复杂聚合物链结构的可控制备与新材料

doi:10.3969/j.issn.0438-1157.2013.02.004

摘要/Abstract

摘要： 自由基聚合与配位聚合的产物通常为宽分子量分布的均聚物或无规共聚物。近二十年来,活性/可控自由基聚合、活性/可控配位聚合、链穿梭聚合的研究取得突破。这些方法使得几乎所有的乙烯基单体,特别是廉价易得的单体,都可用作原料来制备原来无法制备得到的两嵌段、多嵌段共聚物、梯度共聚物等更为复杂聚合链结构。合理设计这些复杂的链结构,有望得到高性能、高附加值合成材料。介绍了这些新型聚合原理的机理、新进展,讨论了它们潜在的应用前景。

关键词: 活性/可控自由基聚合, 活性配位聚合, 穿梭聚合, 嵌段共聚物

Abstract: The product from free radical and coordination polymerization generally are homopolymer or random copolymer with broad molecular weight distribution.In the past two decades, the breakthroughs in controlled/living radical and coordination polymerization and shuttling polymerization make it possible to use almost all vinyl monomers, particularly those cheap monomers, to produce more complex chain structures like di-, tri-block copolymer and gradient copolymers.With rational design, these copolymers might be high performance and high added value synthetic materials.The mechanisms and the up-to-date progress of these polymerization methods were introduced, and their possible applications were discussed.

Key words: controlled/living radical polymerization, living coordination polymerization, shuttling polymerization, block copolymer

中图分类号:

TQ31

罗英武. 复杂聚合物链结构的可控制备与新材料[J]. 化工学报, 2013, 64(2): 415-426.

LUO Yingwu. Controllable preparation of complex polymer chains and novel materials[J]. CIESC Journal, 2013, 64(2): 415-426.

