fonyl diisocyanate, chlorine, and sulfur dioxide in
excellent yields:
At about 400 "C in the presence of catalysts containing
FeC13, sulfonyl diisocyanate is formed directly from
SO3 and cyanogen chloride L711:
[71] K. Mutterstock and R . Gruf, German Pat. 1171 887, Farb-
werke Hoechst AG (1961).
The Degradation of Poly(ethy1ene terephthalate) [**I
BY L. H. BUXBAUM I*]
The penetration of new markets by polyester fibers has emphasized the need for increased
stability of the polyester to ward a variety of degradative reactions. Extensive studies
of the nature of the thermal, hydrolytic, oxidative, and radiation-induced degradation
reactions have been reported. The interpretation of kinetic investigations and the identifi-
cation of the reaction products have been facilitated by using suitable esters as model
compounds in place of the polymeric species.
1. Introduction
Poly(ethy1ene terephthalate) has the reputation of
being a polymer of great resistance to environments
which might be expected to limit its useful life as a
fiber, film, or other end product. However, even the
small amount of decomposition occurring under
normal manufacturing and processing conditions is
important to the manufacture of a uniform product.
Polyester fibers and films, although of excellent dur-
ability, can be affected by hydrolysis, aminolysis, and
various kinds of radiation.
To avoid a gradual deterioration of the physical
properties of the product, such degradation reactions
must be inhibited or retarded. In turn, successful
stabilization must be based on an understanding of
the precise mechanism by which each type of degrada-
tion occurs. Much research in this direction has been
conducted by the polyester producers and by textile
research institutes.
[*I Dr. L. H. Buxbaum
Goodyear Tire and Rubber Co., Polyester Research and
Development Division, Akron, Ohio (USA)
Present address:
Alpine Chemische AG., Schaftenau
A-6330 Kufstein (Austria)
[**I Publication No. 4 from the Polyester Research and
Development Division,
The Goodyear Tire and Rubber Co.,
Akron, Ohio (USA)
182
Sulfonyl diisocyanate is also formed on prolonged
boiling of NCSA with silver cyanate [721.
Sulfonyl diisocyanate appears to be rather less reactive
than NCSA, but reacts with the above-mentioned
classes of compounds, including olefins, to give prod-
ucts similar to those obtained with NCSA. Many of
these reactions can be controlled to give predominant
reaction of both isocyanate groups or of only one iso-
cyanate group [301.
Received: August 10, 1967 [ A 621 IE]
German version: Angew. Chem. 80, 179 1968
Translated by Express Translation Service, London.
[721 R. Appel and W. Senkpiel, Angew. Chem. 70, 271 (1958);
Chem. Ber. 91, 1200 (1958).
1.1. Preparation of Poly(ethy1ene terephthalate)
Poly(ethy1ene terephthalate) is prepared in two stages from
dimethyl terephthalate and ethylene glycol. In the first stage
a precondensate is formed which chiefly consists of the di-
glycol ester together with a certain amount of oligomers (up
to the tetramers).
This trans-esterification, which is catalyzed by small amounts
of metal salts (Zn, Mn, Cd, Pb, Ca, Mg, etc.), is carried out
at 200 "C, the methanol formed being continually removed
by distillation. The complete removal of the methanol is
most important since it can drastically interfere with the
formation of sufficiently long chains; as a monofunctional
alcohol it forms stable end groups and thus prematurely
stops chain growth.
In the second stage, polycondensation of the precondensate
is carried out at ca. 280C in high vacuum (< 1 torr) and
with addition of a heavy metal salt (usually Sb), the glycol
formed being continually removed.
Concentration of catalyst and temperature control are very
significant factors in determining the stability of the resulting
polyesters. Additionally, of course, stabilizers (usually P-
compounds) can also be added.
1.2. Properties of Poly(ethy1ene terephthalate)
Poly(ethy1ene terephthalate) exhibits a number of interesting
physical, and chemical, properties, only the most important
of which shall be briefly mentioned here. On account of the
hydrophobic nature of this polymer (absorption of water at
20 O C and at a relative humidity of 25 % is less than 0.5 %) its
mechanical properties are almost uninfluenced by water (i.e.
Angew. Chem. internat. Edit. 1 VoI. 7 (1968) 1 No. 3
it has a high wet strength, and there is no flat spotting of
the polyester tire cord). Poly(ethy1ene terephthalate) is very
resistant t o attack by most organic solutions and reagents,
especially acids, and also t o biological degradation. It is
much more stable toward the effect of light and atmospheric
conditions than most of the other polymers.
Poly(ethy1ene terephthaiate) fibers are distinguished by
their excellent resilience and by their dimensional sta-
bility. Up t o a temperature of ca. 150C the properties
