The dynamicity and recyclability of a material are the chemical bases of sustainable future smart materials. In this context, the poly(disulfide)s of 1,2-dithiolane are a very significant class of polymers due to the presence of dynamic covalent disulfide bonds in the main-chain polymer. Here we reported an amine-activated cascade initiation of thiolate-induced ring opening polymerization (ROP) of the 1,2-dithiolane ring to synthesize functional poly(disulfide)s at room temperature and under an open-air condition. In situ generation of the thiolate initiator by the reaction of the thiolactone ring and amine, stabilization, and use of the phenyl isocyanate terminator enable us to perform the polymerization in a controlled manner. Additionally, in situ, one-step, dual modification at the polymer chain end by varying amine and thiolate allowed us to access a variety of functional poly(disulfide)s. The primary amine is found to be a more effective activator compared to the secondary amine. We also demonstrated the living nature of the poly(disulfide)s and synthesized tailor-made copoly(disulfide)s. We believe that the ROP of poly(disulfide)s activated by amine is the first report in the literature where we can use a library of amines to functionalize poly(disulfide)s and access diverse structures of polymers. This methodology establishes a versatile platform and opens up enormous opportunities for the synthesis of a variety of dynamic polymers.

中文翻译：

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动态共价聚（二硫化物）开环聚合的级联起始：通过活性聚合实现一步双改性和共聚（二硫化物）合成


材料的动态性和可回收性是可持续未来智能材料的化学基础。在这种情况下，由于主链聚合物中存在动态共价二硫键，因此 1,2-二硫代烷的聚（二硫键）是一类非常重要的聚合物。在这里，我们报道了硫酸盐诱导的 1,2-二硫代烷环的开环聚合 （ROP） 的胺激活级联起始，以在室温和露天条件下合成功能性聚（二硫键）。通过硫内酯环和胺的反应原位生成硫酸盐引发剂、稳定化以及使用苯基异氰酸酯终止剂使我们能够以可控的方式进行聚合。此外，通过改变胺和硫酸盐在聚合物链末端进行原位一步双重修饰，使我们能够获得各种功能性聚（二硫键）。与仲胺相比，发现伯胺是一种更有效的活化剂。我们还展示了聚（二硫化物）的生命性质，并合成了定制的共聚（二硫化物）。我们相信，胺激活的聚（二硫键）的 ROP 是文献中第一个可以使用胺库来官能化聚（二硫键）并获得聚合物的不同结构的报道。该方法建立了一个多功能平台，并为合成各种动态聚合物开辟了巨大的机会。