同時聚合下製備聚苯乙烯/矽膠高分子混成體

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：42

、訪客IP：18.118.144.98

姓名

陳姿秀(Tzu-Hsiu Chen) 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

同時聚合下製備聚苯乙烯/矽膠高分子混成體
(Synthesis of Polystyrene/Silica Gel Polymer Hybrids by in-situ Polymerization Method)

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	★ 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-凝膠法製備環氧樹脂/二氧化矽有機無機混成體
★ 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)

均一透明之聚苯乙烯與矽膠的高分子混成體可藉由同時聚合法製備而得。有機-無機混成體之製備方法為將苯乙烯單體導入在含有起始劑偶氮異二丁月青（AIBN）與四乙氧基矽烷（TEOS）、有機溶劑之溶膠-凝膠反應液中，經混合後在60℃下反應，使得矽膠生成時也同時產生聚苯乙烯高分子。
本研究分兩部份來探討整個混成反應，也就是在探討不精製苯乙烯單體之下製備有機-無機混成體以及精製苯乙烯單體之下製備有機-無機混成體。
不精製苯乙烯單體之下製備有機-無機混成體的研究中，探討改變反應條件是否能製備出透明之有機-無機混成體，例如酸的用量與濃度、水的添加量、起始劑的用量、無機相的添加量與溶劑的用量及種類等。結果顯示，在適量之乙醇或氰甲烷為溶劑下，添加少許水，就能得到透明之有機-無機混成體。當有機-無機混成體為一透明物時，觀察不到其玻璃轉移溫度，可以證明高分子鏈已經均勻分散在不定形之二氧化矽基材中。經由鍛燒後無機物中的孔徑大小（1.88nm）與表面積（325m2/g）、孔洞體積（152mm3/g），可判斷出聚苯乙烯是以奈米單位均勻分散在無機相的矽基材中。
精製苯乙烯單體之下製備有機-無機混成體的研究，以改變反應物中之添加量為主，也就是改變水的添加量以及苯乙烯單體的添加量來製備有機-無機混成體。結果顯示溶膠-凝膠反應液中利用同時聚合法，改變含水量（[H2O] / [TEOS] = 4.35×10-2∼10）與苯乙烯含量（St / TEOS = 0.184∼0.554）都可製備出聚苯乙烯與矽膠的高分子混成體。經由FTIR、DSC、TGA與ASAP之測定可知所製備之物為有機-無機混成體且孔徑大小為奈米單位。當水量含量較多時，其結構較為緊密，耐熱溫度較高。另外增加四乙氧基矽烷含量也會使透明之有機-無機混成體的耐熱溫度增加。經由透明之有機-無機混成體與熱萃殘餘物之TGA數據可算出，在本系統中有機部份與無機部份的組成比為0.232至0.817。

摘要(英)

Homogeneous polystyrene and silica gel polymer hybrids were prepared by in-situ radical polymerization in sol-gel reaction mixture. Styrene monomer was introduced into a sol-gel reaction mixture of tetraethoxysilane (TEOS) and the polymerization was initiated by 2,2’’-azobisisobutyronitrile (AIBN) at 60℃, while sol-gel reaction of TEOS proceeded to form a silica gel.
This study was divided into two parts depended on the preparation of hybrids by using styrene monomer with or without purification.
In the part of the preparation of organic-inorganic hybrids by adding styrene monomer without purification, the main purpose were to confirm transparent hybrids could be prepared by this method or not and also to discuss the preparation conditions, the amount and concentration of acid, the amount of water, AIBN, TEOS and solvent. The results showed that the transparent hybrids were obtained even at adding small amount of water by using ethanol or CH3CN as solvent. The characterizations of the hybrids were determined by the results of GPC, DSC and TGA. The DSC curve of the transparent hybrids did not show any clear glass transition temperature. This lack of glass transition suggests that the polymer chains are uniformly distributed in the inorganic glass network. The porous silica obtained from the hybrids had high surface area and large pore volume and exhibited pore size 1.88 nm. These results indicate that polystyrene was dispersed at a nano-meter level in the silica gel matrix.
In the part of the preparation of organic-inorganic hybrids by adding styrene monomer with purification, the main purpose was to investigate the effect of the concentration of reactants, water and styrene, on the hybrids. The results indicated that the transparent hybrids were obtained by adding various amounts of water（[H2O] / [TEOS] = 4.35×10-2∼10）and styrene（St / TEOS = 0.184∼0.554）by in-situ radical polymerization in sol-gel reaction mixture. The characterizations and pore size of the hybrids were determined by the results of FTIR, DSC, TGA and ASAP. The TGA curves of the transparent hybrids show the higher heat-resistant of hybrids can be obtained by increase the amount of water and TEOS. The ratio of organic to inorganic parts was about 0.232 to 0.817.

