亲/疏水不对称空心聚合物微球制备及纳米粒子装载研究
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摘要
作为一种微反应器,壁上含微孔的空心微球可用于装载磁性粒子或Ag、Au等金属纳米粒子,得到既具有高比表面积、较低密度、“包裹”效应等特点又具有纳米粒子磁效应、体积效应、量子尺寸效应、表面效应等效应的功能复合粒子。该复合粒子在生物医药、仿生材料、催化剂、光电材料等领域具有广泛应用。
本论文的研究内容包括：内外表面组成、性质不对称空心聚合物微球的制备；空心球装载Fe304磁性粒子；空心球装载纳米Au粒子；空心球包覆Ag粒子四部分。
不对称空心聚合物微球的制备是实现选择性装载的前提,其制备过程如下：将[(马来酸酐-醋酸乙烯酯)共聚物]核／[(马来酸酐-二乙烯基苯)共聚物]壳微球壳层烷基溴化,再用[(马来酸酐-醋酸乙烯酯)共聚物]核的良溶剂将核溶蚀,内表面酐基水解,从而制得内表面含亲水羧基、外表面含烷基溴、具有微孔的亲／疏水不对称功能空心聚合物微球。
空心球装载Fe304磁性粒子的关键是如何控制磁性粒子仅在空心球内部生成。制备的空心聚合物微球内外表面具有亲／疏水不对称性,内表面亲水基团与铁离子间相互作用使铁离子在内表面成核、增长,而外表面疏水基团不易吸附铁离子,保证了磁性粒子在空心聚合物微球内部装载。考察了反应配比、温度和时间等参数对装载效果的影响。当Fe2+和Fe3+的摩尔比为2/3,反应温度为80℃,反应1.5 h时,空心聚合物微球装载磁性粒子的效果和装载后微球的磁性能最佳,饱和磁化强度可达12.34 emu/g。
空心球装载纳米Au粒子的方法与磁性粒子的装载方法类似。超声作用下反应物HAuCl4进入空心球内部,洗去表面反应物,加入还原剂反应,在空心聚合微球内部装载单颗金纳米粒子,通过增加HAuCl4用量及二次装载来增大纳米粒子的粒径,实现了纳米粒子粒径一定程度上可控。
空心球外部包覆纳米Ag粒子主要通过氨基改性改善空心球的亲水性,更易吸附Ag+等反应物,在空心球外表面进行还原反应得到纳米银粒子。
As a micro-reactor, hollow microspheres with microporous could be used to load magnetic particles or Ag, Au and other metal nanoparticles, preparing composite particles, which have the function of both hollow spheres and nanoparticles. Such composite particles have application in the biomedical,biomimetic materials, catalyst, optical materials and other areas.
In this thesis, four parts research including:prepare asymmetric hollow polymer microspheres;load Fe3O4 magnetic particles in hollow microspheres; load Au nanoparticles in hollow microspheres; prepare Ag nanoparticles outside the hollow microspheres.
Hollow polymer microspheres with micropores of 14.9 nm, alkyl bromine groups on exterior wall and carboxyl groups on interior wall were produced through three steps:a) synthesis of the core-shell microparticles with copolymer of maleic anhydride (MAn) and divinyl benzene (DVB) as the core, and copolymer of maleic anhydride (MAn) and vinylacetate (VAc)as the shell;b)surface bromizing of the core-shell microparticles; c) etching of the cores with acetone, and followed by the hydrolyzing of the anhydride groups on interior wall.
Using the resultant hollow polymer microsphere as micro-reactors, Fe3O4 magnetic particles were loaded into the cavity by selective adsorption of Fe2+ and Fe3+ on the interior wall, and coprecipitation only inside the hollow polymer microspheres. In addition, influences of parameters relating to the above mentioned reaction, such as the mole ratio of Fe2+ and Fe3+,reaction temperature and reaction time, on the saturation magnetization of the magnetic hollow microspheres were investigated. The results showed that the optimum reaction condition to balance the loading selectivity and value of saturation magnetization was as follows:a Fe2+ to Fe3+ molar ratio of 2/3,reaction temperature is 80℃and reaction time is 1 h.
