研究生: |
粘純嫣 Chun-Yen Nien |
---|---|
論文名稱: |
以RAFT活自由基溶液聚合法合成用於不飽和聚酯及乙烯基酯樹脂具核殼型結構的高分子接枝之氧化石墨烯及高分子接枝之熱脫層氧化石墨烯之抗收縮劑及增韌劑 Synthesis of polymer-grafted graphene oxide and polymer-grafted thermally reduced graphene oxide with core-shell structure as low-profile additives and tougheners for unsaturated polyester and vinyl ester resins by RAFT living free radical solution polymerizations |
指導教授: |
黃延吉
Yan-Jyi Huang |
口試委員: |
邱文英
Wen-Yen Chiu 陳崇賢 Chorng-Shyan Chern |
學位類別: |
碩士 Master |
系所名稱: |
工程學院 - 化學工程系 Department of Chemical Engineering |
論文出版年: | 2017 |
畢業學年度: | 105 |
語文別: | 中文 |
論文頁數: | 207 |
中文關鍵詞: | 高分子接枝之氧化石墨烯 、抗收縮劑 (LPA) 、可逆加成-斷裂鏈轉移聚合法(RAFT) 、氧化石墨烯 、體積收縮 、機械性質 、增韌劑 、乙烯基酯樹脂(VER) |
外文關鍵詞: | polymer grafted graphene oxide, low-profile additive (LPA), reversible addition-fragmentation chain transfer (RAFT), graphite oxide(GO), volume shrinkage, mechanical properties, toughener, vinyl ester resins (VER) |
相關次數: | 點閱:608 下載:5 |
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本文探討用作熱固性樹脂抗收縮劑及增韌劑之具核殼型結構(CSS)高分子接枝之氧化石墨烯的合成,其對低收縮乙烯基酯樹脂在聚合固化後之樣品微觀型態結構、体積收縮特性及機械性質的影響。
這些核殼型結構(CSS),以GO-polymer標示之,係以氧化石墨烯(GO)為核心及有機高分子為外殼,以Z支撐的可逆加成-斷裂鏈轉移聚合法(RAFT),利用S-Benzyl S'-trimethoxysilylpropyl trithiocarbonate (BTPT)作為可偶合的RAFT鏈轉移試劑合成而得。其中,層間距為0.75nm的氧化石墨烯是以modified Hummers 方法將天然石墨氧化合成,而GO -polymer核殼型結構的高分子外殼為丙烯酸甲酯(MA)與甲基丙烯酸環丙氧烷酯(GMA)的共聚合物(poly(MA-co-GMA))、及聚丙烯酸丁酯與丙烯酸甲酯(MA)及甲基丙烯酸環丙氧烷酯(GMA)的共聚合物之團聯共聚合物(PBA-b-poly(MA-co-GMA))。
GO、TRGO、BTPT及GO-Polymer的結構,吾人以FTIR、1H-NMR、13C-NMR、GPC、TGA及XRD鑑定之。本文中,吾人亦探討GO-Polymer對苯乙烯(St)/乙烯基酯(VER)/GO-Polymer之三成分系統於120℃聚合固化後之微觀型態結構、體積收縮及機械性質。
Synthesis of polymer grafted graphene oxide with core-shell structure (CSS) as low-profile additives (LPA) and tougheners for thermoset resins, and their effects on the cured sample morphology, volume shrinkage characteristics and mechanical properties for low-shrink vinyl ester resins (VER) during the cure were investigated.
These CSS designated as GO-polymer, which contained graphene oxide(GO) as the core and organic polymer as the shell, were synthesized by the Z supported reversible addition-fragmentation chain transfer (RAFT) graft polymerization using S-Benzyl S'-trimethoxysilyl propyl trithio-carbonate (BTPT) as the coupable RAFT chain transfer agent (CTA). The graphene oxide (GO) was synthesized from natural graphite powder by a modified Hummers method. The grafted polymer as the shell structure of the GO-polymer was made from copolymer of MA and glycidyl methacrylate(poly(MA-co-GMA)),and poly(butylacrylate)-block-poly(methyl acrylate-co-glycidyl methacrylate)(PBA-block-poly(MA-co-GMA).
