改性石墨烯/丙烯酸酯乳液的合成与性能研究
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摘要
采用种子乳液聚合法,以甲基丙烯酸甲酯、丙烯酸丁酯、丙烯酸为单体,Tween80磺基琥珀酸二钠、OP-10和脂肪醇聚氧乙烯醚磺基琥珀酸单酯二钠为乳化剂,过硫酸铵、羟甲基丙烯酰胺为引发剂,先后合成出纯丙乳液、油酸-十二烷基硫酸钠改性氧化石墨烯/聚合物乳液和油酸-十二烷基硫酸钠改性石墨烯/聚合物乳液。聚合物乳液的结构和性能分析表明,油酸-十二烷基硫酸钠改性的氧化石墨烯或石墨烯成功地参与了乳液聚合中;改性氧化石墨烯/聚合物乳液或改性石墨烯/聚合物乳液的T_(d5%)和T_(d10%)差别不大,但均比对应的纯丙乳液的耐热性提高近50℃。
The acrylic emulsion,the modified graphene oxide(GO)/acrylic emulsion nanocomposites and the modified graphene(GE)/acrylic emulsion nanocomposites were prepared by the method of pre-emulsification and semi-continuous seed emulsion polymerization,at different proportions of monomers,such as styrene(St),methyl methacrylate(MMA),butyl acrylate(BA) and acrylic acid(AA),with ammonium persulfate(APS) as initiators and N-methylol acrylamide as the cross-linking agent,respectively,supplemented with the compounded emulsifiers.The chemical structure and composition,the microstructure as well as the relevant thermoanalysis are characterized to confirm that the OA-SDS was successfully grafted onto the surface of GO or GE sheets.Furthermore,the corresponding thermal and chemical resistance properties of the acrylic nanocomposites filled with the OA-SDS-GO and OA-SDS-GE nanocomposites were studied and compared with those of neat acrylic emulsion.The TG results revealed that,compared with the neat styrene-acrylic emulsion,the OA-SDS-GO and OA-SDS-GE nanocomposites were more thermally stable,and the 5% and 10% thermal decomposition temperatures under N_2 atmosphere were increased at least 50 ℃.
The acrylic emulsion,the modified graphene oxide(GO)/acrylic emulsion nanocomposites and the modified graphene(GE)/acrylic emulsion nanocomposites were prepared by the method of pre-emulsification and semi-continuous seed emulsion polymerization,at different proportions of monomers,such as styrene(St),methyl methacrylate(MMA),butyl acrylate(BA) and acrylic acid(AA),with ammonium persulfate(APS) as initiators and N-methylol acrylamide as the cross-linking agent,respectively,supplemented with the compounded emulsifiers.The chemical structure and composition,the microstructure as well as the relevant thermoanalysis are characterized to confirm that the OA-SDS was successfully grafted onto the surface of GO or GE sheets.Furthermore,the corresponding thermal and chemical resistance properties of the acrylic nanocomposites filled with the OA-SDS-GO and OA-SDS-GE nanocomposites were studied and compared with those of neat acrylic emulsion.The TG results revealed that,compared with the neat styrene-acrylic emulsion,the OA-SDS-GO and OA-SDS-GE nanocomposites were more thermally stable,and the 5% and 10% thermal decomposition temperatures under N_2 atmosphere were increased at least 50 ℃.
引文
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[2] Wang F,Zhang Y B,Tian C S,et al.Gate-variable optical transitions in graphene[J].Science,2008,320:206-209.
[3] Eda G,Chhowalla M.Graphene-based composite thin films for electronics[J].Nano Letters,2009(9):814-818.
[4] Yang X Y,Zhang X Y,Ma Y F,et al.Superparamagnetic graphene oxide-Fe3O4 nanoparticles hybrid for controlled targeted drug carriers[J].Journal of Materials Chemistry,2009,19:2710-2714.
[5] Wu Z S,Pei S F,Ren W C,et al.Field emission of single-layer graphene films prepared by electrophoretic deposition[J].Advanced Materials,2009(21):1756-1760.
[6] Stankovich S,Dikin D A,Dommett G H B.Graphene-based composite materials[J].Nature,2006,442(7100):282-286.
[7] Frank I W,Tanenbaum D M,Zande A M.Mechanical properties of suspended graphene sheets[J].Journal of Vacuum Science & Technology B,2007(25):2558 -2561.
[8] 杨永岗,陈成猛,温月芳,等.氧化石墨烯及其与聚合物的复合[J].新型炭材料,2008,23(3):193-200.
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[10] Hummer W S,Offeman R E.Preparation of graphitic oxide[J].Journal of the American Chemical Society,1958,80(6):1339-1339.
[11] 张建雨,吴琼华.阴-非离子松香乳化剂的制备和应用[J].广东化工,2010,37(1):27-29.
[12] Gannett W,Erickson E,Erni R,et al.Structural study of graphene oxide (GO) and reduced and annealed graphene oxide (raGO) using aberration-corrected TEM[J].Aps March Meeting,2010,320(4):326-373.
[13] 周英杰,朱海娥,张俊,等.无皂乳液聚合制备含铕荧光共聚物乳液的研究及其表征[J].高分子学报,2012(9):923-927.
[14] Yin G N,Zheng Z,Wang H T,et al.Preparation of graphene oxide coated polystyrene microspheres by Pickering emulsion polymerization[J].Journal of Colloid and Interface Science,2013,394:192-198.
[15] Binks B P.Particles as surfactants-similarities and differences[J].Current Opinion Colloid & Interface Science,2002(7):21-41.