改性SBA-15介孔孔道内甲基丙烯酸甲酯的反向原子转移自由基聚合的溶液聚合
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摘要
分别使用硅烷偶联剂KH-151、KH-560、KH-570对介孔材料SBA-15进行改性,以改性前后的介孔材料作为"微反应器",在其内部进行了甲基丙烯酸甲酯(MMA)的反向原子转移自由基聚合(RATRP)。通过X射线衍射、氮气吸附-脱附测试、热重分析、差示扫描量热、凝胶渗透色谱、傅里叶变换红外光谱等手段对所得产物进行了测试表征。结果表明,MMA在改性前后的SBA-15内部聚合成功;聚合后的复合材料仍然保持其SBA-15的母体结构,但比表面积、孔径、孔体积均有所下降;孔道内所得的PMMA较常规RATRP聚合所得的PMMA相对分子质量有所增加,相对分子质量分布变宽,初始热分解温度升高,玻璃化转变温度升高;改性后介孔材料对反应液有更好的吸附能力且对孔道内的MMA的RATRP溶液聚合有更强的孔道限制作用。
Mesoporous SBA-15 was modified with silane coupling agent vinyl-triethoxysilane( KH-151),γ-( 2,3-epoxypropoxy) propy-trimethoxysilane( KH-560),3-methacryloxypropyl-trimethoxysilane( KH-570)( named as M-SBA-15),respectively. Then SBA-15 and M-SBA-15 were served as "microreactor"to carry out the reverse atom transfer radical polymerization( RATRP) of methyl methacrylate( MMA). The products were characterized by XRD,N_2 adsorption/desorption,TG,DSC,GPC and FT-IR. The results demonstrate that the MMA is suuccessfully polymerized in the pores of SBA-15. The mesoporous structures of PMMA/SBA-15 composite materials are maintained,but the regularity decreases. The molecular weights,thermal stability and glass transition temperature( Tg) of the PMMA obtained in the pore are higher than those of the normal PMMA synthesized by RATRP,while the polydispersity indexs are broader. The modified mesoporous SBA-15 exhibits stronger adsorption ability and confined effect than prue SBA-15.
Mesoporous SBA-15 was modified with silane coupling agent vinyl-triethoxysilane( KH-151),γ-( 2,3-epoxypropoxy) propy-trimethoxysilane( KH-560),3-methacryloxypropyl-trimethoxysilane( KH-570)( named as M-SBA-15),respectively. Then SBA-15 and M-SBA-15 were served as "microreactor"to carry out the reverse atom transfer radical polymerization( RATRP) of methyl methacrylate( MMA). The products were characterized by XRD,N_2 adsorption/desorption,TG,DSC,GPC and FT-IR. The results demonstrate that the MMA is suuccessfully polymerized in the pores of SBA-15. The mesoporous structures of PMMA/SBA-15 composite materials are maintained,but the regularity decreases. The molecular weights,thermal stability and glass transition temperature( Tg) of the PMMA obtained in the pore are higher than those of the normal PMMA synthesized by RATRP,while the polydispersity indexs are broader. The modified mesoporous SBA-15 exhibits stronger adsorption ability and confined effect than prue SBA-15.
引文
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[9]Moller K,Bein T,Fischer R X.Entrapment of PMMA polymer strands in micro-and mesoporous materials[J].Chem.Mater.,1998,10:1841-1852.
[2]Moreno J,Sherrington D C.Well-defined mesostructured organic-inorganic hybrid materials via atom transfer radical grafting of oligomethacrylates onto SBA-15 pore surfaces[J].Chem.Mater.,2008,20:4468-4474.
[3]Li C M,Yang J,Wang P Y,et al.An efficient solid acid catalyst:Poly-p-styrenesulfonic acid supported on SBA-15 via surface-initiated ATRP[J].Microporous Mesoporous Mater.,2009,123:228-233.
[4]魏志波,白蕊,张发爱.甲基丙烯酸甲酯在改性介孔分子筛SBA-15孔道中的溶液聚合[J].高分子学报,2013(7):849-855.Wei Z B,Bai R,Zhang F A.MMA solution polymerization in the channels of modified mesoporous molecular sieves SBA-15[J].Acta Polymerica Sinica,2013(7):849-855.
[5]Cao L A,Kruk M.Grafting of polymer brushes from nanopore surface via atom transfer radical polymerization with activators regenerated by electron transfer[J].Polym.Chem.,2010,1:97-101.
[6]魏志波,孙发孟,张发爱.引发剂用量对SBA-15孔道内甲基丙烯酸甲酯溶液聚合的影响[J].高分子材料科学与工程,2014,30(6):29-32.Wei Z B,Sun F M,Zhang F A.Effect of initiator content on methyl methacrylate solution polymerization in the channels of mesoporous SBA-15[J].Polymer Materials Science&Engineering,2014,30(6):29-32.
[7]卢嘉春,黄萍,刘志超,等.氟化碳材料氟碳比的红外谱分析[J].材料保护,2013,46(S2):186-187.Lu J C,Huang P,Liu Z C,et al.IR spectral analysis of fluorinecarbon ratio of fluorinated carbon material[J].Materials Protection,2013,46(S2):186-187.
[8]Zetterlund P B.Controlled/living radical polymerization in nanoreactors:compartmentalization effects[J].Polym.Chem.,2011,2:534-549.
[9]Moller K,Bein T,Fischer R X.Entrapment of PMMA polymer strands in micro-and mesoporous materials[J].Chem.Mater.,1998,10:1841-1852.