of the fiber deteriorate very little. Other properties which are
responsible for the popularity of poly(ethy1ene terephthalate)
fiber in the textile industry are its good permanent-set
property and high melting point (260 C ) .
The excellent electrical properties of poly(ethy1ene tere-
phthalate), such as high specific resistance, high dielectric
strength, together with its thermal stability and small moisture
absorption, make it a very good insulating material.
2. Thermal Degradation
The nature of thermal degradation of polyesters is not
entirely clear. The primary fission of the ester linkage
in the polymer is probably not a homolytic, reaction,
since thermal degradation cannot be inhibited by free
radical trapping agents. The close agreement between
the behavior of poly(ethy1ene terephthalate) (PET)
and model ester compounds (see Section 2.2) suggests
that the mechanism for polymer degradation is prob-
ably similar to that for simple ester pyrolysis.
2.1. Thermal Degradation of Carboxylic Esters
in General
The mechanism by which esters containing at least
one p-hydrogen atom decompose pyrolytically to give
olefins and acids is generally considered to involve a
cyclic transition state ( I ) 1 1 1 .
In (I), the C-H bond and the alkoxy C-0 bond are
partiy broken, while the olefinic C=C bond and the
0-H bond are partially formed. Previous work [21 has
shown that the C-0 bond breakage is heterolytic and
that the alpha-carbon atom develops some carbonium-
ion character in the transition state. It appears that
for a given ester at a fixed temperature, the rate of
decomposition is determined more by the stability of
the breaking alkoxy C-0 bond than by the breaking
C-H bond or the forming C=C bond 131.
111 C. H . DePuy and R . W. Kong, Chem. Reviews 60,431 (1960),
and references therein.
[21 R. Taylor, G. G . Smith, and W. H . Wetzel, J. Amer. chem.
SOC. 84, 4817 (1962).
[31 G . G. Smith, F. D . Bagley, and R . Taylor, J. Amer. chem.
S O C . 83, 3647 (1961).
Angew. Chem. internat. Edit. f Vol. 7 (1968) / No. 3
Maccoll[41 proposed that the reaction is a pseudo bi-
molecular electrophilic substitution, (E2), involving
nucleophilic attack of the carbonyl oxygen atom on
the ?-hydrogen atom.
This field has been widely but unsystematically studied.
A good survey of the earlier literature up to about 1928
has been presented by Uurdr51. Ritchie@l has summa-
rized nine of the breakdown routes which occur most
frequently.
2.2. Thermal Degradation of Model Compounds
Difficulties in studying the polyester itself suggested
the use of simplified model systems representing
specific segments of the intact PET chain, segments
with terminal hydroxyethyl groups and representing
the known incorporation of occasional ether linkages.
Ethylene dibenzoate (2), 2-hydroxyethyl benzoate (3)
and diethylene glycol dibenzoate ( 4 ) have been chosen
most often for such studies. The degradation of (2)
C~HS-CO-O-CH~-CH~-O-CO-C~HS
(21
C6HS-CO-O-CH2-CHzOH
(31
C~H~-CO-O-CH~-CHZ-O-CH~-CH~-O-CO-C~HS
(4)
between 250 Cand 350 C has been well studied [*, 7,9J,
and is thought to proceed via a cyclic transition state.
Benzoic acid (6) and vinyl benzoate (7) are formed.
Ritchie 161 also reported benzophenone as a reaction product,
although there is n o confirmation of this product by other
workers. It is possible that this difference in product forma-
tion may have resulted from the use of different temperatures
in the pyrolysis.
3-Oxapentylene dibenzoate (4) decomposes by a
similar route to give benzoic acid and 2-vinyloxyethyl
benzoate (8).
C~H~-CO-OCHZ-CHZ-OCH=CHZ
(8)
[4] A. Maccoll, J. chem. SOC.(London) 1958, 3398.
151 C. D . Hurd The Pyrolysis of Carbon Compounds. Chemical
Catalog Co., New York 1929.
[6] P. D . Ritchie, Soc. chem. Ind. (London) Monograph No. 13,
107 (1961).
[7] E. P. Goodings, SOC.chem. Ind. (London) Monograph No.
13, 211 (1961).
181 H. V. R. Iengar and P . D . Ritchie, J. chem. SOC. (London)
1987, 2556; 1956, 3563.
191 G. Challa, Makromolekulare Chem. 38, 138 (1960).
183
Despite the importance of 2-hydroxyethyl esters in the
formation of PET, few studies with model compounds
such as 2-hydroxyethyl benzoate (3) have been per-
formed. Iengar and Ritchie [8J studied the pyrolysis of
(3) at temperatures 'between 375 "C and 500 "C and
proposed a complex degradation mechanism. Our
results, which were obtained at 280"C, suggest a
different mechanism involving a seven-membered ring
The vinyl compounds formed during these reactions
react further to give a complex mixture of end products.
The pyrolysis of vinyl benzoate (7) has been studied
extensively and it has been shown, that, as expected,
this vinyl compound reacts very rapidly at 280C.
After 30min at this temperature (7) yielded a black
mass in which benzoic acid (6), benzoic anhydride
(12) and a diene (14) could be detected.

