Polythiourethanes Crosslinked with Dynamic Disulfide Bonds: Synthesis via Nonisocyanate Approach, Thermomechanical and Reprocessing Properties
Polythiourethanes Crosslinked with Dynamic Disulfide Bonds: Synthesis via Nonisocyanate Approach, Thermomechanical and Reprocessing Properties
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动态二硫键交联的聚硫氨酯：通过非异氰酸酯方法合成、热机械和再加工性能
DOI：
10.1002/marc.202000718
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发表时间：
2021-02-04
影响因子：
4.6
通讯作者：
Zheng, Sixun
中科院分区：
文献类型：
--
作者：
Ge, Wenming;Zhao, Bingjie;Zheng, Sixun
通过非异氰酸酯方法合成了与动态二硫键交联的聚硫代氨基甲酸酯（PTU）。首先，通过双酚A的二缩水甘油醚（DGEBA）与二硫化碳（CS2）的反应合成双官能五元环状三硫代碳酸酯（1）。然后，1与不同摩尔质量的α，ω-二氨基聚环氧丙烷进行逐步聚合，得到一系列线性聚（巯基硫代氨基甲酸酯）。这些线性聚（巯基硫代氨基甲酸酯）在形成二硫键时容易交联，二硫键通过与侧巯基的自由基偶联反应产生。这些交联的PTU可以定制成从热固性塑料到交联弹性体的材料，这取决于α，ω-二氨基聚（环氧丙烷）的摩尔质量。更重要的是，这些交联的PTU在高温下显示出优异的再处理性能，这归因于动态二硫键的复分解反应。
Polythiourethanes (PTUs) crosslinked with dynamic disulfide bonds are synthesized via a nonisocyanate approach. First, a difunctional five-membered cyclic trithiocarbonate (1) is synthesized via the reaction of diglycidyl ether of bisphenol A (DGEBA) with carbon disulfide (CS2). Thereafter, the step-growth polymerizations of 1 with alpha,omega-diamino poly(propylene oxide)s with various molar masses are carried out to obtain a series of linear poly(mercapto thiourethane)s. These linear poly(mercapto thiourethane)s are readily crosslinked upon formation of disulfide bonds, which are generated via radical coupling reaction with the side mercapto groups. These crosslinked PTUs can be tailored into the materials from thermosetting plastics to crosslinked elastomers, depending on the molar masses of alpha,omega-diamino poly(propylene oxide)s. More importantly, these crosslinked PTUs display excellent reprocessing properties at elevated temperatures, which is attributable to the metathesis reaction of dynamic disulfide bonds.