Polythioesters are attracting increasing interest in applications requiring degradability or recyclability. However, few general methods exist for the synthesis of these polymers. This report presents a fast and versatile method for synthesizing polythioesters from readily available lactone feedstocks. The two-step process begins with the thionation of lactones to thionolactones, followed by the ring-opening polymerization of the thionolactones to polythioesters. Unlike previous methods that rely on harsh reagents to accomplish this transformation, we demonstrate that the mild tetrabutylammonium thioacetate is a competent initiator for polymerization. This method exhibits broad applicability, as demonstrated by the successful polymerizations of an unstrained 17-membered macrocycle and an N-substituted cyclic thionocarbamate. Furthermore, the generality of this scheme enables the synthesis of polythioesters with highly tunable properties, as demonstrated here by the synthesis of a set of polymers with glass transition temperatures spanning 180 °C. Finally, the polythioesters are efficiently depolymerized into the corresponding thiolactones.

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从内酯原料合成聚硫酯的通用和温和方法


聚硫酯在需要降解性或可回收性的应用中引起了越来越多的关注。然而，合成这些聚合物的通用方法很少。本报告介绍了一种从现成的内酯原料合成聚硫酯的快速通用方法。两步过程从内酯的硫离子化为硫酰酮开始，然后是硫内酯的开环聚合为聚硫酯。与以前依赖刺激性试剂来完成这种转化的方法不同，我们证明了温和的硫代乙酸四丁基铵是一种有效的聚合引发剂。该方法具有广泛的适用性，未过滤的 17 元大环和 N 取代的环状硫代氨基甲酸酯的成功聚合证明了这一点。此外，该方案的通用性使合成具有高度可调性能的聚硫酯，如合成一组玻璃化转变温度为 180 °C 的聚合物所证明的那样。 最后，聚硫酯被有效地解聚成相应的硫代酮。