Prog. Polym. Sci., Vol.

15, 735-750, 1990

Printed in Great Britain. All rights reserved.

0079-6700/90 $0.00 + .50

1990 Pergamon Press pie

ADVANCES
IN PHOTODEGRADATION
AND
STABILIZATION
OF POLYURETHANES
B. P. THAPLIYALand R. CI~NDRA*

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

CONTENTS
I. Introduction
2. Mechanism of photodegradation
3. Effect of physical state on photodegradation
4. Photostabilization of polyurethanes
5. Conclusion
References

735
735
740
743
748
748

I. I N T R O D U C T I O N

All synthetic and natural organic polymers are prone to photodegradation.

However, the rate of deterioration varies enormously with the polymer structure. Although the photodegradation and stabilization of polyurethanes has
been studied since their commercial introduction, it is only recently that the key
photodegradative steps have been confirmed and some progress has been made
in the systematic understanding of the modes of action of effective commercial
stabilization. The systematic development of UV stabilizers for a polymeric
system requires a detailed knowledge of the nature and importance of photoinitiation reactions and the reaction of key intermediates in the photodegradation. In the present review we will critically discuss photodegradation
mechanisms and the effect of chemical and physical structure on degradation
before we consider potential photostabilization mechanisms.
2. M E C H A N I S M

OF PHOTODEGRADATION

Initial studies ~-3 on the photodegradation of polyurethanes were made in the

early 1960s, but a definite mechanism could not be established due to the
difficulties in identification of the principal photodegradation products of the
polymeric systems. Most of the studies were centered around the commercially
available polyurethanes derived from aromatic diisocyanates such as toluene

*To w h o m all correspondence should be addressed.

735

736

B.P. THAPLIYALand R. CHANDRA

diisocyanate (TDI) and diphenylmethane diisocyanate (MDI) which turned

yellow on storage or in actual usage. Aliphatic isocyanate-based polyurethanes
show remarkable photoresistance but their photodegradation studies are limited.
Some investigators, 4~n studying the photodegradation of aromatic polyurethanes, postulated the formation of the following mono- and diquinone
imide products.
..... O2C~NH = = - - ~ - - C H 2 - = = = = = ~ N H ~ C O

2.....

..... O a C ~ N ~ : : : ~ C H ~ N H ~ C O 2

.....

..... O 2 C ~ N @ C @ N ~ C O

2.....

Loss of some4-n useful mechanical properties on exposure to sunlight was

found to result from the UV initiated auto-oxidation of the urethane linkage to
yield quinone-imide type structures. Polyurethanes from MDI were most affected
by light. Polymers based on 4-4'-methylene bis(cyclohexyl isocyanate) had
good spectral and colour stability and excellent stress-strain property retention.
The UV and visible absorption spectra of polymeric films after photoirradiation showed a progressive shift toward the visible region, resulting in a yellow
film. Osawa eta/) 3 suggested that photodegradation of polyurethanes proceeded
via excited triplet states, forming an intrapolymer excimer in the initial stage and
exciplexes between the polymer and the degradation products or intermediates
after irradiation. Polyurethanes were excited by irradiation at 290 and 346 nm
and emitted light at 310 and 420nm.
Allen and McKeller 14 reported an electronic spectroscopy and laser flash
photolysis study on MDI and polyester diol-based polyurethane elastomers.
Fluorescence and phosphorescence emissions were observed. Although the
source of fluorescence could not be identified, the phosphorescence was reported
to originate from a benzophenone-type oxidation impurity. It was found that
after about 25 hr of irradiation, virtually all the fluorescence emission had
disappeared while relatively little change had occurred in the phosphorescence.
With longer periods of irradiation, a gradual decrease in the phosphorescence
intensity was observed, but this change became difficult to monitor satisfactorily
as the yellow-brown discoloration of the film developed. No phosphorescence
was observed for the film irradiated for 400 hr.
Beachell and Chang 15 investigated the systematic photodegradation of
urethane model compounds. The photooxidation products of ethyl N-phenyl

PHOTODEGRADATION AND STABILIZATION OF POLYURETHANES

737

carbamate were identified, The photodegradation of the polyurethane based on

TDI and ethylene glycol, containing a hydrogen atom ~ to the carbamate
nitrogen atom, was postulated to proceed by the following photo-Fries
mechanism.
1t3
.

