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氮氧自由基调控聚合(NMP)是制备微观结构可控(如窄分子量分布)的聚合物材料最主要的技术手段之一。在过去的二十年间,NMP取得了相当大的成就,实现了MMA、n-BA、丙烯酰胺,二烯烃和丙烯腈等多种单体的可控/“活性”聚合,分子量分布达到1.1以下,同时利用NMP制备了具有既定结构的聚合物,如嵌段聚合物、接枝聚合物、星形聚合物和梳形聚合物等。而与光聚合技术的结合,使NMP聚合取得了更大的突破,实现了室温下的光可控/“活性”聚合,且大大提升了聚合反应速率。近年来光引发氮氧自由基调控聚合的研究进展主要集中在光敏化技术方面,包括分子内敏化和分子间敏化,本文对其各自的敏化机理和研究成果进行总结和评述,希望有助于国内读者了解这方面研究工作的状况,促进国内相关研究工作的发展。
Nitroxide-mediated polymerization (NMP) is one of the most important technical means to prepare polymer materials with controlled microstructure (such as narrow molecular weight distribution). NMP has achieved considerable success over the past two decades by enabling controlled / “living” polymerization of a wide range of monomers such as MMA, n-BA, acrylamide, diene and acrylonitrile with molecular weight distributions up to 1.1 or less, a polymer having a predetermined structure such as a block polymer, a graft polymer, a star polymer, a comb polymer and the like was prepared while using NMP. With the combination of photopolymerization technology, NMP polymerization has made a greater breakthrough, achieving room temperature controllable / “activity ” polymerization, and greatly enhance the polymerization rate. In recent years, the research progress of photoinitiated nitroxide-mediated polymerization mainly focuses on photosensitization, including intramolecular sensitization and intermolecular sensitization. In this paper, the respective sensitization mechanism and research results are summarized and reviewed. To help domestic readers understand the status of research in this area, and promote the development of related research work in China.