四氧化三鐵/聚甲基丙烯酸甲酯磁性複合乳膠顆粒：型態，成核機制，動力模擬以及應用

本研究，合成大小均一之功能性奈米含磁性Fe3O4核殼型態複合乳膠顆粒。在實驗方面，首次設計反應的條件，觀察複合乳膠顆粒，推論成核之機制，並利用羧酸基和Fe3O4成功地應用於細胞分離；在理論方面，首次利用成核機制模擬，並分析反應動力。以乳化聚合反應方式合成Fe3O4/聚甲基丙烯酸甲酯 (PMMA) / 聚甲基丙烯酸甲酯 (PMMA)-co- 聚甲基丙烯酸 (PMAA) 之複合乳膠顆粒.此方法共分三步驟，第一步先利用化學共沈法合成合成穩定的Fe3O4 微粒懸浮液體，第二步將甲基丙烯酸甲酯單體在Fe3O4 微粒懸浮液體中進行乳化聚合合成包覆均勻之磁性乳膠顆粒，第三步將第二步所合成的種子乳液在甲基丙烯酸甲酯和聚甲基丙烯酸單體中，再進行種子乳化聚合反應合成核殼型態磁性複合乳膠顆粒，最後再利用此核殼型態磁性複合乳膠顆粒鍵結抗體，並利用磁場分離，達到分離細胞的目的，內容共分六個章節。第一章主要是簡介及文獻回顧。第二章首先探討利用化學共沈法合成合成穩定的Fe3O4微粒，利用超導量子干涉儀探討Fe3O4微粒磁性，利用穿透式電子顯微鏡觀察粒徑大小，找尋適當的界面活性劑處理Fe3O4 微粒，並探討界面活性劑的量對Fe3O4 微粒的影響，利用熱重分析去區分單層界面活性劑的化學鍵結，以及第二層界面活性劑的物理吸附。第三章主要是探討甲基丙烯酸甲酯單體在Fe3O4 磁性流體中進行乳化聚合，利用穿透式電子顯微鏡觀察其成核的現象隨著轉化率之變化，推論出兩種機制-種子聚合以及均相成核，並利用種子成核，均相成核機構和微胞微胞成核機構來計算反應過程中聚體顆粒數目隨轉化率之變化、聚體顆粒內之平均自由基的數目、記算終止速率常數和凝膠效應的關係。第四章主要是製備核殼型磁性複合乳膠顆粒是以聚甲基丙烯酸甲酯包覆四氧化三鐵為種子涵浸甲基丙烯酸甲酯單體以及甲基丙烯酸單體進行乳化聚合，並利用導電度法分析核殼型態複合乳膠顆粒之表面官能基，以及利用熱差分析儀以及傅立葉轉換紅外線光譜儀分析核殼型磁性複合乳膠顆粒。第五章是利用偶合劑，將抗體接枝在核殼型磁性複合乳膠顆粒表面，利用其去分離溶血性病人的血液以及經過白血球分離術的檢體，並通過一磁場達到分離的效果，並利用流式細胞儀去分析分離的結果以及利用掃瞄式電子顯微鏡觀察。第六章是總結及未來的展望。

關鍵字

成核機制；型態；乳膠顆粒；四氧化三鐵；聚甲基丙烯酸甲酯；動力模擬

並列摘要

In this work, Fe3O4/poly(methyl mathacrylate)/poly (methyl mathacrylate-co- mathacrylate acid ) (Fe3O4/PMMA/P(MMA-co-MAA) core-shell magnetic composite latex was synthersized by the emulsion polymerization, which included three steps: the first step was to prepare the stable Fe3O4 colloid (ferrofluid). The second step was to synthesize PMMA in the presence of ferrofluid by emulsion polymerization. The third step was to synthesize the PMMA-co-PMAA in the presence of product from the second step. First, Fe3O4 particles were prepared by chemical coprecipitation. The magnetic properties and particle size of these magnetic fluids, characterized by transmission electron microscopy and superconducting quantum interference device, respectively, indicated the formation of single-domain nanoparticles. Thermogravimetric analysis measurements showed the existence of two distinct populations of surfactants on the particle surface, which suggests the primary and secondary surfactants. Second, magnetic poly (methyl methacrylate) [PMMA] composite latex was prepared by emulsion polymerization in the presence of ferrofluid, and the ferrofluid was prepared by means of a coprecipitation method. The effects of some polymerization parameters, such as monomer concentration, ferrofluid content, and initiator concentration on the conversion curve and particle size of magnetic composite latex particles were examined in detail. The results showed that two nucleation mechanisms, seeded polymerization and self-nucleation polymerization, would vary with the polymerization conditions. In the monomer rich and less ferrofluid system, self-nucleation of PMMA was dominant over the entire course of emulsion polymerization. In the monomer less and ferrofluid rich system, seeded emulsion polymerization was the main course to form the magnetic composite latex particles. A generalized mathematical model was developed to estimate the variation of particle concentration during the entire course of emulsion polymerization of methyl methacrylate (MMA) with ferrofluid. Two mechanisms for the nucleation and growth of particles throughout the polymerization reaction were discussed: MechanismⅠ－seeded polymerization; and MechanismⅡ－self-nucleation polymerization. Here the self-nucleation included homogeneous nucleation and micelle nucleation. Coagulation between particles, which came from different nucleation mechanisms during the course of polymerization, was considered and included in our model. When appropriate parameters were selected, our model could be successfully used to interpret the variation of particle concentration during the entire reaction. Under different conditions, the rate of polymerization, the number of radicals in each particle, the average molecular weight of polymers, and the rate constant of termination were also calculated. All of them explained the experimental results quite well. Third, the magnetic PMMA/P(MMA–MAA) core-shell composite polymer latex was synthesized in the presence of Fe3O4 ferrofluid. Certain kinds of fatty acid modified the surface of Fe3O4 particles, and the resulting Fe3O4 ferrofluid acted as seeds in the polymerization process. Adjusting the MAA shell composition could control the amount of COOH groups on the surface of the magnetic core-shell composite polymer particles. Last but not least, Immuno magnetic latices were derived through the reaction of COOH groups from the magnetic PMMA/P(MMA–MAA) core-shell composite polymer latex with antibodies or streptavidin. The zeta potential indirectly proved the antibodies or streptavidin did bind with magnetic latex. The potential of the immuno magnetic latex in the clinical application of cell separation was evaluated.

並列關鍵字

Kinetic Modeling ； Nucleation Mechanism ； Morphology ； Fe3O4 ； PMMA ； Latex Particles

參考文獻

[1] Halbreich A, Roger J, Pons JN, Da Silva MF, Bacri JC. In: Arshady R, editor. Microspheres, Microcapsules and liposomes: Citus: London, 2001. pp. 459-491.

[22] Hasegawa M, Hanaichi T, Shoji H, Kawaguchi T, Maruno S. Japanese Journal of Applied Physics, Part 1: Regular Papers & Short Notes & Review Papers 1998;37(3A):1029-1032.

[13] Jansen J, Hanks S, Akard L, Martin M, Thompson J, Chang Q, Ash R, Garrett P, Figg F, English D. Bone Marrow Transplant 1995;15(2):271-278.

[2] Widjojoatmodjo MN, Fluit AC, Torensma R, Verhoef J. J Immunol Methods 1993;165(1):11-19.

[7] Ruan C, Wang H, Li Y. Transactions of the American Society of Agricultural Engineers 2002;45(1):249-255.

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四氧化三鐵/聚甲基丙烯酸甲酯磁性複合乳膠顆粒：型態，成核機制，動力模擬以及應用

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