;H3
NH

NH

hv
it_

I
o

C~------------O
O

..... O ~ ~ N H
O
C~O
O

H3

~ O

.....

o
C~-O

Yamagata and coworkers '6 carried out studies on the influence of UV light on
urethane compounds and noted the behavior of thermoplastic polyurethanes
in the presence of UV light. Fluorescence, UV, IR spectroscopy and ESR data
indicated that in the initial stages of UV irradiation the urethane linkage was
broken via an electrophilic mechanism, therefore decreasing density in the initial
stages. Crosslinking occured in the later stages by a radical mechanism and was
accompanied by the formation of colored material. Noack and Schwetlick ~7
suggested that the yellowing of urethane polymers under UV irradiation was
due to oxidation of free-NH2 groups formed by the photolysis of the urethane
groups. UV spectral and ESR studies indicated t8 that photodegradation was
dependent on the kind of polyol used to prepare the polyurethane.
By taking into account the effect of excitation wavelength, Gardette and
Lemaire '9 postulated that the photolysis of MDI-based polyurethanes proceeds
by two entirely unrelated processs. From Gardette and Lemaire's work 2 it can
be concluded that the degradation of aromatic polyurethanes by irradiation
may be acounted for by two mechanisms based on the formation of different

738

B. P. T H A P L I Y A L and R. C H A N D R A

products. The first is observed at short wavelengths ( < 340 nm) and proceeds
through a photo-Fries type reaction. The second mechanism is observed at
longer wavelengths and involves formation of colored species derived from
primary hydroperoxides. These two paths were differentiated both by incorporation of Tinuvin 770 into the polymer and by selection of various irradiation
wavelengths# Quinone-diimide products are obtained when wavelengths of
light above 340 nm are used. However, formation of photo-Fries rearrangement
type products and unsubstituted arylamine cleavage products occur when light
below 340 nm is used for photolysis. 2
h v > 340 n m

hv,~ 34Ohm

..... O 2 C ~ N H ~ H = - - - - ~ N

H-----CO~.....
+

The photooxidative behavior of thermoplastic polyurethanes based on

aromatic and aliphatic diisocyanates and polyether and polyester polyols was
also investigated by the same group. 2~ Upon photooxidation, hydroperoxide
formation takes place in the hydrocarbon moieties of the polyurethanes as
shown below:
R
~ C H ~

R
*'

~ C ~

*'

~ C ~

*,

)
!__o__.

Four types of hydroperoxides were formed, depending upon the structure of the
polyurethane elastomer:
0

.....

..........

o_U_c

.....

!--o--.
(A)
..... O~H~CH~
~--O~H

(c)

(S)
.....

.... - C H ~ N H ~ C ~ O

--HU
(D)

.....

