| Abstract: | During thermal degradation of poly(vinyl chloride) in a nitrogen atmosphere polyene sequences of different lengths are formed by dehydrochlorination. The distribution of the sequence lengths in the polymer is approximated by analysis of the electron spectra, and the spectroscopically determined polyene content is compared with the amount of hydrogen chloride split off. With increasing temperature, as well as with increasing time of degradation, the distribution of the polyene sequence lengths shifts towards shorter sequences. In contrast to degraded poly(vinyl chloride) powder, degraded poly(vinyl chloride) foils exhibit a marked shift towards longer sequences. Vinylisobutyl ether as comonomer unit in the polymer chains effects a considerable shift of the sequence lengths distribution towards shorter polyene sequences. The spectroscopically determined polyene content agrees with the amount of liberated hydrogen chloride only a t very low conversions while with increasing dehydrochlorination a growing polyene deficit is found. Therefore, it is to be concluded that polyene sequences are consumed by consecutive reactions in which primarily the longer polyene sequences are involved. A further conclusion that may be drawn from these experiments is that the formation of long polyene sequences takes place very rapidly once the initial step of dehydrochlorination has occurred at a labile site. Apart from the above mentioned consecutive reactions, only the number, not the average length, of the polyene sequences changes substantially with increasing time of degradation. |