Under appropriate experimental conditions, single gold nanoparticles could be loaded in hollow polymeric microspheres. By increasing the amount of HAuCl4 and loading twice, bigger nano-particle could be obtained.
In addition, polymer microspheres coated silver nanoparticles were prepared used the hollow particles as carrier. By amino-modified, the interaction between hollow microspheres and water/Ag+ were improved, to a better coating of silver nanoparticles on hollow microspheres.
本论文的研究内容包括：内外表面组成、性质不对称空心聚合物微球的制备；空心球装载Fe304磁性粒子；空心球装载纳米Au粒子；空心球包覆Ag粒子四部分。
不对称空心聚合物微球的制备是实现选择性装载的前提,其制备过程如下：将[(马来酸酐-醋酸乙烯酯)共聚物]核／[(马来酸酐-二乙烯基苯)共聚物]壳微球壳层烷基溴化,再用[(马来酸酐-醋酸乙烯酯)共聚物]核的良溶剂将核溶蚀,内表面酐基水解,从而制得内表面含亲水羧基、外表面含烷基溴、具有微孔的亲／疏水不对称功能空心聚合物微球。
空心球装载Fe304磁性粒子的关键是如何控制磁性粒子仅在空心球内部生成。制备的空心聚合物微球内外表面具有亲／疏水不对称性,内表面亲水基团与铁离子间相互作用使铁离子在内表面成核、增长,而外表面疏水基团不易吸附铁离子,保证了磁性粒子在空心聚合物微球内部装载。考察了反应配比、温度和时间等参数对装载效果的影响。当Fe2+和Fe3+的摩尔比为2/3,反应温度为80℃,反应1.5 h时,空心聚合物微球装载磁性粒子的效果和装载后微球的磁性能最佳,饱和磁化强度可达12.34 emu/g。
空心球装载纳米Au粒子的方法与磁性粒子的装载方法类似。超声作用下反应物HAuCl4进入空心球内部,洗去表面反应物,加入还原剂反应,在空心聚合微球内部装载单颗金纳米粒子,通过增加HAuCl4用量及二次装载来增大纳米粒子的粒径,实现了纳米粒子粒径一定程度上可控。
空心球外部包覆纳米Ag粒子主要通过氨基改性改善空心球的亲水性,更易吸附Ag+等反应物,在空心球外表面进行还原反应得到纳米银粒子。
As a micro-reactor, hollow microspheres with microporous could be used to load magnetic particles or Ag, Au and other metal nanoparticles, preparing composite particles, which have the function of both hollow spheres and nanoparticles. Such composite particles have application in the biomedical,biomimetic materials, catalyst, optical materials and other areas.
In this thesis, four parts research including:prepare asymmetric hollow polymer microspheres;load Fe3O4 magnetic particles in hollow microspheres; load Au nanoparticles in hollow microspheres; prepare Ag nanoparticles outside the hollow microspheres.
Hollow polymer microspheres with micropores of 14.9 nm, alkyl bromine groups on exterior wall and carboxyl groups on interior wall were produced through three steps:a) synthesis of the core-shell microparticles with copolymer of maleic anhydride (MAn) and divinyl benzene (DVB) as the core, and copolymer of maleic anhydride (MAn) and vinylacetate (VAc)as the shell;b)surface bromizing of the core-shell microparticles; c) etching of the cores with acetone, and followed by the hydrolyzing of the anhydride groups on interior wall.
Using the resultant hollow polymer microsphere as micro-reactors, Fe3O4 magnetic particles were loaded into the cavity by selective adsorption of Fe2+ and Fe3+ on the interior wall, and coprecipitation only inside the hollow polymer microspheres. In addition, influences of parameters relating to the above mentioned reaction, such as the mole ratio of Fe2+ and Fe3+,reaction temperature and reaction time, on the saturation magnetization of the magnetic hollow microspheres were investigated. The results showed that the optimum reaction condition to balance the loading selectivity and value of saturation magnetization was as follows:a Fe2+ to Fe3+ molar ratio of 2/3,reaction temperature is 80℃and reaction time is 1 h.
