Polymer International 24 (1991) 7-13

Photostability of
Polyetherurethaneureas
8 . P. Thapliyal & R . Chandra*

Department of Chemistry, Delhi College of Engineering, Delhi-110006, India

(Received 31 July 1989; revised version received 20 November 1989; accepted 2 January 1990)

Abstract: Polyetherurethaneureas (PEUUs) were synthesised from polyethyiene-

glycols (PEGS)of molecular weight 400,600 and 1000,4,4-diphenylmethanediiso-
cyanate (MDI) and aliphatic diamine chain extenders, 1,3-propanediamine (PDA)
and 1,6-hexanediamine (HDA). Polymer films were irradiated with 365 nm light at
293 K and the effects of polyether soft segment length and urea hard segment on
photo-oxidative stability were studied by following the variation in weight-average
molecular weight (I@,,,), gel formation and stress-strain properties. Changes in
ultraviolet and infrared spectroscopy were monitored on photo-oxidation and
hydroperoxide content determined. The soft segment length was increased by
increasing the molecular weight of PEG from 400 to 1000 and hard segment
structure was changed by variation of diamine. It was noted that the structure of
urea and polyether soft segment length plays an important role in photostability of
PEUUs. PDA chain extended PEUUs were more stable than H D A chain extended
PEUUs.

Key words: pol yetherurethaneurea, polyethylene glycol, 4,4’-diphenylmethanediiso-

cyanate, 1,3-propanediamine, 1,6-hexanediamine.

