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研究生:蔡茜茜
研究生(外文):Tsia, Chan-Chan
論文名稱:含活性自由基之蒙脫土與苯乙烯聚合研究
論文名稱(外文):The Study of Styrene Polymerization in the Presence of Montmorillonite Containing Living Free Radical Initiator
指導教授:吳震裕
指導教授(外文):Wu, Jeng-Yue
學位類別:碩士
校院名稱:國立中興大學
系所名稱:化學工程學系
學門:工程學門
學類:化學工程學類
論文種類:學術論文
論文出版年:2001
畢業學年度:89
語文別:中文
論文頁數:145
中文關鍵詞:聚苯乙烯/蒙脫土奈米複合材料在位活性自由基聚合蒙脫土活性自由基起始劑接枝
外文關鍵詞:PS/MMT nanocompositein-Situ Living Free Radical PolymerizationmontmorilloniteLiving Free Radical Initiatorgraft
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本研究利用蒙脫土/苯乙烯之在位活性自由基聚合 (in-Situ Living Free Radical Polymerization)的方式,在蒙脫土表面吸附活性自由基起始劑,探討在123℃進行聚合反應不同TEMPO外加濃度及蒙脫土含量對反應時間之變化,製備聚苯乙烯/蒙脫土奈米複合材料。
含活性自由基之蒙脫土(蒙脫土含量為1.55 wt%及3.10 wt%)
的苯乙烯聚合,在不外加TEMPO下,則反應8小時後,蒙脫土表
面接枝PS量為2.28∼2.74 g PS/1g MMT;若外加0.005M TEMPO
,則反應8小時之蒙脫土表面接枝PS量為1.08∼1.21g PS/1g MMT
。有外加TEMPO情形下, 對轉化率為線性關係,具活性自由
基聚合的特徵,反應8小時分子量Mn約50,000∼90,000,聚分散
度較窄約在1.0∼1.2,且大部分蒙脫土之層間距大於4.4 nm。若不
外加TEMPO,則反應8小時後,分子量Mn約170,000∼230,000,
聚分散度較寬約1.3∼1.5,於反應6小時後層間距已大於4.4 nm。
研究結果顯示,藉外加TEMPO濃度變化可製備不同分子量與聚分
散度之PS接枝於蒙脫土表面形成PS/MMT奈米複合材料。
The purpose of this thesis was to investigate the effect of montmorillonite content, the concentration of TEMPO and reaction time on the synthesis of PS/MMT nanocomposites by in situ living free radical polymerization at 123℃.
Polymerization of styrene in presence of montomorillonite(the montomorillonite’s dosage:1.55 and 3.10 wt%) containing living free radical initiator for 8 hours gave the chemical grafting of PS at 2.28 ~ 2.74 g/1gMMT without adding TEMPO and at 1.08 ~ 1.21 g/1gMMT with 0.005M TEMPO addition. The presence of TEMPO exhibited the linear dependence of versus conversion and showed the “living character” of the polymerization. The polydispersity index of 1.0 ~ 1.2 and the number-average molecular weight (Mn) of 50,000~ 90,000 polymer was obtained for 8-hour reaction period and XRD data showed a weak diffraction between 2.9 and 3.5 nm indicating trace amount of montomorillonite not exfoliated. Without the addition of TEMPO, the polydispersity is between 1.3 and 1.5 and the Mn of 170,000 ~ 230,000 could be obtained for 8-hour reaction period. The d-spacing greater than 4.4 nm after a reaction time of 6 hours was observed. In summary, we have demonstrated that PS/MMT nanocomposites can be directly polymerized via adsorbed living free radical initiator. Diversifying molecular weight and polydispersity of polystyrene grafted on the montomorillonite surface can be prepared by varying the external concentration of TEMPO.
