's we obtained using t h i s carbon-13

approach f o r a s e r i e s of commercial epoxy r e s i n s . I t a l s o g i v e s
the v a l u e s obtained by chemical a n a l y s i s and the v a l u e s from
the l i t e r a t u r e (10). The carbon-13 r e s u l t s f a l l i n t o two groups.
For the l i q u i d r e s i n s carbon-13 nmr g i v e s r e s u l t s g e n e r a l l y low*-
er than the ranges given i n the l i t e r a t u r e . For the s o l i d r e s i n s
of medium EEW, the carbon-13 r e s u l t s a r e g e n e r a l l y w i t h i n the
l i t e r a t u r e ranges. Except f o r two cases, the chemical r e s u l t s
are 5-10% higher than the carbon-13 r e s u l t s , and a r e c o n s i s t e n t
l y higher than the l i t e r a t u r e ranges.
T h i s carbon-13 nmr method f o r determining EEW has a number
of f e a t u r e s which make i t worth c o n s i d e r a t i o n as an a l t e r n a t i v e
to other methods. The amount of sample required i s 0.4g or less.

Neither precision weighings nor standardized solutions are need
ed. The analyst i s free for other tasks while the FT nmr spec
trometer automatically accumulates the data. In an analytical
laboratory or quality control environment where EEW measurements
are made on a routine basis, calibration curves and standard
data acquisition procedures should result i n measurement times
of 20 minutes or less.
T
Table III. EEW s Found by Carbon-13 nmr and Chemical Analysis
Resin Carbon-13 Chemical Literature

DER 332LC 178 178 170-175
EPON 826 172 190 180-188
EPON 828 176 194 185-192

EPON 828° 181 196 185-192
ΕΡΙΚ0ΤΕ 828 171 193 185-192
ARALDITE 7071 522 529 450-530
EPON 1001 568 600 450-530
EPON 1002 686 762 6QQ-700
EPON 1004 971 1086 875-1025
^Reference 10
Manufactured i n the United States
^Manufactured i n Canada
Assumed to be the same as the value for EPON 828
Experimental
The samples for the carbon-13 nmr measurements were CDCl^

solutions (O.2g/ml solvent) of commercial samples of the epoxy
resins i n 10mm o.d. sample tubes. The measurements were made at
15MHz with a JEOL FX60Q spectrometer system, A 9Q°ClOMSec) pulse
was used with gated decoupling to surpress the NOE Q). The data
collection block was 2048 points for a spectral width of 2200Hz.
The observation f i l t e r was set at 2000Hz, substantially i n excess
of the 1100Hz used for best signal to noise i n the quadrature
detection mode. This assured negligible attenuation of the
signals of interest due to the Butterworth f i l t e r characteris
t i c s . The data block was expanded by zero f i l l i n g to 16,384
points before Fourier transformation. Exponential multiplica
tion equivalent to a line broadening of 1.6Hz was applied. The
number of accumulations was 512. The pulse repetition rate was
35sec, longer .than 10 times the longest T^ of the carbons of
interest. Relaxation times, T^, were measured by the inversion/
recovery method (11) on the solutions used for the quantitative
measurements. Chemical analysis (HC1 t i t r a t i o n , single determi
nation) of epoxide equivalent weights were performed by Schwarz
kopf Microanalytical Laboratory, Woodside Ν. Y,
Literature cited
1. Poranski, J r . , C.F., and Moniz, W.B., J . Coat. Tech., 1977,
49, (632), 57.
2. Poranski, J r . , C.F., Moniz, W.B., Birkle, D.L., Kopfle, J . T . ,
and Sojka, S.A., "Carbon-13 and Proton NMR Spectra for Char
acterizing Thermosetting Polymer Systems: I. Epoxy Resins
and Curing Agents", Naval Research Laboratory Report 8092,
Washington, D.C., 1977.
3. Garroway, A.N., Moniz, W.B., and Resing, H.A., "Carbon-13
NMR in Solving Macromolecular Problems", ACS Symposium
Series, in press.
4. Zucconi, T.D., "Proceedings of the Fifth Conference on Com
posite Materials: Testing and Design", ASTM Special Publica
tion, Philadelphia, Pa., 1979, in press.

5. Dorsey, J . G . , Dorsey, C . F . , Rutenberg, A.C., and Green, L . A . ,
Anal. Chem., 1977, 49, 1144.
6. Hammerich, A.D., and Willeboordse, F . G . , Anal. Chem., 1973,
45, 1696.
7. Werhli, F.W., and Wirthlin, T., "Interpretation of Carbon-13
NMR Spectra", Heyden and Son, Ltd., New York, 1976, p 264.
8. Shoolery, J . N . , Prog. NMR Spectrosc., 1977, 11, 79.
9. Randall, J . C . , "Polymer Sequence Determination; Carbon-13
NMR Method", Academic Press, New York, 1977, Chap. 5.
10. Tanaka, Y., Okada, Α., and Tomizuka, I., "Epoxy Resins",
C. A. May and Y. Tanaka, Eds., Marcel Dekker, Inc., New
York, 1973, Chap. 2.
11. Mullen, Κ., and Pregosin, P.S., "Fourier Transform NMR
Techniques: A Practical Approach", Academic Press, New York,
1976, p 65.
8
A n Instrumental Method for Measuring the Sterilization
Resistance (Blushing) of Can Coatings
W. RAUDENBUSCH, H. C. J. VENSELAAR, and D. M. PAUL

Koninklijke/Shell-Laboratorium, Amsterdam (Shell Research B.V.),
Badhuisweg 3, 1031 CM Amsterdam-Noord, The Netherlands
Of the various coating materials used for food- or beverage-

-containing cans epoxy resins are some of the most important. World-
wide they account for about one third of the total coating
materials employed in this market. While epoxies are important to
the can-coating market, the reverse is also true: In 1976, epoxy
resin consumption for can and container coatings was around 10 000
metric tons both in the US (1) and in Western Europe, making this
the largest single outlet for epoxies in the entire coating field.
Therefore, as a major producer of epoxy resins, we are devoting a
considerable effort to this application.
One result of this development work is an instrument for
accurately measuring a key property of can coatings, the s t e r i l i -
sation resistance. First, however, a brief description of can
coatings and some of their properties is in order. The discussion
will be limited to coatings to be applied to the interior of food-
-or beverage-containing cans since this application requires the
highest chemical resistance. Most of the work described has been
carried out with can lacquers of the solid epoxy resin/phenolic-
formaldehyde (E/PF) type as these are the predominant type used in
Western Europe.
Can Coatings and Some o f T h e i r P r o p e r t i e s
E/PF can lacquers u s u a l l y are unpigmented and a p p l i e d at dry

f i l m thicknesses around 5 (0.2 m i l ) . On s t o v i n g at or above
200 C glos sy, c l e a r coatings with a yellow-golden colour ("gold
l a c q u e r s " ) are formed. One o f the most important requirements
which can l i n i n g s must meet i s a high s t e r i l i s a t i o n r e s i s t a n c e .
This implies that the l i n i n g s should not be damaged by the food
contents during a steam s t e r i l i s a t i o n (or p a s t e u r i s a t i o n ) process
a p p l i e d a f t e r f i l l i n g and c l o s i n g o f the cans. U n s a t i s f a c t o r y
s t e r i l i s a t i o n r e s i s t a n c e u s u a l l y shows up as a haziness or c l o u d i -
ness i n the c o a t i n g , a phenomenon which i s c a l l e d "blushing". More
pronounced b l u s h i n g i s u s u a l l y accompanied by some l o s s o f surface
gloss while i n even more extreme cases the coatings become rough
and milky-white. Only s l i g h t b l u s h i n g , however, i s s u f f i c i e n t to cause
the r e j e c t i o n of the corresponding lacquer by the can-coating i n d u s t r y .
0-8412-0525-6/79/47-114-091$05.00/0
Nature and Assessment o f Blushing
Some years ago we i n v e s t i g a t e d the nature o f the b l u s h i n g

phenomenon. To t h i s end, E/PF can l i n i n g s on t i n p l a t e panels
were exposed t o water and steam at 121 °C f o r 90 minutes. The
panels were then examined by o p t i c a l and scanning e l e c t r o n micro-
scopy. From t h a t work the f o l l o w i n g conclusions c o u l d be drawn:
1. The b l u s h i n g e f f e c t i s caused by a l a r g e number of voids present
throughout the coatings.
2. The i n t e n s i t y o f b l u s h i n g i s p r o p o r t i o n a l t o the number of v o i d s .
3. Most o f the voids are s p h e r i c a l , with a diameter o f around 1 ym
(0.0Î+ m i l ) , and t h e i r s i z e d i s t r i b u t i o n i s r a t h e r narrow.
k. Voids near the surface tend t o r e s u l t i n bubble and/or c r a t e r
formation. Coalescence o f s e v e r a l c r a t e r s may l e a d t o l a r g e r

c a v i t i e s . This e x p l a i n s the l o s s o f gloss and the surface rough-
ness observed on h e a v i l y blushed specimens.
5. Blushing only becomes v i s i b l e during c o o l i n g of the t e s t panels
t o ambient temperature.
Our theory regarding the formation of these voids i s that they are
caused by excess water absorbed homogeneously ( i . e . i n u n i t below
the l i m i t o f v i s i b i l i t y , <25 nm) during the s t e r i l i s a t i o n t e s t . On
c o o l i n g , t h i s water agglomerates i n s p h e r i c a l c l u s t e r s of about 1 ym
diameter. This i s analogous with the well-known s i t u a t i o n where
excessive water absorbed i n other g l a s s y polymers (e.g. polystyrene)
can cause m i c r o c a v i t i e s and v i s i b l e defects ( 2.,_3 ). The reasons why
some can coatings are more s u s c e p t i b l e t o excessive water absorp-
t i o n - and thus b l u s h i n g - than others s t i l l are not completely
c l e a r . One well-known and e a s i l y proven f a c t i s that i n s u f f i c i e n t
cure can l e a d t o b l u s h i n g . In a d d i t i o n , there are other known
causes, such as the presence of t r a c e s of water-soluble m a t e r i a l s
(e.g. i n o r g a n i c s a l t s ) i n the c o a t i n g s .
Blushing i s u s u a l l y detected by v i s u a l examination of samples
o f coatings before and a f t e r s t e r i l i s a t i o n . For more q u a n t i t a t i v e
assessments s t e r i l i s e d panels are u s u a l l y compared with a set of
reference panels showing d i f f e r e n t degrees of b l u s h i n g , according
t o an a r b i t r a r y s c a l e such as
5: no b l u s h i n g
k: very weak b l u s h i n g
3: weak b l u s h i n g
2: blushing
1: heavy b l u s h i n g
0: very heavy b l u s h i n g .
These methods, however, s u f f e r from various drawbacks:
- Because they r e l y on v i s u a l observation they are s u b j e c t i v e .
- Considerable time and p r a c t i c e are r e q u i r e d t o acquire the obser-
v a t i o n a l s k i l l necessary f o r q u a n t i t a t i v e assessments.
- The c o l o u r o f the c o a t i n g , i f not e x a c t l y the same as that of the
reference panel, can i n t e r f e r e with the assessment.
8. RAUDENBUSCH ET AL. Sterilization Resistance of Can Coatings 93
- The substrate type and q u a l i t y as w e l l as the i l l u m i n a t i o n p l a y

a c r i t i c a l r o l e i n assessments i n the weak t o very weak b l u s h i n g
range ( r a t i n g s 3-5)· In our experience coatings showing only very
weak b l u s h i n g (k) are g e n e r a l l y judged acceptable by the can
i n d u s t r y , perhaps because the b l u s h i n g i s then n o t i c e a b l e only
under i d e a l substrate and l i g h t c o n d i t i o n s .
- Cases o f more pronounced b l u s h i n g (0-2), where the phenomenon as
such i s r e a d i l y recognised, are nevertheless d i f f i c u l t t o c l a s -
s i f y . T h i s makes i t o f t e n problematic t o detect trends which
might be v a l u a b l e f o r f u r t h e r lacquer development work.
For a l l these reasons the development of an instrumental
method which would allow r a p i d , accurate and r e p r o d u c i b l e b l u s h
measurements was thought very d e s i r a b l e .
The Blushmeter
S e v e r a l o p t i c a l techniques were f i r s t screened t o a s c e r t a i n

t h e i r s u i t a b i l i t y f o r b l u s h measurement. Of these, the back-scat-
t e r i n g of l a s e r l i g h t appeared most promising, and t h i s technique
was thus pursued f u r t h e r . I t i s already known from experience that
the v i s u a l assessment of (weak) b l u s h i n g i s s t r o n g l y dependent on
the angle of observation. According t o the s c a t t e r i n g theory of Mie
(k) i t i s p r e d i c t e d that the i n t e n s i t y o f s c a t t e r e d l i g h t should be
i n f l u e n c e d by the i n t e n s i t y and wavelength of the i n c i d e n t l i g h t ,
the s i z e , number and r e f r a c t i v e index of the s c a t t e r i n g c e n t r e s ,
and the s c a t t e r i n g angle. F u r t h e r , theory p r e d i c t s that there
should be an angle at which the b a c k - s c a t t e r i n g i n t e n s i t y reaches
a maximum. In our case, however, the theory can only be used t o
i n d i c a t e the c r i t i c a l parameters owing t o the complexity of the
medium t o be measured: In a d d i t i o n t o the s c a t t e r i n g from the i n s i d e
of the coatings there i s r e f l e c t i o n and s c a t t e r i n g at both the
c o a t i n g / a i r and the c o a t i n g / s u b s t r a t e i n t e r f a c e s . Thus the t r a n s -
m i t t e d , r e f l e c t e d and s c a t t e r e d l i g h t w i l l a l s o depend s t r o n g l y on
the angle of incidence o f the l i g h t beam. Further complications
a r i s e from imperfections or non-uniformities both i n the coatings
and on the s u b s t r a t e .
In view of the complexity of the p h y s i c a l s i t u a t i o n an a d j u s t -
able l a b o r a t o r y set-up was constructed f i r s t t o i n v e s t i g a t e the
t h e o r e t i c a l p r e d i c t i o n s and t o d e f i n e the c o n d i t i o n s f o r an o p t i -
mised apparatus. The p r i n c i p a l components of t h i s arrangement are
shown i n F i g . 1, and i t s s c a t t e r i n g geometry i n F i g . 2. The l i g h t
source was a 15 mW He-Ne l a s e r whose l i g h t was d e f l e c t e d by a m i r r o r
onto the t e s t panel. At a distance of about 30 cm from the panel
the s c a t t e r e d l i g h t was c o l l e c t e d by a 1: 1.3/50 mm lens and detected
by a s i l i c o n photodiode whose output was a m p l i f i e d and read out on
a d i g i t a l voltmeter. In order t o diminish the e f f e c t of a c c i d e n t a l
c o a t i n g i r r e g u l a r i t i e s (scratches etc.) the c o l l e c t i o n o f the back-
s c a t t e r e d l i g h t was i n t e g r a t e d over a l a r g e r surface by expansion
o f the l a s e r beam. This was accomplished by f i t t i n g abeam expander
( O r i e l , type 1590) i n f r o n t of the l a s e r . For most of the work a
f i v e - f o l d beam expansion was used; the i n c i d e n t l a s e r beam then had
a diameter of 0.5 cm.
DETECTORΊ ADJUSTABLE TO
AMPLIFIER > CHANGE BACK-
LENS J SCATTERING ANGLE
DIGITAL VOLTMETER
Figure 1. System components of experimental apparatus
-SCATTERING PLANE
Figure 2. Scattering geometry

This l a b o r a t o r y set-up permitted accurate v a r i a t i o n s of both

the angle of incidence (θ) and the s c a t t e r i n g angle (φ). The t e s t
panels were mounted m a g n e t i c a l l y and could be s h i f t e d two-dimen-
s i o n a l l y t o allow scanning of t h e i r e n t i r e surface.
With t h i s apparatus a set of 15x6 cm t e s t panels (A-F, 5 ym
E/PF coatings on t i n p l a t e , stoved at 200 °C f o r 10 min, and s t e r
i l i s e d i n water at 121 C f o r 90 min) showing v a r i o u s degrees o f
b l u s h i n g was evaluated. At f i x e d angles o f i n c i d e n c e (θ) the
s c a t t e r e d l i g h t was measured over a range of angles φ from 10° t o
80° i n one quadrant of the backward s c a t t e r i n g plane (defined by
M, A and Β i n F i g . 2). A t y p i c a l p l o t i s shown i n F i g . 3, from
which i t i s c l e a r t h a t , i n accordance with the theory, there i s a
b a c k - s c a t t e r i n g maximum l y i n g between 70 and 85°. For t e c h n i c a l
reasons we adopted a standard b a c k - s c a t t e r i n g angle φ of 70° i n our

subsequent work. In a s i m i l a r manner we v a r i e d the angle of i n c i d e n t
l i g h t θ and found a maximum of s c a t t e r i n g at about 60° ( F i g . 3).
With a f i x e d o p t i c a l geometry (θ = 6θ°, φ = 70°) the set of t e s t
panels A-F was then measured s y s t e m a t i c a l l y . On each panel about
50 i n d i v i d u a l measurements were made at d i f f e r e n t spots, c o v e r i n g
the whole surface. The mean instrument readings ( i n mV) correspond
very w e l l with the b l u s h l e v e l s determined v i s u a l l y by two expert
observers (see the t a b l e below). In p a r t i c u l a r , the b a c k - s c a t t e r i n g
method appeared s u f f i c i e n t l y s e n s i t i v e t o d i s t i n g u i s h between the
various degrees o f weak b l u s h i n g , the range where a l t e r n a t i v e
o p t i c a l d e t e c t i o n methods a l l had f a i l e d .
Test No. o f Mean Standard Visual Visual

panel points reading, deviation, blush rating
measured mV mV assessment
A hi 21 h trace U-5
Β kQ 33 5 very weak U
C 52 ^9 16 weak-very weak 3-1+

D 1+8 70 2k weak 3
Ε 52 1U8 k2 blushing 2
F 6k 61U 113 heavy 1
In f u r t h e r work the 15 mW l a s e r was r e p l a c e d by a smaller and l e s s

expensive one having an output o f only 2 mW. S i m i l a r good c o r r e l a
t i o n with v i s u a l assessment of b l u s h i n g was found although the
a c t u a l mV readings o f course were lower.
Based on the experience gained with the l a b o r a t o r y set-up, a
prototype instrument was then b u i l t , the S h e l l "Blushmeter" ( F i g . U).
A 2 mW He-Ne l a s e r i s used and the o p t i c a l arrangement i s essen
t i a l l y the same as d e s c r i b e d above, with φ and θ f i x e d at 70° and
60°, r e s p e c t i v e l y . F l a t t e s t panels are clamped m a g n e t i c a l l y onto
a h o r i z o n t a l sample t a b l e which can be d i s p l a c e d (at 0.2 cm/s) i n
the X and Y d i r e c t i o n s by means of two e l e c t r i c stepping motors.
D i g i t a l read-out o f the a c t u a l p o s i t i o n permits accurate and repro
d u c i b l e scanning o f the e n t i r e panel s u r f a c e .
INTENSITY, mV
500 r
ANGLE
Figure 3. Dependence of scattered light intensity on back-scattering angle φ

and incident beam angle θ
Figure 4. Prototype blushmeter: (1) laser; (2) beam expander; (S) mirror; (4)
panel on sample table; (5) lens; (6) photoamplifier
For the time being, scanning i s c a r r i e d out by manual c o n t r o l

of the stepping motors; between 10 and 50 i n d i v i d u a l readings are
taken over the whole panel s u r f a c e , depending on the u n i f o r m i t y o f
the b l u s h i n g e f f e c t , i n order t o obtain a s t a t i s t i c a l l y sound value.
Since t h i s i s somewhat time-consuming, the instrument i s c u r r e n t l y
being modified t o allow automatic scanning and data processing.
T y p i c a l readings obtained with t h i s instrument f o r various
degrees o f b l u s h i n g were the f o l l o w i n g :
Visual rating Blushmeter reading, mV
No b l u s h i n g 5 1- 5
Very weak b l u s h i n g h 6- ^k
Weak b l u s h i n g 3 28- 35
Blushing 2 6U- 69
Heavy b l u s h i n g 1 120-13U
Very heavy b l u s h i n g 0 226-278
In our experience the prototype "Blushmeter" allows accurate

numerical assessment o f both weak and heavy b l u s h i n g . The only
requirement f o r a comparison o f the performance o f d i f f e r e n t
coatings i s that they be a p p l i e d (at uniform t h i c k n e s s ) t o f l a t
substrates o f the same type and q u a l i t y . The operation o f t h e
Blushmeter i s simple and does not r e q u i r e s p e c i a l s k i l l s . An
i n t e r e s t i n g observation i s that the readings a r e i n s e n s i t i v e t o
c o l o u r changes o c c u r r i n g during the s t e r i l i s a t i o n t e s t .
In our Amsterdam l a b o r a t o r y the prototype Blushmeter has
already helped us t o define c e r t a i n parameters l e a d i n g t o b l u s h i n g
i n can lacquers. As a consequence we have been able t o adapt c e r t a i n
grades o f s o l i d epoxy r e s i n t o b e t t e r meet the needs o f the can-
coating industry.
Abstract
Internal coatings for food and beverage cans are an important

application for epoxy resins. Such coatings must resist the heat
sterilisation (or pasteurisation) process to which the filled cans
are eventually subjected. Unsatisfactory sterilisation resistance
appears as haziness in the otherwise clear coatings, an effect
called "blushing". In typical cases the blushing effect was found
to be caused by many small (~1 µm) voids inside the coatings.
Blushing is customarily assessed by visual methods that require
considerable experience and are difficult to quantify. Based on the
back-scattering of laser light, an instrument has been developed
with which accurate measurements of various degrees of blushing
can be made. A 2 mW laser beam is directed onto a flat test panel
at an angle of 60°. Back-scattered light is detected by a silicon
photodiode, amplified and read out on a digital voltmeter. The
instrument allows reproducible scanning of the whole panel surface.

Instrument readings on coatings showing widely differing degrees
of blushing agreed well with visual ratings. The instrument permits
objective, accurate and reproducible assessments to be made by
inexperienced persons. Moreover, instrument readings were found to
be insensitive to colour changes frequently occurring during
sterilisation.
Acknowledgement
The f o l l o w i n g colleagues have contributed t o t h i s work:

P. de C a r p e n t i e r , D. Cooke, W. F l e i s c h e r , G.A. Pogany,
J.M. Sketchley and F.A. Smid.
Literature Cited
1. Chemical Economics Handbook, Stanford Research Institute,

March 1978.
2. Crank, J.; Park, G.S. "Diffusion in Polymers": Academic Press,
London, 1968.
3. Pogany, G.A. Polymer, 1976, 17, 690.
4. Born, M.; Wolf, E. "Principles of Optics: Electromagnetic
Theory of Propagation, Interference and Diffraction of Light":
Pergamon Press, Oxford, 1975.

9
Phenalkamines—A New Class of Epoxy Curing Agents
ROBERT A. GARDINER and ANTHONY P. MANZARA

3M Company, Saint Paul, MN 55101
Because of proliferating constraints on solvent-based coat-

ings, new materials are being developed for high solids or water-
-borne coatings. A class of curing agents for epoxy coatings
based on proprietary chemistry has been developed by the 3M
Company. These materials are called phenalkamines, a term coined
to indicate their alkyl-aromatic structure and thereby differen-
tiate them from the currently more familiar curing agents such
as polyamides and polyamines.
As a new family of curing agents, the phenalkamines offer
a unique combination of properties making them particularly well
suited for ambient temperature cured high solids epoxy coatings.
Studies on the reactivity of these curing agents and on the
properties of certain cured formulations are presented.
Experimental
Materials used were the standard commercially available

grades. "CARDOLITE" Brand NC-513 is 3M's monofunctional epoxy
reactive diluent; CR-100, 3M's flow control agent; DC-200, Dow-
R
-Corning antifoam; Cab-O-Sil ( ), Cabot fumed silica; Epon 1001-
X-75, Shell solid epoxy resin as 75% solution in xylene; Tint-
R
Ayd( ) EP-30-01, Daniels predispersed titanium dioxide; liquid
epoxy resin, standard bis-phenol-A diglycidyl ether of epoxide
equivalent weight 190 grams/equivalent.
Amine values are reported as m i l l i g r a m s o f KOH e q u i v a l e n t
to the base content o f one gram o f sample, and are obtained by
t i t r a t i o n with p e r c h l o r i c a c i d i n a c e t i c a c i d s o l v e n t using meth-
yl v i o l e t indicator.
The weight per a c t i v e amine hydrogen i s estimated from the
assumed chemical s t r u c t u r e .
V i s c o s i t i e s were measured using a B r o o k f i e l d Model LVF
Viscometer. Gel times were determined by mixing a q u a n t i t y o f
m a t e r i a l (50 g unless otherwise s t a t e d ) manually w i t h a wooden
spatula blade and r e c o r d i n g the time elapsed before the blade
was immobilized by the cured m a t e r i a l .
0-8412-0525-6/79/47-114-099$05.00/0
Color was determined by v i s u a l comparison o f the sample

with a set o f l i q u i d c o l o r standards.
Pigmented coatings were prepared by combining the f i l l e r s
and a d d i t i v e s with the epoxy r e s i n using a high speed high shear
m i x e r , then passing the suspension through a paint m i l l to d i s -
perse the pigment more c o m p l e t e l y . Curing agent was then added
and s t i r r e d i n manually f o r the small samples used i n the s t u d y .
Coatings were a p p l i e d w i t h a k n i f e coater (unless otherwise
s p e c i f i e d ) to a nominal t h i c k n e s s o f 10 m i l s . (0.010 i n c h . )
Spot t e s t s were done a f t e r the one week ambient temperature
cure by keeping the t e s t area wet with 15% a c e t i c a c i d ( i n water)
for 48 hours.
Chemical r e s i s t a n c e immersion t e s t s 'were done on cured d i s c s
(20.15 + 0.15 g) 2.75 inches i n diameter and approximately 0.2
inches t h i c k . These were prepared by manually mixing the appro-

p r i a t e r a t i o o f r e s i n and c u r i n g agent, removing the a i r bubbles
by c e n t r i f u g a t i o n , and pouring the mixture i n t o tared aluminum
d i s h e s . A f t e r seven days at room temperature the d i s c s were
weighed, t h e i r surface hardness measured using a Shore "D" duro-
meter, and then immersed i n the t e s t s o l u t i o n s . A f t e r the t e s t
time period had e l a p s e d , the samples were removed, d r i e d w i t h a
paper t o w e l , allowed to stand f o r one hour at room temperature,
and the weight and hardness remeasured.
In near i n f r a r e d s p e c t r o s c o p i c (NIR) cure r a t e s t u d i e s , a
small amount (10-15 g) o f sample was manually combined using the
i n d i c a t e d r a t i o o f m a t e r i a l s . A f t e r the bubbles had been r e -
moved v i a c e n t r i f u g a t i o n , the mixture (about 1 g) was poured onto
a microscope s l i d e prepared w i t h a 1 mm spacer window cut from
foam tape with adhesive on both s i d e s . Another s l i d e was placed
on t o p , and a z e r o - t i m e measurement was made on the Cary 14
spectrophotometer. The a b s o r p t i o n at 2 . 2 0 5 J U » was used as a meas-
ure o f the amount o f unreacted epoxy r e s i n . The sample was kept
at the a p p r o p r i a t e temperature and spectra were measured at the
indicated times.
Results and D i s c u s s i o n .
Curing Agent P r o p e r t i e s . Table I gives some s p e c i f i c

p r o p e r t i e s on the three commercial phenalkamines, namely
"CARD0LITE" Brand NC-540, NC-541 and NC-542. The three products
have gel times ranging from 40 minutes up to 2 hours w i t h a
v a r i a t i o n i n mixing r a t i o from 40-100 parts per hundred parts
r e s i n . V i s c o s i t i e s cover the range from 2500 cps to 40,000 c p s .
Young and H o w e l l have suggested t h a t 100% s o l i d s epoxy
1
c o a t i n g s w i l l be most s u i t a b l e f o r use as heavy duty maintenance,

i n c l u d i n g marine c o a t i n g s , i n - p l a c e d e c o r a t i v e c o a t i n g s , and
heat-converted systems f o r product f i n i s h i n g . D e s i r a b l e proper-
t i e s f o r c u r i n g agents f o r "heavy duty maintenance" are low
v i s c o s i t y , s u p e r i o r chemical r e s i s t a n c e , and some degree o f
flexibility. For i n - p l a c e d e c o r a t i v e c o a t i n g s , the c u r i n g agent
9. GARDINER AND MANZARA Phenalkamines 101
requirements are good appearance and e p o x y - l i k e p r o p e r t i e s .

Some features not mentioned by Young and Howell are a l s o
important, i . e . , handling c h a r a c t e r i s t i c s , cure r a t e , safety and
cost e f f i c i e n c y . In Table II these d e s i r a b l e p r o p e r t i e s are
l i s t e d , and commercial types o f c u r i n g agents are rated on each
property. In the r a t i n g scheme used, "*" i n d i c a t e s good, "+"
i n d i c a t e s m a r g i n a l l y a c c e p t a b l e , and " - " i n d i c a t e s u n s u i t a b l e .
When r a t i n g "appearance", the c o l o r o f the c u r i n g agent i t -
s e l f plus i t s tendency to b l u s h , a b i l i t y to s e l f l e v e l and s e n s i -
t i v i t y to moisture i n formulated coatings were a l l taken i n t o
c o n s i d e r a t i o n . Experience has shown that f o r a long "pot l i f e "
i n an ambient cured f o r m u l a t i o n one must forego a "fast c u r e " .
S i m i l a r l y to o b t a i n a " f a s t " and/or "low temperature" c u r e , one
must forego a long "pot l i f e " . P l u r a l component a p p l i c a t i o n

equipment r e s o l v e s t h i s dilemma for those c u r i n g agents with
immediate c o m p a t i b i l i t y with the epoxy r e s i n . With some s t a t e -
o f - t h e - a r t c u r i n g agents an i n d u c t i o n period i s recommended,
during which the f i r s t stage o f r e a c t i o n produces adducts which
are m i s c i b l e with the r e s i n . 3M's phenalkamines are immediately
compatible with epoxy r e s i n , r e q u i r e no i n d u c t i o n p e r i o d , and are
i d e a l l y s u i t e d f o r use w i t h p l u r a l component equipment.
An examination o f Table II i l l u s t r a t e s the p r e v i o u s l y men-
tioned unique combination o f p r o p e r t i e s o f the phenalkamines.
Phenalkamine p r o p e r t i e s are p o s i t i o n e d roughly between those
of the polyamines and polyamides. They combine the best proper-
t i e s o f each o f these f a m i l i a r types o f c u r i n g agents. The phen-
alkamines have an intermediate v i s c o s i t y , the chemical and hydro-
l y t i c r e s i s t a n c e o f the polyamines, and the low t o x i c i t y o f the
polyamides. They have the f a s t cure and a b i l i t y to cure at r e -
duced temperatures o f the polyamines w h i l e e x h i b i t i n g b e t t e r
c o m p a t i b i l i t y than e i t h e r the polyamines or the polyamides. The
phenalkamines a l s o provide f l e x i b i l i t y comparable to the p o l y -
amides with s i m i l a r e a s y - t o - u s e , r e l a t i v e l y n o n - c r i t i c a l mix
ratios.
Table II a l s o rates the p r o p e r t i e s o f amidoamines and c y c l o -
a l i p h a t i c amines. None o f these c u r i n g agents appear to s a t i s f y
a l l o f the d e s i r e d p r o p e r t i e s . There are c l e a r l y some u n f u l -
f i l l e d needs here; however, the p a r t i c u l a r combination o f proper-
t i e s o f the p r e s e n t l y commercial phenalkamines comes c l o s e s t to
s a t i s f y i n g the requirements. They are q u i t e s u i t a b l e f o r high
s o l i d s systems.
The p r e s e n t l y commercial phenalkamines have e x h i b i t e d s h o r t -
comings for c e r t a i n a p p l i c a t i o n s where l i g h t e r c o l o r or lower
v i s c o s i t y were r e q u i r e d . To o f f s e t these l i m i t a t i o n s , 3M has
introduced two new phenalkamines on an experimental b a s i s . These
products have p r o p e r t i e s as shown i n Table I . "CARDOLITE" Brand
NC-543 i s l i g h t e r i n c o l o r but otherwise s i m i l a r to "CARDOLITE"
Brand NC-540, w h i l e "CARDOLITE" Brand NC-545 i s l i g h t e r i n c o l o r
and lower i n v i s c o s i t y than any o f the e a r l i e r phenalkamines.
The c o l o r o f the new phenalkamines makes i t e a s i e r to have
Table I
Phenalkamine Curing Agent P r o p e r t i e s
Commercial Experimental
NC-540 NC-541 NC-542 NC-543 NC-545
Amine value 520 340 470 520 480

N-H Eq. Wt. 70 135 75 75 80
V i s c o s i t y , c p , 25° 2500 40,000 3500 2500 350
C o l o r , Gardner 16 17 16 10-12 10-12

Odor S l i g h t Ami ne
Gel t i m e , min. 40 110 90 45 50
Mixing r a t i o , phr 40-60 50-100 40-60 40-60 40-60
( L i q u i d Epoxy)
Table II
5
Comparison o f P r o p e r t i e s o f Classes o f Curing A g e n t s
Property Type o f Curing Agent

Phenalkamines Poly- Poly- Ami do- Ali-
Expt'l. Comm. amides amines amines phatics
Low v i s c o s i t y • + _ • * •
Chemical
resistance • • + * - *
Appearance • + + + + •
Low t o x i c i t y (b) • • + +
-
Long pot 1 i f e - - • - * -
Fast cure • • - • - •
Low tempera-
t u r e cure • • • +
Epoxy compati-
- -
bility * • + +
- -
Cost e f f e c t i v e * • • • • -
(a) * , good; +, m a r g i n a l l y acceptable ; - , unsuitable
(b) * for NC-•543, + to - for NC-545
coatings o f any c o l o r i n c l u d i n g w h i t e , p a s t e l s , and v i v i d dark

c o l o r s . The reduced b l u s h i n g tendency o f NC-545 a l l o w s the easy
preparation o f high gloss c o l o r e d or c l e a r c o a t i n g s . The lower
v i s c o s i t y o f the new m a t e r i a l a l l o w s f o r m u l a t i o n o f c o a t i n g s y s -
tems with l e s s solvent content.
Cure Rate S t u d i e s . The l i t e r a t u r e on c u r i n g o f epoxies

i n d i c a t e d two ways to q u a n t i t a t i v e l y assess the d i f f e r e n c e i n
cure r a t e o f v a r i o u s c u r i n g agents. Fava has reported on cure
2
mechanism studies using d i f f e r e n t i a l scanning c a l o r i m e t r y and
Dannenberg o f S h e l l has reported on epoxy-cure mechanism s t u d i e s
3
by near i n f r a r e d s p e c t r o s c o p y (NIR).
The use o f NIR, i n the study o f epoxy c u r i n g , i s a l s o d i s -
4
cussed i n Lee and N e v i l l e ' s Handbook o f Epoxy R e s i n s . The NIR
method was s e l e c t e d for t h i s study due to i t s speed and ease o f

use.
In the NIR s t u d i e s , 1 mm t h i c k samples were used, prepared
by using a 1 mm spacer between two microscope cover s l i d e s . Be-
cause o f the small s i z e (1 g) and t h i c k n e s s (1 mm) o f the samples
the r e s u l t s obtained i n t h i s study r e l a t e very well to the cure
which would take place i n an actual c o a t i n g . The a b s o r p t i o n at
2.205/A. was used as i n d i c a t i v e o f unreacted epoxy groups. The
r e a c t i o n r a t e (cure r a t e ) i s c o n v e n i e n t l y p l o t t e d as percent un-
reacted or r e s i d u a l epoxy v s . cure time to get curves such as are
shown i n Figure I . In these curves degree o f cure increases as
r e s i d u a l epoxy decreases, i . e . , the curve drops.
In the case o f a simple mixture o f epoxy r e s i n with c u r i n g
agent, although NC-540 (top c u r v e , Figure I) cures the epoxy
r a p i d l y through 24 hours the r e a c t i o n e s s e n t i a l l y stops w i t h 25%
o f the i n i t i a l epoxy c o n c e n t r a t i o n l e f t untouched. This i s i n
s p i t e o f use o f a s t o i c h i o m e t r i c amount o f c u r i n g agent. This
behavior i s t y p i c a l for most, or a l l , c u r i n g agents at room
temperature because as c u r i n g takes p l a c e , a three-dimensional
s t r u c t u r e i s formed - which i n t e r f e r e s with the free t r a n s i a -
t i o n a l movement o f the r e a c t i n g m o l e c u l e s . As r i g i d i t y i n c r e a s -
es, f u r t h e r i n t e r f e r e n c e with the v i b r a t i o n a l movement o f the r e -
a c t i n g groups occurs to where they simply can no longer get c l o s e
enough to each other to r e a c t . The r e a c t i o n becomes a r r e s t e d or
"frozen" i n p l a c e .
5
A. M. P a r t a n s k y has described t h i s e f f e c t . He i n d i c a t e s
t h a t "completeness" o f the r e a c t i o n can be improved by i n c r e a s -
ing the m o b i l i t y o f the r e a c t i n g molecules or groups which can
be accomplished i n a number o f ways, i n c l u d i n g :
1. Increasing the amplitude o f the v i b r a t i o n a l movement o f
the r e a c t i n g components by i n c r e a s i n g t h e i r energy - e . g . ,
r a i s i n g the temperature o f the system.
2. P r o v i d i n g for a greater freedom o f molecular movement by
i n c r e a s i n g the f l u i d i t y o f the system. The use o f d i l u e n t s ,
e i t h e r r e a c t i v e epoxy types or i n e r t solvent t y p e s , i s one
way o f i n c r e a s i n g the f l u i d i t y (and decreasing the c r o s s l i n k
Figure 1.
HOURS AT 23°C
d e n s i t y ) o f a given system. Since s o l i d epoxy r e s i n s con-

t a i n fewer epoxy groups f o r a given weight, t h e i r use a l s o
provides lower c r o s s l i n k d e n s i t y and allows the cure r e a c -
t i o n to proceed f u r t h e r to completion.
The e f f e c t o f adding a mono-epoxy d i l u e n t to reduce the
c r o s s - l i n k i n g d e n s i t y i s shown i n F i g u r e I, middle curve. The
r e a c t i v e d i l u e n t NC-513 has been added to the NC-540-cured system
and t h i s allows the cure to proceed to where o n l y 11% unreacted
epoxy i s present a f t e r 7 days o f r e a c t i o n . S u r p r i s i n g l y , the NC-
540/NC-513 system has an extended pot l i f e even though the maxi-
mum cure i s achieved f a s t e r .
An e x p l a n a t i o n i s apparent by examining the cure curve. Be-
cause the d i l u e n t reduces the c r o s s l i n k i n g d e n s i t y , i t allows the
epoxy to r e a c t more completely. The g r e a t e r extent o f r e a c t i o n

tends to compensate f o r the otherwise p o s s i b l y d e l e t e r i o u s e f f e c t
o f the d i l u e n t on the p r o p e r t i e s o f the cured system. The use o f
d i l u e n t a l s o provides the p r a c t i c a l advantage o f lowered v i s c o s i -
t y i n a formulated system. Since e x c e s s i v e use o f d i l u e n t s can
l e a d to poor chemical r e s i s t a n c e and reduced mechanical s t r e n g t h ,
recommended amounts should not be exceeded.
An a c c e l e r a t o r - d i l u e n t such as nonyl phenol can be employed
to i n c r e a s e both the r a t e o f cure and the completeness o f c u r e ,
as shown i n the bottom curve i n F i g u r e I .
In a c t u a l c o a t i n g s a p p l i c a t i o n s the f i r s t few hours are im-
p o r t a n t . The cure r a t e o f the NC-540/NC-513 system d u r i n g t h i s
period i s shown i n F i g u r e I I . I t can be seen t h a t b e t t e r than
75% o f the cure i s achieved i n o n l y seven hours.
R a i s i n g the temperature o f the system allows one to o b t a i n
proper cure i n minutes r a t h e r than hours ( F i g u r e I I I ) . A t 65°C
(149°F) complete cure i s achieved i n 45 minutes. At 100°C
(212°F) i t takes o n l y 18 minutes and 150°C (302°F) a mere 6 min-
utes. A c t u a l l y the cure time at 150°C i s probably c l o s e r to 2
minutes s i n c e e q u i l i b r a t i o n to oven temperature takes 3-4 min-
utes.
S i g n i f i c a n c e o f F a s t e r Cure. T h i s r a p i d and complete cure
o f two-part epoxies at a r e l a t i v e l y low temperature has not been
e x p l o i t e d i n i n d u s t r i a l f i n i s h i n g o p e r a t i o n s to the extent i t
might be. Such systems formulated to high s o l i d s content would
be q u i t e s u i t a b l e f o r many priming a p p l i c a t i o n s and could a l l o w
s i g n i f i c a n t time and energy savings by a l l o w i n g reduced cure-bake
temperatures and/or cure times. Oven through-put c o u l d be i n -
creased d r a m a t i c a l l y .
In maintenance a p p l i c a t i o n s and other i n - p l a c e c o a t i n g work
i t i s o f t e n d e s i r a b l e to have a f o r m u l a t i o n which cures at tem-
peratures below the normal room temperature. For t h i s reason i t
was o f i n t e r e s t to i n v e s t i g a t e the cure r a t e s o f v a r i o u s epoxy
r e s i n - c u r i n g a g e n t - d i l u e n t - a c c e l e r a t o r mixtures a t lower tempera-
tures.
The e f f e c t o f reducing the temperature on the NC-540 cured
10·
20A
2
3
Figure 2.
4
HOURS AT 23°C
!
EPOXY
RESIN
CHEMISTRY
GARDINER
AND MANZARA
Figure 3.
Phenalkamines
REACTION TIME IN MINUTES

system i s shown i n Figure I V . At 4°C (40°F) the cure i s slowed

down because o f the l o s s o f m o b i l i t y ( v i s c o s i t y i n c r e a s e s ) at the
low temperature. A g a i n , the a d d i t i o n o f NC-513 and nonyl phenol
h e l p s . In t h i s c a s e , the combination o f NC-513 w i t h DMP-30 gives
the most completely cured system. A f t e r seven days the cure s t a t e
o f the DMP-30 a c c e l e r a t e d mixture i s a c t u a l l y at about the same
p o s i t i o n i t was at i n 7 days at room temperature without the acce
lerator. However, at room temperature t h i s degree o f cure i s
a t t a i n e d i n 24 to 48 hours.
A number o f m a t e r i a l s have been examined i n the NIR cure r a t e
studies. Figures V and VI show some comparisons o f several c u r i n g
agents at 23°C (73°F) and at 4°C (40°F) r e s p e c t i v e l y . In these
cases a l l o f the c u r i n g agents were used at s t o i c h i o m e t r i c r a t i o s
w i t h the l i q u i d Bisphenol A epoxy. In g e n e r a l , the phenalkamines
a t t a i n t h e i r maximum cure very r a p i d l y at room temperature and

achieve s a t i s f a c t o r y cure even at reduced temperatures. This i s
i n c o n t r a s t with most o f the other types o f c u r i n g agents. This
property reduces the p r o b a b i l i t y o f damage to a phenalkamine-cured
c o a t i n g should unexpectedly low temperatures p r e v a i l between ap
p l i c a t i o n and use.
Formulation and T e s t i n g o f C o a t i n g s . Table I I I shows two

s o l v e n t - f r e e l i q u i d epoxy c o a t i n g formulations (Formulation I and
2 ) . Although these systems are somewhat l i m i t e d by t h e i r pot l i f e
which i s o n l y 30-50 minutes, they are s u i t a b l e for r o l l e r and
brush a p p l i c a t i o n s where small amounts are mixed. They are a l s o
s u i t a b l e for f l o o r i n g a p p l i c a t i o n s where the mixed m a t e r i a l i s
q u i c k l y spread over the prepared s u r f a c e , which precludes the o c
currence o f an exotherm and a l l o w s 2-3 hours working t i m e . For
spray a p p l i c a t i o n s , a dual-component a i r l e s s spray system w i t h an
i n - l i n e mixer has been used s u c c e s s f u l l y with these f o r m u l a t i o n s .
I n - l i n e mixing r e q u i r e s immediate c o m p a t i b i l i t y o f the c u r i n g
agent w i t h the r e s i n , a c h a r a c t e r i s t i c o f phenalkamines.
Modifying the formulations by adding enough s o l v e n t converts
them to 85% s o l i d s as shown i n Table I I I (Formulations 3 and 4 ) .
Now the v i s c o s i t i e s are o n l y 300-500 c p s , and they are e a s i l y
sprayable using conventional low pressure s p r a y e r s . In a d d i t i o n ,
the pot l i f e f o r the NC-542 cured system has been extended to 2
hours and 20 minutes.
S u b s t i t u t i n g a s o l i d epoxy for the l i q u i d epoxy as shown i n
Table I I I (Formulations 5 and 6 ) , extends the pot l i f e out to 6
hours at 60% volume s o l i d s . Both the s o l i d and l i q u i d epoxy based
systems give e x c e l l e n t coatings with good c o r r o s i o n r e s i s t a n c e .
1
Young and H o w e l l p r e d i c t e d a p o t e n t i a l f o r high to 100% s o l
i d s epoxy coatings i n heat-converted systems f o r product f i n i s h
i n g . They l i s t p o t e n t i a l uses i n can c o a t i n g s , drum l i n i n g s , c o i l
c o a t i n g s , a p p l i a n c e p r i m e r s , automotive p r i m e r s , and automotive
guidecoats. Low v i s c o s i t y a p p l i c a t i o n s are p o s s i b l e through em
ployment o f a heated Part A and Part Β mixed at the point o f ap
p l i c a t i o n . Heating NC-540 and NC-545 to 100°F reduces the
GARDINER
100«
10-
A N D MANZARA
Figure 4.
Phenalkamines
H O U R S A T 4°C
10
οJ
,
24
,
48
Figure 5.
H O U R S A T 23°C
EPOXY
,
168
RESIN
CHEMISTRY
GARDINER
A N D MANZARA
Figure 6.
Phenalkamines
HOURS AT 4°C
Table I I I
Coating Formulations with Phenalkamines
Formulation # 1 2 3 4 5 6
Part A (Parts by weight)
L i q u i d Epoxy Resin 100 100 100 100 _ _
S o l i d Epoxy Resin -20 133 133

