臺灣博碩士論文加值系統

本研究以甲基丙烯酸甲酯(MMA)之無乳化劑乳化聚合法為研究主軸，以甲基丙烯酸(MAA)為共單體，過硫酸鉀(KPS)為起始劑，以水或不同比例之水-甲醇為溶劑，並以改變製程方式衍生出階段連續式空間位阻變化無乳化劑乳化聚合法，進行粒子形態與尺寸之研究。
在無乳化劑乳化聚合研究中，改變進料方式、反應溫度、固含量、共單體比例、轉速，並添加交聯劑，獲得適當的系統反應條件，並發現於共單體比例40~50 wt%時出現粒子急劇增大之臨界現象。溶劑中添加甲醇會導致聚合體完全凝聚為大團塊，由團塊之凝聚情形可佐證共單體聚合過程為其造成系統不穩定現象之主因。
在階段連續式空間位阻變化法中，於不添加任何乳化劑或分散劑之情況下，成功的以單體模擬類似分散聚合之效應，系統穩定性相當高，適當之反應條件範圍較無乳化劑乳化聚合法寬廣許多。本研究以此法成功的製備出膠囊粒子、奈米級粒子，並將粒子大小突破過往乳化聚合與無乳化劑乳化聚合之尺寸極限，在系統穩定之狀態下製備出次微米級粒子，並初步構築階段連續式空間位阻變化法之基本原理與效應。

Soap-free emulsion polymerization of methyl methacrylate (MMA) and methacrylic acid (MAA) was carried out in an water (or ethanol/water) media with potassium persulfate (KPS) as the initiator. Furthermore, Step-continuation space drag changed soap-free emulsion polymerization be come form change production. The particle size and morphology were investigated.

In the Soap-free emulsion polymerization, The change the parameters of reaction add cross-linking reagent to get the appropriate stipulation of the reaction and come out the proportion 40~50% in the particle augmentation quickly of phenomenon. To add methanol to solvent leads polymer agglomeration to be agglomerated at all and it’s agglomeration condition could prove that co-monomer is the master reason of system shake phenomenon.

In the step-continuation space drag changed soap-free emulsion polymerization, which didn’t added any emulsifier or stabilizer instance, the effects of reaction dispersion polymerization it successful used to monomer to simulate. It had high stability, the reaction condition is better than soap-free emulsion polymerization. It successfully produced cachet particle、nano-particle and the particle size breakthrough limit between emulsion polymerization and soap-free emulsion polymerization. At the stability state produce to micro-particle. Alphabet construction step-continuation space drag changed soap-free emulsion polymerization basic theory and effects.

中文摘要
英文摘要
致謝
目錄
第一章 緒論
1.1 簡介
1.2 研究目的
第二章 原理與文獻回顧
2.1 自由基鏈鎖聚合反應
2.2 乳化聚合法
2.3 無乳化劑乳化聚合法
2.4 種子聚合法
2.5 分散聚合法與沉澱聚合法
2.6 懸浮聚合法
2.7 聚合反應成核機構
第三章 實驗
3.1 試藥
3.2 儀器
3.3 實驗方法與流程
3.3.1 無乳化劑乳化聚合實驗流程
3.3.2 階段連續式空間位阻變化法實驗流程
3.3.3 粒子形態觀測
3.3.4 熱性質分析
3.3.5 轉化率測定
第四章 結果與討論
4.1 甲基丙烯酸甲酯之無乳化劑乳化聚合反應行為探討
4.1.1 批式進料與連續式進料
4.1.2 低轉速下之共單體與反應溫度效應
4.1.3 高轉速下之共單體與反應溫度效應
4.1.4 交聯劑效應
4.2 階段連續式空間位阻變化(無乳化劑乳化聚合)法
4.2.1 以水為溶劑之階段連續式空間位阻變化法
4.2.2 以水-甲醇為溶劑之無乳化劑乳化聚合法
4.2.3 以水-甲醇為溶劑之階段連續式空間位阻變化法
4.2.4 階段連續式空間位阻變化法之共單體轉化率效應
4.2.5 階段連續式空間位阻變化法之階段變溫效應
4.3 聚合體基本熱性質與官能基鑑定
4.4 階段連續式空間位阻變化法之綜合原理、命名由來與展望
第五章 結論
參考文獻
附錄