關鍵字(中)

★ 混成體
★ 溶膠-凝膠反應
★ 四乙氧基矽烷
★ 聚苯乙烯

關鍵字(英)

★ sol-gel reaction
★ tetraethoxysilane
★ polystyrene
★ hybrids

論文目次

中文摘要…………………………………………………………………I
英文摘要………………………………………………………………III
表目錄…………………………………………………………………V
圖目錄………………………………………………………………VIII
第一章前言……………………………………………………………1
第二章實驗…………………………………………………………23
2-1實驗藥品………………………………………………………24
2-2實驗儀器………………………………………………………25
2-3有機-無機混成體之製備……………………………………26
2-3-1苯乙烯單體之精製……….………………………………26
2-3-2有機-無機混成體之製備…………………………………26
2-4有機-無機混成體之物性測試………………………………28
2-4-1有機-無機混成體中有機高分子之萃取…………………28
2-4-2聚苯乙烯高分子之分子量………………………………28
2-4-3玻璃轉移溫度測試………………………………………28
2-4-4熱重損失測試……………………………………………29
2-4-5表面積、孔洞體積與孔徑大小之分析…………………29
2-4-6紅外線光譜分析…………………………………………29
第三章結果與討論(I) ………………………………………………30
3-1有機-無機混成體之製備條件探討…………………………31
3-2有機-無機混成體之聚苯乙烯分子量探討…………………43
3-3有機-無機混成體之玻璃轉移溫度探討……………………45
3-4有機-無機混成體之熱性質分析……………………………47
3-5有機-無機混成體表面積、孔洞體積及孔徑大小…………50
3-6結論……………………………………………………………52
第四章結果與討論(II)………………………………………………53
4-1改變水量下製備有機-無機混成體…………………………54
4-1-1有機-無機混成體的製備與性質…………………………54
4-1-2有機-無機混成體之熱分析………………………………60
4-2改變苯乙烯含量下製備有機-無機混成體…………………72
4-2-1有機-無機混成體的製備…………………………………72
4-2-2有機-無機混成體之熱分析………………………………72
4-3結論…………………………………………………………85
第五章總結…………………………………………………………86
參考文獻………………………………………………………………88

