Structure of chlorinated poly(vinyl chloride). I. Determination of the mechanism of chlorination from infrared and NMR spectra

Infrared and NMR spectra of chlorinated poly(vinyl chloride) (CPVC) and of chlorinated α‐deuterated poly(vinyl chloride) (α‐d‐CPVC) have been measured. It was found that the CDCl unit of α‐d‐PVC does not undergo chlorination. By assuming an analogous mechanism of chlorination in normal PVC, the populations of all the three possible types of two‐carbon sequences (CH2CHCl, CHClCHCl, CHCl CCl2) in CPVC could be determined. The mechanism of chlorination of PVC is discussed from the viewpoint of the previous findings on the conformational structure of this polymer. Differences in structure between suspension‐ and solution‐chlorinated PVC have been established.