[1] 杜逸虹, “聚合體學”。
[2] 薛敬和, 高立圖書有限公司, “高分子化學實驗法”。
[3] 謝如嘉, “具螯合官能基單體與苯乙烯之無乳化劑乳化共聚合的反應動力探討” 成功大學碩士論文, 2000年。
[4] Lee, C-F.; Chiu, W-Y., Chern, Y-C., “Kinetic study on the poly(methyl methacrylate) seeded soapless emulsion polymerization of styrene. II. Kinetic model,” Journal of Applied Polymer Science., 1995, 57, 591-603.
[5] Lee, C-F., “The properties of core – shell composite polymer latex. Effect of heating on the morphology and physical properties of PMMA/PS core – shell composite latex and the polymer blends.” Polymer, 2000, 41, 1337-1344.
[6] Huang, X.; Brittain, W.J., “Synthesis and Characterization of PMMA Nanocomposites by Suspension and Emulsion Polymerization.” Macromolecules, 2001, 34, 3255-3260.
[7] Bandyopadhyay, S.; Hsieh, A.J., Giannells, E.P., “Synthesis and kinetic studies of PMMA nanoparticles by non-conventionally initiated emulsion polymerization” European Polymer Journal, 2003, 39, 1839-1846.
[8] Sahoo, P-K.; Mohapatra, R., “Synthesis and kinetic studies of PMMA nanoparticles by non-conventionally initiated emulsion polymerization” European Polymer Journal, 2003, 39, 1839-1846.
[9] Zhang, K.; Zheng, L., Zhang, X., Chen, X., Yang, B., “Silica-PMMA core-shell and hollow nanospheres” Colloids and Surfaces A : Physicochem. Eng. Aspects, 2006, 277, 145-150.
[10] Lee, C-F.; Lin, K-R., Chiu, W-Y., “Kinetics studies of two-stage soapless emulsion polymerization of butyl acrylate and methyl methacrylate” Journal of Applied Polymer Science, 1994, 51, 1621-1628.
[11] Lee, C-F.; Chiu, W-Y., Chern, Y-C., “Kinetic study on the poly(methyl methacrylate) seeded soapless emulsion polymerization of styrene. II. Kinetic model” Journal of Applied Polymer Science, 1995, 57, 591-603.
[12] Taner, T.; Oquz, O., “Kinetics of emulsifier-free emulsion polymerization of methyl methacrylate” Journal of Applied Polymer Science, 1996, 61, 485-493.
[13] Lee, C-F.; Chiu, W-Y., “Kinetic study on the poly(methyl methacrylate) seeded soapless emulsion polymerization of styrene. III. Seeds with crosslinking” Journal of Applied Polymer Science, 1997, 65, 425-438.
[14] 李佩縈, “苯乙烯及甲基丙烯酸的無乳化劑乳化共聚合研究” 中國文化大學碩士論文, 2002年。
[15] Lee, C-F.; Young, T-H., Huang, Y-H., Chiu, W-Y., “Synthesis and properties of polymer latex with carboxylic acid functional groups for immunological” Polymer, 2000, 41, 8565-8571.
[16] Lee, C-F., “The effect of aqueous medium contains poly(acrylic acid) on the morphology of composite polymer particle produced by two stages soapless seeded emulsion polymerization” Polymer, 2002, 43, 5763-5769.
[17] Du, Y-Z.; Tomohiro, T., Kodaka, M., “Synthesis of Hemispherical Poly(2-hydroxylethyl methacrylate-co-methyl methacrylate)/Poly(styrene-co-glycidyl methacrylate) Composite Particles with Heterobifunctional Groups by Soap-Free Seeded Emulsion Polymerization” Macromolecules, 2004, 37, 803-812.
[18] Okaya, T.; Kikuchi, K., Suzuki, A., Ikeda, N., “Dispersion polymerization of vinyl acetate in a mixture of ethanol and water ” Polym. International, 2005, 54, 143-148.