Structure characterizations of BTPT, GO, TRGO,and GO-polymer have been performed by using FTIR, 1H-NMR, 13C-NMR, GPC, TGA and XRD. In this work, the effects of GO-polymer on the volume shrinkage characteristics and mechanical properties of the styrene(St)/ vinyl ester(VER)/ GO-polymer ternary systems during the cure have also been explored.
[1] H. Kim, A. A. Abdala, C. W. Macosko, Macromolecules 2010, 43, 6515.
[2] R. B. Burns, "Polyester molding compounds", Marcel Dekker, New York, 1982
[3] K. E. Atkins, H. G. Kia, Sheet Molding Compounds: Science and Technology, Ch. 4, H.G. Kia, Hanser, New York 1993.
[4] Y. J. Huang, C. M. Liang, Polymer 1996, 37, 401.
[5] Y. J. Huang, C. J. Chu, J. P. Dong, Journal of Applied Polymer Science 2000, 78, 543.
[6] Y.J. Huang, T.S. Chen, J.G. Huang, F. H. Lee, "Polym. Mater. Sci. Eng , 2000, 83, 493 .
[7] Y.J. Huang, J.P. Dong, J.J. Yang, J.H. Lee, D. H. Lai, Polym. Mater. Sci. Eng. 85, 497 2001.
[8] The B.F. Goodriche Co, WO93/21274, Oct. 28.1993.
[9] E. Martuscelli, P. Musto, G. Ragosta, G. Scarinzi, E. Bertotti, Journal of Polymer Science Part B: Polymer Physics 1993, 31, 619.
[10] S. B. Pandit, V. M. Nadkarni, Industrial & Engineering Chemistry Research 1994, 33, 2778.
[11] D. S. Kim, K. Cho, J. H. An, C. E. Park, Journal of Materials Science 1994, 29, 1854.
[12] J. S. Ullett, R. P. Chartoff, Polymer Engineering & Science 1995, 35, 1086.
[13] M. Abbate, E. Martuscelli, P. Musto, G. Ragosta, G. Scarinzi, Journal of Applied Polymer Science 1995, 58, 1825.
[14] M. L. L. Maspoch, A. B. Martinez, Polymer Engineering & Science 1998, 38, 290.
[15] N. A. Miller, C. D. Stirling, Polym. Polym. Comps. 2001 , 9, 31.
[16] R. E. Young, in "Unsaturated Polyester Technology" ed. P.F. Bruins, Gordon and Breach Science Publishers, New York 1976.
[17] M. E. Kelly, in "Unsaturated Polyester Technology" ed. P.F. Bruins, Gordon and Breach Science Publishers, New York 1976, 370.
[18] F. Fekete, in "Unsaturated Polyester Technology" ed. P.F. Bruins, Gordon and Breach Science Publishers, New York 1976, 28.
[19] B. Ellis, "Chemistry and Technology of Epoxy Resins", London: Blackie Academic and Professional 1993.
[20] 陳東課, 環氧樹脂在基層板之應用, 化工技術第四卷第五期, 1996.
[21] 賴耿陽, 環氧樹脂應用實務, 復漢出版社, 台灣, 1999.
[22] 賴家聲, 環氧樹脂與硬化劑(上), 復漢出版社, 台灣, 1999.
[23] S. V. Levchik, G. Camino, M. P. Luda, L. Costa, G. Muller, B. Costes, Polymer degradation and stability 1998, 60, 169.
[24] 黃滄閔,碩士論文,國立成功大學,2001.
[25] T. Mitani, H. Shiraishi, K. Honda, G. E. Owen, 44th Annual Conference Composite Institute, the Society of the Plastics Industry, session RF (Reb3-9) 1989.
