Acidic Metal-Based Functional Ionic Liquids Catalyze the Synthesis of Bio-Based PEF Polyester

Qiao Zhou, Yuanyuan Zhao, Yafei Shi,Rongrong Zheng,Liying Guo

POLYMERS(2024)

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摘要
Utilizing triethylenediamine (DA), 1,3-propanesultone (PS), whose ring opens during the formation of the dizwiterion-intermediate DA-2PS, and the metal chlorides XCly, where X = Sn(IV), Zn(II),Al(III), Fe(III) and Mn(II), are used for the synthesis of five kinds of acidic metal-based functionalized ionic liquid catalysts ([DA-2PS][XCly]2). Their chemical structures, thermal stability and dual acidic active site were analyzed. We investigated the performance of [DA-2PS][XCly]2 in catalyzing the esterification reaction between 2,5-furandicarboxylic acid (FDCA) and ethylene glycol (EG) to synthesize poly (ethylene 2,5-furandicarboxylate)(PEF). Among the catalysts tested, [DA-2PS][SnCl5]2 exhibited the best catalytic performance under identical process parameters, and the optimal catalyst dosage was determined to be 0.05 mol% based on FDCA. The optimal conditions for the reaction were predicted using response surface methodology: a feed ratio of EG:FDCA = 1.96:1, an esterification temperature of 219.86 degrees C, a polycondensation temperature of 240.04 degrees C and a polycondensation time of 6.3 h, with a intrinsic viscosity of 0.67 dL center dot g-1. The resulting PEF was experimentally verified to exhibit an intrinsic viscosity of 0.68 dL center dot g-1 and a number average molecular weight of 28,820 g center dot mol-1. Finally, the structure and thermal properties of PEF were characterized. The results confirmed that PEF possessed the correct structure, exhibited high thermal stability and demonstrated excellent thermal properties.
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关键词
ionic liquid,catalyst,biobased,direct esterification,poly(ethylene 2,5-furandicarboxylate)
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