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Progress in Chemistry 2016, Vol. 28 Issue (2/3): 328-336 DOI: 10.7536/PC150823 Previous Articles   Next Articles

• Review and comments •

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: Revised: Online: Published:
  • Supported by:
    The work was supported by the National Natural Science Foundation of China (No. 20864003, 21264017).
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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

Key words: N-vinyl caprolactam, living/controlled free radical polymerization, atom transfer radical polymerization (ATRP), reversible addition-fragmentation chain transfer (RAFT) polymerization, cobalt-mediated radical polymerization (CMRP)

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[1] Szwarc M, Levy M, Milkovich R. J. Am. Chem. Soc., 1956, 78:2656.
[2] 郑璇(Zheng X), 张立武(Zhang L W). 高分子材料科学与工程(Polymer Materials Science and Engineering), 2006, 22(2):16.
[3] Ramos J, Imaz A, Forcada J. Polym. Chem., 2012, 3:852.
[4] Elena E. Makhaeva, Tenhu H, Khokhlov A R. Macromolecules, 1998, 31:6112.
[5] Laukkanen A, Valtola L, Winnik F M, Tenhu H. Macromolecules, 2004, 37:2268.
[6] Mukhuevu E E, Thanh L T M, Sturodoubtsev S G, Khokhlov A R. Macromol.Chem. Phys., 1996, 197:1973.
[7] Mikheeva L M, Grinberg N V, Mashkevich A Y, Grinberg V Y. Macromolecules, 1997, 30:2693.
[8] Vihola H, Laukkanen A, Hirvonen J, Tenhu H. Eur. J. Pharm. Sci., 2002, 16:69.
[9] Liu J, Debuigne A, Detrembleur C, Jérôme C. Adv. Healthcare Mater., 2014, 3:1941.
[10] Mundargia R C, Rangaswamy V, Aminabhavi T M. Des. Monomers Polym., 2010, 13:325.
[11] Vihola H, Laukkanen A, Tenhu H, Hirvonen J. J. Pharm. Sci., 2008, 97:4783.
[12] Rao K M, Mallikarjuna B, Rao K S V K, Siraj S, Rao K C, Subha M C S. Colloids Surf., B, 2013, 102:891.
[13] Rejinold N S, Baby T, Chennazhi K P, Jayakumar R. J. Biomed. Nanotechnol., 2015, 11:392.
[14] Prabaharan M, Grailer J J, Steeber D A, Gong S Q. Macromol. Biosci., 2008, 8:843.
[15] Janssen S, Schwahn D, Mortensen K, Springer T. Macromolecules, 1993, 26:5587.
[16] Meeussen F, Nies E, Berghmans H, Verbrugghe S, Goethalsb E, Du Prez F. Polymer, 2000, 41:8597.
[17] Maeda Y, Nakamura T, Ikeda I. Macromolecules, 2002, 35:217.
[18] 浦鸿汀(Pu H T), 蔡相宇(Cai X Y), 万德成(Wan D C), 杨根金(Yang G J). 化学进展(Progress in Chemistry), 2008, 20(10):1572.
[19] Wang J S, Matyjaszewski K. J. Am. Chem. Soc., 1995, 117:5614.
[20] Chiefari J, Chong Y K, Ercole F, Krstina J, Jeffery J, Le T P T, Mayadunne R T A, Meijs G F, Moad C L, Moad G, Rizzardo E, Thang S H. Macromolecules, 1998, 31:5559.
[21] Wayland B B, Poszmik G, Mukerjee S L. J. Am. Chem. Soc., 1994, 116:7943.
[22] Debuigne A, Caille J R, Jérôme R. Angew. Chem. Int. Ed., 2005, 44:1101.
[23] Lu Z, Fryd M, Wayland B B. Macromolecules, 2004, 37:2686.
[24] Matyjaszewski K, Xia J H. Chem. Rev., 2001, 101:2921.
[25] 潘祖仁(Pan Z R). 高分子化学(Polymer Chemistry), 北京:化学化工出版社(Beijing:Chemical Industry Press), 2003. 69.
