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系統識別號 U0026-0812200911273192
論文名稱(中文) 酚醛樹脂/改質蒙脫土奈米複合材料的製備及物性研究
論文名稱(英文) Synthesis and Characterization of Phenolic Resin/Montmorillonite nanocomposites
校院名稱 成功大學
系所名稱(中) 化學工程學系碩博士班
系所名稱(英) Department of Chemical Engineering
學年度 93
學期 2
出版年 94
研究生(中文) 江威
研究生(英文) Wei Jiang
電子信箱 jiangjiang29@yahoo.com.tw
學號 n3692135
學位類別 碩士
語文別 中文
論文頁數 110頁
口試委員 口試委員-劉瑞祥
口試委員-侯聖澍
指導教授-陳雲
口試委員-吳逸謨
中文關鍵字 酚醛樹脂  奈米複合材料 
英文關鍵字 nanocomposite  phenolic resin 
學科別分類
中文摘要   酚醛樹脂因為有著獨特良好的性質,所以到今天在高技術應用上仍然是不可取代的材料。然而酚醛樹脂卻很少運用在奈米複合材料上面,這是因為酚醛樹脂是三維的結構,所以要插入矽酸鹽層間是一件很困難的事。通常解決這個問題,可由酚醛樹脂種類或複合材料聚合方法做進一步發展。酚醛樹脂種類可使用線性的novolac型酚醛樹脂ヽresol型低分子量酚醛樹脂或resol型酚醛樹脂。而複合材料聚合方法則有In-situ聚合法ヽ溶液中之高分子插層法以及熔融態高分子直接插層法。此外,易脆性和交聯收縮性是阻礙酚醛樹脂應用的兩大缺點,使其在應用上受到限制。故在酚醛樹酯的應用上,增韌為相當重要的一環。
  本研究是將resol型酚醛樹脂與數種改質蒙脫土2M2HTMMTヽC18MMTヽ2C18MMTヽB2MPMMTヽB2MHMMT和B3EMMT利用in-suit聚合法分別合成酚醛樹脂/改質蒙脫土奈米複合材料。利用XRD與TEM分別觀察蒙脫土改質程度以及複合材料的結構,得到2M2HTMMT-PF與2C18MMT-PF為插層型複合材料(intercalated nanocomposites)以及C18MMT-PFヽB3EMMT-PFヽB2MPMMT-PF與B2MHMMT-PF為脫層型複合材料(exfoliated nanocomposites)。而從TGA測量得知,B3EMMT-PFヽB2MPMMT-PF與B2MHMMT-PF之改質劑因含有benzyl ring,改質劑與酚醛樹脂有著相似的結構,造成良好的化學相容性,所以跟其他改質劑比起來有良好的熱穩定性。總而言之,改質劑對於熱穩定性(thermal stability)與奈米複合材料最終型態(morphology)上扮演著重要的腳色。另外,本研究藉由導入NBR橡膠來增加酚醛樹酯材料的韌性,摻混後利用拉力機測量發現機械性質能夠提升,但是從TGA與DMA得知,對於熱穩定性的影響不大。


英文摘要   Phenolic resins today are indeed irreplaceable materials for selective high- technology applications, because of their excellent ablative properties. However, phenolic resin has been abandoned in the nanocomposite field. The reason is that general phenolic resin has a threedimensional structure that makes phenolic resin very difficult to intercalate in the layered silicate gallery
  In this work, phenolic resin/modified-montmorillonite nanocomposites were synthesized by in-situ polymerization with resol type phenolic resins and organoclays such as 2M2HTMMT, C18MMT, 2C18MMT, B2MPMMT, B2MHMMT, and B3EMMT. XRD measurements and TEM observations showed that clay platelets were exfoliated or intercalated. It is found that 2M2HTMMT-PF and 2C18MMT-PF were intercalated nanocomposites and C18MMT-PF, B3EMMT-PF, B2MPMMT-PF and B2MHMMT-PF were exfoliated nanocomposites. TGA showed the thermal stability of B3EMMT- PF, B2MBMMT-PF, and B2MHMMT-PF were higher than that of C18MMT -PF, 2M2HTMMT-PF and 2C18MMT-PF due to chemical affinity derived from the favorable interaction between the phenolic resin and intercalant containing benzene ring. Conclusively, the modification of layered silicate and the resulting interaction between organic modifier and phenolic resin played an important role in determining the thermal stability and the final morphology of phenolic resin-layered silicate nanocomposite. Phenolic resins were also blended with NBR and the measurements of stress-strain properties, TGA, DMA and TEM. It was observed that the mechanical properties of the blend enhanced on incorporation of NBR into the phenolic resin.