中文摘要……………………………………………………………….I
英文摘要………………………………………………………………II
誌謝…………………………………………………………………..III
目錄…………………………………………………………………..IV
表目錄…………………………………………………………..……Ⅶ
圖目錄…………………………………………………………..……Ⅷ
一、 緒論……………………………………………………………...1
1.1 前言…………………………………………………………1
1.2 研究動機與目的……………………………………………7
1.3 研究方向……………………………………………………9
二、 文獻回顧與研究方法….………………………………………10
2.1 PS/Clay相關文獻…..……………………………………..10
2.2 Clay表面接枝PS相關文獻...……………………………15
2.3 活性自由基聚合PS相關文獻………………….………..19
2.3.1 活性自由基聚合原理…………………………………19
2.3.2 非活性自由基聚合動力學…………………………....25
2.3.3 活性自由基聚合動力學………………………………28
2.3.4 苯乙烯熱聚合反應……………………..……………..35
2.3.5 在TEMPO存在下之苯乙烯熱聚合反應……………40
2.4 Clay表面進行活性自由基聚合接枝PS相關文獻……..52
2.5 研究方法與流程………………………………………….54
三、 實驗………………………………………………….…………57
3.1 實驗材料………………………………………………….57
3.2 實驗儀器………………………………………………….59
3.3 實驗步驟………………………………………………….61
四、 結果與討論………………………………………….…………65
4.1 界面劑單體(VBDDAC)的合成……………………………..65
4.1.1 界面劑單體(VBDDAC)之結構鑑定…………………65
4.1.2 界面劑單體(VBDDAC)之物理性質測定……………67
4.2蒙脫土表面改質……..………………………………………..68
4.2.1 VBDDAC/蒙脫土吸附平衡…..………………..…….…68
4.2.2 蒙脫土吸附活性自由基起始劑……………..……….…71
4.3 PS/MMT奈米複合材料合成與性質分析…………..………..72
4.3.1. 改變TEMPO濃度之苯乙烯123℃熱聚合…………....73
4.3.2. 含活性自由基之蒙脫土(1.55 wt%)於外加不同
濃度TEMPO之苯乙烯聚合………………….……….75
4.3.3. 含活性自由基之蒙脫土(3.10 wt%)於外加不同
濃度TEMPO之苯乙烯聚合………………………….79
4.3.4. 吸附單層VBDDAC之蒙脫土於123℃苯乙烯塊狀
聚合…………………………………………………….84
4.3.5. 總比較………………………………………………….85
五、 結論…………………………………………………………….89
六、參考文獻…………………………………………………..……91
1. 錢國基, 產業經濟, 201期, 第105頁 (1998)
2. 廖建勛, 工業材料, 125期, 第108頁 (1997)
3. Sikka, M.; Cerini, L. N.; Ghosh, S. S. and Winey, K. I., Journal of
Polymer Science: Part B: Polymer Physics, 34, 1443 (1996)
4. Allcock, H. R. and Lamp, F. W., “Contemporary Polymer Chemistry”, 2nd Ed., Pretice-Hall, Inc. (1993)
5. Oyama, H. T.; Sprycha, R.; Xie, Y.; Partch, R. E. and Matijevic, E., Journal of Colloid and Interface Science, 160, 298 (1993)
6. Huang, C.; Partch, R. E. and Matijevic, E., Journal of Colloid and interface Science, 160, 275 (1993)
7. Genetti, W. B.; Grady, B. P. and O’Rear, E. A., Materials Research Society Symposium Proceeding Electronic Packaging Materials Science IX, 445, 153 (1997)
8. Hunter, R. J., “Foundation of Colloid Science”, vol. I, 25, Clareden Press Oxford (1992)
9. Akelah, A. and Moet, A., Journal of Applied Polymer Science:Applied Polymer Symposium, 55, 153 (1994)
10. Adamson, A. W., Adsorption form Solution, 388, Chapter XI,4th
Ed., Wiley-Interscience, New York (1983)
11. 廖建勛, 化工資訊, 12期, 第20頁 (1998)
