Ge Wenming, Zhao Bingjie, Liu Weiming, Nie Kangming, Zheng Sixun
College of Chemistry and Chemical Engineering, Shanghai Jiao Tong University, Shanghai, 200240, P. R. China.
College of Chemistry and Chemical Engineering, Anhui University, Hefei, 230601, P. R. China.
Macromol Rapid Commun. 2021 Apr;42(7):e2000718. doi: 10.1002/marc.202000718. Epub 2021 Feb 4.
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 (CS ). Thereafter, the step-growth polymerizations of 1 with α,ω-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 α,ω-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.
通过非异氰酸酯法合成了与动态二硫键交联的聚硫脲（PTU）。首先，通过双酚A二缩水甘油醚（DGEBA）与二硫化碳（CS₂）反应合成双官能五元环状三硫代碳酸酯（1）。此后，使1与各种摩尔质量的α,ω-二氨基聚环氧丙烷进行逐步聚合反应，以获得一系列线性聚（巯基硫脲）。这些线性聚（巯基硫脲）在形成二硫键时很容易交联，二硫键是通过与侧链巯基的自由基偶联反应生成的。根据α,ω-二氨基聚环氧丙烷的摩尔质量，这些交联的PTU可以制成从热固性塑料到交联弹性体的材料。更重要的是，这些交联的PTU在高温下表现出优异的再加工性能，这归因于动态二硫键的复分解反应。
