溶膠-凝膠法製備環氧樹脂/二氧化矽有機無機混成體

以作者查詢圖書館館藏

、以作者查詢臺灣博碩士

、以作者查詢全國書目

、勘誤回報

、線上人數：53

、訪客IP：3.16.82.140

姓名

蔡松伯(Sung-Po Tsai) 查詢紙本館藏

畢業系所

化學工程與材料工程學系

論文名稱

溶膠-凝膠法製備環氧樹脂/二氧化矽有機無機混成體

相關論文

★ 快速合成具核殼結構之均ㄧ粒徑次微米球與其表面改質之特性研究	★ 高效率染料敏化太陽能電池及製備次模組元件之研究
★ 利用核殼結構次微米球建構具耐溶劑性質及機械性質之光子晶體膜	★ 利用次微米球建構具機械性質之光子晶體薄膜
★ 電漿高分子聚合膜對二氧化碳及甲烷氣體之分離性研究	★ 同時聚合下製備聚苯乙烯/矽膠高分子混成體
★ 甲基丙烯酸酯系列團聯共聚物為界面活性劑之迷你乳化聚合研究	★ 含水溶性藥物之乙基纖維素微膠囊的製備
★ 銅箔基板環氧樹脂含浸液之研究	★ 含光敏感單體之甲基丙烯酸酯系列正型光阻之製備
★ 溶膠-凝膠法製備聚甲基丙烯酸甲酯 / 二氧化矽混成體之研究	★ 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
★ 溶膠-凝膠法製備相轉移材料微膠囊	★ 親疏水性光阻製備
★ 奈米多孔性材料之製備	★ 分子拓印高分子之製備

檔案

[Endnote RIS 格式]

[Bibtex 格式]

[相關文章]

[文章引用]

[完整記錄]

[館藏目錄]

[檢視]

[下載]

本電子論文使用權限為同意立即開放。
已達開放權限電子全文僅授權使用者為學術研究之目的，進行個人非營利性質之檢索、閱讀、列印。
請遵守中華民國著作權法之相關規定，切勿任意重製、散佈、改作、轉貼、播送，以免觸法。

摘要(中)

本研究利用溶膠-凝膠法(sol-gel process)藉由無機中的二氧化矽來製備環氧樹脂( Epoxy)與二氧化矽( SiO2)混成材料，並將製成的混成材料以TGA測試其耐熱性質。
首先無機二氧化矽相是先將系統中的四乙氧基矽烷、水、乙醇在不同酸鹼性環境下進行水解縮合反應，所生成產物稱為「前置物(precursor)」，並將此前置物與有機系統環氧樹脂進行混合再經後製硬化反應即可得環氧樹脂/二氧化矽有機無機混成體，同時稱此種方法為溶膠-凝膠聚合反應。
另外有機系統環氧樹脂部分主要探討含無機二氧化矽的環氧樹脂含浸液對促進劑2-MI的影響，同時利用恆溫DSC分析環氧樹脂含浸液在無機二氧化矽的存下在對反應溫度的影響。
最後在有機無機混成體的製備中，主要探討以下三部分：
(1) 利用矽偶合劑能提供有機無機兩相間良好共價性質並同時改變矽偶合劑的添加量從1%增加到100%，探討是否有助於有機無機混成體的耐熱性質提升。
(2) 提高無機二氧化矽在混成體中的含量從1%增加到10%，探討是否有助於有機無機混成體的耐熱性質提升。
(3) 使用不同矽偶合劑，分別為本身帶有兩個可進行水解縮合的矽乙氧烷官能基KBE-402與帶有三個可進行水解縮合的矽甲氧烷官能基KBM-403，探討有機無機混成體的耐熱性質差異。
研究結果顯示，利用前置物法在酸性觸媒下製得之環氧樹脂/二氧化矽混成體比在鹼性觸媒下所製得之混成體有較好的耐熱性質。同時利用前置物法所製備之混成體也比直接摻混的有機無機產物有較佳的耐熱性。
而在有機環氧樹脂含浸液中因無機二氧化矽的添加使得最大放熱峰從原本的166℃提高至197℃，同時在經改變促進劑的添加量後發現最大放熱峰的位置並沒明顯變化，顯示混成體並不會因促進劑的添加而改變其最大放熱峰的位置。不過在經添加1.17%的促進劑於含有無機二氧化矽的環氧樹脂含浸液後，經恆溫硬化反應可得當反應溫度在170℃反應一個小時後可得最佳耐熱性質之混成體。
另外在無機系統中添加矽偶合劑製成之環氧樹脂/二氧化矽混成體，經由熱重損失分析(TGA)發現高溫熱重損失率降低釵h，顯示矽偶合劑在有機無機相間提供部分的共價鍵能因此更佳提升混成體的耐熱性質，同時發現矽偶合劑在添加2.5%之後即可使混成體耐熱性質提升。
除此之外經由DSC與TGA的測試顯示，隨著無機二氧化矽在混成體中添加量的增加是有助於混成體玻璃轉移溫度與耐熱性質的提升；另外由FTIR也顯示有機無機混成體中同時存在著二氧化矽與環氧樹脂兩種成分。
最後在使用不同矽偶合劑製成之混成體經由TGA顯示其圖形往較高溫處移動，顯示添加此兩種矽偶合劑皆能達到耐熱性質的幼纂C

