复合包覆无机氧化物中空微球的制备研究
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摘要
核壳结构材料具有不同于核壳单一组分的性质，因而一直是材料领域内的一大研究热点。将核壳材料去核后就得到中空材料，这种中空材料具有特殊的空心结构，表面壳层含有大量的微孔，具有渗透性，在药物可控缓释方面具有巨大的应用潜景。目前以硬模板法制备核壳结构微球采用的多是聚苯乙烯模板，并利用该模板制备出纳米尺度的核壳微球，但对于微米级别核壳微球的制备报道相对较少。
本文采用分散聚合法，成功合成出单分散性聚苯乙烯微球，粒径3～5μm，并制备得到磺化聚苯乙烯模板粒子。以磺化聚苯乙烯微球为模板，乙醇为介质，采用水解钛酸丁酯，二次包覆方法制备了PS／TiO_2核壳结构微球。研究了影响核壳结构微球表面形貌以及中空微球结构的因素，结果表明，当磺化聚苯乙烯用量在30mg，钛酸丁酯用量为1.0ml，水用量为0.5ml时，制备的核壳微球有光滑、均匀的包覆表面。当水解包覆反应时间达到2h后，包覆反应基本结束。通过甲苯溶解和高温煅烧的方式去核，制备出中空TiO_2颗粒，从个别破碎微球断口观察，单次包覆厚度为50nm。
以膦酸化壳聚糖改性后的一次包覆PS／TiO_2粒子为模板，在乙醇中氨解正硅酸乙酯制备出PS／TiO_2／SiO_2复合包覆微球。当氨水和去离子水浓度较低时，形成的核壳微球为部分包覆，表面包覆层较粗糙。当氨水和去离子水浓度增大后，形成的是包覆完整、均匀、平滑表面的核壳微球。分别以甲苯溶蚀和高温煅烧的方法去核得到TiO_2／SiO_2双包覆层复合中空微球。
以膦酸化壳聚糖改性的PS／TiO_2为模板，通过Fe_3O_4纳米粒子自组装吸附和水解钛酸丁酯制备了PS／TiO_2／Fe_3O_4／TiO_2多层包覆微球。甲苯去核后得到了TiO_2／Fe_3O_4／TiO_2复合夹心结构中空粒子。以磺化PS为模板，Fe~(3+)、Fe~(2+)化学共沉淀法制备的包覆微球，微球表面吸附的是Fe_3O_4和Fe(OH)_3混合包覆产物，且只有部分包覆。以Fe~(2+)沉淀法制备的核壳微球，包覆较均匀，表面粗糙。通过磁铁的宏观测试表明，微球都具有良好的磁性能。
Core-Shell structure material is an attractive topic in material areas due to its special nature different from the core or shell single component. Hollow materials are formed by removal of the core by a solvent or heating. Hollow microspheres have widely potential applications as delivery vehicles for the controlled release of drugs, dyes due to their special hollow structure. The surface of the shell contains a lot of microporous, was permeability. Polystyrene spheres are more used as a template to prepare core-shell materials nowadays. And nano-scale core-shell spheres produced, but for micron-level core-shell spheres relatively few reports.
Monodisperse polystyrene microspheres with 3～5μm diameter were synthesized by dispersion polymerization. As sulfonated polystyrene microspheres template, Titania coated polystyrene core-shell spheres produced through hydrolysis Tetrabutyl titanate in ethanol. The influence of Tetrabutyl titanate, deionized water and reaction time on the formation of the core-shell microspheres and hollow microspheres are studied. It revealed that core-shell spheres were smooth and homogeneous surface on the condition of 30mg template, 1.0ml Tetrabutyl titanate and 0.5 ml deionized water. Coating reaction almost finished in 2 hours. The resulting hollow titanium dioxide was obtained by removal of the core with toluene or by calcination. From the individual broken particles fracture observation, a single coating thickness about 50nm.
Using chitosan modified PS/TiO_2 core-shell particles as template, silicon dioxide coating formed onto PS/TiO_2 surface by hydrolysis tetraethyl ortho-silicate in ammonia and composite core-shell spheres prepared. Rough and half coating surface in lower ammonia and deionized water concentration. The integrity, uniform and smooth coating surface produced when ammonia and deionized water concentration increased. Hollow microspheres were made by removing template with toluene and calcination.
With the same PS/TiO_2 particles as a template, PS/TiO_2/Fe_3O_4/TiO_2 multilayer coated microspheres produced through Fe_3O_4 nanoparticles adsorption and hydrolysis of Tetrabutyl titanate in ethanol. TiO_2/Fe_3O_4/TiO_2 composite sandwich structure hollow particles obtained when removing cores. Ferrous and ferric as raw materials, magnetic coating spheres prepared by chemical coprecipitation method. It revealed that both Fe_3O_4 and Fe(OH)_3 composite coating formed. The more homogeneous and rough surface core-shell microspheres obtained using ferrous as material by precipitation method. Magnet macro tests showed that these microspheres are good magnetic properties.