(9) as transition state and the formation of an active The following facts can be given as proof that the intermedi-
species ( l o ) [141. This mechanism explains the low ates (11) and (13) are formed in the reaction: Ethylidene di-
benzoate (11) could be isolated from the reaction mixture
activation energy found for this reaction (28 kcal/mole) containing compounds (6) and (7) by gas chromatography
and the formation of ether linkages. (The dehydration and was identified by IR- and NMR-spectroscopy. Starting
reaction is not significant at 280 "C, as could be shown from compound (11) a n equilibrium is once again set up at
with ethylene glycol [91.) 28OoC between (7) and (6) as well as with (12) and acet-
aldehyde. Polyvinyl benzoate (13) (prepared from vinyl
benzoate and a radical chain initiator) similarly gives com-
pounds (6) and (14) at 280 "C; the presence of (14) was con-
firmed by IR- and UV-spectroscopy.
Recently Zimmermann and Leibnitz (101 investigated the
(3) (91 influence of catalysts on a number of theindividual reactions.
The primary chain splitting reaction of ethylene dibenzoate
(2) to benzoic acid (6) and vinyl benzoate (7), as well as the
reaction of (7) with alcohols and the polymerization of (7),
are accelerated e.g. by zinc acetate. It was found that the
catalysts zinc acetate and lead acetate have no influence o n the
HOCH2-CH20H + ICH2CH201 + thermal degradation of polyvinyl benzoate(l3) to (6) and (14)
HOCH2-CH2-O-CH2-CH20H or o n the formation of acetaldehyde and (12) from (7) and (6).
C~HS-CO-O-CH~-CH~OH [CHpCHzOJ + + 2-Vinyloxyethyl benzoate (8), the first degradation
C~HS-CO-O-CH~-CH~-O-CH~-CH~OH product of 3-oxapentylene dibenzoate ( 4 ) , decomposes
further to benzoic acid (6),acetaldehyde, and acetylene
A transesterification reaction takes place also, and at at temperatures above 350 "C 181. At 280 "C, however,
280 "C the equilibrium 2 (3) + (2) + ethylene glycol another reaction is of importance: in the presence of
is established in ca. 10 min. benzoic acid the diester (2) is formed, the "acylal"
Figure 1 shows the thermal degradation of (21, (3), (IZ), which is known to form in the reactions of other
and (4). vinylethers 1111, probably occurring as intermediate.
At 280 "C at least 50 % of the carboxyl groups formed
500 t I in the degradation of ( 4 ) react with the vinyl ether (8)
i to give (2) and acetaldehyde [141.
LOO L
I I
i

