New telechelic polymers and sequential copolymers by polyfunctional initiator-transfer agents (inifers)

Summary

α, ω-Di (nitrile)polyisobutylenes (nitrile-telechelic polyisobutylenes) have been synthesized by reacting α, ω-di (hydroxy) polyisobutylenes (hydroxyl-telechelic polyisobutylenes) with acrylonitrile, p-cyanobenzoyl chloride, p-cyanobenzoic acid and p-cyanobenzyl chloride by the use of a variety of catalysts, e.g. N-benzyltrimethylannnonium hydroxide, 4-N,N′-dimethylaminopyridine, dicyclohexylcarbodiimide, tetrabutylammonium hydrogen sulfate and tricaprylymethylammonium chloride. IR and ¹H-NMR analyses of models and polymer products suggest quantitative functionalization, except with p-cyanobenzyl chloride where only ∼ 80% functionalization was achieved. Methanesulfonation of the polymer-diol with methanesulfonyl chloride followed by reaction with NaCN in the presence of tricaprylymethylammonium chloride phase transfer catalyst gave quantitatively α, ω-di (nitrile) polyisobutylene.