Amine-Catalyzed Chain Polymerization of Ethyl Glyoxylate from Alcohol and Thiol Initiators
Amine-Catalyzed Chain Polymerization of Ethyl Glyoxylate from Alcohol and Thiol Initiators
复制标题
醇和硫醇引发剂胺催化乙醛酸乙酯的链聚合
DOI：
10.1021/acsmacrolett.0c00865
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发表时间：
2021
影响因子：
7.015
通讯作者：
Grubbs, Robert B.
中科院分区：
文献类型：
--
作者：
Hewitt, David R.;Grubbs, Robert B.
聚缩醛具有作为可降解聚合物的显著潜力，但醛聚合通常难以控制。在这里，我们表明，乙醛酸乙酯的聚合可以引发从醇或硫醇活化与三乙胺，以提供聚（乙醛酸乙酯）与可控的分子量和相对较低的分散性（ε = 1.3-1.4），如由MALDI-TOF质谱证明。发现通过用氯甲酸苄酯封端链来稳定解聚，而没有从用异氰酸甲苯酯封端链中观察到的副反应。使用更强的碱DBU导致限制聚合物分子量的竞争性副反应。
Polyacetals have significant potential as degradable polymers, but aldehyde polymerizations are generally difficult to control. Here we show that polymerization of ethyl glyoxylate can be initiated from alcohols or thiols by activation with triethylamine to afford poly(ethyl glyoxylate) with controllable molecular weights and relatively low dispersities (Đ= 1.3–1.4), as evidenced by MALDI-TOF mass spectrometry. Stabilization against depolymerization by chain-capping with benzyl chloroformate was found to proceed without side reactions observed from chain-capping with tolyl isocyanate. The use of the stronger base DBU leads to competing side reactions that limit polymer molecular weight.