Enzymatic synthesis of biobased aliphatic–aromatic oligoesters using 5,5′-bis(hydroxymethyl)furoin as a building block

Baraldi, Serena; Fantin, Giancarlo; Carmine, Graziano Di; Ragno, Daniele; Brandolese, Arianna; Massi, Alessandro; Bortolini, Olga; Marchetti, Nicola; Giovannini, Pier Paolo

doi:10.1039/c9ra06621g

Cited by 12 publications

(9 citation statements)

References 34 publications

(47 reference statements)

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“…176 Another furoin triol, derived by organocatalyzed condensation of two HMF molecules, was used for the enzymatic synthesis of polyesters using succinic and sebacic acids. 177 A feature of this work is the possibility of selectively esterifying only primary hydroxyl groups in the presence of secondary groups, which results in linear polyesters with free alcohol moieties.…”

Section: Linear Typementioning

confidence: 99%

Recent advances in the development of green furan ring-containing polymeric materials based on renewable plant biomass

Karlinskii

Ananikov

2023

Chem. Soc. Rev.

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Section: Linear Typementioning

confidence: 99%

Recent advances in the development of green furan ring-containing polymeric materials based on renewable plant biomass

Karlinskii

Ananikov

2023

Chem. Soc. Rev.

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“…Those values exceeded the values obtained at 80 °C by more than 10-fold. As enzymatic catalysis proved to be better suitable for oligomer production, several attempts to synthesize furan-based oligomers via enzymatic catalysis have been made in recent years, where different aromatic and semiaromatic oligomers were produced. , Other attempts to synthesize semiaromatic diesters via enzymatic catalysis were reported by Pellis et al Aliphatic diols varying in chain length between C 4 –C 8 were reacted with several aromatic monomers such as diethyl furan-2,5-dicarboxylate, diethyl terephthalate, and diethyl isophthalate in addition to different isomers of pyridine dicarboxylic acid. The results showed that the reaction between 2,4-diethyl pyridine dicarboxylate and octane-1,8-diol in diphenyl ether led to the highest molecular weight ( M̅ n = 14 300 g·mol –1 ).…”

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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“…Giovannini and co-workers reported a modified three-stage protocol at lower reaction temperatures (50−60 °C) and higher vacuum degrees (3−18 mmHg) for the enzymatic synthesis of biobased furanic− aliphatic oligoesters from DHMF and diacid ethyl esters. 283 Also, the oligoesters with low M n values (around 1000 g/mol) were obtained within 20 h.…”

Section: Catalytic Esterification and Amidationmentioning

confidence: 91%

“…In addition, these oligoesters were thermally stable at 250 °C, and their glass transition temperature ( T g ) varied from −38 to 4 °C, which was much higher than that of the aliphatic counterparts. Giovannini and co-workers reported a modified three-stage protocol at lower reaction temperatures (50–60 °C) and higher vacuum degrees (3–18 mmHg) for the enzymatic synthesis of biobased furanic–aliphatic oligoesters from DHMF and diacid ethyl esters . Also, the oligoesters with low M n values (around 1000 g/mol) were obtained within 20 h.…”

Section: Catalytic Esterification and Amidationmentioning

confidence: 99%

(Chemo)biocatalytic Upgrading of Biobased Furanic Platforms to Chemicals, Fuels, and Materials: A Comprehensive Review

Zong

2022

ACS Catal.

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Biobased furans, such as furfural, 5-hydroxymethylfurfural, and 2,5-furandicarboxylic acid, are recognized as the top-value platform chemicals in the valorization of biomass to chemicals, fuels, and materials. Biocatalysis has emerged as a promising technique in the chemical and pharmaceutical industries because of exquisite selectivity, mild reaction conditions, environmental friendliness, etc. In this comprehensive review, we summarize the recent advances in (chemo)biocatalytic conversion of biobased furans, based on the reaction types including oxidation, reduction, C–C and C–N bonds formation, esterification, and amidation. Particularly, the biocatalysts and their catalytic mechanisms/pathways are critically discussed to allow the rational design and construction of efficient enzymes/multienzyme systems/chemobiocatalytic systems. Besides, various biocatalyst engineering and reaction engineering strategies are highlighted to intensify the processes. Future research directions are proposed to expand the chemical space of furans as well as to improve the commercial acceptance of biocatalytic processes.

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Enzymatic synthesis of biobased aliphatic–aromatic oligoesters using 5,5′-bis(hydroxymethyl)furoin as a building block

Abstract: Fully bio-based linear oligoesters were obtained by the unprecedented enzymatic polymerization of 5,5′-bis(hydroxymethyl)furoin with succinic and sebacic acid diethyl esters.

Cited by 12 publications

References 34 publications

Recent advances in the development of green furan ring-containing polymeric materials based on renewable plant biomass

Recent advances in the development of green furan ring-containing polymeric materials based on renewable plant biomass

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

(Chemo)biocatalytic Upgrading of Biobased Furanic Platforms to Chemicals, Fuels, and Materials: A Comprehensive Review

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