本論文是以聚乙烯亞胺的合成和微量重金屬之吸附為主要目的。因為含有微量重金屬的水溶液仍會為害人體，所以在水處理上，要如何將水中重金屬離子的含量降至最低成為本研究主要目標所在。
本研究使用含有胺基的TMPTA-Az為螯合金屬離子之主體，加入最佳化比例Acrylic acid使之形成網狀聚合物N-PEI(Networked Polyethyleneimine)；藉由此種交聯特性，本研究順利製作出將TMPTA-Az附著於二氧化矽上可以達到增加螯合表面積進而增加螯合效率的方法。另外利用交聯聚合物本身並不溶於水之特性，我們可以放心將此種螯合劑與水相溶液接觸，且不會帶走螯合劑，確保重複利用可行性Cu2+10次循環仍有70%的再螯合率(20分鐘酸洗條件)，再螯合率87%(1天酸洗條件)；Pb2+10次循環仍有60%的再螯合率(20分鐘酸洗條件)，(1天酸洗條件)。
本研究針對材料特性分析Cu2+、Pb2+金屬離子濃度變化探討、最佳螯合時間探討(40分鐘，Cu2+ 與 Pb2+)、溫度變化探討(83℃，Cu2+ 與 Pb2+)、pH值變化探討(pH5.3，Cu2+ 與 Pb2+)，最後討論PEI等溫吸附模式。

In this research, it well-known that human were hurt by trace heavy metal. So we utilized the subject of TMPTA-AZ and suitable ratio of Acrylic acid that synthesized crosslinking polymer. It called “polyethyleneimine” that can chelated metal ion forming complex . Crosslinking polymer can insoluble in water base solution. The feature is good, because we need a base to concentrated trace heavy metal. The metal ion usually appears in water solution. 
  We successfully created the TMPTA-Az that can be attached to the silica surface area to increase the chelating efficiency.
N-PEI/SiO2 recycles and reuse had a good result for cupric ion (10cycles, 70% chelating efficiency in 20min acid wash; 87% chelating efficiency in 1 day acid wash) and lead ion(10cycles, 60% chelating efficiency in 20min acid wash; 76% chelating efficiency in 1 day acid wash)
N-PEI/SiO2 Material properties of cupric ion(maximum chelating efficiency, 0.141Cu2+/N), lead ion(maximum chelating efficiency, 0.135Pb2+/N) concentrations of metal ions, the best time of adsorption(40 min for Cu2+ and Pb2+ ), changes of temperature(83℃ for Cu2+ and Pb2+), value changes of pH(pH5.3 for Cu2+ and Pb2+), and finally discuss the PEI adsorption isotherm.

中文摘要 ....................................................................................................
英文摘要......................................................................................................
謝誌..............................................................................................................
目錄 ............................................................................................................................ I
圖表索引 .................................................................................................................... V

一、 序    論 1
1-1 前言 1
1-2	動機與目的 1
二、 文獻回顧 3
2-1 高分子螯合材料 3
2-1-1 高分子螯合材料之種類 3
2-2 次乙亞胺之介紹 9
2-3 高分子螯合材料與金屬螯合之機制 14
2-3-1 高分子螯合材料影響因子 14
2-3-2 螯合物與錯合物 15
2-3-2-1 雙芽基團配位基 16
2-3-2-2 雙鹼基配位 17
2-3-2-3 一酸一鹼基配位 17
2-3-2-4 雙酸基配位 17
2-3-2-5 多芽基團配位基 18
2-4 吸附理論 19
2-4-1 吸附平衡 19
2-4-2 物理吸附 19
2-4-3 化學吸附 20
2-4-4-1 Freundlich 等溫吸附模式 21
2-4-4-2 Langmuir 等溫吸附模式 22
2-5 高分子螯合材料之應用 23
2-6 重金屬特性介紹 27
三、 實    驗 29
3-1 儀器與藥品 29
3-2 雙重架橋聚乙烯亞胺之製備 32
3-2-1 含三元次乙亞胺官能基架橋劑(TMPTA-AZ)之合成 32
3-2-2 次乙亞胺之合成 33
3-2-2-1 胺基乙基硫酸氫酯之合成 33
3-2-2-2 次乙亞胺之合成由胺基乙基硫酸氫脂為起始物 33
3-3 聚乙烯亞胺(Polyethyleneimine)之合成 34
3-3-1 Networked PEI薄膜之製備 34
3-3-2 Networked PEI/SiO2粉末之製備 34
3-3-3 Linear PEI之製備 36
3-4 物理性質之測試 37
3-4-1 膠含量測試(Gel content) 37
3-4-2 固含量測試(Solid content) 37
3-5 熱性質之測試 38
3-5-1 熱重分析(TGA) 38
3-6 光譜鑑定 39
3-6-1 傅立葉轉換紅外線光譜儀(FT-IR) 39
3-6-2 紫外光-可見光分子吸收光譜儀(UV-Vis) 40
3-6-2-1 L-PEI最大螯合量(固定TMPTA-Az含量) 42
3-6-2-2 L-PEI最大螯合量(固定銅含量) 42
3-6-3 化學分析影像能譜儀(ESCA, XPS) 43
3-7 吸附實驗 46
3-7-1 平衡吸附時間 46
3-7-2 等溫吸附曲線 46
3-7-3 變溫實驗 47
3-7-4 pH值實驗 47
3-7-5 Recycles and reuse 47
3-8 二價金屬含量測定 49
3-8-1 電化學分析 49
四、結  果  與  討  論 52
4-1 N-PEI/SiO2粉末光譜分析 52
4-2 N-PEI與Cu2+ complex之光譜鑑定 54
4-2-1 UV-VIS光譜 54
4-2-2 IR光譜 56
4-3 N-PEI/SiO2粉末含氮量之測定 61
4-3-1 TGA方法測量N-PEI於SiO2上的含量 61
4-4 N-PEI/SiO2粉末螯合金屬離子能力分析 63
4-4-1 最佳螯合時間 63
4-4-2 等溫吸附曲線 67
4-4-3 金屬離子對於其他變因於PEI螯合效率的變化 73
4-4-4 N-PEI/SiO2 Recycles and reuse 76
五、 結    論 78
六、	參  考  資  料 80

