The kinetics, thermodynamics and mechanistic studies of sulfur homo- and copolymerization with cyclic and vinyl monomers are described as the major subjects of our review article. Besides, the syntheses, homo- and copolymerization of cyclic mono- and polysulfides are added. The analytical text is complemented with review of the related theoretical topics (mostly DFT), and include theoretical studies of the experimental data of the corresponding sections. Recently, mostly because of the elaboration of the novel process of sulfur copolymerization, so called “inverse vulcanization”, there is renewed interest in polymers of sulfur, with expectation of finding industrial applications, mostly as the Li-sulfur batteries, in optics, removal of toxic metals and biomaterials. We are also discussing papers on the equilibrium between polysulfur and sulfur, in homo- and copolymerization of sulfur with cyclic sulfides and with vinyl monomers. Copolymerization of sulfur is described for cyclic sulfides and vinyl monomers. Analysis of interaction with vinyl monomers involves both low temperatures - then sulfur is merely acting as the chain transfer agent, and for temperatures around the floor temperature, when more or less stable copolymers are formed with high sulfur content. It is also shown that with cyclic monomers the high molar mass copolymers of sulfur were prepared (up to 80 % of sulfur). Analysis of papers describing the molecular structures of copolymers of sulfur are complementing the analysis of the kinetics, thermodynamics and DFT of the studied processes, including the living/controlled polymerization of sulfur with cyclic sulfides. In the final section we analyse the published DFT and other theoretical analyses of the subjects discussed in the major text. These methods have been successfully applied to make predictions of the bond dissociation energies, enthalpies of formation, reaction energies and energy barriers, etc., contributing to a deeper understanding of the chemical processes, as it is shown in this review.

中文翻译：

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单质硫和环状硫化物。均聚和共聚。动力学、热力学和 DFT 分析

硫与环状单体和乙烯基单体的均聚和共聚的动力学、热力学和机理研究被描述为我们综述文章的主要主题。此外，还增加了环状单硫化物和多硫化物的合成、均聚和共聚。分析文本辅以相关理论主题（主要是 DFT）的回顾，并包括相应部分的实验数据的理论研究。最近，主要是由于硫共聚新工艺（即所谓的“逆硫化”）的提出，人们对硫聚合物重新产生了兴趣，期望找到工业应用，主要是作为锂硫电池，在光学、去除有毒金属和生物材料。我们还在讨论有关多硫和硫之间的平衡、硫与环状硫化物和乙烯基单体的均聚和共聚的论文。描述了环状硫化物和乙烯基单体的硫共聚。与乙烯基单体相互作用的分析既涉及低温（硫仅充当链转移剂），又涉及底温附近的温度，此时或多或少会形成具有高硫含量的稳定共聚物。还表明，使用环状单体可制备高摩尔质量的硫共聚物（硫含量高达 80%）。描述硫共聚物分子结构的论文分析补充了所研究过程的动力学、热力学和密度泛函分析，包括硫与环状硫化物的活性/受控聚合。在最后一节中，我们分析了已发表的 DFT 和主要文本中讨论的主题的其他理论分析。这些方法已成功应用于预测键解离能、形成焓、反应能和能垒等，有助于更深入地了解化学过程，如本综述所示。