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以2,2-二溴甲基-1,3-二溴丙烷(PEBr4)为引发剂,Cu0粉/三(2-二甲氨基乙基)胺(Me6-TREN)为催化体系,在二甲亚砜(DMSO)和H2O的混合溶剂中实现了苯乙烯(St)的单电子转移活性自由基聚合(SETLRP).通过1H NMR和GPC分析表明,所得聚合物为星形结构并具有较窄的分子量分布Mw/Mn=1.20(MGPCn =25.3×103,转化率为42.6%),且聚合物的链端保留了-Br端基.考察了溶剂、反应温度及相转移催化剂对聚合的影响,结果表明,混合溶剂中H2O的体积分数由10%增加至20%导致了聚合速率的降低,表观聚合速率常数(kappP)由0.0264 h-1减小至0.019 7 h-1;升高反应温度、增加催化剂用量以及相转移催化剂的加入分别导致聚合体系的kappP增加,同时,催化剂用量的增加和相转移催化剂的加入使聚合物的分子量分布系数降低.

参考文献

[1] Percec V,Guliashvili T,Ladislaw J S,et al.Ultrafast Synthesis of Ultrahigh Molar Mass Polymers by Metal-Catalyzed Living Radical Polymerization of Acrylates,Methacrylates,and Vinyl Chloride Mediated by SET at 25 ℃[J].J Am Chem Soc,2006,128(43):14156-14165.
[2] Ladislaw J S.Precision Synthesis of Covalent and Supramolecular Polymers[D].Philadelphia:University of Pennsylvania,2008.
[3] Wang W X,Zhang Z B,Zhu J,et al.Single Electron Transfer-Living Radical Polymerization of Methyl Methacrylate in Fluoroalcohol:Dual Control over Molecular Weight and Tacticity[J].J Polym Sci Part A:Polym Chem,2009,47(22):6316-6327.
[4] Rosen B M,Percec V.Single-Electron Transfer and Single-Electron Transfer Degenerative Chain Transfer Living Radical Polymerization[J].Chem Rev,2009,109(11):5069-5119.
[5] Percec V,Popov A V,Ramirez-Castillo E,et al.Aqueous Room Temperature Metal-Catalyzed Living Radical Polymerization of Vinyl Chloride[J].J Am Chem Soc,2002,124(18):4940-4941.
[6] Percec V,Popov A V,Ramirez C E,et al.Living Radical Polymerization of Vinyl Chloride Initiated with Iodoform and Catalyzed by Nascent Cu0/Tris(2-aminoethyl)amine or Polycthyleneimine in Water at 25 ℃ Proceeds by A New Competing Pathways Mechanism[J].J Polym Sci Part A:Polym Chem,2003,41(21):3283-3299.
[7] Percec V,Popov A V,Ramirez C E,et al.Non-transition Metal-Catalyzed Living Radical Polymerization of Vinyl Chloride Initiated with Iodoform in Water at 25 ℃[J].J Polym Sci Part A:Polym Chem,2004,42(24):6267-6282.
[8] Guliashvili T,Percec V.A Comparative Computational Study of The Homolytic and Heterolytic Bond Dissociation Energies Involved in The Activation Step of ATRP and SET-LRP of Vinyl Monomers[J].J Polym Sci Part A:Polym Chem,2007,45(9):1607-1618.
[9] Huang H M,Liu I C,Tsiang R C C.Studies of Hydrodynamic Properties for Characterizing Star-Shaped Poly(ethylene-copropylene[J].Polymer,2005,46(3):955-963.
[10] Zhang X,Xia J H,Matyjaszewski K.End-Functional Poly(tert-butyl acrylate) Star Polymers by Controlled Radical Polymerization[J].Macromolecules,2000,33(7):2340-2345.
[11] HUA Jing,ZHANG Yifeng,CHEN Dianbao.Atom Transfer Radical Polymerization and Synthesis of Novel Polymeric Materials[J].Polym Mater Sci Eng,2002,18(5):21-25(in Chinese).华静,张一峰,陈滇宝.原子转移自由基聚合及其在新型高分子材料合成中的应用[J].高分子材料科学与工程,2002,18(5):21-25.
[12] SUN Jiaying.Synthesis and Analytical Characterization of Four-Arm Star-shaped Polystyrene[D].Chongqing:Chongqing Universtity,2007(in Chinese).孙家英.四臂星形聚苯乙烯的合成及分析表征[D].重庆:重庆大学,2007.
[13] Lligadas G,Percec V.Synthesis of Perfectly Bifunctional Polyacrylates by Single-Electron-Transfer Living Radical Polymerization[J].J Polym Sci Part A:Polym Chem,2007,45(20):4684-4695.
[14] Coelho J F J,Cavalho E Y,Marques D S,et al.Synthesis of Poly(ethyl acrylate) by Single Electron Transfer-Degenerative Chain Transfer Living Radical Polymerization in Water Catalyzed by Na2S2O4[J].J Polym Sci Part A:Polym Chem,2008,46(21):421-432.
[15] Zhang Z B,Wang W X,Xia H D,et al.Single-Electron Transfer Living Radical Polymerization(SET-LRP) of Methyl Methacrylate(MMA) with a Typical RAFT Agent as an Initiator[J].Macromolecules,2009,42(19):7360-7366.
[16] Nguyen N H,Rosen B M,Percec V.SET-LRP of N,N-Dimethylacrylamide and of N-Isopropylacrylamide at 25 ℃ in Protic and in Dipolar Aprotic Solvents[J].J Polym Sci Part A:Polym Chem,2010,48(8):1752-1763.
[17] YANG Cui.Synthesis of Acrylamide Polymers by SET-LRP[D].Daqing:Northeast Petroleum University,2010(in Chinese).杨翠.单电子转移活性自由基法制备丙烯酰胺类聚合物[D].大庆:东北石油大学,2010.
[18] Ding W,Lv C F,Sun Y,et al.Synthesis of Zwitterionic Polymer by SET-LRP at Room Temperature in Aqueous[J].J Polym Sci Part A:Polym Chem,2011,49(2):432-440.
[19] Michael R W,Carl N U,Michael J M.Synthesis of Linear and 4-Arm Star Block Copolymers of Poly(methyl acrylate-bsolketal acrylate) by SET-LRP at 25 ℃[J].J Polym Sci Part A:Polym Chem,2008,46(18):6346-6357.
[20] Rosen B M,Lligadas G,Hann C,et al.Synthesis of Dendritic Macromolecules Through Divergent Iterative Thio-bromo “Click” Chemistry and SET-LRP[J].J Polym Sci Part A:Polym Chem,2009,47(15):3940-3948.
[21] Ciampolini M,Nardi N.Five-Coordinated High-Spin Complexes of Bivalent Cobalt,Nickel,and Copper with Tris(2-dimethylaminoethyl) amine[J].Inorg Chem,1966,5(1):41-44.
[22] Schurink H B.Pdg ntaerythrityl Bromide and Iodide[J].Org Synth,1937,17:73.
[23] Rosen B M,Jiang X,Wilson C J,et al.The Disproportionation of Cu(Ⅰ)X Mediated by Ligand and Solvent into Cu(0)and Cu(Ⅱ)X2 and Its Implications for SET-LRP[J].J Polym Sci Part A:Polym Chem,2009,47(21):5606-5628.
[24] Nguyen N H,Rosen B M,Lligadas G,et al.Surface-Dependent Kinetics of Cu(0)-Wire-Catalyzed Single-Electron Transfer Living Radical Polymerization of Methyl Acrylate in DMSO at 25 ℃[J].Macrormolecules,2009,42(7):2379-2386.
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