Production of biodegradable polyesters via enzymatic polymerization and solid state finishing

The synthesis of aliphatic polyesters (PEs) derived from diols (1,4-butanediol and 1,8-octanediol) and diacids or their derivatives (diethyl succinate, sebacic acid, 1,12-dodecanedioic acid, and 1,14-tetradecanedioic acid) was achieved in order to produce poly(butylene succinate) (PE 4.4), poly(octylene sebacate) (PE 8.10), poly(octylene dodecanate) (PE 8.12), and poly(octylene tetradecanate) (PE 8.14). The herein suggested procedure involved two stages, both sustainable and in accordance with the principles of “green” polymerization. The first comprised an enzymatic prepolymerization under vacuum, in the presence of diphenylether as solvent using Candida antarctica lipase B as biocatalyst, whereas a low-temperature postpolymerization step [solid state polymerization (SSP)] followed in order to upgrade the PEs quality. In the enzymatically synthesized prepolymers, the range of number–average molecular weight attained was from 3700 to 8000 g/mol with yields reaching even 97%. Subsequently, SSP of PE 4.4 and 8.12 took place under vacuum or flowing nitrogen and lasted 10–48 h, at temperatures close to the prepolymer melting point (Tm − TSSP varied between 4°C and 14°C). The solid state finishing led to increase in the molecular weight depending on the prepolymer type, and it also contributed to improvement of the physical characteristics and the thermal properties of the enzymatically synthesized PEs. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014, 131, 40820.