Under appropriate experimental conditions, single gold nanoparticles could be loaded in hollow polymeric microspheres. By increasing the amount of HAuCl4 and loading twice, bigger nano-particle could be obtained.
In addition, polymer microspheres coated silver nanoparticles were prepared used the hollow particles as carrier. By amino-modified, the interaction between hollow microspheres and water/Ag+ were improved, to a better coating of silver nanoparticles on hollow microspheres.
引文
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[3]Kaori Kamata, Yu Lu, Younan Xia. Synthesis and Characterization of Monodispersed Core-Shell Spherical Colloids with Movable Cores[J].J. Am. Chem. Soc,2003, 125(9):2384～2385.
[4]许涌深,曹同玉,龙复.无皂乳液共聚合的动力学以及机理[J].合成橡胶工业,1992,15(2)：98～108.
[5]Chern C S, Poehlein G W. Polymerization in nonuniform latex particles:Distribution of free radicals [J]. J Polym Sci Part A:Polym Chem,1987,25:617～635.
[6]马千里,顾利霞.复合微球的制备、性能及应用[J].离子交换与吸附,2000,16(1)：88～96.
[7]晏欣,孙卫红,江盛玲,饶秋华.PEMA/PEA自交联乳胶IPN阻尼材料的研究[J].高分子材料科学与工程,2006,22(2)：216～219.
[8]Oliveira P C, Guimaraes A, Cavaille J Y, Chazeau L, Gilbert R G, Santos A M. Poly(dimethylaminoethyl methacrylate) grafted natural rubber fromseeded emulsion polymerization[J]. Polymer,2005,46:1105～1111
[9]王郁翔,吴国旭,林志勇,龚晓光,赵翌颖.核／壳型ACR乳液的聚合研究[J].弹性体,2004,14(2)：43～45
[10]Okubo M, Ikegami K, Yamamoto Y. Preparation of micro-size monodisperse polymer microspheres having chloromethyl group[J].Colloid Polym Sci,1989,267:193～200
[11]Okubo M, Katayama Y, Yamymoto Y. Preparation of micron-size monodisperse polymer microspheres having crosslinked structures and vinyl groups[J].Colloid Polym Sci,1991,269:217～221
[12]Ali S A, Sengupta M. Preparation and characterization of monodisperse polystyrene latexes varying particle sizes without the use of surfactants[J].J Polym Mater,1991,8: 243～249
[13]Vanderhoff J W, Bradford E B, Tarkowski H L, Wilkinson B W. The use of high-energy irradiation in an investigation of the mechanism and kinetics of emulsion polymerization [J].J Polym Sci,1961,50:265～286
[14]Chungli Y, Goodwin J W, Ottewill R H. Studies on the preparation and characterization of monodisperse polystyrene latexes. IV The preparation of latex particles with a size greater than 1μm[J]. Prog Colloid Polym Sci,1976,60:163～175
[15]Ugelstad J, Mfutakamba H R, Mark P C, Ellingsen T, Berge A, Schmid R, Holm L, Jφrgedal A, Hansen F K, Nustad K Preparation and application of monodisperse polymer microspheres[J].J Polym Sci Polym Symp,1985,72:225～240
[16]Ugelstad J, Berge A, Ellingsen T, Schmid R, Nilsen T N, Mark P C, Stenstad P, Homes E, Olsvik 0. Preparation and application of new monosized polymer particles[J].Prog Polym Sci,1992,17:87～161
[17]Okubo M,Shiozaki M,Tsujihiro M,Tsukuda Y Preparation of micron-size monodisperse polymer particles by seeded polymerization utilizing the dynamic monomer swelling method[J]. Colloid Polym Sci,1991,269:222～226
[18]Okubo M, Nakagawa T. Preparation of micron-size monodisperse polymer particles having highly crosslinked structures and vinyl groups by seeded polymerization of divinylbenzene using the dynamic swelling method[J].Colloid Polym Sci,1992,270: 853～858
[19]Jianping Deng, Yong Yu, Shuo Dun, Wantai Yang. Hollow Polymer Particles with Nanoscale Pores and Reactive Groups on Their Rigid Shells:Preparation and Application as Nanoreactors[J].J. Phys. Chem. B,2010,114(8):2593～2601
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