CARDOLITE NC-513 20 20 20 20 20
Ti02 7 7 7 7 7 7
Cab-O-Sil 0.5 0.5 0.5 0.5 0.5 0.5
CR-100 0.2 0.2 0.2 0.2 0.2 0.2
Glycerine 0.15 0.15 0.15 0.15 0.15 0.15
DC-200 0.1 0.1 0.1 0.1 0.1 0.1
Part Β
CARDOLITE NC-542 45 45 17
CARDOLITE NC-545 - 45 - 45 - 16
MIBK/Xylene 50/50 - - 22 22 42 42
Mix P r o p e r t i e s
Volume % Solvent 15 15 40 40
Gel time (1 q t . , 50 30 140 60 >360 >360
minutes
Mix V i s c o s i t y 3150 1375 390 240 255 245
Table IV
3
IMMERSION TEST RESULTS
Curing Agent NC-540 NC-541 NC-542 NC-543 NC-545

b
Phr 40 50 40 40 40
I n i t i a l hardness 85 80 83 83 84
0
Final p r o p e r t i e s
10% aqueous a c e t i c a c i d
Weight gain (%) 4.0 1.5 3.5 2.7 11.1
Hardness (Shore D) 83 80 75 80 73
10% aqueous NaOH

Weight gain (%) 0.45 0.25 0.20 0.3C 0.33
30% aqueous H 2 S O 4
Weight gain (%) 0.5 0.3 0.4 0.4 2.0
'Weight gain (%) 0.4 0.4 0.3 0.25 0.2

(a) For procedure see experimental s e c t i o n

(b) Parts per hundred o f standard l i q u i d epoxy r e s i n , eew 190
(c) A f t e r seven days immersion i n s p e c i f i e d s o l v e n t at 23°C.
v i s c o s i t y to 100 cps o r l e s s . Phenalkamines are e x c e l l e n t f o r

factory-applied industrial finishes.
High s o l i d s phenalkamine epoxies are used i n p r i m e r s , indus-
t r i a l maintenance c o a t i n g s , and marine coatings f o r t h e i r improved
chemical and moisture r e s i s t a n c e . In a c e t i c a c i d spot t e s t s on a
l i q u i d epoxy r e s i n c o a t i n g cured with the designated c u r i n g a*
gents, "CARDOLITE" Brand NC-540 and DETA performed well w h i l e the
polyamide-cured c o a t i n g d i s i n t e g r a t e d . Immersion t e s t s show e x c e l -
l e n t r e t e n t i o n o f hardness and o n l y minor weight gain i n aqueous
a c i d s and bases. (See Table I V . )
Conclusions.
In comparing phenalkamines and other c u r r e n t l y a v a i l a b l e ep-
oxy c u r i n g agents a g a i n s t a l i s t o f p r o p e r t i e s d e s i r a b l e f o r a
c u r i n g agent f o r high-100% s o l i d s epoxy c o a t i n g s , the phenalka-
mines are shown to have the best combination o f p r o p e r t i e s f o r
such a p p l i c a t i o n s . The p r a c t i c a l u t i l i t y o f the phenalkamines has
a l s o been demonstrated by t h e i r i n c o r p o r a t i o n i n t o high s o l i d s and
100% s o l i d s epoxy f o r m u l a t i o n s .
By s p o t - t e s t s on coatings and immersion-tests on c a s t i n g s the
e x c e l l e n t c h e m i c a l - r e s i s t a n c e o f phenalkamine-cured epoxy systems
has been demonstrated. In a d d i t i o n , n e a r - i n f r a r e d cure s t u d i e s
have documented the r a p i d complete cure o f epoxies a t room temper-
ature and a l s o s a t i s f a c t o r y cure at reduced temperatures when
phenalkamines are used as the c u r i n g agents.
This unique combination o f p r o p e r t i e s o f the phenalkamines
suggests they should be the c u r i n g agents o f choice not only f o r
high s o l i d s f i e l d a p p l i e d i n d u s t r i a l c o a t i n g s , but a l s o f o r heat-
cured f a c t o r y a p p l i e d i n d u s t r i a l f i n i s h e s
Acknowledqement.
A s p e c i a l thanks to Thomas E . Forester who c o l l e c t e d much o f
the data used i n t h i s paper.
References.
1. R.G. Young and W.R. Howell, J r . , "Epoxies Offer F u l f i l l -
ment of High Performance Needs", Modern Paint and Coatings,
43-47 (March 1975)
2. R.A. Fava, "Differential Scanning Calorimetry of Epoxy
Resins", Polymer 9, 137-151 (1968)
3. H. Dannenberg, "Determination of Functional Groups in
Epoxy Resins by Near-Infrared Spectroscopy", SPE Transactions
78-88 (January 1963).
4. H. Lee and K. Neville, "Handbook of Epoxy Resins" Chapter
4, page 19, McGraw Hill Book Company (1967).
5. A.M. Partansky, "A Study of Accelerators for Epoxy-Amine
Condensation Reactions", Advances in Chemistry Series, Epoxy
Resins, page 92, Chapter 4 (1970).

10
The Effect of Alkyl Substituents on the Properties of

Cured Hydantoin Epoxy Resins
E. H. CATSIFF, R. E. COULEHAN, J. F. DIPRIMA,

D. A. GORDON, and R. SELTZER
Research Department, Plastics and Additives Division, CIBA-GEIGY Corporation,

Ardsley, NY 10502
Epoxy resins based on glycidylation of bisphenols, cresol

and phenol novolacs, polycarboxylic acids, polyols, amines, and
aminophenols have been long known. Epoxidized linear and cyclic
olefins have also been used as specialty epoxy resins. More
recently, glycidylated heterocycles have been introduced, ini
tially as specialty resins promising improved resistance to
weathering. One heterocycle in particular, the hydantoin ring,
has become of particular interest as an epoxy substrate (1).
A comprehensive review was given by Habermeier (2) of many
types of glycidylated resins based on the hydantoin ring. Much
of the emphasis in his account was on the variations possible
in the position of the glycidyl groups: direct substitution on
either or both of the Ν atoms of the hydantoin ring, glycidoxy-
alkyl substitution in the same positions, and glycidyl esters
and ethers based on substituents in those positions. Also shown
were bis(hydantoins) in which the hydantoin rings were linked
by methylene or other alkylene groups, diester chains, or the
β-glycidoxytrimethylene group derived from epichlorohydrin.
Habermeier also pointed out the ready synthesis of hydan
toins from aldehydes or ketones; the substituents i n the
5-position of the ring were thus determined by the carbonyl
compound used as starting material. Most of the examples cited
had methyl, ethyl, or cyclopentamethylene substitution i n the
5-position. Data were presented on the properties of cured
resins with these substituents and with a broad variety of the
other structural features mentioned.
In t h i s paper we report on a s e r i e s of hydantoin r e s i n s
derived from a somewhat broader choice of aldehydes and ketones,
and show how the 5 - p o s i t i o n s u b s t i t u e n t s i n t e r a c t with s e v e r a l
v a r i a n t s of common epoxy c u r i n g systems t o produce the p r o p e r t i e s
of the f i n a l cured systems.
0-8412-0525-6/79/47-114-115$05.25/0
Hydantoin-Based Epoxy Resins
The simplest c l a s s of hydantoin epoxy r e s i n s are the

1 , 3 - d i g l y c i d y l h y d a n t o i n s of Formula I I . They were r e a d i l y
prepared from the 5 , 5 - d i a l k y l or 5-monoalkylhydantoins and
e p i c h l o r o h y d r i n . The hydantoins (Formula I) were prepared
from ketones or aldehydes v i a the Bucherer r e a c t i o n .
R,-C C
R C R + H C N + N H + C 0
1
I I
1~ ~ 2 3 2
' /VN.
Conversion o f the hydantoins t o epoxy r e s i n s was s t r a i g h t

forward.
Γ ,ο
R, -C C
o o I I q
^ /\ A
50%
ι + Λ A A
CH -CH-CH C1
2 2 aq. NaOH CH -CH-CH
2 2 C CH -CH—CH
2 2
11
Table I l i s t s t y p i c a l p r o p e r t i e s of a baker's dozen of

these r e s i n s , produced by t y p i c a l d i r e c t p r e p a r a t i o n s , without
extensive p u r i f i c a t i o n . O v e r a l l , the v i s c o s i t i e s of these
r e s i n s were q u i t e low, p a r t i c u l a r l y by comparison t o the w e l l
known general purpose epoxy r e s i n s based on the d i g l y c i d y l
ether of bisphenol A (DGEBA). The more s h i e l d e d higher a l k y l -
s u b s t i t u t e d hydantoin r i n g s favored lower v i s c o s i t i e s . Some
anomalies i n these v i s c o s i t i e s presumably r e f l e c t e d e i t h e r a
tendency of c e r t a i n r e s i n s to c r y s t a l l i z e , or the presence o f
some species o f higher molecular weight, formed by r e a c t i o n of
the g l y c i d y l group with a second hydantoin r i n g .
In some instances a much purer d i g l y c i d y l h y d a n t o i n species
has been i s o l a t e d . Pure Resin l i a , 1 , 3 - d i g l y c i d y l - 5 , 5 - d i m e t h y l -
hydantoin, was a r e a d i l y c r y s t a l l i z a b l e s o l i d , m. 72-73°C ( 2 ) ,
epoxy content 8.25 eq/kg. The l e s s pure sample described i n
Table I tended t o supercool f o r a l i m i t e d time, and could then
be handled as a l i q u i d . A d i s t i l l e d grade of Resin l i b ,
10. CATSIFF ET AL. Cured Hydantoin Epoxy Resins 117
TABLE 1
1,3-DIGLYC1DYLHYDANTOINS
Resin
Hydantoin, Y i e l d of Viscosity
Resin R 0 I mPa«s Epoxy/Kg. Theo.
*1
Ia,IIa CH 3 CH 3 >90% Solid 7.6 8.32
lb,lib C H 2 5 CH 3 80% 1400 7.3 7.87
Ic,IIc i-C H 3 7 H 40% Solid 7.6 7.87
Id,lid n-C H 3 7 H 40% 3300 7.0 7.87
Ie,IIe - (CH )5 " (a) 2 90% Solid 6.8 7.13
If,IIf i"C H 4 9 CH 3 80% 1300 6.8 7.08
i g . n g n c H CH 82% 1300 6.9 7.08

~ 4 9 3
Ih,IIh n-C H 5 n H 52% 2500 5.9 7.08
Ii,IIi i - C H 5 u
CH 3 90% 2000 6.6 6.75
i j . n j n-C H 5 n
CH 3 94% 600 6.7 6.75
Ik,Ilk 2-MeBu C H
2 5 93% 1000 6.2 6.44
11,111 n-C H 6 1 3 CH 3 96% 600 6.3 6.44
Im, Ilm i"C H 4 9 i~C H 4 9

40% 900 6.0 6.16
(DGEBA) — 14000 5.3 5.88
(a) cyclopentamethylene group forming a s p i r o - structure.

1,3-diglycidyl-5-methyl-5-ethylhydantoin, had v i s c o s i t y 700 mPa.s

and epoxy content 7.52 eq./kg., r a t h e r than the values given i n
Table I. A d i s t i l l e d grade of Resin l i e , 1 , 3 - d i g l y c i d y l - 5 , 5 -
cyclopentamethylenehydantoin, was a l s o c r y s t a l l i n e , m. 104-106°C
(2), epoxy content 7.07 eq/kg.
P r o p e r t i e s of Cured Hydantoin Epoxy Resins - Glass Temperatures
The e f f e c t of a l k y l s u b s t i t u e n t s i n s h i e l d i n g the p o l a r
hydantoin r i n g was shown by the g l a s s t r a n s i t i o n temperature Tg
achieved a f t e r extensive c r o s s l i n k i n g . As a measure of Tg we
used the " i n i t i a l deformation temperature" (IDT) d e f i n e d i n the
experimental s e c t i o n . The IDT a l s o depended on the s t o i c h i o -
metric r a t i o of c u r a t i v e (hardener) to r e s i n , being highest at
or near exact equivalence. A l s o , since the r e a c t i o n r a t e f e l l

d r a s t i c a l l y when enough c r o s s l i n k i n g had occurred to b r i n g the
glass t r a n s i t i o n temperature up to the r e a c t i o n temperature,
IDT was e f f e c t i v e l y l i m i t e d by the l a t t e r .
1
In Table I I , the IDT s obtained by c u r i n g v a r i o u s d i g l y c i d y l -
hydantoins with hexahydrophthalic anhydride (HHPA) are shown.
H/R i s the r a t i o of moles HHPA to a c t u a l e q u i v a l e n t s of epoxide;
while i t was not kept constant throughout the s e r i e s , experience
has shown t h a t , over the range used (H/R = 0.9 to 1.1), the v a r i -
a t i o n i n IDT was u s u a l l y l e s s than 10°. In a few cases, the f i n a l
cure temperature (150°C) may have l i m i t e d the IDT, but with the
higher a l k y l s u b s t i t u e n t s , c l e a r l y i t d i d not.
Note that the highest IDT was obtained with the c y c l o p e n t a -
methylenehydantoin r e s i n d e r i v e d from cyclohexanone. It i s
tempting to speculate that t h i s i n f l e x i b l e a l k y l e n e moiety was
i n e f f e c t i v e i n s h i e l d i n g the hydantoin r i n g , but subsequent com-
p a r i s o n of the h y d r o p h o b i c - h y d r o p h i l i c balance of amine-cured
r e s i n s appeared to r u l e out t h i s explanation; probably the s t i f f
s p i r o s t r u c t u r e c o n t r i b u t e d to the high Tg, j u s t as i t c o n t r i -
buted to the high melting point of the r e s i n i t s e l f ( l i e ) .
Aside from t h i s e f f e c t , c l e a r l y the longer a l k y l s u b s t i t -
uents d i d reduce i n t e r c h a i n i n t e r a c t i o n s so as to lower Tg.
Another s t e r i c e f f e c t notable i n Table I I i s that Tg was higher
for c l o s e - i n branching of the a l k y l s u b s t i t u e n t s .
As shown i n Table I I I , a l l of the anhydride-cured r e s i n s
were e s s e n t i a l l y hydrophobic. The amount of water uptake
showed l i t t l e or no trend with s i z e or branching of the a l k y l
s u b s t i t u e n t s . Water uptake was r e v e r s i b l e , a l s o .
Hydrophobic-Hydrophilic Balance
A somewhat d i f f e r e n t aspect of the hydrophobic s h i e l d i n g

e f f e c t of a l k y l s u b s t i t u e n t s was r e f l e c t e d i n the r e l a t i v e
h y d r o p h i l i c i t y of a l i p h a t i c amine-cured r e s i n s . A standard
room temperature-curing polyamine, t r i e t h y l e n e t e t r a m i n e (TETA),
was used to cure a s e r i e s of r e s i n s at room temperature. The
CATSIFF ET AL. Cured Hydantoin Epoxy Resins 119
TABLE I I
CYCLOALIPHATIC ANHYDRIDE CURING OF 1,3-DIGLYCIDYLHYDANTOINS
Resin H/R IDT, °C

-1 ^2
lia CH 3 CH 3 0.9 140
lib C H C H
1.0 148
2 5 3
Ile i-C H 3 ? H 1.1 148
lid n-C H 3 ? H 1.1 139

Ile - (CH ) 2 5 - (c) 0.9 153
Ilf i-C H 4 9 CH 3 0.9 129
Hg n-C H 4 9 CH 3 0.9 118
Ili i C H C H
0.9 115
" 5 ll 3
iij n C H C H
0.9 112
~ 5 ll 3
Ilk 2-MeBu C H 2 5 1.1 123
III n-C H 6 13 CH 3 1.0 115
Ilm ^ 4 Η i
" 4 C H 0.9 (a) 111
9 9
(DGEBA) — 1.0 (b) 126
A l l were cured with HHPA and 2 phr BDMA. Except where noted,
a l l were g e l l e d at 80°C and given a f i n a l cure of 2 hr./150°C
(a) g e l l e d at 100°C (b) f i n a l cure 3 hr./150°C
(c) cyclopentamethylene group forming a spiro-structure

TABLE I I I
CYCLOALIPHATIC ANHYDRIDE CURING OF 1,3-DIGLYCIDYLHYDANTOINS

Resin H/R Water Uptake,
Ha CH 3 CH 3 0.9 1.62
lib 0.94 1.49
^2^5
lie i-C H 3 ? H 1.1 1.58
lid n-C H 3 ? H 1.1 1.80
He - (CH ) 2 5 - ( ) C 0.9 1.09
Ilf i-C H 4 9 CH 3 0.9 1.45
Ilg n-C H 4 9 CH 3 0.9 1.17

Hi i-C H 5 n CH, 0.9 1.28
Hj n-C H 5 n CH 3 0.9 1.21

Ilk 2-MeBu C H 2 5 1.1 1.47
III n-C H 6 1 3 CH 3 1.0 1.50
Hm i-C H 4 9 i-C H 4 9 0.9 (a) 0.84
A l l were cured with HHPA and 2 phr BDMA. Except where noted,
a l l were g e l l e d at 80°C and given a f i n a l cure of 2 hr/150°C
(a) G e l l e d at 100°C (b) 4 weeks, room temperature
(c) cyclopentamethylene group forming a s p i r o - structure

stoichiometry chosen was one amine hydrogen/actual epoxide

equivalent. In most cases, some specimens were given a mild
postcure to see the e f f e c t of increased c r o s s l i n k i n g . The
h y d r o p h i l i c i t y of the cured systems was judged by weight gain
of small specimens a f t e r immersion at room temperature i n
deionized water f o r periods of one day to four weeks. (in
some cases, p a r a l l e l specimens were exposed at 35°C i n a 95%
R.H. chamber. These data were g e n e r a l l y c l o s e to the room
temperature immersion r e s u l t s , and with one exception are not
reported here.) The f l e x u r a l modulus of the specimen was a l s o
measured at the time of weighing, since the absorbed water
acted to p l a s t i c i z e the cured r e s i n .
Both weight gain and p l a s t i c i z a t i o n proved to be very sen-
s i t i v e to the a l k y l groups present, as shown i n Table IV. Note
that the m i l d postcure somewhat improved the more hydrophobic

cured r e s i n s (those with and higher s u b s t i t u e n t s ) , notably
p e r m i t t i n g TETA-cured Resin I l k to r e t a i n 95% of i t s f l e x u r a l
modulus a f t e r four weeks. M i l d postcure s i g n i f i c a n t l y reduced
the r a t e of water uptake of the h y d r o p h i l i c cured r e s i n s . But
note a l s o that even with postcure the h y d r o p h i l i c cured r e s i n s
u s u a l l y absorbed so much water i n four weeks that the s w e l l i n g
s t r e s s e s became greater than the cohesive strength and the spec-
imens broke apart. Even these high water uptakes proved to be
r e v e r s i b l e ; i . e . , the water acted only as a s w e l l i n g agent.
In general, the hydrophobic TETA-cured r e s i n s were those
which, i n Table I I , had low IDT. Both p r o p e r t i e s are a t t r i b u t a b l e
to s h i e l d i n g of the hydantoin r i n g by the 5 - p o s i t i o n s u b s t i t u e n t s .
The p r i n c i p a l exception to t h i s c o r r e l a t i o n was 1 , 3 - d i g l y c i d y l -
5,5-cyclopentamethylenehydantoin ( l i e ) which had a high IDT i n
Table I I , but which proved to be q u i t e hydrophobic a f t e r room
temperature cure with amines (30. Thus i t appears that the s p i r o -
j o i n e d c y c l o a l i p h a t i c r i n g was e f f e c t i v e i n s h i e l d i n g the
hydantoin r i n g , but i t s r e l a t i v e s t i f f n e s s r a i s e d Tg c o n s i d e r a b l y .
Since the h y d r o p h o b i c - h y d r o p h i l i c balance of amine-cured
r e s i n s was so s e n s i t i v e to a l k y l s u b s t i t u e n t s on the hydantoin
r i n g , i t i s not s u r p r i s i n g that i t was a l s o s e n s i t i v e to the
hydrocarbon moieties of the amine c u r a t i v e s . The range of be-
h a v i o r depended on the r e s i n s u b s t i t u e n t s . For example, the
already hydrophobic e t h y l amyl s u b s t i t u t e d Resin I l k showed
moderate but s i g n i f i c a n t increases i n h y d r o p h o b i c i t y when cured
with c y c l o a l i p h a t i c , h i g h l y branched a l i p h a t i c , or formulated
aromatic amines. See Table V.
At the other extreme, as shown i n Table VI, a r e s i n mix-
ture c o n t a i n i n g only dimethylhydantoin (DMH) r i n g s was q u i t e
h y d r o p h i l i c with a l l room temperature amine c u r a t i v e s except
the formulated aromatic amine mixture based on methylene-
dianiline. (See Table VII f o r i d e n t i f i c a t i o n of the amines
i n Table V and subsequent t a b l e s . ) This r e s i n mixture was
obtained by hydroxypropylating a p o r t i o n of the DMH, l a .
TABLE IV
ROOM TEMPERATURE CURED HYDANTOIN EPOXY RESINS
Water Uptake, % % Retention of

F l e x Modulus
Resin R
h 2 1 Day 4 Wk 4 Wk.
Ha CH 3 CH 3 27.7 (a) (c,d)

(b) 11.7 (a) 15 (d)
lib C H
2 5 CH 3 13.4 (a) 10 (d)
(b) 5.9 29.5 10
Hd n-C H 3 7 Η 14.5 (a) 10 (d)
Hh η-0 Λ ι Η 2.6 12.5 50

(b) 1.8 10.6 65
Hi i-C H 5 n CH 3 2.4 11.5 70
III n-C H 6 13 CH 3 1.4 6.8 80

(b) 1.5 3.8 80 (g)
Ilk 2-MeBu C H
2 5 1.2 5.9 70
(b) 0.8 4.8 95
A l l were cured with TETA at H/R =1.0 amine hydrogen/epoxide.

A l l were cured at room temperature; 14-21 days without postcure
and at l e a s t 7 days before postcure. Except where noted, expo
sure was by immersion i n deionized water at room temperature.
(a) Fragmented (d) At 1 day

(b) Postcured 6 hr./100°C (g) Exposed to 95% R.H./35°C
(c) Too s o f t to measure
10. CATSiFF ET AL. Cured Hydantoin Epoxy Resins 123
TABLE V
ROOM TEMPERATURE AMINE CURING OF HYDANTOIN EPOXY RESINS
Resin: I l k [1,3-diglycidyl-5-ethyl-5-(2-methylbutyl)hydantoin]
Water Uptake, % % Retention o f

F l e x Modulus
Curative 1 Day 4 Wk 4 Wk
Formulated amine (a) 0.4 1.7 95

TMDA (a) 0.6 2.7 90
MMCHA (a) 0.6 2.6 (b)
TETA (a) 1.2 5.9 70
A l l were cured at H/R = 1.0 amine hydrogen/epoxide.

A l l were cured at room temperature 14-21 days.
Except where noted, exposure was by immersion i n deionized

water at room temperature.
(a) See Table V I I f o r i d e n t i f i c a t i o n .

(b) Too b r i t t l e t o c u t .
CH n CH„
,0
CH--C CH -C Q C
J ι CH^
1
H
/ N
N
C
Ν
Ή
+ / \
CH -CH-CH
0 Q
A A
2 3
H C CH -CH-0H
o
ft
0
la III
As has been pointed out by Habermeier (2_), the non-equiva

lence of the 1- and 3- p o s i t i o n s of the hydantoin r i n g r e a d i l y
permitted monosubstitution. Subsequent g l y c i d y l a t i o n provided
the diepoxide IV.
CH Q
I 3
#
CH -C C
0 50% 0 I I CH Q 0
iii A + >A À A I /\
CH -CH-CH C12 2 aq. NaOH CH "CH-CH
2 2 0
C CH -CH-0-CH -CH-CH
2 2 2
IV
TABLE VI
Resin: f70% H a (1,3-diglycidyl-5,5-dimethylhydantoin)

V30% IV [l-glycidyl-3-(2-glycidoxypropyl)-
5,5-dimethylhydantoin]
Water Uptake, % % Retention of

F l e x Modulus

TMDA (a) 4.7 16.2 5
/30%eq TMDA (a)V
3.9 11.0 (b)
I70%eq MCHA ( a ) /
/l5%eq TMDAY
3.7 10.3 (b)
\85%eq MCHA/
1,4-BAC (a) 5.2 16.9 35
1,3-BAC (a) 5.2 17.1 20
MXDA (a) 7.4 23.1 (b)
IPDA (a) 6.1 14.3 (b)
PMDA (a) (c) — (b)
(d,e)
TETA (a) 23.4 (c)
A l l were cured at H/R = 1.0 amine hydrogen/epoxide.

Except where noted, exposure was by immersion i n deionized

%eq = percent o f amine e q u i v a l e n t s

(b) Too b r i t t l e t o c u t .
(c) Fragmented
(d) At 1 day
(e) Too s o f t to measure
10. CATSIFF ET AL. Cured Hydantoin Epoxy Resins
TABLE V I I
IDENTIFICATION OF MATERIALS
Aniline-formaldehyde c u r a t i v e = Jeffamine® AP-22
BAC = bis(aminomethyl)cyclohexane
BDMA = benzyldimethylamine
DGEBA = d i g l y c i d y l ether of Bisphenol A
Formulated amine = L i q u i d amine mixture c o n t a i n i n g MDA,

described by Habermeier ( 2 ) .
HHPA = hexahydrophthalic anhydride
IPDA = isophoronediamine
= 3,3 -dimethyl-5-aminomethylcyclohexylamine
,
MCHA = 4,4 -methylenebis(cyclohexylamine)
MDA = 4,4*-methylenedianiline
,
MMCHA = 4,4 -methylenebis(2-methylcyclohexylamine)
MXDA = m-xylylenediamine = 1,3-bis(aminomethyl)benzene
PMDA = p-menthanediamine
= l-methyl-4-(l-amino-l-methylethyl)cyclohexylamine
TETA = t r i e t h y l e n e t e t r a m i n e = 1,4,7,10-tetraazadecane
TMDA = 2,2,4-trimethylhexane-l,6-diamine
This r e s i n mixture, which had a low v i s c o s i t y , t y p i c a l l y

about 2500 mPa.s, was found to avoid the c r y s t a l l i z a t i o n tendency
of pure d i g l y c i d y l DMH, l i a . P a r t i c u l a r u t i l i t y has been found
for the r e v e r s i b l e high degree of s w e l l i n g of a room temperature
cured v e r s i o n of a DMH-based r e s i n , as a water-permeable topcoat
for marine a n t i f o u l i n g paints ( . The methylethylhydantoin-based
Resin l i b , as shown i n Table V I I I , gave the g r e a t e s t range of
h y d r o p h i l i c i t y when the amine c u r a t i v e was v a r i e d . This i s i n
keeping with i t s intermediate degree of a l k y l s u b s t i t u t i o n .
A few r e s i n s were given elevated temperature cures with
aromatic amines; here the e f f e c t of a l k y l s u b s t i t u e n t s on water
uptake could be seen, but the o v e r a l l behavior was intermediate
between the elevated-temperature anhydride cures and the room
temperature amine cures.
Solvent/Chemical Resistance
The hydrophobic s h i e l d i n g of the hydantoin r i n g by a l k y l

s u b s t i t u e n t s a f f e c t e d a l l the s o l v e n t - s o l u t e i n t e r a c t i o n s of
cured r e s i n s . Two of the r e s i n s and the DMH-based r e s i n mix-
ture were cured with a commercially a v a i l a b l e aromatic amine
mixture derived from aniline-formaldehyde condensation, iden-
t i f i e d i n Table V I I . Weight gain and solvent p l a s t i c i z a t i o n
were followed i n a number of solvents and aqueous media. Some
of the exposure was at 60°C as w e l l as at room temperature.
For the hydrophobic Resin I l k , the r e s u l t s f o r exposure to
v a r i o u s solvents are shown i n Table IX. The s o l v e n t s are
l i s t e d i n i n c r e a s i n g order of s o l u b i l i t y parameter £(5). I t i s
evident that ( w i t h i n the l i m i t a t i o n s of s o l u b i l i t y parameter
theory) t h i s cured r e s i n was l y o p h i l i c i n the range of Î = 9 -
9.6; there was a l s o a s p e c i f i c i n t e r a c t i o n with methanol.
Table X shows the g e n e r a l l y hydrophobic response of t h i s cured
r e s i n i n aqueous media ( l i s t e d i n i n c r e a s i n g order of pH).
Only strong a c i d had a d e l e t e r i o u s e f f e c t .
Again at the other extreme, the DMH-based h y d r o p h i l i c r e s i n
mixture was s t u d i e d , with r e s u l t s shown i n Tables XI and X I I .
This cured r e s i n was h y d r o p h i l i c (Table X I I ) , though less so than
the room temperature amine-cured systems of Table VI, but note i t s
general l y o p h o b i c i t y , as shown i n Table XI. Of the non-aqueous
media, only methanol and hot t r i c h l o r e t h y l e n e showed much s w e l l i n g
or p l a s t i c i z a t i o n i n 16 weeks. Presumably the poorly shielded DMH
r i n g s permitted strong i n t e r c h a i n i n t e r a c t i o n s ; t h i s v i r t u a l
c r o s s l i n k i n g provided general solvent r e s i s t a n c e .
Resin l i b , which proved somewhat l e s s h y d r o p h i l i c than the
DMH-based r e s i n mixture (see Table V I I I ) , was studied with c e r -
t a i n solvents only, as shown i n Table X I I I . I t s l y o p h o b i c i t y was
somewhat l e s s than the DMH-based mixture, and i n the two aqueous
media i t was somewhat l e s s a f f e c t e d . Thus, again, i t s behavior
r e f l e c t e d the intermediate degree of a l k y l s u b s t i t u t i o n .
10. CATSIFF ET AL. Cured Hydantoin Epoxy Resins
TABLE VIII
Resin: l i b (1,3-diglycidyl-5-methyl-5-ethylhydantoin)
Water Uptake, % % Retention ο

F l e x Modulus

ΤMDA (a) 1.4 5.3 80
f30%eq TMDA ( a ) \
1.5 6.0 (b)
l70%eq MCHA (a);
fl5%eq TMDÀV
1.5 6.0 (b)
\85%eq MCHA/
MMCHA (a) 1.1 4.3 (b)
1,4-BAC (a) 2.4 11.4 (b)
1,3-BAC (a) 1.9 10.4 (b)
MXDA (a) 2.4 9.6 (b)
IPDA
TETA
(a)
(a)
(c)
13.4
—
(c)
(b)
10 (d)
A l l were cured at H/R =1.0 amine hydrogen/epoxide.

Except where noted, exposure was by immersion i n d e i o n i z e d

%eq = percent of amine equivalents

(b) Too b r i t t l e to c u t .
(c) Fragmented
(d) At 1 day
TABLE IX
SOLVENT RESISTANCE OF AROMATIC AMINE-CURED HYDANTOIN EPOXY RESIN
Resin: I l k [ 1 , 3 - d i g l y c i d y l - 5 - e t h y l - 5 - ( 2 - m e t h y l b u t y l ) h y d a n t o i n ]
IDT = 128°C
Solvent Uptake, % % Retention of

Solubility Temp. F l e x Modulus

Solvent Parameter(5) °C 1 Wk. 16 Wk. 16 Wk.
Heptane 7.50 25 0.03 0.54 100
Kerosene 25 0.02 0.10 110

60 0.3 0.9 95
Xylene 8.9 25 0.08 0.8 100

60 0.5 5.3 85
E t h y l Acetate 8.91 25 1.9 29.8 (b) 15
Benzene 9.16 25 0.1 1.2 100
Trichlorethylene 25 3.5 55.1 30 (g)

9.16 60 (a) — ——
Chloroform 9.16 25 (a) — —
Acetone 9.62 25 (a) — —
Isopropyl A l c o h o l 25 -0.08 0.43 100

11.44
Methanol 14.50 25 11.1 20.7 25
A l l were cured with aniline-formaldehyde c u r a t i v e . See Table V I I .

H/R = 1 amine hydrogen/epoxide equivalent
G e l l e d 16 hr./65°C. Postcured 2 hr./150°C
(a) Fragmented (b) Cracked (g) At 8 weeks

CATSiFF ET AL. Cured Hydantoin Epoxy Resins 129
TABLE X
CHEMICAL RESISTANCE OF AROMATIC
AMINE-CURED HYDANTOIN EPOXY RESIN

Resin: H k [1,3-diglycidyl-5-ethyl-5-(2-methylbutyl)hydantoin]
IDT = 128°C
L i q u i d Uptake, % % Retent:
Aqueous Temp. F l e x Modi
Medium °C 1 Wk. 16 Wk. 16 \
25% HC1 25 8.5 38 40
5% A c e t i c A c i d 25 1.3 3.6 105

60 2.9 4.8 95
Water 25 1.2 3.5 —

60 2.9 4.4 95
10% NaCl 25 1.1 3.1 —

60 2.4 3.5 95
10% NH 3 25 1.2 4.3 95
50% NaOH 25 -0.04 0.01 105

60 0.05 0.14 90
A l l were cured with aniline-formaldehyde c u r a t i v e . See

Table V I I .
TABLE XI
SOLVENT RESISTANCE OF AROMATIC AMINE-CURED HYDANTOIN EPOXY RESIN
Resin: 1*70% H a [1,3-diglycidyl-5,5-dimethylhydantoin]

\30% IV [l-glycidyl-3-(2-glycidoxypropyl)-
IDT = 125°C

Solvent Parameter(5) °C. 1 Wk. 16 Wk. 16 Wk
Heptane 7.50 25 0..12 0.84 100
Kerosene 25 0..09 0.29 100

60 0,.5 1.7 105
Xylene 8.9 25 0,.04 1.1 —

60 0..2 2.2 95
E t h y l Acetate 8.91 25 0..06 0.6 100
Benzene 9.16 25 0,.07 1.0 100
T r i c h l o r e t h y l ene 25 0 .15 1.1 95

9.16 60 0 .4 6.8 80
Chloroform 9.16 25 0 .1 1.25 100
Acetone 9.62 25 0 .11 0.96 95
Isopropyl A l c o h o l 25 0 .00 0.13 105

11.44
Methanol 14.50 25 6 .9 21.0 15

CATSIFF ET AL. Cured Hydantoin Epoxy Resins
TABLE XII
CHEMICAL RESISTANCE OF AROMATIC
AMINE-CURED HYDANTOIN EPOXY RESIN
Resin:/70% H a [1,3-diglycidyl-5,5-dimethylhydantoin]
\30% IV [l-glycidyl-3-(2-glycidoxypropyl)-
IDT = 125°C
L i q u i d Uptake, % % Retention of
Aqueous Temp. F l e x Modulus
Medium °C. 1 Wk. 16 Wk. 16 Wk.
25% HC1 25 (a) — —

5% A c e t i c A c i d 25 1.8 10.1 75
60 8.0 15.9 50
Water 25 1.9 10.6 —

60 7.7 12.7 60
10% NaCl 25 1.3 6.5 —

60 4.8 9.5 70
10% NH 3 25 1.8 13.7 55
50% NaOH 25 0.005 0.25 110

60 0.2 -0.15 85
A l l were cured with aniline-formaldehyde c u r a t i v e .