PHOTODEGRADATION AND STABILIZATION OF POLYURETHANES

739

The respective hydroperoxides were formed from the CH2 group ~t to the
phenyi group of diisocyanate (A), the CH2 group a to the ester group (B), the
CH2 group ~t to the ether group (C) and the CH2 group a to the carbamate
nitrogen atom (D).
The primary photochemical reactions in polyurethanes leading to accumulation of free radicals, and further reactions of free radicals by UV photolysis of polyurethanes based on i,4-butanedioI-HDI, 1,6-hexanediol-HDl
copolymer, methyl N-ethyl carbamate and diisopropyl hexamethylenebiscarbamate were studied. 22The primary step in photolysis was cleavage of the C-O
bond of the urethane group. Subsequent degradation followed a radical chain
mechanism.
Brauman e t al. 23 found that the substitution of the aliphatic diisocyanate
methylenebis(4-cyclohexyl isocyanate) for MDI gave a polymer resistant to
light-induced discoloration and degradation. As discussed previously, photodecomposition of aromatic polyurethanes is supposed to proceed via cleavage
of N-C and C-O bonds in the urethane group. Photochemical degradation of
aliphatic urethane groups containing a hydrogen atom on the carbon a to the
carbamate nitrogen, was postulated to resemble that of an amide: an initial
N-C, and possibly C-O, bond cleavage in the urethane group was followed by
hydrogen abstraction. Subsequent oxidative degradation of this site apparently
occurs via a hydroperoxide intermediate. This process does not occur readily if
the hydrogens are not activated, as evidenced by the photolytic stability of these
polyurethanes.
Wiles 24 observed a useful way of studying the interaction of photons with
polymers, i.e. to identify the significant chromophores in each system and to
determine the important primary processes following photon absorption. For
example, such an analysis has been useful in assigning the correct relative
importance to Norrish type I and II photoreactions for polymers containing
carbonyl groups. The irradiation of polyurethanes derived from dimethylglyoxime and hexamethylene diisocyanate 25involved two initial processes of N - O
and C-O bond scission. The ratio of N - O and C-O cleavages depends on the
wavelength of the light used. The C-O bond cleavage resulted in polymer
degradation, while the species formed by N--O bond cleavage were thought to
undergo recombination processes. UV irradiation of solutions and films of
polypropylene glycol-TDI copolymers decreased the urethane group absorption 26"27by breaking N--C and C-O bonds. Such was monitored by UV, IR and
N M R spectroscopy. The influence of the physical state of the polymer and
irradiation dose on the reaction were established.

3. E F F E C T

OF PHYSICAL

STATE

ON PHOTODEGRADATION

The term "polyurethane" is conveniently used to describe a wide variety of

polymeric materials including plastics, elastomers, fibers, foams (flexible and

740

B. P. T H A P L I Y A L and R. C H A N D R A

rigid), surface coatings and adhesives. With the rapid expansion of this class of
materials over the past decades, polyurethanes now include those polymers
which contain a significant number of urethane groups together with a variety
of other structurally important groups, e.g. ester, ether and urea linkages. The
relationship between their chemical and physical forms is crucially important
from the viewpoint of their photostability.
Most commercial polyurethane elastomers derive their high level of strength
and flexibility from the segmented structure. A number of investigators28-33have
shown that polyurethane elastomers consist of alternating hard and soft segments. The soft segments are formed from linear polyether or polyester chains
whose glass transition temperature is sufficiently below the desired service
temperature of the polyurethane. Soft segments which crystallize on chain
extension are particularly desirable from the viewpoint of ultimate tensile
strength. The hard segments originate from a diisocyanate and a chain extender
or a crosslinking agent (e.g. diol or diamine). These hard segments have a T8 or
Tm well above the anticipated service temperature of the polyurethane and
hold the rubber together by "physical crosslinking" (which can involve interchain
hydrogen bonding). These hard segments prevent the material from flowing so
that the elasticity is maintained. These polyurethanes behave as rubbers when
the hard segment content is lower than 40% and as glassy materials when the
hard segment content is greater than 40%.
The photodegradation of polyurethanes34 based on aromatic diisocyanates
can be dependent on the physical state of the polymer. Hoyle eta[. 35-39 have
studied aromatic diisocyanate-based aromatic systems extensively to find out
the effect of the physical state of the polymer on the photostability. In one
investigation39 they have shown that for simple polyurethanes based on MDI
and a single diol, films with low crystallinity and high flexibility degraded
rapidly upon exposure to UV radiation. In the case of segmented polyurethanes
based on MDI and more than one diol, the extent and mechanism of photolytic
decomposition was dependent on the hard segment content in the polymer. As
the content of hard segments increased, both the percent crosslinked gel and
discoloration generated upon photolysis decreased dramatically. The formation
of photo-Fries rearrangement products was found to increase with an increase
in the molecular weight of the poly(ethylene oxide) soft segment.
Fluorescence spectroscopy40was used to determine the effect of flexibility and
crystallinity of the polyurethanes on the degradation pathway. It was observed
that amorphous films yielded an ortho-photo-Fries rearrangement product,
whereas the semicrystalline film did not. Photodegradation of MDI and TDI 4~based polyurethanes depended on the chain flexibility and the matrix crystallinity.
Both absorbance change and gel formation decreased as the stiffness and
crystalline content of the film increases.
There are a wide variety of compositional variables which can affect the
degree of phase segregation and hard segment organization and, accordingly,