本文采用分散聚合法，成功合成出单分散性聚苯乙烯微球，粒径3～5μm，并制备得到磺化聚苯乙烯模板粒子。以磺化聚苯乙烯微球为模板，乙醇为介质，采用水解钛酸丁酯，二次包覆方法制备了PS／TiO_2核壳结构微球。研究了影响核壳结构微球表面形貌以及中空微球结构的因素，结果表明，当磺化聚苯乙烯用量在30mg，钛酸丁酯用量为1.0ml，水用量为0.5ml时，制备的核壳微球有光滑、均匀的包覆表面。当水解包覆反应时间达到2h后，包覆反应基本结束。通过甲苯溶解和高温煅烧的方式去核，制备出中空TiO_2颗粒，从个别破碎微球断口观察，单次包覆厚度为50nm。
以膦酸化壳聚糖改性后的一次包覆PS／TiO_2粒子为模板，在乙醇中氨解正硅酸乙酯制备出PS／TiO_2／SiO_2复合包覆微球。当氨水和去离子水浓度较低时，形成的核壳微球为部分包覆，表面包覆层较粗糙。当氨水和去离子水浓度增大后，形成的是包覆完整、均匀、平滑表面的核壳微球。分别以甲苯溶蚀和高温煅烧的方法去核得到TiO_2／SiO_2双包覆层复合中空微球。
以膦酸化壳聚糖改性的PS／TiO_2为模板，通过Fe_3O_4纳米粒子自组装吸附和水解钛酸丁酯制备了PS／TiO_2／Fe_3O_4／TiO_2多层包覆微球。甲苯去核后得到了TiO_2／Fe_3O_4／TiO_2复合夹心结构中空粒子。以磺化PS为模板，Fe~(3+)、Fe~(2+)化学共沉淀法制备的包覆微球，微球表面吸附的是Fe_3O_4和Fe(OH)_3混合包覆产物，且只有部分包覆。以Fe~(2+)沉淀法制备的核壳微球，包覆较均匀，表面粗糙。通过磁铁的宏观测试表明，微球都具有良好的磁性能。
Core-Shell structure material is an attractive topic in material areas due to its special nature different from the core or shell single component. Hollow materials are formed by removal of the core by a solvent or heating. Hollow microspheres have widely potential applications as delivery vehicles for the controlled release of drugs, dyes due to their special hollow structure. The surface of the shell contains a lot of microporous, was permeability. Polystyrene spheres are more used as a template to prepare core-shell materials nowadays. And nano-scale core-shell spheres produced, but for micron-level core-shell spheres relatively few reports.
Monodisperse polystyrene microspheres with 3～5μm diameter were synthesized by dispersion polymerization. As sulfonated polystyrene microspheres template, Titania coated polystyrene core-shell spheres produced through hydrolysis Tetrabutyl titanate in ethanol. The influence of Tetrabutyl titanate, deionized water and reaction time on the formation of the core-shell microspheres and hollow microspheres are studied. It revealed that core-shell spheres were smooth and homogeneous surface on the condition of 30mg template, 1.0ml Tetrabutyl titanate and 0.5 ml deionized water. Coating reaction almost finished in 2 hours. The resulting hollow titanium dioxide was obtained by removal of the core with toluene or by calcination. From the individual broken particles fracture observation, a single coating thickness about 50nm.
Using chitosan modified PS/TiO_2 core-shell particles as template, silicon dioxide coating formed onto PS/TiO_2 surface by hydrolysis tetraethyl ortho-silicate in ammonia and composite core-shell spheres prepared. Rough and half coating surface in lower ammonia and deionized water concentration. The integrity, uniform and smooth coating surface produced when ammonia and deionized water concentration increased. Hollow microspheres were made by removing template with toluene and calcination.
With the same PS/TiO_2 particles as a template, PS/TiO_2/Fe_3O_4/TiO_2 multilayer coated microspheres produced through Fe_3O_4 nanoparticles adsorption and hydrolysis of Tetrabutyl titanate in ethanol. TiO_2/Fe_3O_4/TiO_2 composite sandwich structure hollow particles obtained when removing cores. Ferrous and ferric as raw materials, magnetic coating spheres prepared by chemical coprecipitation method. It revealed that both Fe_3O_4 and Fe(OH)_3 composite coating formed. The more homogeneous and rough surface core-shell microspheres obtained using ferrous as material by precipitation method. Magnet macro tests showed that these microspheres are good magnetic properties.
