多孔磁性复合微球的合成与表征
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摘要
本文介绍了一种制备均一粒径的磁性微球的方法。在二氧化硅与氢氧化铁的混合溶胶中，加入尿素、甲醛并在酸性条件下引发其发生聚合反应，得到分散良好且粒径分布在4(5(m间的脲醛树脂/二氧化硅/氢氧化铁复合微球。经过真空干燥处理除去微球内部的分子结合水后，按照一定的升温程序对该复合微球高温煅烧，最后得到粒径4(m左右的SiO2/(-Fe2O3复合微球。通过对其进行电镜照相、粒度分布、比表面积及孔径测试、XRD衍射、Fe2O3含量分析、磁性测定、反相色谱分离性能等表征与测试工作，可知该复合微球为一种机械强度较高的磁性多孔复合微球。由于其较大的比表面积、较强的磁性、表面存在的大量硅羟基，该复合微球可以成为一种新的磁性微球，在制药、生物技术和生命科学领域有很好的应用前景。
在SiO2/(-Fe2O3复合微球制备成功的基础上，又探讨了ZrO2/(-Fe2O3复合微球的制备。
This thesis describes a new approach for preparation of uniform and magnetic microspheres. According to this method, the monodisperse urea-formaldehyde resins/SiO2/(-Fe2O3 composite microspheres are obtained through dispersive polymerization of urea and formaldehyde in the presence of the mixture of silica sol and Fe(OH)3 sol. The org/inorganic composite microspheres have the particle sizes in the range of 4(5(m. The dried composite microspheres are then step-heated in an oven to afford SiO2/(-Fe2O3 composite microspheres with particle sizes of about 4(m. The composite microspheres are thoroughly characterizaed by a range of techniques including scanning electron microscopy(SEM)、Sorptometer、X-ray diffraction instrument、Zeeman atomic adsorption spectrophotometry、vibrating sample magnetometer and high-performance liquid chromatography(HPLC). The results show that the SiO2/(-Fe2O3 microspheres are porous, magnetizable and high pressure-resisted. Since the SiO2/(-Fe2O3 composite microspheres have high surface area(152.5m2/g) and lots of silanol on the surface and are easily magnetized in magnetic field, they can be used as magnetic supports and find applications in biotechnology、pharmaceutical and life science research.
Based on the experience wtih preparation SiO2/(-Fe2O3 composite microspheres, we carried out the research on prepararation of ZrO2/(-Fe2O3 composite microspheres.
在SiO2/(-Fe2O3复合微球制备成功的基础上，又探讨了ZrO2/(-Fe2O3复合微球的制备。
This thesis describes a new approach for preparation of uniform and magnetic microspheres. According to this method, the monodisperse urea-formaldehyde resins/SiO2/(-Fe2O3 composite microspheres are obtained through dispersive polymerization of urea and formaldehyde in the presence of the mixture of silica sol and Fe(OH)3 sol. The org/inorganic composite microspheres have the particle sizes in the range of 4(5(m. The dried composite microspheres are then step-heated in an oven to afford SiO2/(-Fe2O3 composite microspheres with particle sizes of about 4(m. The composite microspheres are thoroughly characterizaed by a range of techniques including scanning electron microscopy(SEM)、Sorptometer、X-ray diffraction instrument、Zeeman atomic adsorption spectrophotometry、vibrating sample magnetometer and high-performance liquid chromatography(HPLC). The results show that the SiO2/(-Fe2O3 microspheres are porous, magnetizable and high pressure-resisted. Since the SiO2/(-Fe2O3 composite microspheres have high surface area(152.5m2/g) and lots of silanol on the surface and are easily magnetized in magnetic field, they can be used as magnetic supports and find applications in biotechnology、pharmaceutical and life science research.
Based on the experience wtih preparation SiO2/(-Fe2O3 composite microspheres, we carried out the research on prepararation of ZrO2/(-Fe2O3 composite microspheres.