12. LeBaron, P. C.; Wang, Z. and Pinnavaia, T., J. Applied Clay Science,
15,11 (1999)
13. Alexandre M. and Dubois P., Material Science and Engineering,
28, 1 (2000)
14. 高至鈞, 鮑忠興, 工業材料, 153期, 第102頁(1999)
15. Zanetti M.; Lomakin S. and Camino G., Macromol. Mater. Eng.,
279, 1 (2000)
16. 詹益池, ”蒙脫土表面聚合苯乙烯製備奈米複合材料與物性分析”, 國立中興大學材料工程研究所碩士論文 (1999)
17. 劉開誠, ”高單體含量之蒙脫土/聚苯乙烯奈米複合材料製備方法與物性分析”, 國立中興大學化學研究所碩士論文 (1999)
18. 簡正豐, ”聚苯乙烯/蒙脫土奈米複合材料界面改質之研究”, 國立中興大學化學工程研究所碩士論文 (2000)
19. 吳震裕, 材料會訊, 7卷, 5期, 第16頁 (2000)
20. Nagai K., TRIP, 4, 122 (1996)
21. 王湘雯, ”苯乙烯活性自由基聚合之動力學與溶劑鏈轉移研究”, 國立中興大學化學工程研究所碩士論文 (2000)
22. Cochin, D.; Candau, F. and Zana R., Macromolecules, 26, 5755 (1993)
23. Kato, C.; Kuroda, K. and Takahara, H., Clays and Clay Minerals, 29, 294 (1981)
24. Vaia, R. A.; Jandt, K. D.; Kramer, E. J. and Giannelis, E. P., Macromolecules, 28, 8080 (1995)
25. Doh, J. G. and Cho, I., Polymer Bulletin, 41, 511 (1998)
26. Proter, T. L.; Hagerman, M. E.; Reynolds, B. P.; Eastman, M. P. and Parnell R. A., Journal of Polymer Science: Part B: Polymer Physics, 36, 673 (1998)
27. Hasegawa, N.; Okamoto, H.; Kawasumi, M. and Usuki, A., Journal of Applied Polymer Science, 74, 3359 (1999)
28. Limary, R.; Swinnea, S. and Green, P. F., Macromolecules, 33, 5227 (2000)
29. Okamoto, M.; Morita, S.; Taguchi, H.; Kim, Y. H.; Kotaka, T. and Tateyama, H., Polymer, 41, 3887 (2000)
30. Okamoto, M.; Morita, S. and Kotaka, T., Polymer, 42, 2685 (2001)
31. Moet, A. and Akelah, A., Materials Letters, 18, 97 (1993)
32. Akelah, A. and Moet, A., Journal of Materials Science, 31, 3589 (1996)
33. Meier L. P.; Shelden, R.A.; Caseri, W. R. and Suter, U. W., Macromolecules, 27, 1637 (1994)
34. Laus, M.; Camerani, M.; Lelli, M.; Sparnacci, K. and Sandrolini, F., Journal of Materials Science, 33, 2883 (1998)
35. Velten, U.; Shelden, R.A.; Caseri, W. R.; Suter, U. W. and Li Y.,
Colloids and surfaces: Part A, 154, 87 (1999)
36. Fu, X. and Qutubuddin, S., Materials Letters, 42, 12 (2000)
37. Fu, X. and Qutubuddin, S., Polymer, 42, 807 (2001)
38. Dekking, H. G. G., J. Appl. Polym. Sci., 11, 23 (1967)
39. Biasci, L.; Aglietto, M.; Ruggeri, G. and Ciardelli, F., Polymer, 35, 3296 (1994)
40. Giannelis, E. P., Advanced Materials, 8, 29 (1996)
41. Neckers D. C. and Schaap, A. P., J. Org. Chem., 32, 22 (1967)
42. Moad G. and Rizzardo, E., Macromolecules, 28, 8722 (1995)
43. Veregin, R. P. N.; Odell, P. G.; Michalak, L. M. and Georges, M. K.,
Macromolecules, 29, 2746 (1996)
