臺灣博碩士論文加值系統

聚氮-異丙基丙烯醯胺(PNIPAAm)是一種同時含有親水端與疏水端的高分子溫敏性材料，由於其最低臨界溶液溫度(LCST)約為32℃左右，因此當PNIPAAm在低溫環境下，其親水端會與水產生氫鍵，故溶於水中；而高溫環境下，疏水端彼此相互吸引產生鍵結而團聚，使其不溶於水中。也因為這項特性使得該材料廣泛應用於各領域中，如藥物釋放、廢水處理等，而在廢水處理的應用領域中，去除重金屬離子的研究大多以酸性環境為主，為了突破此酸鹼條件限制，設計出一新穎酸鹼敏感型單體IAM可與NIPAAm鍵結，並使其共聚物具有在強鹼性環境下也能抓取金屬離子的特性。
本研究使用含有兩種酸鹼官能基團單體IAM，與溫度敏感型單體NIPAAm進行共聚，合成P(NIPAAm-co-IAM)微膠，由於IAM單體具有雙官能基團，使其可在鹼性環境下與金屬離子產生螯合作用(Chelate)，並利用共聚物其相變化溫度會因為IAM的添加而升高，以達到在約36 ℃下也能抓取金屬離子的特性。

Poly(N-isopropylacrylamide) is a thermo-sensitive material that containing both hydrophilic and hydrophobic group, its lowest critical solution temperature(LCST) is about 32 ℃. When PNIPAAm in low temperature environment, the hydrophilic sides will have hydrogen bonds with water, so soluble in water; in high temperature environment, the hydrophobic side will have interaction and reunion, making it insoluble in water. But also because of this feature makes the material widely used in various fields, such as drug release, waste water treatment. Now in the wastewater treatment applications, removal of heavy metal ions are mostly in acidic environment, in order to break through this conditions. A novel acid-base-sensitive monomer IAM was designed to bind to NIPAAm and its copolymer had the ability to capture metal ions in strong alkaline environments.

In this study, P (NIPAAm-co-IAM) microgel was synthesized by copolymerizing the temperature-sensitive monomer NIPAAm with two acid-base functional groups, and the IAM monomer had a bifunctional group. In the alkaline environment and metal ions to produce chelating effect (Chelate), and the use of copolymer phase change temperature will increase because of the addition of IAM, in order to achieve at adout 36℃ degree can also capture the metal ions.

摘要 i
Abstract iii
致謝 v
目錄 vi
表目錄 ix
圖目錄 x
第一章 緒論 1
1.1前言 1
1.2研究動機 2
第二章 文獻回顧 3
2.1智慧型材料(Intelligent Materials) 3
2.1.1智慧型高分子材料(Smart Polmer) 4
2.1.1.1溫度敏感型材料(Thermo-sensitive polymers) 6
2.1.1.2酸鹼敏感型材料(pH-sensitive polymers) 8
2.1.1.3光敏感型材料(Light-sensitive polymers) 10
2.1.1.4電場敏感型材料(Electric-sensitive polymers) 11
2.1.1.5 磁場敏感性高分子材料(Magnetic signal-sensitive polymers) 12
2.1.1.6化學物質敏感型材料(Chemical signal-sensitive polymers) 14
2.1.1.7溫度/酸鹼敏感型材料(Thermo/pH-sensitive polymers) 15
2.2微凝膠之相互作用力[21] 16
2.2.1相互作用力種類 16
2.3臨界溶液溫度(Critical solution temperature) 17
2.4氮-異丙基丙烯醯胺(N-isopropylacrylamide)介紹 19
2.5高分子聚合法 20
2.6微乳化/反微乳化(Emulsion/Inverse emulsion) 23
2.7鹽析(salting out) 24
2.8螯合(chelate) 24
2.9共聚物高分子排列 25
第三章 實驗 26
3.1藥品及儀器 26
3.2實驗儀器 29
3.2.1液態超導核磁共振儀 30
3.2.2傅立葉轉換紅外線光譜儀 31
3.2.3雷射光穿透度儀 32
3.2.4動態光散射粒徑儀 33
3.2.5高解析穿透式電子顯微鏡 34
3.2.6熱示差掃描分析儀 35
3.3實驗流程 36
3.3.1合成 36
3.3.1.1以自由基乳化聚合法合成Oil in Water PNIPAAm microgel & P(NIPAAM-co-IAM) microgel 38
3.3.1.2以自由基反乳化聚合法合成Water in Oil PNIPAAm microgel & P(NIPAAM-co-IAM) microgel 39
3.3.2樣品分析及步驟 40
3.3.2.1最低臨界溶液溫度 40
3.3.2.2 DLS樣品處理 40
3.3.2.3 HRTEM樣品處理 40
第四章 結果與討論 41
4.1以自由基乳化聚合法合成Oil in Water PNIPAAm microgel & P(NIPAAM-co-IAM) microgel 41
4.1.1 FT-IR結構鑒定 41
4.1.2 1H-NMR結構鑒定 44
4.1.3相變化測試 48
4.1.4微膠型態觀察 49
4.2以自由基反乳化聚合法合成Water in Oil PNIPAAm microgel & P(NIPAAM-co-IAM) microgel 50
4.2.1 FT-IR結構鑒定 50
4.2.2 1H-NMR結構鑒定 53
4.2.3相變化測試 57
4.2.4粒徑分析探討 66
4.2.5微膠型態觀察 68
4.3兩種聚合法之比較 70
第五章 結論 71
參考文獻 73