引文
[1] 丁小斌，孙宗华，万国祥，磁性高分子微球的制备和应用研究进展，化学通报，1997，1：3~5
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[42] 刘铁岩，屠德荣，国外颗粒磁记录介质最新发展状况，化工进展，1994，(6):43~47
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[2] 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)，865~868
[3] Tartaj P, Teresita González-Carreňo, Carlos J. Serna, Magnetic behaviour of (–Fe2O3 nanocrsystals dispersed in colloidal silica particles, Journal of Physical Chemistry. B, 2003, 107:20~24
[4] Mehta R.V, Charles S.W, Ramchand C.N, et al, Direct binding of protein to magnetic particles, Biotechnology Techniques, 1997, 11:493~496
[5] 李欣，李朝心，何炳林. 磁性珠状纤维素制备工艺研究，离子交换与吸附，1997，13：387~384
[6] Garcia Ⅲ, A., Oh. S., Engler C.R, Cellulase immobilization on Fe3O4 and characterization, Biotechnology and Bioengineering, 1989, 33:321~326
[7] Furusawa K., Nagashima, K., Anzai C, Synthetic process to control the total size and component distribution of multilayer magnetic composite particles, Colloid & Polymer Science, 1994,272:1104~1110
[8] Ugelstad J, Stenstad P, Lilaas L. Monodisperse magnetic polymer particles. Blood Purification, 1993, 11:349~369
[9] Cocker T M, Fee C J, Evans R A, Preparation of magnetically susceptible polyacrylamide/magnetic beads for use in magnetic stabilized fluidized bed chromatography, Biotechnology and Bioengineering, 1997, 53:79~87
[10] Tricot M., Daniel J.C., Process for the preparation of magnetic beads of vinylaromatic polymers, US Pat: 4,339,337, 1982-07-13
[11] Molday R.S., Application of magnetic microspheres in labeling an separation, Nature, 1977, 268: 437~438
[12] 邱广明，邱广亮，大粒径磁性高分子微球的制备，应用化学，1997，14：74~76
[13] Tricot M, Process for the preparation of magnetic beads of vinylaromatic polymers, US Pat: 4339337, 1982-7-13
[14] Margel S, Polyacrolein-type microspheres, US Pat: 4783336, 1988-11-8
[15] Daniel J C, Sebuppiser J L, Tricot M, Magnetic polymer latex and preparation process, US Pat: 4358388, 1982-11-9
[16] Charmot D, Vidil C, Magnetizable composite microspheres of hydrophobic crosslinked polymer, process for preparing them and their application in biology, US Pat: 5356713,1994-10-18
[17] Solc nee Hajna J, Colloidal size hydrophobic polymers particulate having discrete particles of an inorganic material dispersed therein，US Pat: 4421660, 1983-12-20
[18] 邱广明，孙宗华，单分散亚微米级磁性微球的合成, 功能高分子学报，1996，9(4): 565
[19] 邱广明，孙宗华，分散聚合法合成磁性高分子微球，功能高分子学报.1993, 6(2): 123-130
[20] Kondo A., Kamura H., Higashitani K.. Development and application of thermosenstive magnetic immunomicrospheres for antibody purification. Applied ( Microbiology Biotechnology, 1994, 41:99~105
[21] Hwee Peng Khng, Cunliffe, David, Davies ,et al, Synthesis of sub-micron magnetic particles and their use for preparative purification of proteins, Biotechnology and bioengineering, 1998, 60(4): 419-424
[22] 李孝红，孙宗华, 磁性高分子微球的合成研究--带醛基磁性高分子微球的合成及表征, 离子交换与吸附，1996，12(6)：486
[23] 丁小斌 汪英彦, 热敏性高分子包裹的磁性微球的合成, 高分子学报, 1998, (5): 628-631
[24] Richard J, Vaslin S, Latex of calibrated monodisperse magnetizable microspheres, process of preparation and use of the said latex in chemistry or in biology, US Pat: 5976426, 1999-11-2
[25] Khng H. P., Cunliffe D., Davies S., et al. The synthesis of submicron magnetic particles and their use for preparative purification of proteins. Biotechnology and Bioengineering. 1994, 60:419~424
[26] 何炳林，黄文强, 离子交换与吸附树脂，上海：上海科技教育出版社，1995：37~47
