通过酸氧化和酰胺化反应在多壁碳纳米管(MWCNTs)表面引入伯氨基团,再采用表面氧化-还原聚合法在MWCNTs表面接枝甲基丙烯酸甲酯(MMA)。利用红外、拉曼、热失重和透射电镜对产物进行表征,考察了反应时间、引发剂用量和单体用量对接枝率的影响。结果表明:通过伯氨基团和过硫酸铵(APS)所构成的氧化-还原体系可以有效引发MWCNTs表面MMA接枝聚合。在反应时间16h,聚合温度为50℃,APS用量为6mmol/L,MMA为水的5%(质量分数)时,接枝率可达28.6%。改善了MWCNTs在聚偏氟乙烯铸膜液中的分散性。
The surfaces of MWCNTs were treated by acid oxidation and amidation reaction,and MWCNTs-NH2 was prepared.Surface-initiated redox polymerization was constructed for the preparation of MWCNTs grafted poly (methyl methacrylate).FT-IR,Raman,TGA and TEM were applied to characterize the composites respectively.The effects of reaction time,dosage of initiator and monomer concentrations were investigated for optimum reactive condition.The experimental results showed that the grafting polymerization of MMA onto the surface of carbon nanotubes can be effectively initiated by the system-amino group and APS.Under the condition of 16 h reaction time,50℃ of polymerization temperature,6mmol/L of concentration of APS,5wt% of monomer concentration of MMA of the water,grafting percentage can reach 28.6%.The dispersion in PVDF membrane casting solution was improved by grafting polymerization.
[1] Lijima S.Helical microtubules of graphitic carbon[J].Nature,1991,354(6348):56-58.
[2] Forro L,Salvetat J P,Bonard J M,et al.Science and application of nanotubes[M].US:Springer US,2002,297-320.
[3] Lai C Y,Groth A,Gray S,et al.Nanocomposites for improved physical durability of porous PVDF membranes[J].Membranes,2014,4(1):55-78.
[4] Ajayan P M,Stephan O,Colliex C,et al.Aligned carbon nanotube arrays formed by cutting a polymer resin-nanotube composite[J].Science,1994,265(5176):1212-1214.
[5] Sanchez C,Julián B,Belleville P,et al.Applications of hybrid organic-inorganic nanocomposites[J].Journal of Materials Chemistry,2005,15(35-36):3559-3592.
[6] Gao H,Matyjaszewski K.Synthesis of molecular brushes by “grafting onto” method:combination of ATRP and click reactions[J].Journal of the American Chemical Society,2007,129(20):6633-6639.
[7] Johnson J A,Lu Y Y,Burts A O,et al.Drug-loaded,bivalent-bottle-brush polymers by graft-through ROMP[J].Macromolecules,2010,43(24):10326-10335.
[8] Qin S,Qin D,Ford W T,et al.Functionalization of single-walled carbon nanotubes with polystyrene via grafting to and grafting from methods[J].Macromolecules,2004,37(3):752-757.
[9] Klok H A,Genzer J.Expanding the polymer mechanochemistry toolbox through surface-initiated polymerization[J].ACS Macro Letters,2015,4(6):636-639.
[10] Avilés F,Cauich-Rodríguez J V,Moo-Tah L,et al.Evaluation of mild acid oxidation treatments for MWCNT functionalization[J].Carbon,2009,47(13):2970-2975.
[11] Datsyuk V,Kalyva M,Papagelis K,et al.Chemical oxidation of multiwalled carbon nanotubes[J].Carbon,2008,46(6):833-840.
[12] Ramanathan T,Fisher F T,And R S R,et al.Amino-functionalized carbon nanotubes for binding to polymers and biological systems[J].Chemistry of Materials,2005,17(6):1290-1295.
[13] Zhao J,Zhang X,Di J,et al.Double-peak mechanical properties of carbon-nanotube fibers[J].Small,2010,6(22):2612-2617.
[14] 李喜德.新型离子液体聚合物电解质的制备及性能研究[D].长沙:中南大学,2014.
[15] 刘惠,杨海存,叶青,等.凹凸棒石表面接枝γ-氨丙基三乙氧基硅烷[J].硅酸盐学报,2013,41(6):848-853.
基金资助
国家自然科学基金(青年)(21406017);江苏省自然科学基金(青年)(BK20140254);江苏省高校自然科学基金(面上)(14KJB430003)
PDF
(3775KB)
