Synthesis of poly(thiocarbonate)s from the copolymerization of epoxides and carbon disulfide (CS₂) remains a tough challenge, due to inevitable oxygen‐sulfur atom scrambling process. In this work, we utilized the oxygen‐sulfur exchange reaction (O‐S ER) to synthesize a random copolymer with monothiocarbonate and trithiocarbonate units from CS₂ and phenyl glycidyl ether (PGE) via metal‐free Lewis pairs. The copolymers contained monothiocarbonate and trithiocarbonate units of which the molar fraction could be tuned by varying either the types of Lewis pairs or the reaction temperature. Keeping track on the intermediate provided an insight in the process of O‐S ER and thus gave a hint to control the product structure. Production and consumption of phenyl thioglycidyl ether was the key process to regulate the chain structure. Remarkably, the oxygen atoms of PGE could be excluded out of the chain, resulting in the nearly complete production of poly(trithiocarbonate)s. Correspondingly, the refractive index of this kind of copolymer could be regulated in a wide range of 1.73—1.79 (at 590 nm).

中文翻译：

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无金属催化在环状硫代碳酸酯上合成单硫代碳酸酯和三硫代碳酸酯单元的无规共聚物的研究

由于不可避免的氧-硫原子加扰过程，由环氧化物和二硫化碳（CS ₂）的共聚合成聚（硫代碳酸酯）仍然是一个艰巨的挑战。在这项工作中，我们利用氧硫交换反应（O‐S ER）从CS ₂合成具有单硫代碳酸酯和三硫代碳酸酯单元的无规共聚物和无金属路易斯对的苯基缩水甘油醚（PGE）。共聚物包含一硫代碳酸酯和三硫代碳酸酯单元，可以通过改变路易斯对的类型或反应温度来调节其摩尔分数。跟踪中间体可提供有关OS ER过程的见解，从而为控制产品结构提供了提示。苯基硫缩水甘油醚的生产和消费是调节链结构的关键过程。值得注意的是，PGE的氧原子可被排除在链外，从而导致聚（三硫代碳酸酯）几乎完全生成。相应地，可以将这种共聚物的折射率调节在1.73-1.79的宽范围内（在590nm处）。