PHOTODEGRADATION AND STABILIZATION OF POLYURETHANES

741

the sample properties. In the TDI-based polyurethanes, morphological variations

have been observed in polymers from the commonly used isomers,2,4-TDl and
2,6-TDI. 4z In 2,4-TDI polymers, the asymetric placement of the isocyanate
residues with respect to the methyl group can result in some head to tail
isomerization in the hard segment. In 2,6-TDI polymers, this problem is absent
since the molecule is symmetrical. The photostability of polyurethanes based on
these isomers can be explained on the basis of symmetry.
The degradation rate of polyurethanes 43prepared from various diisocyanates
by reacting with refined castor oil increased in the order MDI < TDI < 1,5NDI < HDI upon exposure to atmospheres of 80% and 95% relative humidity.
The degradation was an autocatalytic process and was accelerated by the curing
catalysts, i.e. triethylene diamine and dibutyl tin dilaurate. The stability of
polyurethanes based on HDI-BD is found to be greater than that of the other
polyurethanes."
Peter and coworkers45 studied the effect of composition and morphology on
the photo- and thermocrosslinking of poly(ether urethane ureas) containing
diacetylene linkages. It was seen that copolymers with phase separation composition were more photochemically and thermally reactive towards crosslinking than homogenous polyurethanes.
The changes in chain length and their distributions as well as the changes in
chemical structure were followed by GPC, N M R and IR 46 after subjecting the
polyurethane prepolymers to photooxidative degradation. The chromatographic
results showed that the photooxidative decomposition was followed by a
decrease in molecular mass together with an increase in polydispersity. This
indicated an inhomogenous degradation which was a consequence of the specific
course and of the intensity of photooxidative degradation.
In order to determine the effect of polyol structure, the physico-mechanical
properties of polyurethanes prepared from MDI with 1,4-butanediol and
polyether and polyester polyols were examined after prolonged exposure to
weathering. '~ The lower resistance to weathering found for polyether urethanes,
compared to that of polyester urethanes, reflected their lower resistance to
temperature change and UV radiation.
Structural changes in crosslinked polyurethanes resulting from photooxidative
degradation are determined by the nature of the oligoesters used for their
preparation. 47 The kinetics of oxygen absorption and structural changes were
examined in the photochemical oxidation of polyurethanes prepared from
aliphatic polyisocyanates. The amount of absorbed oxygen depended on the
crosslink density of the polyurethanes and on the nature of the oligoester blocks.
The light stability of polyurethanes and poly(urethane ureas) ~ derived from
poly(ethylene adipate) diol, poly(pentylene adipate) diol, polycaprolactone diol,
poly(propylene oxide) glycol, polyoxypropylene diamine and 1,4 butanediol
were studied by a Xenotest 1200 apparatus and a correlation was established
between the chemical structure and the light stability of the polymers.