論文目次 中文摘要.......................................................................Ⅰ
英文摘要.......................................................................Ⅱ
誌  謝.......................................................................Ⅲ
目  錄.......................................................................Ⅳ
表 目 錄.......................................................................Ⅶ
圖 目 錄.......................................................................Ⅹ


第一章 緒論
1-1 前言.......................................................................1
1-2 理論基礎...................................................................2
 1-2-1 奈米無機層材的種類與結構...............................................2
 1-2-2 改質劑的種類...........................................................5
 1-2-3 有機/無機混成材料之製程...............................................7
1-3 高分子奈米複合材料之優勢...................................................9
1-4 奈米無機層狀材料的新機能與應用............................................11
1-5 奈米高分子複合材料世界發展趨勢............................................13


第二章 文獻回顧
2-1 Resole type酚醛樹酯的製備與特性...........................................15
2-2 奈米複合材料製備法........................................................17
 2-2-1 In-situ 聚合法........................................................17
 2-2-2 溶液中之高分子插層法..................................................18
 2-2-3 熔融態高分子直接插層法................................................18
2-3 黏土/高分子奈米複合材料之型態............................................20
2-4 酚醛樹脂奈米複合材料之發展................................................22
2-5 酚醛樹酯與NBR摻混的相關研究...............................................29
2-6 研究動機..................................................................30


第三章 實驗內容
3-1 實驗裝置與設備............................................................32
3-2 操作及鑑定測量儀器........................................................32
3-3 藥品及材料................................................................35
3-4 實驗步驟與結果............................................................36
 3-4-1 改質蒙脫土的製備......................................................36
 3-4-2 酚醛樹脂/改質蒙脫土奈米複合材料的製備................................40
3-5 聚合原理..................................................................42
3-6 酚醛樹脂/蒙脫土奈米複合材料之Curing......................................43
3-7 TEM試片...................................................................44
 3-7-1 試片製作..............................................................44
 3-7-2 試片切片..............................................................44
3-8 酚醛樹酯與NBR摻混.........................................................45


第四章 結果與討論
4-1 X-ray繞射光譜圖分析.......................................................47
 4-1-1 蒙脫土改質之X-ray繞射光譜圖分析.......................................47
 4-1-2 複合材料之X-ray繞射光譜圖分析.........................................52
4-2 TEM分析...................................................................54
4-3 複合材料熱性質分析........................................................55
4-4 酚醛樹脂與NBR摻混部分.....................................................58
 4-4-1 酚醛樹脂與NBR的相溶性.................................................58
 4-4-2 酚醛樹脂與NBR的混合黏度測定...........................................60
 4-4-3 酚醛樹脂與NBR硬化後的熱性質...........................................61
 4-4-4 酚醛樹脂與NBR硬化後的微相分離情形.....................................63
 4-4-5 酚醛樹脂與NBR硬化後的機械性質.........................................63


第五章 結論
5-1 酚醛樹脂/改質蒙脫土複合材料..............................................64
5-2 酚醛樹脂/NBR之摻混.......................................................66


