Enzymatic Synthesis of a Bio-Based Copolyester from Poly(butylene succinate) and Poly((R)-3-hydroxybutyrate)

• Published in: Biomacromolecules
• Main Authors: Debuissy, Thibaud, Pollet, Eric, Avérous, Luc
• Other Authors: Institut de chimie et procédés pour l'énergie, l'environnement et la santé (ICPEES), Université de Strasbourg (UNISTRA)-Matériaux et nanosciences d'Alsace (FMNGE), Institut de Chimie du CNRS (INC)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)
• Format: Article in Journal/Newspaper
• Language: English
• Published: HAL CCSD 2016
• Subjects: [CHIM.POLY]Chemical Sciences/Polymers; Antarc*; Antarctica
• Online Access: https://hal.archives-ouvertes.fr/hal-03114433; https://doi.org/10.1021/acs.biomac.6b01494

© 2016 American Chemical Society. The enzyme-catalyzed synthesis of fully biobased poly(3-hydroxybutyrate-co-butylene succinate) (poly(HB-co-BS)) copolyesters is reported for the first time. Different Candida antarctica lipase B (CALB)-catalyzed copolyesters were produced in solution, via a one-step or a two-step process from 1,4-butanediol, diethyl succinate, and synthesized telechelic hydroxylated poly(3-hydroxybutyrate) oligomers (PHB-diol). The influence of the ester/hydroxyl functionality ratio, catalyst amount, PHB-diol oligomer chain length, hydroxybutyrate (HB) and butylene succinate (BS) contents, and the nature of the solvent were investigated. The two-step process allowed the synthesis of copolyesters of high molar masses (M n up to 18 000 g/mol), compared to the one-step process (M n ∼ 8000 g/mol), without thermal degradation. The highest molar masses were obtained with diphenyl ether as solvent, compared with dibenzyl ether or anisole. During the two-step process, the transesterification rate between the HB and BS segments (i) increased with increasing amount of catalyst and decreasing molar mass of the PHB-diol oligomer, (ii) decreased when anisole was used as the solvent, and (iii) was not influenced by the HB/BS ratio. Tendencies toward block or random macromolecular architectures were observed as a function of the reaction time, the PHB-diol oligomer chain length, and the chosen solvent. Immobilized CALB-catalyzed copolyesters were thermally stable up to 200 °C. The crystalline structure of the poly(HB-co-BS) copolyesters depended on the HB/BS ratio and the average sequence length of the segments. The crystalline content, T m and T c decreased with increasing HB content and the randomness of the copolymer structure.