引文
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[2] Straight S D, Bosworth J K. Polym Mater Sci & Engi, 2003,88,3391
[3] Donath E, Moya S. Chem- Eur J ,2002,8,5481
[4] Hubert D H W, Jung M, Frederik P M, et al. Vesicle-Directed Growth of Silica. Adv Mater., 2000,12 (17) :1286-1290
[5] Tissot I, Novat C, Lefebvre F, etal. Hybrid Latex Particles Coated with Silica. Macromolecules. 2001,34(17):5737-5739
[6] Xing-Cai Guo , Peng Dong..Multistep Coating of Thick Titania Layers on Monodisperse Silica Nanospheres. Langmuir 1999, 15, 5535-5540
[7] Guo, H x, Zhao, X p, Guo, H 1, et al. Preparation of Porous SiO_2/Ni/TiO_2 Multicoated Microspheres Responsive to Electric and Magnetic Fields. Langmuir, 2003, 19(23): 9799-9803
[8] 杨伏勇．以SiO_2粒子为模板合成功能性核壳材料．[东北师范大学硕士学位论文]．2006
[9] 答鸿，朱以华．核-壳式单分散二氧化硅磁性微球的制备．无机材料学报，2002，17(4)：867-871
[10] Zhu-Zhu Li, Li-Xiong Wen, Lei Shao et al. Fabrication of porous hollow silica nanoparticles and their applications in drug release control .Controlled Release, 2004, 98:245-254
[11] J Chen, J Wang, R Liu ,et al. Synthesis of porous silica structures with hollow interiors by templating nanosized calcium carbonate .Inorg. Chem. Commun., 2004,7 : 447-449
[12] Averitt R D, Sarkar D, Halas N J. Plasmon Resonance Shifts of Au-Coated SiO2 Nanoshells Insight into Multicomponent Nanoparticle Growth, Phys. Rev. Lett., 1997, 78:4217-4220
[13] 夏大学. Ag@TiO_2核壳结构纳米颗粒的制备及其表征. [武汉理工大学硕士论文]. 2005
[14] Alfrey T, Bradford E B, Vanderhoff J W. Optical properties of uniform particle-size latexes. J Opt Soc Am, 1954, 44:603-609
[15] Peng Suilil, Wei Jianhong, Shi Jing, et al. The Synthesis and Electrorheological Properties of BaTiO_3-coated PMMA Microspheres. Journal of Wuhan University of Technology-Mater. Sci. Ed. 2007, 20(1):85-87
[16] C X Song, G H Gu, Y S Lin, et al. Preparation and characterization of CdS hollow spheres. Materials Research Bulletin, 2003,38:917-924
[17] 刘继进，陈宗璋，何莉萍．纳米氧化钛的制备、表征及应用研究．功能材料，2002，33(6)：658—660
[18] Imhof. A. Preparation and Characterization of Titania-Coated Polystyrene Spheres and Hollow Titania Shells. Langrnuir 2001, 17, 3579-3585
[19] Caruso.R A, Susha. A, Caruso. F. Multilayered Titania, Silica, and Laponite Nanoparticle Coatings on Polystyrene Colloidal Templates and Resulting Inorganic Hollow Spheres. Chem. Mater, 2001, 13(2): 400-409
[20] Wang.L, Sasaki.T, Ebina.Y, et al. Fabrication of Controllable Ultrathin Hollow Shells by Layer-by-Layer Assembly of Exfoliated Titania Nanosheets on Polymer Templates. Chem. Mater, 2002, 14(11): 4827-4832
[21] Kai Zhang, Xuehai Zhang, Haitao Chen, et al.Hollow Titania Spheres with Movable Silica Spheres Inside. Langrnuir 2004, 20:11312-11314
[22] Strohm H, Lobmann P. Assembly of hollow spheres by templated liquid phase deposition following the principles of biomineralisation. J Mater Chem, 2004, 14:138-140
[23] Wagner J, Autenrieth T, Hempelmann R. Journal of Magnetism and Magnetic Materials, 2002, 252:4-6
[24] 李群艳，董鹏，刘忍肖等．单分散SiO_2/TiO_2/SiO_2多层复合微球的制备．无机材料学报，2001．16(5)：896-902
[25] Frank Caruso, Heinz Lichtenfeld, Michael Giersig, et al. Electrostatic Self-Assembly of Silica Nanoparticle-Polyelectrolyte Multilayers on Polystyrene Latex Particles.J. Am. Chem. Soc. 1998, 120:8523-8524
[26] Yu Lu, Joe McLellan, and Younan Xia.Synthesis and Crystallization of Hybrid Spherical Colloids Composed of Polystyrene Cores and Silica Shells. Langmuir 2004, 20:3464-3470
[27] Andreas Schmid, Syuji Fujii, Steven P Armes. Polystyrene-Silica Nanocomposite Particles via Alcoholic Dispersion Polymerization Using a Cationic Azo Initiator. Langmuir 2006, 22 (11) :4923-4927
[28] I. Tissot, J. P. Reymond, F. Lefebvre, et al. SiOH-Functionalized Polystyrene Latexes. A Step toward the Synthesis of Hollow Silica Nanoparticles. Chem. Mater. 2002, 14, 1325-1331
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