聚甲基丙烯酸甲酯改性纳米SiO_2及其Pickering乳液稳定性
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摘要
采用γ-甲基丙烯酰氧基丙基三甲氧基硅烷(MPS)对亲水型纳米SiO_2改性得到了MPS-SiO_2纳米粒子,将MPS-SiO_2纳米粒子进一步通过甲基丙烯酸甲酯(MMA)改性得到了PMMA-SiO_2纳米粒子。傅里叶转换红外光谱分析(FT-IR)和接触角测试表明纳米SiO_2改性成功。以亲水型纳米SiO_2、MPS-SiO_2、PMMA-SiO_2、疏水型纳米SiO_2 4种粒子作为乳化剂制备Pickering乳液,研究了油水比(体积比,全文同)、纳米SiO_2浓度、pH值、盐浓度对Pickering乳液稳定性的影响。结果显示:静置24 h后,油水比为1∶1时,质量分数为1%的亲水型纳米SiO_2、MPS-SiO_2、PMMA-SiO_2制备的乳液剩余体积分数依次为48%、80%、76%,表明2种改性后的纳米SiO_2的乳化性能显著增强;亲水型纳米SiO_2、MPS-SiO_2、PMMA-SiO_2制备的Pickering乳液最佳油水比为1∶1,疏水型纳米SiO_2制备的Pickering乳液最佳油水比为1∶2;4种纳米SiO_2粒子的乳化性能均随着其浓度的增加而增强;与其他3种粒子相比,PMMA-SiO_2制备的Pickering乳液受pH、盐浓度的影响较小。
The γ-methacryloxypropyl-trimethoxysilane(MPS) was used to modify hydrophilic nano-silica to obtain MPS-SiO_2 nanoparticles, and the PMMA-SiO_2 nanoparticles were prepared by further modification of MPS-SiO_2 nanoparticles with methyl methacrylate(MMA). Results of FTIR spectra and contact angle measurement show that the surfaces of hydrophilic nano-silica are successfully grafted with MPS and MMA. In addition, Pickering emulsions were prepared based on hydrophilic nano-silica, MPS-SiO_2, PMMA-SiO_2 and hydrophobic nano-silica, respectively. The effects of the volume ratio of oil to water, the concentration of nano-silica, pH value of aqueous solution and the concentration of NaCl on the stability of Pickering emulsions were investigated. The volume fractions of residual emulsions, of which were placed for 24 h and prepared with a mass fraction of 1% of hydrophilic nano-SiO_2, MPS-SiO_2 and PMMA-SiO_2, are 48%, 80% and 76%, respectively. The results indicate that the emulsifying performance of MPS-SiO_2 and PMMA-SiO_2 are better than that of hydrophilic nano-SiO_2. The optimum volume ratio of oil to water for Pickering emulsions prepared by hydrophilic nano-silica, MPS-SiO_2 and PMMA-SiO_2 are all 1∶1, while for hydrophobic nano-silica, that is 1∶2. Moreover, the emulsification properties of four kinds of nano-silica particles enhance with the increase of their concentrations. Compared with the other three nanoparticles, the stability of Pickering emulsion prepared by PMMA-SiO_2 is less affected by pH and the concentration of NaCl.
The γ-methacryloxypropyl-trimethoxysilane(MPS) was used to modify hydrophilic nano-silica to obtain MPS-SiO_2 nanoparticles, and the PMMA-SiO_2 nanoparticles were prepared by further modification of MPS-SiO_2 nanoparticles with methyl methacrylate(MMA). Results of FTIR spectra and contact angle measurement show that the surfaces of hydrophilic nano-silica are successfully grafted with MPS and MMA. In addition, Pickering emulsions were prepared based on hydrophilic nano-silica, MPS-SiO_2, PMMA-SiO_2 and hydrophobic nano-silica, respectively. The effects of the volume ratio of oil to water, the concentration of nano-silica, pH value of aqueous solution and the concentration of NaCl on the stability of Pickering emulsions were investigated. The volume fractions of residual emulsions, of which were placed for 24 h and prepared with a mass fraction of 1% of hydrophilic nano-SiO_2, MPS-SiO_2 and PMMA-SiO_2, are 48%, 80% and 76%, respectively. The results indicate that the emulsifying performance of MPS-SiO_2 and PMMA-SiO_2 are better than that of hydrophilic nano-SiO_2. The optimum volume ratio of oil to water for Pickering emulsions prepared by hydrophilic nano-silica, MPS-SiO_2 and PMMA-SiO_2 are all 1∶1, while for hydrophobic nano-silica, that is 1∶2. Moreover, the emulsification properties of four kinds of nano-silica particles enhance with the increase of their concentrations. Compared with the other three nanoparticles, the stability of Pickering emulsion prepared by PMMA-SiO_2 is less affected by pH and the concentration of NaCl.
引文
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[22] BRIGGS T R.Emulsions with finely divided solids[J].Industrial and Engineering Chemistry,1921,13(11):1008-1010.