See Table V I I .
(a) Fragmented
TABLE XIII
SOLVENT/CHEMICAL RESISTANCE OF
AROMATIC AMINE-CURED HYDANTOIN EPOXY RESIN
Resin: l i b [1,3-diglycidyl-5-methyl-5-ethylhydantoin]
IDT = 149°C

Solvent Parameter(5) °C. 1 Wk. 16 Wk. 16
E t h y l Acetate 8.91 25 0.01 1.0 105
T r i c h l o r e t h y l (ene 25 0.3 1.4 105

9.16 60 2.7 6.5 90
Chloroform 9.16 25 0.3 2.2 100
Acetone 9.62 25 0.12 3.3 85
25% HC1 25 18.7 (a) ~
10% NH 25 1.3 8.5 90

(a) Fragmented
Conclusions
By v a r y i n g the s u b s t i t u e n t s at the 5 - p o s i t i o n on the

hydantoin r i n g , i t i s p o s s i b l e to c o n t r o l the i n t e r m o l e c u l a r
forces of hydantoin-based epoxy r e s i n s . T h i s c o n t r o l i s mani-
fested to some extent i n the monomeric r e s i n s , but i s f a r more
evident i n the g l a s s t r a n s i t i o n temperature of h i g h l y c r o s s l i n k e d
r e s i n - c u r a t i v e systems, and p a r t i c u l a r l y i n the h y d r o p h i l i c -
hydrophobic balance of amine-cured systems. Within l i m i t s
p r e s c r i b e d by the s u b s t i t u e n t s on the hydantoin r i n g , the hydro-
p h i l i c - h y d r o p h o b i c balance i s a l s o g r e a t l y a f f e c t e d by the organic
moieties introduced by the amine c u r a t i v e . Analogous p r i n c i p l e s
may be invoked i n c o n s i d e r i n g the l y o p h i l i c - l y o p h o b i c balance of
aromatic amine-cured hydantoin epoxy r e s i n s .
Experimental Procedures
Mold C o n s t r u c t i o n . C a s t i n g molds were prepared from pre-

cleaned mold-release-coated g l a s s p l a t e s and square-angled
U-shaped s i l i c o n e rubber gaskets. The gasket sheets were about
1.6 mm t h i c k and two or more were p l i e d t o the c a s t i n g t h i c k -
ness d e s i r e d , and spring-clamped between p l a t e s . The molds
were set v e r t i c a l l y with the top edge open f o r pouring, and
u s u a l l y were preheated i n an oven to keep the v i s c o u s c a s t i n g
mixture as f l u i d as p o s s i b l e . The most common p l a t e s i z e used
was about 20 cm square.
Specimen P r e p a r a t i o n . The demolded c a s t i n g s were cut

using a c i r c u l a r saw with a diamond c u t t i n g wheel to provide
specimens f o r the v a r i o u s t e s t s .
Casting. Castings of l i q u i d epoxy r e s i n s cured with hexa-

h y d r o p h t h a l i c anhydride (HHPA) were prepared by h e a t i n g the l i q u i d
r e s i n i n a s t i r r e d 3-necked f l a s k to which the c a l c u l a t e d amount
of premelted HHPA was added. A vacuum was drawn t o p a r t i a l l y
degas the mixture; then 2 phr benzyldimethylamine (BDMA) was added
as a c c e l e r a t o r . A f t e r f u r t h e r degassing, the mixture was poured
i n t o c a s t i n g molds prepared as d e s c r i b e d above. The f i l l e d molds
were put i n t o an oven at the d e s i r e d g e l l i n g temperature; subse-
quently, e i t h e r the oven was reset t o the f i n a l cure temperature
or the molds were t r a n s f e r r e d to a second oven, as convenient.
Castings o f s o l i d epoxy r e s i n s cured with HHPA were pre-
pared s i m i l a r l y , except that the r e s i n a l s o had t o be premelted.
Except where noted i n Table I I , HHPA-cured c a s t i n g s were g e l l e d
at 80°C ( a t l e a s t 3 hours and u s u a l l y overnight) and then cured
2 hr./150°C.
Castings cured with the commercial aromatic amine d e r i v e d
from aniline-formaldehyde were prepared l i k e the HHPA-cured
c a s t i n g s , but without a c c e l e r a t o r . The aromatic amine mixture
was about 90% m e t h y l e n e d i a n i l i n e (MDA) and tended to p a r t i a l l y
s o l i d i f y on standing, so i t had to be prewarmed and w e l l mixed

before use. In the work reported here, the degassed c a s t i n g s
were g e l l e d 16 hr./65°C and given a f i n a l cure of 2 hr./150°C.
For room temperature c u r i n g , preheating was used only when
a b s o l u t e l y necessary to reduce v i s c o s i t y and f a c i l i t a t e mixing.
For t h i s reason, Resin l i e was not considered s u i t a b l e f o r room
temperature c u r i n g , and Resin l i a was so cured on only a few
occasions, a f t e r premelting. Such r e s i n s could be used i n l i q
u i d mixtures, as noted i n Tables VI, XI, and X I I . In a s i m i l a r
way, s o l i d amines, such as MDA and methylenebis(cyclohexylamine),
MCHA, could only be used i n l i q u i d mixtures.
With a l l the amine c u r a t i v e s , the stoichiometry used was
one amine hydrogen/epoxide; e.g., TETA, having two primary and
two secondary amines/molecule, would have s i x equivalents/mole.
The mixture of l i q u i d r e s i n and l i q u i d amine was s t i r r e d and

degassed i n a 3-necked f l a s k , j u s t as f o r the thermal c a s t i n g s ,
but an i c e bath was used to c o n t r o l any exotherm i n the f l a s k , so
that r a p i d v i s c o s i t y increase due to r e a c t i o n would not occur to
i n t e r f e r e with degassing. A f t e r pouring i n t o the mold, the
c a s t i n g was kept at room temperature f o r at l e a s t 14 days before
demolding. When a mild postcure was d e s i r e d , at l e a s t 7 days/room
temperature c u r i n g preceded i t ; the postcure was 6 hr./100°C.
Weight Gain and F l e x u r a l Modulus. Weight gain and p l a s t i -

c i z a t i o n by absorbed l i q u i d were measured on small f l e x bar
specimens (7.62 cm χ 2.54 cm χ 0.32 cm). Most exposure was by
immersion at room temperature, but some specimens were immersed
at 60°C, and some specimens were exposed to 95% R.H. at 35°C i n
a c o n t r o l l e d - h u m i d i t y chamber i n p a r a l l e l to t h e i r immersion i n
water. Deionized water, ten organic s o l v e n t s , and f i v e aqueous
s o l u t i o n s were used as immersion media, as noted i n the appro
p r i a t e t a b l e s . Exposure times ranged from 24 hours to 4 weeks
f o r the water- or humidity chamber-exposed samples, and from 1
to 16 weeks f o r the s o l v e n t - or aqueous media-exposed samples.
At the d e s i r e d i n t e r v a l s , each specimen was removed from i t s
environment, r i n s e d i f necessary f o r safe handling, wiped dry,
and weighed. Then the f l e x u r a l modulus was measured, to a max
imum o u t e r - l a y e r s t r a i n of 0.5%. Thus, the f l e x measurement
was e s s e n t i a l l y non-destructive and the specimen could be
returned to i t s exposure.
I n i t i a l Deformation Temperature (IDT). IDT was determined

as the temperature at which a standard t e s t bar (1.27 cm wide χ
0.635 cm deep), c e n t r a l l y loaded on a 100 mm span, d e f l e c t e d an
a d d i t i o n a l 0.25 mm under a load that gave a maximum (outer-
l a y e r ) s t r e s s of 1.82 MPa, while being heated at a r a t e of
2°C/min. The operating procedure followed ASTM Method D648-72
for " D e f l e c t i o n Temperature of P l a s t i c s Under F l e x u r a l Load"
(6), but the maximum s t r a i n reached at the IDT was h a l f that at
the " d e f l e c t i o n temperature under l o a d " (DTUL), so IDT was
s e v e r a l degrees lower than DTUL.
Abstract
Hydantoin epoxy resins having glycidyl groups in the 1- and

3-positions and one or two alkyl groups in the 5-position were
prepared by the Bücherer reaction, followed by treatment with
epichlorohydrin. These resins were crosslinked with hexahydro-
phthalic anhydride to examine the effect of alkyl substituents
on the glass transition temperatures of the cured systems.
Higher alkyl substituents shielded the hydantoin rings and gave
lower glass temperatures. The same shielding effect was observed
in the reduced hydrophilicity of higher alkyl-substituted hydan-
toin epoxy resins cured with triethylenetetramine.
Steric factors - branching at or close to the hydantoin

ring - raised the glass transition temperature while maintain-
ing the shielding effect. Amines of different structures were
used as room temperature curatives with a few representative
resins, to observe the effect on hydrophilic-hydrophobic
balance. Solvent effects were examined on aromatic amine-cured
resins; the most hydrophilic cured system proved to have the
broadest range of lyophobicity.
Acknowledgement
This work could not have been c a r r i e d out without the tech-
n i c a l a s s i s t a n c e and support o f many c o l l e a g u e s . Particular
thanks go to Dr. J . H. Bateman and Messrs. L. A l t e r , H. B. Dee,
A. T. Doyle, D. N e i d i t c h , and J . V e l t e n .
Literature Cited
1. Catsiff, Ε. H.; Dee, H. B.; Seltzer, R. Modern Plastics,

1978, 55 (7), 54.
2. Habermeier, J . Angew. Makromol. Chem., 1977, 63 (921), 63.
3. Eldin, S., private communication.
4. Weiss, J . Organic Coatings and Plastic Chemistry, 1978, 39, 567.
5. Hoy, K. L. J. Paint Technol., 1970, 42 (541), 76.
6. Lukens, R.P., Ed. "Annual Book of ASTM Standards;" Am. Soc. for
Testing and Materials: Philadelphia, PA, 1976, Part 35, p. 219.

11
Effect of Cross-Link Density Distribution on the
Engineering Behavior of Epoxies
S. C. MISRA, J. A. MANSON, and L. H. SPERLING

Materials Research Center, Lehigh University, Bethlehem, PA 18015
Fundamental knowledge of relationships between

characteristics, synthesis or processing, structure, and mechani-
cal and other properties is required of crosslinked networks used
for critical and demanding applications. Thus, epoxy resins,
which are widely used for engineering purposes, have received
great attention in the past decade. Indeed, many papers have
covered many aspects of epoxies such as: stoichiometry (1-5),
prepolymer structure (6-8), diluents (4,9,12), fillers (13-22),
heat treatment (3,22), and effects of cure conditions (23-25).
However, relatively l i t t l e attention has been given to properties
such as creep and to the effects of the distribution of crosslink
density. Certainly typical commercial epoxy resins usually
exhibit a distribution of molecular weights which should result in
a distribution of crosslink density in the final network. The
broadening of the transition region has been qualitatively attri-
buted to this distribution effect (26). Unfortunately, existing
studies were of insufficient scope to permit correlation of the
engineering behavior of epoxy networks and the distribution of
crosslink density or M (the average molecular weight between
c
crosslinks). Because of its relevance to engineering application,

such a study was thought to be of considerable interest.
With t h i s i n mind, a program was begun to examine the e f f e c t s
of c r o s s l i n k i n g and c r o s s l i n k d i s t r i b u t i o n on s e v e r a l aspects o f
behavior of high-Tg epoxies (27-31). I t was decided that a
thorough c h a r a c t e r i z a t i o n o f v i s c o e l a s t i c behavior i n blends o f
two epoxy r e s i n s , each having a q u i t e d i f f e r e n t molecular weight,
should enable c o r r e l a t i o n s o f d i s t r i b u t i o n s o f M and other n e t -
c
work v a r i a b l e s with the engineering behavior. A c c o r d i n g l y , the

c r o s s l i n k d e n s i t y (M ) was v a r i e d by c u r i n g a homologous s e r i e s o f
c
bisphenol-A-based epoxy prepolymers with methylene d i a n i l i n e (MDA).

Networks were a l s o prepared at constant c r o s s l i n k d e n s i t i e s by
blending low and high-molecular-weight members o f the homologous
series. This paper summarizes the f o l l o w i n g p r o p e r t i e s of the
networks: the s t a t e of cure, M , dynamic mechanical spectroscopy
c
0-8412-0525-6/79/47-114-137$05.00/0
(DMS), creep, and s t r e s s - s t r a i n and impact behavior. More

d e t a i l e d r e s u l t s f o r each t o p i c w i l l be presented and discussed
separately.
Experimental
M a t e r i a l s . The f o l l o w i n g Epon prepolymers ( S h e l l Chemical

Company) were used: Epons 825, 828, 834 ( a l l l i q u i d to semi
s o l i d ) ; and 1001, 1002, and 1004 ( a l l s o l i d s ) . Approximate com
p o s i t i o n s (degree of polymerization) were determined by g e l per
meation chromatography. Bimodal blends were made by mixing Epon
825 with Epon 1004, as shown i n Table 1. Sample p r e p a r a t i o n and
the method of c u r i n g have been described i n the preceding paper
(29).
Table I . Compositions of Homopolymers and Bimodal Blends
Sample Mc Epoxy Resin (wt. % i n blend)
E-l 308 825 (100)

E-2 326 828 (100)
F-l 326 825 (91) + 1004 (9)
F-2 413 825 (62) + 1004 (38)
F-3 419 825 (60) + 1004 (40)
E-3 430 834 (100)
F-4 430 825 (57) + 1004 (43)
E-5 740 1001 (100)
F-5 740 825 (20) + 1004 (80)
E-7 1004 1400 (100)
E-4 493 834 (100) (with s l i g h t excess of
c u r i n g agent)
M a t e r i a l s C h a r a c t e r i z a t i o n . Measurements of complex Young's
?
moduli, i n c l u d i n g the storage modulus E , l o s s modulus E", and
l o s s tangent tan <5, were made using a Rheovibron v i s c o e l a s t o m e t e r ,
model DDV-II (Toyo Measuring Instrument Co.). Measurements were
made at 110 Hz over a temperature range from -80°C to about 40°C
above Tg, at a heating r a t e of l°C/min. Icing of the specimens at
low temperatures was avoided by sweeping dry n i t r o g e n through the
chamber. T e n s i l e measurements were, made using an Instron t e s t e r
at room temperature, a c c o r d i n g to ASTM t e s t D-638-68, type IV
with a crosshead speed o f limn/min (0.05"/min). Young's modulus,
E, u l t i m a t e t e n s i l e strength, o , y i e l d strength, O y , and u l t i m a t e
u
e l o n g a t i o n , e , were determined. In a l l cases, three to four

u
specimens per sample were obtained that d i d not f a i l prematurely.

Impact t e s t s were conducted a c c o r d i n g to the ASTM t e s t D-256-70,
method Β (Charpy type, notched). On the average, 4 to 5 specimens
were t e s t e d .
Studies o f creep as a f u n c t i o n of time and temperature were
c a r r i e d out using a Gehman T o r s i o n a l S t i f f n e s s Tester (32). Creep
11. MISRA ET AL. Cross-Link Density Distribution 139
experiments covered the e n t i r e range o f v i s c o e l a s t i c behavior from

the g l a s s y to the rubbery r e g i o n . Modulus readings were taken a t
v a r i o u s i n t e r v a l s o f time between 10 sec and 1000 sec. The
inverse time-dependent compliance, 1 / J ( t ) , was c a l c u l a t e d from the
angle o f t w i s t o f the specimen induced by the t o r s i o n wire as
i n d i c a t e d by the apparatus, and the time-dependent Young's modu-
l u s , E ( t ) , was assumed to approximately equal 3 / J ( t ) . Master
curves were obtained by s h i f t i n g data obtained at v a r i o u s temper-
atures with respect to a r e f e r e n c e temperature (129°C i n t h i s
c a s e ) . Each curve o f reduced modulus was s h i f t e d with respect to
the curve a t the r e f e r e n c e temperature u n t i l a l l f i t together to
form a smooth curve. Master curves f o r v a r i o u s m a t e r i a l s could
then be e a s i l y compared. Temperatures corresponding to a value o f
0.2 GPa f o r E(10 sec) were taken as T ' s .

Average s w e l l i n g and s o l u b l e content measurements were
conducted at room temperature using acetone as the s o l v e n t .
E q u i l i b r i u m s w e l l i n g was achieved w i t h i n 15 days, and the s w e l l i n g
r a t i o , q, was c a l c u l a t e d by the formula:
swollen volume o f the network

q = (1)
e x t r a c t e d , dry volume o f the network
Density measurements were made at room temperature, ^20°C, u s i n g

the d e n s i t y gradient method. D u p l i c a t e runs were made i n a l l
cases.
A d i f f e r e n t i a l scanning c a l o r i m e t e r (DSC 1-B, Perkin-Elmer
Corporation) was used to determine the extent o f cure; 10-mg to
20-mg specimens were tested at a scanning r a t e o f 10°C/min. An
exothermic peak on the thermograph i n d i c a t e s the heat o f r e a c t i o n
whereas an endothermic peak i n the amorphous polymer i n d i c a t e s the
presence o f r e s i d u a l s t r e s s e s o r the occurrence o f a t r a n s i t i o n
such as the g l a s s t r a n s i t i o n . The presence of an exothermic peak
i n the DSC-scan o f a pre-cured sample i s an i n d i c a t i o n o f incom-
plete curing.
The unreacted epoxy and amine groups present i n the samples
(degree of cure) were determined by chemical t i t r a t i o n , using the
procedure o u t l i n e d by B e l l (33) with a s l i g h t m o d i f i c a t i o n . Cured
epoxy samples were f i l e d and about 1 g of the r e s u l t i n g powder was
placed i n a round-bottomed f l a s k with 50 ml o f 0.2N pyridinium
c h l o r i d e , 50 ml o f reagent i s o p r o p a n o l , and 25 ml o f d i s t i l l e d
water. The mixture was r e f l u x e d f o r 30 min and s t i r r e d c o n t i n u -
ously with a magnetic s t i r r e r . A f t e r c o o l i n g to room temperature,
the s o l u t i o n was poured i n t o a 250-ml beaker. Using a p o t e n t i o -
meter and a buret, standardised 0.505N NaOH was added i n 5-ml
increments u n t i l the pH increased to 7.0. From t h i s point on,
0.2-ml increments were added u n t i l a sharp i n c r e a s e i n pH was
noted (pH ^ 10.5). Since the response i n the amine t i t r a t i o n
r e g i o n was very slow and the pH d i d not s t a b l i z e u n t i l 8 to 10 min
a f t e r each a d d i t i o n o f NaOH, the readings were made at 10-min
intervals.
R e s u l t s and D i s c u s s i o n
D i s t r i b u t i o n of molecular weights i n the commercial r e s i n s .

Gel permeation chromatography (GPC) i n d i c a t e d that the l i q u i d and
s e m i - s o l i d prepolymers (Epon 825, 828, and 834) were composed o f
Α Γ ι3
Η
f
CH -CH-CH |-0-^ -C-^)0-CH CH-CH hO-^C- @-OCH -CH-CH
1 ρ3 A
I
2 2 2 2 2 2
CH 0
CH.
m = 0 (M = 340) and m = 1 (M = 620) components. The percentage o f
m = 0 and m = 1 species was dependent on the average molecular
weight o f the prepolymer, as given i n Table I I .
Table I I . Composition o f the Commercial Epoxy Resins

Epoxy
Sample Components present i n the prepolymer
Resin
E-l 825 352 m=0 (96%) and m=l (4%)

E-2 828 380 m=0 (86%) and m=l (14%)
E-3 834 592 m=0 (29%) and m=l (71%)
E-5 1001 1000 m=l, m=3, and m=7 (major component)
The s o l i d prepolymers were composed as f o l l o w s : Epon 1001, m=7

(M=2328), m=3 (M=1192), and m=l; and Epon 1002 and 1004, m=12
(M=3748), m=3, and m=l (the major component being m=12). The
exact composition o f each component i n the s o l i d prepolymers could
not be completely r e s o l v e d from the peaks of m=7(Epm 1001) or
m=12 (Epm 1002 and 1004) components.
Thus, the bimodal blends ( S e r i e s F) o f Epon 825 and Epon 1004
had the f o l l o w i n g components: m=0, m=l, m=3, and m=12. The
amount o f m=0 component was a t a maximum i n sample F - l but a t a
minumum i n sample F-5. On the o t h e r hand, samples F-2, F-3, and
F-4 contained both m=0 and m=12 s p e c i e s i n a p p r e c i a b l e q u a n t i t i e s .
Degree o f cure. The t i t r a t i o n r e s u l t s given i n Table I I I

r e v e a l that from 98% to 100% o f the f u n c t i o n a l groups had r e a c t e d .
S i m i l a r l y no evidence f o r incomplete cure was observed by DSC o r
by dynamic mechanical spectroscopy (DMS). However, i t may be
pointed out that 2% unreacted f u n c t i o n a l groups could r e s u l t i n
d e t e c t a b l e incoherence (see r e f e r e n c e 29) i n the networks prepared
from high-MW epoxy prepolymers.
11. MisRA ET AL. Cross-Link Density Distribution 141
Table I I I . Unreacted Epoxy and Amine

Concentration i n the Cured Sample
Epoxy content, Amine content,
Sample
meq/g sample meq/g sample
E-l 0.00 0.00

E-2 0.06 -0.02
E-3 0.00 0.00
E-4 0.09 -0.04
E-5 0.04 0.00
E-6 0.03 0.00
F-l 0.00 0.00
F-2 -0.09
0.00
F-3 0.03 0.03
F-4 0.04 0.04
F-5 0.09 0.06
Dynamic mechanical p r o p e r t i e s . The parameters c h a r a c t e r

i z i n g the dynamic mechanical behavior o f S e r i e s Ε and S e r i e s F a r e
summarized i n Table IV. Several o f the v i s c o e l a s t i c parameters
w i l l now be discussed i n d e t a i l .
Table IV. Dynamic Mechanical P r o p e r t i e s of

S e r i e s Ε and S e r i e s F Epoxy Networks
max: V V
M a
Tan 6 (at Ει GPa d
χ 10
Specimen c
C
-n
(theor.) Value T,°C °C E f E'
r 8
2
xlO
E-l 308 -35 0.62 221 207 0.45 22 5.2
E-2 326 -40 0.75 211 197 0.42 21 5.6
E-3 430 -46 0.90 175 165 0.17 20 6.7
E-4 493 -46 0.95 175 165 0.21 20 6.7
E-5 740 -55 1.25 157 145 0.10 19 9.1
E-7 1400 -60 1.52 138 125 0.065 18 10.0
F-l 326 -40 0.75 211 197 0.42 21 5.6
F-2 413 -45 0.75 185 174 0.21 21 5.6
F-3 419 -45 0.80 175 166 0.17 21 5.9
F-4 430 -46 0.75 168 150 0.17 20 5.6
F-5 740 -55 1.25 157 145 0.10 19 9.1
f
^Based on M s of the components
c
From maximum i n tan 6

f
,E r e f e r s to the g l a s s y s t a t e
g 1 0 2
l GPa = 1 0 dynes/cm
e
n = d ( l o g E')/dT, a t Τ (+ 4°C)
Glass t r a n s i t i o n temperature. The e f f e c t of the d i s t r i b u t i o n

of M on T i s shown i n F i g u r e 1. At M = 430, the Τ o f the
c g c
blend sample F-4 was 13°C lower than that of i t s commlrcial

counterpart sample E-3. This i n d i c a t e s that the longer chains,
though present i n the same amount as the s h o r t e r chains (see
Table I ) , dominate the f i n a l network and thus c o n t r o l the Tg of
the blend sample F-4. Due to the higher r e a c t i v i t y , the longer
molecules react f i r s t (29) to give microgels swollen w i t h the
unreacted smaller molecules which r e a c t l a t e r to form an i n t e r
p e n e t r a t i n g network. Thus the secondary microgels r e s u l t i n a
s h e l l and core type s t r u c t u r e (29). On the other hand, at M = c
326 and M = 740, the blend samples F - l and F-5 d i d not have a
c
Tg d i f f e r e n t from t h e i r commercial counterparts, E-2 and E-5,

r e s p e c t i v e l y . At these M 's, l a r g e d i f f e r e n c e s i n d i s t r i b u t i o n
c
between blends and commercial r e s i n s could not be obtained because

the number of p o s s i b l e permutations o f d i s t r i b u t i o n at these M 's c
was very r e s t r i c t e d ; at low M (326), Epon 825 was the major com
c
ponent (90%), whereas at high M (740) Epon 1004 was the major
c
component (80%).
Young's modulus. As expected f o r the g l a s s y s t a t e ( i n which

long-range s e g m e n t a l motions are f r o z e n ) , Young's modulus a t room
temperature, E', was found to be n e a r l y independent of M or the c
d i s t r i b u t i o n of M c(Table I V ) . A l l values f a l l w i t h i n the range

of 2 + 0 . 2 GPa compared to an average of 1.3 GPa obtained from
t e n s i l e s t r e s s - s t r a i n curves (to be d i s c u s s e d l a t e r ) .
Rubbery modulus. Figure 2 shows that the rubbery modulus of

the present networks i s u n a f f e c t e d by the d i s t r i b u t i o n of M . c
Graessley (34) c a l c u l a t e d the f r e e energy of deformation and the

e q u i l i b r i u m dimensions of network chains f o r networks of Gaussian
random c o i l s and showed that the e l a s t i c p r o p e r t i e s of such net
works depend upon the t o t a l number of e l a s t i c a l l y a c t i v e chains
(average M ) and e l a s t i c a l l y a c t i v e j u n c t i o n s , but are independent
c
of the chain l e n g t h d i s t r i b u t i o n (M d i s t r i b u t i o n ) , j u n c t i o n func

c
t i o n a l i t y d i s t r i b u t i o n , and the d e t a i l e d p a t t e r n o f c o n n e c t i v i t y .
Thus, the present experimental r e s u l t s are i n agreement with the
t h e o r e t i c a l p r e d i c t i o n s o f Graessley.
β-transition temperature. The 3 - t r a n s i t i o n temperature

increased with K but was unaffected by the changes i n the d i s t r i
c
b u t i o n of M ( F i g u r e 2 ) . This i s so because T^ i s a r e s u l t o f the

c
motion of small segments of the main chain, r a t h e r than the l a r g e r

segments i n v o l v e d i n the g l a s s t r a n s i t i o n . Therefore, Τβ should
depend on the average M and not on the d i s t r i b u t i o n o f M .
c c
Height of the tan δ peak. The value of the tan 6 m a x
increased a s y m p t o t i c a l l y w i t h M . As expected, the bimodal blend

c
samples F-2, F-3, and F-4, which showed broader t r a n s i t i o n regions

than t h e i r counterparts of the commercial r e s i n samples o f S e r i e s
11. MiSRA ET AL. Cross-Link Density Distribution 143
Figure 1. Ghss transition temperature as a function of M for Series Ε and Series

c
F networks: (Ο) commercial resins; bimodal blends

Figure 2. Impact strength, E , Ύβ, and density as a function of M for Series Ε

r c
and Series F networks

Ε, a l s o showed broader and f l a t t e r tan δ peaks (Figure 3 ) . T h i s

broadening i s a t t r i b u t e d to the broadening o f the d i s t r i b u t i o n of
M.c
1
Slope of the t r a n s i t i o n r e g i o n . The slope of the E v s .
temperature curve i n the g l a s s t r a n s i t i o n r e g i o n a l s o v a r i e d w i t h
M.c In accordance to the creep r e s u l t s ( d i s c u s s e d l a t e r ) values
of the slope (η), obtained from the dynamic mechanical data (see
Figure 3), of the blend samples F - l , F-2, F-3, and F-4 were c l o s e
to that of the commercial-resin sample E - l . In c o n t r a s t , the
slope of the blend sample F-5 was steeper than that of i t s commer
c i a l counterpart, sample E-5. The broadening of the t r a n s i t i o n
r e g i o n o f the blend samples F - l to F-4 i s a t t r i b u t e d to the p r e
sence of broad d i s t r i b u t i o n s of M i n them. c
T e n s i l e behavior. T e n s i l e p r o p e r t i e s f e l l i n the f o l l o w i n g
ranges, as shown i n Figure 4: ( C o n t r o l S e r i e s Ε ) , E = 1.2 (+
g
0.3) GPa, σ = 71 (+ 7) MPa, ε = 11 (+ 2) %; (Bimodal S e r i e s F ) ,

E = 1.0 (+ 0.3) GPa, σ = 69 (+ 10) MPa, ε = 9 (+ 2) %.
g μ No
trends as a f u n c t i o n of M were observed, i n c o n t r a s t to the case
c
of M changed by changing s t o i c h i o m e t r y (2_7,28) . Thus the t e n s i l e

c
p r o p e r t i e s at room temperature are e s s e n t i a l l y independent o f M c
and i t s d i s t r i b u t i o n . This general r e l a t i v e i n s e n s i t i v i t y to

changes i n M and i t s d i s t r i b u t i o n i s not s u r p r i s i n g , because the
c
g l a s s y s t a t e p r o p e r t i e s should be more c l o s e l y r e l a t e d to the

cohesive energy d e n s i t y than to network s t r u c t u r e (35). F u r t h e r
more, the s h i f t f a c t o r s ( l o g a ) obtained from creep experiments
T
(see below) i n d i c a t e that the motion of the main chains of these

networks i s very r e s t r i c t e d . Therefore, as observed experimental
l y , i t can be expected that the room-temperature t e n s i l e proper
t i e s of these epoxy networks having bulky bisphenol-A groups
would be independent of average M or d i s t r i b u t i o n o f M .
c c
Impact strengths v a r i e d i n v e r s e l y with M , values rangingc
from 50 J/m f o r E - l to 34 J/m f o r E-6. However, as shown i n

F i g u r e 2, impact s t r e n g t h was not a f f e c t e d by changes i n the d i s
t r i b u t i o n of M . c
Creep behavior. F i g u r e 5 shows the composite curve o f the

s h i f t f a c t o r s and a l s o i n d i c a t e s that the s h i f t f a c t o r s i n the
g l a s s transition r e g i o n do not f o l l o w the WLF equation:
log a T = -(17.44[T-T ])/(51.6
g + [T-T ])
g (2)
Instead, they f o l l o w an equation of the Arrhenius type given
below (also see F i g u r e 6):
log a T = -H /2.303 RT
a (3)
where R i s the gas constant, Τ i s the absolute temperature, and
H i s the apparent a c t i v a t i o n energy.
a Thus, s h i f t f a c t o r s f o r a l l
the samples o f the present study, i n c l u d i n g samples E-5, E-6, and
E-7 which have r e l a t i v e l y long chains and would be expected to be
Figure 3. Tan hmax and slope of the transition region as a function of M : (O)
c
commercial resins; (A) bimodal blends

ο
• t i JL 1
<
ζ
ο
• t; jj[ i
*τ
- \ i
75
70
: t
1 *l
65 J
> -
60
: ;
:H
°= 1.4-1
Τ H ίr r
tu 1.2
i
300 400 600 800 1000 1 500
Figure 4. Tensile properties of Series Ε and Series F networks as a function of

M : (O) commercial resins; (A) bimodal blends
c
American Chemical
Society Library
1155 16th St. N. W.
Figure 5. Shift factors as a function of (Ύ - T ) for Series Ε and Series F net

g
works
Figure 6. Shift factors as a function of (1/Ύ — 1/Ί )

9 for Series Ε and Series F
networks
f l e x i b l e , s u r p r i s i n g l y gave a b e t t e r f i t to an Arrhenius
r e l a t i o n s h i p as i s g e n e r a l l y the case f o r polymers i n the g l a s s y
state. Thus i t appears that the motion of the main chains o f the
present epoxy networks i s r e l a t i v e l y r e s t r i c t e d even beyond the
glassy state. I t appears that the bulky bisphenol-A groups are
r e s p o n s i b l e f o r the r e s t r i c t e d motion of the main chains observed
even beyond the g l a s s y s t a t e . I t was a l s o noted that the a c t i v a
t i o n energy was independent of M and d i s t r i b u t i o n of M i n those
c c
networks; v a l u e s of 230 kcal/mole and 75 kcal/mole above and below

Τ , r e s p e c t i v e l y , f i t a l l samples. The values are i n good agree
ment with values determined here f o r bisphenol-A-based epoxies
cured w i t h MDA (31) and elsewhere f o r s i m i l a r epoxies cured w i t h
amines (3 7) .
To determine the e f f e c t o f the d i s t r i b u t i o n of M on creep,c
master curves f o r a l l the samples were drawn at 129°C i n s t e a d o f

s e l e c t i n g T^ as the r e f e r e n c e temperature. The temperature
c o r r e c t i o n s were not used to draw the master curves shown i n
F i g u r e 7 because these c o r r e c t i o n s , as mentioned e a r l i e r , were
small and the experimental data d i d not extend to long ranges o f
temperature i n the rubbery r e g i o n . The c h a r a c t e r i s t i c creep time
( T ) was taken as the time r e q u i r e d to r e l a x to a value of l o g
c
E(t) = ( l o g Eg + l o g E ) / 2 , where E and E are the g l a s s y and

r g r
rubbery moduli, r e s p e c t i v e l y . The slopes (n) o f the master curves

were determined a t the time T . c The c h a r a c t e r i s t i c creep time
( T ) was found to be i n v e r s e l y r e l a t e d to M by the f o l l o w i n g
c c
relationship:
log ( τ / τ ) = Κ /MΊ (4)

c co l e
where l o g τ = -10.1 = ( T a t M = «>, obtained by e x t r a p o l a t i o n ) ,
c Q
and K-L = 5.4 χ 10^ (a c o n s t a n t ) . The s t a t i s t i c a l c o r r e l a t i o n

c o e f f i c i e n t was 0.99, showing e x c e l l e n t f i t .
F i g u r e 8 shows that the blend samples F - l and F-5 appear t o
?
have higher T S than t h e i r counterparts E-2 and E-5, r e s p e c t i v e l y ,
C
which were prepared from commercial r e s i n s . On the other hand,

sample F-4 has a lower T than i t s commercial counterpart E-3.
c
These r e s u l t s i n d i c a t e that the d i f f e r e n c e s i n d i s t r i b u t i o n of M

c
affect T . c Samples E-2 and E-3 have network chains composed o f

epoxy molecules having molecular weights o f 340 and 620, r e s p e c
t i v e l y , whereas the major p o r t i o n s o f samples E-5,-E-6, and E-7
are composed o f epoxy molecules having a M.W. o f 2328 o r 3748.
Furthermore, the blend samples F - l and F-5 have a l a r g e r propor
t i o n of epoxy molecules having a molecular weight of 340 than
t h e i r r e s p e c t i v e counterparts E-2 and E-5 (commercial r e s i n s ) ;
t h i s r e s u l t s i n a higher T . c On the other hand, the blend sample
f
F-4 has two epoxy s p e c i e s having M.W. s of 340 and 3748, r e s p e c
t i v e l y , i n equal amounts and i t s commercial counterpart sample
E-3 has epoxy s p e c i e s having M.W.'s o f 340 and 620. The a p p r e c i
a b l e amount o f l a r g e molecules i n F-4 r e s u l t s i n lower T . c Thus,
i t i s concluded that T , besides being s e n s i t i v e to M , i s a l s o
c c
very s e n s i t i v e to the d i s t r i b u t i o n of M ; T would be l a r g e r o r

Q c
MiSRA ET AL. Cross-Link Density Distribution 151
Figure 8. Characteristic creep time and slope of the transition region as a func
tion of M for Series Ε and Series F networks: (À, A ) commercial resins; (Ο, Φ)
c
bimodal blends
smaller depending upon whether the network has greater amounts of

smaller or l a r g e r c h a i n s , r e s p e c t i v e l y .
The s l o p e of the t r a n s i t i o n r e g i o n was found to broaden with
a decrease i n M c (Figure 8 ) . These r e s u l t s i n d i c a t e that an
i n c r e a s e i n c r o s s l i n k d e n s i t y r e s u l t s i n the broadening o f the
slope, as i s o f t e n observed. For example, from dynamic mechanical
s t u d i e s of p o l y e s t e r s , Shibayama and Suzuki (36) had a l s o shown
that the d i s p e r s i o n broadens w i t h an i n c r e a s e i n c r o s s l i n k density.
Furthermore, the bimodal blend samples F - l to F-4 have slopes
c l o s e to that o f sample E - l , prepared from the commercial r e s i n
whereas sample F-5 (bimodal blend) has a slope c l o s e to that o f
sample E-7 (commercial r e s i n ) . The lower values of slope observed
i n the blend samples F - l to F-4 are a r e s u l t of a broader d i s t r i -
b u t i o n of r e l a x a t i o n times which i s not present i n the r e s p e c t i v e

counterparts of S e r i e s E. S i m i l a r l y , sample F-5 showed a higher
slope than i t s counterpart E-5 (even though the slope measured
f o r E-5 i s lower than i t should be), because the former had a
narrower d i s t r i b u t i o n of molecular weights which r e s u l t e d i n a
narrower d i s t r i b u t i o n of r e l a x a t i o n times (see Table I ) .
I t i s concluded that the broadening of the t r a n s i t i o n r e g i o n
could take p l a c e e i t h e r by an i n c r e a s e i n the average c r o s s l i n k
d e n s i t y or by the broadening of the d i s t r i b u t i o n of c r o s s l i n k
density.
Swelling and e x t r a c t i o n . S w e l l i n g and e x t r a c t i o n data are

shown i n F i g u r e 9. The T of the blend sample F-4, which had 57%
g
Epon 825 and 43% Epon 100?, had i n d i c a t e d that Epon 1004 forms the
more continuous network. The s w e l l r a t i o of t h i s sample i s the
same as that o f i t s commercial counterpart, sample E-3. Similar-
l y the blend samples F - l and F-5 a l s o have s w e l l r a t i o s that are
the same as t h e i r r e s p e c t i v e commercial c o u n t e r p a r t s E-2 and E-5.
This i n d i c a t e s that the swell r a t i o i s not very s e n s i t i v e to the
d i s t r i b u t i o n of M .
c On the other hand, samples F-2 and F-3 have
s w e l l r a t i o s that are lower than expected (see F i g u r e 9 ) . These
samples have higher p r o p o r t i o n s of low-molecular-weight prepolymer
( i . e . 62 and 60% by weight, r e s p e c t i v e l y ) . I t i s h i g h l y probable
that the composition o f these samples i s i n a c r i t i c a l range i n
which a phase i n v e r s i o n e x i s t s ; i n other words, some part o f the
network probably has Epon 1004 as the more continuous phase while
another part of the network has Epon 825 as the more continuous
phase. Such a mixed network might w e l l r e s u l t i n anomalous s w e l l -
ing behavior, with s l i g h t l y lower values of the s w e l l r a t i o than
expected i f the low-M epoxy network dominates s w e l l i n g .
The bulk d e n s i t y of the samples a t room temperature decreased
with and, as expected, was not a f f e c t e d by the d i s t r i b u t i o n of
M a t a constant M , as shown i n F i g u r e 2.
c c
Figure 9. Swell ratio and % extraction as a function of M for Series Ε and Series
c
F networks: (O) commercial resins; (A) bimodal blends

Conclusions
The e f f e c t s of M and of i t s d i s t r i b u t i o n may be summarized

i n the f o l l o w i n g c o n c l u s i o n s .
P r o p e r t i e s a f f e c t e d by the d i s t r i b u t i o n of M . C
ΊΓ. The glass t r a n s i t i o n temperature, as i s w e l l known,

i n c r e a s e s w i t h a decrease i n K . c S l i g h t changes i n the d i s t r i b u
t i o n of M do not a f f e c t Tg.
C However, when s i g n i f i c a n t changes i n
the d i s t r i b u t i o n of M e x i s t , Tg i s governed by the dominant com
C
ponent i n the f i n a l network.

2. The slope of the t r a n s i t i o n r e g i o n at Tg increases
with M but decreases ( i . e . broadens) w i t h an increase i n the
C
breadth of the d i s t r i b u t i o n of M .
3. The height of the tan 6 peak increases with M . C
Furthermore, as expected, an i n c r e a s e i n the breadth of the d i s

t r i b u t i o n of M r e s u l t s i n a broadening of the tan 6 peak along
C
with a decrease i n the height of the peak.

