超支化聚缩水甘油的合成及性能  

Synthesis and Properties of Hyperbranched Polyglycidol

作　　者：王宗胜 李少路[2,3] 张克明 胡云霞 WANG Zongsheng;LI Shaolu;ZHANG Keming;HU Yunxia(School of Environmental and Chemical Engineering,Tianjin Polytechnic University,Tianjin 300389,China;School of Material Science and Engineering,Tianjin Polytechnic University,Tianjin 300389,China;State Key Laboratory of Separation Membranes and Membrane Processes,Tianjin Polytechnic University,Tianjin 300389,China)

机构地区：[1]天津工业大学环境与化学工程学院,天津300389 [2]天津工业大学材料科学与工程学院,天津300389 [3]天津工业大学分离膜与膜过程国家重点实验室,天津300389

出　　处：《功能高分子学报》2019年第4期507-512,共6页Journal of Functional Polymers

基　　金：国家自然科学基金委面上项目(21476249);天津市科技发展计划(17PTSYJC00060)

摘　　要：以三羟甲基丙烷为引发剂、缩水甘油(2,3-环氧-1-丙醇)为单体、无水N-甲基吡咯烷酮(NMP)为溶剂,采用阴离子开环聚合、一步法制备了超支化聚缩水甘油(hPG)。通过调控单体与引发剂的物质的量之比,成功合成了3种不同数均分子量的hPG;通过核磁共振氢谱、凝胶渗透色谱、傅里叶红外光谱等表征了hPG的支化结构、分子量及分布、化学官能团;采用差示扫描量热仪、热重分析仪、粒径-电位分析仪等分析了hPG的玻璃化转变温度(Tg)、热降解温度(Td)及热稳定性和溶液性质等参数。结果表明,溶剂NMP的引入有利于hPG数均分子量的快速增加和单分散性的提升;hPG的Tg和Td随着数均分子量的增加略有增加。Hyperbranched polyglycerol(hPG)with controlled molecular weight and narrow polydispersity has been synthesized by one-step anionic ring-opening polymerization(ROP)reaction,in which monomer glycidol(2,3-epoxy-1-propanol)was added dropwise to the mixture solution of timethylolpropane(TMP)initiator,potassium tert-butoxide(K-t-OBu)base,and anhydrous N-methylpyrrolidone solvent,for the prevention of cyclized byproduct.hPGs with three different molecular weights were synthesized through tailoring the molar ratio of initiator to monomer.Various techniques including 1H-NMR,inverse gated(IG)NMR spectroscopy,gel permeation chromatography(GPC)and Fourier transform infrared spectroscopy(FT-IR),were employed to characterize the chemical structure,degree of branching(DB),molecular weight and polydispersity of the synthesized hPG.Differential scanning calorimetry(DSC),thermogravimetric(TG),analyzer particle size and Zeta analyzer were used to analyze their glass transition temperature(Tg),thermal stability and solution properties,respectively.Results demonstrate that three hPGs were synthesized with targeted molecular mass(1.5×10^3,4.6×10^3,11.2×10^3)and polydispersities in the range of 1.82-2.05.Importantly,the solvent N-methylpyrrolidone could rapidly increase the molecular weight of hPG during the reaction and improve its mono-dispersity compared to the non-solvent system.Moreover,the glass transition temperature(Tg)and thermal degradation temperature(Td)of hPG were increased slightly with the increasing molecular weight from 1.5×10^3 to 11.2×10^3.

关 键 词：超支化 聚缩水甘油 阴离子开环聚合 分散指数 玻璃化转变温度 

分 类 号：TQ35[化学工程]