ATRP技术用于热敏性高聚物在硅胶表面的接枝

THE GRAFTING OF THERMOSENSITIVE POLYMER ONTO SUPERFINE SILICA SURFACE BY ATOM TRANSFER RADICAL POLYMERIZATION

在超细硅胶表面引入原子转移自由基聚合(ATRP)的引发基团,通过ATRP技术使N-异丙基丙烯酰胺(NIPAM)在硅胶表面接枝聚合,合成得到了具有温敏性的核-壳复合微粒.通过FTIR,TG,EA,SEM,DSC等分析方法对接枝前后的复合粒子进行了分析与表征,结果证明聚N-异丙基丙烯酰胺(PNIPAM)接在了硅胶表面.TG分析得出PNIPAM在硅胶表面的接枝率达到25.2%;DSC分析表明复合硅胶具有温度敏感性,在34.1℃时发生相转变行为;GPC分析得出从复合硅胶表面"劈下"的聚合物PNIPAM的数均分子量约为8000,分子量分布为1.06.复合微粒表面均匀平坦,显示出活性聚合的优越性.

In order to obtain homogeneous,smooth and size controllable layers of thermosensitive polymer on superfine silica particles,a novel synthetic route was developed.The thermosentive polymer,poly（N-isopro-pylacrylamide）（PNIPAM）,has successfully been grafted onto the surface of superfine silica particles.The synthetic procedure includes the connection of silane coupling agent γ-glycidylpropyltrimethoxysilane（KH-560） with the superfine silica particles,reaction of diethanolamine with glycidyl group of KH-560,and reaction of 2-bromoisobutyryl bromide with resulting hydroxy groups respectively,and finally the ATRP reaction of N-isopropylacrylamide grafting on the superfine silica particle surface.The ATRP was carried out at room temperature in the present of CuCl as a catalyst,ME6TREN as a Ligand,and（50∶50,V/V） DMF/H2O as a reaction medium.The resultant composite particles afforded a core-shell structure.The composites particles were characterized by FTIR,TG,EA,SEM,DSC.The weight losses in TG analysis showed that γ-glycidylpropyltrimethoxysilane,diethanolamine,2-bromoisobutyryl bromide and PNIPAM attached to the silica particles step by step according to the designed route.The grafting ratio of PNIPAM on the surface of silica particles reached to 25.2% based on the superfine silica.The diagram of DSC indicated the composite silica particle was thermosensitive with LCST of 34.1℃.The GPC measurements for the PNIPAM cleaved from the composite silica particles gave an average molecular weight of 8000,and the molecular weight distribution of 1.06.The SEM images revealed that the modified composite particles had smooth surface,displaying the superiority of active polymerization of ATRP.The results showed that the grafting ratio in this method was higher than that of other methods,the thermosentive polymer on the surface of superfine silica particles formed a homogeneous,smooth and flat layer film,and the modified superfine silica particles will potentially have applications in HPLC.