The nature of the branches in poly(vinyl chloride)

The presence of branches in poly(vinyl chloride) as indicated by previous IR measurements on the polymer reduced to polyethylene by means of lithium aluminum hydride is believed to affect materially the morphology and solid state properties of poly(vinyl chloride); however, up to the present, the nature of these branches has not been known. By use of 13C-NMR on reduced poly(vinyl chloride) it is demonstrated that the brances are methyl groups, presumably corresponding to chloromethyl groups in the original polymer. In the sample studied, the frequency is ca. 3 methyl groups per 1000 CH2 groups, but this is expected to depend on the temperature of polymerization. There is also some evidence for long branches, probably not exceeding 1 per 1000 CH2 groups.