Anionic graft polymerization of lithiated poly(2,6-dimethyl-1,4-phenylene ether)

Lithiated poly(2,6-dimethyl-1,4-phenylene ether) has been used as an initiator for the graft polymerization of isoprene, methyl methacrylate, hexamethylcyclotrisiloxane, and phenyl isocyanate with the use of toluene and tetrahydrofuran as solvents. The products were examined by gel-permeation chromatography for evidence of homopolymerization and graft polymerization. The composition of the graft copolymers was determined by NMR, and for isoprene and hexamethylcyclotrisiloxane, termination by trialkylchlorosilanes enabled chain lengths to be determined by NMR. The use of toluene gave rise to some homopolymerization, but with tetrahydrofuran, only hexamethylcyclotrisiloxane gave homopolymer. In all cases, graft copolymers were formed. With isoprene and methyl methacrylate, soluble graft copolymers were formed in good yield. In the former case approximately 60% 3,4 and 40% 1,4 addition was found. In the latter case 1,1-diphenylethylene was used to reduce crosslinking, in its absence, methyl methacrylate gave only crosslinked gels in tetrahydrofuran. Hexamethylcyclotrisiloxane added only one molecule per lithium on the polymer, the remainder giving homopolymer. Phenyl isocyanate gave some soluble graft copolymer in toluene, but only crosslinked products were obtained when tetrahydrofuran was used as reaction solvent.