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Organoboron chemistry towards controlled and precise polymer synthesis

Science China Chemistry 2023年第12期66卷 3467-3483页

作者： Yuxuan Du Jin Dong Chaoran Xu Xiangcheng Pan State Key Laboratory of Molecular Engineering of polymers Department of Macromolecular ScienceFudan UniversityShanghai 200438China

Organoboron reagents have garnered considerable attention due to their distinct properties. In recent years, boronic acids and boronate esters have been important intermediates for cross-coupling reactions and other functional group construction and are often used to synthesize small organic molecules, drugs, and bioactive substances. In this feature article, we encapsulate the strategy of harnessing the unique properties of organoboron reagents to overcome challenges encountered in conventional polymer synthesis. We delve into the synthesis of boron-containing monomers and polymer materials, unraveling the unique attributes of these newfound polymers while offering innovative insights into their application within recyclable or reprocessable materials. We develop organoboron-based photocatalysts, employing their inner-sphere electron transfer(ISET) mechanisms to initiate controlled radical polymerization. We utilize alkylborane to initiate controlled radical polymerization and further designed B-alkylcatecholboranes to prepare ultra-high molecular weight polymers. Notably, we also propose a liquid-phase synthesis method based on organoboron tags and apply it to the precise synthesis of sequence-controlled conjugated *** advancements open up new frontiers in the realm of polymer science, and the versatility and potential of organoboron reagents in polymer synthesis continue to inspire exciting research endeavors.

关键词： organoboron boron-containing polymer controlled radical polymerization polymer synthesis

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boron-containing Phthalonitrile Resin:Synthesis,Curing Behavior,and Thermal Properties

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Chinese Journal of polymer Science 2022年第11期40卷 1349-1359页

作者： Shu-Yi Zhan Yue Han Yu-Huan Wu Jiang-Nan Ding Xiang Liu Ying Guo Heng Zhou Tong Zhao Key Laboratory of Science and Technology on High-tech polymer Materials Institute of Chemistry Chinese Academy of SciencesBeijing100190China University of Chinese Academy of Sciences Beijing100049China South China Advanced Institute for Soft Matter Science and Technology South China University of TechnologyGuangzhou510640China

A novel boron-containing monomer,(4-(3,4-dicyanophenoxy)phenyl)boronic acid(BPhPN)was synthesized and used to promote the curing process of phthalonitrile monomer 1,3-bis(3,4-dicyanophenoxy)benzene(MPN).Differential scanning calorimetry and rheological analysis were used to study the curing behaviors of BPhPN/MPN(namely B-MPN),and results suggested that B-MPN systems have better *** spectra and solid-state 13C-NMR exhibited triazine and isoindoline have been formed in the curing ***-containing Lewis acid curing mechanism was preliminarily speculated and verified by two model compounds with different boron chemical *** thermogravimetric analysis and dynamic mechanical analysis demonstrated that the cured B-MPN polymers showed excellent thermal stability and heat resistance,which were comparable with conventional catalytic systems for phthalonitrile *** study not only presented a novel curing system for phthalonitrile resins,but also shed light on future design of high temperature thermosets.

关键词： Curing agent Phthalonitrile resins Thermosets boron-containing polymer

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