Cyclopolymerizations of unsymmetrical non-conjugated dienes.

Abstract

Copolymers of styrene with acrylonitrile or methyl acrylate are of commercial importance. Most often strictly regular alternation of the functional groups along the polymer backbone cannot be produced. Since regular alternation of the functional groups could yield polymers which possess more desirable properties, we have developed a novel strategy for strict control of functional group alternation by free radical cyclopolymerizations of unsymmetrical non-conjugated dienes. Our preliminary results have yielded polymers with molecular weights up to 8100 and which appear to possess the anticipated cyclic structure. The presence of the desired pendant functional groups is indicated by IR spectroscopy. ¹H NMR spectra of the polymers show no vinyl protons from pendant alkenes. The polymers are soluble in common organic solvents suggesting that the monomers were completely cyclopolymerized and that cross-linking was minimal. The comparison of thermal properties of the cyclopolymers with those of the corresponding copolymers shows that the cyclopolymers are as stable as the copolymers but more highly ordered than the copolymers. This dissertation will describe the polymers design strategy, the syntheses of monomers of several carbon skeletal types, the results of polymerizations, and structural studies of these new polymers.