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
|
摘要
利用介孔分子筛SBA-15的介孔孔道结构,通过调节引发剂过氧化苯甲酰的用量,在其内部进行了甲基丙烯酸甲酯(MMA)的原位溶液聚合反应,利用X射线衍射、N2吸附-脱附、傅里叶变换红外光谱、凝胶渗透色谱、热重、差示扫描量热等测试手段对所得复合材料及孔道内的聚合物进行研究。结果表明,聚合后,复合材料的比表面积、孔径、孔容降低,但仍保持介孔结构;孔道内聚合物相对分子质量是常规溶液聚合的几十倍,随着引发剂用量的增加,孔道内部聚合的PMMA含量增加,相对分子质量下降,相对分子质量分布变宽,热稳定性提高,玻璃化转变温度降低。
In-situ solution radical polymerization of methyl methacrylate( MMA) was carried out in the channels of mesoporous SBA-15. PMMA /SBA-15 composite and polymers in the channels were characterized by XRD,N2adsorption-desorption,FT-IR,GPC,TGA and DSC. The results show that,compared with SBA-15,the surface areas,pore size and pore volume of the composites decrease,the composites retain mesoporous structures. The molecular weight of PMMA in pores is over 10 times than of one prepared without SBA-15. As increase of the initiator content,it produces higher content of PMMA in the channels,lower molecular weight,broader molecular weight distribution,higher thermal stability,and lower glass transition temperature of the polymer.
In-situ solution radical polymerization of methyl methacrylate( MMA) was carried out in the channels of mesoporous SBA-15. PMMA /SBA-15 composite and polymers in the channels were characterized by XRD,N2adsorption-desorption,FT-IR,GPC,TGA and DSC. The results show that,compared with SBA-15,the surface areas,pore size and pore volume of the composites decrease,the composites retain mesoporous structures. The molecular weight of PMMA in pores is over 10 times than of one prepared without SBA-15. As increase of the initiator content,it produces higher content of PMMA in the channels,lower molecular weight,broader molecular weight distribution,higher thermal stability,and lower glass transition temperature of the polymer.
引文
[1]闫继娜,施剑林,陈航榕,等.纳米介孔材料的催化应用前景[J].无机材料学报,2003,18(4):725-730.Yan J N,Shi J L,Chen H R,et al.Catalytic applied prospect of mesoporous materials[J].Journal of Inorganic Materials,2003,18(4):725-730.
[2]Hong C Y,Li X,Pan C Y.Fabrication of smart nanocontainers with a mesoporous core and a pH-responsive shell for controlled uptake and release[J].J.Mater.Chem.,2009,19(29):5155-5160.
[3]Zhang Y B,Qian X F.Preparation of polystyrene core-mesoporous silica nanoparticles shell composite[J].Mater.Lett.,2004,58(1-2):222-225.
[4]Zhou Z Y,Zhu S M,Zhang D.Synthesis of multifunctional nanocomposites based on highly ordered mesoporous silica[J].Chem.Lett.,2006,35(6):618-619.
[5]Pattantyus-Abraham A G,Wolf M O.A PPV/MCM-41 composite material[J].Chem.Mater.,2004,16(11):2180-2186.
[6]Li X,Hong C Y,Pan C Y.Preparation and characterization of hyperbranched polymer grafted mesoporous silica nanoparticles via self-condensing atom transfer radical vinyl polymerization[J].Polymer,2010,51(1):92-99.
[7]张发爱,宋程,余彩莉.介孔材料孔道内进行的自由基聚合反应研究进展[J].高分子通报,2011(2):73-77.Zhang F A,Song C,Yu C L.The progress of the free radical polymerizations in the channel of mesoporous molecular sieve[J].Polymer Bulletin,2011(2):73-77.
[8]魏志波,白蕊,张发爱.甲基丙烯酸甲酯在改性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 channel of modified SBA-15[J].Acta Polymerica Sinica,2013(7):849-855.
[9]Das S K,Bhunia M K,Bhaumik A.Highly ordered Ti-SBA-15:Efficient H2adsorbent and photocatalyst for eco-toxic dye degradation[J].J.Solid State Chem.,2010,183(6):1326-1333.
[10]Krishnan R,Srinivasan K S V.Synthesis and characterization of amphiphilic block copolymers of methyl methacrylate with poly(ethylene oxide)macroinitiators formed by atom transfer radical polymerization[J].J.Appl.Polym.Sci.,2005,97(3):989-1000.
[11]Cai J,Chen T,Wang G Z,et al.The study on the reverse atom transfer radical polymerization of MMA catalyzed by acetylacetonate cobolt(II)complex supported by ionic liquid[J].Adv.Mater.Res.,2012,476-478:2188-2192.
[2]Hong C Y,Li X,Pan C Y.Fabrication of smart nanocontainers with a mesoporous core and a pH-responsive shell for controlled uptake and release[J].J.Mater.Chem.,2009,19(29):5155-5160.
[3]Zhang Y B,Qian X F.Preparation of polystyrene core-mesoporous silica nanoparticles shell composite[J].Mater.Lett.,2004,58(1-2):222-225.
[4]Zhou Z Y,Zhu S M,Zhang D.Synthesis of multifunctional nanocomposites based on highly ordered mesoporous silica[J].Chem.Lett.,2006,35(6):618-619.
[5]Pattantyus-Abraham A G,Wolf M O.A PPV/MCM-41 composite material[J].Chem.Mater.,2004,16(11):2180-2186.
[6]Li X,Hong C Y,Pan C Y.Preparation and characterization of hyperbranched polymer grafted mesoporous silica nanoparticles via self-condensing atom transfer radical vinyl polymerization[J].Polymer,2010,51(1):92-99.
[7]张发爱,宋程,余彩莉.介孔材料孔道内进行的自由基聚合反应研究进展[J].高分子通报,2011(2):73-77.Zhang F A,Song C,Yu C L.The progress of the free radical polymerizations in the channel of mesoporous molecular sieve[J].Polymer Bulletin,2011(2):73-77.
[8]魏志波,白蕊,张发爱.甲基丙烯酸甲酯在改性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 channel of modified SBA-15[J].Acta Polymerica Sinica,2013(7):849-855.
[9]Das S K,Bhunia M K,Bhaumik A.Highly ordered Ti-SBA-15:Efficient H2adsorbent and photocatalyst for eco-toxic dye degradation[J].J.Solid State Chem.,2010,183(6):1326-1333.
[10]Krishnan R,Srinivasan K S V.Synthesis and characterization of amphiphilic block copolymers of methyl methacrylate with poly(ethylene oxide)macroinitiators formed by atom transfer radical polymerization[J].J.Appl.Polym.Sci.,2005,97(3):989-1000.
[11]Cai J,Chen T,Wang G Z,et al.The study on the reverse atom transfer radical polymerization of MMA catalyzed by acetylacetonate cobolt(II)complex supported by ionic liquid[J].Adv.Mater.Res.,2012,476-478:2188-2192.