Novel polymeric structures via the chlorination of cis-1,4-polybutadiene in the presence of aryl nucleophiles

The addition chlorination of cis-1,4-polybutadiene in the presence of a variety of aryl nucleophiles resulted in the formation of head-to-head poly(vinyl chloride) with pendant aromatic functional groups. Chlorination in methylene chloride solution with benzoic acid gave chlorinated polymers with pendant benzoate esters. Chlorination in the presence of phenol and benzhydrol provided polymers with pendent phenyl and diphenyl methyl ethers, respectively. Acetophenone participated during chlorination to affored polymer with pendant α-chloroether groups, while benzonitrile gave a polymer with pendant imidoyl chlorides. The extent of participation of these nucleophiles was estimated from elemental analysis and NMR spectral data, and the effect of aryl substitution on density, glass transition temperature, and linear coefficient of thermal expansion was determined. © 1993 John Wiley & Sons, Inc.