Die Angewandte Makromolekulare Chemie 93 (1981) 27- 42 (Nr.

1411)

Chalmers University of Technology,

Department of Engineering Chemistry,
S-412 96 Gothenburg, Sweden

Urea-Formaldehy de Resins*
4. Formation of Condensation Products during Resin Preparation

Kjell Kumlin and Rune Simonson

(Received 18 January 1980)

SUMMARY:
The formation of diurea compounds containing methylene and dimethylene ether
bridges, respectively, as well as the formation of more highly condensed compounds
during the preparation of urea-formaldehyde resins under different conditions have
been investigated. The quantitative determination of each individual diurea compound
was carried out by means of liquid chromatography. Identification of diurea com-
pounds with a dimethylene ether bridge was made by H-NMR spectroscopy.

ZUSAMMENFASSUNG :
Die Bildung von Diharnstoffverbindungen mit Methylen- bzw. Dimethylenather-
brilcken sowie die Bildung hOher kondensierter Verbindungen wiIhrend der Herstel-
lung von Harnstoff-Formaldehyd-Harzen unter verschiedenen Bedingungen wurden
untersucht. Die quantitative Bestimmung jeder einzelnen Diharnstoffverbindung
wurde mit Hilfe der Flilssigchromatographie durchgefilhrt. Die Diharnstoffverbin-
dungen mit einer Dimethylenetherbrilcke wurden durch H-NMR-Spektroskopie
identifiziert.

Introduction

In the preparation of urea-formaldehyde (UF) resins the purpose of the

initial methylolation step normally is to obtain a mixture consisting pre-
dominantly of low molecular weight components. However, condensation
of the monourea methylol compounds primarily formed usually occurs to
some extent. It has been suggested that these condensation reactions can

* Part 3 Cf..

0 1981 Htlthig & Wepf Verlag, Basel 0003-3 146/81/0093-0027$03.00/0 27

 K. Kumlin and R. Simonson

proceed in two different ways, by the formation of either methylene bridges

(I) or dimethylene ether bridges (11), e.g.

0 0 0
I1
H2NCNHCH2OH + H2NCNHCHzOH
II II

0 0
I1 II
HzNCNHCHzOH + HOCH2HNCNHCH2OH P
0 0
II II
H2NCNHCH2OCHZHNCNHCH20H + H20

Examination of the former reaction path has been reported by several

authors. For example, Kadowaki prepared different compounds containing
methylene bridges' and de Jong and de Jonge studied the kinetics in acidic
media2. Recently, 'H-NMR3m4and I3C-NMRS- spectroscopy have provided
information about the presence of methylene bridges in UF resins. This type
of linkage has been claimed to be formed only in acidic solution^^^^- I I .
Concerning the formation of dimethylene ether bridges the evidence so far
presented is somewhat ambiguous12. One reason for this has undoubtedly
been the lack of a suitable analytical method. In the common chemical
analysis of the amount of methylol groups the alkaline conditions prevailing
cause a decomposition of these bridges and the resulting formaldehyde is
also included in the determinati~n'~. It has been proposed that an estimate
of the amount of ether linkages may be obtained by a comparison of the
amounts of methylol groups found with and without addition of an amine
during the determinationI4.
On the basis of indirect methods, Zigeuner proposed the presence of ether
linkages in different UF p r o d ~ c t s ~ By
, ' ~ means
. of IR spectroscopy, Becher
found absorption bands which were ascribed to the occurrence of di-
methylene ether bridgest6. In I3C-NMR spectra, signals have also been
assigned to this type of linkages-*. It is believed that ether bridges are
formed in alkaline, neutral, as well as in weakly acidic media9-".
In part 3 of this series", the formation and reactions of monourea
methylol compounds during resin preparation under different conditions
were reported. The diurea compounds formed in these cases are dealt with in
the present paper. The quantitative determination of each individual diurea
compound was made by means of the liquid chromatography (LC) system
described earlierI8. The formation of more highly condensed compounds as

28
 Urea-FormaldehydeResins, 4

well as the identification of diurea compounds containing dimethylene ether

bridges are presented.

