聚氧化乙烯相对分子质量对聚苯乙烯复合乳粒稳定性的影响
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摘要
为了研究聚氧化乙烯(PEO)表面活性剂对毫米级复合乳粒的稳定机制,在外水相(W2)中引入不同相对分子质量PEO制备聚苯乙烯(PS)复合乳粒,考察其对复合乳粒稳定性的影响。结果表明,随着PEO相对分子质量增大,聚合物流体力学半径增大,空间位阻效应越强,界面强度增大,复合乳粒稳定性增加。此外,PEO水溶液黏度也随着相对分子量增加而增大,复合乳粒在溶液中发生位移或形变时受到的阻力增大,复合乳粒不易发生破裂或聚并。因此,当PEO相对分子质量为100和200 kg×mol~(-1)时,PS复合乳粒稳定性较差;当PEO相对分子质量大于600 kg×mol~(-1)时,PS复合乳粒稳定性较好。此外,还分析了多包覆PS复合乳粒的失稳行为。
In order to investigate the stability mechanism of poly(ethylene oxide)(PEO) in millimeter-scale compound droplets, polystyrene(PS) compound droplets were prepared by adding different molecular weight PEO into external water phase(W2), and the effects of molecular weight was investigated. The experimental results indicate that both hydrodynamic radius and viscosity of PEO aqueous solutions increase with the increase of PEO molecular weight. With the increase of hydrodynamic radius, steric hindrance effects become dominant, while higher viscosity can prevent the change of compound droplet shape to improve stability. Therefore, the stability of PS compound droplets is poor when the relative molecular weights of PEO are 100 kg×mol~(-1) and 200 kg×mol~(-1). When the relative molecular weight is over 600 kg×mol~(-1), PS compound droplets become stable. Moreover, the stability of multi-encapsulated PS compound droplets is also analyzed.
In order to investigate the stability mechanism of poly(ethylene oxide)(PEO) in millimeter-scale compound droplets, polystyrene(PS) compound droplets were prepared by adding different molecular weight PEO into external water phase(W2), and the effects of molecular weight was investigated. The experimental results indicate that both hydrodynamic radius and viscosity of PEO aqueous solutions increase with the increase of PEO molecular weight. With the increase of hydrodynamic radius, steric hindrance effects become dominant, while higher viscosity can prevent the change of compound droplet shape to improve stability. Therefore, the stability of PS compound droplets is poor when the relative molecular weights of PEO are 100 kg×mol~(-1) and 200 kg×mol~(-1). When the relative molecular weight is over 600 kg×mol~(-1), PS compound droplets become stable. Moreover, the stability of multi-encapsulated PS compound droplets is also analyzed.
引文
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[19]李传宪,杨飞,林名桢,等.草桥稠油O/W乳状液的稳定性与流变性研究[J].高校化学工程学报,2008,22(5):755-761.LI C X,YANG F,LIN M Z,et al.Stability and rheological properties of caoqiao heavy Oil-in-Water Emulsions[J].Journal of Chemical Engineering of Chinese Universities,2008,22(5):755-761.
[2]TAYLOR P.Ostwald ripening in emulsions[J].Advances in Colloid and Interface Science,1998,75(2):107-163.
[3]MEZZENGA R,FOLMER B,HUGHES E.Design of double emulsions by osmotic pressure tailoring[J].Langmuir,2004,20(9):3574-3582.
[4]谭伟强,臧渡洋,李云飞,等.SiO2纳米颗粒与聚氧乙烯对Pickering乳液的协同稳定作用[J].高等学校化学学报,2014,35(1):85-91.TAN W Q,ZANG D Y,LI Y F,et al.Synergistic stabilization effect of SiO2 nanoparticles and polyoxyethylene on Pickering emulsion[J].Chemical Journal of Chinese Universities,2014,35(1):85-91.
[5]赵国强,刘红晶,贺高红,等.表面活性剂和高分子增稠剂对W/O/W多重乳液稳定性的影响[C].全国化学工程与生物化工年会论文摘要集,北京:[出版者不详],2004:1073-1074.ZHAO G Q,LIU H J,HE G H,et al.Effects of surfactants and polymer thickeners on the stability of W/O/W multiemulsions[C].Chinese National Chemical and Biochemical Engineering Annual Meeting,Beijing:[s.n.],2004:1073-1074.
