Poly (ethylene furanoate) synthesis with renewable-linker MOF catalyst: Mechanistic insights and thermo-rheological characterization

IF 4.5 2区化学 Q2 POLYMER SCIENCE

Polymer Pub Date : 2026-04-09 Epub Date: 2026-03-06 DOI:10.1016/j.polymer.2026.129808

N.V. Fathima Safeeda , Meera Balachandran , Minu Elizabeth Thomas , Jesús Esteban , Johan Stanley

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Abstract

Poly (ethylene furanoate) (PEF) is a promising bio-based polyester that serves as a biobased alternative to the petroleum derived poly (ethylene terephthalate) (PET) polymer. Conventionally, heavy metal-based catalysts dominate polyester synthesis. Considering the concerns over the environmental impact of the catalyst, a novel, greener and safer Ti-based hybrid catalyst using 2,5-furan dicarboxylic acid (FDCA) as an organic linker was developed. In this work, the Ti-FDCA MOF catalyst was synthesized by the hydrothermal method, and a detailed structural characterization of catalysts was done. A comparative analysis with Ti-based catalyst such as conventional titanium Ⅳ butoxide (TBT) and Ti-FDCA MOF in the melt polycondensation of FDCA and ethylene glycol was also studied. While exhibiting similar polymer yield of 85.7%, Ti-FDCA MOF catalyzed PEF resulted in an intrinsic viscosity value of 0.69 dL/g compared to 0.52 dL/g with the TBT catalyzed PEF. The presence of Lewis acid sites on the Ti-FDCA MOF catalyst shows that this is a good candidate for PEF polymerization. The proposed catalytic reaction mechanism was elucidated by DFT calculation, with the rate limiting step having an activation energy of 25.9 kcal mol⁻¹. Moreover, investigation of thermal and rheological characteristics showed that the green Ti-FDCA MOF catalyst exhibited comparable behavior to that of TBT, indicating good compatibility for polymerization.

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用可再生连接剂MOF催化剂合成聚呋喃酸乙烯：机理和热流变学表征

聚呋喃乙酯（PEF）是一种很有前途的生物基聚酯，可作为石油衍生的聚对苯二甲酸乙酯（PET）聚合物的生物基替代品。传统上，重金属基催化剂在聚酯合成中占主导地位。考虑到催化剂对环境的影响，以2,5-呋喃二羧酸（FDCA）为有机连接剂，开发了一种新型、更环保、更安全的钛基杂化催化剂。本文采用水热法合成了Ti-FDCA MOF催化剂，并对催化剂进行了详细的结构表征。对比分析了钛基催化剂（如常规钛Ⅳbuoxide (TBT)）和Ti-FDCA MOF对FDCA与乙二醇熔融缩聚反应的影响。虽然聚合物收率为85.7%，但Ti-FDCA MOF催化PEF的特性粘度值为0.69 dL/g，而TBT催化PEF的特性粘度值为0.52 dL/g。Ti-FDCA MOF催化剂上路易斯酸位点的存在表明它是PEF聚合的良好候选物。通过DFT计算对所提催化反应机理进行了分析，发现限速步骤的活化能为25.9 kcal mol−1。此外，热流变特性研究表明，绿色Ti-FDCA MOF催化剂表现出与TBT相当的行为，表明具有良好的聚合相容性。

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来源期刊

Polymer 化学-高分子科学

CiteScore

7.90

自引率

8.70%

发文量

959

审稿时长

32 days

期刊介绍： Polymer is an interdisciplinary journal dedicated to publishing innovative and significant advances in Polymer Physics, Chemistry and Technology. We welcome submissions on polymer hybrids, nanocomposites, characterisation and self-assembly. Polymer also publishes work on the technological application of polymers in energy and optoelectronics. The main scope is covered but not limited to the following core areas: Polymer Materials Nanocomposites and hybrid nanomaterials Polymer blends, films, fibres, networks and porous materials Physical Characterization Characterisation, modelling and simulation* of molecular and materials properties in bulk, solution, and thin films Polymer Engineering Advanced multiscale processing methods Polymer Synthesis, Modification and Self-assembly Including designer polymer architectures, mechanisms and kinetics, and supramolecular polymerization Technological Applications Polymers for energy generation and storage Polymer membranes for separation technology Polymers for opto- and microelectronics.