The design of unsaturated aliphatic (co)polyester systems, based on different diester‐modified muconic acid isomers, was performed via an eco‐friendly pathway by utilizing enzymatic polymerization using Candida antarctica lipase B (CALB) as catalyst. The obtained fully unsaturated oligoesters and polyesters reached lower molecular weights from 2210 to 2900 g mol⁻¹ for the cis,cis‐(Z,Z)‐muconate isomer, and higher molecular weights of up to 21 200 g mol⁻¹ for the polymers with cis,trans‐(Z,E) isomeric structures. The obtained (co)polyesters were thoroughly characterized and compared with their saturated polyester analogues. The applied biobased catalyst Novozym®435 (an immobilized form of CALB) showed higher selectivity towards the open cis,trans‐muconate compared to the more closed‐structure cis,cis‐muconate. Results of ¹H NMR analysis showed that alkene functionality is present, and no stereo conformational changes were detected in the resulting polymers. The thermal properties of the muconate‐based polyesters showed a glass transition between −7 and 12 °C, and a one‐step degradation process with a maximum rate of weight loss between 415 and 431 °C, depending both on the conformation of the applied diester derivatives and on the segment lengths of the polyoxyalkylenes. Mass spectrometric analysis of the resulting saturated and unsaturated polyesters revealed five different microstructures with different terminal end groups, such as ester/hydroxyl, acid/ester, ester/ester and acid/hydroxyl, and cyclic polyesters without functional end groups. Overall, this study demonstrates that enzymatic polymerization is a robust approach for the synthesis of unsaturated polyesters. © 2020 The Authors. Polymer International published by John Wiley & Sons Ltd on behalf of Society of Industrial Chemistry.

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粘康酸基不饱和聚合物体系的酶促合成与表征

基于不同的二酯改性的粘康酸异构体的不饱和脂族（共）聚酯体系的设计，是通过生态友好的途径，利用南极假丝酵母脂肪酶B（CALB）作为催化剂，通过酶促聚合进行的。将所得到的完全不饱和的低聚酯和聚酯达到较低的分子量2210年至2900年克摩尔^-1的顺式，顺式- （Ž，Ž）-muconate异构体和最多的更高的分子量，以21200克摩尔^-1的聚合物与顺式，反式-（Z，E）异构体结构。对获得的（共）聚酯进行了彻底的表征，并与它们的饱和聚酯类似物进行了比较。所施加的生物基催化剂Novozym®435（CALB的固定化形式）表现出较高的选择性朝向打开顺，反式相比，更封闭结构-muconate顺，顺-muconate。结果¹1 H NMR分析表明存在烯烃官能度，并且在所得聚合物中未检测到立体构象变化。粘康酸酯基聚酯的热性能显示在-7至12°C之间发生玻璃化转变，并且一步降解过程的最大失重速率在415至431°C之间，这取决于所应用的构象。二酯衍生物和聚氧化烯的链段长度。所得饱和和不饱和聚酯的质谱分析显示具有五个不同端基的不同微结构，例如酯/羟基，酸/酯，酯/酯和酸/羟基，以及没有官能端基的环状聚酯。全面的，这项研究表明，酶促聚合是合成不饱和聚酯的可靠方法。©2020作者。约翰·威利父子有限公司（John Wiley＆Sons Ltd）代表工业化学协会出版的《聚合物国际》。