Results and Discussion

Identification of Diurea Compounds Containing a Dimethylene Ether
L inkage

As expected from the distribution of monourea compounds1', the pre-

paration of a resin under proper conditions resulted, for samples taken at a
late stage, in the appearence on the LC chromatogram of six main peaks
eluted after the monourea compounds (Fig. la). By comparison with the
results obtained from analysis of synthesized sample^'.'^, three peaks were
found to correspond to methylenediurea (MDU), monomethylolmethylene-
diurea (MMMDU), and dimethylolmethylenediurea (DMMDU), respec-
tively. Besides the investigation presented earliert8,MDU was isolated from
a preparative LC column and analyzed by means of 'H-NMR. The chemical
shifts of the protons in MDU (Tab. 1) agree well with those reported in the
literature3*20*2' .
The other three peaks recorded were found on analysis of resins prepared
under acidic or neutral as well as alkaline conditions (Fig. 1 a and 1 b). These
peaks were assumed to correspond to oxymethylenediurea (OMDU), mono-
methyloloxymethylenediurea (MMOMDU), and dimethyloloxymethylene-
diurea (DMOMDU), respectivelyI8. For the purpose of identification each
substance was collected in a chromatographic run on preparative scale and
analyzed by means of 'H-NMR spectroscopy. Although care was taken to
perform the isolation at low temperature22, some decomposition and
formation of ethyl ethers occurred in the fractions supposed to contain
OMDU and MMOMDU, respectively. This could be shown by LC analysis
of the isolated fractions and was also indicated by the 'H-NMR analysis. On
the other hand, DMOMDU seemed to be quite stable.
As evident from Fig. 2, no 'H-NMR signals derived from methylene
protons in methylene bridges ( 2 4 . 2 ppm), methylol groups on tertiary
nitrogen (4.6 - 4.7 ppm)=, or hemiformals (4.6 - 4.7 ~ p m were ) ~ observed.
From the intensities (integrals) recorded, it could be seen that the com-
pounds isolated contained, relative to the number of hydroxyl protons, too
many CH2-groups (4.4 - 4.5 ppm) interlinking a secondary nitrogen atom
and an oxygen atom to correspond solely to CH,OH-groups. Thus in the
case of the sample supposed to be DMOMDU, a comparison of the

29
u
0

Tab. 1 . Chemical shifts of protons in diurea compounds.

?;:
Compounda Chemical shifts (ppm) 7c
C
!E
-CH2- -NHCHzOH >NCHzOCHzN< -NHCHZOH -NHZ -NH- 5'
Ea
MDU 4.19 5.63 6.47
OMDU 4.44 5.74 6.76 P
(I)
MMOMDU 4.4 - 4.5 4.4 - 4.5 5.29 5.74 6.75; 6.85 5'
DMOMDU 4.4 - 4.5 4.4 - 4.5 5.29 6.84; 6.86 0

E
Y
a Designations: see text.
 Urea-FormaldehydeResins, 4

Chart reading
MMMDU a

I MMOMDU b

I\ DMOMDU

I I I 1 I
200 250 300 350
Eluate volume, cm3

Fig. 1. Separation of diurea compounds in UF resin by means of LC; F/U = 1.4,

70C, 120 min; a pH = 7.0; b pH = 9.4; Column Aminex AS, Li+ form, 50
f 0.1 "C, 1250.4.1 mm; Eluent 85 wt.-% aqueous ethanol, 0.01 M with
respect to LiCI;

1
0
II
MMMDU = H2N NHCH,HNCNHCH,OH,

1
0
II
DMMDU = HOCH2HNCNHCH2HN NHCHZOH,

1
0
II
MMOMDU = H2N HNCH20CH2HNCNHCH20H,

i
DMOMDU = HOCHZHN NHCHZOCHzHNCNHCH,OH,
0
II
x = unknown substance, probably a diurea compound containing a tertiary
nitrogen atom.

intensities for the CH2- and the OH-protons, respectively, showed that half
of the CH,-protons were accounted for in the form of methylol groups. A
further comparison of the intensities (-NH- and -CHI-) showed that
the secondary amine and methylene groups were equal in number. In the
spectrum obtained for the substance assumed to be OMDU, a doublet was

31
 K. Kumlin and R. Simonson

MMOMDU

_- f
DMOYW
1

I'
i

1 I I
7 6 5 4
Chemicol shifts, ppm

Fig. 2. 270 MHz 'H-NMR spectra of MMOMDU and DMOMDU; solvent

DMSO-4; internal standard TMS; room temp.

found in the CH2-range showing a coupling with just one proton. On the
basis of these findings it was concluded that the substances consisted of
diurea compounds containing a dimethylene ether linkage. (CH,-protons in
uron compounds are found more downfield (4.6 - 4.9 ppm) as will be dealt
with in a forthcoming paper. Furthermore, urons are eluted early on the LC
column and ahead of the common monourea compounds.) An examination
of the chemical shifts and intensities (Fig. 2 and Tab. 1) showed the com-
pounds to be those predicted.
Analogously to the results found for the monourea and the methylene-
diurea compounds'8, respectively, a linear relationship was also obtained in

32
 Urea-FormaldehydeResins, 4

the case of the oxymethylenediurea compounds, when log D, (D, = volume

distribution coefficient) was plotted versus the number of methylol groups.

