Enzymatic synthesis of lignin derivable pyridine based polyesters for the substitution of petroleum derived plastics
Enzymatic synthesis of lignin derivable pyridine based polyesters for the substitution of petroleum derived plastics
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DOI：
10.1038/s41467-019-09817-3
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发表时间：
2019-04-16
影响因子：
16.6
通讯作者：
Farmer, Thomas J.
中科院分区：
文献类型：
--
作者：
Pellis, Alessandro;Comerford, James W.;Farmer, Thomas J.
随着对全球塑料污染日益严重的担忧，人们对生物基和可生物降解替代品的生产和表征的兴趣正在上升。在目前的工作中，一系列完全生物基替代品的基础上，2，4-，2，5-和2，6-吡啶二羧酸衍生的聚合物通过酶催化的合成报告。还合成了类似系列的基于2，5-呋喃二甲酸二乙酯和基于石油的对苯二甲酸二乙酯和对苯二甲酸二乙酯的芳族-脂族聚酯。在这里，我们表明，从2，4-二乙基吡啶二羧酸开始的酶促合成导致最好的聚合物的分子量（M-n = 14.3和M-w的32.1 kDa的1，8-辛二醇结合时），在二苯醚中聚合。在无溶剂条件下的聚合也是成功的，导致可以进一步官能化的生物基低聚酯的合成。DSC分析表明，吡啶二甲酸2，4-二乙酯和对苯二甲酸二乙酯（无定形聚合物）之间以及吡啶二甲酸2，5-二乙酯和对苯二甲酸二乙酯（结晶聚合物）之间的热行为具有明显的相似性。
Following concerns over increasing global plastic pollution, interest in the production and characterization of bio-based and biodegradable alternatives is rising. In the present work, the synthesis of a series of fully bio-based alternatives based on 2,4-, 2,5-, and 2,6-pyridinedicarboxylic acid-derived polymers produced via enzymatic catalysis are reported. A similar series of aromatic-aliphatic polyesters based on diethyl-2,5-furandicarboxylate and of the petroleum-based diethyl terephthalate and diethyl isophthalate were also synthesized. Here we show that the enzymatic synthesis starting from 2,4-diethyl pyridinedicarboxylate leads to the best polymers in terms of molecular weights (M-n = 14.3 and M-w of 32.1 kDa when combined with 1,8-octanediol) when polymerized in diphenyl ether. Polymerization in solventless conditions were also successful leading to the synthesis of bio-based oligoesters that can be further functionalized. DSC analysis show a clear similarity in the thermal behavior between 2,4-diethyl pyridinedicarboxylate and diethyl isophthalate (amorphous polymers) and between 2,5-diethyl pyridinedicarboxylate and diethyl terephthalate (crystalline polymers).