IOU C'i _________----------

*
i
I -

0 1 2 3 L
m t lhl-
Fig. 1 . Thermal degradation of ethylene dibenzoate (2) -, 3-oxa-
pentyl enedibenzoate (41 -,and 2-hydroxyethyl benzoate (3) .- .-
at 280 "C under nitrogen.
[lo] H . Zimmermann and E. Leibnitz, Faserforsch. u. Textil-
techn. 16, 282 (1965).
[Ill M . F. Shostakovskii, 2. ObSE. Chim .18, 1989 (1948); Chem.
Abstr. 43, 3785 h (1949).

184 Angew. Chem. internat. Edit. VoI. 7 (1968) / No. 3

In general, caution is necessary in correlating the
results obtained from studies with model compounds
with the reactions of the polymer itself. However, it
has been found that in this case model compound
reactions d o not differ much from the reactions taking
place during the thermal degradation of PET, especi-
ally at temperatures between 200 "C and 300 "C.
2.3. Thermal Degradation of
Poly(ethy1ene terephthalate)
Various research teams have studied the thermal
degradation of polyester during the last few years[6.7,
10-131. From their results and from extensive studies
with model compounds we know that PET breaks
down by a molecular mechanism with random chain
scission at the ester links. Although a radical mech-
anism has been proposedf121, no evidence for such a
mechanism could be established.
Pohl1131 proposed that the principal point of weakness
in the polyester chain is the P-methylene group. The
main reactions in the thermal degradation of PET are
summarized in the following scheme:
f o r m a t i o n of
crosslinks 11
-C6H4-COOH + Polyene
Scheme I .
If 2-hydroxyethyl end groups are present in the poly-
mer the following reactions take place also:
Scheme 2.
Thus, as long as free hydroxyl end groups exist in a
PET melt, every broken polymer link will be reformed.
When most of the hydroxyl end groups have been
consumed, the molecular weight will begin to fall.
2.3.1. P r o d u c t s of T h e r m a l D e g r a d a t i o n
When PET is maintained in a molten state under
nitrogen at about 28OoC, it decomposes slowly to
gaseous and to solid, low molecular weight products;
I121 I. Marshall and A . Todd, Trans. Faraday SOC.49, 67 (1953).
1131 H. A. Pohl, J . Amer. chem. SOC. 73, 5660 (1951).
Angew. Chem. internat. Edit. J Vol. 7 (1968) No. 3
the functional groups react with one another, and the
polymer becomes colored.
2.3.1.1. G a s e o u s P r o d u c t s
A gaseous mixture with the following composition
(concentration in mole- %) is formed at temperatures
between 280 "C and 306 "C [73: C O = 8.0; C 0 2 = 8.5;
H20 = 0.8; CH3CH0 = 79.5; CzH4 = 2.0; 2-methyl-
dioxolane =- 0.4; CH4 = 0.4; C6H6 = 0.4. Although
this composition varies appreciably with temperature
acetaldehyde is always the major product.
2.3.1.2. N o n - g a s e o u s P r o d u c t s , O l i g o m e r s
During melt spinning of PET a white "dust" is formed
and covers various parts of the spinning apparatus [ 1 5 a I .
A similar sublimate can be produced in the laboratory
by bubbling nitrogen through molten polyester. This
sublimate consists primarily of terephthalic acid and
acidic oligomers 17,141.
Cyclic oligomers (mainly the trimer) are also formed
during the thermal degradation of PET. A kind of
equilibrium between the cyclic oligomers and the
polymer seems to exist. After extracting these oligo-
mers from PET and heating the extracted polymer for
J-
Polyenaldehyde
about one hour at 280"C, the same amount of cyclic
oligomer is again formedr16J. It is not known how
these oligomers are formed in the polymer, although
a transesterification involving end groups can be
assumed.
Goodings "1 isolated a number of compounds, mainly
derivatives of substituted benzoic acids and biphenyl-
di- and monocarboxylic acids, from extensively pyro-
lyzed PET. However, these materials were found in
very low concentration (0.005-0.09 wt. %).
-
[14] Unpublished observations by the Polyester Research &
Development Division, Goodyear Tire & Rubber Co., Akron,
Ohio (USA).
[15] H . Zimmermann, Faserforsch. u. Textiltechn. 17,228 (1964).
[15a] A. Mifine, S . Ishida, A . Kobayashi, and S . Sakajiri, Kogyo
Kagaku Zassi 65, 992 (1962).
[16] I. Goodman and B. F. Nesbitt, Polymer (London) I , 384
(1960); J. Polymer Sci. 19, 423 (1960).
185
2.3.1.3. Reactions of Functional G r o u p s energies found by different authors using one or more
of the methods mentioned above. It is interesting that
PET has an average molecular weight of 25000 all the rate constants have the same order of magnitude.
(intrinsic viscosity [q] = 0.68 dl g-1). The concentration
The effect of molecular weight (or intrinsic viscosity)
of carboxyl groups depends on the catalyst and is of
on the thermal degradation of PET per unit time, and
the order 10-50 equiv/l06 g of polymer. The concen-
at various temperatures, is shown in Figure 2.
tration of hydroxyl end groups is about 60 equiv/l06 g.
During thermal degradation, the concentration of
Table 1. Reaction rate constant and activation energy of the thermal
hydroxyl groups tends to fall and the carboxyl group degradation of PET.
content of the polymer increases. Anhydride groups
can be formed; they begin to accumulate when most k and Ea calculated from 1 k(h-1.103) at 282C 1 Ea (kcal/mol)
of the hydroxyl end groups have been consumed[71. I711 [a1 1.3 2.3 1.4 62.3
The anhydride groups are formed by the reaction of M.V. [bl 1.7 (290 "C) 32.0 48
Total gas - 38
vinyl end groups with carboxyl groups and by dehy-
-COOH 3.5 41.7
dration of two carboxyl groups. Goodings [71 reported -OH 2.4
that PET which had been degraded at 306C for 65 -CHO 0.2
Total end groups 1.2 58.7
hours under nitrogen gave an IR-spectrum indicating References r71 1121 r141 171 1121 r171 r141
that anhydride and carboxyl groups were present in
[a] Intrinsic viscosity.
the ratio 1:2.6.
[bl Melt Viscosity.