摘要(英)

This project is base on sol-gel process, which is using inorganic SiO2 to produce hybrid is blended from Epoxy and SiO2 together. Also test the hybrid’s heat-resistant property by using the TGA process.
To beginning with the inorganic system (SiO2) that is use Tetraethoxysilane, water, and Ethanol under different acidity and alkalinity catalysts and proceeded with hydrolysis-condensation reaction and the product which is called precursor. Also blended precursor and organic system (epoxy) then proceeded with curing reaction. According to the reaction then will produce the epoxy resin and SiO2 organic/inorganic mixtures. This method is called sol-gel polymerization.
Additional in the organic system, which is focus on effect of the inorganic SiO2’s epoxy varnish to the accelerating agent (2-MI). In the meantime, to proceed analyzed the epoxy varnish under the inorganic SiO2 the effect of reaction temperature by using isothermal DSC method.
In conclusion, there have three main conditions in organic-inorganic hybrids process.
1. Using silane coupling agent can provide good covalence between organic and inorganic also it has change amount of the silane coupling agent from 1% to 100%. This is discussing is it help to rise up the heat-resistant property of the organic/inorganic hybrid.
2. Increasing amount of inorganic SiO2 in hybrid from 1% to 10%. This is to discussing is it help to rise up the heat-resistant property of the organic/inorganic hybrid.
3. By using different silane coupling agents, individually, itself carry two KBE-402 (γ-glycidoxypropyl-methyldiethoxysilane) and three KBM-403 (γ-glycidoxypropyl-trimethoxysilane) to proceeded hydrolysis reaction, this is to discussing difference of the heat-resistant property between organic/inorganic hybrids.
The conclusion has shown, the method of precursor under acid catalyst can produce better heat-resistant property of the epoxy / SiO2 hybrid to compare with base catalyst. In the meantime, use the method of precursor to produce hybrid has better heat-resistant property than direct blend method products.
However, the epoxy varnish caused add inorganic SiO2 has resulted the maximum of exothermic peak has been increase from 166℃ to 197℃. At the same time it has been change the accelerating agent quantities the resulted has exhibited the position of maximum of exothermic peak didn’t obviously change, also exhibited hybrid doesn’t change the position of maximum of exothermic peak caused to increase accelerating agent. But after inorganic SiO2’s epoxy varnish has been add 1.17% accelerating agent and through the isothermal test and curing reaction, it can resulted when reaction temperatures in 170℃ has been processed one hour latter can produce great hybrid with heat-resistant property.
Additional, by add silane coupling agent’s hybrid into inorganic system which is made from epoxy / SiO2, it has been to heat weight less analysis (TGA) and found the heat weight less rate has decrease. It is show that silane-coupling agent between organic and inorganic has provided part of covalent bond. Therefore it also can promote hybrid’s heat-resistant property. In the meantime, also it can found out after add 2.5% silane coupling agent; it can rise up hybrid’s heat-resistant property.
Besides, resulted from DSC and TGA test, the quantity of the inorganic SiO2 has increase in hybrid it can help to transfer temperature from hybrid glass and promote the heat-resistant property. In addition from FTIR has shown in inside the organic-inorganic hybrids has two elements which is SiO2 and epoxy.
In conclusion, this graph shows it has move on high temperature by using different silane-coupling agent to produce hybrid and through the TGA method, it is shown there all can achieved the efficiency of heat-resistant property, by add two kinds of silane-coupling agent.

