Melt polycondensation of 2,5-tetrahydrofurandimethanol with various dicarboxylic acids towards a variety of biobased polyesters

Jin, Chenhao; Liu, Lipeng; Tu, Zhu; Wang, Bo; Wang, Pei; Wei, Zhiyong

doi:10.1039/d2py00975g

Cited by 6 publications

(6 citation statements)

References 53 publications

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“…Over the past decades a large number of biopolymers originating from various types of microorganisms have also been reported [24] . The polyhydroxyalkanoates (PHAs) are biodegradable polyesters that are synthesized intracellularly and deposited as granules in bacterial cultures in the presence of excess carbon source and a growth limiting nutrient.…”

Section: Resultsmentioning

confidence: 99%

“…[22] Over the past decades a large number of biopolymers originating from various types of microorganisms have also been reported. [24] The polyhydroxyalkanoates (PHAs) are biodegradable polyesters that are synthesized intracellularly and deposited as granules in bacterial cultures in the presence of excess carbon source and a growth limiting nutrient. PHAs are typically obtained as a polymer of 103 to 104 monomers and can be accumulated by gram-positive and negative bacteria in the form of cytoplasmic inclusions 0.2-0.5 μm in diameter (Figure 5).…”

Section: Bio-sourced Building Blocks and Polymersmentioning

confidence: 99%

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Synthesis of Bio‐Based Polymers and Adjuvants through Biomass Valorization: Challenges and Opportunities

Serra Sampaio,

Wojcieszak,

Itabaiana Junior

2023

ChemCatChem

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In recent years, the synthesis of bio‐based polymers and compounds has grown due to greater environmental concerns and the need to develop green and sustainable products as substitutes for fossil derivatives. In this context, lignocellulosic biomass is an important source of raw materials, as it is abundant and low‐cost, in addition to its chemical variety. Thus, chemical catalysis and biocatalysis have been important tools for obtaining these high value‐added compounds. With the aim of detecting the current scenario, as well as the main challenges and opportunities in the production of bio‐based polymers through the valorization of biomass, this work carried out a technological investigation of articles published in the last 10 years, establishing a relationship between the conditions of each production route and its main challenges. The results show a growing number of publications in the last 6 years involving the application of biomass‐derived molecules as monomers to obtain various classes of polymers, where polyesters and polyurethanes have been the most studied. The use of heterogeneous chemical catalysts is still the predominant production strategy, due to the extreme conditions required for production. However, the application of enzymes such as lipases to obtain polyesters and microbial biotransformation to obtain polyhydroxyalkanoates have been emerging as promising strategies within the context of biorefineries. Almost all works are at the proof‐of‐concept stage, where most of the molecules produced have been obtained from synthetic starting materials, demonstrating the need to integrate technologies for obtaining monomers directly from biomass and synthesis protocols for the advent of new processes that are more sustainable and competitive with traditional routes.

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Section: Resultsmentioning

confidence: 99%

Section: Bio-sourced Building Blocks and Polymersmentioning

confidence: 99%

Synthesis of Bio‐Based Polymers and Adjuvants through Biomass Valorization: Challenges and Opportunities

Serra Sampaio,

Wojcieszak,

Itabaiana Junior

2023

ChemCatChem

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“…[1] 2,5-Furandicarboxylic acid (FDCA) derived from biomass have similar chemical structures to terephthalic acid (PTA), endowed with the potential to become an alternative for petroleum-based aromatic compounds. [2] In recent years, FDCA-based polyester has attracted much academic attention. The nonlinear structure of FDCA renders furan less prone to flipping compared to TPA, making the thermal, mechanical, gas barrier and UV shielding properties of FDCAbased polyester differ significantly from those of TPA-based polyester.…”