Influence of the pH

The yields of the six main diurea compounds formed during the resin
preparation versus the pH are shown in Fig. 3. The results refer to resins
with a F/U molar ratio of 1.4. The reaction temperature was 70C. These
conditions were the most exhaustively studied ones".

'ield, '10
> NCH,N : > NCH20CH,N <

10
I
I
60 min

120 min
-,---

120 mtn I
I
I

I 1 I I

6 7 8 9
PH
Fig. 3. Yields of different diurea compounds vs. the pH value at a F/U molar ratio
of 1.4; reaction times 60 and 120 rnin; temp. 7OOC; the yield (Vo) was cal-
culated on basis of urea according to mole diurea*200/mole urea fed;
- _ _ MDU, -MMMDU, - . - DMMDU, - - - OMDU, - * . -
MMOMDU, - - DMOMDU.

33
 K. Kumlin and R. Simonson
Although LC-runs on a preparative scale resulted in the isolation of
substances sufficiently pure to permit identification, the determination of
response factors (mghnit peak area) could not be made in the normal way
by addition of known amounts of each diurea compound to the LC-column.
A calculation of the refractive indicesz3for the different diurea compounds
showed, however, that these differed only slightly. Based on a mass balance
for resins containing only mono- and diurea compounds, an average value of
the response factor, the same for all diurea compounds, was therefore
estimated.
As shown in Fig. 3, diurea compounds containing a methylene bridge were
formed a t pH values below 8, the amounts being considerably increased
when the pH was lowered, e. g. from 7.5 to 6.5. The monomethylol form
was obtained in the highest yield, a finding which is consistent with the
relative composition of the monourea compounds in the resin and the high
relative reactivity of the methylol group in monomethylolurea (MMU)Z. Re-
markably, MDU was found in low yield ( c 1 To) even in preparations made
at pH 28.
Diurea compounds with a dimethylene ether bridge were formed in all
resins prepared. However, there was a strong pH dependence for this type of
bridge, a minimum in the rate of formation appearing at pH around 8 (cf.
also Fig. 4b). The different yield curves exhibited a fairly symmetrical shape
and it is noteworthy that at low pH values the yield of diurea compounds
with an ether linkage was of the same order of magnitude as that of the
compounds with a methylene bridge.
At pH values 26.5, diurea compounds were found in the resin after 30
min, whereas at lower pH values condensation products were already ap-
parent in the sample taken after 15 min. In Fig. 4 the sum of the yields of the
different diurea compounds with a methylene bridge as well as that of the
compounds containing a dimethylene ether linkage versus the reaction time
is given. Within the pH interval 6.5 - 7.5, the formation of oxymethylene-
diurea compounds was at an early stage at least as rapid as that of the com-
pounds containing a methylene bridge. At pH 6.0, the appearance of com-
pounds with an ether linkage was delayed somewhat and the total yield after
30 min was less than that of the compounds with the other bridge type. This
might be explained by the observation that the formation of N,N-di-
methylolurea (N,N -DMU) by further methylolation of MMU seemed to be
less rapid, when pH was lowered below 7.0. The increased content of
unsubstituted amide groups could then favour the formation of methylene
bridges. At pH 5.1 only trace amounts of diurea compounds containing an

34
 Urea-Formaldehyde Resins, 4

20

15

10

Reaction time, min

Fig. 4. The sum of the yields of the different diurea compounds with a methylene
and a dimethylene ether bridge, respectively, vs. the reaction time at dif-
ferent pH values; F/U = 1.4; temp. 70C.

ether bridge could be found. This might merely be a result of the further
increased content of NH,-groups and, consequently, a decreased accessibil-
ity of methylol groups, but might also reflect an influence on the reaction
mechanism of the increased acidity rendering the formation of ether linkages
more difficult. It is noteworthy, however, that some DMOMDU was formed
when N,N'-DMU was treated in a similar way at such a low pH value as 3.5.
The main reaction products were methylene bridge containing compounds
evidently formed after hydrolysis of N,N '-DMU.
On the alkaline side, a change in pH, e.g. from 9.0 to 9.4, considerably
increased the formation of oxymethylenediurea compounds, the initial rate
of formation at 9.4 being comparable to that at pH 6.5.
With increased reaction time more highly condensed compounds were
formed at low pH values but also at pH 9.4 (120 min). This can be seen from
the lines (Fig. 6) designated by lOO-MU-DU, which correspond to the mole

