Semiaromatic Polyesters Derived from Renewable Terpene Oxides with High Glass Transitions

5 years ago

Semiaromatic Polyesters Derived from Renewable Terpene Oxides with High Glass Transitions

Leticia Peña Carrodeguas, Carmen Martín, Arjan W. Kleij

The formation of bio-derived materials is gaining momentum in academic and industrial laboratories, though the use of terpene oxides as renewable monomers for the preparation of bio-based polymers yet remains limited. In order to advance the impact of such monomers, we have investigated the use of terpene-derived epoxides (limonene oxide, carene oxide, limonene dioxide, and menthene oxide) for the ring-opening copolymerization (ROCOP) in the presence of various aromatic anhydrides. These copolymerization reactions were mostly performed under mild reaction conditions (65 °C; low loading of catalyst: 0.50 mol %) using a binary catalyst composed of a Fe(III)-based aminotriphenolate complex and PPNCl (bis(triphenylphosphine)iminium chloride) providing partially bio-based semiaromatic polyesters with molecular weights of up to 25 kg/mol (Đ = 1.54) and glass transitions spanning a wide range from 59 to 243 °C. The copolymerization reactions proceed with excellent selectivity toward fully alternating polyesters (≥98% ester bonds) with modular thermal properties that depend on the nature of the terpene oxide used and are potentially useful toward the development of new coating and thermoset materials.

Publisher URL: http://dx.doi.org/10.1021/acs.macromol.7b00862

DOI: 10.1021/acs.macromol.7b00862