參考文獻......................................................................104


自述..........................................................................110
參考文獻 [1] Theng, B.K.G. Formation and Properties of Clay-Polymer Complexes Chapter 
  1,Amsterdam Oxford New York. 1979.
[2] Yang, R.; Atsushi, T.; Wong, C.P. 8th Int Symp On Adv Packag Mater, 2002,
  pp.188-193.
[3] Natitoal Center for Manufacturing Sciences, Embedded Decoupling Capacitance
  Project Final Report, NCMS Project No. 160213, 2000.
[4] Sugimoto, W.; Shirata, M.; Sugahara, Y.; Kuroda, K.; J Am Chem Soc, 1999,
  121, 11602.
[5] Mills A.; Le Hunte, S. J Photochem Photobiol A: Chem, 1997, 108, 1.
[6] Hagfeldt, A.; Gratzel, M. Acc Chem Res, 2000, 33, 2699.
[7] Akelah, A.; Moet, A.; J Appl Polym Sci: Appl Polymer Symp, 1994, 55, 153.
[8] Messer Smith, P. B.; Giannelis, E. P. Chem Mater, 1994, 16, 1719.
[9] Vaia, R. A.; Giannelis, E. P. Macromolecules, 1997, 30, 8000-8009.
[10] Vaia, R. A.; Jandt, K. D.; Kramer, E. J.; Giannelis, E. P. Macromolecules,
   1995, 28, 8080-8085.
[11] Vaia, R. A.; Jandt, K. D.; Kramer, E. J.; Giannelis, E. P. Chem Mater, 1996,
   8, 2628-2635.
[12] Saegusa, T. Pure and Appl Chem 1995, 67, 1965.
[13] Novak, B. M. Adv Mater, 1993, 5, 422.
[14] Japanese R&D trend analysis advanced materials-phase VI, Rep. No.1;
   Organic-In Organic polymer hybrids, KRI, May 1994.
[15] Wang, J. F.; Merino, J.; Ananda, P.; Galvan, J. C.; J Mater Chem, 1999, 19,
   161.
[16] Bremer, L. G. B.; verbong, M. W. C. G.; Webers, M. A. M.; van Doorn, M. A.
   M. M. Synth Mat, 1997, 84, 355.
[17] Okada, A.; Usuki, A.; Kurauchi, T.; Kamigaito, O. Hybrid Organic- InOrganic
   Composite, ACS Symp Series, 1995, 55, 585.
[18] Depege, C.; Elmetoui, F. E.; Forano, C.; Roy, A. D. Chem Mater, 1996, 8,
   952.
[19] Hunter, R. J. Clareden Press Oxford. Foundation of Colloid Science, 1992, 1,
   25-31.
[20] Giannelis. E. P.; Krishnamoorti, R.; Manias, E. Adv Polym Sci 1999, 118,
   108-147.
[21] Okada, A. et al. Mater Res Soc Proc, 1990, 171, 45.
[22] Lee, D. C. et al. J Appl Polym Sci, 1996, 61, 1117.
[23] Agag, T. et al. Polym, 2000, 42, 3399.
[24] Okada, A. et al. J Polym Sci A: Polym Chem, 1997, 35, 2289.
[25] Chang, F. C. et al. J Appl Polym Sci, 2000, 79, 1902.
[26] Wei, K. H. et al. Chem Mater, 1999, 11, 1942.
[27] Gilman, J. W. et al. SAMPE J, 1997, 33, 40.
[28] 鍾松政,徐錦上,胡志明;中華民國陶業研究學會會刊,第二十一卷第三期,P.36~37.
[29] 李世陽,蔡宗燕;化工科技與商情,第二十四期,2001
[30] Zanetti, M.; Lomakin, S.; Camino, G. Macromol Master Eng 2000, 279, 1-9.
[31] Lebaron, P. C.; Zhen, W.; Thomas, J. P. Applied Clay Science, 1999, vol.15,
   pp.11-29.
[32] 蔡宗燕, 黏土奈米層狀材料之應用與開發, 成功大學資源工程研究所專題演講內容,
