α,α‐Dibromotoluene as a monomer for poly (substituted methylene) synthesis: Magnesium‐mediated polycondensation of α,α‐dibromotoluene and magnesium/copper‐mediated copolycondensation of α,α‐dibromotoluene with 1,6‐dibromohexane

Abstract

Abstractα,α‐Dibromotoluene 1 was found to be polymerized by the reaction with excess Mg to give poly(phenylmethylene)s 2, whose main chains were partially dehydrogenated to carbon–carbon double bonds (CC). The CCs in 2 can be brominated by treatment with Br2. The polymerization mechanism was presumed to include the formation of Grignard reagents of various species with benzylic CBr bonds and the nucleophilic attacks of the Grignard reagents to various compounds with benzylic CBr bonds. Copolymerization of 1 with dichlorodimethylsilane successfully proceeded. Mg/Cu‐mediated copolycondensation of 1 with 1,6‐dibromohexane proceeded to give polymers that have similar compositions to those of random copolymers of ethylene and styrene. © 2006Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 5661–5671, 2006