INTROD UCTlO N Since polyurethanes do not exist in the same

The effects of light on the service life of poly-
urethanes have attracted considerable interest, and
attention has been given over the past two decades
to the study of photodegradation processes,’ -
but the photostability of polyetherurethaneurea
(PEUU) has not been studied extensively. Beachell
and Chang” investigated the systematic photo-
degradation of urethane model compounds and
established the primary photodegradation pro-
cesses. Gardette and Lemaire l 3 postulated that the
photodegradation of 4,4’-diphenylmethanediiso-
cyanate (MDI) based polyurethanes depends on the
excitation wavelength and proceeds by two entirely
unrelated processes. Quinone diimide products were
formed when wavelengths of light above 340 nm
were used and photo-Fries rearrangement along
with unsubstituted arylamine products were pro-
posed for wavelengths of light below 340nm.
*To whom all correspondence should be addressed.
7
Polymer International 0959-8 103/90/$03.50 0 1990 SCI. Printed in Great Britain
physical state, they find a variety of applications in
diverse fields. Therefore, generalisations projected
from small molecule model compound studies, or
studies of a single polyurethane in a particular
physical state, cannot be of interest for all poly-
urethanes. Hoyle and Kim14 studied the role played
by the polyurethane matrix in photodegradation
processes, i.e. how does the polymer crystallinity and
chain flexibility affect the photodecomposition. In
the present investigation the photostability of
PEUUs having different physical structures is
studied. The most interesting feature of the physical
structure of polyurethane elastomers is their seg-
mental nature. The soft block of a linear polyether,
or polyester, segment attached to a hard block of a
urethane group provides a two-phase morphology
and the elastomeric characteristics depend on the per-
centage content of these blocks. The hard segments
cause physical crosslinking by hydrogen bonding,
whereas the soft segments increase the flexibility of
the polyurethane with increasing polyol chain
8 B. I? Thupliyal, R. Chandru
length. PEUUs with different degrees of soft segment
flexibility were prepared by reacting MDI with
polyethyleneglycol (PEG) of different molecular
weights (400,600 and 1000)and chain extended with
1,3-propanediamine (PDA) or 1,6-hexanediamine
(HDA). The chain extension with different aliphatic
diamines provides varying degrees of strength to the
material.
EXP E R IME NTAL
Materials
The PEUUs used in the present investigation were
synthesised by two-stage solution polymerisation.
The prepolymers formed by the reaction of poly-
ethyleneglycol (0.5 mol) and 4,4’-diphenylmethane-
diisocyanate (1.0 mol) were chain extended with
diamine coupling agent (0.5 mol) to yield high
molecular weight polymers. MDI (E. Merck) was
vacuum distilled before use. Three PEGS (Fluka), of
molecular weights 400, 600 and 1000, were dried
under vacuum. The chain extenders, PDA and HDA
(E. Merck), were vacuum distilled prior to use.
Dimethylformamide (DMF) extra pure was dried
and distilled over calcium hydride twice. Six polymer
samples were synthesised and designated as follows:
PEG 400-PDA PEG 400-HDA
PEG 600-PDA PEG 600-HDA
PEG 1000-PDA PEG 1000-HDA
depending on the molecular weight of PEG and type
of diamine used.
Procedure
Films of uniform thickness ( z120 pm) were cast on a
quartz plate from solution (3% PEUU in DMF) and
dried under vacuum to constant weight. Photo-
oxidative degradation was carried out in air with a
250-W high-pressure mercury vapour lamp. The
films were irradiated with monochromatic light (365
nm) in a chamber at a temperature of 293K. The
temperature was controlled within 1.0 K. The
changes in weight-average molecular weight (M,)
were determined by a Brice-Phoenix light scattering
photometer (Phoenix Precision Instrument Co.,
Philadelphia, USA). The refractive index increment
(dnldc) for various polyurethane samples in D M F
were determined using a Brice-Phoenix differential
refractometer. The values at ,I= 546 nm were
PEG 400-PDA = 0.06 1
PEG 400-HDA = 0.063
PEG 600-PDA = 0-077
PEG 600-HDA = 0.082
PEG 1000-PDA = 0.087
PEG 1000-HDA = 0,088
The percentage gel contents of irradiated samples
at ambient temperature were determined in D M F
with occasional agitation of capped centrifuge tubes.
Stress-strain properties were determined on a
Zwick universal testing machine (model 1435). The
changes in UV and IR spectra were recorded on a
Hitachi UV-Visible-NIR spectrophotometer
(model 330) and a Perkin-Elmer infrared spectro-
photometer (model 783), respectively.
RESULTS AND DISCUSSION
Variation in ,@I of PEUUs as a function of
irradiation time with 365 nm light at 293 K is shown
in Fig. 1. The plots show a rapid decrease in M,,
which then slows down, suggesting that the initial
drop in Mw is due to random scission of bonds at
various weak links, which may be distributed along
the polymer chain. The loss in molecular weight of
these copolyurethanes can result from chain
cleavage at the urethane, urea and polyether
linkages. After long exposures there are visible
opalescences due to crosslinking, with microgel
formation by the fragments of the polymer mol-
ecule. It is obvious from Fig. l that initial chain
scission is at a maximum in the case of PEG 1000
and at a minimum for PEG 400 based copolymers.
For PEG 1000 based copolymers ether cleavage may
be the largest contributor to loss in molecular
weight. Figure 2 shows the increase in gel content of
PEUUs with irradiation time. From Figs 1 and 2 it is
seen that PDA chain extended copolyurethanes
show more photostability than HDA chain ex-
tended copolyurethanes. Thus, for these aliphatic
diamine extended PEUUs, the chemical structure of
9 oc
1 PEG 400-Pa4 2 PEG 400-HDA
3 PEG 600-PDA 4 PEG BOO-HDA
5 PEG 1000-PDA 6 PEG 1000-HDA
I
1 I I I I I 1 I
4 8 12 16 20 24 28
Time (h)
Fig. 1. Changes in A, of PEUU films irradiated with 365 nm
light in air at 293 K as a function of irradiation time.
POLYMER INTERNATIONAL VOL. 24, NO. 1,1991
Photostability of polyetherurethaneureas
1 PEG 400-PDA 2 PEG 400-HDA
3 PEG 600- PDA 4 PEG 600-HDA
5 PEG 1000-PDA 6 PEG 1000-HDA
Time (h )
Fig. 2. Increase in gel content of PEUU films irradiated with
365 nm light in air at 293 K as a function'of time.
the resulting urea linkage is as important as that of
the urethane linkages. Morphological studies of the
polyurethane urea system have shown that the use of
diamine instead of diol permits better phase
separation. The effect of chain extenders on the
photo-oxidative stability of polyurethanes can be
explained on the basis of the number of CH,
carbons in the extender. The superior properties of
PDA chain extended polyurethanes are explained
on the basis of the regularity of the backbone and the
ease of hydrogen bond formation. Bonart et a l l 5
have shown that the hard segment T, of MDI-
diamine systems decreases when diamines con-
taining higher numbers of CH, groups are used.
The stress-strain curves of different PEUUs are
shown in Fig. 3. Variation in stress and elongation at
break of various PEUUs with exposure time are
shown in Figs 4 and 5. It is well known that the
tensile behaviour of a segmented polyurethane
generally depends upon the size, shape and per-
centage content of the hard segment, intermolecular
bonding within the hard domain and the molecular
1 PEG 400-PDA 2 PEG 400-HDA
3 PEG 600-PDA 4PEG 600-HDA
5 PEG 1ooO-PDA 6PEG 1000-HDA
-6
Elongation (%)
Fig. 3. Stress-strain behaviour of various PEUUs at 293 K.
POLYMER INTERNATIONAL VOL. 24, NO. 1,1991
9
1 PEG 400-PDA 2 PEG 400-HDA
3 PEG 600-PDA 4 PEG 600-HDA
5 PEG 1ooO -PDA 5 PEG 1000-HDA
20-
Fig. 4. Variation in stress at break of PEUUs after irradiation
with 365 nm light in air at 293 K as a function of time.
weight of the soft segment. On the basis of the stress-
strain results, it is seen that PEG 1000 based
polymers begin to show some loss in both stress and
elongation at break, consistent with the losses in
their molecular weight. At higher periods of
irradiation there is some increase in breaking
strength but no significant change in the elongation.
This may be because of crosslinking by the
fragments of the polymer molecules. The ultimate
tensile strength and elongation of PEG 400 based
polyurethanes are unexpected and are the most
affected by irradiation. Morphological studies of
these failures after long periods of exposure will be
reported elsewhere. The PDA chain extended
PEUUs show better properties than HDA chain
extended PEUUs after photo-irradiation.
100
I
1 PEG 400-PDA 2 PEG 400-HDA
3 PEG 600-PDA 4 PEG 600-HDA
5 PEG 1000-PDA 6 PEG 1000-HDA
800
20 40 60 80
Time ( h )
Fig. 5. Variation in elongation at break of PEUUs after
irradiation with 365 nm light in air at 293 K as a function of time.
10 B. P Thapliyal, R. Chandra