[1] 高長有、馬列 編著，醫用高分子材料，化學工業出版社，第34-44頁。
[2] 林資隆，γ-PGA高分子水膠的化工製程與開發應用，碩士論文，國立雲林科技大學化學工程與材料工程所碩士班，雲林，2007。
[3] Brannon-Peppas, L.; Peppas, N. A., Dynamic and equilibrium swelling behaviour of pH-sensitive hydrogels containing 2-hydroxyethyl methacrylate. Biomaterials 1990, 11 (9), 635-644.
[4] 姚康德、成國祥, 智慧材料-Intelligent Materials. 五南圖書出版公司 2003, 1-378.
[5] Dimitrov, I.; Trzebicka, B.; Müller, A. H. E.; Dworak, A.; Tsvetanov, C. B., Thermosensitive water-soluble copolymers with doubly responsive reversibly interacting entities. Progress in Polymer Science 2007, 32 (11), 1275-1343.
[6] Staudinger, H. F., J, Über die Hydrierung des Kautschuks und über seine Konstitution. Helv. Chim. Acta 1922, 5, 785-806.
[7] Zhou, X.; Weng, L.; Chen, Q.; Zhang, J.; Shen, D.; Li, Z.; Shao, M.; Xu, J., Investigation of pH sensitivity of poly(acrylic acid-co-acrylamide) hydrogel. Polymer International 2003, 52 (7), 1153-1157.
[8] Qiu, Y.; Park, K., Environment-sensitive hydrogels for drug delivery. Advanced Drug Delivery Reviews 2001, 53 (3), 321-339.
[9] 姚康德、成國祥，智慧材料-Intelligent Materials，五南圖書出版公司，2003，1-378。
[10] Hu, S.-H.; Liu, T.-Y.; Liu, D.-M.; Chen, S.-Y., Controlled Pulsatile Drug Release from a Ferrogel by a High-Frequency Magnetic Field. Macromolecules 2007, 40 (19), 6786-6788.
[11] Liu, T.-Y.; Hu, S.-H.; Liu, T.-Y.; Liu, D.-M.; Chen, S.-Y., Magnetic-Sensitive Behavior of Intelligent Ferrogels for Controlled Release of Drug. Langmuir 2006, 22 (14), 5974-5978.
[12] Liu, T.-Y.; Hu, S.-H.; Liu, K.-H.; Liu, D.-M.; Chen, S.-Y., Preparation and characterization of smart magnetic hydrogels and its use for drug release. Journal of Magnetism and Magnetic Materials 2006, 304 (1), e397-e399
[13]Xulu, P. M.; Filipcsei, G.; Zrínyi, M., Preparation and Responsive Properties of Magnetically Soft Poly(N-isopropylacrylamide) Gels. Macromolecules 2000, 33 (5), 1716-1719.
[14] Suzuki, A.; Tanaka, T., Phase transition in polymer gels induced by visible light. Nature 1990, 346 (6282), 345-347.
[15] Ichikawa, H.; Fukumori, Y., A novel positively thermosensitive controlled-release microcapsule with membrane of nano-sized poly(N-isopropylacrylamide) gel dispersed in ethylcellulose matrix. Journal of Controlled Release 2000, 63 (1–2), 107-119.
[16] Chun, S.-W.; Kim, J.-D., A novel hydrogel-dispersed composite membrane of poly(N-isopropylacrylamide) in a gelatin matrix and its thermally actuated permeation of 4-acetamidophen. Journal of Controlled Release 1996, 38 (1), 39-47.
[17] Yu, H.; Grainger, D. W., Thermo-sensitive swelling behavior in crosslinked N-isopropylacrylamide networks: Cationic, anionic, and ampholytic hydrogels. Journal of Applied Polymer Science 1993, 49 (9), 1553-1563.