   2000.
[33] Okada, A.; Kawasumi, M.; Kurauchi, T.; Kamigaito, O. Polym Prepr 1981, 28,
   447.
[34] Mehrotra, E. P.; Giannelis. Solid State Commun 1991, 77, 155.
[35] Kurauchi, T.; Okada, A.; Nomura, T.; Nishio, T.; Saegua, S.; Deguchi, R. SAE
   Technical Paper Ser, 910584, 1991
[36] Giannelis, E. P.; Mehrotra, V.; Tse, O.; Vaia, R. A.; Sung, T. in:
  “Synthesis and Processing of Ceramics: Scientific Issues”, MRS Proc.,
   Pittsburgh, PA, 1992.
[37] Giannelis, E. P. J Met 1992, 44, 28.
[38] Mehrotra, V.; Giannelis, E. P. Solid Sate Ionics 1992, 51, 115.
[39] Messersmith, P. B.; Giannelis, E. P. Chem Mater 1993, 5, 1064.
[40] Yano, K.; Usuki, A.; Okada, A.; Kurauchi, T.; Kamigaito, O. J Polym Sci:
   Part A: Polym Chem 1993, 31, 2493.
[41] Kojima, Y.; Usuki, A.; Kawasumi, M.; Okada, A.; Fukushima, Y.; Kurauchi, T.;
   Kamigaito, O. J Mater Res 1993, 8, 1185.
[45] Wang, M. S.; Pinnavaia, T. J. Chem Mater 1994, 6, 468.
[43] Messersmith, P. B.; Giannelis, E. P. Chem Mater 1994, 6, 1719.
[44] Lan, T.; Pinnavaia, T. J. Chem Mater 1994, 6, 2216.
[45] Biasci, L.; Aglietto, M.; Ruggeri, G.; Ciardelli, F. Polymer 1994, 35, 3296.
[46] Messersmith, P. B.; Giannelis, E. P. J Polym Sci: Part A: Polym Chem 1995,
   33, 1047.
[47] Biasci, L.; Aglietto, M.; Ruggeri, G.; D’Alessio, A. Polym Adv Technol
   1995, 6, 662.
[48] Akelah, A.; Moet, A. J Mat Sci 1996, 31, 3589.
[49] Reichert, P.; Kressler, J.; Tomann, R.; Mu¨lhaupt, R.; Stoppelmann, G. Acta
   Polym 1998, 49, 116.
[50] Zilg, C.; Tomann, R.; Mu¨lhaupt, R.; Finter, J. Adv Mater 1999, 11, 49.
[51] Arada, P.; Ruiz-Hitzky, E. Adv Mater 1990, 2, 545.
[52] Arada, P.; Ruiz-Hitzky, E. Chem Mater 1992, 4, 1395.
[53] Wu, J.; Lerner, M. M. Chem Mater 1993, 5, 835.
[54] Tunney, J. J.; Detellier, C. Chem Mater 1996, 8, 927.
[55] Tyan, H. C.; Liu, Y. C.; Wei, K. H. Chem Mater 1999, 10, 1942.
[56] Fischer, H. R.; Gielgens, L. H.; Koster, T. P. M. Acta Polym 1999, 50, 122.
[57] Vaia, R. A.; Ishii, H.; Giannelis, E. P. Chem Mater 1993, 5, 1694.
[58] Burnside, S. D.; Giannelis, E. P. Chem Mater 1995, 7, 1596.
[59] Vaia, R. A.; Vasudevan, S.; Krawiec, W.; Scanlon, L. G.; Giannelis, E. P.
   Adv Mater 1995, 7, 154.
[60] Vaia, R. A.; Jandt, K. D.; Kramer, E. J.; Giannelis, E. P. Macromolecules
   1995, 28, 8080.
[61] Vaia, R. A.; Jandt, K. D.; Kramer, E. J.; Giannelis, E. P. Chem Mater 1996,
   8, 2628.
[62] Vaia, R. A.; Giannelis, E. P. Macromolecules 1997, 30, 7990.
[63] Vaia, R. A.; Giannelis, E. P. Macromolecules 1997, 30, 8000.
[64] Kawasumi, M.; Hasegawa, N.; Kato, K.; Usuki, A.; Okada, A. Macromolecules
   1997, 30, 6333.
[65] Burnside, S. H.; Wang, H. C.; Giannelis, E. P. Chem Mater 1999, 11, 1055.