I Oh- Figure 6 shows UV spectra of the irradiated

PEUUs. The spectral changes are greatest for PEG
1000-PDA and smallest for PEG 400-PDA. The
absorption increases in intensity and shifts towards
the visible region on photo-oxidation. Similar
bathochromic shifts have been observed for other
polyurethanes during phot~degradation.~.~~'~*'
Figure 7 shows the variation in yellowing index with
irradiation time. The yellowing of MDI based
polyurethanes is attributed to the photodecom-
position of urethane linkages to give quinone
diimide p r o d u ~ t s , ~ * ' ~which
, ' ~ * ' ~are activated in the
presence of oxygen when irradiated with light of
365 nm, as shown below:
0 0
O
H
--dN
@
-H@
2-0c+
- II

IhY

0
1 0
- 0 L N ~ C ~ I1N ~ o
- -
The photodecomposition of an aromatic urethane
Wavelength (nm) group is believed to proceed via cleavage of N-C
Fig. 6. Changes in UV spectra of PEUUs after different and C-0 bonds in the urethane g r o ~ p . ~ , ' ~ , ' ~ , ' ~
periods of irradiation with 365 nm light in air at 293 K. '
Beachell and Chang and Schultze l 7 have sug-
gested that the N-C cleavage occurs preferentially
in aromatic urethanes to give conjugated azo
compounds:
1 PEG 400- PDA2 PEG 400-HDA
3 PEG BOO-PDA 4 PEG 600-HDA
5pEG 1000-PDA 6 PEG 1000-HDA

I /6
which are responsible for the discoloration of
polyurethanes on storage. The following reactions

8C
rn
n
L
51
n
Q
-Oh
_-___
40h
I I 1 I I I I I I I I I I
4 8 12 16 20 24 28 4c K) 3000 2000 1600 loo0 600
Time ( h ) Wavenumber (cm-')
Fig. 7. Variation in yellowing index of PEUUs as a function of Fig. 8. Changes in main IR absorptions after irradiation with
irradiation time. 365 nm light.