2.3.1.4. Di scol oration

Discoloration is a serious problem in the production

of PET since the consumer of white polyester goods
demands a brilliant white color. As PET degrades, its
color changes first to yellow, then to brown, and
finally to black. Since the chromophoric substances
involved are very difficult to isolate, contradictory
results have been reported about their nature and com-
position. At least part of thechromophore seems to be
chemically bonded to the polymer. The chromophore
is believed to be a highly unsaturated aliphatic mole-
cule with a molecular weight of about 300-1000 17,141.
Two routes leading to color formation in PET are
discussed in the literature. Goodings 171 assumes the
formation of polyenaldehydes from acetaldehyde.
Zimmermann [ l o , 151, on the other hand, has shown
that unsaturated, color forming molecules are formed
from polyvinyl esters. Our own studies show that both
reactions contribute to color formation; the precise
polymerization conditions will determine which
reaction sequence predominates.
2.3.2. K i n e t i c s
Investigations on the kinetics of simple esters r3-51
show that their decomposition reactions are homo-
geneous, follow first order kinetics in both the vapor
and the liquid phase, and are unaffected by radical
scavengers. The activation energy found for ester
pyrolysis was about 40 kcal/mole; on a theoretical
basis pure chain scission of the ester link would re-
quire an activation energy of almost 60 kcal/mole. The
lower value observed indicates a mechanism probably
involving a cyclic transition state ( I ) .
The rate of thermal degradation of PET can be meas-
ured in terms of: a) the products formed, b) the rate of
change of molecular weight of the polymer (as meas-
ured by the melt viscosity or the intrinsic viscosity),
or c) the rate of change in concentration of end groups.
Table 1 shows reaction rate constants and activation
[?I Idl.g"1-
Fig. 2. The thermal degradation of PET per minute as a function of [71l
at different temperatures.
3. Oxidation
The degradation of PET in various oxygen-nitrogen
mixtures between 280C and 325C has been in-
vestigated by Marshall and Todd[l21. The rate of
degradation (measured by the decrease in the melt
viscosity) increased linearly with increasing oxygen
content. Passing oxygen through molten polyester
causes rapid degradation, noticeable by color forma-
tion, an increase in carboxyl content and a decrease in
molecular weight 1141.
3.1. Course of Oxidation
No generally accepted concept for the course of the
oxidation of PET has been reported. In previous
studies, the mechanism developed by Bolland et. a/[191
for the oxidation of hydrocarbons has generally been
referred to and adopted in the interpretation of the
oxidation of polymers [181.
The high molecular weight of PET and the influence
of the physical structure make it difficult to study the
oxidation of the polymer directly. Consequently,
[17] S. Straus and L. A . Wall, J. Res. nat. Bur. Standards, A . 60,
39 (1958).
[18] W. L. Hawkins, SPE Trans. July 1964, 187.
[19] J. L. Bolland, Quart. Rev. chem. SOC.(London) 3, 1 (1949).

186 Angew. Chenz. internat. Edit. Vol. 7 (1968) I No. 3

studies with model compounds have provided most of which oxygen and moisture play an important role in
the mechanistic information available. 3-Oxapentylene the degradation.
dibenzoate ( 4 ) oxidizes readily at 130 oC[2*1 to give Stephenson et al. [211 and Marcotte et al. 1 2 showed
~
2-benzoyloxyethyl benzoyloxyacetate, 2-benzoyIoxy- that the polymer turns to an amber color, becomes
ethyl formate, benzoyloxyacetic acid, benzoic acid, brittle, evolves gas (mainly CO and COz), and be-
formic acid and water. Ethylene dibenzoate (2), and 2- comes partly insoluble in trifluoroacetic acid, after it
hydroxyethyl benzoate, ( 3 ) , can not be oxidized at has been exposed to monochromatic light of wave-
130 OC; above 200 C decomposition occurs, but this lengths 2537 and 3130 A. From their results the reac-
is probably a combination of oxidative and thermal tion sequencegshown in Scheme 4 seem probable:
degradation. The mechnism of the oxidation of these
two model compounds is therefore inaccessible to
direct study. When comparing the degradation of
these compounds under oxygen and under nitrogen at
210 C, the higher carboxyl-group content and the
darker color of the samples heated under oxygen sug-
gest a breakdown to acidic and color forming species
similar to those obtained from ( 4 ) .
The results from these model compound studies are in
good agreement with results obtained with PET.
Diethylene glycol links lower the stability of polyester
toward oxidation. The reaction sequences shown in Hydrogen abstraction from neighboring molecules
Scheme 3 have been proposed as an interpretation of leads to the formation of radicals such as (21) and (22).
the oxidation of PET:

1
These radicals can recombine to form crosslinks, the
nature of which is, at present, unknown. The forma-
tion of polyphenyl systems, in which reactions involv-
ing the radical (22) (see section 4.2.) seem to be of
little importance, has also been suggested [221.
4. Degradation by Radiation

4.1. Photolysis

Generally speaking poly(ethy1ene terephthalate) is

very stable toward ultraviolet light; however, some
long term degradation occurs especially when it is
exposed to light of wavelength 3000-3300 ,k[21aI.
There seems to be a threshold photon energy of about
3 eV below which no damage is done[211.
The present understanding of the photodegradation
of polyesters is very rudimentary since most reports
on this subject are of weathering experiments, in
1201 L. H. Buxbaum, ACS Polymer Preprints, 8, 552 (1967).
[21] C. V . Stephenson, B. D . Moses, and W. S . Wilcox, J. Poly-
mer Sci. 55,451, 465,477 (1961).
[21a] F. B. Marcotte, D . Campell, J. A . Cleaveland, and D . T .
Turner, J. Polymer Sci. A-1, 5,481 (1967).
For practical purposes, weathering experiments give a
good picture of the performance of PET in specific outdoor
applications. Under these conditions the ether content of the
polymer is of extreme importance. Coleman [221 exposed
copolymers of PET containing polyoxyethylene gIycoI to
ultraviolet light. After 300 hours of exposure, a yarn con-
taining 17% by weight of polyoxyethylene glycol (MW =
2800) showed a 40% decrease in intrinsic viscosity while
pure PET was not affected. Therefore this copolymer was not
12-21 D. Coleman, J. Polymer Sci. 14, 15 (1954).