参考文献 71

[1]	Barghoorn P, Stebani U, Balsam M.Trends in applied polymer chemistry 1997[J].Adv.Mater., 1998, 10(9):635-641
[2]	Pan Zuren(潘祖仁).Polymer Chemistry(高分子化学)[M].4th ed.Beijing:Chemical Industry Press, 2007
[3]	Szwarc M, Milkovich R, Levy M.Polymerization initiated by electron transfer to monomer:a new method of formation of block polymers[J].J.Amer.Chem.Soc., 1956, 78:2656-2657
[4]	Miymoto M, Sawamoto M, Higashimura T.Living polymerizaiton of isobutyl vinyl ether with hydrogen iodide/iodine initiating system[J].Macromolecules, 1984, 17:265-268
[5]	Mitani M, Nakano T, Fujita T.Unprecedented living olefin polymerization derived from an attractive interaction between a ligand and a growing polymer chain[J].Chem.Eur.J., 2003, 9:2396-2403
[6]	Arriola D J, Carnahan E M, Hustad P D, Kuhlman R L, Wenzel T T.Catalytic production of olefin block copolymers via chain shuttling polymerization[J].Science, 2006, 312:714-719
[7]	Georges M K, Veregin R P N, Kazmaier P M, Hamer G K. Narrow molecular weight resins by a free-radical polymerization process[J].Macromolecules,1993, 26:2987-2988
[8]	Wang J S, Matyjaszewski K.Controlled/"living" radical polymerization.Halogen atom transfer radical polymerization promoted by a Cu(Ⅰ)/Cu(Ⅱ)redox process[J].Macromolecules,1995, 28(23):7901-7910
[9]	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.Living free-radical polymerization by reversible addition-fragmentation chain transfer:the RAFT process[J].Macromolecules, 1998, 31:5559-5562
[10]	Qiu J, Charleux B, Matyjaszewski K.Controlled/living radical polymerization in aqueous media:homogeneous and heterogeneous systems[J].Prog.Polym.Sci.,2001, 26:2083-2134
[11]	Cunningham M F.Living/controlled radical polymerizations in dispersed phase systems[J].Prog.Polym.Sci.,2002, 27:1039-1067
[12]	Davis K A, Matyjaszewski K.Statistical, gradient and segmented copolymers by controlled/living radical polymerizations[J].Adv.Polym.Sci.,2002, 159:1-169
[13]	Kamigaito M, Ando T, Sawamto M.Metal-catalyzed living radical polymerization[J].Chem.Rev.,2001,101:3689-3745
[14]	Goto A, Fukuda T.Kinetics of living radical polymerization[J].Prog. Polym.Sci.,2004, 29:329-385
[15]	Hawker C J, Bosman A W, Harth E.New polymer synthesis by nitroxide mediated living radical polymerizations[J].Chem.Rev.,2001, 101:3661-3688
[16]	Matyjaszewski K, Xia J H.Atom transfer radical polymerization[J].Chem.Rev.,2001, 101:2921-2990
[17]	Zetterlund P B, Kagawa Y, Okubo M.Controlled/living radical polymerization in dispersed systems[J].Chem. Rev.,2008, 108:3747-3794
[18]	Edson J, Wang Z, Kramer E J, Coates G W.Fluorinated bis(phenoxyketimine)titanium complexes for the living, isoselective polymerization of propylene:multiblock isotactic polypropylene copolymers via sequential monomer addition[J].J.Am.Chem.Soc.,2008, 130:4968-4977
[19]	Gilbert R G.Emulsion Polymerization:A Mechanistic Approach[M].London:Academic Press, 1995
[20]	Butte A, Storti G, Morbidelli M.Miniemulsion living free radical polymerization by RAFT[J].Macromolecules,2001, 34:5885-5896
[21]	Luo Y, Wang R, Yang L, Yu B, Li B, Zhu Z.Effect of reversible addition-fragmentation transfer(RAFT)reactions on(mini)emulsion polymerization kinetics and estimate of RAFT equilibrium constant[J].Macromolecules,2006, 39:1328-1337
[22]	Yang L, Luo Y, Liu X, Li B.Reversible addition fragmentation transfer(RAFT)polymerization of styrene in a miniemulsion:a mechanistic investigation[J].Polymer, 2009, 50:4334-4342
[23]	Moad G, Rizzardo E, Thang S H. Living radical polymerization by the RAFT process[J]. Austr.J.Chem., 2005, 58:379-410
[24]	Gao J, Luo Y, Wang R, Zhang X, Li B, Zhu S.Effect of monomer composition on apparent chain transfer coefficient irreversible addition fragmentation transfer(RAFT)copolymerization[J].Polymer, 2009, 50:802-809
[25]	Luo Y, Liu X.Reversible addition-fragmentation transfer(RAFT)copolymerization of methyl methacrylate and styrene in miniemulsion[J].J.Polym.Sci.,Part A:Polym.Chem., 2004, 42:6248-6258