4. The c h a r a c t e r i s t i c creep time ( x ) i s the most sen
c
s i t i v e v a r i a b l e to the d i s t r i b u t i o n of M . I t s value i s higher

C
or lower depending on whether the network i s composed of higher

f r a c t i o n s of short or long chains, r e s p e c t i v e l y .
P r o p e r t i e s not a f f e c t e d by the d i s t r i b u t i o n of M . C
T~. The rubbery modulus ( E ) decreases with an increase

R
i n M but as p r e d i c t e d t h e o r e t i c a l l y (34 ) i s not a f f e c t e d by the

C
d i s t r i b u t i o n of M . C
2. The room-temperature t e n s i l e p r o p e r t i e s f o r the pre

sent epoxy networks are independent of M or the d i s t r i b u t i o n of
C
M . C This independence i s a s c r i b e d to the r e s t r i c t e d motion of the

main chains, even above Tg, as deduced from the creep experiments.
3. The s o l u b l e content increases s t e a d i l y w i t h M but C
i s not a f f e c t e d by changes i n the d i s t r i b u t i o n of M . C
4. The d e n s i t y increases w i t h a decrease i n M but i s C
not a f f e c t e d by changes i n the d i s t r i b u t i o n of M . C
5. The s w e l l r a t i o i n c r e a s e s w i t h M but i s unaffected

C
by the d i s t r i b u t i o n of M , except i n some unusual networks having

C
a phase i n v e r s i o n .
6. The room-temperature impact strength i n c r e a s e s with
a decrease i n M but i s unaffected by the d i s t r i b u t i o n of M .
C C
7. The β-transition temperature i n c r e a s e s w i t h a

decrease i n MQ but i s not a f f e c t e d by the d i s t r i b u t i o n of M . Q
8. The experimental s h i f t f a c t o r s , f o r DGEBA-epoxy

networks, are independent of M or the d i s t r i b u t i o n of
C
Instead of f o l l o w i n g the WLF equation, values of the s h i f t f a c t o r

f o l l o w an Arrhenius-type r e l a t i o n s h i p with temperature, i n d i c a t i n g -
that the chain segment m o b i l i t y i s r e s t r i c t e d even i n the rubbery
state.
Acknowledgements
The authors wish to acknowledge support from the A i r Force

M a t e r i a l s Laboratory, through Contract No. F33615-75-C-5167.
D i s c u s s i o n s with Dr. S. L. Kim and the help o f Mr. C. Worman ( A i r
Products & Chemicals, Inc.) i n performing the GPC c h a r a c t e r i z a
t i o n s are a l s o very much a p p r e c i a t e d .
Literature Cited
1. Murayama, T. and Bell, J . P. J . Polym. Sci. (1970), A-2(8),

437.
2. Hirai, T. and Kline, D. E. J . Appl. Polym. Sci. (1972), 16,
3145.
3. Hirai, T. and Kline, D. E. J . Appl. Polym. Sci. (1973), 17,

31.
4. Whiting, D. A. and Kline, D. E. J . Appl. Polym. Sci. (1974),
18, 1043.
5. Selby, K. and Miller, L . E. J . Mat. Sci. (1975), 10, 12.
6. Hata, N. and Kumanotani, J., J. Appl. Polym. Sci. (1971), 15,
2371.
7. Johnson, R. E. and Fricke, A. L. Proc. Conf. Reinf. Plast./
Compos. Div., Soc. Plast. Ind. (1972), 27, 19F, 1.
8. Kitoh, M. and Suzuki, K. Kobunshi Ronbunshu (1976), 33, 1,
19.
9. Kenyon, A. S. and Nielsen, L. E. J . Macromol. Sci., Chem.
(1969), A3(2), 275.
10. Hata, N. and Yamuchi, R. J . Appl. Polym. Sci. (1973), 17,
473.
11. Hata, N. and Kumanotani, J., J. Appl. Polym. Sci. (1977), 21,
1257.
12. Moehlenpah, A. E . ; Ishai, O.; and Dibenedetto, A. T.
J. Appl. Polym. Sci. (1969), 13, 1231.
13. Manson, J . A. and Chiu, Ε. H. ACS Polymer Preprints (1973),
14(1), 469.
14. Manson, J . A. and Chiu, E. H. J . Polym. Sci.-Symp. No. 41
(1973), 95.
15. Meeks, A. C. Polymer (1974), 15, 675.
16. DeRosset, W. S. J . Composite Mat. (1975), 9, 114.
17. Bascom, W. D.; Cottington, R. L.; Jones, R. L. and Peyser, P.
J . Appl. Polym. Sci. (1975), 19, 2545.
18. Galparin, I. J . Polym. Sci. (1967), 11, 1475.
19. Lewis, Τ. Β. and Nielsen, L. E. J . Appl. Polym. Sci. (1970),
14, 1449.
20. Michael, P.; Ebdon, P.; and Delatycki, O. J . Polym. Sci.,
Polym. Phy. Ed. (1976), 12, 1555.
21. Peyser, P. and Bascom, W. D. Polym. Preprints (1976), 17(2),
157.
22. Merrall, G. T. and Meeks, A. C. J . Appl. Polym. Sci. (1972),
16, 3389.
23. Morgan, R. J . and O'Neil, J . E. in "Chemistry and Properties,

of Crosslinked Polymers." Ed. by S. S. Labana., Academic
Press, Κ. Y. (1977), p. 289.
24. Suzuki, K., et al., Kobunshi Ronbunshu (1976), 33(5), 271.
25. Brett, C. L. J . Appl. Polym. Sci. (1976), 20, 1431.
26. Nielsen, L. E. J . Macromol. Sci. (1969), C3, 69.
27. Manson, J . Α.; Sperling, L. H. and Kim, S. L. Final Report,
AFML Contract No. F33615-75-C-5167, 1977 (AFML-TR-77-109.
28. Kim, S. L . ; Skibo, M.; Manson, J . Α.; Hertzberg, R. W. and
Janiszewski, J . ACS Org. Coatings and Plastics Chemistry
(1977), 37, 544; in press, Polym. Eng. Sci.
29. Misra, S. C.; Manson, J . A. and Sperling, L. H. This publi
cation, 1978.
30. Misra, S. C. Ph.D. Dissertation, Department of Chemical

Engineering, Lehigh University, 1978.
31. Kim, S. L . ; Manson, J . A. and Misra, S. C. This publication,
1978.
32. ASTM D-1043, American Society of Testing Materials, Philadel
phia, Pa. (1974).
33. Bell, J . P. J . Polym. Sci. (1970), A2(8), 417.
34. Graessley, W. W. Macromolecules (1975), 8(6), 865.
35. Kaelble, D. A. In "Epoxy Resin Chemistry and Technology."
Ed. by C. A. May and Y. Tanaka, M. Dekker, 1973, Chap. 5.
36. Shibayama, K. and Suzuki, Y. J . Polym. Sci. (1965), A-3,
2637.
37. Kito, M. and Suzuki, K. Kobunshi Ronbunshu (1976), 32, 19.

12
Network Morphology and the Mechanical Behavior
of Epoxies
S. C. MISRA, J. A. MANSON, and L. H. SPERLING

Materials Research Center, Coxe Laboratory #32, Lehigh University,
Bethlehem, PA 18015
Since the properties of thermosetting polymers depend on

their network structures, the morphology of such polymers has
long been a subject of considerable theoretical and practical
interest. Thus, i t is well known that the tensile strength of
thermoset resins is less than predicted theoretically on the
basis of the breakage of primary van der Waal's bonds (1,2), and
it was proposed long ago (3) that this discrepancy was due to the
rupture of weak regions created during network formation. Indeed,
it has been shown (4) that high internal stresses can be developed
during curing, especially when the curing rate is low. This view
of the role of structural defects is also given credence by modern
theories of fracture mechanics (5), which emphasize the concept of
the concentration of stress at a flaw.
Two-Phase Networks
Other investigators (4,6-33) have emphasized a view of the

network essentially as a composite, with a high-crosslink-density
(essentially spherical) phase (often considered as a microgel)
embedded in a less-crosslinked matrix. In fact, i t i s probably
generally accepted that, regardless of specific details, the
curing of thermosets results i n an inhomogeneous, two-phase net-
work. Inhomogeneity has been attributed to incompatibility or to
non-optimum curing conditions (8) but has also been proposed to be
inherently characteristic of a l l gelling systems (14) . It has
also been postulated (7) that these microgels are colloidal i n
nature, at least for some epoxy systems.
The existence of inhomogeneities has been inferred from
results of diverse investigations using techniques such as elec-
tron and optical microscopy (13-26,29,30,31,32), thermomechanical
measurements (34), d i f f e r e n t i a l swelling (12,35), and d i f f e r e n t i a l
scanning calorimetry (36). In contrast, the use of microtomed
thin sections and small-angle x-ray scattering f a i l to indicate
two-phase structures (37). Dispersed phases have been referred to
11
by such terms as "micelles, "globules," "floccules," "nodules,"
and "microgels." In this study, the term "microgel" w i l l be used.
0-8412-0525-6/79/47-114-157$06.50/0
I t has been suggested by Bobalek et a l . (27), Solomon (33),

and Labana et a l . (14) that the two-phase system i s produced by
m i c r o g e l a t i o n p r i o r to the formation of the macrogel. Some i n
v e s t i g a t o r s (4_5l4_,16) have p o s t u l a t e d that these microgels are
l o o s e l y connected to the surrounding matrix, and have a l s o sug
gested (12) that these l o o s e connections are developed during the
l a t t e r stages of the c u r i n g process.
In g e n e r a l , two l e v e l s of s i z e s have been reported i n the
l i t e r a t u r e — o n e (type A) ranging from 6 nm to 40 nm, and the
other (type B) ranging from 20 pm to 200 pm. I t has a l s o been
shown (4) that slow c u r i n g r a t e s r e s u l t i n l a r g e r microgels (type
Β ) , which r e s u l t i n a network having a higher Tg, d e n s i t y , and
r e s i s t a n c e to etching. The s u r f a c e p r o p e r t i e s of the network
depend on the s u r f a c e energy of the mold m a t e r i a l and on the

atmospheric environment (7,30). The s i z e and d e n s i t y of micro-
g e l s have a l s o been r e l a t e d to the presence of p l a s t i c i z e r (23),
r a d i a t i o n damage (26), prolonged exposure to heat (17) and aging
of the r e s i n (24).
Studies of i n t e r f a c e s (30,31) have a l s o shown that c e r t a i n
substrates such as T e f l o n and s i l i c o n e - c o a t e d sheets g i v e f e a
t u r e l e s s s u r f a c e s ; however, subsequent etching of the s u r f a c e
r e v e a l s a two-phase s t r u c t u r e . I t was f u r t h e r shown that the
m i c r o g e l s i z e decreases w i t h i n c r e a s i n g amounts of c a t a l y s t .
Both low t e n s i l e strengths and nodular morphology i n thermo
sets have been r e l a t e d to d i f f e r e n c e s i n c r o s s l i n k d e n s i t y (7,10,
14,27,28,32). At the same time, the f a c t that the y i e l d s t r e n g t h
of some epoxies i s f a i r l y independent of s t o i c h i o m e t r y has been
a t t r i b u t e d to the r o l e of microgels as primary flow p a r t i c l e s
(29). Thus, morphology must p l a y an important r o l e i n determin
ing network p r o p e r t i e s . However, s u r f a c e morphology should not
a f f e c t the mechanical behavior of the network as much as bulk
morphology. D i f f u s i o n phenomena, on the other hand, should
depend on the morphology of both the outer s u r f a c e and of the
bulk.
Though there have been s e v e r a l p o s t u l a t e s of morphological
changes during the c r o s s l i n k i n g process and of the morphology of
the f i n a l network, experimental evidence has been scarce. As
part of a comprehensive study (38) o f the e f f e c t s of c r o s s l i n k
d e n s i t y on the behavior of epoxies and other polymers, the pre
sent morphological i n v e s t i g a t i o n was conducted on epoxies w i t h
emphasis on the r o l e s of s t o i c h i o m e t r y , molecular weight of the
epoxy prepolymer, and the d i s t r i b u t i o n of molecular weight b e t
ween c r o s s l i n k s ( M ) .
c Bisphenol-A-based prepolymers were used
throughout; most were cured w i t h methylene d i a n i l i n e (MDA), a few
were cured with a polyamide.
Experimental
Sample Design. The v a r i o u s formulations are d e s c r i b e d i n
Table 1. To examine the e f f e c t of s t o i c h i o m e t r y , S e r i e s A was
12. MisRA ET AL. Network Morphology and Mechanical Behavior 159
prepared u s i n g d i f f e r e n t proportions o f Epon 828 with MDA ( S h e l l

Chemical Co.). To provide a b a s e l i n e f o r examining the e f f e c t s
of M a t constant s t o i c h i o m e t r y , S e r i e s E, based on the f o l l o w i n g
c
prepolymers, was prepared using s t o i c h i o m e t r i c amounts of MDA as

curing agent: Epon 825, 828, 834, 1001, 1002, and 1004 ( S h e l l
Chemical Co.) To vary the d i s t r i b u t i o n of M , S e r i e s F was pre
c
pared to y i e l d r e s i n s which had the same average M values as c
Epon 828, Epon 834, and Epon 1001. T h i s was done by blending
Epon 825 (narrow d i s t r i b u t i o n of molecular weight) with v a r i o u s
proportions o f Epon 1004. The d i s t r i b u t i o n s of M thus obtained c
are e s s e n t i a l l y bimodal, with l i t t l e o v e r l a p . F i n a l l y , to com

pare behavior with that of a polyamide-cured epoxy, Sample G - l
was prepared by c u r i n g Epon 828 with an e q u i v a l e n t p r o p o r t i o n of
Versamid 140 (General M i l l s Chemical Co.).
Table I . Compositions of the Samples Prepared i n

Epoxy Resin S e r i e s A, E, and F.
Series A S e r i e s Ε and S e r i e s F
Sample Amine/epoxy M c
Sample epoxy Mc
No. Ratio No. (wt. %)
A-7 0.7:1 1523 E-l 825(100) 308

A-8 0.8:1 526 E-2 828(100) 326
A-10 1.0:1 326 F-l 825(91)4-1004(9) 326
A-ll 1.1:1 370 F-2 825(62)+1004(38) 413
A-14 1.4:1 592 F-3 825(60)+1004(40) 419
A-16 1.6:1 924 E-3 834(100) 430
A-18 1.8:1 1922 F-4 825(57)4-1004(43) 430
A-20 2.0:1 CO E-5 1001(100) 740
(linear) F-5 825(20)+1004(80) 740
E-6 1002(100) 980
E-7 1004(100) 1400
C a l c u l a t e d u s i n g B e l l ' s equation (39).

'For reasons discussed by B e l l (39), a c t u a l M values f o r s p e c i
c
mens A-16 to A-20 may be somewhat i n e r r o r . In any case, the

e r r o r w i l l not a f f e c t the trends observed as a f u n c t i o n of
stoichiometry.
Resin P r e p a r a t i o n . For systems using l i q u i d epoxy p r e p o l y

mers (e.g., Epon 825 and 828) with MDA as the c u r i n g agent, the
c u r i n g c y c l e was s i m i l a r to that used by B e l l (39). A f t e r heating
to 80°C, the r e s i n and c u r i n g agent were mixed together, evacuated
f o r 5 to 15 min. to remove a i r bubbles, and cast and cured as
f o l l o w s : 45 min. i n a c i r c u l a t i n g a i r oven a t 60°C, 30 min. a t
80°C, 2.5 h r . a t 150°C, and f i n a l l y slow c o o l i n g to room
temperature. The mold assemblies comprised clamped 13-cm by 13-

cm Mylar sheets, separated by 0.5-rom, 1.5-mm, o r 6-mm T e f l o n or
ethylene-propylene-copolymer spacers backed by g l a s s p l a t e s .
T h i s cure cycle was reported by B e l l to g i v e e s s e n t i a l l y complete
c u r i n g , and was a l s o shown (through chemical t i t r a t i o n of the
epoxy and amine groups) to be s i m i l a r l y e f f e c t i v e i n t h i s l a b o r a
t o r y (38,41,42).
S o l i d epoxies were f i r s t melted and then evacuated to remove
the entrapped a i r bubbles. In order to avoid a i r entrapment, the
c u r i n g agent was mixed in, using a magnetic s t i r r e r , under vacuum.
Samples were prepared u s i n g the f o l l o w i n g c u r i n g c y c l e : 1.5 h r .
at 100°C, 2.5 hr. a t 150°C, followed by slow c o o l i n g to room
temperature. The Versamid-140-cured sample (G-l) was one of the
samples prepared by Manson and Chiu (40), using the f o l l o w i n g
cure c y c l e : overnight c u r i n g a t room temperature, 2 hr. at 60°C,

2 hr. a t 100°C, and 4 h r . at 140°C.
Using these techniques, i t was p o s s i b l e to prepare reproduc
i b l e samples s u i t a b l e f o r t e s t i n g , a l b e i t with c o n s i d e r a b l e
d i f f i c u l t y i n the case of s o l i d epoxies.
E l e c t r o n Microscopy. V a r i o u s etching techniques were t r i e d

to study the micro- and macro-structures of MDA-cured epoxy n e t
works ("macro" implying a morphological f e a t u r e on the s c a l e of 1
pm or l a r g e r ) . E t c h i n g may be presumed to p r e f e r e n t i a l l y a t t a c k
regions of r e l a t i v e l y lower l o c a l c r o s s l i n k d e n s i t y . A f t e r the
examination of etched samples under the ETEC Autoscan scanning
e l e c t r o n microscope (SEM), i t was concluded that etching f o r 7 h r .
with 1 M aqueous Ο ^ Ο β a t 80°C was more e f f e c t i v e than the f o l l o w
ing techniques: etching f o r 30 min with HF; etching f o r 15 days
with acetone; e t c h i n g f o r 10 hr. w i t h argon a t h i g h v o l t a g e under
vacuum. The study of etching time i n d i c a t e d that a t l e a s t one hr.
was needed to produce adequate etching with Ο ^ Ο β . Finally,
etching times o f 4 hr. and 7 hr. were found to be convenient f o r
f
samples having M s above and below 500, r e s p e c t i v e l y . The gross
c
morphology was examined under the SEM while the f i n e s t r u c t u r e

was examined using a P h i l l i p s 300 t r a n s m i s s i o n e l e c t r o n m i c r o
scope (TEM), using two-stage carbon-platinum r e p l i c a s of the e t c h
ed s u r f a c e s . I t should be noted that one must be very c a r e f u l i n
i n t e r p r e t i n g statements about f e a t u r e s seen i n r e p l i c a s . Thus a
nodule on a two-stage r e p l i c a a r i s e s from a dimple (not a nodule)
on the polymer s u r f a c e .
I s o l a t i o n of M i c r o g e l s . The f o l l o w i n g experiments were made

to i s o l a t e m i c r o g e l s during the process of c u r i n g and from the
etchant s o l u t i o n :
1. The formation of m i c r o g e l s during the c u r i n g process was
v e r i f i e d experimentally on samples E-2 and E-5 by d i s s o l v i n g them
i n acetone, before g e l a t i o n . Sample E-2, which has a longer g e l
a t i o n time than E-5, was d i s s o l v e d a f t e r c u r i n g a t 60°C f o r 30
min and a t 80°C f o r another 15 min whereas sample E-5 was
12. MISRA ET AL. Network Morphology and Mechanical Behavior 161
d i s s o l v e d a f t e r c u r i n g f o r only 10 min a t 100°C. The s o l u t i o n

was d i l u t e d to a c o n c e n t r a t i o n of 100 ppm, and e l e c t r o n micro-
scope g r i d s were made and examined under the TEM.
2. Etched samples were removed, the etching s o l u t i o n was
d i l u t e d with d e i o n i z e d water to a very low c o n c e n t r a t i o n , and
e l e c t r o n microscope g r i d s were prepared by platinum shadowing.
S i m i l a r l y , a l e s s d i l u t e s o l u t i o n (from the etching of sample E-
5) was placed on a c l e a n microscope s l i d e , allowed to dry, and
examined under the SEM.
Results
F i g u r e 1 shows t y p i c a l macrostructures, with f e a t u r e s i z e s
from ca. 10 ym to 40 ym, revealed by p r o g r e s s i v e etching by the
aqueous ( ^ 0 3 . The e f f e c t s of d i f f e r e n t v a r i a b l e s on morphology

are discussed below.
E f f e c t of Stoichiometry. Examination of the etched surfaces

under the SEM (Figures 2 and 3) revealed a two-phase s t r u c t u r e .
Dimples were observed on the surface, the dimple s i z e increased
with d e v i a t i o n from equivalent stoichiometry. Samples having an
excess of epoxy appeared to have fewer dimples than samples
having a s i m i l a r M but excess amine. The s i z e s of the dimples
c
v a r i e d from ca. 10 ym to 70 ym, depending on the percent excess

of r e a c t a n t s , i n general agreement with s i z e s reported by Cuth-
r e l l (7) and Selby and M i l l e r (37). I t was a l s o observed that
above an amine/epoxy r a t i o of 1.6/1 the morphological d i f f e r -
ences were n e g l i g i b l e .
The two-stage r e p l i c a s examined with the TEM a l s o revealed
the existence of two phases on a much f i n e r s c a l e (Figure 4). The
r e p l i c a s showed nodules on the s u r f a c e s , corresponding to dimples
on the polymer s u r f a c e s . The dimple s i z e s i n these samples were
i n the range of 25 nm to 50 nm except f o r the case of 100% excess
amine (A-20) where a l a r g e d i s t r i b u t i o n of s i z e s , ranging from
20 nm to 200 nm, was observed. The d i s t r i b u t i o n of phase s i z e
tends to broaden with i n c r e a s i n g proportions of excess amine;
the average s i z e a l s o tended to i n c r e a s e with the p r o p o r t i o n o f
excess amine. On the other hand, an i n c r e a s e i n the amount of
excess epoxy d i d not show s i g n i f i c a n t changes from the morphology
observed a t equal s t o i c h i o m e t r y . These observations d i f f e r from
those of Racich and Koutsky (31), who found that the domain s i z e
decreased with i n c r e a s i n g amounts of c a t a l y s t and with the pre-
sence of saturated vapor of the c u r i n g agent. They argued that
the c r o s s l i n k d e n s i t y i n c r e a s e s with i n c r e a s i n g amounts of c a t a -
l y s t , r e s u l t i n g i n smaller domain s i z e s . The present r e s u l t s
i n d i c a t e that, as reported by Racich and Koutsky, the domain s i z e
tends to increase with a decrease i n c r o s s l i n k d e n s i t y , but only
i n the excess-amine case; the domain i s not s i g n i f i c a n t l y a f f e c t -
ed by changes i n c r o s s l i n k d e n s i t y f o r the excess-epoxy case.
Figure 1. Micrographs of Cr O -etched surfaces of Epon 1004-MDA (Specimen

2 s
E-7). Etching times: (A) 2 hr; (B) 4 hr; (C) 7 hr; (D) 11 hr
Figure 2. Scanning electron micrographs of 7-hr-etched samples having different

stoichiometric ratio of MDA to Epon 828: (A) 0.7/1; (B) 0.8/1; (C) 1/1; (D) 1.1/1
Figure 3. Scanning electron micrographs of 7-hr-etched samples having different

stoichiometric ratio of MDA to Epon 828: (A) 1.4/1; (B) 1.6/1; (C) 1.8/1; (D) 2.0/1
MisRA E T A L . Network Morphology and Mechanical Behavior 165
Figure 4. Transmission electron micrographs of replicas of 4-hr-etched samples

having different stoichiometric ratio of MDA to Epon 828: (A) 0.7/1; (B) 0.8/1;
(C) 1.1/1; (D) 1.4/1; (E) 1.6/1; (F) 2.0/1
E f f e c t of Molecular Weight of the Prepolymer. When the

c r o s s l i n k d e n s i t y was changed by changing the molecular weight of
the epoxy prepolymers, a two-phase s t r u c t u r e , s i m i l a r to that
found f o r the case of v a r i a b l e s t o i c h i o m e t r y , was observed even
at the macro l e v e l (Figures 5 and 6 ) . A marked d i f f e r e n c e i n
morphology was observed i n networks prepared from l i q u i d r e s i n s
as compared to those from s o l i d or s e m i - s o l i d r e s i n s . The
l i q u i d - r e s i n (Epon 825, 828) samples had dimples which had a d i s
t r i b u t i o n of s i z e ranging from 5 ym to 25 ym. In a d d i t i o n to
dimples, small r i d g e s were a l s o seen i n both agglomerated and
i s o l a t e d forms. In samples from s e m i - s o l i d and s o l i d r e s i n s
(Epon 834, 1001, 1002 and 1004), e t c h - r e s i s t a n c e (and, hence,
presumably h i g h l y c r o s s l i n k e d ) s h e l l s were observed throughout
the c r o s s - s e c t i o n (Figure 7), encapsulating the l e s s c r o s s l i n k e d

m a t e r i a l . These shell-and-core-type s t r u c t u r e s were present i n
these samples i n a range of s i z e s from 2.5 ym to 25 ym. I t was
found that the range narrowed but that the average s i z e increased
with an increase i n the molecular weight of the prepolymer. T h i s
t y p i c a l morphology was a l s o observed i n samples that were solvent
cast from acetone s o l u t i o n s and cured a f t e r most of the acetone
evaporated. Since i t has been shown that c u r i n g does not take
place i n the presence of acetone i n the Epon-MDA system (39), i t
can be assumed that the acetone-cast samples were s i m i l a r to the
bulk-cured samples. Indeed no d i f f e r e n c e s i n mechanical proper
t i e s i n bulk and acetone-cast samples were observed (41, Ch. 6).
Etched under s i m i l a r c o n d i t i o n s , s o l v e n t - c a s t samples showed the
same shell-and-core-type morphology (Figure 7d), i n d i c a t i n g that
t h i s t y p i c a l morphology was not due to inadequate mixing.
A l l the samples made from s o l i d or s e m i - s o l i d prepolymers
had the same f i n e s t r u c t u r e , with the s i z e of the discontinuous
phase i n the range from 15 nm to 25 nm, whereas the samples made
from l i q u i d prepolymers had s l i g h t l y l a r g e r discontinuous phases
i n the range from 25 nm to 50 nm.
E f f e c t of the D i s t r i b u t i o n of Molecular Weight i n the P r e

polymer . The gross morphologies (both at macro and micro l e v e l s )
i n the bimodal blend samples ( S e r i e s F) appeared to be a p p r o x i
mately s i m i l a r to those of the counterparts prepared from the
S e r i e s Ε commercial r e s i n s (see F i g u r e 8 f o r a t y p i c a l compari
son) .
E f f e c t of High-Molecular-Weight Curing Agent. Sample G-l

(cured w i t h Versamid 140) a l s o showed the shell-and-core-type
morphology (Figure 9). The s i z e s of the shell-and-core s t r u c t u r e
(range from 2.5 ym to 25 ym) and the discontinuous phase were
l a r g e r than those cured w i t h MDA, probably because t h i s sample
had a higher M . c F i g u r e 9 shows a s h e l l ( e n c i r c l e d i n black)
which was not etched open by the chromic a c i d a t the time the
sample was removed. A semi-open s h e l l can a l s o be seen which
looks s i m i l a r to a dimpled nodule (though of a much l a r g e r s i z e )
12. MiSRA E T A L . Network Morphology and Mechanical Behavior 167
Figure 5. Scanning electron micrographs of 7-hr-etched networks prepared from

equivalent stoichiometric amounts of Epon-MDA resins: (A) Epon 825; (B) Epon
828; (C) Epon 834; (D) Epon 1001; (E) Epon 1002; (F) Epon 1004
Figure 6. Transmission electron micrographs of replicas of networks prepared

from equivalent stoichiometric ratios of Epon-MDA resins etched for 4 hr:
(A) Epon 825; (B) Epon 828; (C) Epon 834; (D) Epon 1001; (E) Epon 1002; (F)
Epon 1004
12. MiSRA E T A L . Network Morphology and Mechanical Behavior 169
Figure 7. Scanning electron micrographs of Epon 1001-MDA sample (E-5)

etched for 7 hr: (A) and (B) sample cross section; (C) sample surface; and (D) sur-
face of solvent-cast sample
Figure 8. Scanning electron micrographs of Series F networks along with their

Series Ε counterparts etched for 7 hr: (A) Epon 828; (B) blend (Epons 825 and
1004) equivalent to Epon 828; (C) Epon 1001; (D) blend (Epons 828 and 1004)
equivalent to Epon 1001
12. MISRA E T A L . Network Morphology and Mechanical Behavior
Figure 9. Scanning electron micrographs

of Epon 828 resin cured with Versamid
140 (network comprising 25% ghss
beads by volume; etched for 7 hr)
shown by Racich and Koutsky (31).

To check i f the shell-and-core-type s t r u c t u r e observed i n
s e m i - s o l i d and s o l i d prepolymers was due to f a s t c u r i n g , Epon
828 ( l i q u i d prepolymer) and MDA ( i n s t o i c h i o m e t r i c a l l y e q u i v a l e n t
amounts) were cured at 150°C f o r 4 hr. T h i s sample, a f t e r being
etched as described e a r l i e r , d i d not show any d i f f e r e n c e i n mor-
phology from the sample cured through the r e g u l a r c u r i n g c y c l e .
I t t h e r e f o r e appears that t h i s p e c u l i a r morphology depends on the
molecular weight of the prepolymer and not on the r a t e of c u r i n g
or inhomogeneous mixing.
I s o l a t e d M i c r o g e l s . The e l e c t r o n micrographs (Figures 10,

11a and l i b ) c l e a r l y show the i n d i v i d u a l microgels (ranging i n
s i z e from 20 nm to 200 nm) and c l u s t e r s of m i c r o g e l s that were
etched out from the network s u r f a c e . The appearance of these

microgels i s i n good agreement w i t h the observations made on
r e p l i c a s and i n d i c a t e s that sample E-2 (prepared from l i q u i d
prepolymers) had l a r g e r m i c r o g e l s ( s i z e s from 50 nm to 150 nm)
as compared to sample E-5 (prepared from s o l i d prepolymer, s i z e s
from 25 nm to 60 nm). These micrographs prove that the dimples,
observed through r e p l i c a s , on the s u r f a c e s of the epoxy networks
were due to the e t c h i n g of the weak connections o f the microgels
or c l u s t e r s of m i c r o g e l s and not to the etching of m a t e r i a l
having a low average c r o s s l i n k d e n s i t y . The platinum shadows i n
F i g u r e s 11a and l i b i n d i c a t e that the microgels are s o l i d and
n e a r l y s p h e r i c a l i n shape (a c o n f i g u r a t i o n having minimum s u r f a c e
energy) and can pack i n a hexagonal a r r a y .
S i m i l a r l y the e l e c t r o n micrographs ( F i g u r e s 11c and l i d )
show the existence of m i c r o g e l s even before g e l a t i o n (darker
phase) i n the s i z e range from 30 nm to 100 nm.
Thus, i n both cases d i s c r e t e m i c r o g e l p a r t i c l e s were observ-
ed, i n d i c a t i n g that microgel formation takes p l a c e before g e l a -
t i o n and that the m i c r o g e l s are d i s p e r s e d and l o o s e l y connected
to each other and i n some cases ( n o n - s t o i c h i o m e t r i c compositions)
to a weaker continuous phase. These r e s u l t s a l s o show that the
discontinuous phase (though etched out f i r s t as clumps) i s com-
posed of microgels that are stronger than the continuous phase.
I t i s the connections between the aggregates that are weak. The
s i z e and number of these g e l s probably continues to i n c r e a s e
u n t i l the v i s c o s i t y becomes high enough f o r p h y s i c a l g e l a t i o n to
take p l a c e .
Discussion
General Proposed Model f o r Network Formation. As mentioned

e a r l i e r , e l e c t r o n microscopic evidence shows that m i c r o g e l p a r t i -
c l e s form p r i o r to g e l a t i o n (Figures 10 and 11), both with low
and h i g h molecular weight epoxies and with epoxy and amine-rich
systems. T h i s o b s e r v a t i o n i s i n accord with the suggestions of
other i n v e s t i g a t o r s (14,27,28). Some i n v e s t i g a t o r s have observed
12. MisRA E T A L . Network Morphology and Mechanical Behavior
Figure 10. Scanning electron micro-

graphs of isolated secondary microgels
from Epon 828-MDA sample (E-2)
Figure 11. Transmission electron micrographs of isolated primary microgeh:

(A) and (B) gel particles etched out by Cr O solutions at70°C after 4 hr; (C) and
2 s
(D) microgels formed before gelation of the epoxy resins. [A and C—E-2; Β and
D—E-5]
these microgels i n s i z e s smaller than 0.5 ym while others have

reported l a r g e r than 5 ym. The present r e s u l t s i n d i c a t e the pre-
sence of microgels at both l e v e l s ; a lower l e v e l (10 nm to 50 nm)
and a higher l e v e l (2 ym to 50 ym). I t i s , t h e r e f o r e , probable
that the systems studied by other i n v e s t i g a t o r s a l s o had micro-
g e l s at both l e v e l s . In order to d i f f e r e n t i a t e between the two
s i z e l e v e l s , the term primary microgels i s used to r e f e r to
microgels i n the s i z e range from 10 nm to 50 nm, whereas second-
ary microgels r e f e r s to s i z e s l a r g e r than 1 ym.
In view of the morphological and property data at hand, a.
model f o r network formation i s proposed. The p r i n c i p a l p o i n t s to
consider i n c l u d e the f o l l o w i n g questions: the b a s i c morphologi-
c a l u n i t s , the phase c o n t i n u i t y , and the c r o s s l i n k d e n s i t y and
other p r o p e r t i e s of the v a r i o u s e n t i t i e s . The proposed mechanism

which e s s e n t i a l l y comprises a s y n t h e s i s of the mechanisms pro-
posed by Bobalek et a l . (27) , Solomon (33) and Labana et a l . (14),
considers that the formation of the macrogel takes place i n three
s e q u e n t i a l steps (Figure 12): formation of the primary microgels,
formation of the secondary m i c r o g e l s , and formation of the macro-
g e l . F o l l o w i n g Labana et a l . (14), i t i s a l s o proposed that the
secondary microgels and the macrogel are not completely coherent
(that i s , they have some unconnected dangling c h a i n s ) .
Formation of the Primary M i c r o g e l s . The r e a c t i v i t i e s of the

primary and secondary amine groups i n MDA are approximately i n
the r a t i o of 1.4/1 (39). The primary amine groups should, t h e r e -
f o r e , r e a c t f i r s t to give a l i n e a r s t r u c t u r e . Due to a combina-
t i o n of an exothermic heat of r e a c t i o n with poor heat t r a n s f e r ,
the temperature should r i s e i n the v i c i n i t y of these molecules,
r e s u l t i n g i n the r e a c t i o n of the secondary amine groups. Indeed,
i t has been shown that the primary and secondary amine groups
react almost simultaneously even when t h e i r r e a c t i v i t i e s d i f f e r
by a f a c t o r of two (43), The growth of the n u c l e i continues
u n t i l the r e a c t i v e polymer molecules can d i f f u s e to the r e a c t i v e
s i t e s of the n u c l e i . During t h i s process s e v e r a l new n u c l e i are
a l s o developed. Therefore, a d i s t r i b u t i o n of s i z e of the primary
microgels would be expected at a l l times during the c u r i n g proc-
cess. T h i s phenomenon has been p r e d i c t e d s t a t i s t i c a l l y by Labana
et a l . (14), who termed i t a n u c l e a t i o n process resembling the
one that occurs i n c r y s t a l l i z a t i o n .
Formation of the Secondary M i c r o g e l s . A f t e r a c e r t a i n con-

c e n t r a t i o n has been reached, the primary microgels and the grow-
ing n u c l e i begin to i n t e r a c t with each other and g i v e r i s e to new
n u c l e i f o r the secondary m i c r o g e l s . These n u c l e i grow i n part
due to c a p i l l a r y f o r c e s which w i l l encourage p h y s i c a l s i n t e r i n g
and i n part due to the r e a c t i o n of unreacted f u n c t i o n a l groups i n
the primary m i c r o g e l s . Thus, the secondary microgels are not as
coherent as the primary m i c r o g e l s . The s i z e of a p a r t i c u l a r
secondary microgel would depend on the c o n c e n t r a t i o n of the
PRIMARY GROWING PRIMARY SECONDARY SECONDARY

NUCLEI NUCLEI MICROGEL .NUCLEI MICROGEL MACROGEL
MACROGEL
Figure 12. Proposed model for network formation

12. MisRA E T A L . Network Morphology and Mechanical Behavior 177
primary m i c r o g e l s near the secondary nucleus. A s i z e d i s t r i b u -

t i o n i n the secondary m i c r o g e l s should a l s o be expected.
Formation of the Macrogel ( F i n a l Network). At a c r i t i c a l

s o l i d s c o n c e n t r a t i o n (-74% f o r monodispersed spheres arranged i n
a hexagonal packing), the secondary m i c r o g e l s pack together and
the experimental g e l point i s observed. At t h i s stage, phase
i n v e r s i o n takes p l a c e d u r i n g which the secondary m i c r o g e l s become
the matrix and the unreacted or p a r t i a l l y reacted prepolymers
become the dispersed phase. By the time of complete r e a c t i o n ,
the secondary m i c r o g e l s become l o o s e l y connected to each other
with the help of the i n t e r s t i t i a l prepolymer or due to s e l f -
d i f f u s i o n of r e a c t i v e dangling groups. Thus, the i n t e r c o n n e c -
t i o n s between the secondary m i c r o g e l s would be weaker than those

between the primary m i c r o g e l s . The p r o p e r t i e s o f the f i n a l n e t -
work should be a f f e c t e d by the coherence of the network. In n e t -
works prepared by n o n - s t o i c h i o m e t r i c compositions, the secondary
microgels would be embedded i n a matrix of lower c r o s s l i n k den-
s i t y but s t i l l connected to each other through chemical bonds.
Based on the above model, the morphological d i f f e r e n c e s and
mechanical behavior observed i n the samples of d i f f e r e n t s e r i e s
are i n t e r p r e t e d below.
Morphological D i f f e r e n c e s . In epoxy prepolymers, the

r e a c t i v i t y i n c r e a s e s with the number of hydroxyl groups present
i n the prepolymer c h a i n (44) . Thus, an i n c r e a s e i n the molecular
weight of the epoxy prepolymer would not only reduce i t s d i f f u -
s i v i t y but would a l s o i n c r e a s e i t s r e a c t i v i t y , r e s u l t i n g i n a
reduced time of m i c r o g e l formation. T h i s combined e f f e c t would
r e s u l t i n a smaller s i z e of the primary m i c r o g e l s , as observed
experimentally.
In the case of n o n - s t o i c h i o m e t r i c compositions, the s i z e of
the primary m i c r o g e l s should be expected to be governed both
by the v a l u e of M and by the s t r u c t u r e , because the d i f f u s i v -
c
i t y and the r e a c t i v i t i e s of the prepolymers should be almost the

same at a l l s t o i c h i o m e t r i e s . In the Epon 828/MDA system ( S e r i e s
A), an excess i n amine c o n c e n t r a t i o n should i n i t i a l l y y i e l d many
l i n e a r molecules whose l e n g t h would depend on the amount of
excess amine. The premature r e a c t i o n of the secondary amines of
these long molecules would r e s u l t i n l a r g e r m i c r o g e l s . Thus, i n
the case of amine excess, the s i z e of primary m i c r o g e l s , as
observed experimentally, should i n c r e a s e w i t h i n c r e a s i n g amounts
of excess amine. In the case of excess epoxy, a branched s t r u c -
ture having four epoxy molecules attached to one amine molecule
i s formed (39). Thus, the s i z e of the m i c r o g e l s formed at 100%
epoxy-excess would be much smaller than those formed at 100%
amine excess. The experimental r e s u l t s showed a s i m i l a r trend.
For systems having a slower r a t e of r e a c t i o n (such as
samples of S e r i e s A, sample E - l , sample E-2, and sample F-2,
which were made from l i q u i d prepolymers) the higher d i f f u s i v i t y
and lower r e a c t i v i t y r e s u l t i n s l i g h t l y l a r g e r primary

microgels. However, the loose connections of the adjacent
secondary microgels can be r e a d i l y attacked, r e s u l t i n g i n the
etching of the secondary microgels and thus formation of dimples
on the surface (as was observed e x p e r i m e n t a l l y ) . The s e m i - s o l i d
and s o l i d r e s i n s are composed of high-M and low-M prepolymer
components; the amount of low-M component decreases with the
average M of the prepolymer (41, Ch. 3). The more r e a c t i v e h i g h -
M components form the microgels that get dispersed i n the low-M
component, which r e a c t s l a t e r to give a high c r o s s l i n k d e n s i t y
s h e l l . A decrease i n the p r o p o r t i o n of the low-M component
should i n c r e a s e the s i z e but decrease the number of the s h e l l -
and-core-type of s t r u c t u r e as was found experimentally.
Dynamic Mechanical Spectroscopy. As pointed out above, the

heterogeneous morphology, observed i n the present study, i m p l i e s
network flaws (weak connections between the primary and secondary
m i c r o g e l s ) . However, the low c y c l i c s t r a i n s a p p l i e d i n dynamic
mechanical t e s t s d e t e c t only the e f f e c t of the b a s i c network
s t r u c t u r e and not the network flaws. Therefore, as observed
experimentally (38,41), dynamic mechanical spectroscopy should
not i n d i c a t e heterogeneity i n the samples.
Soluble Content. The morphological s t u d i e s i n d i c a t e d an

increase i n the dimple s i z e of M . c A dimple a c t u a l l y represents
a b i t of m a t e r i a l extracted from the network. This observation
i s i n good agreement with the e x t r a c t i o n r e s u l t s (41,42) that
showed an i n c r e a s e i n s o l u b l e content with M . c
Mechanical Behavior. At present, i t i s not p o s s i b l e to

r e c o n c i l e a l l the d i v e r s e dependences on s t o i c h i o m e t r y . However,
c l e a r l y there i s no a p r i o r i reason f o r trends i n a l l p r o p e r t i e s
to be r e l a t e d . By a m o d i f i c a t i o n of the G r i f f i t h equation (45)
1 / 2
a u = ( 2 ES / a ) (1)
where o = u l t i m a t e t e n s i l e strength, Ε = Young's modulus, S =

u
f r a c t u r e energy, and a. = c h a r a c t e r i s t i c flaw s i z e . Thus o at u
constant Ε depends on how S v a r i e s with a.; S may change while

o does not, i f changes i n a_ compensate f o r changes i n S. For
u
the Epon 828/MDA system, both B e l l (46) and Kim et a l . (45) have
shown that o i s almost independent of s t o i c h i o m e t r y .
u Further
more, i t has a l s o been shown that impact toughness i s a t a maxi
mum not a t 100% s t o i c h i o m e t r y but at a 1/1.4 epoxy/amine r a t i o
(37,45,46). The impact strength f o r the case of excess epoxy was
a l s o reported to be higher than that at equal stoichiometry.
Under these circumstances, i t has been shown that the apparent
c r i t i c a l flaw s i z e a i s a l i n e a r f u n c t i o n of the amine/epoxy
r a t i o , changing from 32 ym to 141 ym (45).
12. MISRA E T A L . Network Morphology and Mechanical Behavior 179
Whether the c r i t i c a l flaw s i z e corresponds to the

