Structure and properties of polyvinylchloride. 1. Molecular structure of chlorinated PVC

A commercial PVC sample was chlorinated in water suspension under UV irradiation. The chlorine content increased gradually from one to two chlorine atoms per monomer unit indicating an apparent saturation. No significant degradation of the polymer occurred. High resolution NMR‐analysis showed that the initial stage of the reaction was a formation of CHClCHCl‐groups. At later stages CH 2 CCl 2 ‐groups were also formed but not adjacent to each other along the chains.