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Lipase-catalyzed synthesis of furan-based aliphatic-aromatic biobased copolyesters: Impact of the solvent
European Polymer Journal ( IF 5.8 ) Pub Date : 2021-08-23 , DOI: 10.1016/j.eurpolymj.2021.110717
Alfred Bazin 1 , Luc Avérous 1 , Eric Pollet 1
Affiliation  

Enzymatic polymerization is a promising route for a greener synthesis of biobased polyesters. However, this approach is still often limited to aliphatic polyesters, which present limited properties such as low thermal resistance. In this context and till now, introduction of aromatic monomers into polyesters very often resulted in low molar mass chains. Herein, aliphatic–aromatic copolyesters based on dimethyl-2,5-furandicarboxylate were enzymatically synthesized using immobilized Candida antarctica lipase B with a particular focus on the influence of the solvent used. Two series of poly(hexylene adipate)–co-(hexylene furanoate) and poly(butylene adipate)–co-(butylene furanoate) copolyesters were successfully synthesized in diphenyl ether, displaying high molar masses (Mn up to 19 000 g.mol−1) for aromatic monomer contents up to 70 and 50%, respectively. High aromatic content resulted in reduced molar masses due to a loss of solubility of the growing aromatic chains. Replacing diphenyl ether by acetophenone, which had never been used before as solvent for enzymatic synthesis of polyesters, led to significantly enhanced solubility and thus an increase in the average molar masses of poly(hexylene furanoate) and poly(butylene furanoate). The resulting polyesters showed greater thermal stability and higher Tg, offering new perspectives for expanding the potential applications of such enzymatically-produced biobased aromatic copolyesters.



中文翻译:

脂肪酶催化合成呋喃基脂肪族-芳香族生物基共聚酯:溶剂的影响

酶促聚合是一种更有前景的生物基聚酯合成途径。然而,这种方法仍然通常仅限于脂肪族聚酯,其表现出有限的特性,例如低耐热性。在这种情况下并且直到现在,将芳族单体引入聚酯中经常会导致低摩尔质量链。在此,基于 2,5-呋喃二甲酸二甲酯的脂肪族-芳香族共聚酯使用固定化的南极念珠菌脂肪酶 B酶促合成,特别关注所用溶剂的影响。在二苯醚中成功合成了两个系列的聚(己二酸己二酸己酯)-共聚(呋喃己酸己酯)和聚(己二酸丁二醇酯)-共聚(呋喃丁二醇酯)共聚酯,显示出高摩尔质量(M n高达 19 000 g.mol -1 ) 的芳族单体含量分别高达 70% 和 50%。由于增长的芳族链的溶解度损失,高芳族含量导致摩尔质量降低。用苯乙酮代替二苯醚,苯乙酮以前从未用作聚酯酶促合成的溶剂,导致溶解度显着提高,因此聚(呋喃己酸己酯)和聚(呋喃丁二醇酯)的平均摩尔质量增加。所得聚酯显示出更高的热稳定性和更高的 T g,为扩大这种酶法生产的生物基芳香族共聚酯的潜在应用提供了新的视角。

更新日期:2021-09-08
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