44. Moad, G.; Rizzardo, E. and Solomon, D. H., J. Macromol. Soc.
Chem., 17, 51 (1982)
45. Billmeyer, F. W., “Text Book of Polymer Science”, 3rd Ed., p.56, John
Wiley, New York (1984)
46. Brandrup, J. and Immergut, E. H., 3rd Ed., Polymer Handbook, Part
Ⅱ, p.85, John Wiley, New York (1989)
47. Mayo, F. R.; Gregg, R. A. and Matheson, M. S., J. Am. Chem. Soc.,
73, 1691 (1951)
48. Pryor, W. A. and Coco, J. H., Macromolecules, 3, 501 (1970)
49. Mayo, F. R., J. Am. Chem. Soc., 65, 2324 (1943)
50. Mayo, F. R., J. Am. Chem. Soc., 75, 6133 (1953)
51. Veregin, R. P. N.; Georges, M. K.; Kazmaier, P. M. and Hamer, G.
K., Macromolecules, 26, 5316 (1993)
52. Veregin, R. P. N.; Georges, M. K.; Hamer, G. K. and Kazmaier, P.
M., Macromolecules, 28, 4391 (1995)
53. Fukuda, T.; Goto, A.; Ohno, K. and Tsujii, Y., “Controlled Radical
Polymerization”, American Chemical Society, 685, Chapter 11,
180 (1998)
54. Marestin, C.; Noel, C.; Guyot, A. and Claverie, J., Macromolecules
, 31, 4041 (1998)
55. Devonport, W.; Michalak, L.; Malmstrom, E.; Mate, M.; Kurdi, B.
and Hawker, C. J., Macromolecules, 30, 1929 (1997)
56. Fischer, A.; Brembilla, A. and Lochon, P., Macromolecules, 32,
6069 (1999)
57. Moad, G. and Solomon, D. H., “The Chemistry of Free Radical
Polymerization”, 1st Ed., p234, Elsevier Science, Australia (1995)
58.蔡信行博士主編, “聚合物化學”, 第三版, 第153頁, 文京圖書有
限公司 (1996)
59. Georges, M. K.; Veregin, R. P. N.; Kazmaier, P. M. and Hamer, G.
K., Macromolecules, 26, 2987 (1993)
60. Fukuda, T.; Terauchi, T.; Goto, A.; Ohno, K.; Tsujii, Y. and
Miyamoto, T., Macromolecules, 29, 6393 (1996)
61. Mayo, F. R., J. Am. Chem. Soc., 90, 1289 (1968)
62. Hiatt, R. R. and Bartlett, P. D. , J. Am. Chem. Soc., 81, 1149 (1959)
63. Hui, A. W. and Hamielec, A. E., J. Appl. Polym. Sci., 16, 749
(1972)
64. Moad, G.; Rizzardo, E. and Solomon, D. H., Polymer Bulletin, 6,
589 (1982)
65. Mardare, D. and Matyjaszewski, K., Polymer Preprint, 35, 778
(1994)
66. Matyjaszewski, K.; Gaynor, S.; Greszta, D.; Mardare, D. and
Shigemoto, T., Macromol. Symp., 98, 73 (1995)
67.Matyjaszewski, K., “Controlled Radical Polymerization”, American
Chemical Society, 685, Chapter 1, 2 (1998)
68. Greszta, D. and Matyjaszewski, K., Macromolecules, 29, 7661,
(1996)
69. Michalak, L.; Malmstrom, E.; Devonport, W.; Mate, M. and
Hawker, C. J., Polymer Preprints, 38, 727 (1997)
70. Hawker, C. J.; Barclay, G. G. and Dao, J., J. Am. Chem. Soc., 118,
11467 (1996)
71. Boutevin, B. and Bertin, D., European Polymer Journal, 35, 815
(1999)
72. Husseman, M.; Malmström, E. E.; McNamara, M.; Mate, M.;
Mecerreyes, D.; Benoit, D. G.; Hedrick, J. L.; Mansky, P.; Huang,
E.; Russell, T. P. and Hawker, C. J., Macromolecules, 32, 1424
(1999)
73. Hawker, C.; Hedrick, J. L.; Benoit, D.; Mecerreyes, D.; Rees, I.;
Husseman, M.; Russell, T. P.; Huang, E. E.; Shah, R. R. and
Abbott, N. L., Polymer Preprints, 40, 101 (1999)
74.Weimer, M. W.; Chen, H.; Giannelis, E. P. and Sogah, D. Y., J.
Am. Chem. Soc., 121, 1615 (1999)
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