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

physical state, they find a variety of applications in
The effects of light on the service life of poly- diverse fields. Therefore, generalisations projected
urethanes have attracted considerable interest, and from small molecule model compound studies, or
attention has been given over the past two decades studies of a single polyurethane in a particular
to the study of photodegradation processes,’ - physical state, cannot be of interest for all poly-
but the photostability of polyetherurethaneurea urethanes. Hoyle and Kim14 studied the role played
(PEUU) has not been studied extensively. Beachell by the polyurethane matrix in photodegradation
and Chang” investigated the systematic photo- processes, i.e. how does the polymer crystallinity and
degradation of urethane model compounds and chain flexibility affect the photodecomposition. In
established the primary photodegradation pro- the present investigation the photostability of
cesses. Gardette and Lemaire l 3 postulated that the PEUUs having different physical structures is
photodegradation of 4,4’-diphenylmethanediiso- studied. The most interesting feature of the physical
cyanate (MDI) based polyurethanes depends on the structure of polyurethane elastomers is their seg-
excitation wavelength and proceeds by two entirely mental nature. The soft block of a linear polyether,
unrelated processes. Quinone diimide products were or polyester, segment attached to a hard block of a
formed when wavelengths of light above 340 nm urethane group provides a two-phase morphology
were used and photo-Fries rearrangement along and the elastomeric characteristics depend on the per-
with unsubstituted arylamine products were pro- centage content of these blocks. The hard segments
posed for wavelengths of light below 340nm. cause physical crosslinking by hydrogen bonding,
whereas the soft segments increase the flexibility of
*To whom all correspondence should be addressed. the polyurethane with increasing polyol chain
7
Polymer International 0959-8 103/90/$03.50 0 1990 SCI. Printed in Great Britain
8 B. I? Thupliyal, R. Chandru

length. PEUUs with different degrees of soft segment The percentage gel contents of irradiated samples
flexibility were prepared by reacting MDI with at ambient temperature were determined in D M F
polyethyleneglycol (PEG) of different molecular with occasional agitation of capped centrifuge tubes.
weights (400,600 and 1000)and chain extended with Stress-strain properties were determined on a
1,3-propanediamine (PDA) or 1,6-hexanediamine Zwick universal testing machine (model 1435). The
(HDA). The chain extension with different aliphatic changes in UV and IR spectra were recorded on a
diamines provides varying degrees of strength to the Hitachi UV-Visible-NIR spectrophotometer
material. (model 330) and a Perkin-Elmer infrared spectro-
photometer (model 783), respectively.
EXP E R IME NTAL
RESULTS AND DISCUSSION
Materials
Variation in ,@I of PEUUs as a function of
The PEUUs used in the present investigation were irradiation time with 365 nm light at 293 K is shown
synthesised by two-stage solution polymerisation. in Fig. 1. The plots show a rapid decrease in M,,
The prepolymers formed by the reaction of poly- which then slows down, suggesting that the initial
ethyleneglycol (0.5 mol) and 4,4’-diphenylmethane- drop in Mw is due to random scission of bonds at
diisocyanate (1.0 mol) were chain extended with various weak links, which may be distributed along
diamine coupling agent (0.5 mol) to yield high the polymer chain. The loss in molecular weight of
molecular weight polymers. MDI (E. Merck) was these copolyurethanes can result from chain
vacuum distilled before use. Three PEGS (Fluka), of cleavage at the urethane, urea and polyether
molecular weights 400, 600 and 1000, were dried linkages. After long exposures there are visible
under vacuum. The chain extenders, PDA and HDA opalescences due to crosslinking, with microgel
(E. Merck), were vacuum distilled prior to use. formation by the fragments of the polymer mol-
Dimethylformamide (DMF) extra pure was dried ecule. It is obvious from Fig. l that initial chain
and distilled over calcium hydride twice. Six polymer scission is at a maximum in the case of PEG 1000
samples were synthesised and designated as follows: and at a minimum for PEG 400 based copolymers.
PEG 400-PDA PEG 400-HDA For PEG 1000 based copolymers ether cleavage may
PEG 600-PDA PEG 600-HDA be the largest contributor to loss in molecular
PEG 1000-PDA PEG 1000-HDA weight. Figure 2 shows the increase in gel content of
PEUUs with irradiation time. From Figs 1 and 2 it is
depending on the molecular weight of PEG and type
seen that PDA chain extended copolyurethanes
of diamine used.
show more photostability than HDA chain ex-
Procedure tended copolyurethanes. Thus, for these aliphatic
diamine extended PEUUs, the chemical structure of
Films of uniform thickness ( z120 pm) were cast on a
quartz plate from solution (3% PEUU in DMF) and 9 oc
1 PEG 400-Pa4 2 PEG 400-HDA
dried under vacuum to constant weight. Photo- 3 PEG 600-PDA 4 PEG BOO-HDA
oxidative degradation was carried out in air with a 5 PEG 1000-PDA 6 PEG 1000-HDA

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 I
PEG 600-PDA = 0-077 1 I I I I I 1 I
4 8 12 16 20 24 28
PEG 600-HDA = 0.082 Time (h)

PEG 1000-PDA = 0.087 Fig. 1. Changes in A, of PEUU films irradiated with 365 nm
PEG 1000-HDA = 0,088 light in air at 293 K as a function of irradiation time.