POLYMER INTERNATIONAL VOL. 24, NO. 1,1991

Photostability of polyetherurethaneureas
are given for photodecomposition at the N-C
bond:
' C 4 - C H 2-CH2-0-
II
0
0 hy
~ - C - 0 - 4 H II2 - C H 2 - - O - -
(photo-Fries rearrangement)
0 results in volatilisation of low molecular weight
II
@- NH + 'C-O--CH2-CHZ-0-
I from urethane or urea cleavage contribute to
-HzdH--O-+
CO, + cH2-CH2-O-
(abstraction of hydrogen from polyether segment)
Oxidative coupling of substituted aniline products
can lead to conjugated azo compounds.
It is seen that PEG400-PDA is the most stable
polymer and does not yellow, or develop chromo-
phores, as rapidly as PEG 600-PDA and PEG 1000-
PDA. The substitution of HDA for PDA gives
polyurethanes that degrade rapidly upon
irradiation.
Figure 8 shows the changes in main IR absorp-
tions of polyurethanes on exposure. It is seen that
the N-H absorption (3330cm- ') increases with
exposure due to the formation of amine, unsub-
stituted urethane and urea products resulting from
cleavage of urethane and urea bonds. The C-0-C
absorption (1110 cm- ') decreases more rapidly with
R' + 4 - - C H 2 2 H 2 - 0 -
I (C)
1 peroxy (0-0) group, but the influence of the
-04H2-CH-0-
I more significant as the peroxy bond is often
J 0 4 - H
&CH,-C-H + '0-
II
0 peroxide on the N-H stretching vibration and at
POLYMER INTERNATIONAL VOL.. 24, NO. 1,1991
11
exposure than does the urethanes C-0 absorption
(1230cm- l), indicating that the polyether segment
degrades more rapidly than the urethane linkage.
Degradation products from the polyether could
account for the appearance of OH and some
increase in C=O absorption. The abstraction of
hydrogen from methylene groups of the polyether
by radicals resulting from the cleavage of urethane
or urea groups accelerates the oxidative degradation
and cleavage of the polyether.
Studies on polypropyleneglycol based aromatic
p o l y ~ r e t h a n e s ~ have
~ ' ~ ~shown
'~ that the degra-
dation of polyether involves oxygen uptake and
hydrocarbons. The increase in absorption at 1730
cm- was assigned to oxidised polyether residues,
while other carbonyl-containing products expected
broadening of this peak.
On photo-oxidative degradation hydroperoxide
formation takes place in the hydrocarbon moieties
of the polyurethanes. Gardette and LemaireZ0have
observed four types of hydroperoxy groups depend-
ing upon the structure of the polyurethane
elastomers. The possible hydroperoxides in the
PEG-MDI-diamine based copolyurethanes may be
4-CH-CH 2-
I
0-0-H
(B)
0
II
&)--NH-C-NH-CH+-CH2-),-
\ / - I
0-0-H
x=3forPDA x=5forHDA
caused by hydroperoxidation of (A)the CH, group a
to the phenyl group of the diisocyanate, (B) the CH2
group ct to the ether group, and (C) the CH, group a
to the urea group.
In the IR region there is an absorption due to the
peroxide bond on absorption of other groups is
obscured. IR spectra of the PEG-MDI-diamine
based polyurethane on photo-irradiation shows at
'
3330 cm- the effect of a neighbouring hydro-
12 B. P. Thapliyal, R. Chandra

The semi-aromatic urea linkage in these polymers

should be unstable, probably about as unstable as
the urethane linkage. Degradation of the urea
linkage is relatively extensive only in PEG 1000-
PDA. For PEG 400-PDA and PEG 600-PDA, the
urethane and urea linkages degrade at about the
2
+
10- same rate. Figure 10 shows that the ratio of urea
8 carbonyl(l635 cm-') to urethane C-0 (1230cm-')
$ 8- absorptions after time t
6-

