Synthesis of Polyesters I: Hydrolase as Catalyst for Polycondensation (Condensation Polymerization)

Kobayashi, Shiro; Uyama, Hiroshi

doi:10.1007/978-981-13-3813-7_5

Cited by 7 publications

(6 citation statements)

References 195 publications

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“…The first step has been to modify the ferulic acid to optimize its reactivity toward CALB. Indeed, CALB catalyzed polymerization results in faster kinetics and higher molar masses by transesterification with methyl or ethyl esters than by polycondensation [41][42][43]. The small alcohol adduct in transesterification can easily be eliminated, compared to water, shifting the equilibrium of the reaction.…”

Section: Polyesters Based On Ferulic Diestersmentioning

confidence: 99%

Ferulic Acid as Building Block for the Lipase-Catalyzed Synthesis of Biobased Aromatic Polyesters

2021

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Enzymatic synthesis of aromatic biobased polyesters is a recent and rapidly expanding research field. However, the direct lipase-catalyzed synthesis of polyesters from ferulic acid has not yet been reported. In this work, various ferulic-based monomers were considered for their capability to undergo CALB-catalyzed polymerization. After conversion into diesters of different lengths, the CALB-catalyzed polymerization of these monomers with 1,4-butanediol resulted in short oligomers with a DPn up to 5. Hydrogenation of the double bond resulted in monomers allowing obtaining polyesters of higher molar masses with DPn up to 58 and Mw up to 33,100 g·mol−1. These polyesters presented good thermal resistance up to 350 °C and Tg up to 7 °C. Reduction of the ferulic-based diesters into diols allowed preserving the double bond and synthesizing polyesters with a DPn up to 19 and Mw up to 15,500 g·mol−1 and higher Tg (up to 21 °C). Thus, this study has shown that the monomer hydrogenation strategy proved to be the most promising route to achieve ferulic-based polyester chains of high DPn. This study also demonstrates for the first time that ferulic-based diols allow the synthesis of high Tg polyesters. Therefore, this is an important first step toward the synthesis of competitive biobased aromatic polyesters by enzymatic catalysis.

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Section: Polyesters Based On Ferulic Diestersmentioning

confidence: 99%

Ferulic Acid as Building Block for the Lipase-Catalyzed Synthesis of Biobased Aromatic Polyesters

2021

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“…Kobayashi et al [ 55 ] had a study to polymerize carboxylic anhydride monomer and ethylene glycol via enzyme-catalyzed copolymerization, and a high yield of polymer was obtained. In later studies, carboxylic anhydride monomers were expanded to include anhydrides of various diacids [ 56 , 57 ]. Jiang et al [ 58 ] successfully used Novozym 435 to catalyze the enzyme-catalyzed copolymerization of ω-pentadecalactone (PDL), diethyl succinate, and 1,4-butanediol to synthesize a new ternary polyester.…”

Section: Enzyme-catalyzed Synthesis Of Polyestersmentioning

confidence: 99%

Recent Advances in the Enzymatic Synthesis of Polyester

Wang

Liu²,

Lee

et al. 2022

Polymers

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Polyester is a kind of polymer composed of ester bond-linked polybasic acids and polyol. This type of polymer has a wide range of applications in various industries, such as automotive, furniture, coatings, packaging, and biomedical. The traditional process of synthesizing polyester mainly uses metal catalyst polymerization under high-temperature. This condition may have problems with metal residue and undesired side reactions. As an alternative, enzyme-catalyzed polymerization is evolving rapidly due to the metal-free residue, satisfactory biocompatibility, and mild reaction conditions. This article presented the reaction modes of enzyme-catalyzed ring-opening polymerization and enzyme-catalyzed polycondensation and their combinations, respectively. In addition, the article also summarized how lipase-catalyzed the polymerization of polyester, which includes (i) the distinctive features of lipase, (ⅱ) the lipase-catalyzed polymerization and its mechanism, and (ⅲ) the lipase stability under organic solvent and high-temperature conditions. In addition, this article also focused on the advantages and disadvantages of enzyme-catalyzed polyester synthesis under different solvent systems, including organic solvent systems, solvent-free systems, and green solvent systems. The challenges of enzyme optimization and process equipment innovation for further industrialization of enzyme-catalyzed polyester synthesis were also discussed in this article.

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“…Both direct and reverse reactions can be catalyzed by lipase. Some authors consider that the only way to obtain the polymeric product effectively is by removing (or at least reducing the concentration of) the by‐product (water or an alcohol) from the reaction mixture 23,24 . Masutani and Kimura alleged that water concentration in the reaction medium is directly related to M n through the equilibrium constant of said polymerization.…”

Section: Synthetic Routes Towards Poly‐esterificationsmentioning

confidence: 99%

“…Some authors consider that the only way to obtain the polymeric product effectively is by removing (or at least reducing the concentration of) the by-product (water or an alcohol) from the reaction mixture. 23,24 Masutani and Kimura alleged that water concentration in the reaction medium is directly related to M n through the equilibrium constant of said polymerization. A typical plot for M n versus water concentration reveals that PLA (M n > 50 kDa) may be produced when the condensed water is efficiently removed to a level of 1 ppm from the polymerization system.…”

Section: Knowledge About Lipase-catalyzed Esterification Relevant For...mentioning

confidence: 99%

Evaluation of biocatalytic pathways in the synthesis of polyesters: Towards a greener production of surgical sutures

Nicolás

Lassalle

Ferreira

2022

Polymers for Advanced Techs

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This review presents an updated and alternative perspective on enzymatic synthesis to obtain polyesters, with a focus on the precursor materials for absorbable sutures: poly‐lactic, poly‐glycolic, and poly‐lactic‐co‐glycolic acids. Currently, the profitable path towards the industrial synthesis of polyesters is ring‐opening polymerization (ROP) of lactones, which is an experimentally complex process and implies a hazardous environmental impact due to the need for energy consumption, use of large volumes of toxic organic solvents and of non‐biocompatible metal‐based catalysts. On the contrary, enzymatically driven reactions may be performed under mild conditions in simple reactors. Mechanistic and experimental issues of the two major biocatalyzed strategies ‐direct condensation and ROP‐ were analyzed from a green chemistry perspective. These enzyme‐catalyzed poly‐esterifications often return low yield and/or low final molecular weight (Mw). Considering all the analyzed published data available, possible strategies to overcome these limitations were postulated: implementation of aqueous biphasic reaction systems, use of ultrasound agitation and sequential addition of reactants or co‐solvents. To promote Mw increment, post‐reaction treatments can be carried out such as thermally induced short‐chain polymerization under vacuum and incorporation of glycols as chain extenders.

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Synthesis of Polyesters I: Hydrolase as Catalyst for Polycondensation (Condensation Polymerization)

Cited by 7 publications

References 195 publications

Ferulic Acid as Building Block for the Lipase-Catalyzed Synthesis of Biobased Aromatic Polyesters

Ferulic Acid as Building Block for the Lipase-Catalyzed Synthesis of Biobased Aromatic Polyesters

Recent Advances in the Enzymatic Synthesis of Polyester

Evaluation of biocatalytic pathways in the synthesis of polyesters: Towards a greener production of surgical sutures

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