ATRP/RAFT联用制备星型多臂共聚物h-PCMS-g-PMMA-b-PBMA
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摘要
以4-氯甲基苯乙烯(CMS)为单体,CuCl/2,2′-联吡啶(bpy)为催化体系,通过原子转移自由基聚合反应(ATRP)制得超支化聚4-氯甲基苯乙烯(h-PCMS);再采用黄原酸钾对h-PCMS表面的功能端基进行修饰,制得端基带有大量双硫酯基团的大分子链转移剂(h-PCMS macro-CTA);通过可逆加成-断裂链转移聚合(RAFT)方法,以h-PCMS macro-CTA依次引发甲基丙烯酸甲酯(MMA)和甲基丙烯酸丁酯(BMA)聚合制备星型多臂聚合物h-PCMS_(2300)-g-PMMA_(5500)-b-PBMA_(33000),分子量分布为1.6,其结构和性能经~1H NMR, IR, GPC和DSC表征。
Hyperbranched poly(4-chloromethyl styrene)(h-PCMS) was prepared by atom transfer radical polymerization(ATRP), using 4-chloromethyl styrene(CMS) as monomer, CuCl/2,2′-bipyridine(bpy) as catalyst system. The functional terminal group of h-PCMS was modified by potassium xanthate, and a large molecular chain transfer agent, with a large number of dithiol groups, h-PCMS macro-CTA was prepared. By reversible addition fragmentation chain transfer polymerization(RAFT), methyl methacrylate(MMA) and butyl methacrylate(BMA) were polymerized successively to afford multi-armed star-like polymer h-PCMS_(2300)-g-PMMA_(5500)-b-PBMA_(33000), the molecular weight distribution is about 1.6. The polymers were characterized by ~1H NMR, IR, GPC and DSC.
Hyperbranched poly(4-chloromethyl styrene)(h-PCMS) was prepared by atom transfer radical polymerization(ATRP), using 4-chloromethyl styrene(CMS) as monomer, CuCl/2,2′-bipyridine(bpy) as catalyst system. The functional terminal group of h-PCMS was modified by potassium xanthate, and a large molecular chain transfer agent, with a large number of dithiol groups, h-PCMS macro-CTA was prepared. By reversible addition fragmentation chain transfer polymerization(RAFT), methyl methacrylate(MMA) and butyl methacrylate(BMA) were polymerized successively to afford multi-armed star-like polymer h-PCMS_(2300)-g-PMMA_(5500)-b-PBMA_(33000), the molecular weight distribution is about 1.6. The polymers were characterized by ~1H NMR, IR, GPC and DSC.
引文
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[3] 欧阳春平,王瑀,赵顺新,等.八臂星形共聚物8-PLGA的合成[J].合成化学,2012,20(5):620-622.
[4] SHI Y,GRAFF R W,CAO X,et al.Chain-growth click polymerization of AB2 monomers for the formation of hyperbranched polymers with low polydispersities in a one-pot process[J].Angewandte Chemie International Edition,2015,54(26):7631.
[5] AMIN A,AHMED E H,SABAA M W,et al.Preparation and evaluation of hyperbranched p-chloromethyl styrene polymers/montmorillonite clay nanocomposites as dielectric materials[J].Polymer Bulletin,2016,73(1):147-162.
[6] 钟玲.超支化多臂星型嵌段共聚物的RAFT合成及其自组装行为研究[D].上海:上海交通大学,2008.
[7] 张士福,罗宁,曾光新.原子转移自由基偶联法合成星形聚合物[J].合成橡胶工业,1999,22(3):155-158.
[8] YOU Y Z,HONG C Y,PAN C Y,et al.Synthesis of a dendritic core-shell nanostructure with a temperature-sensitive shell[J].Advanced Materials,2004,16(21):1953-1957.
[9] LIU C,ZHANG Y,HUANG J L.Well-defined star polymers with mixed-arms by sequential polymerization of atom transfer radical polymerization and reverse addition-fragmentation chain transfer on a hyperbranched polyglycerol core[J].Macromolecules,2008,41:325-331.
[10] 姚军善,赵庸,张勇林,等.借助ATRP法合成两亲性星型多臂h-PCMS-g-mPEG接枝共聚物[J].现代化工,2014,34(5):108-112.
[11] HOU J,YAN D Y.Synthesis of a star-shaped copolymer with a hyperbranched poly(3-methyl-3-oxetanemethanol) core and tetrahydrofuran arms by one-pot copolymerization[J].Macromolecular Rapid Communications,2015,23(8):456-459.
[12] WANG A,XU H,ZHOU Q,et al.A New all-solid-state hyperbranched star polymer electrolyte for lithium ion batteries:Synthesis and electrochemical properties[J].ElectrochimicaActa,2016,212:372-379.
[13] WANG A,XU H,LIU X,et al.The synthesis of a hyperbranched star polymeric ionic liquid and its application in a polymer electrolyte[J].Polymer Chemistry,2017,8(20):3177-3185.