Section: Introductionmentioning

confidence: 99%

−COOH & −OH Condensation Reaction Utilization for Biomass FDCA‐based Polyesters

Yi,

Dai,

et al. 2024

ChemSusChem

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A green and sustainable ‐COOH & ‐OH condensation solution polymerization method was hereby reported for FDCA‐based polyesters to avoid discoloration and toxic solvents. First, taking poly(ethylene 2,5‐furandicarboxylate) (PEF) as the representative of FDCA‐based polyester, enabling good white appearance PEF with Mn = 6.51×103 g mol‐1 from FDCA and ethylene glycol in green solvent γ‐valerolactone (GVL), catalyzed by 4‐dimethylaminopyridine (DMAP) and N‐(3‐dimethylaminopropyl)‐N’‐ethylcarbodiimide hydrochloride (EDC). Additionally, the molecular weight of PEF was rapidly improved (Mn > 2.5 × 104 g mol‐1) via remelting polycondensation within minutes, with the dispersity still kept relatively low dispersity (Đ <1.40). Importantly, the ‐COOH & ‐OH condensation solution polymerization method was successfully applied for the synthesis of various FDCA‐based polyesters, including diols with varying carbon chain lengths (3 to 11 carbons) and cycloalkyl diols, especially the applicability of this method to diols containing C=C double bonds, which was found to exhibit low heat resistance. Lastly, assisting with 13C labeled 1,4‐succinic acid and in‐situ 13C‐NMR, an in‐depth study of the possible catalytic mechanism was proposed, by which, EDC activated FDCA, and then DMAP catalyzed it with diol to yield macromolecular chain of polyester. Overall, the results provided a green and sustainable strategy for the synthesis of FDCA‐based polyesters.

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“…Ether linkages gave strong polarity, hydrophilicity, and biocompatibility to polyesters, and nonlinear structure was more rigid that produced high T g and great mechanical properties. [28][29][30] In this study, THFDM was introduced into the PET as a sustainable copolymer monomer to synthesize poly (ethylene-co-tetrahydrofurandimethanol terephthalate) (PETT) for replacing the previous role of CHDM or IPA. Due to the high price of THFDM, only a small amount (≤6 mol%) of THFDM was added during copolymerisation to design a new sustainable copolyester with similar properties to PET but with easier processing and less crystallization activity.…”

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

2,5-Tetrahydrofurandimethanol as a sustainable comonomer for modification of polyethylene terephthalate: Liter-level pilot test and non-isothermal crystallization kinetics

Liu,

Zheng,

Chen

et al. 2023

Journal of Thermoplastic Composite Materials

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2,5-tetrahydrofurandimethanol (THFDM), which is an alicyclic diol in products of 5-hydroxymethylfurfural (HMF), is a sustainable monomer to protect environment for replacing the role of isophthalic acid (IPA) and 1,4-cyclohexanedimethanol (CHDM) which were optimized polyethylene terephthalate (PET) performance. By direct esterification method, poly (ethylene-co-tetrahydrofurandimethanol terephthalate) (PETT) was synthesized in 2.5 L reactor. The results showed that the contents of THFDM in copolyester were less than that feeding ratio attributed to its lower reaction reactivity. The color of PETT slightly turned yellow. PETT performed broader processing temperature window, while Tg maintained in good range because of the cyclic structure of THFDM. Especially, the cold crystallization occured in PETT but not in PET after finishing melt crystallization. Otherwise, the thermal stability and crystal structure of PETT remained the same as PET. The crystallization activity of PETT became significantly lower than PET. What proved THFDM was effective in reducing PET crystallinity was that crystallization kinetics using Jeziorny theory and the trend of activation energy of melt crystallization which was calculated by Friedman method. And PETT-2 fibre had comparable mechanical property to PET fibre. In the advancement of green chemistry, THFDM has added a choice of cyclic bio-based comonomers.

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Melt polycondensation of 2,5-tetrahydrofurandimethanol with various dicarboxylic acids towards a variety of biobased polyesters

Abstract: This study investigated the effects of the molecular structure of 2,5-tetrahydrofurandimethanol (THFDM) on its reactivity and polyester properties. 2,5-Furanediformic acid2,5-Furandicarboxylic acid (FDCA) was employed as representative diacid, by investigating the...

Cited by 6 publications

References 53 publications

Synthesis of Bio‐Based Polymers and Adjuvants through Biomass Valorization: Challenges and Opportunities

Synthesis of Bio‐Based Polymers and Adjuvants through Biomass Valorization: Challenges and Opportunities

−COOH & −OH Condensation Reaction Utilization for Biomass FDCA‐based Polyesters

2,5-Tetrahydrofurandimethanol as a sustainable comonomer for modification of polyethylene terephthalate: Liter-level pilot test and non-isothermal crystallization kinetics

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