Radical copolymerization of alkyl cyclobutenecarboxylates fused with cycloaliphatic framework with alkyl (meth)acrylates

ABSTRACT Radical copolymerization behavior of alkyl cyclobutenecarboxylate‐derivatives 4‐6 and related norbornene‐derived compounds 7–9 is described. A variety of alkyl cyclobutenecarboxylates fused with cycloaliphatic framework ( 4–6 ) were prepared by [2 + 2] cycloaddition of five, six, and eight‐membered cycloolefins with alkyl propiolates [alkyl = Me, 2‐hydroxyethyl, and 3‐γ‐butyrolactonyl (γ‐BL)]. The fused cyclobutenecarboxylates 4–6 were radically copolymerized with n ‐butyl acrylate ( n BA) to afford random copolymers, and terpolymerized with alkyl methacrylates with bulky ester groups [alkyl = γ‐BL and 3‐(3‐methyladamantyl)]. The cyclobutane‐containing bicyclic framework incorporated in the resulting polymer backbone contributes to raising T g of resulting copolymers. Similar results were obtained when a mixture of related norbornene‐derived compounds were used as monomers with an apparently enhanced T g ‐raising effect in the copolymerization with n BA. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 2716–2724