[19] Yasuda, M.; Seki, H., Yokoyama, H., Ogino, H., Ishimi, K., Ishikawa, H., “Simulation of a Particle Formation Stage in the Dispersion Polymerization of Styrene” Macromolecules, 2001, 34, 3261-3270.
[20] Cao, K.; Yu, J., Li, B-G., Li, B-F., Pan, Z-R., “Micron-size uniform poly(methyl methacrylate) particles by dispersion polymerization in polar media 1. Particle size and particle size distribution” Chemical Engineering Journal, 2000, 78, 211-215.
[21] Yang, W.; Zhou, H., Tao, Z., Hu, J., Wang, C., Fu, S., “DISPERSION COPOLYMERIZATION OF STYRENE AND N-VINYL CARBAZOLE IN POLAR SOLVENTS” J.M.S.-PURE APPL. CHEM., 2000, 37(7), 659-675.
[22] 廖火生, “製備甲基丙烯酸甲酯包裹無機導熱材之聚合研究” 中原大學碩士論文, 2002年。
[23] T. V. Nilolayeva.; A. YE. Kulilova., I. N. Vishnevslaya., I. N. Razinskaya., A. D. Gutkovich., V. L. Yermolayeva., “PREPARATION OF HETEROPHASE GRAFT ACRYLIC COPOLYMERS WITH A STRUCTURE BY LATEX-SUSPENSION POLYMERIZATION” Polymer Science, 1990, 32, 1069-1074.
[24] 歐進祿, “均一粒徑無乳化劑次微米粒子之合成及種子溶脹製備均一粒徑微米級之緻密或交聯結構粒子” 中央大學博士論文, 2001年。
[25] Huang, C-F.; Chang, F-C., “Comparison of hydrogen bonding interaction between PMMA/PMAA blends and PMMA-co-PMAA copolymers” Polymer, 2003, 44, 2965-2974.
[26] Chern, C. S.; Lin, F. Y., Chen, Y. C., Lin, C. H., “Characterization of carboxylated poly(butyl acrylate) lattices produced by a semibatch process” Applied Polymer Science, 1996, 62, 585-594.
[27] Tsavalas, john G.; Luo, Yingwu., Schork, F., joseph., “Grafting mechanisms in hybrid miniemulsion polymerization” Journal of Applied Polymer Science, 2003, 87, 1825-1836.
[28] Wang, Ping-Cheih.; Lee, Chia-Fen., Young, Tai-Horng., Lin, Dong-Tsamn., Chiu, Wen-Yen., “Preparation and clinical application of immunomagnetic latex” Journal of Polymer Science, Part A : Polymer Chemistry, 2005, 43, 1342-1356.
[29] Mandal, S.; Pangarkar, V. G., “Pervaporative dehydration of 1-methoxy propanol with acrylonitrile based co-polymer membranes prepared through emulsion polymerization : a solubility parameter approach and study of structural impact” Journal of Membrane Science, 2002, 209, 53-66.
[30] 李育德，顏文義，莊祖煌，“聚合物物性”。
[31] Pan, T-G.; Kuo, J-F., Chen, C-Y., “Effect of sodium methacrylate on the soapless emulsion copolymerization of methyl methacrylate and n-butyl acrylate” Journal of Polymer Science, Part A: Polymer Chemistry, 1991, 709-718.
[32] Zhang, H-T.; Yuan, X-Y., Huang, J-X., “Study of kinetic and nucleation mechanism of dispersion copolymerization of methyl methacrylate and acrylic acid” Reactive & Functional Polymers, 2004, 39, 23-31.
[33] Kuchta, F-D., Herk, A-M., German, A. L., “Propagation Kinetics of Acrylic and Methacrylic Acid in Water and Organic Solvents Studied by Pulsed-Laser Polymerization” Macromolecules, 2000, 3641-3649.
[34] Rufino, E.S., Monteiro, E.E.C., “Infrared study on methyl methacrylate-methacrylic acid copolymers and their sodium salts” Polymer, 2003, 44, 7189-7198.