Angew. Chem. internat. Edit. / VoZ. 7 (1968) 1 No. 3 187

accepted on the market even though the dyeability of fibers
of this material was much superior to that of fibers prepared
from the homopolymer.
4.2. Degradation by High Energy Ionizing Radiation
The mechanical properties of PET fibers are relatively
unchanged by moderate doses of high energy radia-
tion. When subjected to doses of more than 50 Mrad
the tensile strength and ultimate elongation of the
PET begin to decrease considerably and deteriorate
rapidly when the dose reaches the 100-500 Mrad
range. Radiation doses exceeding 1000 Mrad 1231 lead
to the lowering of the glass transition temperature,
which probably results from the lowering of the mole-
cular weight by chain cleavage and from plasticization
Crosslinking: (24)
by the low molecular weight fragments formed. It is
interesting to note that by simply exchanging the
benzene rings in PET for naphthalene rings a polymer
is formed which is much more stable toward ionizing
radiation. Although cross-linked, an unoriented film
of poly(ethy1ene 2,6-naphthalene dicarboxylate) was
still tough and flexible after 1000 Mrad of gamma
radiation 1401.
Rather contradictory results have been reported
concerning the reactions occurring during high energy
irradiation. Both crosslinking 124,261 and chain cleav-
age [*51 have been claimed to be predominant; the
former claim was based upon partial insolubilization
of the polymer, while the latter was based upon com-
plete solubility, a steady decrease in molecular weight
with increasing dose, and physical evidence of chain
cleavage.
More recent evidence suggests that both chain cleav-
age and crosslinking occur and that the reaction
conditions determine which process is predominant.
Dose rate, kind of radiation, temperature, crystallinity,
and impurities, such as waterQ61 or oxygen, are ex-
amples. At low dose rates of gamma-rays, carboxyl
[23] D . E. KIine and J . A. Sauer, Polymer (London) 2,401 (1961).
[24] 0. Terszler and H . A . Rutherford, Textile Res. J. 26, 96
(1956).
[25] K . Little, Nature (London) 170, 1075 (1952); A. Todd, ibid.
174, 613 (1954).
f261 K . H . HeNwege, V .Johnson, and W. Seuofert, Angew. Chem.
76, 59 (1964); Kolloid-Z., Z. Polymere 188, 11 (1963).
188
groups are formed - and no gel formation has been
observed. At higher dose rates (over 5000 Mrad) a
network is formed in the polymer [291 and fewer car-
boxyl groups are formed.
Some investigations have been carried out using high speed
electrons [26,281 instead of gamma-rays 1271. The results of
these experiments were expected to be different since elec-
trons are known to cause a temperature increase in the poly-
mer (electron microscopy) and are reported to destroy
crystallinity in PET by changing the steric conformation of
the chainc281. No gel formation has been observed at tem-
peratures up to 175 "C for doses of up to 2000 Mrad [29aI; at
temperatures above 200 'C rapid gelation occurs even with
low doses.
ESR studies of free radicals formed by gamma-irradi-
ation of PET1291 support the suggestion of the reac-
tion sequences shown in Scheme 5 as being the prim-
ary steps in the degradation:
+ (23) + -CsH4-CO-O-CH-CH2-O-OC-C6H4-
I
CHz-CHz-O-OC-Cs&-
(24) - c o l o r formation Scheme 5 .
The differences between photolysis of PET and degra-
dation by high energy radiation can be summarized
as follows:
Photolysis:
Primary reaction products:
- C6H4. + CO f 'OCH2-CH2-O-OC-C6H4 -;
Only few carboxyl groups, and no hydrogen, are
formed.
Crosslinking occurs.
Degradation by high energy radiation:
Primary reaction products:
- C6H4-CO-O-CH-CH2-O-Oc-c6H4
0
- + H'
Hydrogen and carboxyl groups are formed.
No gelation occurs (up to 2000-5000 Mrad).
I271 S. D. Burow, D . T. Turner, G. F. Pezdirtz, and G. D. Sands,
J. Polymer Sci. A-1, 4, 613 (1966).
[28] N. A . Slovokhotova, G. K . Sadovskaya, and V. A . Kargin,
J. Polymer Sci. 58, 1293 (1962).
[29] K . Araki, D . Campell, and D . T . Turner, ACS Polymer
Preprints 6, 1007 (1965).
I29a] S. D . Burow, D . T . Turner, G . F. Pezdirtr, and G. D . Sands,
ACS Polymer Preprints 5, 396 (1964).
Angew. Chem. internat. Edit. Vol. 7 (1968) No. 3
5. HydroIytic Degradation
In contrast to other polyesters, PET is very resistant
to attack by water, acids, and bases; this is due,
presumably, to its aromatic character and to the
tight packing of its chains. Nevertheless, it does
hydrolyze at temperatures above 100 "C. Of the forms
of degradation discussed thus far, hydrolysis is by far
the most troublesome reaction. The hydrolysis of
PET at 100"-120"C and 100% relative humidity
proceeds 10000 times faster than that of thermal
degradation and 5000 times faster than that of oxida-
tion in air in the same temperature range 1311.
It is known that dry PET adsorbs moisture rapidly
and that the extent of adsorption is dependent upon
the time of exposure, the particle size, crystallinity, and
relative humidity.
5.1. Neutral-, and Acid-Catalyzed Hydrolysis
5.1.1. A d s o r p t i o n a n d D i f f u s i o n o f W a t e r
The hydrolysis of ester bonds must proceed via (i) the
adsorption of water on the surface of the polymer and
(ii) diffusion to the interior of the polymer from the
point of attack. Knowledge of the rates of adsorption
and diffusion are of practical and theoretical impor-
tance. The adsorption of water by dry PET cubes of
length 3/16" (or 0.4762 cm) amounts to 0.025 % after
112 h, and, by dry PET powder (40 mesh), to ca. 0.125 %.
The influence of the diffusion of moisture on the rate
of hydrolysis has been considered by several groups of
workers, but the results are contradictory. Golike and
Lasoski[30] and McMuhon et al. [311 assume that the
diffusion of moisture into the polymer is the rate-
controlling step. However, the rate of diffusion of
water into PET at temperatures above 100C is at
least 1000-fold higher than the rate of hydroIysis [32,331.
The observed differences are probably due to dif-
ferences in morphology and molecular geometry of
the polymers studied.
5.1.2. C o u r s e o f H y d r o l y s i s
The hydrolysis of esters in neutral or acid media
generally proceeds according to the reactions shown
in Scheme 6:
s
R-C-0-R' + PH
H@ +e R - C - 0 - R '
O (I960).
?H
R-C-0-R' + HzO
?H
R-C-0-R' Z
PH B
R-C-O,O
O I
HOH
O
?H
R-C-O,O
FI R'-OH + PH
R-CO
::
R-C-OH
