Control of coordination polymerization behavior by counter-anionic effects

IF 26 1区 化学 Q1 POLYMER SCIENCE
Ryo Tanaka, Oluwaseyi Aderemi Ajala, Yuushou Nakayama, Takeshi Shiono
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引用次数: 0

Abstract

In coordination polymerization chemistry, the most active species are cationic transition metals which bear vacant sites for monomer coordination. The steric and electronic properties around the metal center are strongly related to the polymerization behavior. Thus, the development of the catalyst system mainly represents the design of neutral metal complex precursors, especially the structure of the ligand. On the other hand, the choice of counteranions derived from the cocatalysts sometimes plays a crucial role in the controlled coordination polymerization. Some unusual polymerization behaviors on stereospecificity, activity, and monomer reactivity ratios have been reported by designing the structure of these cocatalysts.

The review summarizes these examples of polymerization controlled by cocatalysts. Various cocatalysts, such as methylaluminoxane (MAO), fluoroarylboranes, and borates with different activation mechanisms, are introduced based on their structural analysis and molecular design. Heterogeneous cocatalysts, important for industrial applications, are also mentioned with their various characterization methods. The application of these cocatalysts is discussed, along with the introduction of several techniques evaluating the relationship between cocatalysts and polymerization behavior. Moreover, the counter-anionic effect in the late-transition metal-catalyzed polymerization chemistry, which recently attracted many researchers for its versatile applicability for polar monomers, is reviewed.

Abstract Image

用反阴离子效应控制配位聚合行为
在配位聚合化学中,最活跃的物质是带有单体配位空位的阳离子过渡金属。金属中心周围的空间和电子性质与聚合行为密切相关。因此,催化剂体系的发展主要表现在中性金属配合物前驱体的设计,尤其是配体的结构。另一方面,在可控配位聚合中,由助催化剂产生的反阴离子的选择有时起着至关重要的作用。通过设计这些助催化剂的结构,已经报道了在立体专一性、活性和单体反应性比上的一些不寻常的聚合行为。本文综述了用助催化剂控制聚合的实例。在结构分析和分子设计的基础上,介绍了具有不同活化机理的甲基铝氧烷、氟芳基硼烷和硼酸盐等多种助催化剂。本文还介绍了具有重要工业应用价值的非均相共催化剂及其各种表征方法。讨论了这些助催化剂的应用,并介绍了几种评价助催化剂与聚合行为之间关系的技术。此外,还综述了过渡后金属催化聚合化学中的反阴离子效应,该效应因其对极性单体的广泛适用性而近年来引起了许多研究人员的关注。
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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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