Enzymatic Polycondensation of 1,6-Hexanediol and Diethyl Adipate: A Statistical Approach Predicting the Key-Parameters in Solution and in Bulk

Nasr, Kifah; Meimoun, Julie; Favrelle-Huret, Audrey; Winter, Julien De; Raquez, Jean-Marie; Zinck, Philippe

doi:10.3390/polym12091907

Cited by 16 publications

(20 citation statements)

References 48 publications

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“…The M n of the polyester (17,900 g•mol −1 ) is comparable to values obtained for equivalent fully aliphatic polyesters synthesized by CALB-catalyzed polymerization. However, lower DP n (58 for 4a) values were obtained with aromatic monomers when compared to aliphatic ones (81-83 [52]) due to the high molar mass of the ferulic-based diester monomer. Moreover, hydrogenation of the ferulic-based monomers led to polymer T g up to 7 • C, which was below ambient temperature.…”

Section: Discussionmentioning

confidence: 93%

“…The Mn of 5a (17,900 g.mol −1 ) is comparable to values obtained for equivalent aliphatic polyesters enzymatically synthesized with 1,6-HDO. However, the aromatic polyesters show lower DPn compared to aliphatic ones because of the high molar mass of the ferulic-based diesters (58 for 4a compared to 81-83 in the literature [52]).…”

Section: Polyesters Based On Ferulic Diolsmentioning

confidence: 93%

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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: Discussionmentioning

confidence: 93%

Section: Polyesters Based On Ferulic Diolsmentioning

confidence: 93%

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

2021

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“…Previously, we introduced a statistical approach that allowed us to predict the M̅ n of poly(hexylene adipate) simply by tuning the values of certain parameters such as vacuum, enzyme loading, and temperature. 59 In our current work and on the basis of the promising properties of furan-based terpolyesters, such as their excellent mechanical properties and biodegradability, we investigate the enzyme-catalyzed synthesis of furan-based semiaromatic terpolyesters by reacting diethyl furan-2,5-dicarboxylate (DEFDC) with variable aliphatic linear dicarboxylic esters and primary diols. A special emphasis was made on the influence of furan loading and the chain length of the diols and diesters and how such factors can influence the reactivity, molecular weight, and thermal properties of the endproduct.…”

Section: ■ Introductionmentioning

confidence: 99%

The Impact of Diethyl Furan-2,5-dicarboxylate as an Aromatic Biobased Monomer toward Lipase-Catalyzed Synthesis of Semiaromatic Copolyesters

Nasr

Favrelle-Huret²,

Mincheva

et al. 2022

ACS Appl. Polym. Mater.

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Furan-2,5-dicarboxylic acid has been introduced in recent years as a green aromatic monomer toward the design of aromatic (co)polyesters with enhanced properties, i.e., polyethylene furanoate (PEF) that can definitely compete with its petroleum-based counterpart, i.e., polyethylene terephthalate (PET). In an attempt to produce biobased semiaromatic copolyesters in an efficient eco-friendly approach, we report herein the polycondensation of diethyl furan-2,5-dicarboxylate (DEFDC) with different aliphatic diols and diesters of variable chain length catalyzed by an immobilized lipase from Candida antarctica using a two-step polymerization reaction carried out in diphenyl ether. The influence of diol and diester chain length, the molar concentration of DEFDC, and the effect of enzyme loading were assessed via nuclear magnetic resonance (NMR), gel permeation chromatography (GPC), differential scanning calorimetry (DSC), and wide-angle X-ray scattering (WAXS). With high quantities of DEFDC, significant differences in terms of M̅ n buildup were noticed. Only longer diols starting from octane-1,8-diol successfully reacted with up to 90% DEFDC as opposed to only 25% DEFDC reacting with short diols such as butane-1,4-diol. While varying the chain length of the diester, it was evident that shorter diols such as hexane-1,6-diol have better reactivity toward longer diesters, while dodecane-1,12-diol was reactive toward all tested diesters. The incorporation of long chain fatty dimer diols such as Pripol 2033 led to polyesters with higher M̅ n and was successfully used to overcome the limitations of poor reactivity observed in the case of short diols in the presence of high furan content. The DSC results showed a pseudoeutectic behavior as a function of increasing the mol % of DEFDC, and a change in the crystalline phase was confirmed via WAXS analysis. Finally, this work showed the successful enzyme-catalyzed synthesis of several DEFDC biobased semiaromatic copolyesters with variable interesting properties that can be further optimized for possible applications in food packaging as well as other possibilities.

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“…The reusability of N435 during transesterification reactions has been studied by Nasr et al [88]. The researchers used 1,6-hexanediol and diethyl adipate in bulk and solvent (diphenyl ether) systems to produce enzymatically poly(hexylene adipate).…”

Section: Type and Characteristics Of The Used Enzyme For Pbs Enzymatic Polymerizationmentioning

confidence: 99%

Enzymatic Polymerization as a Green Approach to Synthesizing Bio-Based Polyesters

Gkountela

Vouyiouka

2022

Macromol

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Given the fossil fuel crisis and the steady consumption of finite resources, the use of green polymers is becoming necessary. However, the term “green” describes materials that present green properties (such as biological origin and/or biodegradability) and are produced via sustainable processes conducted under mild conditions and not requiring the use of chemical catalysts, toxic solvents or reagents. Truly green materials must combine these characteristics; consequently, enzymatically synthesized bio-based and/or biodegradable polymers can be characterized as truly green. The present review focuses on the most promising, commercially available aliphatic and alipharomatic polyesters that can be synthesized enzymatically. In particular, the recent developments in the enzymatic polymerization of PLA and PBS and alipharomatic furan-based polyesters (e.g., PBF) are herein analyzed. Based on this analysis, it can be concluded that important steps have been taken toward synthesizing sustainably green polymers. Still, it is necessary to evaluate the applied methods regarding their capability to be used on an industrial scale.

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Enzymatic Polycondensation of 1,6-Hexanediol and Diethyl Adipate: A Statistical Approach Predicting the Key-Parameters in Solution and in Bulk

Cited by 16 publications

References 48 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

The Impact of Diethyl Furan-2,5-dicarboxylate as an Aromatic Biobased Monomer toward Lipase-Catalyzed Synthesis of Semiaromatic Copolyesters

Enzymatic Polymerization as a Green Approach to Synthesizing Bio-Based Polyesters

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