1 PEG 400-PDA 2 PEG 400-HDA

4r 3 PEG 600-PDA 4 PEG 600-HDA
I I// 5 PEG 1ooO-PDA 6 PEG l 0 0 O H D A
on irradiation is fairly constant. There is less drop in
this ratio for PDA based polyurethanes. Use of
diamine chain extenders increases the primary and
0
r 4
I I
8
I
12 16
I I
20
I
24 secondary valence crosslinks in urethane elastom-
Time (h)
ers" and, in the case of PDA based polyurethanes,
Fig. 9. Variation in hydroperoxide concentration of PEUU further stability is imparted by increasing the
films irradiated with 365 nm light in air as a function of time.
molecular symmetry of the extended chain.22
For all polymers the polyether segments degrade
1745 cm-' the effect of hydroperoxide in proximity more rapidly than the urethane linkages. It is seen
of a carbonyl group. Figure 9 shows the concen-
tration of hydroperoxide as a function of irradiation
time as determined by spectroscopic measure- 1 PEG 400-PDA 2 PEG 400-HDA
ments. '' 8 3 PEG 600-PDA 4 PEG 600-HDA
5 PEG 1OOO-PDA 6 PEG 1000-HDA
From limited studies on urea,I6 photochemical
degradation of urea groups appears to follow the
same general degradation pathway as outlined for
urethanes. Thus for aliphatic ureas the pathway may
be the same as that of aliphatic urethanes and for
aromatic ureas similar to that of aromatic urethanes.

1 PEG 400-PDA 2 PEG 400-HDA (a)

3 PEG 600-PDA 4 PEG BOO-HDA 70
5 PEG 1000-PDA 6 PEG 1000-HDA I I 1 I I I
4 0 12 16 20 24
Time(h)

11ob 1 PEG 400-PDA 2 PEG 400-HDA

3 PEG 600-PDA 4 PEG 600-HDA
8
r
5 PEG 1000-PDA 6 PEG 1000-HDA
X

t: IF:
8
X

? IP

-x-x5
-4
-6

I I I I I I 4 8 12 16 20 24
4 8 12 16 20 24 Time ( h )
Time ( h ) Fig. 11. Changes in the ratios of (a) ether C-0-C (1110
Fig. 10. Changes in the ratios of urea carbonyl (1635cm-')/ cm-')/urethane C-0 (1230cm-') absorptions and (b) ether
urethane C-0 (1230cm-') absorptions of PEUU films after C-0---C (1 1 lOcm-')/urea carbonyl (1635 cm-') absorptions
time t on irradiation with 365 nm light. of PEUU films after time t on irradiation with 365 nm light.

POLYMER INTERNATIONAL VOL. 24, NO. 1,1991

Photostability of polyetherurethaneureas
that the C-0-C absorption (1 1 10cm- ') decreases
more with exposure than does the urethane C-0
(1230cm-'). Figure l l ( a ) shows the ratios of
C-0-C (1110cm-')/urethane C-0 (1230cm-')
absorptions. Similarly, the polyether segment in the
polymers degrades more rapidly than the urea
linkage (Fig. 1l(b)).
These studies show the influence of physical state
on the photostability of polyurethanes. PEUUs
based on low molecular weight PEG are more
resistant to photo-oxidative discoloration and
develop comparatively fewer chromophores than
PEUUs based on high molecular weight PEG. But
the loss of mechanical properties is significantly
higher in PEG 400 based PEUU in comparison with
the PEUUs synthesised from higher molecular
weight PEGS (600 and 1000).This behaviour reflects
the importance of morphological changes taking
place as a result of photo-oxidation. Therefore the
structural changes of a particular block/segment
may lead to failure of the system because of
weathering on storage, or in actual usage.
ACKNOWLEDGEMENT
One of the authors (B.P.T.)is thankful to CSIR, New
Delhi, for providing financial assistance to carry out
the work.
POLYMER INTERNATIONAL VOL. 24, NO. 1,1991
13
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