關鍵字(中)

★ 耐熱性質
★ 混成體
★ 溶膠-凝膠法
★ 環氧樹脂

關鍵字(英)

★ epoxy
★ heat-resistant property
★ hybrids
★ sol-gel

論文目次

目錄
目錄…………………………………………………………………….Ⅰ
表索引………………………………………………………………….Ⅱ
圖索引………………………………………………………………….Ⅳ
第一章緒論…………………………………………………………….1
第二章實驗……………………………………………………………19
2-1 實驗藥品..………………………………………………………20
2-2 實驗儀器..………………………………………………………21
2-3 有機無機混成體之製備…..……………………………………22
2-3-1 前置物之製備(無機部分)…………………………………22
2-3-2 自製無機二氧化矽粉體.………………………………….22
2-3-3 環氧樹脂含浸液之製備(有機部分)………………………22
2-3-4 環氧樹脂/二氧化矽混成體之製備……………………….22
2-4 產物測試條件…………………………………………………..24
2-4-1 熱重損失測試……………………………………………..24
2-4-2 DSC 測試條件……………………………………………..24
2-4-2-1 升溫式DSC測試條件………………………………...24
2-4-2-2 恆溫式DSC測試條件………………………………...24
2-4-2-3 玻璃轉移溫度測試 ………………………………….24
2-4-3 紅外線光譜儀分析 ……………………………………….25
2-4-4 二氧化矽粉體粒徑鑑定…………………………………..25
第三章結果與討論……………………………………………………26
3-1無機部分製備條件的探討探討………………………………….27
3-2有機部分製備條件的探討探討………………………………….35
3-2-1促進劑添加量的影響……………………………………….35
3-2-2恆溫硬化分析……………………………………………….41
3-3環氧樹脂/二氧化矽混成體的製備探討………………………..50
3-3-1矽偶合劑添加量對混成體的影響………………………….50
3-3-2改變前置物添加量對混成體的影響……………………….56
3-3-3不同矽偶合劑對混成體的影響…………………………….64
3-4環氧樹脂/二氧化矽混成體定性分析…………………………..69
第四章結論……………………………………………………………71
參考文獻……………………………………………………………….73