I 1351 D. R. Sheard, unpublished results.
AH R ' OH
Scheme 6 .
Angew. Chem. internut. Edit. / Vol. 7 (1968) J No. 3
The reaction rate depends on both the proton con-
centration and the amount of water. This is in agree-
ment with the observation that the hydrolysis rate for
PET depends on the relative humidity. The adsorp-
tion isotherm[331 shows that the rate of hydrolysis is
directly proportional to the concentration of water in
the polymer.
The influence of proton concentration on the hydro-
lysis rate is evident in the hydrolysis of PET in hydro-
chloric acid [33-36,42-441. The rate is only slightly
influenced by acid concentrations below 3 N but
increases rapidly at concentrations above this value.
Ravens 1341 explains this by considering the acid con-
centration not in the aqueous phase, but in the poly-
mer itself. Because of the low dielectric constant of
PET (< 4), one can assume that the acid in the poly-
mer is only slightly dissociated. This is in agreement
with the work of Sheard"'], who observed that am-
monia will diffuse through films of PET whereas am-
monium ions will not. The importance of the dielectric
constant is further emphasized by the fact that the
rate of acid hydrolysis is slower in drawn fibers than
it is in undrawn fibers.
in drawn fibers the crystallinity is of a higher order
than it is in undrawn fibers. During crystallization,
the molecules assume a trans-configuration; hence,
the polymer has a smaller dipole moment and there-
fore a smaller dielectric constant. This in turn leads
to a decrease in the degree of dissociation of the hy-
drochloric acid, so that the proton concentration
within the polymer is lower than that in the surround-
ing medium.
Organic acids, e.g. adipic acidC451, also catalyze the
hydrolysis of PET 1363. Terminal carboxyl groups of a
polyester, which enter into all reactions characteristic
of carboxylic acids, also have a catalytic effect. From
investigations on polymers with initial carboxyl-group
concentrations of from 8 to 97 equiv./lWgram of
polymer, Ravens and Ward1331 concluded that the
hydrolysis rate can be expressed by
d[-COOH] / dt = k[-COOH] 'h
where the square root term arises from the weakly
acidic nature of the carboxyl group of the polymer.
This is a catalytic effect and is not due to adsorption
of water in the polymer at carboxyl end groups only,
since the adsorption isotherm is independent of the
carboxyl end group concentration 1331.
~-
[301 R. C. Golike and S . W . Lasoski, J. physic. Chem. 64, 895
1311 W. McMahon, H. A . Birdsall, G. R. Johnson, and C . T.
CamiIIi, J. chem. Engng. Data 4, 57 (1959).
I321 T. Davies, P. L. Goldsmith, D . A . S . Ravens, and I . M . Ward,
AH R ' J. physic. Chem. 66, 175 (1962).
1331 D . A . S . Ravens and I. M . Ward, Trans. Faraday SOC. 57,
150 (I 961).
+ HO
1341 D . A . S. Ravens, Polymer (London) I , 375 (1960).
1361 W. Brennecke and H. Richier, Melliand Textilbei. 40, 531
(1959).
189
5.2. Base Catalyzed Hydrolysis
Very little has been published about the base catalyzed
hydrolysis of PET. This is especially important in view
of the potential interactions between polyester fibers
and various organic and inorganic bases used in dyeing,
aftertreatment, and washing.
Sodium or potassium hydroxide solutions normally
attack only the surface of a PET fiber; however,
changes in the fine structure of the inner part of the
fiber after such treatment have been observed recent-
ly[371. The dielectric properties of the polymer and
the formation of carboxylate ions on the fiber surface
presumably present a barrier to the penetration of the
polymer by hydroxyl ions. The formation of a skin
around the fiber and the fact that the rate constant for
base catalyzed hydrolysis of esters of dibasic acids is
smaller than the rate constant for acid hydrolysis is
taken as further evidence for the greater stability of
polyester fibers in alkaline solutions than in acid solu-
tions.
The degradation of PET in the presence of amines is
accompanied by the formation of amide bonds. The
final formation of the terephthalic acid diamide takes
place via oligoester amides and oligoamides [37,3*1.
The morphology of the polymer is again of great
importance. Thus Farrow, Ravens, and Wardt391 have
shown that a fiber sample with high orientation and
[37] H. Pfeifer, Forsch.-Ber. Landes Nordrhein-Westfalen Nr.
1212 (1964).
[38] H . Zahn and H . Pfeifer, Polymer (London) 4 , 429 (1963).
1391 G. Farrow, D. A . S . Ravens, and I. M . Ward, Polymer 3, 17
(~1962).
crystallinity was unattacked after 1 6 hours in aqueous
methylamine, whereas samples having other morpho-
logical properties were considerably degraded. The
attack by methylamine takes place in three stages:
The initial attack is in the amorphous regions; in the
second stage, scission produces more low molecular
weight material and gives rise to an increase in the
degree of crystallinity of the polymer; the third stage,
distinguished by a gradual decrease in the rate of reac-
tion, is attributed to a decrease in the rate of attack on
both crystalline and amorphous regions.
The rate of aminolysis in the presence of primary and second-
ary amines is of the same order of magnitude as the rate of
alcoholysis [371. Tertiary amines react with polyester only at
higher temperatures; but these reactions are not, as yet, fully
understood. For example, the products of the thermal de-
gradation of PET seem to react with the tertiary amine; the
products of this reaction and the amine itself are subject t o
further thermal and oxidative degradation. The known
catalytic effect of hydroxyl compounds on the aminolysis of
esters [411 further complicates the picture.
The author gratefulry acknowledges permission by the
Goodyear Tire and Rubber Company to publish this
work.
Received: June 8, 1967 [A 622 IEI
German version: Angew. Chem. SO, 225 (1968)
[40] Chem. Engng. News 43, No. 20, p. 38 (1965).
[41] M . Gordon, J. C . Miller, and A . B. Day, J. Amer. chem. SOC.
71, 1245 (1947).
[42] B. P. Ridge, J. Textile Inst. 44, 48 (1953).
[43] E. Dyhrenfurth, Dissertation ETH Zurich 1954; Textil-
Rdsch. (St. Gallen) II, 573 (1956).
[44] E. Furrer, Dissertation ETH Zurich 1955; Textile-Rdsch.
(St. Gallen) 13, 129 (1958).
[45] V . V. Korsak, N. I. Bekasowa, and Y . A . Zamjatina, Dok-
lady Akad. Nauk SSSR 1958, 614.