[26]	Monteiro M J, Hodgson M, DeBrouwer H.The influence of RAFT on the rates and molecular weight distributions of styrene in seeded emulsion polymerizations[J].J. Polym. Sci., Part A:Polym.Chem.,2006, 44:2837-2847
[27]	Luo Y, Tsavalas J G, Schork F J.Theoretical aspect of particle swelling in 'living' free radical miniemulsion polymerization[J].Macromolecules, 2001, 34:5501-5507
[28]	Luo Y, Cui X.Reversible addition-fragmentation transfer(RAFT)polymerization of methyl methacrylate(MMA)in emulsion[J].J.Polym.Sci.,Part A:Polym.Chem., 2006, 44:2837-2847
[29]	Yang L, Luo Y, Li B.Reversible addition fragmentation transfer(RAFT)polymerization of styrene in a miniemulsion:a mechanistic investigation[J].Polymer, 2006, 47:751-762
[30]	Wang X, Luo Y, Li B, Zhu S.Ab initio batch emulsion RAFT polymerization of styrene mediated by poly(acrylic acid-b-styrene)trithiocarbonate[J].Macromolecules, 2009, 42(17):6414-6421
[31]	Luo Y, Wang X, Li B, Zhu S.Toward well-controlled ab initio RAFT emulsion polymerization of styrene mediated by 2-(((dodecylsulfanyl)carbonothioyl)sulfanyl)propanoic acid[J].Macromolecules,2011, 44:221-229
[32]	Ferguson C J, Hughes R J, Nguyen D, Pham B T T, Gilbert R G, Serelis A K, Such C H, Hawkett B S.Ab initio emulsion polymerization by RAFT-controlled self-assembly[J].Macromolecules, 2005, 38:2191-2204
[33]	Rieger J, Stoffelbach F, Bui C, Alaimo D, Jerome C, Charleux B.Amphiphilic poly(ethylene oxide)macromolecular RAFT agent as a stabilizer and control agent in ab initio batch emulsion polymerization[J].Macromolecules, 2008, 41:4065-4068
[34]	Doi Y, Ueki S, Keii T. "Living" coordination polymerization of propene initiated by the soluble V(acac)3-Al(C2H5)2Cl system[J].Macromolecules, 1979, 12:814-819
[35]	Matsui S, Fujita T.FI catalysts:super active new ethylene polymerization catalysts[J].Catal.Today, 2001, 66:63-73
[36]	Mitani M, Saito J, Ishii S, Nakayama Y, Makio H, Matsukawa N, Matsui S, Mohri J, Furuyama F, Terao H, Bando H, Tanaka H, Fujita T.FI catalysts:new olefin polymerization catalysts for the creation of value-added polymers[J].Chem.Rec., 2004, 4:137-158
[37]	Sakuma A, Weiser M-S, Fujita T.Living olefin polymerization and block copolymer formation with FI catalysts[J].Polym.J., 2007, 39:193-207
[38]	Coates G W, Waymouth R W.Oscillating stereocontrol:a strategy for the synthesis of thermoplastic elastomeric polypropylene[J].Science, 1995, 267:217-219
[39]	Hustad P.Frontiers in olefin polymerization:reinventing the world's most common synthetic polymers[J].Science, 2009,325:704-707
[40]	Bates F S, Hillmyer M A, Lodge T P, Bates C M, Delaney K T, Fredrickson G H.Multiblock polymers:panacea or Pandora's box?[J].Science, 2012, 336:434-440
[41]	Holden G, Legge N R, Schroeder H E, Quirk R P. Thermoplastic Elastomer[M]. Beijing:Chemical Industry Press,2001
[42]	Hustad P D, Kuhlman R L, Arriola D J, Carnahan E M, Wenzel T T.Continuous production of ethylene-based diblock copolymers using coordinative chain transfer polymerization[J].Macromolecules, 2007, 40 :7061-7064
[43]	Luo Y, Wang X, Li B, Zhu S.Polystyrene-block-poly(n-butyl acrylate)-block-polystyrene triblock copolymer thermoplastic elastomer synthesized via RAFT emulsion polymerization[J].Macromolecules,2010, 43:7472-7481
[44]	Argon A S, Cohen R E.Toughenability of polymers[J].Polymer, 2003, 44:6013-6032
[45]	Schierholz J U, Hellmann G P.In situ graft copolymerization:salami morphologies in PMMA/EP blends[J].Polymer,2003, 44:2005-2013
[46]	Hillmyer M A, Lipic P M, Hajduk D A, Almdal K, Bates F S.Self-assembly and polymerization of epoxy resin-amphiphilic block copolymer nanocomposites[J].J. Am. Chem.Soc., 1997, 119:2749-2750
[47]	Ruiz-Pe' rez L, Royston G J, Fairclough P A, Ryan A J.Toughening by nanostructure[J].Polymer, 2008, 49:4475-4488
[48]	Oshinski A J, Keskkula H, Paul D R.The role of matrix molecular weight in rubber toughened nylon 6 blends(Ⅱ):Room temperature Izod impact toughness[J].Polymer,1996, 37:4909-4918
[49]	Knoll K, Niessner N.Styrolux and Styroflex—from transparent high impact polystyrene to new thermoplastic elastomers[J].Macromol.Symp., 1998, 132:231-243