742

B.P. THAPLIYAL and R. CHANDRA

The light resistance and photodegradation 49of aromatic polyesters, aromatic

polycarbonates and polyurethanes based on aliphatic diisocyanates and polyester
aliphatic ester and aromatic ester polyols and of aromatic diisocyanates and
polyether polyois have also been investigated. The appearance of polyurethanes
from aliphatic diisocyanates and polyester polyols remained unchanged after
72 hr in a Xenotest apparatus, while polyurethanes from aromatic diisocyanates
and polyether polyols showed some change in appearance (but less than some
other types of polyurethanes).
In general, major photoprocesses observed in solid polymers are dependent
upon temperature. Above the glass transition temperature (Tg) relatively large
segments of the molecule can undergo extensive motion. Above Tg polymer
chain mobility is sufficient to form cyclic intermediates, just as in solution.
Photoacoustic spectroscopic studies ~ have shown that the degradation of
polyurethanes can be initiated at a relatively low temperature and low UV
dosage above Tg. It was seen that effect of heat is more pronounced than the
effect of light.
Naphthyl carbamates have been shown to form excimers that are stabilized
by hydrogen bonding inherent in the participating species. 52 Substitution of a
methyl group on the central nitrogen atom of the carbamate moiety severely
limits excimer formation. A polyurethane based on napthylene diisocyanate
(NDI) forms intramolecular excimers in dilute solutions in both good and poor
solvents. However, the excimer formation is significantly enhanced in poor
solvents, where intramolecular contact between napthylene carbamate groups is
favoured. The photophysics of excimer formation in the polyurethane is interpreted on the basis of an "isolated monomer" scheme?
Polyurethanes containing dianthracene units in the main chain were photochemically dissociated by irradiation at 300 n l ' D . 53 The efficiency of photochemical
reassociation gave an indication of the mobility of the terminal polymer segments containing anthracene groups. During photolysis the terminal anthracene
groups produced sandwich dimers which generally dissociated upon warming:
the polyurethane showed retention of the sandwich dimer structure at room
temperature.
The reported photodecomposition of a polyester diol-MDI polyurethane and
its model compounds in solution was not influenced by piperylene or triplet
quenchers, indicating that photodecomposition does not start from the external
triplet state but from the excited singlet stateJ 4 The energy levels and lifetime of
polyurethane photodecomposition were 98.6 Kcal/mol and 3.2 nsec respectively
in the excited singlet state and 2.93 nsec in the excited triplet state.
4. P H O T O S T A B I L I Z A T I O N

OF POLYURETHANES

Although a large number of different types of compounds are known to be

effective UV stabilizers, only a few classes of these compounds are useful in

PHOTODEGRADATION AND STABILIZATION OF POLYURETHANES

743

preventing the photodegradation of polyurethanes. It is well known that many

inorganic pigments such as iron oxides (Fe203 and Fe304), chromic oxide
(Cr203), red lead oxide (Pb304), zinc oxide (ZnO) and titanium dioxide (TiO2)
have been used as stabilizers for polyurethanes. ZnO is reported to be one of the
most efficient and economical white inorganic photostabilizers, 55 especially in
the UV region from 240 to 380 nm. Chase e t al. 56 prepared metal oxide particles,
e.g. ZnO, Sb203, WO3 and MoO3 of average diameter for stabilizing polyurethane films. Crekov and his colleagues 57 made efforts to improve the mechanical, thermal, hydrolytic and light stability of polyurethane films by filling
with CuO, MOO3, BizO3, Cr20~, TiO2 and WO3. Water absorption decreased
when polyurethanes were filled with metal oxides. The filled polymer was more
resistant to acids than to alkalis.
Gardette and Lemaire 58 showed that TiO2 inhibited the photooxidation of
HDI-polyether and polyester polyurethanes more effectively than aromatic
diisocyanate-based polyurethanes. The effect of "/-Fe203 on the thermal and
photooxidation of polyurethane coatings was remarkable. 59
Many organic pigments such as azo, anthraquinone and thioindigo compounds, quinacridones, isoindolinones, perylenes, dioxazines and phthalocyanines
have wide application in the plastic industry. 6'6~ Fedoseev e t al. 6z found that
various indophenols are stabilizers for polyurethanes. Some azo compounds 6~
such as p-hydroxyazobenzene and p-aminoazobenzene were effective retarders
in comparison to the UV absorbers Tinuvin 326, 2,4-dihydroxybenzophenone
and dibutyldithiocarbamates.
Photostable colored aromatic polyurethanes were prepared from polyols
structurally dyed with anthraquinone derivatives by Litvinenko and his colleagues. 64 The color of the dyed polyol depended upon the anthraquinone
comonomer used. Flexible polyurethane coatings were prepared by the reaction
of the polyols with TDI. The increase in photostability of polyurethanes based
on structurally dyed polyols was due to the o-hydroxyketone photoisomerization in the polyol molecule.
Fluorescent photostabilizers absorb light and immediately reemit the light at
a longer wavelength in the form of fluorescent light. Numerous optical brightening agents absorb UV radiation and reemit the energy as visible light. Such
"brightening" compounds are commonly used to compensate for the yellowing
during the processing of polymeric materials and to increase brilliance and
whiteness. Coumarins and stilbenes are examples of the common optical brightening compounds used in polymers. The effect ofcoumarins, stilbene derivatives
and other common brightening agents on the photodegradation of polyester
polyurethanes was studied by investigating the changes in residual breaking
strength. 65 Some of the coumarin and stilbene derivatives were found to be
effective retarders of the photodegradation of polymers and their effectiveness
was comparable to that of common stabilizers, e.g. triazole derivatives. The
retardation mechanism of the representative compounds was discussed on the

