无皂乳液聚合制备多孔聚苯乙烯纳米微球
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摘要
苯乙烯(St)单体、过硫酸钾(KPS)和二乙烯基苯(DVB)通过无皂乳液聚合,在70℃下反应8 h,合成聚苯乙烯(PS)纳米粒子,PS磺化,得到磺化聚苯乙烯(SPS),通过正庚烷和乙醇溶胀后,水进入粒子内部发生相分离,形成多孔聚苯乙烯PS,在-30 k Pa负压条件下,负载缓蚀剂苯丙三氮唑(BTA)。考察单体量和反应时间对粒子形态的影响。结果表明,采用10 g St,0.05 g KPS,100 mL去离子水,反应2 h后加入0.05 g DVB,可以得到粒径合适、球形完整的PS纳米微球。PS微球磺化6 h,n(乙醇)∶n(水)∶n(正庚烷)=5∶5∶1,造孔10 h时,可得到形貌和孔径合适的多孔SPS纳米微球。SEM、TEM和FTIR表明,多孔SPS微球表面和内部负载上了一定量的缓蚀剂BTA。
Styrene( St) monomer,potassium persulfate( KPS) and divinylbenzene( DVB) were synthesized by soap-free emulsion polymerization at 70 ℃ for 8 h. Porous polymer particles were obtained using sulfonated polystyrene( SPS) particles with heptane as the phase separation agent,in an ethanol/water medium. Under the condition of-30 k Pa pressure loading corrosion inhibitor of benzotriazole( BTA).Investigate the influence of amount of monomer and reaction time on the particle morphology. The results show that the 10 g St,0. 05 g KPS,100 mL of deionized water,add in 0. 05 g DVB after reaction 2 h,can get the PS nanometer microspheres of appropriate particle size and spherical completely. PS microspheres sulfonated 6 h,n( ethanol) ∶ n( water) ∶ n( n-heptane) = 5 ∶ 5 ∶ 1,pore-forming 10 h,can be obtained the porous SPS nanometer microspheres with the appropriate morphology and pore size. SEM,TEM and FTIR showed that surface and internal of the porous SPS microsphere load on a certain amount of corrosion inhibitor BTA.
Styrene( St) monomer,potassium persulfate( KPS) and divinylbenzene( DVB) were synthesized by soap-free emulsion polymerization at 70 ℃ for 8 h. Porous polymer particles were obtained using sulfonated polystyrene( SPS) particles with heptane as the phase separation agent,in an ethanol/water medium. Under the condition of-30 k Pa pressure loading corrosion inhibitor of benzotriazole( BTA).Investigate the influence of amount of monomer and reaction time on the particle morphology. The results show that the 10 g St,0. 05 g KPS,100 mL of deionized water,add in 0. 05 g DVB after reaction 2 h,can get the PS nanometer microspheres of appropriate particle size and spherical completely. PS microspheres sulfonated 6 h,n( ethanol) ∶ n( water) ∶ n( n-heptane) = 5 ∶ 5 ∶ 1,pore-forming 10 h,can be obtained the porous SPS nanometer microspheres with the appropriate morphology and pore size. SEM,TEM and FTIR showed that surface and internal of the porous SPS microsphere load on a certain amount of corrosion inhibitor BTA.
引文
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[4]Okubo M,Ito A,Kanenobu T.Production of submicron sized multihollow polymer particles by alkali/cooling method[J].Colloid and Polymer Science,1996,274:801-804.
[5]Kobayashi H,Miyanaga E,Okubo M.Preparation of multihollow polymer particles by seeded emulsion polymerization using seed particles with incorporated nonionic emulsifier-part CCXCV of the series“studies on suspension and emulsion”[J].Langmuir,2004,23:8703-8708.
[6]Zha T,Song L Y,Chen P P,et al.Nonsolvent/solvent-induced phase separation to multi-porous sulfonated polystyrene/chitosan/silver particles and their application in adsorbing chromium ion(Ⅲ)and reduction of methylene blue[J].Colloids and Surfaces A:Physicochemical and Engineering Aspects,2015,481:423-430.
[7]Gao Q,Wang C,Liu H,et al.Dual nanocomposite multihollow polymer microspheres prepared by suspension polymerization based on a multiple pickering emulsion[J].Polymer Chemistry,2010,1:75-77.
[8]Weng H Q,Huang X F,Wang M Z.Formation of cagelike sulfonated polystyrene microspheres via swelling-osmosis process and loading of Cd S nanoparticles[J].Langmuir,2013,29:15367-15374.
[9]Ge X P,Wang M Z,Wang H,et al.Novel walnut-like multihollow polymer particles:synthesis and morphology control[J].Langmuir,2010,26(3):1635-1641.
[10]李璐,文秀芳,皮丕辉,等.功能型多孔聚合物微球的制备及其缓释性能研究[J].功能材料,2006,37(8):1318-1321.
[11]Ge X P,Ge X W,Wang M Z,et al.A novel approach for preparation of“cagelike”multihollow polymer microspheres through sulfonated polystyrene particles[J].Colloid and Polymer Science,2012,290(17):1749-1757.
[12]Tetsuya Y,Kan K,Yuya T.Particle size control in the soap-free emulsion polymerization of styrene by an oil-soluble initiator with a weakly acidic water-soluble initiator[J].Colloids and Surfaces A:Physicochemical and Engineering Aspects,2016,502:1-5.
[13]Ishii H,Ishii M,Nagao D,et al.Advanced synthesis for monodispersepolymer nanoparticles in aqueous media with sub-millimolar surfactants[J].Polymer,2014,55:2772-2779.
[14]Yamamoto T.Soap-free emulsion polymerization of aromatic vinyl monomerusing AIBN[J].Colloid and Polymer Science,2012,290:1833-1835.
[15]Yamamoto T,Kawaguchik.Effect of electrolyte species on size of particle through soap-free emulsion polymerization of styrene using AIBN and electrolyte[J].Colloid and Polymer Science,2015,293:1003-1006.
[16]Yamamoto T.Effect of the amount ofπelectrons in aromatic monomer on the surface potential of polymeric particles obtained through soap-free emulsion polymerization using AIBN[J].Chemistry Letters,2015,44:1555-1556.
[17]胡欣.羧酸功能化聚苯乙烯微球的制备及其在乳液聚合中的应用[D].合肥:中国科学技术大学,2009.
[18]范欣,范平,吴跃焕.无皂乳液聚合法合成单分散阴离子聚苯乙烯微球[J].山西化工,2014(4):1-3.
[19]朱雯,黄芳婷,董观秀.无皂乳液聚合法制备单分散聚苯乙烯微球[J].功能材料,2012,43(6):775-778.
[20]Gu Z Z,Chen H H,Zhang S,et al.Rapid synthesis of monodisperse polymer spheres for self-assembled photonic crystals[J].Colloids and Surfaces A:Physicochemical and Engineering Aspects,2007,302:312-319.
[21]Yamaday,Sakamoto T,Gu S C,et al.Soap-free synthesis for producing highly monodisperse,micrometer-sized polystyrene particles up to 6 micron[J].Journal of Colloid and Interface Science,2005,281(1):249-252.