參考文獻

參考文獻
1. Schrade, Resins from Epichlorohydrin, Kunststoffe, Vol.43, 1953
2. P. Castan, CIBA Co., Swiss.211116, (1937)
3. P. Castan, CIBA Co., Brit.518057, (1937)
4. P. Castan, CIBA Co., U.S.2324483, (1937)
5. P. Castan, CIBA Co., U.S.2444333, (1937)
6. Greenlee, Devoe-Raynolds, U.S.2493486, (1939)
7. Greenlee, Devoe-Raynolds, U.S.2521911, (1939)
8. 賴耿陽,環氧樹脂應用實務,復漢出版社, (1999) 120
9. J. L. Hedrick, I. Yilgor, G. L. Wilkes, J. E. McGrath, Polymer Bulletin, 33 (1985) 303
10. H. Batzer, J. Appl. Polym. Sci., 19 (1975) 601
11. Honda, Nobuyuki, Sugiyama, Tsuyosi, Suzuki, Tetsuaki, Toshiba Chemical Corporation, EP.0795570, (1997)
12. Sicken, Martin, Hoechst Aktiengesellschaft, U.S.5728746, 1996
13. Von Gentzkow, Wolfgang, Huber, Jurgen, Siemens Aktiengesellschaft, U.S.5817736, (1996)
14. Horold, Sebastian, Hoechst Aktiengesellschaft, U.S.5854371, (1997)
15. Sumitomo Bakelite Co., Ltd. JP.97-200522, (1997)
16. Mitsubishi Gas Chemical Co., Ltd. JP.97-101635, (1997)
17. Gentzkow, Wolfgang von, Dr. Dipl.-Chem., Kleinsendelbach, Siemens A–G, DE.9719747553, (1997)
18. G. Wisanrakkit, J. K. Gillham, J. Coat. Technol., 63 (1983) 35
19. W. A. Rosser, S. H. Imani, H. Wise, Combust. Flame., 30 (1966) 387
20. M. J. Drews, R. H. Barker, Development of Flame Retardants for Polyester/Cotton Blends, (1976) 76
21. S. K. Brauman, J. Fire Retard. Chem., 7 (1980) 3
22. E. R. Larsen, R. B. Ludwing, J. Fire Flammability, 30 (1979) 69
23. C. S. Wang , C. H. Lin, J. Polym. Sci., Part A: Polym. Chem., 37 (1999) 3903
24. Schroeder, H. Phys. Thin Film, 5 (1969) 87
25. Woodhead, J. L. Silicate Ind., 37 (1972) 191
26. L. Levene, I. M. Thomas, U.S. Patent 3,640,093(1972)
27. Dislich, H. Angewandt Chemie, 10 [6] (1971) 363
28. G. S. Sur, J. E. Mark, Eur. Polym. J., 21 (1985) 1051
29. J. E. Mark, G. S. Sur, Polym. Bull., 14 (1985) 325
30. S. J. Clarson, J. E. Mark, Polym. Commun., 28 (1987) 249
31. Y. Imai, Advances in polymer science., 1 (1999) 140
32. H. J. L. Samuelson, L. L. Kumar, J. S. Tripathy, Advanced Materials, 11 (1999) 435
33. M. Guglielmi, G. Brusatin, G. Facchin, M. Gleria, Appiled Organometallic chemistry, 13 (1999) 339
34. Y. Takahashi,; A. Maeda, K. Kojima, K. Uchida, J. Luminescence, 87 (2000) 767
35. M. Opallo, Kukulka, J. Electrochemistry Communications, 2 (2000) 394
36. S. Mimura, H. Naito, Y. Kanemitsu, K. Matsukawa, H. Inoue, J. Organometallic Chemistry, 40 (2000) 611
37. S. H. Jang, M. G. Han, S. S. Im, Synthetic Metals, 17 (2000) 110
38. T. C. Chang, Y. T. Wang, Y. S. Hong, H. B. Chen, J. C. Yang, Polymer Degradation and Stability, 69 (2000) 317
39. Kai Dallmann, Buffon, Regina. Catalysis Communications, 1 (2000) 9
40. Whan Cho, Jae, Il Sul, Kyung, Polymer, 42 (2001) 727
41. H. K. Schmidt, Mater. Res. Soc. Symp. Proc., 32 (1984) 327
42. Society, Washington, 1988, 333
43. H. K. Schmidt, Mater. Res. Soc. Symp. Proc., 180 ( 1990) 961
44. J. D. M ackenzie, J. Sol-Gel Sci. Tech., 2 (1994) 81 and references therein.
45. U. Schubert, Hu¨ sing, N. Lorenz, A. Chem. Mater., 7 (1995) 2010
46. D. A. Loy, K. J. Shea, Chem. Rev., 95 (1995) 1431
47. Judenstein, P. Sanchez, C. J. Mater. Chem., 6 (1996) 511
48. K. J. Shea, D. A. Loy, O.W. Webster, Chem. Mater., 1 (1989) 574
49. K. J. Shea, D. A. Loy, O.W. Webster, J. Am. Chem. Soc., 114 (1992) 6700 and references therein.
50. K. M. Choi, K. J. Shea, J. Am. Chem. Soc., 116 (1994) 9052
51. K. M. Choi, K. J. Shea, Phys. Chem., 98 (1994) 3207
52. K. M. Choi, J. C. Hemminger, K. J. Shea, J. Phys. Chem., 99 (1995) 4720
