Ring-Opening Metathesis Polymerization of δ-Pinene: Well-Defined Polyolefins from Pine Sap

Well-controlled ring-opening metathesis polymerization (ROMP) of δ-pinene is reported. The monomer is produced through a facile, metal-free, three-step synthesis from highly abundant and sustainable α-pinene. Using Grubbs third-generation catalyst, δ-pinene undergoes ROMP to high conversion (>95%) with molar mass up to 70 kg mol^-1 and narrow dispersity (<1.2). A highly regioregular propagation mechanism was concluded by NMR spectroscopic analysis that revealed a head-to-tail (HT, >95%) microstructure and high trans content (>98%). Successful ROMP is corroborated with density functional theory calculations on δ-pinene's ring strain energy (∼35 kJ mol^-1). Poly(δ-pinene) has a high glass transition temperature (∼104 °C) and a unique chiral microstructure bearing gem-dimethylcyclobutane rings. Controlled ROMP also allowed the synthesis of block copolymers containing segments of poly(δ-pinene) and polynorbornene which are discussed. Finally, bulk polymerization of δ-pinene is possible, indicating a greener approach to these materials, albeit with some loss of control.