AbstractRadical polymerization of several alkyl crotonates (RCr) was carried out in bulk or in benzene in the presence of radical initiators. Homopolymerization of RCr bearing bulky ester alkyl groups, e.g.tert‐butyl (tBCr), 1‐adamantyl (AdCr), and 3,5‐dimethyl‐1‐adamantyl crotonate (DMAdCr) proceeded to give a polymer with molecular weight of several thousands despite of the steric hindrance and chain transfer by the presence of the β‐methyl group, while the methyl and ethyl esters gave no polymer. The kinetics of the polymerization was examined in detail and absolute rate constants were evaluated by means of electron spin resonance spectroscopy. The propagation rate constants of RCr were 0.41–1.0 L/mol s, being much smaller than those of the corresponding methacrylates (530–570 L/mol s). The termination rate constants were also determined from the analyses of steady state and non‐steady state polymerizations. Radical copolymerizations of AdCr (M2) with several vinyl monomers (M1) were carried out in bulk at 60°C and the rate constants for cross propagations were calculated to examine reactivities of the monomer and its polymer radical. The structure and thermal properties of the resulting poly (AdCr) were also investigated. Onset temperature of decomposition and glass transition temperature of poly(AdCr) were revealed to be much high as 302 and 234°C, respectively. © 1994