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[24] YANG F,LIU S,XU J,et al.Pickering emulsions stabilized solely by layered double hydroxides particles:The effect of salt on emulsion formation and stability[J].Journal of Colloid and Interface Science,2006,302(1):159-169.
[2] PICKERING S U.Pickering:emulsions[J].Journal of the Chemical Society Transactions,1907,91(23):2001-2021.
[3] 陈博,陈学琴,任军,等.纳米二氧化硅表面改性研究进展[J].有机硅材料,2017,31(5):396-400.
[4] 公绪强,王雅祺,张利.改性纳米二氧化硅增强增韧聚对苯二甲酸丁二醇酯[J].材料导报,2016,30(4):52-56.
[5] YIN J,DENG T,ZHANG G.Preparation and size control of highly monodisperse vinyl functionalized silica spheres[J].Applied Surface Science,2012,258(6):1910-1914.
[6] ABDOLLAHI M ,ROUHANI M ,SALARIZADEH P ,et al.Using fumed silica nanoparticles modified with hydrophilic sulfonated polymers in the proton exchange nanocomposite membranes[J].Polymer Science,2015,57(5):1-8.
[7] GAO X ,CHEN K ,LIANG S ,et al.Effects of raw and poly(propylene oxide) grafted nanosilica on the morphology and thermal and mechanical properties of polyurethane foam[J].Journal of Applied Polymer Science,2015,132(32):42400-42410.
[8] ZHENG J,ZHU R,HE Z,et al.Synthesis and characterization of PMMA/SiO2 nanocomposites by in situ suspension polymerization[J].Journal of Applied Polymer Science,2010,115(4):1975-1981.
[9] ZHANG Q,HUANG W,ZHONG G.Towards transparent PMMA/SiO2 nanocomposites with promising scratch-resistance by manipulation of SiO2 aggregation followed by in situ polymerization[J].Journal of Applied Polymer Science,2016,134(12):44612-44621.
[10] MCCOSH K,KAPILA M,DIXIT R,et al.Continuous improvement inslop-mud treatment technology[J].SPE Drilling & Completion,2009,24(3):418-423.
[11] AGARWAL S,PHUOC T X,SOONG Y,et al.Nanoparticle-stabilized invert emulsion drilling fluids for deep-hole drilling of oil and gas[J].The Canadian Journal of Chemical Engineering,2013(10):1641-1649.
[12] QI D M,BAO Y Z,HUANG Z M,et al.Anchoring of polyacrylate onto silica and formation of polyacrylate/silica nanocomposite particles via in situ emulsion polymerization[J].Colloid and Polymer Science,2008,286(2):233-241.
[13] SUGIMOTO H,DAIMATSU K,NAKANISHI E,et al.Preparation and properties of poly (methylmethacrylate)-silica hybrid materials incorporating reactive silica nanoparticles[J].Polymer,2006,47(11):3754-3759.
[14] ZHANG K,ZHENG L,ZHANG X,et al.Silica-PMMA core-shell and hollow nanospheres[J].Colloids and Surfaces A:Physicochemical and Engineering Aspects,2006,277(1):145-150.
[15] 魏铭,余新光,刘晓芳,等.分散聚合法制备PMMA/SiO2核壳型杂化微球[J].武汉理工大学学报,2010(10):29-32.
[16] ZHOU J,WANG L,QIAO X,et al.Pickering emulsions stabilized by surface-modified Fe3O4 nanoparticles[J].Journal of Colloid and Interface Science,2012,367(1):213-224.
[17] YAN N,GRAY M R,MASLIYAH J H.On water-in-oil emulsions stabilized by fine solids[J].Colloids and Surfaces A:Physicochemical and Engineering Aspects,2001,193(1):97-107.
[18] STILLER S,GERS-BARLAG H,LERGENMUELLER M,et al.Investigation of the stability in emulsions stabilized with different surface modified titanium dioxides[J].Colloids and Surfaces A:Physicochemical and Engineering Aspects,2004,232(2):261-267.
[19] BINKS B P,LUMSDON S O.Effects of oil type and aqueous phase composition on oil-water mixtures containing particles of intermediate hydrophobicity[J].Physical Chemistry Chemical Physics,2000,2(13):2959-2967.
[20] YAN N,MASLIYAH J H.Effect of pH on adsorption and desorption of clay particles at oil-water interface[J].Journal of Colloid and Interface Science,1996,181(1):20-27.
[21] YANG F,NIU Q,LAN Q,et al.Effect of dispersion pH on the formation and stability of Pickering emulsions stabilized by layered double hydroxides particles[J].Journal of Colloid and Interface Science,2007,306(2):285-295.
[22] BRIGGS T R.Emulsions with finely divided solids[J].Industrial and Engineering Chemistry,1921,13(11):1008-1010.
[23] BINKS B P,LUMSDON S O.Stability of oil-in-water emulsions stabilised by silica particles[J].Physical Chemistry Chemical Physics,1999,1(12):3007-3016.
[24] YANG F,LIU S,XU J,et al.Pickering emulsions stabilized solely by layered double hydroxides particles:The effect of salt on emulsion formation and stability[J].Journal of Colloid and Interface Science,2006,302(1):159-169.