35
 K. Kumlin and R. Simonson

fraction of urea converted into condensation products > diurea (DU)

compounds at F/U = 1.4. After 60 min at pH 6.0, about 40% of the urea
could be found in molecular forms > DU compounds, whereas as much as
63% appeared in this form already after 30 min at pH 5.1. This latter yield
value can be compared with the corresponding value of 100-MU (MU =
monourea compounds) amounting to 77% 17. Evidently, the molecular
growth proceeded at a rather high rate on only a moderate increase of the
acidity .
At pH 9.4, no compounds > DU had appeared after 60 min and even in
the sample taken after 120 min (F/U = 1.4) only about 7% of the urea were
converted into such compounds. A further increase of pH resulted, however,
in a considerably increased formation of condensation products. Thus,
about 19% of the urea were found in the form of diurea compounds after 60
min at pH 10.5 (F/U = 1.4), while 32% were found in more highly
condensed forms.
The continued condensation resulted in the formation of a precipitate
either on the dilution prior to the LC-analy~is'~, or, under more extreme pH
conditions, already in the reactor. Some precipitates formed were repeatedly
treated with 85 wt.-To EtOH and the extracts were analyzed on the LC-
column. The results obtained showed that only a few permillage of the
diurea (and monourea) compounds present in the resin was occluded. To
obtain the relative molecular mass distribution in a resin, a gel permeation
chromatography system based on the use of dimethylsulphoxide was
developed". As an example, the chromatogram obtained for the resin
sample taken after 2 h at pH 6.5 is given in Fig. 5 . The number average of the
relative molecular mass (M,) was evaluated to be about 160. The largest
molecules had a relative molecular mass of about 650. The value 100-MU-
DU amounted to 20% (Fig. 6b).
The pronounced formation of more highly condensed compounds at low
p H values is reflected by the shape of the yield curves obtained for the diurea
compounds (Fig. 3). Since the formation of diurea compounds containing a
methylene bridge was strongly favoured when the reaction mixture was made
acidic, the condensation to larger molecules at low pH values also had to
proceed to a large extent through methylene bridge formation. Considering
the high yields of the diurea compounds with a dimethylene ether bridge
obtained at pH 6.5, a further condensation through the formation of ether
linkage also seemed possible within this pH range. At F/U = 1.4, the extent
of this further formation of ether linkages might, however, be less than that
of methylene bridges, since the consumption of methylol groups connected

36
 Urea-FormaldehydeResins, 4

MW 600 400 200 100 60

I I I

0 50 60 70
Retention volume, cm3

Fig. 5. Gel permeation chromatography of a resin prepared at F/U = 1.4. pH =

6.5, 70C, 120 min; Column Sephadex LH-20, 30 f 0.1 "C, 940.12.7 mm;
eluent DMSO/H,O = 9/1 w/w.

with the formation of diurea compounds as well as the lowered rate of

methylolation with decreased pH might result in a decrease of the probabil-
ity of a further reaction between two methylol groups.

Influence of the F/U Molar Ratio

With regard to the relative composition of the monourea compounds in

the resin", on prolonged heating an increased F/U molar ratio resulted in
considerably increased yields of N,N '-DMU and trimethylolurea (TMU),
whereas the yield of MMU decreased. At F/U = 2.2, only a few percent of
the urea remained unreacted after 1 h.
The predominant diurea compound found at F/U = 2.2 was DMOMDU,
whereas at F/U = 1.4 MMOMDU was the most abundant one, on the acidic
side together with MMMDU (Fig. 3). Furthermore, an increased F/U molar
ratio resulted in the formation of new diurea compounds compared to those
given in Fig. 1. Most probably these were derived from condensation
reactions involving TMU.

37
 K. Kumlin and R. Simonson

As shown in Fig. 6, the increased content of methylol groups in the resin at

F/U = 2.2 and, consequently, the increased probability of formation of
dimethylene ether linkages, caused at pH > 8 a pronounced increase in the

field, % a 60 min
50
1 F/U=IL I

LO
\ i
I
I

i
IFIU.22
30

20

10

Fig. 6. Yield of condensation products vs. pH at different F/U molar ratios.