aggregates f i r s t formed p r i o r to phase i n v e r s i o n or whether i t
corresponds to the i n c l u s i o n s i s , of course, not known. Indeed,
the r e a l i t y of a flaw corresponding to the c a l c u l a t e d value of
a. i s not proven. Nevertheless, the c l o s e agreement between
m i c r o s c o p i c evidence of the present study and the computed flaw
s i z e (45) i s s t r o n g l y suggestive of a c o r r e l a t i o n .
Though the modulus, E, does not decrease ( i n f a c t i n c r e a s e s
s l i g h t l y (45,46) w i t h an i n c r e a s e i n amine content, the o v e r a l l
p l a s t i c deformation should i n c r e a s e due to the p l a s t i c i z i n g
character of the amine. Hence, S i n c r e a s e s (E i t s e l f may
increase due to enhanced c o n t i n u i t y of the network). At the same
time, the flaw s i z e i n c r e a s e s a l i t t l e but not as f a s t as S so
that t e n s i l e s t r e n g t h a c t u a l l y increases a l i t t l e . But with an
epoxy excess, the decreased flaw s i z e (corresponding to smaller

aggregates) more than balances out the lower value of S so that
the s t r e n g t h again i n c r e a s e s . However, the toughness otherwise
seen a t high amine contents i s v a s t l y reduced by the high l o a d i n g
r a t e i n impact; while with epoxy excess, the smaller flaw s i z e i s
a b l e to d e l a y f r a c t u r e .
In the case i n which the M i s v a r i e d by v a r y i n g the molecu
c
l a r weight of the epoxy r e s i n a t equal s t o i c h i o m e t r y ( S e r i e s Ε ) ,

the u l t i m a t e t e n s i l e s t r e n g t h i s independent of M but the impact
c
strength decreases with M (38,41). When the molecular weight of

c
the epoxy i s i n c r e a s e d , a d i f f e r e n t behavior occurs. The

inherent S of the epoxy components i s low compared to that of
amine and, hence, the t e n s i l e s t r e n g t h does not i n c r e a s e and
impact s t r e n g t h decreases.
The Glass T r a n s i t i o n Temperature. Samples having a bimodal

d i s t r i b u t i o n of molecular weight ( S e r i e s F) showed the same Tg as
t h e i r counterparts having a broad d i s t r i b u t i o n i n the high
(> 700) and the low (< 400) ranges of M „ At intermediate M *s,
c c
the Tg was found to be lower i n samples having a bimodal d i s t r i

bution (42). Though the morphology of the bimodal and broad d i s
t r i b u t i o n was the same, the p r o p e r t i e s of the former w i l l be
determined by the dominant component i n the f i n a l network. I f
t h i s i s a high-molecular-weight r e s i n (which i s more r e a c t i v e ) ,
t h i s network may be expected to dominate and Τ w i l l be low,
β
perhaps because the i n i t i a l f a s t r e a c t i o n r e s u l t s i n g r e a t e r

incoherence. At intermediate compositions, a j u d i c i o u s balancing
may occur and r e s u l t i n a more coherent network. Thus p r o p e r t i e s
may be governed by the low-molecular-weight component.
The f a c t that small-angle X-ray s c a t t e r i n g and stained or
unstained microtomed t h i n s e c t i o n s f a i l to i n d i c a t e a two-phase
s t r u c t u r e (37,41) a l s o supports the present model, which e x p l a i n s
that heterogeneity i n networks i s p r i m a r i l y due to incoherence on
a l o c a l s c a l e and not to major v a r i a t i o n s i n average c r o s s l i n k
density.
Although t h i s d i s c u s s i o n i s c l e a r l y s p e c u l a t i v e , i t does
e x p l a i n some of the behavior noted and suggests ideas capable of
t e s t i n g i n the l a b o r a t o r y .
Conclusions
From the present study and the s t u d i e s of other i n v e s t i g a

t o r s (discussed e a r l i e r ) , i t i s c l e a r that c r o s s l i n k e d networks
i n many epoxy r e s i n s and i n some alkyd r e s i n s a r e heterogeneous
i n nature.
According to the proposed model, small primary microgels
ranging i n s i z e from 10 nm to 100 nm a r e formed much before the
i n s e t of p h y s i c a l g e l a t i o n . These primary m i c r o g e l s agglomerate
together through weak connections to produce secondary m i c r o g e l s
ranging from 0.5 ym to 50 ym. The secondary m i c r o g e l s c o a l e s c e

together and the experimental g e l point i s observed. The f i n a l
c r o s s l i n k e d network i s produced a f t e r complete r e a c t i o n of the
unreacted prepolymers l e f t i n the i n t e r s t i c e s of the coalesced
secondary m i c r o g e l s . As compared to primary m i c r o g e l s , these
secondary m i c r o g e l s a r e g e n e r a l l y connected to each other through
"weaker" or l e s s coherent l i n k s . In networks prepared through
n o n - s t o i c h i o m e t r i c compositions, the secondary m i c r o g e l s a r e
embedded i n a matrix of lower c r o s s l i n k d e n s i t y but s t i l l con
nected to each other through chemical bonds.
The coherence o f the f i n a l network (macrogel) depends on the
d e n s i t y s t r e n g t h of the connections between the secondary m i c r o -
g e l s which i n turn governs i t s t e n s i l e p r o p e r t i e s .
In the case i n which the prepolymers have a bimodal d i s t r i
bution of molecular weight, the p r o p e r t i e s of the network a r e
governed by the component that i s more dominant i n the m i c r o g e l s .
Though s u f f i c i e n t experimental evidence i s not p r e s e n t l y
a v a i l a b l e , the o p t i m i z a t i o n o f c u r i n g c o n d i t i o n s should a l s o p l a y
an important r o l e i n a c h i e v i n g maximum coherence i n the network.
Ac kno wl ed g em en t s
The authors wish to acknowledge support f o r the f i r s t part

of t h i s work through AFMC C o n t r o l No. F33615-75C-5167. A d d i t i o n
a l support from the M a t e r i a l s Research Center and the Ford Motor
Fund i s a l s o much a p p r e c i a t e d .
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13
Creep Behavior of Amine-Cured Epoxy Networks:
Effect of Stoichiometry
1
S. L. KIM , J. A. MANSON, and S. C. MISRA
Materials Research Center, Coxe Laboratory #32, Bethlehem, PA 18015
Creep studies are not only important in the theory of

viscoelasticity but also of great practical importance in any
engineering application in which the polymer must sustain loads
for long times. With a thermoset resin, creep can vary a great
deal, depending on the degree of crosslinking, the perfection,
and the morphology of the network structure.
While many studies of the effects of crosslinking on
behavior have been made, most have been restricted in scope and
many have used relatively uncharacterized materials. For this
reason, a systematic examination was conducted to elucidate the
effects of crosslink density and its distribution on a wide range
of properties including basic viscoelastic response, stress-
-strain and impact behavior, and fatigue crack propagation. The
same base prepolymer type and curing agent were used throughout,
and a given crosslink density was obtained by changing the
stoichiometry and by changing the molecular weight of the pre-
polymer at constant stoichiometry.
Related Studies
In some epoxy systems ÇL,_2) , i t has been shown that, as

expected, creep and s t r e s s r e l a x a t i o n depend on the s t o i c h i o m e t r y
and degree of cure. The time-temperature s u p e r p o s i t i o n p r i n c i p l e
(3) has been a p p l i e d s u c c e s s f u l l y to creep and r e l a x a t i o n behavior
i n some epoxies (4-6)as w e l l as to other mechanical p r o p e r t i e s
(5-7). More r e c e n t l y , K i t o h and Suzuki (8) showed that the
W i l l i a m s - L a n d e l - F e r r y (WLF) equation (3) was a p p l i c a b l e to net-
works (with equivalence of f u n c t i o n a l groups) based on n i n e t e e n -
carbon a l i p h a t i c segments between c r o s s l i n k s but not to t i g h t e r
networks such as those based on bisphenol-A-type prepolymers
cured with m-phenylene diamine. R e l a x a t i o n i n the l a t t e r r e s i n
followed an Arrhenius-type equation.
C u r r e n t address: F i b e r and Polymer Product Research Division,
Goodyear T i r e & Rubber Co., Akron, Ohio 44316.
0-8412-0525-6/79/47-114-183$05.00/0
In t h i s study, the i m p e r f e c t i o n of the networks was v a r i e d

by v a r y i n g the s t o i c h i o m e t r y o f an Epon 828-methylene d i a n i l i n e
system. Related s t u d i e s of morphology, other p r o p e r t i e s , and
creep as a f u n c t i o n of molecular weight and d i s t r i b u t i o n of the
prepolymer are described elsewhere (9-13).
Experimental
The m a t e r i a l s used were Epon 828 epoxy r e s i n and methylene

d i a n i l i n e (Tonox), both from the S h e l l Chemical Co. The r e s i n
and c u r i n g agent were melted together, mixed, degassed, and cast
between g l a s s p l a t e s . The cure c y c l e was as f o l l o w s : 45 min at
60°C, 30 min at 80°C, and 2.5 hr at 150°C; then slow c o o l i n g to
room temperature. The amine to epoxy r a t i o (A/E) was v a r i e d from
0.7 to 2.0 ( i n terms o f e q u i v a l e n t s ) . Compositions are given i n

Table I .
Table I . Composition of Epoxy Specimens f o r Creep Study

a
Sample Amine/Epoxy M
c
Ratio
A-7 0.7 721

A-8 0.8 457
A-10 1.0 303
A-12 1.2 420
A--20 2.0 1381
d
M i s c a l c u l a t e d based on the rubbery moduli from dynamic
mechanical measurements (10), and used as a r e l a t i v e and e f f e c -
t i v e M^ throughout t h i s study.
Creep was measured u s i n g a Gehman t o r s i o n a l t e s t e r (14).

[In f a c t , the shear compliance J ( t ) was measured e x p l i c i t l y ; the
data are presented as moduli by taking E ( t ) - 3 / J ( t ) . ] Master
curves were obtained i n the usual manner ( 3 ) .
T y p i c a l creep-modulus behavior i s shown i n F i g u r e 1; v i s c o -

e l a s t i c parameters deduced from the master curve are given i n
Table I I , and d i s c u s s e d below.
G l a s s - t r a n s i t i o n temperature ( T ) . The modulus-temperature

g
curves tor a l l trie specimens were composed by p l o t t i n g the 10-sec

modulus a t each temperature, as shown i n F i g u r e 2. The g l a s s -
t r a n s i t i o n temperatures (corresponding to a modulus of 0.2 GPa)
are given i n Table I . C a l c u l a t i o n s show that Tg i s i n v e r s e l y
p r o p o r t i o n a l to the average molecular weight between c r o s s l i n k s
KIM ET AL. Amine-Cured Epoxy Networks 185
Log t, seconds
Figure 1. Typical curves of creep modulus vs. log t at different temperatures

(epoxy specimen A-10). Master curve at 169°C shown as solid curve.
Temperature. °C
Figure 2. Dependence of creep modulus (10-sec) on temperature for series of

epoxy resins: (Ο) Α·7; (A) A-8; (Π) A-IO; (·) A-12; (A) A-20
13. κίΜ ET AL. Amine-Cured Epoxy Networks 187
(M ); as proposed
c by N i e l s o n (15):
( D
M
where T = 350°K, the e x t r a p o l a t e d value o f T f o r M ^ «, d g c a n
4
k = 2.9 χ 1 0 . Results are i n e x c e l l e n t agreement with those
from other t e s t s (Table II) such as dynamic mechanical s p e c t r o
scopy and d i f f e r e n t i a l scanning c a l o r i m e t r y (10).
TABLE I I . Creep C h a r a c t e r i s t i c s o f Epoxy Resins
No. Τ a
r° d
τ
b
°C T c
g '° c Ε ,MPa log x
g ' C
g 9 C
r' c
η
A-7 132
101 114 30 -9.7 -0.36

A-8 162 127 140 33 -2.5 -0.38
A-10 198 164 168 50 4.0 -0.42
A-12 185 146 151 44 0.3 -0.38
A-20 119 93 100 10 -13.0 -0.63
bB y dynamic mechanical spectroscopy a t 110 Hz ( 9 ) .

cB y d i f f e r e n t i a l scanning c a l o r i m e t r y (9).
^From the temperature dependence o f creep modulus ( F i g u r e 2)
From slope of t r a n s i t i o n r e g i o n i n creep curves;
η = d[ln 3 / J ( t ) ] / d(£n t)
S h i f t f a c t o r ( a ) . Experimental s h i f t f a c t o r s were d e t e r
T
mined by composing smooth master curves from the data a t v a r i o u s

temperatures, taking Tg as the r e f e r e n c e temperature i n each case.
Temperature c o r r e c t i o n s were made o n l y f o r the data above Tg; the
c o r r e c t i o n s were found to be small (^10%).
A smooth composite curve was obtained by p l o t t i n g l o g a ^ v s .
(T-T ) f o r a l l the specimens, as shown i n F i g u r e 3. The
composite curve f o l l o w i n g the p r e d i c t i o n o f WLF equation (3) o n l y
i n the l i m i t e d range between ( T - 10°C) to ( T + 20°C).
g g While
one does not expect the WLF p r e d i c t i o n s to hold below Tg, the
p r e d i c t i o n s a r e u s u a l l y good to temperatures as h i g h as
(T +100°C). In f a c t , the data could be represented over the
e n t i r e temperature range by p l o t t i n g the s h i f t f a c t o r s a g a i n s t
1/T ( i . e . , i n an A r r h e n i u s - p l o t f a s h i o n ) , as shown i n F i g u r e 4.
When the data were p l o t t e d a g a i n s t (1/T - 1 / T ) , two g
s t r a i g h t l i n e s f o r a l l the specimens were obtained as shown i n

F i g u r e 5, c o n s i s t e n t w i t h an Arrhenius-type r e l a t i o n s h i p :
-E
l o g a„ (2)
2.303 RT
where R i s the gas constant, Τ i s the a b s o l u t e temperature, and
E i s the apparent a c t i v a t i o n energy.
a From the slopes o f the
s t r a i g h t l i n e s , the a c t i v a t i o n energies were found to be 950 k j /
mole (227 kcal/mole) above T and 356 kj/mole (85 kcal/mole)
g
Figure 3. Composite curve of experimental shift factors as a function of (Ύ — T )

g
(symbols are as in Figure 2). The curve predicted by the WLF equation (3) is
indicated by the solid line.
13. κίΜ ET AL. Amine-Cured Epoxy Networks 189
Figure 4. Plots of experimental shift factors for epoxy specimens vs. inverse tem
perature (symbols are as in Figure 2)
-30 -20 -10 0 10 20 30
(l/T-l/Tg) xlO ,
2
(OK)" 1
Figure 5. Composite plot of experimental shift factors for all epoxy specimens
as a function of (1/T — 1/T ) (symbols are as in Figure 2)
g
below Tg. As shown i n Table I I I , these v a l u e s are i n e x c e l l e n t

agreement with the values observed by K i t o h and Suzuki (8) i n a
bisphenol-A-type epoxy cured w i t h phenylene diamine: 962 kJ/mole
(230 kcal/mole) above T and 381 kJ/mole (91 kcal/mole) below T .
g g
Values a l s o agree reasonably w e l l w i t h the apparent a c t i v a t i o n

energies that were determined i n our p a r a l l e l study i n which M c
was v a r i e d by changing prepolymer molecular weight (13) . In com

p a r i s o n , apparent energies of a c t i v a t i o n [at Tg, assuming a
2 2
v i s c o s i t y of 1 0 ^ N.s.nT" (16, p. ) ] , are c a l c u l a t e d to range
between 900 kJ/mole (215 kcal/mole) f o r T = 100°C and 1259 kJ/ g
mole (301 kcal/mole) f o r T = 168°C. Further, the WLF equation

g
p r e d i c t s a continuous decrease i n E as Τ i n c r e a s e s above T .

a g
Table I I I . Comparison of Apparent Energies of

A c t i v a t i o n f o r R e l a x a t i o n i n Epoxies
Range of Τ Ε^, kJ/mole (kcal/mole)
Τ > Τ 950 a
(227) 960 b
(230) 962° (230)
g
Τ < Τ 360 a
(86) 356 b
(75) 381° (91)
g
a
T h i s study.
P a r a l l e l study with Mc changed by changing prepolymer
molecular weight (13).
K i t o h and Suzuki ( 8 ) , f o r bisphenol-A-type r e s i n cured
w i t h m-phenylene diamine.
Thus, w h i l e our v a l u e s o f E (as w e l l as those i n r e f e r e n c e s

a
«8 and 13) agree w e l l with WLF p r e d i c t i o n s a t T when Tg - 100°C, g
they do not agree q u a n t i t a t i v e l y or q u a l i t a t i v e l y f o r higher-Tg

specimens at T or f o r any specimens a t Τ >) T .
g Interestingly,
g
other authors (5,14) have reported v a l i d i t y of the WLF treatment

f o r l e s s - d e n s e l y - c r o s s l i n k e d epoxy systems. A l s o , we f i n d that a
p l o t of data by Murayama e t . a l . (]7) shows that an Arrhenius-type
treatment of dynamic mechanical s h i f t f a c t o r s i s p r e f e r r e d f o r
oriented poly(ethylene terephthalate).
C h a r a c t e r i s t i c creep time. A l l master curves were e m p i r i

c a l l y s h i f t e d to the most convenient common temperature, 150°C,
as shown i n F i g u r e 6. For convenience, only t r a n s i t i o n regions
are shown. An i n c r e a s e i n c r o s s l i n k d e n s i t y (nearing to equiva
l e n t s t o i c h i o m e t r y ) s h i f t s the curves to longer times as expected.
The c h r a c t e r i s t i c creep time, T , was taken as the time to creep
c
to a modulus v a l u e of l o g E ( t ) = ( l o g E + l o g Er)/2, where Egg
and E are the g l a s s y and rubbery modulus, r e s p e c t i v e l y . [While

r
T i s analogous to a r e t a r d a t i o n time, the l a t t e r d e s i g n a t i o n i s

c
not used, because our T i s determined from p l o t s of 3 / J ( t ) , not

c
J / ( t ) , and i s hence not n u m e r i c a l l y equal to the corresponding

KIM ET AL. Amine-Cured Epoxy Networks 191
log t, second
Figure 6. Creep-modulus master curves for all epoxy specimens as a function of

log tat a reference temperature of 150° C
r e t a r d a t i o n time. x i s , s t r i c t l y speaking, a r e l a x a t i o n time.]

c
C h a r a c t e r i s t i c creep time i s shown as a f u n c t i o n of the A/E r a t i o

and a l s o as a f u n c t i o n of 1/M ( F i g u r e 7 ) . The good s t r a i g h t -
C
l i n e r e l a t i o n s h i p between l o g T and 1/M again shows c o n s i s t e n c y

c C
i n the behavior of these specimens:

T 3
Ί c 7.7 χ 10
log — = — (3)
Coo C
where l o g T C o oi s found by e x t r a p o l a t i o n to equal -18, which i s
the c h a r a c t e r i s t i c creep time at about 150°C f o r a network having
an i n f i n i t e value of M . c
Since both x and Tg are i n v e r s e l y r e l a t e d to M and the

c Q
a c t i v a t i o n energies of the s h i f t f a c t o r s are independent of M , a

common segmental motion must be i n v o l v e d i n the creep behavior o f

a l l these s p e c i m e n s v a r y i n g the c r o s s l i n k d e n s i t y merely s h i f t s
the curves along the time a x i s .
D i s t r i b u t i o n of r e l a x a t i o n times, Η ( τ ) . In t h i s
d i s c u s s i o n , u s i n g p l o t s of 3 / J ( t ) , we s h a l l d i s c u s s the d i s t r i b u
t i o n of c h a r a c t e r i s t i c response times i n terms of r e l a x a t i o n
times. The r e l a x a t i o n - t i m e spectrum, Η(τ), can be determined as
a f i r s t approximation (18) by the f o l l o w i n g r e l a t i o n s h i p :
Η(τ) = - d[E(t)] / d (log t ) L

(4)
. _ E ( t ) f d
nos E
(t>il
M U
L
d ( l o g t) J _
P l o t s of Η(τ) vs l o g t f o r a l l specimens are given i n F i g u r e 8.
When data are r e p l o t t e d at the T of each specimen, the d i s t r i
g
b u t i o n of r e l a x a t i o n times f o r the 5 d i f f e r e n t specimens n e a r l y

c o i n c i d e with each other u n t i l the rubbery r e g i o n , where some
s c a t t e r i s seen ( F i g u r e 9 ) . This confirms that the same mechan
ism f o r r e l a x a t i o n i s i n v o l v e d f o r a l l 5 specimens. The slope of
Η(τ) ( i . e . , d [ l o g H ( i ) ] / d ( l o g t ) ] a t the g l a s s t r a n s i t i o n r e g i o n
(the right-hand p a r t of F i g u r e 9) i s about -0.42, which compares
f a i r l y w e l l with the value of -0.33 obtained by K i t o h and Suzuki
(8) f o r a bisphenol-A epoxy r e s i n cured with m-phenylene diamine,
c o n s i d e r i n g the d i f f e r e n c e s i n the epoxy system and i n the t e s t i n g
modes. C l e a r l y the data f o r our p a r a l l e l study (13) i n which M c
i s v a r i e d by changing prepolymer molecular weight are i n d i s

t i n g u i s h a b l e from those of t h i s study (note t r i a n g l e s i n F i g u r e 9 ) .
Conclusions
In c o n c l u s i o n , the temperature dependence of s h i f t f a c t o r s

f o r the networks s t u d i e d here do not f o l l o w the WLF equation, but
r a t h e r an Arrhenius-type r e l a t i o n s h i p . The apparent a c t i v a t i o n
energies are independent of s t o i c h i o m e t r i c v a r i a t i o n [as they are
when M c i s v a r i e d by changing prepolymer molecular weight (13)] .
13. KIM ET AL. Amine-Cured Epoxy Networks 193
1.0 1.5 2.0 10 20 30

A/E l/Mc XIO^
Figure 7. Characteristic creep time for all epoxy specimens as a function of

stoichiometry and M : (%) epoxy-rich; (O) amine-rich; (Δ) different series with
c
M varied by changing prepolymer molecular weight (IS)

c
log t. second
Figure 8. Distribution of relaxation times for all epoxy specimens as a function

of log t (symbols as in Figure 7)
-5
log
t,
0
Figure 9.
second
5
10
13. κ ί Μ ET AL. Amine-Cured Epoxy Networks 195
Nearing to s t o i c h i o m e t r y (decrease i n M ) merely s h i f t s the

c
creep curves to a longer time s c a l e . Although the c r o s s l i n k den

s i t y was lowered ( i n c r e a s e i n M ) more than f o u r - f o l d by v a r y i n g
c
the A/Ε r a t i o , apparently the aromatic r i n g s i n the bisphenol-A

and diamine group must be c o n t r o l l i n g ( s t i f f e n i n g ) the segmental
motions i n the networks. Thus, c o n s i d e r i n g the r e s u l t s of t h i s
work and those o f K i t o h and Suzuki (8) and Murayama e t . a l , (17),
we might expect an Arrhenius-type r e l a t i o n s h i p i n the temperature
dependence o f s h i f t f a c t o r s f o r r e l a t i v e l y r i g i d networks.
Acknowledgement
The authors g r a t e f u l l y acknowledge f i n a n c i a l support from

the A i r Force M a t e r i a l s Laboratory through Contract No. F33615-

75-C-5167.
Literature Cited
1. Kosuga, N. and Tsugawa, S. Kobunshi Ronbunshu, 1975, 32,

252.
2. Delmonte, J . Plastics Technol., 1958, 4, 913.
3. Ferry, J . D. "Viscoelastic Properties of Polymers," 2nd
Ed., John Wiley & Sons, Inc., New York, NY, 1970, Chap. 11.
4. Theocaris, P. Rheol. Acta, 1962, 2, 92.
5. Kaelble, D. H., J . Appl. Polym. Sci., 1965, 9, 1213.
6. Shito, N. and Sato, M. J . Polym. Sci.-C., 1967, 16, 1069.
7. McCrum, N. G. and Pogany, G. A. J . Macromol. Sci.-Phys.,
1970, B4(1), 109.
8. Kitoh, M. and Suzuki, K. Kobunshi Ronbunshu, 1976, 33, 19.
9. Manson, J . Α.; Sperling, L. H. and Kim, S. L. "Influence
of Crosslinking on the Mechanical Properties of High-T g
Polymers," Technical Report AFML-TR-77-109, July 1977.

10. Kim, S. L. and Manson, J . A. "Dynamic Mechanical Behavior
of Amine-Cured Epoxy," 19th Canadian High Polymer Forum,
Ottawa, Canada, August 1977, to be published.
11. Kim, S. L . ; Skibo, M.; Manson, J . Α.; Hertzberg, R. W. and
Janiszewski, J . Polym. Eng.-Sci., 1977.
12. Misra, S. C. Ph.D. Thesis, Lehigh University, 1978.
13. Misra, S. C.; Manson, J . A. and Sperling, L . H. This
publication, 1979.
14. ASTM D-1043, American Society of Testing Materials,
Philadelphia, PA.
15. Nielson, L . E. J . Macromol. Sci.-Rev. Macromol. Chem., 1969,
C3(1), 69.
16. Nielsen, L . E. "Mechanical Properties of Polymers," Van
Nostrand Reinhold, New York, 1962.
17. Murayama, T.; Dumbleton, J . H. and Williams, M. L. J . Polym.
Sci., 1968, part A-2, 6, 787.
18. Tobolsky, Α. V. "Properties and Structure of Polymers,"
John Wiley & Sons, Inc., New York, NY, 1960, Chap. 3.
14
Self-Cross-Linkable Polyepoxides
YOSHIO TANAKA
Research Institute for Polymers & Textiles, 4 Sawatari, Kanagawa,
Yokohama 221, Japan
The l i t e r a t u r e contains numerous references to the

reactive copolymers of 2,3-epoxy-1-propyl esters such

as 2,3-epoxy-1-propyl methacrylate, acrylate and v i n y l -
sulfonate with other v i n y l compounds l i k e p r o p i o n i t r i l e ,
methyl a c r y l a t e , and vinylbenzene (1), and to the addi-
t i o n reaction of amino, carboxy, and hydroxy compounds
with the epoxy ring of these copolymers (2). 2,3-Epoxy-
-1-propyl-2-propenyl ether i s found (2) to have a strong
tendency to l i m i t the molecular weight of a polymer by
chain transfer through the a l l y l portion of the mole-
cule. Relatively little attention has been paid to the
copolymers of 2 , 3 - e p o x y - 1 - p r o p y l e t h e r s such as 1-
ethenyl-4-(2,3-epoxy-1-propoxy) benzene, and to the
s e l f - a d d i t i o n reaction of the epoxy group with c a t a l y t i c
or reactive functional groups, being capable of opening
or adding to the epoxy r i n g , in the copolymers. This
paper, therefore, reports the r a d i c a l copolymerization
of 2,3-epoxy-1-propyl methacrylate or 1-ethenyl-4-(2,3-
epoxy-1-propoxy)benzene with 4- and 2 - v i n y l p y r i d i n e s and
with 5 - e t h y l - 2 - v i n y l p y r i d i n e , and the s e l f - c r o s s l i n k i n g
reaction of these copolymers.
Experimental
Reagent-grade 2,3-epoxy-1-propyl methacrylate and

v i n y l p y r i d i n e s were distilled at reduced pressure, and
the middle fractions were collected for use. 1-Ethenyl-
4 - ( 2 , 3 - e p o x y - l - p r o p o x y ) b e n z e n e was p r e p a r e d f r o m 4 -
e t h e n y l p h e n o l and l - c h l o r o - 2 , 3 - e p o x y p r o p a n e by a two-
s t e p p r o c e s s (_1). 1
2, 2 - A z o i s o b u t y r o n i t r i l e was r e c r y s -
t a l l i z e d from i t s a l c o h o l i c s o l u t i o n .
An epoxide and a v i n y l p y r id i n e were d i s s o l v e d i n
10 ml of d r y t e t r a h y d r o f u r a n f o l l o w e d by the a d d i t i o n
of 0 . 5 mole-% of the i n i t i a t o r . The s o l u t i o n was
t r a n s f e r e d t o a p o l y m e r i z a t i o n tube, c o o l e d i n a l i q u i d
n i t r o g e n b a t h , degassed, and s e a l e d under vacuum a f t e r
0-8412-0525-6/79/47-114-197$05.00/0
f l u s h i n g w i t h a stream of oxygen-free n i t r o g e n . The

t u b e was t h e n p l a c e d i n a c o n s t a n t t e m p e r a t u r e bath
a t 60.0 ± 0.2°C f o r s e v e r a l h o u r s . A t the end of the
r e a c t i o n t i m e t h e t u b e was c o o l e d and o p e n e d . The
r e a c t i o n m i x t u r e s was d i s s o l v e d i n a s m a l l amount o f the
s o l v e n t and poured i n t o anhydrous p e t r o l e u m e t h e r . The
i n s o l u b l e m a t e r i a l was c o l l e c t e d and washed w i t h c o l d
petroleum e t h e r . A f l u f f y y e l l o w o r brown s o l i d was
p u r i f i e d by r e d i s s o l v i n g twice and r e p r e c i p i t a t i n g i n a
l a r g e e x c e s s of n o n s o l v e n t . I t was f i n a l l y d r i e d t o
c o n s t a n t weight under vacuum a t a room temperature. Co
polymer c o m p o s i t i o n s c a l c u l a t e d from carbon and n i t r o g e n
analyses. The r e a c t i v i t y r a t i o s were c a l c u l a t e d by
Mayo-Lewis t e c h n i q u e (3).
V i s c o s i t i e s o f t h e p o l y m e r i c m a t e r i a l s were ob
t a i n e d i n t e t r a h y d r o f u r a n w i t h an Ubbelohde-type v i s c o m
e t e r a t 30.00 ± 0.02°C. The i n f r a r e d a b s o r p t i o n s p e c t r a
i n the r e g i o n of 400-4000/cm were measured f o r the sam
p l e by H i t a c h i Model EPI-G3 i n f r a r e d spectrophotometer.
The samples were p r e p a r e d by the KBr p e l l e t t e c h n i q u e .
The thermal b e h a v i o r of the specimens was observed w i t h
a Rigakudenki DSC-TGA a p p a r a t u s . The X-ray d i f f r a c t i o n
p a t t e r n of the powdered polymer was taken i n the r e g i o n
o f 3-37° by a R i g a k u d e n k i M o d e l 3D-F X - r a y d i f f r a c -
tometer w i t h the use o f N i - f i l t e r e d copper Κ radiation.
C o p o l y m e r i z a t i o n of the epoxides w i t h these v i n y l -

p y r i d i n e s i n t e t r a h y d r o f u r a n under reduced p r e s s u r e w i t h
2 , 2 ' - A z o i s o b u t y r o n i t r i l e a t 60°C gave s t a b l e y e l l o w or
brownish p o l y m e r i c m a t e r i a l s . In F i g u r e 1-3, the con
c e n t r a t i o n of M2 ( v i n y l p y r i d i n e ) i n the monomer m i x t u r e
a r e p l o t t e d a g a i n s t the c o r r e s p o n d i n g mole f r a c t i o n M2
of v i n y l p y r i d i n e i n the copolymer. The l i n e s i n the
f i g u r e s were c a l c u l a t e d from t h e monomer r e a c t i v i t y
r a t i o s and the p o i n t s r e p r e s e n t e x p e r i m e n t a l d a t a . The
r e a c t i v i t y r a t i o s f o r these epoxy compounds w i t h the
p r e s e n t comonomers have not y e t been r e p o r t e d , but can
be compared w i t h those p r e d i c t e d by the Q-e scheme. The
Q-e v a l u e s f o r the i n d i v i d u a l v i n y l p y r i d i n e were c a l c u
l a t e d by assuming Q=0.78 and e=-0.02, Q=0.85 and e=0.10,
and Q=0.87 and e=0.40 f o r 2 , 3 - e p o x y - l - p r o p y l methacry
l a t e ; these a r e g i v e n i n T a b l e I . Assuming Q=1.30 and
e=-0.50 f o r 2 - v i n y l p y r i d i n e , and Q=1.37 and e=-0.74 f o r
5 - e t h y l - 2 - v i n y l p y r i d i n e , the Q-e v a l u e s f o r the epoxide
were a l s o c a l c u l a t e d and are shown i n T a b l e I, compared
with those o b t a i n e d from P r i c e ' s (£) or Tamikado's (!5)
Q-e v a l u e s f o r t h e p y r i d i n e . The Q-e v a l u e s f o r 1-
ethenyl-4-(2,3-epoxy-l-propoxy) benzene were a l s o c a l
c u l a t e d by assuming Q=0.82, e=-0.20 f o r 4 - v i n y l p y r i d i n e ,
14. TANAKA Self-Cross-Linkable Polyepoxides 199
0.0 0.2 0.4 0.6 0.8 1.0
VINYLPYRIDINE IN MONOMER
( MOLE FRACTION )
Journal of Polymer Science, Polymer Chemistry Edition

Figure 1. Monomer-copolymer composition curve for l-ethenyl-4-(2 3-epoxy-l- 9
propoxy) benzene (Mi) with 4-vinylpyridine (M ): ( ) rj = 0.467 and r =

g 2
0.638
0.0 0.2 0.4 0.6 0.8 1.0
( MOLE FRACTION )

Figure 2. Monomer-copolymer composition curves for l-ethenyl-4-(2,3-epoxy-l-
propoxy) benzene (Mj) or 2,3-epoxy-l-propyl methacrylate (M ) with 2-vinyl- t
pyridine (M ): (
2 ) l-ethenyl-4-(2,3-epoxy-l-prpoxy) benzene with rj = 0.556
and τ = 1-25; (
2 ) 2,3-epoxy-l-propyl methacrylate with r = 0.51 and r =2 2
0.62
0.0 0.2 0.4 0.6 0.8 1,0
( MOLE FRACTION )

Figure 3. Monomer-copolymer composition curves for l-ethenyl-4-(2,3-epoxy-l-
propoxy) benzene or 2,3-epoxy-l-propyl methacrulate (MJ with 5-ethyl-2-vinyl-
pyridine (M ): (
2 ) l-ethenyl-4(2,3-epoxy-l-propoxy) benzene with T = 0.639 t
and τ = 1.38; (
2 ) 2,3-epoxy-l-propyl methacrylate with r = 0.57 and x =
2 2
0.62
Table I
Monomer R e a c t i v i t y R a t i o s and Q-e V a l u e s i n C o p o l y m e r i z a t i o n o f
a
2 , 3 - E p o x y - l - p r o p y l M e t h a c r y l a t e (M ) w i t h V i n y l p y r i d i n e s ( M )
x 2
M 2 rι r 2 ei e 2 Qi Q2
b c b
2-Vinylpyridine 0.51 0.62 -0.02 ' -0.85 0.78 'Ç 1.15
b d b d
0.10 ' -0.73 0.85 ' 1.14
b e
0.40b,e -0.43 0.87 ' 0.91
b d b d
0.54 -0.50 > 1.23 1.30 '
b
-1.17 -0.lb,f 1.55 1.07 /f
b
-1.67 -0.6b,g 0.93 1.09 rg
5-Ethyl-2-vinylpyridine 0.57 0.62 -0.02b,c -1.04 0.78*>,c 1.40
b d
0.10*>,d -0.92 0.85 ' 1.35
b e
0.40^,e -0.62 0.87 ' 1.02
b d
0.28 -0.74 ' 1.04 1.37*>,d
a P o l y m e r i z a t i o n c o n d i t i o n s : 0.02 mole o f monomers; p o l y m e r i z a t i o n i n t e t r a h y d r o -

1
f u r a n w i t h 0.5 mole-% o f 2 , 2 - a z o i s o b u t y r o n i t r i l e a t 60°C.
b R e f e r e n c e d a t a used f o r c a l c u l a t i o n o f Q-e v a l u e s ,
c Data o f Young ( J . Polym. S c i . , 1961, 54, 4 1 1 ) .
d Data o f Young and Kennedy ( i n C o p o l y m e r i z a t i o n , G. E . Ham, Ed., I n t e r s c i e n c e ,
New York, 1964, Appendix B . ) .
e Data o f Iwakura e t a l . (Makromol. Chem., I960, 44/46, 570).
f Data o f P r i c e ( J . Polym. S c i . , 1948, 3, 7 7 2 ) .
g Data o f Tamikado ( J . Polym. S c i . , 1960, 43, 4 8 9 ) .
Q=1.30, e=-0.50 f o r 2 - v i n y l p y r i d i n e , and Q=1.37, e=-0.74

f o r the other p y r i d i n e ; these a r e g i v e n i n T a b l e I I .
The monomer-copolymer compostion curve c a l c u l a t e d from
the monomer r e a c t i v i t y r a t i o s , ri=0.514 and r2=0.715,
gave a p o o r e r f i t to the e x p e r i m e n t a l p o i n t s w i t h
4-vinylpyridine. To d e s c r i b e the d a t a o b t a i n e d w i t h
2 - v i n y l p y r i d i n e , the c a l c u l a t e d curve with Q=1.5 and
e=-1.2 was p o o r e r f i t than t h a t w i t h Q=1.4 and e = - l . l ,
b u t b e t t e r t h a n t h a t w i t h Q=1.2 and e=-1.0 f o r 1-
e t h e n y l - 4 - ( 2 , 3 - e p o x y - l - p r opoxy)benzene. These calcu-
l a t e d w i t h Q=1.5, e=-1.2; Q=1.3, e = - l . l ; and Q=1.2,
e=-1.0 f o r l - e t h e n y l - 4 - ( 2 , 3 - e p o x y - l - p r o p o x y ) b e n z e n e gave
an e x c e l l e n t f i t c o r r e s p o n d i n g c l o s e l y to the p o i n t s
w i t h 5 - e t h y l - 2 - v i n y l p y r id i n e .
The copolymers w i t h these p y r i d i n e s have a c h a r a c

t e r i s t i c band due to an i n t e r m o l e c u l a r hydrogen bond
i>(OH) of OH group of polymers about a t 3500/cm as shown
i n F i g u r e 4. The bands a t 1660 t o 1640/cm a s s i g n e d t o
the s t r e t c h i n g modes of the C=C bond of o l e f i n i c hydro
carbons are not o b s e r v e d . The bands a s s i g n e d t o the
i n - p l a n e and the o u t - o f - p l a n e bending modes f o r o l e f i n i c
CH groups a r e a l s o not observed d i s t i n c t l y i n the 1450-
1300/cm and 1000-800/cm r e g i o n s of the i n f r a r e d s p e c t r a
of the copolymers. The s y m m e t r i c a l and the asymmetrical
s t r e t c h i n g bands of the epoxy r i n g seem t o occur near
1250/cm and 910/cm, r e s p e c t i v e l y . The i n t e n s i t y of the
band a t 910/cm d e c r e a s e d and d i s a p p e a r e d i n the s p e c t r a
of the heated samples which became i n s o l u b l e and i n
fusible.
The homo- and copolymers of these e p o x i d e s w i t h the
v i n y l p y r i d i n e s were h i g h l y amorphous as judged by the
X-ray d i f f r a c t o g r a m s Under the e x p e r i m e n t a l c o n d i t i o n s ,
the r e s u l t i n g copolymers were s o l u b l e i n o r g a n i c s o l
v e n t s s u c h a s t e t r a h y d r o f u r a n , c h l o r o f o r m , and Ν,Ν
α imethylformamide, w h i l e i n a humid a t m o s p h e r e t h e
copolymers, e s p e c i a l l y those w i t h 4 - v i n y l p y r i d i n e , were
apt to be c o n v e r t e d t o the i n s o l u b l e m a t e r i a l s d u r i n g
r e p r e c i p i t a t i o n or d r y i n g a t a room temperature. Dif
f e r e n t i a l s c a n n i n g c a l o r i m e t r y and thermogravimetry
s t u d i e s show t h e s e c o p o l y m e r s do n o t m e l t b u t r e a c t
a u t o c a t a l y t i c a l l y a t 90-200°C and degrade e x t e n s i v e l y
above 300°C.
The p o l y m e r i c m a t e r i a l s were c r u s h e d , mixed w i t h
KBr powder and p r e s s e d i n t o the form of a KBr d i s k . The
samples were heated i n a f o r c e d d r a f t oven, taken out a t
c o n v e n i e n t i n t e r v a l s , c o o l e d i n a d e s i c c a t o r , and the
i n t e n s i t y of the band a t 910/cm was measured. The i n
t e n s i t y of IR a b s o r p t i o n spectrum of the epoxy group a t
910/cm was found to d e c r e a s e i n p r o p o r t i o n to the de
c r e a s e of the epoxy compound i n the r e a c t i o n system (2).
Table I I
Monomer R e a c t i v i t y R a t i o s and Q-e V a l u e s i n C o p o l y m e r i z a t i o n o f 1 - E t h e n y l -

a
4 - ( 2 , 3 - e p o x y - l - p r o p o x y ) b e n z e n e (Mi) w i t h V i n y l p y r i d i n e s ( M ) 2 (
b b
M 2
ri r 2 ei e 2 Qi Q*
4-Vinylpyridine 0.467 0.638 -1.3 -0.20 1.6 0.82

d d
0.514c 0.715C -1.2 1.4
d d
2-Vinylpyridine 0.531C 1.15C -1.2 -0.50 1.5 1.30
0.556 1.25 -1.1 1.4
d d
0.560C 1.39C -1.0 1.2
d
5-Ethy1-2-vinylpyridine 0.630c 1.28C -1.2d -0.74 1.5 1.37
0.639 1.38 -1.1 1.3
c d d
0.675C 1.38 -1.0 1.2
a P o l y m e r i z a t i o n c o n d i t i o n s : 0.02 mole o f monomers; p o l y m e r i z a t i o n i n tetrahydro-

1
f u r a n w i t h 0.5 mole-% o f 2 , 2 - a z o i s o b u t y r o n i t r i l e a t 60OC.
b R e f e r e n c e d a t a used f o r c a l c u l a t i o n o f Q-e v a l u e s ,
c C a l c u l a t e d v a l u e s from t h e assumed Q-e v a l u e s ,
d Assumed v a l u e s used f o r c a l c u l a t i o n o f r i and r values.
2

Κ)
ο
f ΙΙΚ0.172)
ΙΙΙΙΙΜΙΙΙΜΙΙ L J L
4000 3500 3000 2500 2000 1900 1800 1700 1600 1500 WOO 1300 1200 1100 1000 900 800 700 650
1
WAVE NUMBER ( CM" ) M
Figure 4. IR spectra of l-ethenyl-4-(2,3-epoxy-l-propoxy) benzene and its homopolymers and

copolymers with 2-vinylpyridine. Number in parentheses shows the mole fraction of pyridine
in the copolymer: (I) monomer; (II) homopolymer; (III) copolymer
The c h a r a c t e r i s t i c bands of the methyl or methylene, and

the p h e n y l groups a t 1440 and 1505/cm were used as s t a n
d a r d s f o r copolymers o f these e p o x i d e s , r e s p e c t i v e l y ,
b e c a u s e t h e i r i n t e n s i t i e s d i d n o t change d u r i n g t h e
reactions. The r e s u l t s of t y p i c a l e x p e r i m e n t s w i t h the
copolymers of l - e t h e n y l - 4 - ( 2 , 3 - e p o x y - l - p r o p o x y ) b e n z e n e
are p l o t t e d i n F i g u r e 5 , i n which the r e l a t i v e i n t e n s i t y
changes of 910 t o 1505/cm are p l o t t e d a g a i n s t the r e a c
t i o n time and f o l l o w , i n some c a s e s , s i g m o i d a l c u r v e s
showing an i n d u c t i o n p e r i o d . The i n d u c t i o n p e r i o d was
found to be dependent on the r e a c t i o n temperature and on
the c o n t e n t of the v i n y l p y r i d i n e u n i t i n c o p o l y m e r s .
The r e l a t i o n s h i p of the r a t e of consumption of the
epoxy group, - ά ( Μ ] ^ t / l , o ) / ' M d t
w i t h the epoxy groups
remaining M i , t / l O ' M
f i n the copolymers o f 1 - e t h e n y l -
4-(2,3-epoxy-l-propoxy)benzene i s shown in Figure 6.
M s e
l , i ^ th c o n t e n t o f t h e epoxy g r o u p a t r e a c t i o n
time i . The maximum r a t e o f consumption o f the epoxy
group i n c r e a s e d as the mole f r a c t i o n o f the p y r i d i n e to
the epoxy g r o u p i n c r e a s e d . A t t h e maximum r a t e o f
r e a c t i o n t h e r a t e o f c o n s u m p t i o n o f t h e epoxy g r o u p
r e a c h e d the s t a t i o n a r y s t a g e , i n d e p e n d e n t of the
c o n t e n t of the epoxy group, the r e g i o n of which became
l o n g e r as the f r a c t i o n of the p y r i d i n e i n c r e a s e d . The
s l o p e of the l i n e a r p a r t of the c u r v e o b t a i n e d f o r the
r e l a t i o n s h i p d e c r e a s e d w i t h i n c r e a s i n g the c o n t e n t of
the p y r i d i n e u n i t e x c e p t i n the i n i t i a l s t a g e of the
reaction. Then, the r a t e of d i s a p p e a r a n c e of the epoxy
group v a r i e s w i t h the mole f r a c t i o n of the epoxy group
and the o r d e r of r e a c t i o n w i t h r e s p e c t t o the c o n c e n t r a
t i o n of the epoxy group cannot be determined by t h i s
experiment. The t i m e - c o n v e r s i o n c u r v e s , however, are
s i m i l a r to those observed i n the t e r t i a r y a m i n e - c a t a -
l y z e d o l i g o m e r i z a t i o n of epoxy compounds (2), i n which
the r a t e i s f i r s t - o r d e r w i t h r e s p e c t t o the epoxy com
pound e x c e p t i n t h e i n i t i a l stage of the r e a c t i o n .
I f the r a t e of r e a c t i o n i s g i v e n as a f u n c t i o n of
the c o n c e n t r a t i o n s of the epoxy and the p y r i d y l groups,
the r a t e e q u a t i o n i s shown by:
- dM]/dt = k f(Μχ) g(M ) 2
and may be r e w r i t t e n a s :
- J d M i / f f M i ) = k g(M ) t i 2
where f ( M j ) and g(M ) a r e f u n c t i o n s of the c o n c e n t r a

2
t i o n s of the epoxide and the p y r i d i n e , k i s the r a t e

c o n s t a n t , and t i i s the r e a c t i o n time when the c o n v e r
s i o n of the epoxy group r e a c h e s i . Assuming t h a t g(M ) 2
i s c o n s t a n t under the c o n d i t i o n , we can o b t a i n

g(M ) t i = K i
2
where K i i s a c o n s t a n t shown by -[/dM^/f(Μχ)]/k.

