Biomass-derived polymers are emerging as critically needed alternatives to their petrochemical counterparts. Terpenes, which are among the most natural products, represent particularly fertile space for monomer development (given their inherent structural complexity). Here, we present the living vinyl-addition polymerization of β-pinadiene (the cumulated congener of β-pinene) at room temperature. Employing [(π-allyl)NiOCOCF3]2 as a catalyst afforded the desired polymers with good control over molecular weight and dispersity. Interestingly, the bicyclic pinane core was retained in the isolated materials (which starkly contrasts prototypical pinene polymerizations). Additionally, the bicyclic pinane architecture could be incorporated into copolymers with varying degrees of bicyclic content. High levels of cyclic monomer incorporation were achieved, and a linear relationship was observed between Tg and cyclic monomer content. Importantly, these trends could be used to predict Tg in polymers with known cyclic monomer content and mechanical properties could be tailored when the pinane architecture was incorporated into block-copolymer systems.

Controlled polymerization of β-pinadiene: Accessing unusual architectures and propeties with terpene-derived polymers

ACS Spring 2022

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