Structure of chlorinated poly(vinyl chloride). IV. Chlorination of β,β-d2-poly(vinyl chloride) as model for determination of the mechanism of chlorination

Chlorinated β,β-dideuterated poly(vinyl chloride) (β,β-d₂-CPVC) was prepared by photochemical suspension chlorination in concentrated hydrochloric acid with chloroform as swelling agent, and thermally in tetrachloroethane solution. ¹H-NMR (nuclear magnetic resonance) spectra of β,β-d₂-CPVC were recorded. The content of deuterium was determined in combustion products of β,β-d₂-CPVC as the D₂O:(H₁D)₂O ratio by means of mass spectroscopy. Both in the photochemical suspension chlorination and in the thermal solution chlorination of β,β-d₂-PVC, a decrease of the concentration of ? CHCl? groups was observed. The differences in structure of the suspension chlorinated and solution chlorinated β,β-d₂-PVC were confirmed.