Reaction times 60 and 120 min; 100 - MU (Yo) = 100 - Z yields (Yo)of the
different monourea compounds; 100 - MU - DU (Yo) = 100 - Z yields
(Yo)of the different mono- and diurea compounds.

content of condensation products (expressed as 100-MU ("0)). As evident

from the lines (Fig. 6b) designated by 100-MU-DU (Vo), an increased degree
of methylolation resulted in formation of more highly condensed com-
pounds, which was far above that found at F/U = 1.4.In other words, an
increased F/U molar ratio at pH > 8 led to a reactivity which to a consider-
able extent was maintained even after the initial combination of two mono-
urea compounds.
As shown in Fig. 7, a decrease of pH at F/U = 1.4 led to an increased
fraction of the diurea compounds present containing a methylene bridge. At

38
 Urea-FormaldehydeResins, 4

I DU with -CH20CH2-,

1 I I

6 7 8 9
PH

Fig. 7. Fraction of diurea compounds containing a dimethylene ether bridge ex-

pressed as percentage of the total diurea content vs. pH; reaction time 120
min; all calculations based on urea.

pH 6.5, the two bridge types were about equally represented among the
diurea compounds found after 2 h. The rapid increase in the formation of
condensation products, expressed as 100-MU (Fig. 6, F/U = 1.4), connected
with a lowering in pH below that corresponding to the minimum (pH 8) was
consistent with the results given in Fig. 3. A comparison of the curves 100-
MU and 100-MU-DU (F/U = 1.4) shows that at fairly neutral conditions
(pH 7.0 f 0.5) the condensation to a large extent implied a formation of
diurea compounds, the DU part being 80% at pH 7. As mentioned earlier, a
further decrease of pH resulted in a rapid increase of the relative molecular
mass.
At the increased F/U molar ratios, a minimum in the formation of
condensation products was also found. A displacement towards lower pH
values compared to that found at F/U = 1.4 had occurred, however, and the
minimum found at F/U = 2.2 appeared at a pH just above 7. This
apparently parallel displacement of the 100-MU curve at F/U = 2.2 might
be due to the circumstance that at high F/U molar ratio the condensation
reactions mainly proceeded via N,N'-DMU and TMU as well as methylolat-
ed diurea compounds, whereas at low F/U ratio MMU (or even urea) was to
a large extent involved in the molecular growth of the resin. The low content
of unsubstituted amine groups at F/U = 2.2 indicated that the formation of
condensation products containing methylene bridges (pH <7.5) was

39
 K. Kumlin and R. Simonson

probably of less importance. As shown in Fig. 7, only about one fifth of the
diurea compounds present after 2 h at pH 6.0 contained a methylene bridge,
whereas at higher pH values this bridge type was almost absent in the diurea
compounds.
Although the formation of methylene bridges could not be neglected at
low pH values even in a resin with a high degree of methylolation, it was
assumed that the curves 100-MU and 100-MU-DU at F/U = 2.2 roughly
corresponded to condensation products containing a dimethylene ether
linkage. Since the curves were almost symmetrical around the minimum
point, it might be further assumed that in this case the formation of ether
linkages was activated by H + and OH- almost t o the same extent.

Influence of the Reaction Temperature

As can be seen from Fig. 8, condensation reactions occurred to a

negligible extent at pH 8.5 and 60C even after 120 min. With increased

50

LO

30

20

10

Reaction time, min

Fig. 8. Yield of condensation products (100 - MU ('4'0)) vs. reaction time at dif-
ferent temperatures and pH; -pH 7.0; - - - pH 8.5.

40
 Urea-FotmaldehydeResins, 4

reaction temperature, the influence of the reaction time became more pro-
nounced and after 120 min at 80C about 30% of the urea fed was found in
the form of condensation products.
At pH 7.0, the reactions were considerably more dependent on the tem-
perature. An increase from 60 to 80C thus increased the conversion into
molecules 2DU from 9 to 54% for samples taken after 120 min.
The results show that in order to optimize the formation of condensed
compounds during the resin preparation a careful control of the tempera-
ture-time relationship was necessary.

Conclusions

As pointed out in a previous paper, a pH value outside a rather narrow

range can easily result in an uncontrolled condensation during the resin pre-
paration. At low F/U molar ratios, a minimum in the formation of condens-
ed products is found at a pH value of about 8. Within the pH interval
7.5 - 9.0, the formation of diurea compounds is still kept below a conversion
of about 10% based on urea at a reaction time of 2 h. With increased F/U
ratio (F/U = 2.2), the reaction minimum is found at a pH value of about
7.2, the interval which gives low amounts of condensed products being quite
narrow. A change in pH by half a unit in this case will result in a conside-
rable increase of the content of molecular forms > DU, whereas the diurea
content will remain fairly constant. A high reaction temperature greatly
increases the condensation.

Financial support from Perstorp AB, Sweden, is gratefully acknowledged.

The authors are indebted to Dr. Jan-Erik Vik for valuable discussions and
Miss Christina Lidkn for typewriting the manuscript.

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 K. Kumlin and R. Simonson

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42