Poly(vinyl chloride)‐poly(ethylene oxide) block copolymers have been synthesized in solution and emulsion. The polymers were made by first synthesizing macroazonitriles through the reaction of 4,4′‐azobis‐4‐cyanovleryl chloride with hydroxy‐terminated poly(ethylene oxide) of varying molecular weights. These macroazonitriles had molecular weights in the range of 3000–88,000 and degrees of polymerization from 5 to 24. Thermal decomposition of the azolinkages in the presence of vinyl chloride monomer yielded block copolymers containing form 2 to 20 wt % poly(ethylene oxide). The structures of the block copolymers were characterized by spectrometric, elemental and molecular weight analyses. The possibility of some graft polymerization occurring via free‐radical extraction of a methylene hydrogen from the poly(ethylene oxide) was considered. Polymerization of vinyl chloride with an azonitrile initiator in the presence of a poly(ethylene oxide) yielded predominately homopolymer with some grafted poly(vinyl chloride).
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Laverty et al. (1977) studied this question.
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