參考文獻

1.Sur, G. S. and Mark, J. E. Eur Polym. J., 21 (1985) 1051
2.Mark, J. E. and Sur, G. S. Polym. Bull., 14 (1985) 325
3.Clarson, S. J. and Mark, J. E. Polym. Commun., 28 (1987) 249
4.Sun, C.-C. and Mark, J. E. Polymer, 30 (1989) 104
5.Mark, J. E. Chemtech., April (1989) 230
6.Wung, C. J.; Pang, Y.; Prasad, P. N. and Karasz, F. E. Polymer, 32 (1991) 605
7.Motakef, S.; Suratwala, T.; Roncone, R. L.; Boulton, J. M.; Teowee, G.; Neilson, G. F. and Uhlmann, D. R. J. Non-Cryst Solids, 178 (1994) 31
8.Motakef, S.; Suratwala, T.; Roncone, R. L.; Boulton, J. M.; Teowee, G.; Uhlmann, D. R. J. Non-Cryst. Solids, 178 (1994) 37
9.Yoshida, M. and Prasad, P. N. Appl. Opt., 35 (1996) 1500
10.Xu, C.; Eldada, L.; Wu, C.; Norwood, R. A.; Shacklette, L. W.; Yardley, J. T. and Wei, Y. Chem. Mater., 8 (1996) 2701
11.Dave, B. C.; Dunn, B.; Valentine, J. S. and Zink, J. I. Anal. Chem., 66 (1994) 1120
12.Claude, C.; Garetz, B.; Okamoto, Y. and Tripathy, S. Mater. Lett., 14 (1992) 336
13.L-Davies, B.; Samoc, M. and Woodruff, M. Chem. Mater., 8 (1996) 2586
14.Sakka, S.：NEW GLASS, 日刊工業新聞社 (1987) 1
15.Sakka, S.：NEW GLASS, 3 (1987) 1
16.Dislich, H.：Angew. Chem. Int. Ed. Engl., 10 (1971) 363
17.Mazdiyasni, K. S., Dolloff R.T., and Smith, J. S.：J. Amer. Ceram. Soc., 52 (1969) 523
18.Novak, B. M., Adv. Mater., 5 (1993) 422
19.Hench, L. L. and West., J. K., Chem. Rev., 90 (1990) 33
20.Mackenzie, J. D., J. Non-Cryst. Solids, 48 (1982) 1
21.Brinker, C.J. and Scherer, G. W., J. Non-Crystalline Solids, 70 (1985) 301
22.Sakka, S.：Treatise on Materials Science and Technology, 22. Glass III, ed. M. Tomozawa and R. Doremus, Academic Press, New York (1982) 129
23.Brinker, C.J., J. Non-Crystalline Solids, 100 (1988) 31
24.Aelion, R., Loebel, A. and Eirich, F., Am. Chem. Soc. J., 72 (1950) 124
25.Aelion, R., Loebel, A. and Eirich, F., Recueil, 69 (1950) 61
26.Yoldas, B. E., J. Mater. Sci., 14 (1979) 1843
27.Nogami, M. and Moriya, Y., J. Non-Cryst. Solids, 37 (1980) 191
28.Klein, L. C. and Garvey, G. J., J. Non-Cryst. Solids, 38 (1980) 39
29.Makherju, S. P., J. Non-Cryst. Solids, 42 (1980) 477
30.Partlow, D. P. and Yoldas, B. E., J. Non-Cryst. Solids, 46 (1981) 153
31.Yoldas, B. E., J. Non-Cryst. Solids, 51 (1982) 105
32.Paoting, Y., Hsiaoming, L. and Yuguang, W., J. Non-Cryst. Solids, 52 (1982) 511
33.Schaefer, D.W. and Keefer, K. D., Mater. Res Soc. Symp. Proc., 73 (1986) 277
34.Pope, E. J. A. and Mackenzie, J. D., J. Non-Crystalline Solids, 87 (1986) 185
35.Zerda, T. W., Artaki, I. and Jonas, J., J. Non-Crystalline Solids, 81 (1986) 365
36.Himmel, B., Gerber, T. and Burger, H., J. Non-Crystalline Solids, 91 (1987) 122
37.Chujo, Y. et al., Makromol. Chem., Macromol. Symp., 42/43 (1991) 303
38.Chujo, Y., Ihara, E., Kure, S. and Saegusa, T., Macromolecules, 26 (1993) 5681
39.Landry, C. J. T., Coltrain, B. K. and Brady, B. K., Polymer, 33 (1992) 1486
40.Landry, C. J. T., Coltrain, B. K., Wesson, J. A., Zumbulyadis, N. and Lippert, J. L., Polymer, 33 (1992) 1496
41.Chujo, Y., Matsuki, H., Kure, S., Saegusa, T., and Yazawa, T., J. Chem. Soc., Chem. Commun., (1994) 635
42.Tamaki, R.; Samura, K. and Chujo, Y., Chem. Commun., (1998), 1131
43.Judeinstein, P. and Sanchez, C., J. Mater. Chem., 6 (1996) 511
44.Fitzgerald, J. J., Landry, C. J. T., and Pochan, J. M., Macromolecules, 25 (1992) 3715
45.Pope, E. J. A., Asami, M., and Mackemzie, J. D., J. Mater. Res., 4 (1989) 1018
46.Mark, J. E. and Sun, C. C., Polym. Bull., 18 (1987) 259
47.Huang, H. H. and Wilkes, G. L., Polym. Prepr. (Am. Chem. Soc., Div. Polym. Chem), 28 (1987) 244
48.Novak, B. M., Ellsworth, M., and Davis, C., Extended Abstracts, Tapan-U.S. Joint Seminar on Inorganic and Organometallic Polymers, (1991) 160
