文献类型：期刊文献

中文题名：基于Bergman环化反应的高分子合成方法

英文题名：Bergman Cyclization Polymerization

作者：胡爱国[1]

机构：[1]华东理工大学材料科学与工程学院,上海200237

年份：2016

卷号：26

期号：12

起止页码：1635

中文期刊名：高分子学报

外文期刊名：Acta Polymerica Sinica

收录：CSTPCD;;Scopus;WOS:【SCI-EXPANDED(收录号:WOS:000397212400002)】；北大核心:【北大核心2014】；CSCD:【CSCD2015_2016】；

基金：国家自然科学基金(基金号21474027)资助项目

语种：中文

中文关键词：Bergman环化反应;原位聚合;高分子纳米复合材料;二维聚合物;高分子可控合成

外文关键词：Bergman cyclization; In situ polymerization; Polymer nanocomposites materials; Two dimensional polymers; Controlled synthesis of polymers;

摘要：高分子合成化学是高分子科学的基础,高效的聚合反应是合成高分子材料的关键.Bergman环化反应是一种可以形成芳香双自由基活性物质的化学过程.芳基双自由基可以快速偶联形成聚芳烃,为此类聚合物的合成提供简洁的方法.本文系统地介绍了Bergman环化反应进入高分子科学后的发展轨迹,阐述了我们研究组利用该反应的原位聚合机制以及不需要催化剂不产生副产物的特点,在明确该反应的聚合反应机理的基础上,建立了线形聚合物、聚合物粒子、面形聚合物等具有多种特殊拓扑结构形貌以及功能的聚合物纳米材料的工作.最后,对Bergman环化反应中尚存在的问题进行总结并对其未来在高分子科学中的发展予以展望.
Synthetic polymeric chemistry is one of the basic parts of polymer science,and highly efficient polymerization reactions are essential for the synthesis of high performance polymeric materials,for which the development of new synthetic methods for the emerging polymer science is of great importance. Bergman cyclization is a chemical process during which highly reactive aryl diradicals are formed from enediyne precursors. Bergman cyclization has shown strong impacts on a number of application fields including pharmaceutics,synthetic chemistry and material science. The diradicals intermediates stemmed from enediynes can cause DNA cleavage under physiological conditions,leading to the strong cytotoxicity of many naturally occurred enediyne antibiotics. Meanwhile,the diradicals intermediates can quickly couple with each other to construct polyarylenes,providing a novel method to synthesize this kind of conjugated polymers thanks to the advantages of facile operation,high efficiency,tailored structure and catalyst-free feature. Moreover,the conjugated polymers generated through Bergman cyclization show many remarkable properties,such as excellent thermal stability,good solubility and processability,which enables these polymers to be further manufactured into carbon-rich materials. In this article,a brief overview of the trajectory of Bergman cyclization in polymer science was introduced,followed by the introduction of the research advances mainly from our group in developing polymerization methods with Bergman cyclization,taking advantages of its catalyst-free,by-productfree features and in situ polymerization mechanism to synthesize new polymeric materials with various structures and morphology. These synthetic strategies include fabrication of rod-like polymers with polyester,dendrimer and chiral imide side chains,functionalization of carbon nanomaterials by surface-grafting conjugated polymers,formation of nanoparticles by intramolecular collapse of single polymer chains,construction of carbon nanomembranes on the external and internal surface of inorganic nanomaterials. These polymers with novel structural features were further used in a variety of fields like energy transformation,energy storage,catalyst support,and fluorescent detection. At the end of this article,an outlook of the future development of Bergman cyclization in medicinal chemistry and especially in polymer science is presented.