744

B.P. THAPLIYALand R. CHANDRA

basis of the decay of ethyl phenyl carbamate during photoirradiation and on the
basis of fluorescence emission of the polymer with and without the additive.

SO~R
R3N

H~O

COUMARINS

NAPI-r~OTRIAZOLYLSTILBENF~

Fluorescent compounds are very effective photostabilizers but unfortunately

the poor light and thermal stability of most of these fluorescent materials results
in a gradual decrease in their efficiency. (Only one light-stable fluorescent
compound, 6,13-dichloro-3,10 diphenyltriphenodioxazine, was found to be an
excellent UV stabilizer for cellulose ester plastics. 66)
ct

Phenyl esters of benzoic acid were the first photostabilizers to be used technically and they are still available because of their low price. Unfortunately most
of them turn yellow on exposure to UV light. This problem limits their use as
UV absorbers for colorless and transparent polymers. It is well known that the
yellowing of these compounds is due to a photochemical rearrangement of the
Fries type, giving derivatives of dihydroxybenzophenones. 67-7 Among the
hydroxybenzophenones, the o-hydroxybenzophenones are good stabilizers
while p-hydroxybenzophenones act as photodegradation sensitizers. The 1,4dihydroxybenzophenone isomer is, however, a very good photostabilizer for
polyurethanesf'

o "-o

*(n,A*)
it~t l (-,,)
0~) H~O(~

l~(n. ;~")
O""H ""0

PHOTODEGRADATION AND STABILIZATION OF POLYURETHANES

745

Many workers have found that UV absorbers, e.g. Tinuvin 326 and 2,4
dihydroxybenzophenone, are effective for retardation of the photodegradation
of polyurethanes.63'7~ In addition, benzotriazole derivatives have been used as
stabilizers for polyurethanes.72 As in the case of o-hydroxybenzophenones, the
(o-hydroxyphenyl)benzotriazoles may form internal hydrogen bonds. Their
photostabilization mechanism is considered to be a rapid tautomerism in the
excited state: ~'73'74

Merril and Bennett75found that (o-amidophenyl)benzotriazoles may form an

intramolecular hydrogen bond:
R

N--H

N H

The distribution of a benzotriazole stabilizer (Tinuvin 328) in crystalline polypropylene has been investigated by UV microscopy.76The results show that the
stabilizer accumulates in the non-crystalline region and between polypropylene
spherulites, and is rejected by crystalline regions. These observations are very
important for understanding the photostabilization mechanism of polymers.
The excellent mechanical properties of benzotriazole-polyurethane systems offer
scope for interesting studies which involve varying the crystallinity and flexibility of the polyurethanes.
The hydroxphenyl-s-triazines are a new class of stabilizers which have recently
been investigated by Heller73 and used in polyurethanes.77