POLYMER INTERNATIONAL VOL. 24, NO. 1,1991

Photostability of polyetherurethaneureas 9

1 PEG 400-PDA 2 PEG 400-HDA 1 PEG 400-PDA 2 PEG 400-HDA

3 PEG 600- PDA 4 PEG 600-HDA 3 PEG 600-PDA 4 PEG 600-HDA
5 PEG 1000-PDA 6 PEG 1000-HDA 5 PEG 1ooO -PDA 5 PEG 1000-HDA

20-

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 Fig. 4. Variation in stress at break of PEUUs after irradiation
polyurethane urea system have shown that the use of with 365 nm light in air at 293 K as a function of time.
diamine instead of diol permits better phase
separation. The effect of chain extenders on the weight of the soft segment. On the basis of the stress-
photo-oxidative stability of polyurethanes can be strain results, it is seen that PEG 1000 based
explained on the basis of the number of CH, polymers begin to show some loss in both stress and
carbons in the extender. The superior properties of elongation at break, consistent with the losses in
PDA chain extended polyurethanes are explained their molecular weight. At higher periods of
on the basis of the regularity of the backbone and the irradiation there is some increase in breaking
ease of hydrogen bond formation. Bonart et a l l 5 strength but no significant change in the elongation.
have shown that the hard segment T, of MDI- This may be because of crosslinking by the
diamine systems decreases when diamines con- fragments of the polymer molecules. The ultimate
taining higher numbers of CH, groups are used. tensile strength and elongation of PEG 400 based
The stress-strain curves of different PEUUs are polyurethanes are unexpected and are the most
shown in Fig. 3. Variation in stress and elongation at affected by irradiation. Morphological studies of
break of various PEUUs with exposure time are these failures after long periods of exposure will be
shown in Figs 4 and 5. It is well known that the reported elsewhere. The PDA chain extended
tensile behaviour of a segmented polyurethane PEUUs show better properties than HDA chain
generally depends upon the size, shape and per- extended PEUUs after photo-irradiation.
centage content of the hard segment, intermolecular

100
bonding within the hard domain and the molecular
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
1 PEG 400-PDA 2 PEG 400-HDA
3 PEG 600-PDA 4PEG 600-HDA
5 PEG 1ooO-PDA 6PEG 1000-HDA
800

-6

20 40 60 80
Time ( h )
Elongation (%) Fig. 5. Variation in elongation at break of PEUUs after
Fig. 3. Stress-strain behaviour of various PEUUs at 293 K. irradiation with 365 nm light in air at 293 K as a function of time.

POLYMER INTERNATIONAL VOL. 24, NO. 1,1991

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 11

are given for photodecomposition at the N-C exposure than does the urethanes C-0 absorption
bond: (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
' C 4 - C H 2-CH2-0- hydrogen from methylene groups of the polyether
II by radicals resulting from the cleavage of urethane
0
0 hy or urea groups accelerates the oxidative degradation
and cleavage of the polyether.
~ - C - 0 - 4 H II2 - C H 2 - - O - -
Studies on polypropyleneglycol based aromatic
(photo-Fries rearrangement) p o l y ~ r e t h a n e s ~ have
~ ' ~ ~shown
'~ that the degra-
dation of polyether involves oxygen uptake and
0 results in volatilisation of low molecular weight
II hydrocarbons. The increase in absorption at 1730
@- NH + 'C-O--CH2-CHZ-0- cm- was assigned to oxidised polyether residues,
while other carbonyl-containing products expected
I from urethane or urea cleavage contribute to
broadening of this peak.
-HzdH--O-+ On photo-oxidative degradation hydroperoxide
formation takes place in the hydrocarbon moieties
of the polyurethanes. Gardette and LemaireZ0have
CO, + cH2-CH2-O- observed four types of hydroperoxy groups depend-
(abstraction of hydrogen from polyether segment) ing upon the structure of the polyurethane
Oxidative coupling of substituted aniline products elastomers. The possible hydroperoxides in the
can lead to conjugated azo compounds. PEG-MDI-diamine based copolyurethanes may be
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 4-CH-CH 2-

exposure due to the formation of amine, unsub- I

0-0-H
stituted urethane and urea products resulting from
cleavage of urethane and urea bonds. The C-0-C (B)
absorption (1110 cm- ') decreases more rapidly with 0
II
&)--NH-C-NH-CH+-CH2-),-
R' + 4 - - C H 2 2 H 2 - 0 - \ / - I
0-0-H
I (C)
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
1 peroxy (0-0) group, but the influence of the
peroxide bond on absorption of other groups is
-04H2-CH-0-
I more significant as the peroxy bond is often
J 0 4 - H obscured. IR spectra of the PEG-MDI-diamine
&CH,-C-H + '0- based polyurethane on photo-irradiation shows at
'
3330 cm- the effect of a neighbouring hydro-
II
0 peroxide on the N-H stretching vibration and at

POLYMER INTERNATIONAL VOL.. 24, NO. 1,1991

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 13

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POLYMER INTERNATIONAL VOL. 24, NO. 1,1991