Figure 5. Time-conversion curves for the epoxy group of poly[l-ethenyl-4-(2,3-

epoxy-l-propoxy)benzene] in KBr pellet at 105°C for copolymers with various
mole fractions of pyridine: (I) 0.274; (II) 0.399; (III) 0.584
EPOXY GROUPS REMAINING ( % )
Journal of Polymer Science, Polymer Letters Edition
Figure 6. Dependence of the rate of consumption of the epoxy group at 130°C

on the remaining epoxy group in copolymers obtained at reduced pressure with
various mole fractions of pyridine: (I) 0.258; (II) 0.502; (III) 0.597
Thus, v a r i o u s r e c i p r o c a l v a l u e s of the r e a c t i o n
t i m e t i , a t w h i c h t h e c o n v e r s i o n o f t h e epoxy g r o u p
reaches i , a r e p l o t t e d a g a i n s t the mole f r a c t i o n o f the
p y r i d i n e , M , as shown i n F i g u r e 7.
2 The r e a c t i o n r a t e
i n c r e a s e s with i n c r e a s i n g the c o n t e n t of the p y r i d y l
group, reaches a maximum v a l u e about a t 0.5 or 0.6, and
then d e c r e a s e s w i t h the f r a c t i o n of the p y r i d i n e . The
r i n g - o p e n i n g r e a c t i o n of the epoxy group i n these c o
p o l y m e r s may be c a r r i e d o u t i n t h e p r e s e n c e o f t h e
p y r i d y l group by the c o c a t a l y t i c a c t i o n o f the h y d r o x y l
group i n the polymer c h a i n . The mechanism o f t h i s s e l f -
c r o s s l i n k i n g r e a c t i o n o f t h e c o p o l y m e r s seems t o be
s i m i l a r to those (2^) proposed f o r the o l i g o m e r i z a t i o n o f
the epoxy compound and the c u r i n g of the epoxy r e s i n by
a t e r t i a r y amine. The r e a c t i v i t y d i f f e r e n c e i n these

self-crosslinking r e a c t i o n s between these copolymers
seems to be d e s c r i b e d m a i n l y by t h e p o l a r e f f e c t o f any
of the p o s s i b l e o r g a n i c m o i e t i e s of the copolymer e x c e p t
the epoxy group.
The r i n g - o p e n i n g r e a c t i o n o f the epoxy compound can
be g e n e r a l l y e x p l a i n e d by the m o d i f i e d T a f t e q u a t i o n ( 6 ) .
As a l i n e a r r e l a t i o n s h i p has been observed between the
p o l a r s u b s t i t u e n t c o n s t a n t o* and the b a s i c i t y o f e t h e r s
(2) t the r e a c t i v i t y towards n u c l e o p h i l i c s p e c i e s w i l l
d e c r e a s e and t h a t towards e l e c t r o p h i l i c r e a g e n t s may i n
c r e a s e as the b a s i c i t y o f the epoxy compound i n c r e a s e s ,
i . e . , as the σ* v a l u e d e c r e a s e s . The σ * v a l u e s f o r the
s u b s t i t u e n t s R [R=CH CHC6H40CH and C H C ( C H 3 ) C 0 C H ] o f
2 2 2 2 2
the epoxy compounds, OCH CHR, can not be found i n the

2
l i t e r a t u r e , but t h e i r r e l a t i v e o r d e r may be e s t i m a t e d
from those (σ*=0.600 and 1.9) (6>) f o r CgHs and CH3CO, σ *
f o r 1,2-epoxypropane (R=CH3) being 0. T h e r e f o r e , the
r e a c t i v i t y o f t h e epoxy group i n the copolymers o f 1-
ethenyl-4-(2,3-epoxy-l-propoxy)benzene can be c o n s i d e r e d
to be h i g h e r towards e l e c t r o p h i l i c s p e c i e s and t o be
lower towards n u c l e o p h i l i c compounds than t h a t i n the
copolymers o f 2 , 3 - e p o x y - l - p r o p y l m e t h a c r y l a t e . In the
self-crosslinking reaction, actually, the former was
c o n v e r t e d to the i n s o l u b l e m a t e r i a l s f a s t e r and a t a
lower temperature than the l a t t e r .
The pKa v a l u e s o f u n s u b s t i t u t e d , 2 - v i n y l and 4-
v i n y l p r i d i n e s a r e 5.17, 4.92-4.98, and 5.62 ( 2 ) · A
m e t h y l o r an e t h y l g r o u p i n 2- o r 6 - p o s i t i o n o f t h e
p y r i d i n e n u c l e u s causes an i n c r e a s e i n b a s i c i t y as w e l l
as t h a t i n 3- or 4 - p o s t i o n . Consequently, a similar
i n c r e a s e i n r a t e would be a n t i c i p a t e d i f the r a t e was
p r o p o r t i o n a l t o the b a s i c i t y o f t h e p y r i d y l group i n c o
polymers. N e v e r t h e l e s s , the r a t e of r e a c t i o n c a t a l y z e d
by 2 , 5 - d i s u b s t i t u t e d p y r i d y l group a r e n o t l a r g e r but
s m a l l e r than 2- or 4 - s u b s t i t u t e d p y r i d y l group as shown
12
10
0.2 0.1 0.6 0.8 1.0
VINYLPYRIDINE IN COPOLYMER
( MOLE FRACTION )
Figure 7. Effect of the mole fraction of pyridine on the reaction at 130°C of the
epoxy group in copolymers of l-ethenyl-4-(2,3-epoxy-l-propoxy) benzene (Φ, O,
Φ) or 2,3-epoxy-l-propoxy methacrylate (O) with various vinytpyridines. Where
10/tj at 30% conversion of the epoxy group is plotted: (Q) copolymers with 2-
vinylpyridine; (%) copolymers with 4-vinylpyridine; ((D) and Ο copolymers with
5-ethyl-2-vinylpyridine.
i n F i g u r e 7. T h i s might be a t t r i b u t e d t o the s t e r i c
e f f e c t o f any o f t h e p o s s i b l e o r g a n i c m o i e t i e s of the
copolymer e x c e p t the p y r i d y l group. The s i m i l a r i d e n
t i t y o f these r e s u l t s has been r e t a i n e d i n t h e r e a c t i o n
of 2 , 3 - e p o x y - l - p r o p y l phenyl e i t h e r w i t h b e n z o i c a c i d
c a t a l y z e d by s u b s t i t u t e d p y r i d i n e s and i n many o t h e r
reactions (2).
Synopsis
S o l u b l e and s e l f - c r o s s l i n k a b l e l i n e a r copolymers
w i t h pendant epoxy and p y r i d y l groups were o b t a i n e d from
l - e t h e n y l - 4 - ( 2 , 3 epoxy-l-propoxy) benzene or 2,3-epoxy-l-
p r o p y l m e t h a c r y l a t e and v i n y l p y r i d i n e s by t h e a c t i o n o f
2,2'-azoisobutyronitrile. The monomer r e a c t i v i t y r a t i o s

were determined i n t e t r a h y d r o f u r a n a t 60°C, and the Q
and e v a l u e s f o r these e p o x i d e s were c a l c u l a t e d w i t h t h e
r e p o r t e d Q-e v a l u e s f o r these p y r i d i n e s . The i n t r i n s i c
v i s c o s i t i e s o f t h e copolymers were found t o be 0.15-0.38
i n t e t r a h y d r o f uran a t 30°C and t o be dependent on the
copolymer c o m p o s i t i o n . The copolymers were amorphous,
had no c l e a r m e l t i n g p o i n t s , and became i n s o l u b l e c r o s s -
l i n k e d polymers under h e a t i n g w i t h o u t f u r t h e r a d d i t i o n
o f any c u r i n g a g e n t s . The r e a c t i v i t y d i f f e r e n c e i n
these s e l f - c r o s s l i n k i n g r e a c t i o n s among these copolymers
was d e s c r i b e d by t h e s t e r i c as w e l l as t h e p o l a r e f f e c t
of any o f t h e p o s s i b l e o r g a n i c m o i e t i e s o f t h e c o p o l y
mers.
Literature Cited
1. Tanka, Y; Okada, A; Tomizuka, I.,in "Epoxy Resins";

May, C. A., Tanaka, Y . , E d . ; Dekker: New York, 1973;
Chap. 2.
2. Tanaka, Y.; M i k a , T . F., i n "Epoxy R e s i n s " ; May,
C. Α . , Tanaka, Y., E d . ; Dekker: New Y o r k , 1973;
Chap. 3.
3. Mayo, F . R . ; L e w i s , F . M . , J. Amer. Chem. S o c . ,
1944, 66, 1594.
4. P r i c e , C . C., J. Polym. Sci., 1948, 3, 772.
5. Tamikado, T., J. Polym. Sci., 1960, 43, 489.
6. T a f t , R. W. Jr., i n " S t e r i c E f f e c t s i n Organic
Chemistry"; Newman, M. S . , E d . ; W i l e y : New Y o r k ,
1956; Chap 13.
7. P e r r i n , D. D. E d . , " D i s s o c i a t i o n Constants of
Organic Bases in Aqueous Solution"; Butterworths:
London, 1965.

15
Some Studies on the Preparation of Glycidyl
2-Ethylhexanoate
D. A. CORNFORTH, B. G. COWBURN, Κ. M. SMITH,

C. W. STEPHENS, and C. G. TILLEY
Anchor Chemical Company Ltd., Clayton, ManchesterM114SR, England
The preparation of glycidyl 2-ethylhexanoate has been

studied in order to gain an insight into the general mechanism
of the reaction of epichlorohydrin with carboxylic acids. The
investigation was carried out in two stages. The first stage
of the reaction involves the catalysed addition of 2-ethyl-
hexanoic acid to epichlorohydrin to yield 2-hydroxy-3-chloropro-
pyl 2-ethylhexanoate. The reaction is then completed by de-
hydrochlorination of 2-hydroxy-3-chloropropyl 2-ethyl-hexanoate
to yield glycidyl 2-ethylhexanoate (Fig. 1). This compound
was selected in order to give intermediates and products of
acceptable volatility to allow gas chromatography to be used as
the principal analytical tool.
Results and Discussion
Reaction of Epichlorohydrin with 2-Ethylhexanoic

Acid
The cetyl trimethy1ammonium bromide catalysed addition of

epichlorohydrin to 2-ethylhexanoic acid has been studied at
levels of 1, 5 and 7 molar ratios of epichlorohydrin to 2-
ethylhexanoic acid. The reactions were carried out in toluene
in order to facilitate removal of water from the final product
(glycidyl 2-ethylhexanoate) by azeotropic distillation. A
further advantage in using toluene as solvent is that where
glycidyl esters of high molecular weight are being considered
the solution viscosities may be kept sufficiently low to effect
filtration, i f required, before final distillation. The
reaction products were determined by gas chromatography. The
rate of consumption of the starting materials was also
determined by gas chromatography and other standard analytical
techniques.
0-8412-0525-6/79/47-114-211$05.00/0
Figure 2. Reaction of epichlorohydrin with 2-ethylhexanoic acid (1:1 mol ratio)

15. CORNFORTH ET AL. Glycidyl 2-Ethylhexanoate 213
1;1 Molar Ratio of E p i c h l o r o h y d r i n to 2-Ethylhexanoic A c i d
The concentration-time curve f o r the reactants i s shown i n

F i g . 2, and the concentration-time curve f o r the products i s
depicted i n F i g . 3. Examination of F i g . 3 shows that as w e l l
as the d e s i r e d r e a c t i o n product (the c h l o r o h y d r i n e s t e r ) , there
are two other major product components. These were i d e n t i f i e d
as 1,3-dichloropropan-2-ol (OL-dichlorohydrin) and g l y c e r o l -
1,3-di(2-ethylhexanoate) (hydroxy d i e s t e r ) . The s t r u c t u r e of
the hydroxy d i e s t e r was confirmed by i t s independent synthesis
from g l y c i d y l 2-ethyl hexanoate and 2-ethyl hexanoic a c i d . The
y i e l d of c h l o r o h y d r i n e s t e r was only 50.4%, the remainder of the
2-ethylhexanoic a c i d being converted to the undesirable hydroxy
diester. F i g . 4 shows the s t r u c t u r e of the products obtained
i n the 1:1 r e a c t i o n . F i g . 5 d e p i c t s the formation of the

hydroxy d i e s t e r from g l y c i d y l 2-ethylhexanoate and 2 - e t h y l -
hexanoic a c i d .
A mechanism which i s c o n s i s t e n t with the experimental
observations f o r the production of the c h l o r o h y d r i n e s t e r i s
given i n F i g . 6. The f i r s t stage of the r e a c t i o n i n v o l v e s
i o n i s a t i o n of 2-ethylhexanoic a c i d by the c a t a l y s t c e t y l t r i -
methy1ammonium bromide. Subsequent attack of the carboxyanion
on e p i c h l o r o h y d r i n leads u l t i m a t e l y to the d e s i r e d r e a c t i o n
product of the f i r s t stage of the r e a c t i o n . Examination of
F i g . 3 shows that the r a t e of formation of O^-dichlorohydrin and
the hydroxy d i e s t e r c l o s e l y f o l l o w each other i n d i c a t i n g that
t h e i r formation i s interdependent. The by-product formation
seems best accommodated by the mechanism shown i n F i g . 7 which
involves breakdown of the intermediate chloro-oxy anion by
i n t e r n a l n u c l e o p h i l i c displacement, to y i e l d g l y c i d y l 2 - e t h y l -
hexanoate. The g l y c i d y l 2-ethylhexanoate subsequently r e a c t s
with the carboxyanion to y i e l d u l t i m a t e l y the hydroxy d i e s t e r .
TheOC-dichlorohydrin may be formed by c h l o r i d e i o n attack on
e p i c h l o r o h y d r i n with subsequent p r o t o n a t i o n of the dichloro-oxy
anion.1" Further evidence f o r t h i s mechanism i s a l s o provided
by the d i r e c t synthesis of the hydroxy d i e s t e r from g l y c i d y l 2-
ethylhexanoate and 2-ethylhexanoic a c i d ( F i g . 5 ) . I t i s also
p o s s i b l e that the c h l o r o h y d r i n may break down thermally to give
the undesirable by-products ( F i g . 8).
Summary of 1:1 Reaction
The r e a c t i o n of e p i c h l o r o h y d r i n with 2-ethylhexanoic a c i d

i n a 1:1 molar r a t i o gives r i s e to only 50% of the d e s i r e d
product, the c h l o r o h y d r i n e s t e r . The mechanism depicted above
i n d i c a t e s that the undesirable hydroxy d i e s t e r i s formed by
r e a c t i o n of 2-ethylhexanoic a c i d with g l y c i d y l 2-ethylhexanoate.
I t appears therefore that formation o f the hydroxy d i e s t e r
competes d i r e c t l y with the c h l o r o h y d r i n e s t e r formation ( F i g . 9 ) .
2-5 h
J I I I ' ι ι I I I I
0 1 2 3 4 5 6 7 8 9 10 11
REACTION TIME - HRS
Figure 3. Reaction of epichlorohydrin with 2-ethylhexanoic acid (1:1 mol ratio;

product composition)
(?)
w
R - C O - O - C H 2 - C H - CH 2
I I
OH C£
1
2-HYDROXY - 3 CHLOROPROPYL - 2·ETHYLHEXANOATE (
^CHLOROHYDRIN^
@ C!-CH -CH-CH -Ci

2 2
OH
1,3 - DICHLOROPROPAN -2 -OL
*α - DICHLOROHYDRIN^cc-DCH
(3) R -CO-O-CH2-CH-CH2-O-CO-R
OH
GLYCEROL -1,3- Dl -^2 - ETHYLHEXANOATE^

r 1
HYDROXYDIESTER H DE
Figure 4. Product structures

CORNFORTH ET AL. Glycidyl 2-Ethylhexanoate
RC0 H +RCO2 C H C H - C H — • R C 0 C H
2 2 2 2 2 CHCH C0 R 2 2
V O'H
R = C H g 0 CH -
4
C H 2 5
Figure 5. Glycerol-l,3-di-2-ethylhexanoate synthesis

1 1·
R*NBr + CH2-CH-CH2CI • BrCHi-CH-CHiCI + R4N
Br C H - C H -CH2CI + R C0 H
2 2 • B r C H - CH - C H C I 2 2 +RCcf 2
θ
Ο OH
CH -CH-CH CI
2 2 + RCO® • R C0 - CH - CH -CH CI
2 2 Z
\ /
0
J RCO H[° 2
RC0 2 + R C 0 - C H - CH-CH2CI
2 2
I
OH
Figure 6. Proposed reaction mechanism Part A
RCO2- C H - C H - C H c T - 2 2
/ %
->RC0 -CH -CH-CH +Cl
2 2 2
RCO® V
ECH
|R=CH CH CH CH CH (C H,)-J
3 2 2 2 2 CICH CHCH CI 2 2
I
RC0 CH CHCH 0 CR
2 2 2 2
I
O ft
RCO2H
RC0 H 2
R C0 + R C0 CH CH CH 0 CR «
2 2 2 2 2 CICH CHCH CI + RC0
2 2 2
OH OH
Figure 7. Proposed reaction mechanism Part Β

R C 0 C H C H C H Cl
2 2 2 • R C0 2 C H CH C H +2 2 HCI
I \ /
OH , 0
ECH
RC0 H 2
RC0 CH CHCH
2 2 2 0 2 CR 4- CICH2 CHCHi CI
I I
OH OH
Figure 8. By-product formation
C H - C H C H CI
2 2
V
- • R C0 2 C H CH C H C I
2 2
I
OH
R CO2 H H
- • R C0 CH 2 2 CH C H C 0 R
2 2
I
OH
R C0 2 CH C H - C H
2 2
V
Figure 9. Competition reaction
CHLOROHYDRIN
REACTION TIME - HRS
15. CORNFORTH E T A L . Glycidyl 2-Ethylhexanoate 217
I t i s apparent t h e r e f o r e that an increase i n the e p i -

c h l o r o h y d r i n concentration should promote the formation of the
c h l o r o h y d r i n e s t e r , at the expense of the hydroxy d i e s t e r .
5:1 and 7:1 Molar Ratio of E p i c h l o r o h y d r i n to 2-ethylhex-

anoic a c i d
The concentration-time curve f o r the products of the 5:1

r e a c t i o n are shown i n F i g . 10 and that f o r the 7:1 r e a c t i o n
depicted i n F i g . 11. As expected the c h l o r o h y d r i n e s t e r i s
produced almost e x c l u s i v e l y a t the expense of the hydroxy
d i e s t e r , the y i e l d of the l a t t e r compound being reduced to 2.9%
i n the 5:1 r e a c t i o n and 1.4% i n the 7:1 r e a c t i o n (ca 50% i n the
1:1 r e a c t i o n ) .
Examination of F i g s . 10 and 11 show that the c h l o r o h y d r i n
e s t e r formation reaches a maximum a f t e r 3 to 4 hours, t h i s
maximum c o i n c i d i n g with the consumption o f a l l the 2—ethylhex—
anoic a c i d . I n t e r e s t i n g l y i f the r e a c t i o n i s allowed to
continue f o r an excess p e r i o d the concentration of the c h l o r o -
h y d r i n e s t e r begins to decrease i n the r e a c t i o n mixture. The
decrease i n c h l o r o h y d r i n e s t e r concentration i s concomitant
with the formation of g l y c i d y l 2-ethylhexanoate and i s
accompanied by the formation ofOC-dichlorohydrin. This shows
that the c h l o r o h y d r i n i s breaking down (thermally or
c a t a l y t i c a l l y ) as depicted i n F i g . 12. At t h i s p o i n t i n the
r e a c t i o n a l l the a c i d has been consumed and i t i s t h e r e f o r e not
a v a i l a b l e to underto f u r t h e r r e a c t i o n with the epoxy compound
to give the hydroxy d i e s t e r as i n the 1:1 r e a c t i o n .
At f i r s t s i g h t i t may not seem undesirable to allow the
r e a c t i o n to continue, i n order to allow conversion o f the
c h l o r o h y d r i n e s t e r to the epoxy compound ( F i g . 12) as the
u l t i m a t e aim i s , i n f a c t , to form g l y c i d y l 2-ethylhexanoate by
r i n g c l o s u r e of the c h l o r o h y d r i n e s t e r intermediate. However
i t was noted that formation of the epoxy compound i s
accompanied by formation o f 0 ( ^ d i c h l o r o h y d r i n , and i t was shown
i n a separate experiment that f u r t h e r r e a c t i o n of these two
compounds could be e f f e c t e d under the r e a c t i o n c o n d i t i o n s ,
probably g i v i n g r i s e to f u r t h e r undesirable by-products ( F i g .
13).
Conclusion
The products formed during the r e a c t i o n of e p i c h l o r o h y d r i n

with 2-ethylhexanoic a c i d are governed by the r e l a t i v e
concentrations of the two r e a c t a n t s . E p i c h l o r o h y d r i n must be
present i n excess i n order to achieve a high y i e l d of c h l o r o -
hydrin e s t e r . In order to optimise the y i e l d of c h l o r o h y d r i n
e s t e r the r e a c t i o n must be terminated when a l l the a c i d has
been consumed otherwise the r e a c t i o n i s complicated by
decomposition and f u r t h e r r e a c t i o n s of t h i s m a t e r i a l .
CHLOROHYDRIN
2 3 A 5 6
REACTION TIME - HRS
R C0 CH 2 2 CH C H C I - 2 • R C0 2 C H 2 C H - C H 2 + H* + cf
I \ /
OH Ο
C H 2 - C H C H 2 C I + H* + C I 6
— • C I C H Î C H C H 2 C I
1
\ /
Ο OH
Figure 12. Chlorohydrin ester decomposition
INTRACTABLE
R C 0 C H CH - C H + ( θ C H ) CH OH
2 2 2 2
LIQUID
V
Figure 13. Further by-product formation
Stage I I Ring Closure Reaction
In order to study the r i n g c l o s u r e r e a c t i o n i n d e t a i l a

masterbatch of the c h l o r o h y d r i n ester was prepared i n 50%
toluene s o l u t i o n using a 5:1 molar excess of e p i c h l o r o h y d r i n to
2-ethylhexanoic a c i d .
The f i r s t r i n g c l o s u r e process i n v e s t i g a t e d used a
technique whereby 50% aqueous sodium hydroxide was added at a
constant r a t e under c o n d i t i o n s where the water was removed by
azeotropic d i s t i l l a t i o n with the excess e p i c h l o r o h y d r i n and
toluene s o l v e n t , g i v i n g a d e h y d r o c h l o r i n a t i o n under e s s e n t i a l l y
anhydrous c o n d i t i o n s . F i g . 14 shows the conversion of
c h l o r o h y d r i n e s t e r to g l y c i d y l 2-ethylhexanoate using two
d i f f e r e n t rates of a d d i t i o n of sodium hydroxide s o l u t i o n (0.25
mol. h r . ~ l and 0.125 mol. h r . ~ " l ) . E x c e l l e n t conversion to

g l y c i d y l 2-ethylhexanoate was obtained which may be seen to be
r e l a t i v e l y independent of the r a t e of sodium hydroxide a d d i t i o n .
However i n order to a t t a i n high y i e l d s (>99%) i t may be seen
that 40-50% excess (based on c h l o r o h y d r i n ester) sodium
hydroxide was r e q u i r e d .
The e p i c h l o r o h y d r i n concentration was a l s o followed during
the r e a c t i o n and i t can be seen ( F i g . 14) that t h i s component
was a l s o consumed during the r i n g c l o s u r e r e a c t i o n (12-14%
conversion). I t can be seen therefore that e p i c h l o r o h y d r i n
competes with the c h l o r o h y d r i n e s t e r f o r sodium hydroxide during
the d e h y d r o c h l o r i n a t i o n r e a c t i o n . Two competing r e a c t i o n s are
e s s e n t i a l l y taking place and indeed i t was found that the
excess sodium hydroxide r e q u i r e d was d i r e c t l y a t t r i b u t a b l e to
h y d r o l y s i s of e p i c h l o r o h y d r i n . Epichlorohydrin hydrolysis i s
h i g h l y undesirable i n the r i n g c l o s u r e r e a c t i o n as i t leads to
polymer formation i n the f i n a l product(2,3).
The polymeric m a t e r i a l was i s o l a t e d from the r e a c t i o n
mixture as a c o l o r l e s s water i n s o l u b l e m a t e r i a l . The polymer
was t e n t a t i v e l y assigned the c r o s s - l i n k e d s t r u c t u r e depicted i n
F i g . 15 based on mass spectrometric evidence. Interestingly
the mass spectrum d i d not show any c h l o r i n e c o n t a i n i n g
s t r u c t u r e s i n the polymer showing that sodium hydroxide was i n
f a c t h y d r o l y s i n g the c h l o r i n e atom of e p i c h l o r o h y d r i n e i t h e r
before or a f t e r p o l y m e r i s a t i o n .
In an attempt to overcome e p i c h l o r o h y d r i n h y d r o l y s i s i n
the r i n g c l o s u r e r e a c t i o n an a l t e r n a t i v e approach using sodium
hydroxide/sodium carbonate s o l u t i o n was sought. A patent(4)
i s held by the Dow Chemical Company which describes the use of
a s o l u t i o n of an a l k a l i metal hydroxide and an a l k a l i metal
carbonate to e f f e c t d e h y d r o c h l o r i n a t i o n . The patent claims
that using t h i s technique e p i c h l o r o h y d r i n h y d r o l y s i s i s g r e a t l y
reduced. A c c o r d i n g l y t h i s technique was i n v e s t i g a t e d whereby
a mixture c o n t a i n i n g sodium carbonate (9.8%), sodium hydroxide
(15.7%) and water (74.5%) was s t i r r e d with the c h l o r o h y d r i n
e s t e r masterbatch prepared above. The r e a c t i o n was studied i n
MOLE RATIO-SODIUM HYDROXIDE TO CHLOROHYDRIN
Figure 14. Conversion of chlorohydrin and epichlorohydrin in the presence of

sodium hydroxide under azeotropic conditions: ( ) NaOH added 0.25 mol/hr;
( ) NaOBadded 0.125 mol/hr
CH f 2
CH 2
I
Ο CH CH
Χ-£θ CH 2
CH
J—F 2
0 CH 2 CH - -
X=C H,CHC0
4 or ( C H , CHCC0
4
H - CH
~ *) 2
2 2 CHO -
C H 2 5
C H
2 5
Figure 15. Polymer isolated from product

15. coRNFORTH ET AL. Glycidyl 2-Ethylhexanoate 221
d e t a i l at 40°C and 75°C using a molar r a t i o of sodium

hydroxide to c h l o r o h y d r i n e s t e r of 2:1. The r e a c t i o n s were
monitored by gas chromatography. F i g . 16 shows the r a t e of
conversion of c h l o r o h y d r i n e s t e r to g l y c i d y l 2-ethylhexanoate
and the r a t e of e p i c h l o r o h y d r i n h y d r o l y s i s at both
temperatures.
I t may be seen that at 75°C e p i c h l o r o h y d r i n h y d r o l y s i s i s
i n f a c t the major r e a c t i o n (51.7% conversion) and that only
30% conversion to g l y c i d y l 2-ethylhexanoate i s obtained. The
graph c l e a r l y shows that at 75°C the low y i e l d i s not due to
consumption of the c h l o r o h y d r i n ester i n an undesirable
manner, but i s simply due to removal of sodium hydroxide by
r a p i d h y d r o l y s i s of e p i c h l o r o h y d r i n . The r e a c t i o n at 40°C was
more encouraging. A f t e r 6.5 hours, at which time a l l the
sodium hydroxide had been consumed, a 75% conversion of

c h l o r o h y d r i n e s t e r to g l y c i d y l 2-ethylhexanoate was obtained.
However, i t can be seen that even at 40°C e p i c h l o r o h y d r i n
h y d r o l y s i s i s o c c u r r i n g (15.6% conversion) and a l a r g e amount
of sodium hydroxide i s consumed i n t h i s r e a c t i o n .
The organic phase from the above r e a c t i o n was removed and
r e t r e a t e d with a f u r t h e r p o r t i o n of the sodium hydroxide/
sodium carbonate mixture and the r e a c t i o n continued at 40 C.
A high conversion to g l y c i d y l 2-ethylhexanoate was u l t i m a t e l y
achieved by t h i s technique (>99%) although by t h i s time the
e p i c h l o r o h y d r i n h y d r o l y s i s (24.3%) was considered to be too
high f o r t h i s method to be used commercially.
In an attempt to reduce the o v e r a l l e p i c h l o r o h y d r i n
h y d r o l y s i s the e f f e c t of removal of t h i s component from the
r e a c t i o n system was i n v e s t i g a t e d . A sample of the above
r e a c t i o n mixture was removed a f t e r the i n i t i a l treatment w i t h
sodium hydroxide/sodium carbonate s o l u t i o n and the excess
e p i c h l o r o h y d r i n and toluene removed by vacuum d i s t i l l a t i o n .
The r e s u l t i n g mixture of c h l o r o h y d r i n e s t e r and g l y c i d y l 2-
ethylhexanoate was r e s o l v a t e d with toluene and r e t r e a t e d with
a f u r t h e r p o r t i o n of sodium carbonate s o l u t i o n at 40 C.
However i t was found that no f u r t h e r conversion of the
c h l o r o h y d r i n e s t e r to epoxy compound was obtained i n d i c a t i n g
that e p i c h l o r o h y d r i n i s required i n the r e a c t i o n system to
effect r i n g closure.
Indeed, i n a patent h e l d by the Dow Chemical Company(1)it
i s observed that e p i c h l o r o h y d r i n (or other s u i t a b l e 1,2-
epoxide) i s r e q u i r e d i n order to o b t a i n high y i e l d s of
g l y c i d y l esters from 2-hydroxy-3-chlorophenyl e s t e r s . A
mechanism i n v o l v i n g transepoxidation was proposed ( F i g . 17).
No polymer formation was observed i n the above r e a c t i o n ;
however, some water s o l u b l e organic components were detected
by gas chromatography which were presumably derived from
h y d r o l y s i s of e p i c h l o r o h y d r i n . A n a l y s i s of the aqueous
residues showed that the sodium carbonate was e s s e n t i a l l y
unchanged during the r e a c t i o n , which lead to examination of
Figure 16. The % conversion of chlorohydrin and % epichlorohydrin consumed

at 40°C and 75° C in sodium hydroxide/sodium carbonate aqueous solution
RCOOCH 2 CHCH 2 CI CH -CHR

2
I \ /
OH 0
R CO 0 CH2 CH - C H 2 R CH CH^CI
I
V OH
R —C<H9 CH — R= Η,ΟΗΐ CI, etc

C 2 H 5
Figure 17. Transepoxidation reaction
Figure 18. Product composition in aqueous sodium hydroxide at40°C

the use of aqueous sodium hydroxide alone to e f f e c t r i n g

closure.
A c c o r d i n g l y , sodium hydroxide (17% aqueous s o l u t i o n ) was
s t i r r e d with the c h l o r o h y d r i n e s t e r masterbatch prepared above.
The r e a c t i o n was followed at 40°C using a molar r a t i o of sodium
hydroxide to c h l o r o h y d r i n e s t e r of 2:1. The r e a c t i o n was
followed by gas chromatography. F i g . 18 shows the rates of
conversion of e p i c h l o r o h y d r i n and c h l o r o h y d r i n e s t e r during the
reaction. Again, i t was shown that a f t e r 6.5 hours a l l the
sodium hydroxide had been consumed ( c f . sodium hydroxide/sodium
carbonate r e a c t i o n at 40°C) at which time only 64% conversion
to the epoxy compound was observed. Correspondingly the
e p i c h l o r o h y d r i n h y d r o l y s i s (25%) had increased i n comparison to
the sodium hydroxide/sodium carbonate method (15.6% at 40 C).
In order to continue the comparison of the aqueous sodium

hydroxide d e h y d r o c h l o r i n a t i o n with the aqueous sodium hydroxide/
sodium carbonate method the organic phase from the above
r e a c t i o n was removed and r e t r e a t e d with aqueous sodium
hydroxide (a f u r t h e r 2 molar excess). U l t i m a t e l y a 98%
conversion to g l y c i d y l 2-ethylhexanoate was achieved but by
t h i s time very extensive e p i c h l o r o h y d r i n h y d r o l y s i s had
occurred (56%). I t was a l s o found d i f f i c u l t to separate the
organic phase from t h i s r e a c t i o n due to e m u l s i f i c a t i o n with the
aqueous phase i n order to c a r r y out the f i n a l p u r i f i c a t i o n
stage by d i s t i l l a t i o n .
Conclusion
Three techniques were evaluated f o r the r i n g c l o s u r e

reaction:
1. Aqueous sodium hydroxide/sodium carbonate

2. Aqueous sodium hydroxide
3. Azeotropic system
In aqueous systems i t was shown that a temperature of 40 C was

most p r a c t i c a l . At higher temperatures e p i c h l o r o h y d r i n
h y d r o l y s i s was too r a p i d to give r i s e to a v i a b l e process.
Although at 40 C good conversion to the g l y c i d y l e s t e r could be
obtained, a high p r o p o r t i o n of sodium hydroxide (based on
chlorohydrin) had to be used (up to 4 molar e x c e s s ) . However
even at 40 C the h y d r o l y s i s of e p i c h l o r o h y d r i n was a serious
competitive r e a c t i o n to the r i n g c l o s u r e . The e p i c h l o r o h y d r i n
h y d r o l y s i s using a mixture of sodium carbonate/sodium hydroxide
was considerably reduced i n comparison to that obtained by
using sodium hydroxide (24.3% i n the former r e a c t i o n : 56% with
NAOH). This i s i n agreement with the Dow patent.
The best technique for ring closure evaluated to date

involves continuous addition of 50% aqueous sodium hydroxide to
the reaction mixture at such a rate that water may be obtained
by azeotropic d i s t i l l a t i o n . Although polymeric material i s
formed during the reaction this can be removed, along with the
salt formed during dehydrochlorination, prior to isolation of
the glycidyl ester by d i s t i l l a t i o n .
Future Process Optimisation
Modifications to the above techniques may be envisaged for

process improvement. In the above reactions epichlorohydrin
is present in excess after the i n i t i a l formation of the
chlorohydrin ester (4 molar excess) as a consequence of the
requirements of the stage I reaction. However i t has been

shown that epichlorohydrin hydrolysis competes with the
required reaction in stage II of the process. It would
therefore be desirable to reduce the concentration of
epichlorohydrin prior to ring closure. It has however been
shown that epichlorohydrin i s required to effect ring closure
(transepoxidation) and work i s in hand to optimise the
concentration of this component during the dehydrochlorination
reaction.
LITERATURE CITED
1. D. R. Smith, U.S. Patent 3,335,156 (1967)
2. I. Ondus, Chem Prum., 21 (4), 168 (1971)
3. L. N. Finyakin, V. V. Kafarov, M. F. Sorokin,

L. G. Shode and G. V. Onosov, Tr. Mosk.Khim. -
-Teknol. Inst., No. 70, 80 (1972).
4. D. R. Smith, U.S. Patent 3,372,142 (1968).