Ra

The mechanism by which the photostabilization of aromatic polyurethanes is

achieved by o-hydroxyphenyl-s-triazines is similar to that of o-hydroxybenzophenones and o-hydroxyphenylbenzotriazoles. The light fastness and protective powers of hydroxyphenyl-s-triazines are influenced by:
(1) The number of o-hydroxy groups. Compounds with a higher number of
o-hydroxyphenyl groups show better protective power and stronger absorption of UV light of long wavelengths.

746

B. P. THAPLIYALand R. CHANDRA

(2) The basicity of the triazine ring is reduced by the substituents R, and R: and
the light fastness of the resulting compound increases.
Intramolecular bonds are obviously not a prerequisite for a stabilizing mechanism. Triazoles 73 which are photochemicaily active have, however, no photostabilizing effect and the compounds may act as photosensitizers.

~ "R2

~R2

R3

~
R:

Rt
4H - 1,2,4- triazoles

R3
2H - 1,2,4- triazoies

These compounds sensitize the discoloration of polyester resins. However,

they can be useful in extending the shelf life of uncured polyurethane mixtures.
A heat-curable polyurethane with good shelf life was prepared by adding a small
amount of triazole to the polymerfl Thus a prepolymer prepared from a poly(tetramethylene adipate)polyol and TDI was melt blended with 1,4-butanediol,
1,2,6-hexanetriol, 4H-1,2,4-triazole and triphenyllead acetate at 60C. It hardened
at room temperature and was granulated. The granules gelled at ! 50C in 8 min
after one or two weeks storage but polymer without triazole had a gel time of
5 min after one week and was infusible after two weeks storage.
Amines and phenols act as typical antioxidants and their effectiveness is
highly dependent upon the nature of the polymer to which they are added.
Aromatic polyurethanes have been stabilized 79 by mixing with primary monofunctional phenols and primary or secondary amines (0.2-2 g mol/g mol of free
NCO) immediately after synthesis. Solutions of amino acid hydrazide chainextended polyurethanes were stabilized by addition of amines, s The solution
with triethylamine showed no change in viscosity or color on standing overnight.
The fluorescence of TDI-based polyurethanes was quenched by salicylic acid
esters, amides and hydrazides, s' Quenching approximately obeyed the Foerter
and Perrin equation accompanied by a sensitization of the fluorescence of the
salicylic acid derivatives. The photoyellowing of the polyurethanes was also
inhibited by the salicylic acid derivatives.
Nickel chelates such as nickel dibutyldithiocarbamate have industrial applications as typical quenchers for polyurethanes, s2
CH3(CH2)3.

~S ]2Ni

\~c//

CH3(CH:)3~

~S-

Yamagata and his associates 83 observed the effect of UV light on urethane

compounds and the effect of ringlet oxygen and stabilizer on the photodegradation of polyurethane resins. The effect of added stabilizers, e.g. the