[50]	Pernot H, Baumert M, Court F, Leibler L.Design and properties of co-continuous nanostructured polymers by reactive blending[J].Nat.Mater., 2002, 1:54-58
[51]	Pu G, Luo Y, Wang A, Li B.Tuning polymer blends to cocontinuous morphology by asymmetric diblock copolymers as the surfactants[J].Macromolecules,2011, 44:2934-2943
[52]	Thompson R B, Matsen M W.Improving polymeric microemulsions with block copolymer polydispersity[J].Phys.Rev.Lett., 2000, 85:670-673
[53]	Widin J M, Schmitt A K, Schmitt A L, Im K, Mahanthappa M K.Unexpected consequences of block polydispersity on the self-assembly of ABA triblock copolymers[J].J.Am.Chem.Soc., 2012, 134(8):3834-3844
[54]	Yang S, Yang J A, Kim E S, Jeon G, Oh E J, Choi K Y,Hahn S K, Kim J K.Single-file diffusion of protein drugs through cylindrical nanochannels[J].ACS Nano, 2010, 4:3817-3822
[55]	Ruiz R, Kang H, Detcheverry F A, Dobisz E, Kercher D S, Albrecht T R, de Pablo J J, Nealey P F.Density multiplication and improved lithography by directed block copolymer assembly[J].Science, 2008, 321:936-939
[56]	Jackson E A, Hillmyer M A.Nanoporous membranes derived from block copolymers:from drug delivery to water filtration[J].ACS Nano, 2010, 4:3548-3553
[57]	Peinemann K V, Abetz V,Simon P F W.Asymmetric superstructure formed in a block polymer via phase separation[J].Nature,2007, 6:992-996
[58]	Matyjaszewski K.Architecturally complex polymers with controlled heterogeneity[J].Science, 2011,333:1104-1105
[59]	Wang R, Luo Y, Li B, Sun X, Zhu S.Design and control of copolymer composition distribution in living radical polymerization using semi-batch feeding policies:a model simulation[J].Macromol.Theory Simul.,2006, 15:356-368
[60]	Sun X, Luo Y, Wang R, Li B, Zhu S.Semibatch RAFT polymerization for producing ST/BA copolymers with controlled gradient composition profiles[J].AIChE J.,2008,54:1073-1087
[61]	Sun X, Luo Y, Wang R, Li B, Liu B, Zhu S.Programmed synthesis of copolymer with controlled chain composition profile via semi-batch RAFT copolymerization[J].Macromolecules,2007, 40:849-859
[62]	Zhao Y, Luo Y, Ye C, Li B, Zhu S.Model-based design and synthesis of gradient MMA/tBMA copolymers by computer-programmed semibatch atom transfer radical copolymerization[J].J.Polym.Sci.,Part A:Polym. Chem., 2009, 47:69-79
[63]	Zhao Y, Luo Y, Li B, Zhu S.pH responsivity and micelle formation of gradient copolymers of methacrylic acid and methyl methacrylate in aqueous solution[J].Langmuir,2011:27:11306-11315
[64]	Listak J, Jakubowski W, Mueller L, Plichta A, Matyjaszewski K, Bockstaller M R.Effect of symmetry of molecular weight distribution in block copolymers on formation of "metastable" morphologies[J].Macromolecules,2008, 41:5919-5927
[65]	Lynd N A, Meuler A J, Hillmyer M A.Polydispersity and block copolymer self-assembly[J].Prog. Polym. Sci.,2008,33:875-893
[66]	Li S, Register R A, Landes B G, Hustad P D, Weinhold J D.Crystallization in ordered polydisperse polyolefin diblock copolymers[J].Macromolecules, 2010, 43:4761-4770
[67]	Kim J, Michelle M M, Robert W S, Dong J W,Torkelson J M.Uniquely broad glass transition temperatures of gradient copolymers relative to random and block copolymers containing repulsive comonomers[J].Macromolecules,2006, 39:6152-6160
[68]	Matyjaszewski K, Ziegler M J, Arehart S V, Greszta D, Pakula T.Gradient copolymers by atom transfer radical copolymerization[J].J.Phys.Org.Chem.,2000, 13:775-786
[69]	Mok M M, Kim J, Torkelson J M.Gradient copolymers with broad glass transition temperature regions:design of purely interphase compositions for damping applications[J].J.Polym.Sci.,Part B:Polym.Phy., 2008, 46:48-58
[70]	Wang R, Li W, Luo Y, Li B, Shi A, Zhu S.Phase behavior of ternary homopolymer/gradient copolymer blends[J].Macromolecules, 2009, 42:2275-2285
[71]	Kim J, Gray M K, Zhou H Y, Nguyen S T, Torkelson J M.Polymer blend compatibilization by gradient copolymer addition during melt processing:stabilization of dispersed phase to static coarsening[J].Macromolecules, 2005, 38:1037-1040