Characterizations of radicals formed in radical polymerizations and transfer reactions by electron spin resonance spectroscopy

Abstract

Electron spin resonance (ESR, aka electron paramagnetic resonance, EPR) investigations have been conducted on radicals formed during radical polymerizations and provide a detailed characterization of the active radical species. Active propagating radicals can be observed during actual radical polymerizations by ESR/EPR. The chain lengths of the observed radicals were estimated by a combination of atom transfer radical polymerization (ATRP) and ESR/EPR. The structures of the chain end radicals were determined by analysis of the ESR/EPR spectra. An increase in the dihedral angles between terminal p-orbital of radical and Cβ-H bonds was observed with increasing chain lengths of methacrylate polymers. Radical transfer reactions were observed during radical polymerization of acrylates. A combination of ATRP and ESR/EPR clarified a 1,5-hydrogen shift mechanism of the radical transfer reactions using model adamantyl acrylate radicals. Penultimate unit effects were also observed. Time-resolved ESR/EPR (TR ESR) spectroscopy clarified the initiation processes of an alternating copolymerization of styrene with maleic anhydride and the copolymerization of styrene with 1,3-butadiene. Several unsolved problems in conventional radical polymerization processes have been clarified using combinations of ATRP with ESR/EPR and TR ESR. Characterization of the radicals in radical polymerizations using various ESR techniques would definitely provide interesting and useful information on conventional radical polymerizations.