16
Reactions in a Typical Epoxy-Aliphatic Diamine System
JOHN J. KING and JAMES P. BELL

University of Connecticut U-139, Storrs, CT 06268
A large amount of work has been reported in the literature

concerning the nature of the reaction of epoxides with aliphatic
amines (1-12). Schecter, Wynstra and Kurkjy (1) suggested that
only reactions (1), (2) and (3) need be considered in the ab-
sence of strong tertiary amines:
Of these, they determined (3) was negligible for most near-

-stoichiometric amine concentrations, leaving (1) and (2) with
rate constants k and k respectively.
1 2
Ingbermand and Walton (2) found that the secondary alipha-

tic amino hydrogen reacted as readily as the primary. This is
in contrast to Oshior et al, (3,4) Harrod, (5) Kakurai et al, (6)
and Isaacs and Parker (7) who found an unequal activity of pri-
mary and secondary amino groups to epoxy.
The difference in activity among various amines may be
attributed to steric hinderances of and substituent groups on the
reactants. Kakurai et al (6) found a decrease in reactivity of
amines as the bulkiness of the side chains increased. Data
collected by Iwakura et al, (8) Allen et al (9) and Ingberman
et al (2) suggest that hydroxyl substituted amines react more
readily by forming a reactive transition state, reaction (4).
0-8412-0525-6/79/47-114-225$08.25/0
An i n c r e a s e i n consumption of r e a c t a n t s has been noted i n

the presence of c e r t a i n Lewis a c i d s . This c a t a l y t i c e f f e c t has
been r e l a t e d t o the p K v a l u e s of the v a r i o u s groups, w i t h a c t i
a
v i t i e s arranged as: a c i d s > phenols > water > a l c o h o l s

n i t r i l e s > aromatic > hydrocarbons > dioxane > d i i s o p r o p y l e t h e r
(6,10). The a l c o h o l s a r e included i n t h i s l i s t due to t h e i r
weakly a c i d i c nature. The a c c e l e r a t i n g e f f e c t of a l c o h o l s i s de
pendent on s t r u c t u r e : methanol > ethanol > n-propanol > t e r t -
butanol > n-butanol > i s o b u t a n o l > cyclohexanol (6,10).
I t was suggested by Harrod (5) that the r a t i o k 2 / M i s
v i r t u a l l y independent of temperature and composition but depen
dent on the amine and epoxide used. Dusek et a l (11) s t a t e that
ki and k2 depend on the a u t o c a t a l y t i c e f f e c t of the hydroxyls and
r e t a r d a t i o n caused by hydroxyl complexing with amine hydrogens

but present no evidence to support t h i s statement. They a l s o
mention data to support the constancy of k2/ki«
The presence of hydroxyl groups during the r e a c t i o n should
be included w i t h i n the r a t e e x p r e s s i o n s . Schecter e t a l (1) f i r s t
proposed a termolecular mechanism to d e s c r i b e the e f f e c t of
hydroxyl groups on the r e a c t i o n , r e a c t i o n s (5) and ( 6 ) .
1 ?
R NH + C ^ R
2 + HO-X -> R NH
2 C-C-R (5)
0
HO-X
! T
R NH-
0 C-CR -+ R NC-CR 0 + HO-X (6)
2 v/ 2 ι
0 OH
HO-X
In t h i s system, hydroxyl groups i n the solvent a c c e l e r a t e the

epoxy r i n g opening by hydrogen bonding to the epoxy group during
transition.
Smith (10) proposed a v a r i a t i o n of t h i s mechanism. He
suggests that a hydrogen bond forms between the a c i d and the oxy
gen on the epoxide r i n g followed by a three molecule t r a n s i t i o n
s t a t e which i s r a t e determining, r e a c t i o n s ( l a ) , ( l b ) and ( l c ) ,
F i g u r e 1.
(la)
(lb)
16. KING AND BELL Epoxy-Aliphatic Diamine System 227
•£R' slow M HX (lc)

fasÇ £ *
R
+
Figure 1.
More r e c e n t l y Mika and Tanaka (12) suggested a mechanism

based on the hydrogen bonding of amine to a hydrogen donor, re-
a c t i o n s (2a) , (2b) and (2c) .
R NH + HX ^
2 [R NH- · - HX]
2 (2a)
f
[R NH---HX] + (^£R
2 ^ ^R^.-.C^-CR^ (2b)
R N f
£ 2 |" " * R N-C-£R
2 + HX (2c)
Figure 2.
This system i s supported by the work of Iwakura et a l (8) who

studied the r e a c t i o n of amines and epoxide i n a c r y l o n i t r i l e -
g l y c i d y l methacrylate copolymers. An a c c e l e r a t i n g e f f e c t by
formed hydroxyl groups was noted but the cyano group, which should
r e t a r d a c t i v i t y , by the hypothesis of Smith, acted as an a c c e l -
e r a t o r by i t s i n t e r a c t i o n w i t h amine. Harrod (13) observed
hydrogen bonding i n epoxy-amine systems w i t h both n i t r o g e n and
oxygen. E q u i l i b r i u m hydrogen bonding would be more favorable be-
tween hydroxyl and amine groups than epoxy and hydroxyls due to
the d i f f e r e n c e i n b a s i c i t y . I t was a l s o found that epoxy reacted
more r e a d i l y when the added water was equal to amine.
Mika and Tanaka a l s o suggested that i f r e a c t i o n (10) occurs,
then the r e t a r d a t i o n e f f e c t caused by maleic and p h t h a l i c a c i d s ,
ketones and e s t e r s may be a t t r i b u t e d to formation of imides,
ketimines and amides. The i n h i b i t i o n caused by dioxane, t e t r a -
hydrofuran and d i i s o p r o p y l ethers may be a t t r i b u t e d to the f a c t
that the (R2NH*··ΗΧ) r e a c t s w i t h ethers to y i e l d a complex,
thereby preventing the epoxides from r e a c t i n g . T h i s would be
expected because the four, f i v e and s i x member r i n g s are b e t t e r
hydrogen donors than three component epoxy r i n g s .
This r e p o r t compares the three mechanisms i n l i g h t of data
c o l l e c t e d f o r an Epon 828/diaminobutane epoxy system. I t a l s o
s t u d i e s the e f f e c t of low molecular weight hydroxyl groups on
the mechanisms and r a t e of r e a c t i o n .
Experimental
M a t e r i a l s . The d i g l y c i d y l ether of bisphenol A, DGEBA,

(Epon 828) (Registered trademark of S h e l l Chemical Co.), having
the s t r u c t u r e shown i n S t r u c t u r e 1 (n - 0.2) was used i n a l l
tests.
Structure 1
The r e s i n was placed i n a vacuum of 30 i n Hg f o r two hours, then

sealed i n a n i t r o g e n atmosphere. Resin with a higher hydroxyl
content was prepared i n a s i m i l a r manner except before s e a l i n g
the b o t t l e , i s o p r o p y l a l c o h o l (Reagent, Lehigh V a l l e y Chemical)
was added. C h a r a c t e r i z a t i o n of these m a t e r i a l s by a modified
procedure of K n o l l et a l (14) gave the epoxide content, Table I .
Hydroxyl content was c a l c u l a t e d from the s t r u c t u r a l formula.
These epoxy values were used to determine the s t o i c h i o m e t r i c

r a t i o s of c u r i n g agent.
1-4, Diaminobutane, DAB ( A l d r i c h ) , Di-n-Butylamine, DBA
( A l d r i c h ) , and Tri-n-Butylamine, TBA (Eastman Organic Chemicals),
were used as c u r i n g agents. Each was d i s t i l l e d under Helium a t
one atmosphere and s e a l e d . The amine a n a l y s i s of C r i t c h f i e l d
and Johnson (15)was conducted to determine p u r i t y , Table I . The
p u r i t y and the t h e o r e t i c a l equivalence were used to determine
the weight of amine needed f o r a given weight of r e s i n .
Curing Process. Two to f i v e grams of r e s i n were weighed

i n t o a 10 m i l l i l i t e r beaker. The a p p r o p r i a t e amount of amine
was added and mixed thoroughly by s t i r r i n g with a s p a t u l a f o r
30 seconds. T h i s mixture was placed i n s e v e r a l 1 cc syringes
which served as batch r e a c t o r s during the cure.
Every h a l f hour, 0.5 to 1.0 m i l l i l i t e r of sample was added
to a reagent s o l u t i o n f o r a n a l y s i s . A l l reagent s o l u t i o n s used
stopped the cure almost immediately. .The s y r i n g e was weighed
before and a f t e r the a d d i t i o n to o b t a i n the exact sample weight.
For these s t u d i e s i t was d e s i r a b l e to maintain a constant
temperature of about 22° C (room temperature). Since the amine-
epoxy p o l y m e r i z a t i o n i s an exothermic process, the syringes must
have s u f f i c i e n t s u r f a c e area to d i s s i p a t e the evolved heat
r a p i d l y . Tests with Leeds and Northrup Potentiometer and a small
alumel-chromel thermocouple, i n s e r t e d i n t o the center of the
s y r i n g e , showed a maximum temperature r i s e of l e s s than 2° C
during the e n t i r e r e a c t i o n time. T h i s was s u f f i c i e n t l y small to
assume that isothermal c o n d i t i o n s were maintained.
A n a l y t i c a l Methods. The a n a l y t i c a l methods u t i l i z e d f o r

t h i s paper were a combined epoxy-amine a n a l y s i s as d e s c r i b e d by
B e l l Ç16) and a spectrophotometric determination f o r primary
and secondary amines based on work by Toome and Manhart (17).
Pyridinium Chloride A n a l y s i s . The p y r i d i n i u m method of

a n a l y s i s was developed by B e l l (16) based on methods d e s c r i b e d
16. KING AND BELL Epoxy-Aliphatic Diamine System
Table I - S t a r t i n g M a t e r i a l s
Resin Epoxy Hydroxyl

meq/g - sample meq/g - sampl
Epon 822 5.16 0.52

Resin
Prepared 4.65 2.12

Resin I
Prepared 4.10 3.82

Resin I I
Prepared 2.92 6.72

Resin I I I
Curing Agent Purity
1,4-Diamino butane (DAB)

H N-(CH )4-NH
2 2 2 97%
Di-n-butylamine (DBA)
(CH CH CH CH ) NH
3 2 2 2 2 99%
Tri-n-butylamine (TBA)
(CH CH CH CH ) N
3 2 2 2 3 98.6%
by K n o l l et a l (14) and C r i t c h f i e l d and Johnson 0.5). Epoxy

f i r s t r e a c t s w i t h excess p y r i d i n i u m c h l o r i d e i n the" reagent s o l u
t i o n , the remaining p y r i d i n i u m c h l o r i d e i s t i t r a t e d with 0.5N
NaOH to a pH endpoint of about 11.0. The d i f f e r e n c e between a
blank run and t h i s f i r s t endpoint i s the epoxy equivalent present.
Carbon d i s u l f i d e i s added; t h i s r e a c t s with primary and secondary
amine hydrogens to form t h e i r corresponding thiocarbamic a c i d s .
The a c i d i s then t i t r a t e d with 0.5N NaOH to a pH endpoint of
around 10.0. The d i f f e r e n c e between the f i r s t and second end-
point i s the amount of primary and secondary amine.
Spectrophotometric A n a l y s i s . Florescamine (Fluram*, Roche

D i a g n o s t i c s ) i s a n o n f l u o r e s c e n t compound that r e a c t s with p r i
mary and secondary amines to form f l u o r e s c e n t compounds. I t has
been used c h i e f l y i n the spectrophotometric i n v e s t i g a t i o n and

assays of b i o l o g i c a l compounds. This i n v e s t i g a t i o n u t i l i z e d the
compound to determine c o n c e n t r a t i o n s of primary and secondary
amines.
Excess Fluram r e a c t s w i t h primary and secondary amine
forming s t r u c t u r e s that have absorptions of 375 - 410 and 310 -
320 nm, r e s p e c t i v e l y . The remaining Fluram i s hydrolyzed by
water. The procedure developed was based on work done by Toome
and Manhart (17).
The change i n primary and secondary amine c o n c e n t r a t i o n s
versus time i s shown i n F i g u r e 3. The system used i s Epon 828
and DAB. Both curves a r e accurate when compared w i t h primary
and secondary amine p o i n t s obtained by another method (16).
The secondary amine peak was found to disappear a t 2.0 hours.
T h i s i s e x p l a i n a b l e by the l a r g e s i z e o f the Fluram molecule. At
90 minutes t e r t i a r y amine production i s i n i t i a t e d ; t h i s i s where
branching of the molecule most l i k e l y s t a r t s . When 2 hours i s
reached, a h i g h l y branched molecule i s present. A t t h i s p o i n t
the secondary amines are probably too s t e r i c a l l y hindered to
allow the l a r g e planar Fluram molecule to r e a c t . The primary
amine i s s t i l l a v a i l a b l e because i t i s a dangling end, exposed
to the reagent s o l u t i o n .
Results
A s e t of m a t e r i a l balances were developed to determine the

concentrations of v a r i o u s r e a c t i v e groups based on data c o l l e c
ted by the method of B e l l (,16) . These m a t e r i a l balances assume
that any s i d e r e a c t i o n s are~~negligible.
A - i n i t i a l primary amine c o n c e n t r a t i o n
0
A -primary amine c o n c e n t r a t i o n
B - i n i t i a l epoxy c o n c e n t r a t i o n
Q
Β - epoxy c o n c e n t r a t i o n
R - i n i t i a l secondary amine c o n c e n t r a t i o n
0
R - secondary amine c o n c e n t r a t i o n
S - i n i t i a l t e r t i a r y amine c o n c e n t r a t i o n
0
S - t e r t i a r y amine c o n c e n t r a t i o n
5.0 ρ
0 1.0 2.0 3.0
TIME , HRS
Figure S. Change in epoxy and primary, secondary, and tertiary amines vs. time:
(i) method of Bell (16), calculated with 95% confidence limits, compared to (A)
spectrophotometric method (1.0:1.0 epoxy to amine stoichiometry)
Given: A , B and R = S = 0.0

Q Q Q 0
Data c o l l e c t e d : B, (A + R)
It follows that:
S = A - (A + R) (7)
ο
0.0 = (Β - Β ) + (R - R ) + 2.0(S - S ) (8)
ο ο ο
A = R - (A + R) (9)
T h i s data alone i s s u f f i c i e n t to determine a l l r e a c t i v e groups

present, that i s , epoxy, hydroxyl and primary, secondary and
t e r t i a r y amines, provided no s i g n i f i c a n t r e a c t i o n s take place
other than between the amino hydrogens and epoxy r e s i n , r e a c t i o n s
(1) and ( 2 ) .
To date, i n v e s t i g a t i o n s have supported t h i s absence of s i d e
r e a c t i o n s (1,6,18,19) with some s p e c i a l exceptions; low amine
concentrations (20,21) l e s s than a 1.0:1.0 amine:epoxy s t o i c h i o -
metry, y i e l d e t h e r i f i c a t i o n , r e a c t i o n ( 3 ) . High c u r i n g tempera
ture has had the same e f f e c t ( 6 ) .
Since the s t o i c h i o m e t r y of epoxy to amine i s not l e s s than
1.0:1.0 and the cure proceeds a t a low temperature, one would
p r e d i c t that only r e a c t i o n s (1) and (2) would take p l a c e . To
t e s t t h i s assumption f o r the DAB- DGEBA system, s e v e r a l i d e n t i c a l
runs were analyzed by the method of B e l l (16). U t i l i z i n g the
m a t e r i a l balances found above (which assume no s i d e r e a c t i o n s ) ,
the v a r i o u s r e a c t i v e groups were determined and averaged with 95%
confidence l i m i t s . A s i m i l a r run u s i n g the spectro-photometric
method gave the amounts of primary and secondary amines separa
t e l y . T h i s y i e l d s a c a l c u l a t e d and a c t u a l c o n c e n t r a t i o n of p r i
mary and secondary amines. Provided there are no s i d e r e a c t i o n s ,
the two values should be i d e n t i c a l . The r e s u l t s were p l o t t e d i n
F i g u r e 3 and found to f a l l on the same curve, w i t h i n experimental
e r r o r . T h i s v e r i f i e s the assumption that only r e a c t i o n s (1) and
(2) need be considered.
DBA and TBA, a secondary and t e r t i a r y amine r e s p e c t i v e l y ,
when used as c u r i n g agents a t 1.0:1.0 s t o i c h i o m e t r i e s , showed no
n o t i c e a b l e r e a c t i o n with Epon 828 over a p e r i o d of f i v e hours.
A f t e r two days, however, the DBA-resin mixture turned i n t o a
c l e a r g l a s s y s o l i d . Hydroxyl groups were c a l c u l a t e d from the
s t r u c t u r e of epoxy given i n S t r u c t u r e 1 with η = 0.2. For each
epoxy consumed one hydroxyl was produced.
OH - hydroxyl c o n c e n t r a t i o n
OH - added hydroxyl c o n c e n t r a t i o n ( i s o p r o p y l a l c o h o l )
OH = 0.1 (B) + OH + (Β - B) (10)

a ο
O r i g i n a l data and c a l c u l a t e d values used i n the development of
t h i s paper appear i n Tables I I through V I I .
Table I I - Data f o r 1.0:1.0 epoxy amine s t o i c h i o m e t r y . I n i t i a l hydroxyl c o n c e n t r a t i o n = 0.46 meq/g-

sample
Experimental Data C a l c u l a t e d Data

ta
Primary and Primary Secondary Tertiary
Epoxy Secondary amine Hydroxyl amine amine amine •β
Time (meq/g) (meq/g) (meq/g) (meq/g) (meq/g) (meq/g) I
-s*
0 4.62 2.30 0.46 2.30 0.0 0.0 r
30 4.41 2.30 0.67 2.09 0.21 0.0
60 4.15 2.31 0.93 1.83 0.47 0.0 s-
90 3.96 2.29 1.12 1.67 0.64 0.01
120 3.70 2.21 1.38 1.47 0.74 0.09 CO
«S
150 3.41 2.09 1.67 1.30 0.79 0.21 (S
3
180 3.24 2.01 1.84 1.21 0.80 0.29
ES
CO
ES
Table I I I - Data f o r 1.0:2.0 epoxy-amine s t o i c h i o m e t r y . I n i t i a l hydroxyl c o n c e n t r a t i o n - 0.42 meq/g

sample
Epoxy Secondary amine Hydroxyl amine amine amine
Time (meq/g) (meq/g) (meq/g) (meq/g) (meq/g) (meq/g)
0 4.17 4.21 0.42 4.21 0.0 0.0

30 3.81 4.22 0.78 3.84 0.38 0.0
60 3.33 4.21 1.26 3.37 0.84 0.0
90 2.95 4.19 1.64 3.01 1.18 0.02
120 2.52 4.09 2.07 2.68 1.41 0.12
150 2.02 3.88 2.57 2.39 1.49 0.33
180 1.73 3.73 2.86 2.25 1.48 0.48
Table IV - Data f o r 1.0:3.0 epoxy-amine s t o i c h i o m e t r y . I n i t i a l hydroxyl c o n c e n t r a t i o n = 0.38 meq/g

sample
0 3.82 5.71 0.38 5.71 0.0 0.0

30 3.35 5.71 0.85 5.24 0.47 0.0
60 2.67 5.71 1.53 4.56 1.15 0.0
90 2.12 5.71 2.08 4.01 1.70 0.0
120 1.59 5.61 2.61 3.56 2.05 0.10
150 0.90 - 3.30 - -
180 0.54 5.04 3.66 3.10 1.94 0.67
Table V - Data f o r 1.0:1.0 epoxy-amine s t o i c h i o m e t r y . I n i t i a l hydroxyl c o n c e n t r a t i o n = 1.91 meq/g

sample

0 4.20 2.12 1.91 2.12 0.0 0.0

30 3.62 2.00 2.49 1.66 0.34 0.12
60 3.24 1.97 2.87 1.31 0.66 0.15
90 2.84 1.83 3.27 1.05 0.78 0.29
120 2.61 1.83 3.50 0.82 1.01 0.29
150 2.36 1.75 3.75 0.65 1.10 0.37
Table VI - Data f o r 1.0:1.0 epoxy-amine s t o i c h i o m e t r y . I n i t i a l hydroxyl c o n c e n t r a t i o n = 3.50 meq/g

sample

(meq/g) (meq/g) (meq/g) (meq/g) (meq/g) (meq/g)
Time
3.76 1.85 3.50 1.85 0.0 0.0

0
3.11 1.80 4.53 1.25 0.55 0.05
30
2.81 1.66 4.83 1.09 0.57 0.19
60
2.43 1.59 5.21 0.78 0.81 0.26
90
2.16 1.56 5.48 0.54 1.02 0.29
120
150
180 1.71 1.32 5.93 0.33 0.99 0.53
Table VII - Data f o r 1.0:1.0 epoxy-amine s t o i c h i o m e t r y . I n i t i a l hydroxyl c o n c e n t r a t i o n 7.08 meq/g

sample

0 2.74 1.33 7.08 1.33 0.0 0.0
30
60 1.80 1.21 8.29 0.51 0.70 0.12
90 1.49 1.07 8.60 0.34 0.73 0.26
120 1.33 0.86 8.76 0.39 0.47 0.47
150 1.17 0.73 8.92 0.36 0.37 0.60
180
Figures 4, 5, and 6 show the c o n c e n t r a t i o n of v a r i o u s r e -

actants as a f u n c t i o n of time f o r v a r y i n g s t o i c h i o m e t r i e s . In
a l l three cases, the epoxy drop seems r e l a t i v e l y l i n e a r through-
out the t e s t p e r i o d and shows an i n c r e a s i n g r a t e of consumption
as the s t o i c h i o m e t r i c amount of amine i n c r e a s e s . T e r t i a r y amine
formation i s not apparent u n t i l 1.5 hours of r e a c t i o n f o r a l l
amine concentrations.
Figures 7, 8, and 9 demonstrate the e f f e c t of increased
hydroxyl c o n c e n t r a t i o n (by adding i s o p r o p y l a l c o h o l ) on the r a t e
of production or consumption of the v a r i o u s r e a c t i v e groups. The
r a t e of epoxy drop i s no longer constant i n c o n t r a s t with the
e a r l i e r s i t u a t i o n when no a l c o h o l was added, but v a r i e s with time.
The production of t e r t i a r y amine i s immediate i n a l l cases where
hydroxyl groups were added; t h i s i s a l s o i n c o n t r a s t to the
e a r l i e r case.
Discussion
The E f f e c t of Hydroxyl Concentration on Epoxy-Amine Reactions.

P r i o r work completed with polyamine-epoxy systems has i n d i c a t e d
a second order r a t e law, supporting the S 2 mechanism f o r nucleo-
n
p h i l i c a t t a c k on the epoxy r i n g . (8,10,22,23) F i g u r e 10 i s the

r e s u l t of an i n i t i a l r a t e a n a l y s i s , described by L e v i n s p i e l , (24)
of the present epoxy r e s i n s c o n t a i n i n g low molecular weight hy-
d r o x y l s , Resins I, I I , I I I , Table I. The graph demonstrates a
p o s s i b l e second order r e a c t i o n . T h i s i s i n c o n t r a s t , however, to
the apparent zero order dependence of the epoxy r e a c t i o n shown i n
Figures 4, 5 and 6. To be v a l i d , any model must be able to r e -
s o l v e t h i s d i f f e r e n c e i n order.
The mechanisms of Smith (10) and Mika and Tanaka (12),
although d i f f e r i n g , both c o n t a i n an intermediate complex, S t r u c -
tures 2 and 3:
k HX )
Structure 2 Structure 3
Smith Mika and Tanaka
I t can be seen by examination of the two mechanisms, Figures 1

and 2, that i f the hydroxyl groups, when complexing to form t h e i r
intermediates, S t r u c t u r e s 4 and 5, i n equations ( l a ) and (2a),
are s t e r i c a l l y hindered (thereby being l e s s r e a c t i v e ) causing a
slow r a t e of epoxy consumption, a small amount of intermediate
i s formed.
1.0 2.0 3.0
TIME , HRS
Figure 4. Change in primary, secondary, and tertiary amines, epoxy, and hy
droxyl groups vs. time for 1.0:1.0 stoichiometry (initial hydroxyl concentration =
0.46 meq/g-sample) (O) epoxy; (•) primary amine; (A) hydroxyl groups; (Φ)
secondary amine; ( J ) tertiary amine
T I M E , HRS
droxyl groups vs. time for 1:2 stoichiometry (initial hydroxyl concentration = 0.42
meq/g-sample) (O) epoxy; (Q) primary amine; (A) hydroxyl groups; (Φ) sec
ondary amine; (J^) tertiary amine
ω
-I
Q.
<
CO
0.38 meq/g-sample) (O) epoxy; (\J) primary amine; (Δ) hydroxyl groups; (Φ)
secondary amine; (Ή) tertiary amine
CL
<
GO
σ
UJ
Σ
CO
UJ
ζ
<
ο
ζ
<
χ
ο
ο
>-
χ
ο
Q.
droxyl groups vs. times for 1.0:1.0 stoichiometry (initial hydroxyl concentration =
1.91 meq/g-sample) (H) tertiary amine; (O) epoxy; (Q) primary amine; (A)
hydroxyl groups; (Φ) secondary amine
KING AND BELL Epoxy-Aliphatic Diamine System 243
ω 5.0 ρ
_ι
Q.
Σ
<
CO
ô 4.0 -
TIME , HRS
Figure 8. Change in primary, secondary, and tertiary amines, epoxy, and hy-
3.50 meq/g-sample) (O) epoxy; (\Z\) primary amine; (A) hydroxyl groups; (%)
secondary amine; (H) tertiary amine
0.0 1.0 2.0 3.0
TIME , HRS
Figure 9. Change in primary, secondary, and tertiary amines, epoxy, and hy-
7.08 meq/g-sample) (O) epoxy; (Π) primary amine; (A) hydroxyl groups; (Φ)
secondary amine; (Ή) tertiary amine
Figure 10. Log of the initial rate of consumption of primary amine vs. the log of
the initial primary amine concentration to determine the reaction order
R NH-·-HX
2
Structure 4 Structure 5
Smith Mika and Tanaka
An e q u i l i b r i u m i s set up i n equations ( l b ) and (2b) and the zero

order behavior observed f o r the epoxy consumption may be a t t r i b u -
ted to the slow breakdown and low c o n c e n t r a t i o n of the t e r n a r y
intermediate, S t r u c t u r e s 2 and 3. On the other hand, i f the
hydroxyls are more r e a c t i v e , e q u i l i b r i u m formation of the i n t e r -
mediates, S t r u c t u r e s 4 and 5 w i l l be f a r to the r i g h t and equa-
t i o n s ( l a ) and (2a) may be neglected. I t may a l s o be assumed
that when the hydroxyls are much more t i g h t l y bound to the amine
or epoxy, s h i f t i n g equations ( l b ) and (2b) to the l e f t , then the

a s s o c i a t i o n of hydroxyl complexes with epoxy or amine, equations
(lb) and (2b), tend to c o n t r o l the r a t e of r e a c t i o n and not the
breakdown of t e r n a r y complex, equations ( l c ) and ( 2 c ) . T h i s
would cause an apparent second order r e a c t i o n .
F i g u r e 11 represents the f r a c t i o n a l epoxy drop f o r the data
shown i n F i g u r e s 4, 5 and 6. I t may be noted that as the s t o i -
chiometric amounts of amine increase by f a c t o r s of two and three,
the slopes of the corresponding l i n e s i n c r e a s e by the same f a c -
t o r . F i g u r e s 12 and 13 are p l o t s of the f r a c t i o n a l drops of
primary amine and production of t e r t i a r y amine, r e s p e c t i v e l y . A
s i n g l e curve may be drawn through the data f o r the d i f f e r e n t
stoichiometries.
Taking the value of epoxy present as one, i t can be observed
i n the model of Mika and Tanaka, (12) that as the amine concen-
t r a t i o n i s increased by f a c t o r s of two and three, the i n t e r m e d i -
ate present, S t r u c t u r e 5, increases by that f a c t o r thereby i n -
c r e a s i n g the consumption of epoxy by the same f a c t o r . When the
amine i s taken as one, then the epoxy i s reduced by f a c t o r s of a
h a l f and a t h i r d . Assuming that the c o n c e n t r a t i o n of S t r u c t u r e
5 i s low, due to the low r e a c t i v i t y of the hydroxyls, then the
consumption of amine would remain constant due to the l a r g e ex-
cess of epoxy ready to r e a c t . The same l i n e of reasoning may be
used to e x p l a i n the mechanism of Smith (10). When the epoxy i s
one, then the e q u i l i b r i u m e s t a b l i s h e d i n equation ( l a ) i s constant
and as the amine i s increased by f a c t o r s of two and three, the
disappearance of epoxy i s a c c e l e r a t e d by the same f a c t o r . I f the
amine i s u n i t y and the e q u i l i b r i u m i n equation ( l a ) produces a
s u f f i c i e n t amount of intermediate, S t r u c t u r e 4, to r e a c t with the
amine then the r a t e s of amine consumption i n equation ( l b ) could
be the same f o r lower epoxy c o n c e n t r a t i o n s . T h i s l i n e of reason-
ing a l s o supports the model of Smith (10). F i g u r e s 14 and 15
summarize the p o s s i b l e e f f e c t s of hydroxyl groups on the two
mechanisms.
TIME , HRS
Figure 11. Ε feet of initial epoxy: amine stoichiometrics on the fractional con
sumption of epoxy (0)1.0:1.0, epoxy-.amine; (\Z\) 1.0:2.0, epoxy .amine; (A) 1.0:3.0,
epoxy.amine
3 0.8
± 0.6
0.4
0.2
0.0
1.0 2.0 3.0
TIME HRS
Figure 12. Effect of initial epoxy.amine stoichiometrics on the fractional con

sumption of primary amines (O) 1.0:1.0, epoxy.amine; (\2) 1.0:2,0, epoxy.amine;
(A) 1.0:3.0, epoxy.amine
KING AND BELL Epoxy-Aliphatic Diamine System 247
TIME , HRS
Figure 13. Effect of initial epoxy.amine stoichiometrics on the fractional rise of

tertiary amine. Total conversion to tertiary amine is 1.0. (O) 1.0:1.0, epoxy.amine;
(Q) 1.0:2.0, epoxy.amine; (A) 1.0:3.0, epoxy.amine
American Chemteaf
Society Library
1155 16th St. N. W.
Slightly reactive hydroxyl groups:

R2NH • H X « = [R2NH«OOHX]
fast
[Η ΝΗ···ΗΧ)
2 • C-ÇRi
[ ΧΗ····0 J
ΓΗ ϊ«···0-ρΐ]
2 slow R N-C-£Ri
2 • H X
y ΧΗ«>.··6 J m
Highly reactive hydroxyl groups*
R NH».«HX
2 • C-αΐχ slow [R Np..c-CRil
2
V
[ 3Μ····0 J
fast R N-C-CRi
2 • HX
OH
Figure 14. Possible effect of hydroxyl groups on the mechanism of Mika and
Tanaka
Slightly reactive hydroxyl groups:
CQCRI • H X ± —
R 2 N H . R l ^ C f a s t
HX
slow R
2
- p i C - p i • HX
^"1
»HX Η
Highly reactive hydroxyl groups:
R NH • RC-p R NH
ψ
2 8 l o w 2
HX
R NH2
fast R
2**
fc-ÇR • HX
I OH
HX
Figure 15. Possible effect of hydroxyl groups on the mechanism of Smith

The E f f e c t of pK Values on the Reaction of Amines with Epoxy.

a
According to Mika and Tanaka (12), an acid-amine e q u i l i b r i u m i s

f i r s t e s t a b l i s h e d , equation (2a). T h i s would r e q u i r e two e q u i -
l i b r i a to be present f o r the r e a c t i o n of primary amine, one f o r
the primary and the other with the formed secondary, r e a c t i o n s
(11) and (12).
R-NH + HX 2 (RNH - · - HX)

2 (11)
R NH
2 + HX (R NH-"HX)
2 (12)
Such an a s s o c i a t i o n would depend on many f a c t o r s , i n c l u d i n g the

r e l a t i v e ease of removal of the amine hydrogen, i . e . , b a s i c i t y .
This a b i l i t y may be r e l a t e d to the pK v a l u e s of the amine.

a DAB
c o n s i s t s of two primary amine groups separated by four carbons.
It has been found that these two amines have d i f f e r i n g pK a
values (25) of 11.15 and 9.71. Such values would be i n t e r p r e t e d

to mean that the f i r s t primary amine could r e a c t more q u i c k l y
than the remaining one. Damusis (26) found that the r e a c t i o n of
two to s i x carbon, a l i p h a t i c diamines i s r a p i d f o r the f i r s t
amino group, but the r e a c t i o n of the second primary group i s not
d e t e c t a b l e , being achieved only by c a t a l y t i c a c t i o n . I t i s also
i n d i c a t e d (25) that a l i p h a t i c secondary amines have a pK value a
of around 10.7, f a l l i n g between the values of the two primary

groups.
If the hydroxyl groups present are not very r e a c t i v e , as i n
the high molecular weight r e s i n s , then i t would be assumed that
the f i r s t group on the diamine would r e a c t f i r s t , followed by
the secondary amine and the second primary amine group.
F i g u r e 12 shows a l e v e l i n g out of the primary amine concen-
t r a t i o n at 50%, suggesting that l a t e r i n the r e a c t i o n the p r i -
mary does not react as q u i c k l y as the secondary. F i g u r e 16 i s
a p l o t of the percent of t e r t i a r y amine produced versus primary
amine consumed. As can be seen, only primary amine r e a c t s u n t i l
about 30% consumption then t e r t i a r y amine i s produced. At about
50% primary amine remaining, the r a t e of secondary amine r e a c t i n g
i s twice that of primary. This would tend to i n d i c a t e a three-
step r e a c t i o n which could be d e s c r i b e d by a two-step primary and
a secondary r e a c t i o n .
The secondary-alcohol amine has been found to be more r e -
a c t i v e due to the hydroxyl group (8). L a i r d and Parker (27)
have suggested and presented evidence that the hydroxyl group
has an i n t e r m o l e c u l a r " s e l f - s o l v a t i n g " e f f e c t ; a s i m i l a r s t a t e -
ment was made by A l l e n and Hunter (28). A h y p o t h e t i c a l i n t e r -
mediate being formed between the secondary-alcohol amine and
epoxy i s presented i n S t r u c t u r e 6.
0.15 ρ
FRACTIONAL PRIMARY AMINE REMAINING
Figure 16. Primary vs. tertiary amine, fractional changes for varying stoichiome
trics (O) 1.0:1.0, epoxy.amine; (Q) 1.0:2.0, epoxy.amine; (A) 1.0:3.0, epoxy.amine
0.2 h
I
0.0 1.0 2.0 3.0
TIME , HRS.
Figure 17. Effect of initial hydroxyl concentration on the fractional drop of epoxy
for a 1.0:1.0 stoichiometry (O) intial hydroxyl = 0.46 meq/g-sample; (•) initial
hydroxyl = 1.91 meq/g-sample; (A) initial hydroxyl = 3.50 meq/g-sample; (Φ)
initial hydroxyl = 7.08 meq/g-sample
CH 0 -CHR
So/
Structure 6
Further evidence of the p r o b a b i l i t y of the Mika and Tanaka

model (of hydroxyls complexing with amine) i s an o b s e r v a t i o n
during experimentation. In Resin I I I , the i s o p r o p y l a l c o h o l was
not t o t a l l y s o l u b l e ; when the mix was homogenized i t formed an
emulsion. As amine was added, the mixture became m i s c i b l e as

evidenced by the almost immediate disappearance of t u r b i d i t y .
Added low molecular weight hydroxyl groups a c c e l e r a t e the
r e a c t i o n between amines and epoxy as noted i n Figure 17. This
r e p r e s e n t a t i o n shows the f r a c t i o n a l l o s s of epoxy f o r Epon 828
and Resin systems I, I I and I I I , each of which has i n c r e a s i n g
hydroxyl c o n c e n t r a t i o n s , Table I. There i s an obvious disappear-
ance of l i n e a r i t y when one compares Epon 828 to systems I, I I and
I I I ; t h i s change i s probably due to the more a c t i v e added hydrox-
y l s as opposed to the formed hydroxyls.
Figure 18 demonstrates the increased r e a c t i v i t y of the amine
groups when i n the presence of h y d r o x y l s . I t p l o t s the change of
primary to t e r t i a r y amines. Resins with high hydroxyl group con-
c e n t r a t i o n s are more r e a c t i v e and show an immediate production of
t e r t i a r y amine.
A r e l a t i o n was developed i n Figure 19 f o r e f f e c t of the
hydroxyl to epoxy r a t i o on the i n i t i a l r a t e of r e a c t i o n . As the
hydroxyl c o n c e n t r a t i o n r i s e s , the i n i t i a l r a t e of r e a c t i o n i n -
creases; t h i s would probably hold true u n t i l d i l u t i o n e f f e c t s
dominate. S i m i l a r r e l a t i o n s have been developed by Bowen and
Whiteside (29). I t should be f u r t h e r noted that t h i s curve r e -
presents i s o p r o p y l a l c o h o l as the hydroxyl source. The slope
would s h i f t f o r other a l c o h o l s depending on t h e i r r e a c t i v i t y .
K i n e t i c Modeling Approaches. This s e c t i o n contains some

p o s s i b l e approaches to modeling of the data and mechanisms pro-
posed i n t h i s paper. I t a l s o i n c l u d e s recommendations f o r f u t u r e
work to analyze the v a l i d i t y of the suggested models. The cases
presented take i n t o account the zero order behavior at low
hydroxyl concentrations (Case I) and the second order r e a c t i o n
observed at high hydroxyl concentrations i n c o n j u n c t i o n with the
three step mechanism proposed p r e v i o u s l y (Case I I ) .
Case I :
Case I examines the runs made with low i n i t i a l concentra-

t i o n s of high molecular weight h y d r o x y l s . This data i s represen-
ted i n Figures 4, 5 and 6.
2.5 r
a. 2.0
<
ι.5 μ
ζ
<
(Τ
ι.ο μ\
<
2Ε
0.5 h
0.0 ι
0.1 0.2 0.3 0.4 0.5 0.6 0.7
TERTIARY AMINE, M E Q / G - S A M P L E
Figure 18. Effect of initial hydroxyl concentration on primary vs. tertiary amine
for a 1.0:1.0 stoichiometry (O) hydroxyl = 0.46 meq/g-sample; (•) hydroxyl =
J.91 meq/g-sample; (A) hydroxyl = 3.50 meq/g-sample; (Φ) hydroxyl = 7.08
meq/g-sample
Figure 19. Initial hydroxyl to epoxy ratio vs. initial rate of epoxy consumption
for a 1.0:1.0 stoichiometry
Figure 11 shows that the consumption of epoxy i s apparently

zero order. I t a l s o shows that as the amount of amine i n c r e a s e s ,
the r a t e of epoxy consumption increases p r o p o r t i o n a l l y . This i s
i n contrast to the normal zero order equation that s t a t e s :
rn = dB = k (13)
B
dT
This equation has no p r o v i s i o n f o r changes i n s t o i c h i o m e t r y . To
e x p l a i n t h i s , one must take i n t o account the complexing of hy-
droxyls with amine as shown i n Figure 15. Assume:
1) hydroxyls only complex with amines
2) a l l amine-hydroxyl complexes are e q u a l l y r e a c t i v e
with epoxies.
I n i t i a l l y only primary amines are present. An increase i n the

amount of amine w i l l cause a p r o p o r t i o n a l increase i n the amount
of hydroxyl intermediate formed :
k
i
A + Η A-H (1A)
k *^2
ν - _L _ (A-H) ( 1 5 )
K ( 1 5 )
2 k "(A) (H)
Increasing the amine, then, does not change the value of the
e q u i l i b r i u m constant but does allow f o r a p r o p o r t i o n a l increase
i n the amount of hydroxyl intermediate present, which i n t u r n ,
i s a v a i l a b l e to r e a c t with the epoxy. T h i s would account f o r the
p a r a d o x i a l e f f e c t of the v a r y i n g r a t e s i n Figure 11. Assume:
3) r a t e of r e a c t i o n i s dependent only on the breakdown
of the ternary intermediate (zero o r d e r ) ; a l l ternary
complexes breakdown at the same r a t e
4) consumption of various r e a c t i v e groups i s dependent
only upon t h e i r r e l a t i v e composition i n the hydroxyl
complex s t a t e .
Given: A = 1st primary amine
Β = 2nd primary amine
C = secondary amine
Η = hydroxyl
Ε = ternary complex
D = epoxy
F = t e r t i a r y amine
The f i r s t r e a c t i o n i s the hydroxyl complexing with amine:
k
i
A + H A-H (16)
k
2
V
Β + Η Β·Η (17)
k '
C + H - i * C-H (18)
k "
*2
Assume :
5) the complexing of epoxy with the hydroxyl complex i s
rapid,
Α·Η + D • E A (19)
B-H + D • Ε β (20)
C'H + D • E c (21)
Ε • products + 2H (22)
From the above assumptions the f o l l o w i n g model i s proposed:

k k
Κ
A + Η Ε -=—*• C + Β + 2H (23)
V k
3
Β + Η τ ^ — * Ε-, > C + 2Η (24)
R
2
k " k
C + Η 7^—> Ε — • F + 2H (25)
R
2
The disappearance of the v a r i o u s r e a c t a n t s may be d e s c r i b e d by
the f o l l o w i n g d i f f e r e n t i a l equations:
ft = r A = - k x (A) (H) + k 2 (E ) A (26)
g = r B - - k l ' (Β) (H) k '

+ 2 (E ) B + k 3 (E )
A (27)
f - r c - - k " x (C) (H) + k » 2 (E ) + k c 3 (E A + Eg) (28)
The consumption of epoxy would equal the breakdown of E and x be

described by the zero order r e a c t i o n observed i n Figure 11
f t - -k 3 (29)
Therefore the slope of the 1.0:1.0 s t o i c h i o m e t r i c case would y i e l d

the value of k^. I t i s recommended that the k i and k2 r a t e con
s t a n t s be determined by e q u i l i b r i u m experiments done s e p a r a t e l y
with the use of IR to determine the extent of hydrogen bonding.
The use of IR f o r determination of E , Ε and E would be im A β c
p o s s i b l e i n the r e a c t i o n mixture s i n c e the absorption bands f o r

these three components would f a l l w i t h i n the same area; an over
a l l amount of hydrogen bonding may be c a l c u l a t e d by IR. I t
should be noted that hydroxyls need not only a s s o c i a t e with

amines but may a l s o bond with epoxies simultaneously.
Case I I .
Case I I examines the runs made with added low molecular
weight hydroxyls. The d a t a i s shown i n Figures 7, 8 and 9.
Figure 15 shows the proposed sequence of r e a c t i o n s i n the
presence of these low molecular weight hydroxyl groups. Based
on t h i s and the f o l l o w i n g assumptions, a model may be proposed.
Assume :
1) the formation of hydroxyl intermediate i s r a p i d and
A = A-H (30)
Β = Β-Η (31)
C = CH (32)
2)the breakdown of the t e r n a r y intermediate i s r a p i d when

compared to the formation.
From these assumptions the f o l l o w i n g mechanism may be proposed:
k
i
A + D —±+ Β + C + 2H (33)
k
2
Β + D — C + 2H (34)
k
3
C + D — ^ F + 2H (35)
The disappearance of the v a r i o u s r e a c t a n t s may be described by
the f o l l o w i n g d i f f e r e n t i a l equations:
g=r A - - k l (A) (D) (36)
g = r fi - kj_ (A) (D) -k 2 (B) (D) (37)
~ = r c = k x (A) (D) + k 2 (B) (D) - k 3 (C) (D) (38)
d i v i d i n g the f i r s t two equations we o b t a i n :
dA k 1 (A)
When t h i s i s s o l v e d , using the i n i t i a l and f i n a l concentrations

of A and Β as l i m i t s , the f o l l o w i n g equation i s obtained:
1 k
A " '
B
= " W + ( B
o o" '
A k +
'ΏΠ- > *'
Α
< >
40
1
This would then y i e l d values f o r k = ^/k^. When equation 3 i s
d i v i d e d by equation 1, the f o l l o w i n g d i f f e r e n t i a l equation i s
obtained :
k
3
where k" = S u b s t i t u t i n g equation (40) i n t o (41)
1 _ k
A '
f - - iSr - ' o V ' -f^-> '
1+ k (B k + Ak _ 1+ k
"i ( 4 2 )
This equation may then be i n t e g r a t e d u s i n g the i n i t i a l and f i n a l

concentrations of A and C as l i m i t s . k^/k3 then may be c a l c u -
lated.
The above d e s c r i p t i o n s provide an i n i t i a l approach t o
modeling the data. A f i n a l model should be able t o take i n t o
account the e f f e c t of hydroxyls on a l l epoxy systems i n general.
Such a model would be a combination o f Cases I and I I and would
probably be much more d i f f i c u l t than the two cases i n d i v i d u a l l y .
Conclusion
Hydroxyl groups are an important c o n s t i t u e n t i n the r e a c t i o n

between amines and epoxy. The hydroxyls have an a c c e l e r a t i n g
e f f e c t accompanied by an i n c r e a s e i n the order of r e a c t i o n from
zero to two. They most l i k e l y i n t e r a c t with amines to form com-
plexes as described by Mika and Tanaka (12). In the case of DAB
there are three d i s t i n c t r e a c t i o n s i n v o l v e d , the f i r s t primary
amine, the second primary amine and the formed secondary a l c o h o l
amine r e a c t i o n . The r a t e s of these r e a c t i o n s are probably de-
termined by the r e l a t i v e b a s c i t i e s of the amines present, thereby
c o n t r o l l i n g t h e i r a b i l i t y to complex with hydroxyls. I f amines,
such as d i e t h e l e n e t r i a m i n e (DETA) , c o n t a i n i n g secondary amines
were used, a f o u r t h r e a c t i o n would most l i k e l y come i n t o p l a y .
The r e a c t i o n appears to be more complicated than assumed
i n i t i a l l y and an attempt t o d e s c r i b e parameters i n terms of a
g e n e r a l i z e d simple model would be d i f f i c u l t .
The authors a p p r e c i a t e the help of Mr. W. Ku i n formulation
of the model.
References
1. L. Schecter, J . Wynstra and R. E. Kurkjy, Ind. Eng. Chem.,
48, 94 (1956).
2. A. K. Ingberman and R. K. Walton, J . Polymer S c i . , 28, 468
(1958).
3. Y. Oshiro, M. Ochiai, S. Komori, Kogyo Kagaky Zasshi, 64,
1588 (1961).
4. Y. Oshiro, T. Tsunoda, S. Komori, Kogyo Kagaky Zasshi, 64,

2132 (1961).
5. J . F. Harrod, J . Appl. Polymer S c i . , 6, 863 (1962).
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485 (1960).
7. N. S. Isaacs and R. E. Parker, J . Chem. Soc., 1960, 3497.
8. Y. Iwakura, T. Kurosaki, Y. Imai, Makromol. Chem., 86 (1957).
9. F. J . Allen and W. M. Hunter, J . Appl. Chem., 7, 86 (1957).
10. I. T. Smith, Polymer, 2, 95 (1961).
11. K. Dusek, M. Ilavsky, S. Lunak, J . Polymer S c i . , Symposium
53, 29 (1975).
12. Y. Tanaka and T. F. Mika in Epoxy Resins Chemistry and
Technology (C. A. May and Y. Tanaka, eds.) Marcel Dekker,
New York, 1973, p. 135.
13. J . F. Harrod, J . Polymer S c i . , 1A, 385 (1963).

