The structure of chlorinated poly(vinyl chloride). VI. Comparison of the chlorination of poly(vinyl chloride) and β,β-d2-poly(vinyl chloride) with 1H-NMR and 13C-NMR spectroscopy

Samples of chlorinated poly(vinyl chloride) (CPVC) and chlorinated β,β-dideuterated poly(vinyl chloride) (β,β-d₂-CPVC) were prepared under identical reaction conditions. The microstructure of CPVC and β,β-d₂-(CPVC) was characterized by a combination of ¹H-NMR, ¹³C-NMR spectroscopy, and analytically determined chlorine content. A difference was observed in the reaction rates of chlorination of PVC and β,β-d₂-PVC, and, in their thermal chlorination in solution, also in the structure of the chlorinated products. It was proved that in the chlorination of β,β-d₂-PVC a new chlorine atom can also enter the original? CHCl? group. The results are discussed from the standpoint of the chlorination mechanism.