Synthesis, solution properties, and glass transition temperatures of polymethacrylates with alicyclylmethyl side groups

The synthesis, solution properties, and glass transition temperatures of polymethacrylates having alicyclic rings connected to the ester linkage via methylene spacers are reported. The rings cover the range in size from cyclobutyl to cycloundecyl. An attempt was also made to prepare and study poly(cyclopropylmethyl methacrylate), but free radical solution polymerization led to gels. Solution and thermal properties of these polymers are compared to those previously reported for polymethacrylates with both alicyclyl and n‐alkyl substituents. The introduction of the methylene spacer between the ester linkage and the ring results, for small rings, in diminished characteristic ratios relative to those obtained for the alicyclyl materials. Chain flexibilities of poly(alicyclylmethyl methacrylates) are instead found to be identical to those of poly(n‐alkyl methacrylates) having the same number of carbons. The glass transition temperatures of the poly(alicyclylmethyl methacrylates) are generally intermediate to those observed for alicyclyl and n‐alkyl methacrylates, but are closer to the former.