[66] Zilg, C.; Mu¨lhaupt, R.; Finter, J. Macromol Chem Phys 1999, 200, 661.
[67] Heieman, J.; Reichert, P.; Thomann, R.; Mu¨lhaupt, R. Macromol Rapid Commun
   1999, 20, 423.
[68] Akelah, A.; Moet, A.; J App Polym Sci, App Polym Sym 1994, 55, p.153.
[69] Zilg, C.; Thomann, R.; Miilhaupt, R.; Finter, J. Adv Mater 1999, 11, p.49.
[70] LeBaron, P. C.; Wang, Z. S.; Pinnavaia, T. Appl Clay Sci 1999, 15, p.11.
[71] Usuki, A.; Mizutani, T.; Fukushima, Y.; Fujimoto, M.; Fukomori, K.; Kojima,
   Y.; Sato, N.; Kurauchi, T.; Kamikaito, O. U.S. Patent, 889,885 1989.
[72] Choi, M. H.; Chung, I. J.; Lee, J. D. Chem Mater 2000, 12, 2977-2983.
[73] Byun, H. Y.; Choi, M. H.; Chung, I. J. Chem Mater 2001, 13, 4221- 4226.
[74] Wu, Z. G.; Zhou, C, X.; Rongrong, Q. polym composites, Vol. 23, No. 4 2002.
[75] Wang, H. S.; Zhao, T.; Zhi, L. J.; Yan, Y. H.; Yu, Y. Z. Macromol Rapid
   Commun 2002, 23, 44-48.
[76] Choi, M. H.; Chung, I. J. Appl Polym Sci 2003, 90, 2316-2321.
[77] Liu, Y. L.; Lin, Y. L.; Chen, C. P.; Jeng, R. J. Appl Polym Sci 2003, 90
   4047-4053.
[78] Chiang, C. L.; Ma, C. C. M.; Wu, D. L.; Kuan, H. C. J Polym Sci: Part A:
   Polym Chem 2003, 41, 905-913.
[79] Williams, E. P. M.; Seferis, J. C.; Wittman, C. L.; Parker, G. A.; Lee, J.
   H.; Nam, J.-D. J Polym Sci: Part B: Polym Phys 2004, 42, 1-4.
[80] Lee, S. M.; Hwang, T. R.; Song, Y. S.; Lee, J. W. Polym Eng Sci 2004, 44,
   1170-1177.
[81] Wang, H. S.; Zhao, T.; Yan, Y. H.; Yu, Y. Z.; Appl Polym Sci 2004, 92,
   791-797.
[82] Lee, J. W.; Kim, J. Y.; Lee, Y. J.; Yoon, S. H.; Oh, S. M.; Hyeon, T. G.
   Chem Mater 2004, 16, 3323-3330.
[83] Chiang, C. L.; Ma, C. C. M. Polym Deg and Stab 2004, 83, 207-214.
[84] Shafizadeh, J. E.; Guionnet, S.; Tillman, M. S.; Seferis, J. C. J Appl Poly
   Sci, 1999, 73, 505-514.
[85] Camino, G.; Alba, E.; Buonfico, P.; Vikoulov, K. J Appl Poly Sci, 2001, 82,
   1346-1351.
[86] Achary, P. S.; Gouri, C.; Ramaswamy, R. J Appl Poly Sci, 2001, 81,
   2597-2608.
[87] Manfredi, L. B.; Riccardi, C. C.; Osa, O.; Vazquez, A. Poly Inter, 2001, 50,
   796-802.
[88] Samui, A. B.; Suryavanshi, U. G.; Patri, M.; Chakraborty, B. C.; Deb, P. C.
   J Appl Poly Sci, 1998, 68, 255-266.
[89] Sousa, M. F.; Peres, C. C.; Nunes, C. R.; Visconte, L. Y. Furtado, R. G. J
   Appl Poly Sci, 2002, 84, 505-513.
[90] Achary, P. S.; Ramaswamy, R. J Appl Poly Sci, 1998, 69, 1187-2101.
[91] Sposito, G.; Prost, R. Chem. Rev. 1982, 82, 553.
[92] Lin, J. J.; Cheng, I. J.; Wang. R.; Lee, R. J. Macromolecules 2001, 34,
   8832-8834.
[93] Ouchi, K.; Honda, H. Fuel 1959, 38, 429.
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