Preparation of Unsaturated Linear Aliphatic Polyesters Using Condensation Polymerization

A versatile method for preparing linear, unsaturated polyesters through condensation polymerization of trans -β-hydromuconic acid (HMA) with a variety of diols using Sn(Oct) 2 and Novozyme-435 as catalysts was explored. Poly(1,8-octanediol hydromuconoate) was the highest molecular weight homopolymer prepared with a 〈 M n 〉 of 10.5 × 10 3 g/mol and polydispersity of 2.0. These materials showed unique melting behavior that was dependent on the number of carbons in the diol. Melting points ranged from 40 to 70 °C. Copolymers where the amount of HMA was diluted by adipic acid were prepared and had a 〈 M n 〉 as high as 13.0 × 10 3 g/mol and polydispersities below 2.0. The double bonds of these materials were chemically modified through epoxidation in yields greater than 93% and with no degradation of the polymer backbone. Materials with hydroxyl end groups were prepared through stoichiometric mismatch. Unsaturated poly(ester ether)s that are amorphous liquids with T g below −40 °C were prepared using diethylene glycol as the diol.