RADICAL POLYMERIZATION OF 4-TERT-BUTYLCYCLOHEXYL METHACRYLATE - POLYMERIZATION KINETICS AND POLYMER PROPERTIES

Radical polymerizations of trans-4-tert-butylcyclohexyl methacrylate (trans-BCHMA) or mixtures of the trans and cis isomers were carried out with 2,2'-azobis(isobutyronitrile) as an initiator in benzene at 60-degrees-C. The polymerization kinetics were investigated in detail. From electron spin resonance studies, propagation and termination rate constants (k(p) and k(t)) of trans-BCHMA were evaluated to be 550 and 1.9 x 10(6) L/(mol.s), respectively. This k(p) was similar to the values reported for methyl methacrylate and k(t) was much smaller, resulting in the high polymerization reactivity of trans-BCHMA. From the results of the copolymerization of trans- and cis-BCHMA, it was clarified that the trans isomer had a slightly higher reactivity than the cis isomer. The solubility, microstructure, and thermal decomposition behavior of the resulting polymers were examined. It was also revealed that the glass transition temperature of poly(BCHMA) varied from 178 to ca. 130-degrees-C depending on the geometric structure, i.e., the trans contents, in the polymer side chain.