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[71] K. Mutterstock and R . Gruf, German Pat. 1171 887, Farb- [721 R. Appel and W. Senkpiel, Angew. Chem. 70, 271 (1958);
werke Hoechst AG (1961). Chem. Ber. 91, 1200 (1958).
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.
between 250 Cand 350 C has been well studied [*, 7,9J,
2.1. Thermal Degradation of Carboxylic Esters and is thought to proceed via a cyclic transition state.
in General
Benzoic acid (6) and vinyl benzoate (7) are formed.
(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
0 1 2 3 L
m t lhl- [lo] H . Zimmermann and E. Leibnitz, Faserforsch. u. Textil-
Fig. 1 . Thermal degradation of ethylene dibenzoate (2) -, 3-oxa- techn. 16, 282 (1965).
pentyl enedibenzoate (41 -,and 2-hydroxyethyl benzoate (3) .- .- [Ill M . F. Shostakovskii, 2. ObSE. Chim .18, 1989 (1948); Chem.
at 280 "C under nitrogen. Abstr. 43, 3785 h (1949).
f o r m a t i o n of
crosslinks 11 J-
-C6H4-COOH + Polyene Polyenaldehyde
Scheme I .
about one hour at 280"C, the same amount of cyclic
If 2-hydroxyethyl end groups are present in the poly- oligomer is again formedr16J. It is not known how
mer the following reactions take place also: these oligomers are formed in the polymer, although
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
- + H'
Dose rate, kind of radiation, temperature, crystallinity, Hydrogen and carboxyl groups are formed.
and impurities, such as waterQ61 or oxygen, are ex- No gelation occurs (up to 2000-5000 Mrad).
amples. At low dose rates of gamma-rays, carboxyl
I271 S. D. Burow, D . T. Turner, G. F. Pezdirtz, and G. D. Sands,
[23] D . E. KIine and J . A. Sauer, Polymer (London) 2,401 (1961). J. Polymer Sci. A-1, 4, 613 (1966).
[24] 0. Terszler and H . A . Rutherford, Textile Res. J. 26, 96 [28] N. A . Slovokhotova, G. K . Sadovskaya, and V. A . Kargin,
(1956). J. Polymer Sci. 58, 1293 (1962).
[25] K . Little, Nature (London) 170, 1075 (1952); A. Todd, ibid. [29] K . Araki, D . Campell, and D . T . Turner, ACS Polymer
174, 613 (1954). Preprints 6, 1007 (1965).
f261 K . H . HeNwege, V .Johnson, and W. Seuofert, Angew. Chem. I29a] S. D . Burow, D . T . Turner, G . F. Pezdirtr, and G. D . Sands,
76, 59 (1964); Kolloid-Z., Z. Polymere 188, 11 (1963). ACS Polymer Preprints 5, 396 (1964).
5.1.2. C o u r s e o f H y d r o l y s i s where the square root term arises from the weakly
acidic nature of the carboxyl group of the polymer.
The hydrolysis of esters in neutral or acid media This is a catalytic effect and is not due to adsorption
generally proceeds according to the reactions shown of water in the polymer at carboxyl end groups only,
in Scheme 6: since the adsorption isotherm is independent of the
carboxyl end group concentration 1331.
s
R-C-0-R' + PH
H@ +e R - C - 0 - R '
~-
[301 R. C. Golike and S . W . Lasoski, J. physic. Chem. 64, 895
O (I960).
1311 W. McMahon, H. A . Birdsall, G. R. Johnson, and C . T.
?H
R-C-0-R' + HzO
?H
R-C-0-R' Z
PH B
R-C-O,O
CamiIIi, J. chem. Engng. Data 4, 57 (1959).
O I I321 T. Davies, P. L. Goldsmith, D . A . S . Ravens, and I . M . Ward,
HOH AH R ' J. physic. Chem. 66, 175 (1962).
O
1331 D . A . S . Ravens and I. M . Ward, Trans. Faraday SOC. 57,
150 (I 961).
?H
R-C-O,O
FI R'-OH + PH
R-CO
::
R-C-OH + HO
1341 D . A . S. Ravens, Polymer (London) I , 375 (1960).
I 1351 D. R. Sheard, unpublished results.
AH R ' OH
1361 W. Brennecke and H. Richier, Melliand Textilbei. 40, 531
Scheme 6 . (1959).
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.