Semiaromatic Polyesters Derived from Renewable Terpene Oxides with High Glass Transitions

Abstract

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 (65ºC, low loading of catalyst: 0.50 mol%) using a binary catalyst comprising of a Fe(III) based aminotriphenolate complex and PPNCl (bis(triphenylphosphine)iminium chloride) providing partially bio-based semi-aromatic polyesters with molecular weights of up to 25 Kg/mol (Ð = 1.54) and glass transitions spanning a wide range from 59 to 243 ºC. The copolymerization reactions proceed with excellent selectivity towards fully alternating polyesters ( 98% ester bonds) with modular thermal properties that depend on the nature of the terpene oxide used, and are potentially useful towards the development of new coating and thermoset materials.

Renewable Aliphatic Polyesters from Fatty Dienes by Acyclic Diene Metathesis Polycondensation

“…Glass transitions below rt are typical for aliphatic polymers that contain flexible backbones (Carrodeguas et al, ; Li et al, ). As is the case with other thermal properties of polymers, incorporation of rigidity via introduction of branching, cross‐linking and/or aromaticity would likely increase T g significantly (Carrodeguas et al, ; Odian, ). T g defines one end of the temperature range over which a rubbery polymer may be used, with T m signifying the upper limit.…”

Renewable Poly(Thioether‐Ester)s from Fatty Acid Derivatives via Thiol‐Ene Photopolymerization

“…Glass transitions below rt. are typical for polymers that contain flexible backbones and thioether linkages (Carrodeguas et al, ; Li et al, ). T g defines one endpoint of the temperature range over which a polymer may be used.…”

Terpene- and terpenoid-based polymeric resins for stereolithography 3D printing

“…[19][20][21][22] This class of monomer is widely available, and may be found in essential oils, tree sap and materials, citrus fruit, and even as by-products from other manufacturing processes, such as the paper industry's Kraft process, or simply through the processing of citrus fruits and other renewable resources. [23][24][25][26] The inherent double bonds present in mono-, di-, tri-, and other polyterpenes make them excellent candidates for the creation of sustainably-sourced photo-crosslinkable resins, yet to date only a few studies have investigated their application beyond utilizing appended (meth)acrylate or epoxide functionalities for (controlled) radical polymerisation 27,[28][29][30] modified polysaccharides, 31 polycarbonates, 32 and even polysilanes, 33 with processing still being limited in such studies. Herein, we report our study of the application of five terpenes: limonene, terpinene, geraniol, nerol and linalool ( Fig.…”