53. H. W. Oviatt, K. J. Shea, S. Y. Kalluri, W. H. Steier, L. R. Dalton, Chem. Mater., 7 (1995) 493
54. H. W. Oviatt, K. J. Shea, J. H. Small, Chem. Mater., 5 (1993) 943
55. D. A. Loy, G. M. Jamison, B. M. Baugher, S. A. Myers, R. A. Assink, K. J. Shea, Chem. Mater., 8 (1996) 656
56. R. J. P. Corriu, D. Leclercq, A. Vioux, M. Pauthe, J. Phalippou, Mackenzie, in: J.D. Ulrich( Eds.), D.R. Ultrastructure Processing of Advanced Ceramics, J. Wiley and Sons., (1988) 113
57. R. J. P. Corriu, D. Leclercq, Angew. Chem. Int. Ed. Engl., 35 ( 1996) 1420 and references therein.
58. Sakka, S. Kamiya, K. J. Non-Cryst. Solids, 42 (1980) 403
59. C. J. Brinker, G. W. Scherer, Sol-Gel Science: the Physics and Chemistry of Sol-Gel Processing, Academic Press, San Diego, 1990.
60. L. C. Klein, Ann. Rev. Mater. Sci., 15 (1985) 227
61. L. L. Hench, J. K. West, Chem. Rev., 90 (1990) 33
62. C. D. Chandler, M. C. Roger, Hampden-Smith, J. Chem. Rev., 93 (1993) 1205
63. R. K. Iler, Chemistry of Silica, J. Wiley and Sons, New York, 1979.
64. J. Livage, M. Henry, C. Sanchez, Prog. Solid State Chem., 18 (1988) 259
65. R. Aelion, A. Loebel, F. Eirich, Am. Chem. Soc. J., 72 (1950) 124
66. R. Aelion, A. Loebel, F. Eirich, Recueil, 69 (1950) 61
67. Yoldas, B. E., J. Mater. Sci., 14 (1979) 1843
68. M. Nogami, Y. Moriya, J. Non-Cryst. Solids, 37 (1980) 191
69. L. C. Klein, G. J. Garvey, J. Non-Cryst. Solids, 38 (1980) 39
70. S. P. Makherju, J. Non-Cryst. Solids, 42 (1980) 477
71. D. P. Partlow, B. E. Yoldas, J. Non-Cryst. Solids, 46 (1981) 153
72. B. E. Yoldas, J. Non-Cryst. Solids, 51 (1982) 105
73. Y. Paoting, L. Hsiaoming, W. Yuguang, J. Non-Cryst. Solids, 52 (1982) 511
74. D.W. Schaefer, K. D. Keefer, Mater. Res Soc. Symp. Proc., 73 (1986) 277
75. E. J. A. Pope, J. D. Mackenzie, J. Non-Cryst. Solids, 87 (1986) 185
76. T. W. Zerda, I. Artaki, J. Jonas, J. Non-Cryst. Solids, 81 (1986) 365
77. B. Himmel, T. Gerber, H. Burger, J. Non-Cryst. Solids, 91 (1987) 122
78. R. J. P. Corriu, J. J. E. Moreau, P. Thepot, M. C. Wong, Chem. Mater., 4 (1992) 1217.
79. G. Cerveau, R. J. P. Corriu, C. J. Lepeytre, Organomet. Chem. 548 (1997) 99.
80. G. Cerveau, R. J. P. Corriu, C. Lepeytre, to be published.
81. R. K. Iler, The Chemistry of silica (Wiley, New York, 1979).
82. B. E. Yoldas, J. Mater. Sci., 14 (1979) 1843
83. M. Nogami, Y. Moriya, J. Non-Cryst. Solids, 37 (1980) 191
84. 詹佳樺,中央大學化學工程研究所碩士論文,(2001) 13
85. R. Tamaki, K. Naka, Y. Chujo, Polymer Bulletin, 39 (1997) 303
86. R. Tamaki, T. Horiguchi, Y. Chujo, Bull. Chem. Soc. Jpn., 71 (1998) 2749
87. R. Tamaki, Y. J. Chujo, Mater. Chem., 8 (1998) 1113
88. R. Tamaki, Y. Chujo, Organometal. Chem., 12 (1998) 755
89. 詹佳樺,中央大學化學工程研究所碩士論文,(2001) 67
90. R. Tamaki, Y.Chujo, Chem. Mater., 11 (1999) 1719
91. J. L. Nell, G. L. Wilkes, D. K. Mohanty, J. Appl. Polym. Sci., 40 (1990) 1177
92. J. Teofil, K. Andrzej, J. Non-Cryst. solids, 277 (2000) 45
93. A. Nigel, R. B. Jamea, Composites part A , 29A (1998) 939
94. M. E. Connell, W. M. Cross, T. G. Snyder, R. M. Winter, J. J. Kellar Composites part A, 29A (1998) 495
95. G. H. Hsiue, W. J. Wang, F. C. Chang, J. Appl. polym. Sci., 73 (1999)1231
96. W. J. Wang, L. H Perng, G. H. Hsiue, F. C. Chang, Polymer, 41 (2000) 6113
97. J. B. Enns, J. K. Gillham, J. Appl. Polym. Sci., 38 (1983) 3567
98. J. K. Gillham in Developments in Polymer Characterization, J.V. Dawkins Eds, Appl. Sci. Publ., London, (1983) 359

指導教授

陳暉(Hui Chen)

審核日期

2002-6-18

推文