Elemental sulfur and cyclic sulfides. Homo- and copolymerizations. Kinetics, thermodynamics and DFT analysis

IF 26 1区 化学 Q1 POLYMER SCIENCE
Stanislaw Penczek, Marek Cypryk, Julia Pretula, Krzysztof Kaluzynski, Piotr Lewinski
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引用次数: 0

Abstract

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.

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元素硫和环状硫化物。均聚和共聚。动力学、热力学和 DFT 分析
这篇综述文章的主要主题是硫与环状单体和乙烯基单体均聚和共聚的动力学、热力学和机理研究。此外,文章还介绍了环状单硫化物和多硫化物的合成、均聚和共聚。在分析文章的基础上,我们还对相关的理论课题(主要是 DFT)进行了综述,并对相应章节的实验数据进行了理论研究。最近,主要由于硫磺共聚新工艺(即所谓的 "反硫化")的发展,人们对硫的聚合物重新产生了兴趣,并期望找到工业应用,主要是锂硫电池、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。论文介绍了硫与环状硫化物和乙烯基单体的共聚。分析硫与乙烯基单体的相互作用涉及低温和底温两种情况--低温下硫只是作为链转移剂,而在底温附近的温度下,硫含量高时或多或少会形成稳定的共聚物。研究还表明,使用环状单体可以制备出高摩尔质量的含硫共聚物(含硫量高达 80%)。对描述硫共聚物分子结构的论文进行分析,是对所研究过程的动力学、热力学和 DFT 分析的补充,包括硫与环状硫化物的活体/可控聚合。在最后一节中,我们分析了已发表的 DFT 和其他理论分析,这些分析涉及主要文本中讨论的主题。正如本综述所示,这些方法已成功应用于预测键解离能、形成焓、反应能和能障等,有助于加深对化学过程的理解。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
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来源期刊
Progress in Polymer Science
Progress in Polymer Science 化学-高分子科学
CiteScore
48.70
自引率
1.10%
发文量
54
审稿时长
38 days
期刊介绍: Progress in Polymer Science is a journal that publishes state-of-the-art overview articles in the field of polymer science and engineering. These articles are written by internationally recognized authorities in the discipline, making it a valuable resource for staying up-to-date with the latest developments in this rapidly growing field. The journal serves as a link between original articles, innovations published in patents, and the most current knowledge of technology. It covers a wide range of topics within the traditional fields of polymer science, including chemistry, physics, and engineering involving polymers. Additionally, it explores interdisciplinary developing fields such as functional and specialty polymers, biomaterials, polymers in drug delivery, polymers in electronic applications, composites, conducting polymers, liquid crystalline materials, and the interphases between polymers and ceramics. The journal also highlights new fabrication techniques that are making significant contributions to the field. The subject areas covered by Progress in Polymer Science include biomaterials, materials chemistry, organic chemistry, polymers and plastics, surfaces, coatings and films, and nanotechnology. The journal is indexed and abstracted in various databases, including Materials Science Citation Index, Chemical Abstracts, Engineering Index, Current Contents, FIZ Karlsruhe, Scopus, and INSPEC.
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