圖表索引
Scheme 3-1 TMPTA-Az 合成流程圖 ...................................................... 32
Scheme 3-2 Aziridine 合成流程圖 ......................................................... 33
Scheme 3-3 Networked PEI 薄膜合成流程圖 ........................................ 34
Scheme 3-4 Networked PEI/SiO2 粉末合成流程圖 ................................ 35
Scheme 3-5 Linear PEI 合成示意圖 ........................................................ 36
表2-1 物理吸附與化學吸附之比較 ...................................................... 21
表3-1 光譜儀器應用範圍 ...................................................................... 39
表3-2 有機物發色團種類與躍遷型態 .................................................. 42
表4-1 N-PEI 於SiO2 上的含量 ............................................................... 62
表4-2 銅離子最佳螯合時間 .................................................................. 65
表4-3 鉛離子最佳螯合時間 .................................................................. 66
表4-4 銅離子等溫螯合表 ...................................................................... 69
表4-5 鉛離子等溫螯合表 ...................................................................... 69
表4-6 金屬離子於其他變因對PEI 螯合效率的變化 .......................... 74
表5-1 結論總表 ...................................................................................... 79
圖2-1 Aziridine 質子化 ........................................................................... 10
圖2-2 Aziridine 自身聚合示意圖 ........................................................... 11
圖2-3 Aziridine 鏈延長示意圖 ............................................................... 11
圖2-4 PEI 基本架構 ................................................................................ 12
圖2-5 線性Polyethyleneimine ............................................................... 13
圖 3-1 N-PEI/SiO2 粉末合成示意圖 ...................................................... 36
圖3-2 電子躍遷型態 .............................................................................. 41
圖3-3 電子鍵結型態 .............................................................................. 41
圖3-4 ESCA 躍遷機制示意圖 ................................................................ 43
圖3-5 化學分析影像能譜儀 .................................................................. 45
圖3-6 吸附示意圖 .................................................................................. 46
圖3-7 Recycles and reuse 示意圖 ........................................................... 48
圖4-1 N-PEI/SiO2 粉末之IR 圖 .............................................................. 53
圖4-2 差異銅離子濃度與同當量L-PEI 之UV-Vis 光譜圖 ................ 57
圖4-3 差異銅離子濃度與同當量L-PEI(contain L-PEI ) ..................... 57
圖4-4 差異銅離子濃度與同當量L-PEI(without L-PEI, blank ) ......... 58
圖4-5 最大吸收值之吸收差值 .............................................................. 58
圖4-6 最大吸收峰之波長比較 .............................................................. 59
圖4-7 PEI-Cu2+與PEI 之IR 圖譜 .......................................................... 59
圖4-8 含三級胺之結構式 ...................................................................... 60
圖4-9 含三級胺之X-Ray 單晶繞射圖 ................................................. 60
圖4-10 N-PEI 螯合金屬離子的最佳時間 ............................................. 66
圖4-11 螯合效率與濃度變化 ................................................................ 70
圖4-12 N-PEI 對銅離子之Freundlich 吸附模式 ................................. 70
圖4-13 N-PEI 對銅離子之Langmuir 吸附模式 ................................... 71
圖4-14 N-PEI 對鉛離子之Freundlich 吸附模式 ................................. 71
圖4-15 N-PEI 對鉛離子之Langmuir 吸附模式 ................................... 72
圖4-16 螯合效率與溫度變化 ................................................................ 75
圖4-17 螯合效率與pH 值變化 ............................................................. 75
圖4-18 N-PEI/SiO2 於Cu2+溶液重複使用之效果 ................................. 77
圖4-19 N-PEI/SiO2 於Pb2+溶液重複使用之效果 ................................. 77

1.H.P. Gregor, M. Taifer, L. Citarel, E.I. Becker, Industrial and Engineering Chemistry, 44, 2834 (1952)

2.B.L. Rivas, I.M. Villoslada, Journal of Applied Polymer Science, 69, 817 (1998)

3.B. Gao, F. An, K. Liu, Applied Surface Science, 253, 1946 (2006)