Formation and Properties of Solvated Electrons

BY U. SCHINDEWOLF I *I

In the formulation of many chemical reactions, electrons are regarded as readily trans-
ferable particles, though their participation in these reactions cannot be directly ob-
served. However, the discovery that electrons can be produced in various ways in suitable
solutions and that they are stabilized by solvation and can thus be studied directly has
recently led to a rapid growth of interest in these, the simplest and mcst reactive particles
of chemistry. The solvated electron has physical properties that permit its detection by
various methods even at very low concentrations, so that it is also possible to follow its
many reactions, most of which are extremely fast.

1. General ever, dissolved electrons are by no means a very

It has been shown in recent years that dissolved elec-
trons [1,21 occur as reaction intermediates in the
course of many energy-consuming chemical processes.
They are formed on radiolysis, photolysis, and electrol-
ysis of aqueous and other polar systems. They also
occur in the base-promoted ionization of hydrogen in
sohtion, and probably in some redox processes. How-
recent discovery, but were observed more than a
hundred years ago on dissolution of alkali metals in
['I Doz. Dr. u . Schindewolf
Institut fur Kernverfahrenstechnik
der Universitat und des Kernforschungszentrums
75 Karlsruhe Postfach 947 (Germany)
[l] American Chemical Society Publication: Solvated Electron,
Advances Chem. Ser. 50, 1965.
[21 E. J . Hart in M . Haissinsky: Actions Chimiques et Bio,ogi-
ques des Radiations 10,1 (1966).

190 Angew. Chem. internat. Edit.1 Vol. 7 (1968) 1 No. 3