Light-mediated olefin coordination polymerization and photoswitches,Organic Chemistry Frontiers

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Light-mediated olefin coordination polymerization and photoswitches
Organic Chemistry Frontiers ( IF 4.6 ) Pub Date : 2020-06-15 , DOI: 10.1039/d0qo00426j
Mingyuan Li _{1,

2,

3,

4} , Ruibin Wang _{1,

2,

3,

4} , Moris S. Eisen _{1,

2,

3,

4,

5} , Sehoon Park _{1,

2,

3,

4,

6}

Affiliation

Polyolefins are important polymeric materials in the plastics industry. While classical Ziegler–Natta catalysts are still superior in global polyolefin production, it is challenging to control their polymerization behavior due to intrinsic heterogeneity. A significant number of molecular olefin polymerization catalysts based on transition metals are capable of harnessing polymerization behavior thanks to their finely-tunable ligand sets, where ligand variation acts as electronic and/or steric factors towards the active metal center. Light has been utilized as a green and specific stimulus in the context of coordination olefin polymerization to mainly alter the electronic state of active catalytic sites, which enables photo-controlled chain propagation. A handful of examples of polymerization catalytic systems that have precise controllability under photoirradiation have been developed to provide a broad range of polyolefins in terms of polymeric (micro)structure. In this Review, we wish to outline photo-responsive, transition metal-based coordination polymerization catalysts ranging from homogeneous to heterogeneous, and monometallic to bimetallic regimes. Specific but varied roles of light depending on the employed catalysts for olefin polymerization are presented with a strong emphasis on the photo-altered properties of the active species.

中文翻译：

光介导的烯烃配位聚合和光开关

聚烯烃是塑料工业中重要的聚合材料。尽管经典的齐格勒-纳塔催化剂在全球聚烯烃生产中仍具有优势，但由于其固有的非均相性，控制其聚合行为仍具有挑战性。大量基于过渡金属的分子烯烃聚合催化剂由于其可微调的配体组而能够利用聚合行为，其中配体的变化对活性金属中心起着电子和/或位阻作用。在配位烯烃聚合的背景下，光已被用作绿色和特定的刺激，主要改变了活性催化部位的电子状态，从而实现了光控链的扩散。已经开发了在光辐照下具有精确可控性的少量聚合催化体系的实例，以提供在聚合物（微）结构方面广泛的聚烯烃。在这篇综述中，我们希望概述从均相到非均相，从单金属到双金属范围的光敏过渡金属基配位聚合催化剂。根据烯烃聚合所使用的催化剂，提出了光的特定但变化的作用，其中强烈强调了活性物质的光改变性质。过渡金属基配位聚合催化剂，范围从均相到非均相，从单金属到双金属。根据烯烃聚合所使用的催化剂，提出了光的特定但变化的作用，其中强烈强调了活性物质的光改变性质。过渡金属基配位聚合催化剂，从均相到非均相，从单金属到双金属。根据烯烃聚合所使用的催化剂，提出了光的特定但变化的作用，其中强烈强调了活性物质的光改变性质。

更新日期：2020-07-28

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