49.Wei, Y., Wang, W., Teh, J. M., Wang, B., and Murrary, J. K., Adv. Mater., 2 (1994) 337
50.Wei, Y., Yang, D. C., and Tang, L.G., Makromol. Chem. Rapid Commun., 14 (1993) 273
51.Wei, Y., Bakthavatchalam, R., and Whitecar, C. K., Chem. Mater., 2 (1990) 337
52.Huang, Z. H. and Qiu, K. Y., Chem. J. Chin. Universities, 18 (1997) 803
53.Huang, Z. H. and Qiu, K. Y., Acta Polym. Sin., No.4 (1997) 434
54.Huang, Z. H. and Qiu, K. Y., Polym. Bull., 35 (1995) 607
55.Huang, Z. H. and Qiu, K. Y., Polymer, 38 (1997) 521
56.Huang, Z. H., Qiu, K. Y., Dong, J. H., and Wei, Y., J. Appl. Polym. Sci., 66 (1997) 853
57.Huang, Z. H., Qiu, K. Y., and Wei, Y., J. Polym. Sci., Part A: Polym. Chem., 35 (1997) 2403
58.Mascia, L. and Kioul, A., Polymer, 36 (1995) 3649
59.Wei, Y.; Yang, D.; Tang, L. and Hutchins, M. K., J. Mater. Res., 1993, 8, 1143
60.Zhou, W., Dong, J. H., Qiu, K. Y., and Wei, Y., J. Polymer Science: Polymer Chemistry, 36 (1998) 1607
61.Sakurai, K., Douglas, E., and MacKnight, W. J., Macromolecules, 25 (1992) 4506
62.Sakurai, K., Douglas, E., and MacKnight, W. J., Macromolecules, 26 (1993) 208
63.Bakeev, K. N., Chugunov, S. A., Teraoka, I., MacKnight W. J., Zezin, A. B., and Kabanov, V. A., Macromolecules, 27(1994) 3926
64.Bakeev, K. N., Shu, Y. M., MacKnight, W. J., Zezin, A. B., and Kabanov, V. A., Macromolecules, 27 (1994) 300
65.Ng, C.-W. A., Lindway, M. J., and MacKnight, W. J., Macromolecules, 27 (1994) 3027
66.Ng, C.-W. A., and MacKnight, W. J., Macromolecules, 27 (1994) 3033
67.Ng, C.-W. A., and MacKnight, W. J., Macromolecules, 29 (1996) 2421
68.Ng, C.-W. A., and MacKnight, W. J., Macromolecules, 29 (1996) 2412
69.Backov, R., Bonnet, B., Jones, D. J., and Rozie're, J., Mater. Chem., 9 (1997) 1812
70.Chaneac, C., Tronc, E., and Jolivet, J. P., J. Mater. Chem., 6 (1996) 1905
71.Clevenger, M. B., Zhao J., and McDevitt J. T., Chem. Mater., 8 (1996) 2693
72.Fikushima, Y., and Tani M., J. Chem. Soc., Chem. Commun., (1995) 241
73.Kotov, N. A., Magnov, S., and Tropsha, E., Chem. Mater., 10 (1998) 886
74.Wang, Z., Lan, T., and Pinnavaia, T. J., Chem. Mater., 8 (1996) 2200
75.Krishnamoorti, R., Vaia, R. A., and Giannelis, E. P., Chem. Mater., 8 (1996) 1728
76.Harmer, M. A., Farneth, W. E., Sun, Q., J. Am. Chem. Soc., 118 (1996) 7708
77.Deng, Q., Hu, Y., Moore, R. B., McCormick, C. L., and Mauritz, K. A., Chem. Mater., 9 (1997) 36
78.Shi, Y., and Seliskar, C. J., Chem. Mater., 9 (1997) 821
79.Sun, Q., Harmer, M. A., and Farneth, W. E., Chem. Commun., (1996) 1201
80.Sauer, J. A., and Hara, M., Adv. Polym. Sci., 91/92 (1990) 69
81.Tamaki, R. and Chujo, Y. Chem. Mater., 11 (1999) 1719
82.Tamaki, R., Chujo, Y., Polym. Prepr. Jpn., 47 (1998) 4227
83.Ellsworth, M. W., Novak, B. M., J. Am. Chem. Soc., 113 (1991) 2756
84.Tamaki, R., Naka, K., and Chujo, Y., Polymer Journal, 30 (1998) 60
85.Zarzycki, J., J Sol-Gel Sci Technol , 8 (1997) 17
86.Mackenzie, J. D., J Sol-Gel Sci Technol, 2 (1994) 81
87.Mackenzie, J. D., J Sol-Gel Sci Technol, 1 (1993) 7
88.Tamaki, R., Naka, K., and Chujo, Y., Polymer Bulletin, 39 (1997) 303
89.Tamaki, R.; Horiguchi, T. and Chujo, Y. Bull. Chem. Soc. Jpn., 71 (1998) 2749
90.Nell, J. L. W., Wilkes, G. L., and Mohanty, D. K., J. Appl. Polym. Sci., 40 (1990) 1177
91.Imai, Y., Yoshida, N., and Chujo, Y., Polymer Journal, 31 (1999) 258
92.Imai, Y., Naka, K., and Chujo, Y., Polymer Journal, 30 (1998) 990
93.Cicillini, S. A., Calefi, P. S., Neri, C. R., Nassar, E. J., and Serra, O. A., J. Non-Crystalline Solids, 247 (1999) 114
94.Ellsworth, M.W., Novak, B. M., Chem. Mater., 5 (1993) 839
95.Tamaki, R. and Chujo, Y. J. Mater. Chem., 8 (1998) 1113
96.Tamaki, R. and Chujo, Y. App;. Organometal. Chem., 12 (1998) 755

指導教授

陳暉(Hui Chen)

審核日期

2000-6-14

推文