14. Knoll et al in Handbook of Epoxy Resins (H. Lee and K.
Neville, Eds.) McGraw-Hill, New York, 1967, Chap. 4, p. 17.
15. F. E. Critchfield and J. B. Johnson, Anal. Chem., 29, 957
(1957).
16. J . P. Bell, J . Poly. S c i . , A-2, 6, 417 (1972).
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1959, 1925.
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Gould, ed.) ACS Publications, Washington, D.C., 1970, p. 48.

17
Epoxy Resins Containing a Specific Vulnerability
JAMES R. GRIFFITH
Chemistry Division, Naval Research Laboratory, Washington, DC 20375
The concept of a coating with a built in vulnerability to

destruction by specific reagents has been used successfully in
some applications. For example, floor finishes which can be
removed readily when renewal is required by the application of
dilute ammonia, or another mild reagent, are available and
convenient. The extension of this concept to rugged, durable
coatings, such as epoxies, entails the requirement that a means
be found to degrade an "infinite network" molecular structure
which is inherently resistant to attack. A need exists for such
materials, however, because the factors of toughness and
durability which are desirable when epoxy coatings are applied
become expensive, troublesome obstacles to removal when the time
arrives for renewal. The present work concerns some efforts to
synthesize epoxy resins which contain a cleavable weak link that
allows the cured network to be chemically degraded into smaller
fragments. The consequence of such degradation should be that
such coatings would peel from surfaces or become soluble in
common solvents after treatment with a "triggering" reagent.
For convenience, such a selectively destructible polymer is
called a command-destruct resin.
P r o p e r t i e s o f An I d e a l Command-Destruct Resin
An i d e a l command-destruct r e s i n should r e t a i n the d e s i r a b l e

p r o p e r t i e s o f conventional epoxies; i n c l u d i n g , reasonable c o s t ,
cure by a v a i l a b l e c u r i n g agents, a b i l i t y t o be compounded with
s o l v e n t s , pigments, etc. t o form h i g h - q u a l i t y p a i n t s , and
provide long s e r v i c e l i f e . In a d d i t i o n , the cured coatings
should r e t a i n the a b i l i t y t o be destroyed q u i c k l y and e f f e c t i v e l y
by s e l e c t e d reagents not l i k e l y t o be encountered i n the s e r v i c e
environment. A high degree o f destruct agent s p e c i f i c i t y insures
against a c c i d e n t a l l o s s o f the coating. Also, the destruct
This chapter not subject to U.S. copyright.

Published 1979 American Chemical Society
agents should be m i l d chemicals without harmful environmental

effects.
A l l of the i d e a l p r o p e r t i e s may never be found i n r e a l
systems because of a m u l t i p l i c i t y of problems concerning
economics, s y n t h e s i s p o s s i b i l i t i e s , d e s t r u c t e f f e c t i v e n e s s
l i m i t a t i o n s and environmental s t a b i l i t y . However, some o f the
necessary a t t r i b u t e s of e f f e c t i v e m a t e r i a l s are being incorpo-
rated i n t o the f o l l o w i n g r e s i n types.
Cleavage o f O l e f i n i c Bonds
One approach t o an e f f e c t i v e command-destruct epoxy i s that

of i n c o r p o r a t i n g one or more o l e f i n i c bonds i n t o each molecule
such that the f i n a l network can be degraded by the well-known
r e a c t i o n of o l e f i n s with powerful o x i d i z i n g agents, such as

a c i d i c permanganate:
! f
R-CH=CH-R > RC00H + H00CR
One o f the simpler compounds o f t h i s type i s the d i g l y c i d y l ether

of h ,if-dihgdroxystilbene, although the expense and high-melting
point {2Qk C) o f t h i s diphenol make the substance i m p r a c t i c a l :
C H ^ C H C ^ O ^ ^ C H = C H ^ ^ 0 C H C H CH,
2
The product obtained i n a standard d i g l y c i d y l ether r e a c t i o n with

e p i c h l o r o h y d r i n and a l k a l i was an o f f - w h i t e c r y s t a l l i n e powder
melting at 191°-193°C.
A lower m e l t i n g diphenol which contains s e v e r a l o x i d i z a b l e
s i t e s i s curcumin. This i s an i n t e n s e l y c o l o r e d pH i n d i c a t o r
which undergoes v a r i o u s v i v i d c o l o r changes during the s y n t h e s i s
of the d i g l y c i d y l ether. The f o l l o w i n g formula shows the
simplest form, although the a c t u a l products obtained t o date have
apparently been polymeric:
H C0
3 0 0 0CH 3
CHgCHCHgO CH=CHCCH CCH=CH

2 OC^CH CH 2
0 0
A t h i r d compound o f the o l e f i n i c type, and the most

promising obtained t o date, i s the d i g l y c i d y l ether o f 2,6-
d i v a n i l l y l i d e n e cyclohexanone, which i s produced by the
conventional r e a c t i o n o f the diphenol with e p i c h l o r o h y d r i n :
17. GRIFFITH Epoxy Resins with a Specific Vulnerability 261
CH 0 3 ο ÔCH 3
CH CHCH 0
2 2 CH= ^ =CH ^ ) OC^CH CH 2
o \y 0
This b r i g h t yellow, c r y s t a l l i n e compound has a m e l t i n g

range of 1^3 -ihQ C, and i t i s v i r t u a l l y i n s o l u b l e i n common
epoxy s o l v e n t s . However, i t -will react with polyamide c u r i n g
agents, and f i l m s of good q u a l i t y have been produced by use o f
dimethyl s u l f o x i d e as solvent. The f i l m s so produced are
r e a d i l y destroyed by a s o l u t i o n of potassium permanganate i n
50% a c e t i c a c i d - water. Permanganate i n water alone i s
i n e f f e c t i v e , and the solvency of the a c e t i c a c i d i s necessary
i n order t o s w e l l and s o f t e n the cured f i l m s enough f o r the

permanganate t o penetrate to the o l e f i n i c s i t e s . After
degradation, the f i l m residue may be e a s i l y brushed away from
the surface t o which the f i l m was formerly t i g h t l y bonded.
Another approach t o a d i g l y c i d y l ether of t h i s type which
r e s u l t s i n a product of improved s o l u b i l i t y c h a r a c t e r i s t i c s i s
the r e a c t i o n of two moles of a pure d i g l y c i d y l ether of
Bisphenol-A w i t h one mole of 2 , 6 - d i v a n i l l y l i d e n e cyclohexanone.
This r e s u l t s i n a r e s i n with g l y c i d y l ether t e r m i n a l s which i s
p a r t i a l l y s o l u b l e i n ketone s o l v e n t s , p a r t i c u l a r l y methyl e t h y l
ketone.
Further work w i l l be necessary t o produce p r a c t i c a l p a i n t s
from the 2 , 6 - d i v a n i l l y l i d e n e cyclohexanone system, but as an
example of the p o s s i b i l i t i e s of the o l e f i n i c approach t o
c l e a v a b l e epoxy r e s i n s , i t has been reasonably s u c c e s s f u l .
Cleavable T e r t i a r y Carbamate Epoxy Resins
T e r t i a r y carbamates, or urethanes, are not produced as

r e a d i l y as the primary and secondary compounds, but an e f f e c t i v e
s y n t h e s i s has been d e s c r i b e d ( l ) . This molecular u n i t can be
r e a d i l y cleaved by warm s o l u t i o n s o f m i n e r a l a c i d s ( 2 ) , and the
ease of cleavage may be c o n t r o l l e d by proper s e l e c t i o n o f
the components o f the t e r t i a r y r a d i c a l :
0 H+
f
R R"R"* COCNHR >R'R"R"' COH + C0 2 + H NR
Δ
Epoxy r e s i n s may be produced which c o n t a i n t e r t i a r y
carbamates by the use of g l y c i d o l as the c h a i n - t e r m i n a t i n g
alcohol i n a diisocyanate - d i o l reaction. For example, a
stepwise r e a c t i o n has been used i n which one e q u i v a l e n t of
g l y c i d o l has been reacted w i t h 1,6-hexamethylene d i i s o c y a n a t e
t o produce a mixture represented i d e a l l y by the r e a c t i o n :
CH CHCH 0H + 0=C=N(CH ).N=C=0

o o o >
0
0
CH CHCH OCNH(CH )^N= C= 0
0 0 0
2 2 2 6
\ /
0
The a v a i l a b l e remaining isocyanate may then react with a

t e r t i a r y a l c o h o l when d i b u t y l t i n d i a c e t a t e i s used as
catalyst. An i n t e r e s t i n g d i o l c o n t a i n i n g both primary and
t e r t i a r y terminals i s h y d r o x y c i t r o n e l l o l , a derivative o f
n a t u r a l products :
CH„ CH 0
HOC (CH ) C
2 3 CH CH 0H
2 2
CH 3
The complex epoxy r e s i n obtained from t h i s system i s a low-

melting wax which i s nominally represented by the formula:
0 0 CH- 3
CH
3
0 0 0
II, x ΝI I x H , x U
CH CHCH 0CNH(CH ).NHC0C (CH ) C CH CH 0CNH(CH )^NHC0CH CH C H
\ ds
O
d
o
do
o
I 3 d
0 0
d
O
d
o
do
o
d \ / d
O Q
0 CH 3 0
This r e s i n may be melted and blended with amine c u r i n g agents t o

produce tough polymers which are v u l n e r a b l e t o cleavage at the
t e r t i a r y linkage.
As with the o l e f i n - c o n t a i n i n g epoxies, much i s y e t t o be
done with t e r t i a r y carbamate epoxies i n order t o produce
p r a c t i c a l systems, but the s y n t h e s i s p o s s i b i l i t y has been
established. A v a r i e t y o f d i i s o c y a n a t e s and t e r t i a r y a l c o h o l s
are a v a i l a b l e . A general s y n t h e s i s e f f o r t i s needed t o screen
the most e f f e c t i v e compositions with regard t o solvency,
compounding, cure, environmental s t a b i l i t y , and the e f f e c t i v e n e s s
of v a r i o u s d e s t r u c t agents and c o n d i t i o n s .
Literature Cited
1. Bailey, W. J. and Griffith, J. R. Polymer Preprints, 1964,
5 (1), 266-278.
2. Bailey, W. J. and Griffith, J. R. Polymer Preprints, 1964,
5 (1), 279-290.

INDEX
A Β
Acid-amine equilibrium 249 Benzenediazonium hexafluorophos-
Acrylonitrile-glycidyl methacrylate phates 26i
copolymers 227 Binder(s)
Adhesion promoters, alkali-resistant .. 59 anionic 57-69
Alcohol(s) 226 ED 59
amine, secondary- 249 cationic 65-69
Alkali-resistant adhesion promoters .. 59 for electrodeposition coatings with
Amidoamines 101 high corrosion resistance,
Publication Date: December 3, 1979 | doi: 10.1021/bk-1979-0114.ix001
Amine(s) epoxy resin-based 57-69

-catalyzed oligomerization of epoxy with high corrosion resistance,
compounds, tertiary 205, 208 anionic E D 61-65
-cured hydrolytic stability of 64
epoxy networks, creep behavior LMPB-based 57-69
of 183-195 OH-rich 65
hydantoin epoxy resin oil-free cationic 67
chemical resistance of aro performance of anionic E D 58f
matic 129*, 131f Bisphenol A
solvent resistance of aro -based epoxy prepoly-
matic 128f, 130f mers 49,108,137-156,158
solvent/chemical resistance of diglycidyl ether of
aromatic 132i (DGEBA) 83-90,227,261
resins, hydrophobic-hydrophilic Blushing of can coatings, steriliza
balance of 118,121 tion resistance of 91-98
curing of hydantoin epoxy resins, Blushmeter 93-98,96/
room temperature ...123*, 124f, 127i Br0nsted acids 2, 7
cycloaliphatic 101 Biicherer reaction 116
equilibrium, acid- 249
with epoxy, effect of pK values on
a
the reaction of 249

—hydroxyl complexes 253 Calorimeter, differential scanning 8
reactions, effect of hydroxyl con Can
centration on epoxy- 239 coatings, sterilization resistance
secondary-alcohol 249 (blushing) of 91-98
tertiary 225 end coatings 72
Ammonium halides, quaternary 48 formulation and performance
Anhydride-cured epoxy resins, quater properties for 73i
nary phosphonium compound lacquers, E / P F 91-98
latent accelerators for 47-56 Carbamate epoxy resins, cleavable
Anhydride curing agents 48 tertiary 261-262
Aqueous epoxy resins for electrical- Carbon-13 NMR 84, 87
reinforced plastics industry 77-82 Carboxylic acids, reaction of epi-
ARALDITE 488 71-75 chlorohydrin with 211-224
Arrhenius-type relationship 187 Cardolite 99-114
Arsonium compounds, quaternary 55 CARDURA E10 62
Aryldiazonium salts 1—16 Catalysts, latent 47-56
photolysis of 1-16 Cationic polymerization
Aryliodonium salts 19 of cyclic ethers 19
Automotive primer coatings 73 of epoxides, photoinitiators for 17
formulation and performance prop of epoxy resins, photoinitiated 1-15
erties for 74t Cetyltrimethylammonium bromide ... 213
2,2'-Azoisobutyronitrile 198 Chemical resistance immersion tests .. 100
265
p-Chlorobenzenediazonium hexa- Curing

fluorophosphate 19 agents
Chlorohydrin ester 213 anhydride 48
decomposition 218/ comparison of properties of 102*
Circuit boards, epoxy printed- 84 -diluent-accelerator mixtures,
Coating(s) epoxy resin 105
can end 72 epoxy 99-114
epoxy ester 59 properties 100
formulations phenalkamine 102*
with phenalkamines 112* process 33
and performance properties for of thermosets 157-182
automotive primer 74* Cycloaliphatic
and performance properties for amines 101
can end 73* anhydride curing of 1,3-diglycidyl-
solvent-free liquid epoxy 108 hydantoins 119*, 120*
with high corrosion resistance, epoxide 35
epoxy resin-based binders for Cyclohexane oxide, photopolymeri-
electrodeposition 57-69 zation of 8,9/

light-curable epoxide 17-42 Cyclopentamethylenehydantoin 118
prepared from high molecular
weight epoxy resins, water-
borne 71-75
salt-spray resistance of cationic E D 69 DAB (1-4, diaminobutane) 228
sterilization resistance ( blushing ) DBA (Di-N-butylamine) 228,232
of can 91-98 Dehydechlorination reaction 219
surface 1-16 DGEBA (see Diglycidyl ether of
Command-destruct resin, properties bisphenol A) 24, 48, 83-90,116
of an ideal 259 5,5-Dialkylhydantoins 116
Corrosion resistance 59 Diaminobutane epoxy system, Epon
epoxy resin-based binders for elec 828 227
trodeposition coatings with 1,4-Diaminobutane (DAB) 228
high 57-69 Diaryliodonium salts 2
Creep 183-195 arylation of 3
behavior photoinitiators 7,24, 28
of amine-cured epoxy net Diazonium salt(s) 19-24
works 183-195 reactivity of epoxides toward 25*
of epoxy resins 145, 187* Di-N-butylamine (DBA) 228
-modulus behavior 184 α-Dichlorohydrin ( 1,3-dichloro-
Cross-link density ( M )c 137-156,161 propan-2-ol ) 213
distribution on the engineering be Dielectric breakdown voltage 79
havior of epoxies, effect Differential scanning calorimeter 8
of 137-154,183-185 Diglycidyl D M H 126
properties affected by the distribu Diglycidyl ether ( s )
tion of 154 of bisphenol A (DGEBA)
properties not affected by the dis 24, 83-90, 227, 261
tribution of 154 epoxy resins based on 83-90
Cross-linking of epoxides 42 resin, rate of cure of 38*
Curcumin 260 of 4,4-dihydroxystilbene 260
Cure of 2,6-divanillylidene cyclohexanone 260
of DGEBA resin, rate of 38* l,3-Diglycidyl-5,5-cyclopentamethyl-
effect enehydantoin 118
of epoxide structure on rate of .... 35 l,3-Diglycidyl-5,5-dimethylhydantoin 116
of humidity on rate of 35 1,3-Diglycidylhydantoins 116,117*
of photoinitiator concentrator cycloaliphatic anhydride curing
on rate of 22* of 119*, 120*
of epoxy resins, UV- 1-16 1.3- Diglycidyl-5-methyl-5-ethyl-
rate studies 103 hydantoin 118
near infrared spectroscopic 4.4- Dihydroxystilbene, diglycidyl
(NIR) 100 ether of 260
INDEX 267
Diisocyanate-diol reaction 261 Epoxide(s) (continued)

Dimethylhydantoin (DMH) 121 monomers, low-viscosity 40
-based hydrophilic resin 126 photoinitiators for
diglycidyl 126 cationic polymerization of 17
Dimethylolpropionic acid (DMPA) .. 61 cross-linking of 18f
Diphenol 260 photosensitized 17-42
2,6-Divanillylidene cyclohexanone, storage stability of 22, 24, 32
diglycidyl ether of 260 structure on rate of cure, effect of .. 35
DMPA (Dimethylolpropionic acid) .. 61 tack-free time of 36i
Dynamic mechanical properties of toward diazonium salt, reactivity of 25i
epoxy resins 141 1,2-Epoxide 221
Epoxy ( see also Resin ( s ) )
Ε -aliphatic diamine system, reactions
in an 225-256
E C C ( 3,4-epoxycyclohexylmethyl-3,4- -amine reactions, effect of hydroxyl
epoxy cyclohexane carboxylate ) .. 32 concentration on 239
E D (see Electrodeposition) —anhydride resins
E E W (Epoxide equivalent weight) .83-90 containing quaternary phos

Electrical properties of cured epoxy- phonium compounds, elec
anhydride resins containing quat trical properties of cured 54i
ernary phosphonium compounds 54i gel time data for quaternary
Electrodeposition (ED) 57-69 phosphonium latent acceler
binders 59 ators in 51i
cationic 65-69 viscosity ( storage ) data for
with high corrosion resistance, quaternary phosphonium
anionic 61-65 accelerators in 52i
performance of anionic 58i bisphenol A 108
coatings coating formulations, solvent-free
with high corrosion resistance, liquid 108
epoxy resin-based binders coatings, volatility of photosensi
for . 57-69 tized 40-41
salt-spray resistance of cationic .. 69 compounds, tertiary amine-cata-
paints, pigmented 65 lyzed oligomerization of 205, 208
Electron microscope, scanning curing agents 99-114
(SEM) 160 effect of cross-link density distri
Electron microscope, transmission bution on the engineer behav
(TEM) 160 ior of 137-154
Emulsions, oil-in-water 71—75 effect of pK values on the reaction
a
E/PF (see Epoxy resin/phenolic- of amines with 249

formaldehyde) 91-98 ester coatings 59
Epichlorohydrin 116, 260 liquid 108
with carboxylic acids, reaction networks
of 211-224 creep behavior of amine-
with 2-ethylhexanoic acid, reaction cured 183-195
of 211-224 micro- and macro-structures of
hydrolysis of 219-224 MDA-cured 160
EPIKOTE 1007 (E-1007) 59 morphology
Epon effect of molecular weight of
828/diaminobutane epoxy system .. 227 the prepolymer on 166
828-methylene dianiline system 184 effect of stoichiometry on 161
prepolymers 138 and the mechanical behavior
Epoxide(s) of 157-180
coatings, light-curable 17-42 two-phase 157-182
cross-linking of 42 prepolymers 177
cycloaliphatic 35 bisphenol-A-based 137-154
equivalent weight (EEW) 83-90 printed-circuit boards 84
determination by carbon-13 rate determining factors in the
nuclear magnetic resonance photoinitiated polymerization
(NMR) 83-89 of 10
Epoxy (continued) Ester(s)

resin(s) amine-modified epoxy resin 67
-based binders for electrodeposi- chlorohydrin 213
tion coatings with high cor- decomposition 218/
rosion resistance 57—69 glycidyl 211-224
based on DGEBA 83-90 2-hydroxy-3-chlorophenyl 221
chemical resistance of aromatic 1- Ethenyl-4- ( 2,3-epoxy-l-propoxy ) -
amine-cured hydantoin .129*, 13 It benzene 197-210
cleavable tertiary carbamate .261-262 copolymers of 205,208
creep behavior of 145,187* with vinylpyridines, monomer reac-
-curing agent-diluent-accelerator tivity ratios 203*
mixtures 105 Ethers, cationic polymerization of
dynamic mechanical properties of 141 cyclic 19
effect of alkyl substituents on the 2- Ethylhexanoic acid 213
properties of cured reaction of epichlorohydrin with 211-224
hydantoin 115-135 5-Ethyl-2-vinylpyridine 197-210
for electrical-reinforced plastics
industry, aqueous 77-82

emulsion, thermoplastic modified 75* F
esters, amine-modified 67
glass transition temperature Florescamine (Fluram) 230
(T ) of
g 142 Foaming of the resin 78-79
hydantoin-based 116 Fourier transform (FT) NMR 87
intermolecular forces of hydan-
toin-based 133
latent catalysts for 48 G
/phenolicformaldehyde (E/PF) 91-98
can lacquers 91—98 Gehman Torsional Stiffness Tester .... 138
photoinitiated cationic polymeri- Glass transition temperature
zation of 1-15 (T )
g 118,179,184
properties of cured hydantoin .... 118 of epoxy resins 142
quaternary phosphonium com- Glycerol-l,3-di-2-ethylhexanoate 213
pound latent accelerators for synthesis 213,215/
anhydride-cured 47-56 Glycidol 261
room temperature amine curing Glycidylated heterocycles 115-135
of hydantoin .122*, 123*, 124*, 127* Glycidyl
rubbery modulus of 142 esters 211-224
solvent resistance of aromatic 2-ethylhexanoate, preparation of 211-224
amine-cured hydantoin .128*, 130* methacrylate copolymers, acrylo-
solvent/chemical resistance of nitrile 227
aromatic amine-cured
hydantoin 132*
systems, bisphenol A 49 H
tensile behavior of 145 Halfester linkage 64
UV-cureof 1-16 Halfesters of trimellitic anhydride
water-based 77-82 (TMA) 64
water-borne coatings prepared Halides, quaternary ammonium 48
from high molecular weight 71-75 Heterocycles, glycidylated 115-135
Young's modulus of 142 Hexafluorophosphates
solid 108 benzenediazonium 8*
3,4-Epoxycyclohexylmethyl-3,4-epoxy- p-chlorobenzenediazonium 19
cyclohexane carboxylate (ECC) 32 preparation of p-methoxybenzene-
2,3-Epoxy-l-propyl methacrylate ...197-210 diazonium 41
copolymers of 208 Hexahydrophthalic anhydride
with vinylpyridines, monomer re- (HHPA) 118
activity ratios in copolymeri- Hexamethoxymethylmelamine
zation of 201* (HMMM) 59
INDEX 269
Hydantoin p-Methoxybenzenediazonium hexa-

-based epoxy resins 116 fluorophosphate (PM) 22
intermolecular forces of 133 photoinitiators 31
epoxy resin preparation of 41
chemical resistance of aromatic Methylene dianiline (MDA) .137-154,158
amine-cured 129f, 131i -cured epoxy networks, micro- and
properties of cured 118 macro-structures of 160
effect of alkyl substituents system, Epon 828 184
on 115-135 1-Methyltetrahydrophthalic anhydride 49
room temperature amine curing Microgels 157-180
of 122f, 123i, 124f, 127* formation 172
solvent/chemical resistance of aro of primary 175
matic amine-cured 128ί, 130ί, 132£ of secondary 175
ring 115-135 isolation of 160
Hydrophilic resin, DMH-based 126 Modulus of epoxy resins, rubbery 142
Hydrophobic-hydrophilic balance of Modulus of epoxy resins, Yonug's 142
amine-cured resins 118,121 5-Monoalkylhydantoins 116
Hydroxy diester 213

2-Hydroxy-3-chlorophenyl esters 221
Hydroxycitronellol 262 Ν
Hydroxyl Near infrared spectroscopy (NIR) .... 103
complexes, amine— 253 cure rate studies 100
concentration on epoxy-amine Network(s)
reactions, effect of 239 creep behavior of amine-cured
groups 225-246 epoxy 183-195
formation, model for 172
I morphology
effect of molecular weight of the
Initial deformation temperature prepolymer on epoxy 166
(IDT) 118,134 effect of stoichiometry on epoxy .. 161
Insulation materials 47-56 and the mechanical behavior of
Insulation properties of laminate, epoxies 157—180
electrical 79 surface properties of the 158
two-phase epoxy 157—182
Κ NIR (Near infrared spectroscopy) .... 103
cure rate studies 100
Kinetic modeling 251-256 NMR (see Nuclear Magnetic
Resonance )
L NOE (Nuclear Overhauser effect) .... 88
Nuclear magnetic resonance (NMR)
Laminate(s) carbon-13 84
electrical insulation properties of .. 79 epoxide equivalent weight deter
process 77/ mination by carbon-13 83-90
properties of 80/, 82/ Fourier transform (FT) 87
T and pressure cooker test results 79, 81/
g
proton 84
Laser, He-Ne 93 Nuclear Overhauser effect (NOE) 88
Laser light, back-scattering of 93
Low-molecular-weight polybutadienes
(LMPB) 57-69 Ο
-based binders 57—69 Olefinic bonds, cleavage of 260-261
Lyophobicity 126 Olefins, epoxidized 35
Oligomerization of epoxy compounds,
M tertiary amine-catalyzed 205, 208
Oligomers 83-90
Macrogel, formation of 175,177 Onium salts 17,19, 28
MDA (Methylene dianiline) .137-154,158 Onium salt photoinitiators 20i
Mechanical shift factors, dynamic 190 UV absorbance spectra of 30/
Ρ Polymerization
of cyclic ethers, cationic 19
Paints, pigmented E D 65 of epoxides, photoinitiators for
Permanganate, acidic 260,261 cationic 17
Phenalkamines 99—114 of epoxides, rate determining fac
coating formulations with 112* tors in the photoinitiated 10
curing agent properties 102* of epoxy resins, photoinitiated
Phenolicformaldehyde, epoxy resin/ cationic 1-15
(E/PF) 91-98 living 33
Phosphonium Prepolymers, Epon 138
compounds Prepolymers, epoxy 177
electrical properties of cured Pressure cooker test 79
epoxy-anhydride resins con results, comparison of laminate
taining quaternary 54* T and 79, 81/
g
latent accelerators for anhydride- Primer coatings, automotive 73
cured epoxy resins, quater formulation and performance prop
nary 47-56 erties for 74*
nonhalide 53 Printed circuit board industry 77-82

quaternary 49 Pyridine 205
structures of 50* Pyridinium chloride analysis 228
latent accelerators in epoxy-anhy
dride resins, gel time data for
quaternary 51* Q
latent accelerators in epoxy-anhy
dride resins, viscosity ( storage ) Q-e scheme 198
data for quaternary 52* Quaternary
Phosphorous pentafluoride 21 ammonium halides 48
Photoinitiated cationic polymeriza arsonium compounds 55
tion of epoxy resins 1-15 phosphonium compound(s) 49
Photoinitiator(s) 2 electrical properties of cured
for cationic polymerization of epoxy-anhydride resins
epoxides 17 containing 54*
concentration on rate of cure, effect latent accelerators for anhydride-
of 22* cured epoxy resins 47-56
for cross-linking of epoxides 18* structures of 50*
phosphonium latent accelerators in
diaryliodonium salts 7,24, 28
epoxy-anhydride resins, gel
onium salt 20*
UV absorbance spectra of 30/ time data for 51*
PM 31 phosphonium latent accelerators in
TPS 31 epoxy-anhydride resins, vis
triarylsulfonium salt 2—15 cosity ( storage ) data for 52*
stibonium compounds 55
Photolysis of an aryldiazonium salt.... 1—16
Photopolymerizations 15
Photosensitized epoxides, storage R
stability of 22,24, 32
Photosensitized epoxy coatings, vola Relaxation-time spectrum 192
tility of 40-41 Resin ( s ) ( see also Epoxy )
DMH-based hydrophilic 126
pK values on the reaction of amines
a
foaming of 78-79
with epoxy, effect of 249 hydrophobic—hydrophilic balance
Plastics industry, aqueous epoxy resins of amine-cured 118,121
for electrical-reinforced 77-82 hydrophobic TETA-cured 121
PM ( p-methoxybenzenediazonium latent catalysts for epoxy 48
hexafluorophosphate ) 22 preparation 159-160
Polyamides 101 properties of an ideal command-
Polyamines 101 destruct 259
Polybutadienes, low-molecular rate of cure of DGEBA 38*
weight (LMPBs) 57-69 solvent-borne 72
Polyepoxides, self-cross-linkable ...197-210 thermoset 157-182
INDEX 271
Rheovibron viscoelastometer 138 Triarysulfonium halides 3

Ring closure reaction 219-224 Triarysulfonium salt(s) 2,13
Rubbery modulus of epoxy resins 142 photoinitiators 2—15
preparation of 4t-5t
S Triethylenetetramine (TETA) 118
-cured resins, hydrophobic 121
Salt-spray resistance 59, 74 Trimellitic anhydride (TMA) half-
of cationic E D coatings 69 esters of 64
Salt-spray testing 59 Tri-N-butylamine (TBA) 228
SA (Succinic anhydride) 61 Triphenylsulfonium, hexafluoro-
Scanning electron microscope ( SEM ) 160 arsenate 3
Scattering of laser light, back- 93 Triphenylsulfonium hexafluoro-
Schieman reaction 21 phosphate (TPS) 28,29
SEM (Scanning electron microscope) 160 photoinitiators 31
Sodium carbonate 219
Sodium hydroxide 219
Solvent-borne resin 72 U
Spectroscopy, near infrared (NIR) .... 103 Uranyl nitrate 55

Sterilization resistance ( blushing ) of Urethanes 261
can coatings 91-98 UV-cure of epoxy resins 1-16
Stibonium compounds, quaternary .... 55
Stress relaxation 183-195 V
Styrene oxide, photopolymerization of 8, 9/
Succinic anhydride ( SA ) 61 Varnish formula, organic solvent 78/
Sulfonium salts 28-29 Varnish formula, water-based 78/
Varnishes, problems with water-
Τ based 78-79
Vinylpyridine(s) 198
Tack-free time 31 Q-e values in copolymerization of
device for measuring 30i l-ethenyl-4- ( 2,3-epoxy-l-
of epoxides 36i propoxy) benzene with 203i
Tack test 31 Q-e values in copolymerization of
TBA (Tri-N-butyïamine)i"! ...228, 232 2,3-epoxy-l-propyl meth-
T E M (Transmission electron acrylate with 20U
microscope ) 160 4-Vinylcyclohexene dioxide 3
Tensile behavior of epoxy resins 145 2-Vinylpyridines 197-210
T E T A (Triethylenetetramine) 118 4-Vinylpyridines 197-210
T and pressure cooker test results,
g
Viscoelastic behavior 137-156
comparison of laminate 79, 81/ Viscoelastic parameters 184-192
Thermoplastic-modified epoxy resin Viscoelastometer, Rheovibron 138
emulsion 75i
Thermoset resins 157-182
W
Toluene 211-224
Torsional Stiffness Tester, Gehman .... 138 Water-based epoxy resins 77-82
TPR ( Triphenylsulfonium hexa- W L F (Williams-Landel-Ferry)
fluorophosphate) 28,29 equation 183,187
Transepoxidation 221
reaction 222/ Y
Transmission electron microscope
(TEM) 160 Young's modulus of epoxy resins 142

(Ronald S. Bauer (Eds.) ) Epoxy Resin Chemistry

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(Ronald S. Bauer (Eds.) ) Epoxy Resin Chemistry

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Publication Date: December 3, 1979 | doi: 10.1021/bk-1979-0114.

Epoxy Resin Chemistry

Ronald S. Bauer, EDITOR

Shell Development Company

Based on a symposium sponsored

Organic Coatings and Plastics

at the 176th Meeting of the

American Chemical Society,

Miami Beach, Florida,

September 11-15, 1978.

ACS SYMPOSIUM SERIES 114

AMERICAN CHEMICAL SOCIETY

Library of Congress CIP Data

M . Joan Comstock, Series Editor

Kenneth B. Bischoff James P. Lodge

Donald G . Crosby John L. Margrave

Robert E. Feeney Leon Petrakis

Jeremiah P. Freeman F. Sherwood Rowland

E. Desmond Goddard Alan C. Sartorelli

Jack Halpern Raymond B. Seymour

Robert A . Hofstader Aaron W o l d

James D . Idol, Jr. Gunter Zweig

The ACS SYMPOSIUM SERIES was founded in 1974 to provide

pounds. This sustained growth of epoxy resins is a result of the wide

Shell Development Company RONALD S. BAUER

The importance of epoxy resins in the fabrication of surface

presence o f an epoxy r e s i n , boron t r i f l u o r i d e c a t a l y z e s the

X" = B F " , A s F 4 6 , PF 6 , SbCl 6 , etc.

In our l a b o r a t o r y , we have found t h a t t r i a r y l s u l f o n i u m

SbF ~ e t c . , are e x c e l l e n t p h o t o i n i t i a t o r s f o r the p o l y m e r i z a t i o n

Although the r e a c t i o n shown i n equation 2 i s simple and d i r e c t ,

Using the above s y n t h e s i s , a wide v a r i e t y o f t r i a r y l s u l f o n -

time i n months f o r various concentrations of ( C s ^ J q S ASF5" i n

BF/ 191-193 227(21,000) calc. 61.71 4.28 9.14

AsF " 6 195-197 227(21,000) calc. 47.63 3.31 7.06

133-136 237(20,400) calc. 56.90 4.96 6.90

AsFg" - 225(21,740) calc. 46.49 3.88 5.90

BF/ 162-165 243(24,700) calc. 64.28 5.35 8.16 g

Figure 1. Thermogravimetric analysis of (C H ) S AsF ~ in nitrogen and air at

a programmed heating rate of 10°C/min

Figure 2. Solution stability study with various concentrations of (C H ) S AsF 6 5 s

in 4-vinylcyclohexene dioxide at55°C

a f t e r one year storage o f these s o l u t i o n s i n the dark at 55°C.

2Ar- > Ar-Ar e

Ar- + YH > ArH + Y· f (6)

monomer, YH, i n step c r e s u l t s i n the r e l e a s e o f a proton i n

a c e t a l s or e s t e r s was found to a p p r e c i a b l y attenuate the r e a c t i v ­

fonium s a l t s having d i f f e r e n t a n i o n s . Since i t has been shown

The above model s t u d i e s w i t h monofunctional epoxy compounds

Figure 4. Photopolymerization of styrene oxide using 10% (C H ) S* X' salts

UV Cure o f ERL 4221 Using Various T r i p h e n y l s u l f o n i u m S a l t s

Photoinitiator Cure Rate (ft/miη)*

*1.0 mil f i l m s cured using three 200W/in. Hanovia Hg arc

measure o f the r e a c t i v i t y o f the p o l y m e r i z a t i o n system under

4221. The optimum cure rates are obtained at concentrations o f

played i n Figure 7. In t h i s f i g u r e , I i s the i n c i d e n t l i g h t

i n t e n s i t y d e l i v e r e d by a GE H3T7 medium pressure mercury arc

t IRRAD. TIME (MIN.)

Figure 6. Concentration dependency of the cure rate of ERL 4221 on %

0 ' 60 1120 180 240

Figure 8. Effect of temperature on the cure rate of ERL 4221 with 2%

Figure 8 shows the e f f e c t o f temperature i n the p o l y m e r i z a -

i n most epoxy monomers w i t h o u t s e r i o u s l y a f f e c t i n g t h e i r p o l y m e r i z -

a c e t a l s or e s t e r s was found to a p p r e c i a b l y attenuate the r e a c t i v

18. May, C. B. and Tanaka, Y . , "Epoxy Resin Chemistry and Tech

Coatings which harden or "cure" by photoinduced polymeriza