Abstract
While in recent years a large number of living/controlled polymerization systems for petrochemical-derived vinyl monomers have been described, bio-based polymer materials from renewable resources become attractive from a viewpoint of environmentally benign and sustainable chemistry. In this study, we examined controlled/living (co)polymerization of a series of naturally-occurring alicyclic terpenes, such as β-pinene and d-limonene, as alternatives for those from traditional petrochemical products. For example, the living cationic polymerization of β-pinene was achieved using the HCl/EtAlCl2/Lewis base system to produce relatively high molecular weight polymers with Mw > 105, which was subsequently hydrogenated into a bio-based cycloolefin polymer. Also, the radical copolymerization of β-pinene and d-limonene with maleimide derivatives proceeded in unprecedented 1:2 alternating fashion when polymerized in fluorinated alcohol solvents, of which the combination with RAFT polymerization resulted in end-to-end sequence-regular copolymers.
