Controlled Radical Copolymerization of Naturally-Occurring Terpenes with Acrylic Monomers in Fluorinated Alcohol

Naturally-occurring terpenes, such as d-limonene and beta -pinene, were copolymerized with electron-withdrawing polar vinyl monomers including methyl acrylate (MA) or methyl methacrylate (MMA). Fluorinated alcohols as the solvents enhanced the copolymerizability to produce copolymers with moderate incorporation of the terpenes up to 34 mol% for the copolymerization with MA. The thermal properties of the obtained copolymer improved as the incorporation of terpenes increased, in which the glass transition temperature of the MA-based copolymers reached around 80 degrees C. Furthermore, the controlled/living radical copolymerizations of the terpenes with MA were investigated with a trithiocarbonate as the RAFT agent.