[27] Dekker R.F.M., Applied Biochemistry and Biotechnology, 1989, 22: 289
[28] Josephson, Magnetic particles for use in separations, US Pat: 4,672,040. 1987-06-09
[29] 郑必胜，郭祀远，李琳等。高梯度磁分离的特性及应用，华南理工大学学报(自然科学版),1999,27(3):41~45
[30] Gareth P. Hatch, Richard E. Stelter, Magnetic design considerations for devices
and particles used for biological high-gradient magnetic separation(HGMS) systems, Journal of Magnetism ( Magnetic Materials, 2001, 225: 262~276
[31] Flygare S., Wikstr?m P., Johansson G., et al. Magnetic aqueous two phase separation in preparative applications. Enzyme ( Microbial Technology, 1990, 12:85~103
[32] 吕秀菊，曲洪波，从威等，磁场流化床在生化过程中的应用，化工进展，2001，3：7~10
[33] 张宏，丁晓军，固定化增殖细胞磁场流化床反应器连续生产转化糖的研究， 工业微生物，1992，22(4): 19~23
[34] Poynton C.H., Biological magnetic colloids, US Pat: 4,920,061, 1990-04-24
[35] Suzuki M., Shinkai M., Kamihira M.. Preparation and characteristics of magnetite labeled antibody with the use of poly (ethylene glycol) derivatives. Biotechnology and Applied Biochemistry. 1995, 21:335~345
[36] Pourfarzanch M., Kamel R.S., Landon J., et al. The use of magnetizable particles in solid phase immunoassay. Methods of Biochemistry Analysis. 1982, 28:267~295
[37] Ruxandra G.., Yoshiharu M., Robert L., Biodegradable particles，1995, WO patent 95/03357
[38] 邱广明，孙宗华，磁性高分子微球共价结合中性蛋白酶，生物医学工程学杂志，1995，12(3)：209~213
[39] Dauer R.R., Dunlop E.H.. High gradient magnetic separation of yeast. Biotechnology and Bioengineering，1991, 37:1021~1028
[40] Wistr?m P., Flygare S., Gr?ndalen A., et al. Magnetic aqueous two phase separation: a new technique to increases rate of phase separation using dextran ferrofluid or larger iron oxide particle. Analytical Biochemistry, 1987, 167:331~339
[41] Wong, Yuan N., Production and use of magnetic porous inorganic materials, US Pat: 5,610,274, 1997-03-11
[42] 刘铁岩，屠德荣，国外颗粒磁记录介质最新发展状况，化工进展，1994，(6):43~47
[43] 王之平，陈白珍，李义兵，透明氧化铁黄超微粒子的研制，中国涂料，2001，3：36
[44] 张立德，牟季美. 纳米材料和纳米结构，北京：科学出版社，2001：476
[45] Kurikka V. P.M. Shafi, Abraham Ulman, Ansil Dyal, et al, Magnetic enhancement of (-Fe2O3 nanoparticles by sonochemical coating, Chemistry of Materials, 2002, 14: 1778
[46] Dmitry G. Shchukin, Igor L. Radtchenko, Gleo B.Sukhorukov, Synthesis of nanosized magnetic ferrite particles inside hollow polyelectrolyte capsules, Journal of Physical Chemistry B., 2003，107(1): 86(90
[47] de Costa G M, de Grave E, de Bakker P M A, et al. Synthesis and characterization of some iron oxides by sol-gel method. Journal of Solid State Chemisty, 1994, 113: 405~412
[48] Qian Y T, Xie Y, He C. et al. Hydrothermal preparation and characterization of ultrafine magnetite powders, Material Research Bulletin, 1994, 29(9):953~957
[49] Kang Y S, Risbud S, Rabott J F, et al. Synthesis and characterization of nanometer-size Fe3O4 and (-Fe2O3 particles, Chemistry of Materials, 1996, 8: 2209~2211
[50] Ronald F. Ziolo, Emmanuel P. Giannelis, Bernard A. Weinstein, et al, Matrix-mediated synthesis of nanocrystslline (-Fe2O3: a new optically transparent magnetic material, Science, 257: 219
[51 高春华，纳米材料的基本效应及其应用，江苏理工大学学报(自然科学版)，2001，22(6): 45~49
[52] Lei Zhang, Georgia C. Papaefthymiou, Ronald F. Ziolo, et al. Novel (-Fe2O3 /SiO2 magnetic nanocomposites via sol-gel matrix-mediated synthesis, Nanostructured Materials, 1987, 9: 185~188
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