[6]刘梅芳,初巧妹,李洁,等.聚丙烯酸相对分子质量对聚苯乙烯复合乳粒形变的影响[J].高分子材料科学与工程,2016,32(12):60-64.LIU M F,CHU Q M,LI J,et al.Influences of poly(acrylic acid)molecular weight on deformation of polystyrene compound droplets[J].Polymer Materials Science and Engineering,2016,32(12):60-64.
[7]LIU M F,ZHENG Y Q,LI J,et al.Effects of molecular weight of PVA on formation,stability and deformation of compound droplets for ICF polymer shells[J].Nuclear Fusion,2017,57(1):016018.
[8]王清清,魏取福,蔡以兵,等.水包油(O/W)型乳液静电纺丝[J].材料导报,2011(s1):228-230.WANG Q Q,WEI Q F,CAI Y B,et al.Water in oil(O/W)emulsion electrospinning[J].Materials Review,2011(s1):228-230.
[9]JOKSIMOVIC R,PRéVOST S,SCHWEINS R,et al.Interactions of silica nanoparticles with poly(ethylene oxide)and poly(acrylic acid):Effect of the polymer molecular weight and of the surface charge[J].Journal of Colloid and Interface Science,2013,394:85-93.
[10]SADTLER V,RONDON-GONZALEZ M,ACREMENT A,et al.PEO-covered nanoparticles by emulsion inversion point(EIP)method[J].Macromolecular Journals,2010,31(11):998-1002.
[11]林畅,贺高红,陈国华,等.石油醚W/O乳状液及其液膜稳定性[J].高校化学工程学报,2004,18(2):92-98.LIN C,HE G H,CHEN G H,et al.Stability of W/O emulsion and its liquid membrane[J].Journal of Chemical Engineering of Chinese Universities,2004,18(2):92-98.
[12]刘红晶,贺高红,林畅,等.W/O/W多重乳液中水传递的控制[J].物理化学学报,2007,23(6):935-939.LIU Hong-jing,HE Gao-hong,LIN Chang,et al.Controlling water transport in W/O/W multiple emulsion[J].Acta Physico-Chimica Sinica,2007,23(6):935-939.
[13]魏慧贤,钟芳,麻建国.初乳乳化工艺对W/O/W型复乳稳定性和药物包埋率的影响研究[J].高校化学工程学报,2008,22(4):659-665.WEI H X,ZHONG F,MA J G.Influences of emulsifying parameters on the stability and drug encapsulation efficiency of W/O/Wmultiple emulsions[J].Journal of Chemical Engineering of Chinese Universities,2008,22(4):659-665.
[14]王军.乳化与微乳化技术[M].北京:化学工业出版社,2012.WANG J.Emulsification and microemulsification[M].Beijing:Chemical Industry Press,2012.
[15]RIEGER J,STOFFELBACH F,BUI C,et al.Amphiphilic poly(ethylene oxide)macromolecular raft agent as a stabilizer and control agent in abinitio batch emulsion polymerization[J].Macromolecules,2008,41(12):4065-4068.
[16]刘文丽,焦纬洲,刘有智,等.W/O/W型多重乳液的稳定性和应用研究进展[J].日用化学工业,2012,42(5):366-370.LIU W L,JIAO W Z,LIU Y Z,et al.Progress in study of stability and application of W/O/W multiple emulsion[J].China Surfactant Detergent and Cosmetics,2012,42(5):366-370.
[17]TADROS T,IZQUIERDO P,ESQUENA J,et al.Formation and stability of nano-emulsions[J].Advances in Colloid and Interface Science,2004,108/109:303-318.
[18]徐乙文,刘会平,陈苓,等.玉米油W1/O/W2型多重乳状液稳定性的研究[J].高校化学工程学报,2012,26(1):175-181.XU Y W,LIU H P,CHEN L,et al.Stability of corn oil W1/O/W2 multiple emulsions[J].Journal of Chemical Engineering of Chinese Universities,2012,26(1):175-181.
[19]李传宪,杨飞,林名桢,等.草桥稠油O/W乳状液的稳定性与流变性研究[J].高校化学工程学报,2008,22(5):755-761.LI C X,YANG F,LIN M Z,et al.Stability and rheological properties of caoqiao heavy Oil-in-Water Emulsions[J].Journal of Chemical Engineering of Chinese Universities,2008,22(5):755-761.