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.