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Enzymatic Synthesis of a Bio-Based Copolyester from Poly(butylene succinate) and Poly((R)-3-hydroxybutyrate): Study of Reaction Parameters on the Transesterification Rate.
Biomacromolecules. 2016 12 12; 17(12):4054-4063.B

Abstract

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 (Mn up to 18 000 g/mol), compared to the one-step process (Mn ∼ 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, Tm and Tc decreased with increasing HB content and the randomness of the copolymer structure.

Authors+Show Affiliations

BioTeam/ICPEES-ECPM, UMR CNRS 7515, Université de Strasbourg , 25 rue Becquerel, 67087 Strasbourg Cedex 2, France.BioTeam/ICPEES-ECPM, UMR CNRS 7515, Université de Strasbourg , 25 rue Becquerel, 67087 Strasbourg Cedex 2, France.BioTeam/ICPEES-ECPM, UMR CNRS 7515, Université de Strasbourg , 25 rue Becquerel, 67087 Strasbourg Cedex 2, France.

Pub Type(s)

Journal Article
Research Support, Non-U.S. Gov't

Language

eng

PubMed ID

27936726

Citation

Debuissy, Thibaud, et al. "Enzymatic Synthesis of a Bio-Based Copolyester From Poly(butylene Succinate) and Poly((R)-3-hydroxybutyrate): Study of Reaction Parameters On the Transesterification Rate." Biomacromolecules, vol. 17, no. 12, 2016, pp. 4054-4063.
Debuissy T, Pollet E, Avérous L. Enzymatic Synthesis of a Bio-Based Copolyester from Poly(butylene succinate) and Poly((R)-3-hydroxybutyrate): Study of Reaction Parameters on the Transesterification Rate. Biomacromolecules. 2016;17(12):4054-4063.
Debuissy, T., Pollet, E., & Avérous, L. (2016). Enzymatic Synthesis of a Bio-Based Copolyester from Poly(butylene succinate) and Poly((R)-3-hydroxybutyrate): Study of Reaction Parameters on the Transesterification Rate. Biomacromolecules, 17(12), 4054-4063.
Debuissy T, Pollet E, Avérous L. Enzymatic Synthesis of a Bio-Based Copolyester From Poly(butylene Succinate) and Poly((R)-3-hydroxybutyrate): Study of Reaction Parameters On the Transesterification Rate. Biomacromolecules. 2016 12 12;17(12):4054-4063. PubMed PMID: 27936726.
* Article titles in AMA citation format should be in sentence-case
TY - JOUR T1 - Enzymatic Synthesis of a Bio-Based Copolyester from Poly(butylene succinate) and Poly((R)-3-hydroxybutyrate): Study of Reaction Parameters on the Transesterification Rate. AU - Debuissy,Thibaud, AU - Pollet,Eric, AU - Avérous,Luc, Y1 - 2016/11/29/ PY - 2016/12/13/entrez PY - 2016/12/13/pubmed PY - 2017/9/14/medline SP - 4054 EP - 4063 JF - Biomacromolecules JO - Biomacromolecules VL - 17 IS - 12 N2 - 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 (Mn up to 18 000 g/mol), compared to the one-step process (Mn ∼ 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, Tm and Tc decreased with increasing HB content and the randomness of the copolymer structure. SN - 1526-4602 UR - https://www.unboundmedicine.com/medline/citation/27936726/Enzymatic_Synthesis_of_a_Bio_Based_Copolyester_from_Poly_butylene_succinate__and_Poly__R__3_hydroxybutyrate_:_Study_of_Reaction_Parameters_on_the_Transesterification_Rate_ L2 - https://dx.doi.org/10.1021/acs.biomac.6b01494 DB - PRIME DP - Unbound Medicine ER -