Radical polymerization of dicyclohexyl fumarate and its derivatives as studied by electron spin resonance spectroscopy

The radical polymerization of dicyclohexyl fumarate (DCHF) and its derivatives was carried out with dimethyl 2,2'-azobisisobutyrate in benzene at 60 degrees C. The propagation and termination rate constants (k(p) and k(t)) were determined by electron spin resonance spectroscopy. The k(p) and k(t) values were 0.48-0.91 l/mol sec and 14-23,000 l/mol sec, depending on the DCHF concentration (0.1-1.5 mol/l). It has been revealed that the alkyl substituents on the cyclohexyl ring have important effects on the polymerization reactivity of the DCHF derivatives. The 2-substituted cyclohexyl derivatives showed a lower polymerization reactivity because of the decrease in k(p). The propagation manner of the 2-substituted derivatives is discussed, based on the results of the investigation of the tacticity of the polymer in comparison with those of non- or 4-substituted derivatives. Copyright (C) 1996 Elsevier Science Ltd