P H O T O D E G R A D A T I O N A N D STABILIZATION O F P O L Y U R E T H A N E S

747

dibutyldithiocarbamates of Ni or Zn, Irganox 1010, BHT and Sanol on the

photodegradation of a polyurethane was examined in the presence of ringlet and
triplet oxygen. The higher the quenching capacity of the stabilizer for singlet
oxygen, the smaller the photodegradation rate of the polyurethane. The presence
of singlet oxygen was more important in photodegradation of polyurethanes in
the initial stages compared to that of triplet oxygen. No difference was observed
between the ringlet and triplet oxygen after prolonged irradiation.
Propylene glycol-xylene diisocyanate polymers having improved thermal and
weathering stability were prepared by the addition of nickel dialkyldithiocarbamate u at any stage before completion of the urethane polymer formation.
MDI-poly(oxypropylene)-glycerol ether copolymer and an acrylic polyolMDI copolymer were photostabilized by antioxidants8s (e.g. nickel dibutyldithiocarbamate and Irganox) having large quenching indexes for singlet oxygen. A linear relation was observed between the yellowing index and color index.
An aromatic polyurethane having a tertiary hydrogen in the polymer chain was
susceptible to photodegradation but was stabilized by the addition of an antioxidant. The gloss index was decreased with increasing yellowing and coloration.
Nickel dodecylthiophosphates6 is also described for quenching the excited
state of polyurethanes. Zinc dibutyldithiocarbamates63 were also found to be
effective as UV absorbers and for the retardation of photodegradation, as were
some azo compounds.
Some patents recommending various chemical compounds as efficient photostabilizers have been published in the last decade. The majority of these compounds have not, however, found application on an industrial scale. Piperidine,
stilbene and coumarin derivatives have been used as stabilizers for polyurethanes.
Morimura e t al. s7 prepared and used 2,2,6,6-tetramethylpiperidine derivatives as
stabilizers for polyurethanes.
Ishada e t al. ~8 increased the light and heat resistance of polyurethanes by the
addition of cytidine, uridine or a similar pyrimidine base to the polymer.
Synergism in the stabilization effect was also observed. Polymer containing
0.5% cytidine lost only 1.0% of its weight during I hr at 220C and was
unchanged in color after 192hr in a Fadeometer. Similarly 100 parts polyurethane ~9 melt-blended with 0.25 part (4-organo oxy-2,2,6,6-tetramethyl
piperidines) and bis(2,2,6,6-tetramethyl piperidyl esters) was molded into
0.5 mm thick plates and tested for light stability in a Fadeometer at 45C.
Murayama e t al. 9 prepared 4-alkoxy-2,2,6,6-tetramethyl-l,2,5,6-tetrahydropyridines and melt-blended these stabilizers with polyurethanes. Molded sheets,
when exposed to UV radiation, become embrittled only after 660 hr, whereas a
control sample containing no stabilizer became embrittled within 60 hr.
Keberle and coworkers9~improved the light stability of aromatic polyurethanes
by adding sodium 2-(fl-aminopropionamido)-2-methylpropanesulphonate as
additive. The additive was added to anionic-emulsifier-free polyurethane dispersions which were used to prepare colorless films or coatings with good light
resistance.

748

B. P. THAPLIYAL and R. CHANDRA

The methods of possible direct determination of light stabilizer and antioxidant content of polyurethanes are illustrated by Mody. 92 Different analytical
techniques were used for determining additive concentrations, e.g. GC, HPLC
and GPC. Also, a general method for screening the additives in the polymer
using thin-layer chromatography was developed. These techniques were used to
assure the addition of the proper amount and concentration of the additive to
the polymer before and after processing and during the aging of polyurethanes.
5. C O N C L U S I O N

A better understanding of the mechanisms of photodegradation and photostabilization has produced polyurethanes with increased photoresistance
through the use of more effective stabilizers. However, more knowledge is
needed about the primary and secondary reactions involved in oxidative
photodegradation.
Urethane model systems have already received increased attention and their
use has facilitated the separation of the factors involved in the complex photodegradation process. However, generalizations projected from small-molecule
model compound structures for studies of a single polyurethane in a particular
physical state cannot be of interest for all polyurethanes. Therefore, studies of
photodegradation and stabilization of polyurethanes having different physical
structures may provide better understanding of the urethane systems. In a recent
study 93 it has been observed that morphological changes take place as a result
of photooxidative degradation and are the primary cause of the failure of
aromatic urethane systems. The research field of polyurethane photodegradation,
therefore, offers ample opportunity for the polymer chemist and physicist to
collaborate in work that is not only intellectually stimulating but of practical
importance as well.

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