4.I.M. Villoslada, F. González, M. Jofré, P. Chandía, S. Hess, B.L. Rivas, Macromolecular Chemistry and Physics, 206, 1541 (2005)

5.B.L. Rivas, S.A. Pooley, E.D. Pereira, R. Cid, M. Luna, M.A. Jara, K.E. Geckeler, Journal of Applied Polymer Science, 96, 222 (2005)

6.M. Ghoul, M. Bacquet, M. Morcellet, Water Research, 37, 729 (2003)

7.B. Salih, N. Pekel, O. Guven, Journal of Applied Polymer Science, 82, 446 (2001)

8.B.L. Rivas, E.D. Pereira, Journal of Applied Polymer Science, 80, 2578 (2001)

9.B.L. Rivas, S.A. Pooley, B. Ruf, P. Reyes, G. Cardenas, Journal of Applied Polymer Science, 83,1501 (2002)

10.A. Denizli, N. Sanli, B. Garipcan, Chemical Reaction Engineering, 43, 19 (2004)

11.S. Pramanik, S. Dey, P. Chattopadhyay, Analytica Chimica Acta, 584, 469 (2007)

12.U.D.N. Bajpai, S. Rai, A. Bajpai., Polymer lnternational, 32, 215 (1993)

13.S. Meesri, N. Praphairaksit, A. Imyim, Microchemical Journal, 87, 47 (2007)

14.T. Saegusa, S. Kobayashi, K. Hayashi, A. Yamada, Polymer Journal, 10, 403 (1978)

15.Z.-X. Su, Y.-B. Zhou, X.-J. Chang, Y. Jin, S.-K. Qi, Journal of Applied Polymer Science, 84, 962 (2002)

16.A. Jyo, K. Yamade, H. Egawa, Separation Science and Technology, 31, 513 (1996)

17.H. Wenker, Journal of American Chemical Society, 57, 2328 (1935)

18.J.W. Rosthauser, K. Nachtakamp, Journal of Coated Fabrics, 16, 39 (1986)

19.D. Dieterich, Progress in Organic Coatings, 9, 281 (1981)

20.C.-H. Shao, T.-Z. Wang, G.-N. Chen, K.-J. Chen, J.-T. Yeh, K.-N. Chen, Journal of Polymer Research, 7, 41 (2000)

21.K. Geckeler, G. Lange, H. Eberhardt, E. Bayer, Pure and Applied Chemistry, 52, l88 (1980)

22.C.D. Dudgeon, M.R. Winstead, U. S. Patent, 4, 493, 912 (1985)

23.E.G. Shur, Americal Paint Journal, Sep. 4 (1972)

24.L. Kanerva, H. Keskinen, P. Autio, Clinical and Experimental Allergy, 25, 432 (1995)

25.E.J. Goethals, R.R. Declercq, New Method for Polymer Synthesis, Chap 3 (1992)

26.P.-C. Chen, S.-C. Wang, C.-Y. Huang, J.-T. Yeh, K.-N. Chen, Journal of Applied Polymer Science, 104, 809 (2006)

27.S.-C. Wang, P.-C. Chen, J.-T. Yeh, K.-N. Chen, Journal of Applied Polymer Science, 110, 725 (2008)

28.M.-L. Roan, Y.-H. Chen, H.-H. Liao, C.-Y. Huang, K.-N. Chen, J.-T. Yeh, Macromolecular Symposia, 286, 116 (2009)

29.S. Oh, T. Kang, H. Kim, J. Moon, S. Hong, J. Yi, Journal of Membrane Science, 301,118 (2007)

30.C.F. Bell, Principles and Applications of Metal Chelation, Chap.1 (1977)

31.S. Simonovic, A.C. Whitwood, W. Clegg, R.W. Harrington, M.B. Hursthouse, L. Male, R.E. Douthwaite, European Journal of Inorganic Chemistry, 13, 1786 (2009)

32.K.-Y. Choi, M.-H. Kim, Transition Metal Chemistry, 29, 904 (2004)

33.A. Denizli, G. Ozkan, M.Y. Arica, Journal of Applied Polymer Science, 78, 81 (2000)

34.R. Sliba, H. Gauthier, R. Gauthier, M.P. Ramel, Journal of Applied Polymer Science, 75, 1624 (2000)

35.J.-S. Park, J.-H. Kim, Y.-C. Nho, O.-H. Kwon, Journal of Applied Polymer Scence, 69, 2213 (1998)

36.N.M. El-Sawy, F.A. Sagheer, European Polymer Journal, 37, 161 (2001)

37.C. Wu, J. Fu, Y. Zhao, Macromolecules, 33, 9040 (2000)

38.Y. Liu, L. Chen, B. Su, A. Huang, J. Hua, W. Sang, J. Min, Z. Meng, Journal of Applied Polymer Science, 84, 1263 (2000)

39.W. Maketon, C.Z. Zenner, K.L. Ogden, Environmental Science and Technology, 42, 2124 (2008)

40.D.A. Skoog, F.J Holler, T.A Nieman, Principle of Instrumental Analysis, 5th edition, p331, p539