Sustainable ABA Triblock Methacrylate Copolymers Incorporating Both High and Low Tg Terpene-Derived Monomers

We report the synthesis of novel terpene-based monomers: nopinyl acrylate and methacrylate, from naturally abundant beta-pinene. A very high Tg value was observed for poly(nopinyl methacrylate) when synthesised by free radical polymerisation, and well-defined polymers have been produced via RAFT polymerisation. This exciting new high Tg material shows promise as a hard block in thermoplastic elastomers. ABA triblock copolymers have been synthesised which also incorporate a low Tg renewable soft block, poly(tetrahydrogeraniol methacrylate), using a divergent, difunctional RAFT polymerisation method. Initial phase separation behaviour and adhesive properties have been investigated to highlight the potential of these copolymer materials as renewably sourced thermoplastic elastomers.