[18] Schild, H. G., Poly(N-isopropylacrylamide): experiment, theory and application. Progress in Polymer Science 1992, 17 (2), 163-249
[19] Odian, G., Principles of Polymerization, 4th Edition. A JOHN WILEY & SONS, INC., PUBLICATION 2004.
[20] Hsieh, H. Q., R, Anionic Polymerization: Principles and practical applications. Marcel Dekker, Inc: New York 1996.
[21] 王駿傑，異丙基烯醯胺與磺基甜菜鹼共聚水凝膠之製備與性質研究及其於藥物控制釋放之行為，碩士論文，國立中央大學化學工程與材料工程學系碩士班，2012。
[22] Y. Tamai and H. Tanaka, "Molecular Dynamics Study of Polymer-Water Interaction in Hydrogels. 1. Hydrogen-Bond Structure," Macromolecules, vol. 29, pp. 6750-6760, 1996.
[23] Dong, L. C.; Hoffman, A. S. J Control Release 1990, 13, 21.
[24] Stoffer, J. O.; Bone, T. J Polym Sci Polym Chem Ed 1980, 18, 2641.
[25] Gan, L. M.; Chieng, T. H.; Chew, C. H. Langmuir 1994, 10, 4022.
[26] Palani Raj, W. R.; Sasthav, M.; Cheung, H. M. Polymer 1995, 13, 2637.
[27] Nurettin, S.; Mohit, S. Polymer 2007, 48, 2827.
[28] Guo, X.; Lin, L.; Chin, G. R.. Chem Lett 2004, 15, 691.
[29] Sasthav, M.; Cheung, H. M. Langmuir 1991, 7, 1378.
[30] Li, T. D.; Gan, L. M.; Chew, C. H. J Membr Sci 1997, 133, 177.
[31] Zhang, G. X.; Xu, X. L.; Tang, J. G. J Appl Polym Sci 2000, 77, 1989.
[32] Ye, Q.; Zhou, W.; Liu, H. R. Acta Polym Sin 2005, 1, 40.
[33] Mitchell, D. J.; Ninham, B. W. J Chem Soc Faraday II 1981, 77, 609.
[34] Scriven, N. C. Nature (London) 1976, 263, 123.
[35] Co, C. C.; Cotts, P.; Burauer, S.; de Vries, R.; Kaler, E. W. Macromolecules, 2001, 34, 3245.
[36] Shimaa M. Elsaeed, Reem K. Farag, Nermien S. Maysour, Synthesis and Characterization of pH-Sensitive Crosslinked (NIPA-co-AAC) Nanohydrogels Copolymer. Journal of Applied Polymer Science, Vol. 124, 1947–1955 (2012)
[37] Mamada, A.; Tanaka, T.; Kungwatchakun, D.; Irie, M., Photoinduced phase transition of gels. Macromolecules 1990, 23 (5), 1517-1519.
[38] Zrínyi, M.; Barsi, L.; Büki, A., Ferrogel: a new magneto-controlled elastic medium. Polymer Gels and Networks 1997, 5 (5), 415-427.
[39] J.M.G. Cowie, V. A., Polymers: Chemistry and Physics of Modern Materials, Third Edition. CRC Press Taylor&Francis Group 2007.
[40] Viran P. Mahida, Manish P. Patel, Removal of heavy metal ions from aqueous solution by superabsorbent poly (NIPAAm/DAPB/AA) amphoteric nanohydrogel, Desalination and Water Treatment 57 (2016) 13733–13746
[41] J.J. Chen, A.L. Ahmad, B.S. Ooi, Thermo-responsive properties of poly (N-isopropylacrylamide-co-acrylic acid) hydrogel and its effect on copper ion removal and fouling of polymer-enhancedultrafiltration, Journal ofMembraneScience469(2014)73–79
[42] 陳建智,，合成溫度/酸鹼敏感型水膠及微膠：聚N-異丙基丙烯醯胺及其共聚物行為探討，碩士論文，國立台北科技大學有機高分子研究所，2015。
[43] 許永家，NIPAM/IAM/β-CD之共聚合成及凝膠藥物釋放研究，碩士論文，國立台北科技大學有機高分子研究所，2016。