化学类硕士开题报告

非线形结构高分子的合成与自组装研究姓名：葛治伸导师：刘世勇2005.12.9基本思路树枝形/线形嵌段共聚物AB4型星形嵌段聚合物嵌段聚合物胶束催化有机反应简介树枝形/线形嵌段共聚物树枝状大分子的合成方法主要分为收敛法和扩散法，我们采用收敛法合成聚苯醚，将尾部端基转化为RAFT试剂，引发单体聚合。K2CO3,18-C-6monorAB4型星形嵌段共聚物该聚合物同时具有温敏和pH敏感性，主要研究其在不同温度和不同酸碱性条件下的胶束化行为。嵌段聚合物胶束催化有机反应HnNONNmNO2OCCH3O+H2O35oCNO2OH+CH3COOH工作进展一:树枝形/线形嵌段共聚物AIBN,80oC80oC(1)(2)H2O,SSCSCSBrMgNIPAMPyBA,AIBN,80oCNIPAM[G-3]-CH2Br[G-3]-CH2SSCPh[G-3]-PNIPAMn(n=220)[G-3]-PNIPAMn-Pym(n=250,m=2.8)SSCnCONHmCOOOOOOOOOBrOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOSSCnCONHOOOOOOOOOOOOOO987654321/ppma)b)c)12151821Retentiontime/min[G-3]RAFTAgentMw/Mn=1.02[G-3]-PNIPAM220Mw/Mn=1.16[G-3]-PNIPAM250-Py2.8Mw/Mn=1.20a)[G-3]-CH2Brb)[G-3]-CH2SSCphc)[G-3]-PNIPAM2201H-NMR及GPC024681012140204060800.51.01.5Conversion/%Time/hLn([M0]/[Mt])a)203040506070800123451.01.21.41.61.8Mn10-4Conversion/%b)Mw/Mn动力学曲线说明该聚合为活性可控聚合。-7.0-6.5-6.0-5.5-5.0-4.5-4.0-3.540506070[G-3]-PNIPAM220[G-2]-PNIPAM225/mN/mlogC(g/mL)a)由于[G-3]的疏水性大于[G-2]，因此[G-3]-PNIPAM220的CMC小于[G-2]-PNIPAM235。表面张力测CMC组装后的电镜照片11010010000.00.20.40.60.81.0f(Rh)Rh/nm15oC31oCa)152025303540010203040Mw,app×10-6/gmol-1Temperature/oC在32oC以前，聚合物胶束是稳定存在于溶液中的。光散射表征粒径分布及表观分子量随温度的变化152025303540203040506070R/nmTemperature/oCRhRga)1520253035400.70.80.91.01.1Rg/RhTemperature/oCb)当温度从15oC升到32oC时，Rg/Rh值从1.1降到0.71，说明胶束从伸展状态塌缩成一个球体。光散射表征Rg，Rh及Rg/Rh随温度的变化20253035404550405060708090100Transmittence/%Temperature/oC受到疏水性基团[G-3]的影响，PNIPAM的LCST降低到30oC.透过率随温度的变化3604505400244505400.00.10.20.30.40.50.60.70.820oC15oC28oC32oC36oCWavelength/nmFluoresceceIntensity1520253035400.040.080.120.160.20Ie/ImTemperature/oC荧光标记表征胶束表面PNIAPAM链的塌缩过程ZhishenGe,ShizhongLuo,ShiyongLiu,JournalofPolymerScience,PartA:PolymerChemistry,2006,inPressSNOHNOOnOOOOOOSNOHNOOONOOOOOODEAmDEAmDEAmmOBrBrBrBrDEACuCl/Me6TREN工作进展二:AB4型星形嵌段共聚物87654321SNOHNOOnOOOOOOdBrBrBrBrabcppmab+c+d87654321PH=455oCPH=420oCSNOHNOOnONOOOOOODEAmDEAmDEAmmObcdappm(a)(b)(c)(d)abc+dddcCDCl3D2OPH=820oCabab18192021222324252627Mn=54400Mw=68500Mw/Mn=1.26Mn=7400Mw=9000Mw/Mn=1.22Elutiontime(min)大分子引发剂及共聚物的1H-NMR和GPC分别在pH=4和pH=8的条件下测试的透过率随温度的变化15202530354045505560020406080100Transmittence/%Temperature/oCPH=4PH=8pH=4和pH=8时透过率开始下降的温度分别为35oC和30oC152025303540450.30.40.50.60.70.80.91.01.1Temperature/oCScatteringintensity222426283032346080100120140Rh/nmTemperature/oC变温光散射表征胶束随温度的变化pH=4时散射光强随温度的变化pH=8时Rh随温度的变化24681.01.52.02.53.03.54.04.55.05.5ScatteringintensityTime(s)0.350.30.250.20.150.10.050.20.40.60.070.080.090.100.110.120.130.20.40.60.50.60.70.80.91.01.11.20.20.40.60.480.520.560.600.640.680.72Relaxationtime/s1Polymerconcentration/g.L-12fStopped-flow检测pH值从5跳跃到11时不同浓度聚合物胶束化过程24681.62.02.42.83.23.6ScatteringintensityTime/sT2882912942972.302.322.342.362.382.402.422.442882912942970.060.080.100.120.140.162882912942970.520.560.600.64ln(1/1)ln(1/2)Temperature/Kln(1/f)ZhishenGe,ShizhongLuo,ShiyongLiu,TobesubmittedtoMacromolecules用stopped-flow在不同温度下检测pH值跳跃导致胶束化过程工作计划合成其它类型树枝大分（例如水溶性树枝状大分子）来制备树枝形/线形嵌段共聚物进行自组装研究合成聚合度相当的线形PNIPAM-PDEA进行胶束化研究，并与PNIPANM-4PDEA比较开始PNIPAM-PVIM嵌段共聚物胶束催化有机反应的研究谢谢！