Biobased cycloolefin polymers: Carvone-derived cyclic conjugated diene with reactive exo-methylene group for regioselective and stereospecific living cationic polymerization

Carvone, a naturally abundant chiral cyclic α,β-unsaturated carbonyl compound, was chemically transformed into cyclic exo-methylene conjugated dienes. The exo-methylene group had high reactivity in cationic polymerization and was efficiently polymerized in a controlled manner via regioselective 1,4-conjugated additions using initiating systems effective for living cationic polymerization of vinyl ethers. The obtained polymers with 1,3-cyclohexenyl units and tetra-substituted olefins in the main chain showed high glass transition temperatures over 110 °C. The chiral monomer underwent stereospecific polymerization to result in polymers with low solubility and weak packing of the rigid main chain in the lamellar layers. The racemic mixture resulted in soluble amorphous polymers, which were subsequently hydrogenated into cycloolefin polymers with enhanced thermal properties.