Enzymatic approach for the synthesis of biobased aromatic–aliphatic oligo-/polyesters

Fodor, Csaba; Golkaram, Milad; Woortman, Albert J. J.; Dijken, Jur van; Loos, Katja

doi:10.1039/c7py01559c

Cited by 27 publications

(32 citation statements)

References 43 publications

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“…Based on previous reports on enzymatic polymerizations conducted using CaLB as biocatalyst, two different approaches were used, and herein, they will be referred to as (A) bulk reaction without solvent, until now only reported for aliphatic monomers 28,29 and (B) reactions in organic media, a traditional reaction system for the enzymatic polycondensation of aromatic moieties 30,31 .…”

Section: Resultsmentioning

confidence: 99%

Enzymatic synthesis of lignin derivable pyridine based polyesters for the substitution of petroleum derived plastics

et al. 2019

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Following concerns over increasing global plastic pollution, interest in the production and characterization of bio-based and biodegradable alternatives is rising. In the present work, the synthesis of a series of fully bio-based alternatives based on 2,4-, 2,5-, and 2,6-pyridinedicarboxylic acid-derived polymers produced via enzymatic catalysis are reported. A similar series of aromatic-aliphatic polyesters based on diethyl-2,5-furandicarboxylate and of the petroleum-based diethyl terephthalate and diethyl isophthalate were also synthesized. Here we show that the enzymatic synthesis starting from 2,4-diethyl pyridinedicarboxylate leads to the best polymers in terms of molecular weights (M n = 14.3 and M w of 32.1 kDa when combined with 1,8-octanediol) when polymerized in diphenyl ether. Polymerization in solventless conditions were also successful leading to the synthesis of bio-based oligoesters that can be further functionalized. DSC analysis show a clear similarity in the thermal behavior between 2,4-diethyl pyridinedicarboxylate and diethyl isophthalate (amorphous polymers) and between 2,5-diethyl pyridinedicarboxylate and diethyl terephthalate (crystalline polymers).

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Section: Resultsmentioning

confidence: 99%

Enzymatic synthesis of lignin derivable pyridine based polyesters for the substitution of petroleum derived plastics

et al. 2019

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“…[41] Based on a recently developed protocol, we selected an immobilized preparation of Candida antarctica lipase B (iCaLB) as catalyst and diphenyl ether (DPE) as the solvent. [42][43][44] Results from the enzyme-catalysed synthesis were encouraging, with molecular masses ranging from 1.3-3.6 kDa for M n and 3.3-26 kDa for M w depending on the used diol. Part of the very high M w may be attributed to branching that may have started to form before the GPC analysis.…”

Section: Synthesis Of Polyesters Of Furandiyl Diacrylic Esters (Pfae)mentioning

confidence: 99%

Work‐hardening Photopolymer from Renewable Photoactive 3,3’‐(2,5‐Furandiyl)bisacrylic Acid

et al. 2020

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The design of a photopolymer around a renewable furan‐derived chromophore is presented herein. An optimised semi‐continuous oxidation method using MnO2 affords 2,5‐diformylfuran from 5‐(hydroxymethyl)furfural in gram quantities, allowing the subsequent synthesis of 3,3’‐(2,5‐furandiyl)bisacrylic acid in good yield and excellent stereoselectivity. The photoactivity of the diester of this monomer is confirmed by reaction under UV irradiation, and the proposed [2+2] cycloaddition mechanism supported further by TD‐DFT calculations. Oligoesters of the photoreactive furan diacid with various aliphatic diols are prepared via chemo‐ and enzyme‐catalysed polycondensation. The latter enzyme‐catalysed (Candida antarctica lipase B) method results in the highest Mn (3.6 kDa), suggesting milder conditions employed with this protocol minimised unwanted side reactions, including untimely [2+2] cycloadditions, whilst preserving the monomer's photoactivity and stereoisomerism. The photoreactive polyester is solvent cast into a film where subsequent initiator‐free UV curing leads to an impressive increase in the material stiffness, with work‐hardening characteristics observed during tensile strength testing.

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“…Their synthesis can be done either by the ring-opening polymerization of cyclic esters, or by polycondensation reactions. The conventional method for the polycondensation of aliphatic monomers uses metal-based catalysts and requires elevated temperatures [ 5 , 6 , 7 ]. However, reactions using metal-based catalysts can suffer from certain issues such as color changes, degradation due to high temperature, lack of selectivity and difficulty in the removal of residual metals from the synthesized polymer [ 8 , 9 ].…”

Section: Introductionmentioning

confidence: 99%

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

Nasr

Meimoun²,

Favrelle-Huret³

et al. 2020

Polymers

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Among the various catalysts that can be used for polycondensation reactions, enzymes have been gaining interest for three decades, offering a green and eco-friendly platform towards the sustainable design of renewable polyesters. However, limitations imposed by their delicate nature, render them less addressed. As a case study, we compare herein bulk and solution polycondensation of 1,6-hexanediol and diethyl adipate catalyzed by an immobilized lipase from Candida antarctica. The influence of various parameters including time, temperature, enzyme loading, and vacuum was assessed in the frame of a two-step polymerization with the help of response surface methodology, a statistical technique that investigates relations between input and output variables. Results in solution (diphenyl ether) and bulk conditions showed that a two-hour reaction time was enough to allow adequate oligomer growth for the first step conducted under atmospheric pressure at 100 °C. The number-average molecular weight (Mn) achieved varied between 5000 and 12,000 g·mol−1 after a 24 h reaction and up to 18,500 g∙mol−1 after 48 h. The statistical analysis showed that vacuum was the most influential factor affecting the Mn in diphenyl ether. In sharp contrast, enzyme loading was found to be the most influential parameter in bulk conditions. Recyclability in bulk conditions showed a constant Mn of the polyester over three cycles, while a 17% decrease was noticed in solution. The following work finally introduced a statistical approach that can adequately predict the Mn of poly(hexylene adipate) based on the choice of parameter levels, providing a handy tool in the synthesis of polyesters where the control of molecular weight is of importance.

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Enzymatic approach for the synthesis of biobased aromatic–aliphatic oligo-/polyesters

Abstract: Aromatic moieties containing oligoesters and polyesters synthesized by enzymatic and conventional polymerizations of AB-type alkylenehydroxybenzoates.

Cited by 27 publications

References 43 publications

Enzymatic synthesis of lignin derivable pyridine based polyesters for the substitution of petroleum derived plastics

Enzymatic synthesis of lignin derivable pyridine based polyesters for the substitution of petroleum derived plastics

Work‐hardening Photopolymer from Renewable Photoactive 3,3’‐(2,5‐Furandiyl)bisacrylic Acid

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

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