Catalytic effect of hydrogen chloride on the degradation of poly(vinyl chloride)

The distribution of polyenes which results from the chemical dehydrochlorination of poly(vinyl chloride) has been studied in dichloromethane (DCM) and tetrahydrofuran (THF) solvents. A higher percentage of longer polyenes is formed in DCM than in THF. On the addition of trifluoroacetic acid to DCM solutions of the polyenes, new species are formed with strong absorptions in the region 500–800 nm. The absorptions are probably due to polyenylic ions formed by protonation of the polyenes, and the interrelated changes in their intensities can be explained by the migration of short polyene sequences along the polymer chain with the formation of longer sequences. The species are extremely photosensitive and are bleached in a few seconds with light from a medium-pressure mercury lamp. The relevance of these experiments to the effect of HCl on the polyene distribution and on the rate of photocrosslinking is discussed.