[26] Yang Y Z, Li J, Hu M Q, Chen L, Bi Y M. J. Polym. Res. 2014, 21:1.
[27] Negru I, Teodorescu M, Stanescu P O, Draghici C, Lungu A, Sarbu A. Mater. Plast., 2010, 47:35.
[28] Teodorescu M, Matyjaszewski K. Macromolecules, 1999, 32:4826.
[29] Singh P, Srivastava A, Kumar R. J. Polym. Sci. Part A:Polym. Chem., 2012, 50:1503.
[30] Kavitha T, Kang I K, Park S Y. Colloids Surf., B, 2014, 115:37.
[31] Patel R, Ahn S H, Chi W S, Kim J H. Ionics, 2012, 18:395.
[32] Yang Y Z, Tang G, Hu M Q, Shao L D, Li J, Bi Y M. Polymer, 2015, 68:213.
[33] Xia Y, Yin X C, Burke M A D, Stöver H D H. Macromolecules, 2005, 38:5937.
[34] 杨兴兵(Yang X B), 张立武(Zhang L W), 刘静(Liu J), 沈进明(Shen J M), 李圆圆(Li Y Y), 郑妍(Zhen Y). 涂料工业(Paint and Coatings Indusrty), 2010, 10(5):71.
[35] Qian W H, Xu P C, Lu G L, Huang X Y. Chin. J. Chem., 2014, 32:1049.
[36] Moad G, Chiefari J, Chong Y K, Krstina J, Mayadunne R T A, Postma A, Rizzardo E, Thang S H. Polym. Int., 2000, 49:993.
[37] Chong Y K, Le T P T, Moad G, Rizzardo E, Thang S H. Macromolecules, 1999, 32:2071.
[38] 万德成(Wan D C), 周青(Zhou Q). 高分子通报(Polymer Bulletin), 2008, (1):33.
[39] Chiefari J, Mayadunne R T A, Moad C L., Moad G, Rizzardo E, Postma A, Skidmore M A, Thang S H. Macromolecules, 2003, 36:2273.
[40] Chong Y K, Krstina J, Le T P T, Moad G, Postma A, Rizzardo E, Thang S H. Macromolecules, 2003, 36:2256.
[41] Wan D C, Satoh K, Kamigaito M, Okamoto Y. Macromolecules, 2005, 38:10397.
[42] Nguyen T L U, Eagles K, Davis T P, Kowollik C B, Stenzel M H. J. Polym. Sci. Part A:Polym. Chem., 2006, 44:4372.
[43] Destarac M, Bzducha W, Taton D, Gauthier-Gillaizeau I, Zard SZ. Macromol. Rapid Commun., 2002, 23:1049.
[44] Stenzel M H, Cummins L, Roberts G. E, Davis T P, Vana P, Kowollik C B. Macromol. Chem. Phys., 2003, 204, 1160.
[45] Favier A, Kowollik C B, Davis T P, Stenzel M H. Macromol. Chem. Phys., 2004, 205:925.
[46] Coote M L, Radom L. Macromolecules, 2004, 37:590.
[47] 蒋波(Jiang B), 易玲敏(Yi L M), 詹晓力(Zhan X L), 陈碧(Chen B), 陈丰秋(Chen F Q). 化学进展(Progress in Chemistry), 2008, 20(7/8):1128.
[48] Nakabayashi K, Mori H. Eur. Polym. J., 2013, 49:2808.
[49] Beija M, Marty J D, Destarac M. Chem. Commun., 2011, 47:2826.
[50] Yu Y C, Li G X, Kim J S, Youk J H. Polymer, 2013, 54:6119.
[51] Liu J, Detrembleur C, Gillet M C D P, Mornet S, Duguet E, Jérôme C. Polym. Chem., 2014, 5:799.
[52] Liang X, Kozlovskaya V, Cox C P., Wang Y, Saeed M, Kharlampieva E. Polym. Sci. Part A:Polym. Chem., 2014, 52:2725.
[53] Destarac M, Charmot D, Franck X, Zard S Z. Macromol. Rapid Commun., 2000, 21:1035.
