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化学进展 2016, Vol. 28 Issue (2/3): 328-336 DOI: 10.7536/PC150823 前一篇   后一篇

• 综述与评论 •

N-乙烯基己内酰胺的活性/可控自由基聚合

何福喜, 唐刚, 闵晓燕, 胡敏奇, 邵立东, 毕韵梅*   

  1. 云南师范大学化学化工学院 昆明 650500
  • 收稿日期:2015-08-01 修回日期:2015-10-01 出版日期:2016-03-15 发布日期:2016-01-07
  • 通讯作者: 毕韵梅 E-mail:yunmeibi@hotmail.com
  • 基金资助:
    国家自然科学基金项目(No.20864003,21264017)资助

Living/Controlled Free Radical Polymerization of N-Vinyl Caprolactam

He Fuxi, Tang Gang, Min Xiaoyan, Hu Minqi, Shao Lidong, Bi Yunmei*   

  1. College of Chemistry and Chemical Engineering, Yunnan Normal University, Kunming 650500, China
  • Received:2015-08-01 Revised:2015-10-01 Online:2016-03-15 Published:2016-01-07
  • Supported by:
    The work was supported by the National Natural Science Foundation of China (No. 20864003, 21264017).
聚(N-乙烯基己内酰胺)(PNVCL)是一种重要的温度响应性聚合物,其最低临界溶液温度(LCST)在生理温度范围内,而且PNVCL水解不会产生有毒的小分子胺,其单体价格便宜,因此PNVCL及其共聚物在生物医药领域具有潜在的应用价值和较好的工业化前景。活性/可控自由基聚合是合成PNVCL及其共聚物的重要手段。本文综述了N-乙烯基己内酰胺(NVCL)的原子转移自由基聚合(ATRP),可逆加成-断裂链转移(RAFT)聚合和有机钴调控自由基聚合(CMRP)的研究进展。对配体、溶剂、引发剂对NVCL 的ATRP的影响进行了讨论。概述了黄原酸酯、二硫代酸酯、二硫代氨基甲酸酯、三硫代酸酯链转移剂调控的NVCL的RAFT聚合。对单体加入顺序对合成基于PNVCL的嵌段共聚物的影响和活性/可控自由基聚合在合成拓扑结构高分子中的应用进行了介绍。最后对NVCL的活性/可控自由基聚合的发展方向进行了展望。
Poly(N-vinylcaprolactam) (PNVCL) is a thermoresponsive polymer with a lower critical solution temperature (LCST) close to body temperature. The hydrolysis of PNVCL does not produce toxic amine compounds. And PNVCL derives from an inexpensive commercially available monomer, N-vinyl caprolactam (NVCL). These make PNVCL and PNVCL-based polymers highly useful for biomedical applications and open perspectives for industrialization. But NVCL is a typical non-conjugated monomer and it can only be polymerized via radical polymerization, thus living/controlled free radical polymerization of NVCL is the only possible means to obtain the desired well-defined polymeric structure. This review summarizes recent advances regarding the living/controlled radical polymerization of N-vinylcaprolactam, including atom transfer radical polymerization (ATRP), reversible addition-fragmentation chain transfer (RAFT) polymerization, and cobalt-mediated radical polymerization (CMRP). The influence of ligands, solvents, and initiators on ATRP of NVCL is introduced. RAFT polymerizations of NVCL are discussed by xanthate-mediated, dithiocarbamate-mediated, dithioester-mediated and trithiocarbonate-mediated controlled radical polymerization. We also highlight recent results in influence of the sequence of monomer addition on synthesis of NVCL-based block copolymers and the controlled synthesis of PNVCL-containing topological macromolecules, such as linear-dendritic block copolymers, star polymers, hyperbranched block copolymers and cyclic polymers obtained by controlled radical polymerization of NVCL. The future directions in living/controlled free radical polymerization of N-vinylcaprolactam are also discussed.

Contents
1 Introduction
2 ATRP of NVCL
2.1 Influence of ligands
2.2 Influence of solvents
2.3 Influence of initiators
3 RAFT polymerization of NVCL
3.1 Xanthate-mediated RAFT polymerization
3.2 Dithiocarbamate-mediated RAFT polymerization
3.3 Dithioester-mediated RAFT polymerization
3.4 Trithiocarbonate-mediated RAFT polymerization
4 CMRP of NVCL
5 Influence of the sequence of monomer addition on synthesis of NVCL-based block copolymers
6 Combination of two different living/controlled free radical polymerization techniques
7 The controlled synthesis of PNVCL-containing topological macromolecules
8 Conclusion

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