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

Abstract 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.