[54] Benaglia M, Chiefari J, Chong Y K, Moad G, Rizzardo E, Thang S H. J. Am. Chem. Soc., 2009, 131, 6914.
[55] Wan D C, Zhou Q, Pu H T, Yang G J. Polym. Sci. Part A:Polym. Chem., 2008, 46:3756.
[56] Tian W, Lv X Y, Huang L B, Ali N, Kong J. Macromol. Chem. Phys., 2012, 213:2450.
[57] 陈卫星(Chen W X), 范晓东(Fan X D), 刘郁杨(Liu Y Y). 高分子材料科学与工程(Polymer Materials Science and Engineering), 2006, 22(6):44.
[58] Tebaldi M L D S, Chaparro T C, Santos A M. Mater. Sci. Forum., 2010, 636/637:76.
[59] Singh P, Srivastava A, Kumar R. Polymer, 2015, 57:51.
[60] Ponce-Vargas S M, Cortez-Lemus N A, Licea-Claveríe A. Macromol. Symp., 2013, 325/326:56.
[61] Shao L D, Hu M Q, Chen L, Xu L, Bi Y M. React. Funct. Polym., 2012, 72:407.
[62] Peng C H, Fryd M, Wayland B B. Macromolecules, 2007, 40:6814.
[63] Debuigne A, Willet N, Jérôme R, Detrembleur C. Macromolecules, 2007, 40:7111.
[64] Debuigne A, Michaux C, Jérôme C, Jérôme R, Poli R, Detrembleur C. Chem. Eur. J., 2008, 14:7623.
[65] Yusa S I, Yamago S, Sugahara M, Morikawa S, Yamamoto T, Morishima Y. Macromolecules, 2007, 40:5907.
[66] Bunck D N, Sorenson G P, Mahanthappa M K. J. Polym. Sci. Part A:Polym. Chem., 2011,49:242.
[67] Liao C M, Hsu C C, Wang F S, Bradford B. Waylandb B B, Peng C H. Polym. Chem., 2013, 4:3098.
[68] Debuigne A, Poli R, Jérôme C, Jérôme R, Detrembleura C. Prog. Polym. Sci., 2009, 34:211.
[69] Hurtgen M, Liu J, Debuigne A, Jérôme C, Detrembleur C. J. Polym. Sci. Part A:Polym. Chem., 2012, 50:400.
[70] Kermagoret A, Fustin C A, Bourguignon M, Detrembleur C, Jérôme C, Debuigne A. Polym. Chem., 2013, 4:2575.
[71] Kermagoret A, Mathieu K, Thomassin J K, Fustin C A, Duchêne R, Jérôme C, Detrembleura C, Debuigne A. Polym. Chem., 2014, 5:6534.
[72] Thomassin J M, Mathieu K, Kermagoret A, Fustin C A, Jérôme C, Debuigne A. Polym. Chem., 2015, 6, 1856.
[73] Jiang X Y, Li Y J, G L, Huang X Y. Polym. Chem., 2013, 4:1402.
[74] Jiang X Y, Lu G L, Feng C, Li Y J, Huang X Y. Polym. Chem., 2013, 4:3876.
[75] 陈忠春(Chen Z C), 唐建斌(Tang J B), 申有青(Shen Y Q), 王新平(Wang X P). 中国科学:化学(Science China Chemistry), 2011, 41(2):281.
[76] Bi Y M, Yan C X, Shao L D, Wang Y F, Ma Y C, Tang G. J. Polym. Sci. Part A:Polym. Chem., 2013, 51:3240.
[77] García-Olaiz G D, Montoya-Villegas K A, Licea-Claverie A, Cortez-Lemus N A. React. Funct. Polym., 2015, 88:16.
[78] Cai T, Li M, Zhang B, Neoh K, Kang E. J. Mater. Chem. B, 2014, 2:814.
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[2] Li Bin, Yu Bo, Ye Qian, Zhou Feng. External Stimuli Regulated Surface-Initiated Atom Transfer Radical Polymerization [J]. Progress in Chemistry, 2015, 27(2/3): 146-156.
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