[26] W. Li, L. J. Lee, Polymer 1998, 39, 5677.
[27] M. Kinkelaar, S. Muzumdar, L. J. Lee, Polymer Engineering & Science 1995, 35, 823.
[28] R. R. Hill, S. V. Muzumdar, L. J. Lee, Polymer Engineering & Science 1995, 35, 852.
[29] W. Crc for Polymers Pty. Ltd., WO97,43339 Nov 20,1997.
[30] J. Chiefari, Y. K. Chong, F. Ercole, J. Krstina, J. Jeffery, T. P. T. Le, R. T. A. Mayadunne, G. F. Meijs, C. L. Moad, G. Moad, Macromolecules 1998, 31, 5559.
[31] G. M. T. P. Le, S. H. T. E. Rizzardo, PCT Int. Appl. WO9801478 A1980115 1998.
[32] D. J. Keddie, G. Moad, E. Rizzardo, S. H. Thang, Macromolecules 2012, 45, 5321.
[33] Y. Zhao and S. Perrier," Macromolecules, 2007, 40, 9116-9124.
[34] H. Kim, Y. Miura, C. W. Macosko, Chemistry of Materials 2010, 22, 3441.
[35] H. Kim, C. W. Macosko, Macromolecules 2008, 41, 3317.
[36] W. Huang, X. Ouyang, L. J. Lee, ACS Nano, 6, 10178, 2012.
[37] J. Z. Xu, C. Chen, Y. Wang, H. Tang, Z. M. Li, B. S. Hsiao, Macromolecules, 2011, 44, 2808.
[38] J.R.Potts, O.Shankar, L. Du, and R.S. Ruoff, Macromolecules 2012, 45, 6045.
[39] S. Wang, M. Tambraparni, J. Qiu, J. Tipton, D. Dean, Macromolecules, 2009, 42, 5251.
[40] S. Ganguli, A. K. Roy, D. P. Anderson, Carbon 2008, 46, 806.
[41] M. Martin-Gallego, R. Verdejo, M. A. Lopez-Manchado, M. Sangermano, Polymer 2011, 52, 4664.
[42] S. Stankovich, D. A. Dikin, R. D. Piner, K. A. Kohlhaas, A. Kleinhammes, Y. Jia, Y. Wu, S. T. Nguyen, R. S. Ruoff, Carbon 2007, 45, 1558.
[43] W. S. Hummers, R. E. Offeman, J. Am. Chem. Soc., 1958, 80, 1339.
[44] H. C. Schniepp, J. L. Li, M. J. McAllister, H. Sai, M. Herrera-Alonso, D. H. Adamson, R. K. Prud'homme, R. Car, D. A. Saville, I. A. Aksay, The Journal of Physical Chemistry B 2006, 110, 8535.
[45] Y. Yang, J. Wang, J. Zhang, J. Liu, X. Yang, H. Zhao, Langmuir 2009, 25, 11808
[46] F.Beckert,C.Friedrich, R.Thomann, R.Mulhaupt , Macromolecules 2012, 45, 1346
[47] 彭俊昇,碩士論文,國立台灣科技大學,2000.
[48] H. R. Allcock, F. W. Lampe, "Contemporary Polymer Chemistry, 2nd Ed." Prentice-Hall, New Jersey, 1990, p.50.
[49] C.S.Brazel and S.L. Rosen, "Fundamental Principles of Polymeric Materials, 3rd Ed." Wiley, New York, 2012.
[50] 張容瑋,碩士論文,國立台灣科技大學, 2008.
[51] M. Szwarc, Nature, 178, 1168, London, 1956.
[52] T. Otsu, M. Yoshida, Makromol Chem Rapid Commun. 1982, 3, 127, 542.
[53] K. Matyjaszewski, J. Xia, Chemical Reviews 2001, 101, 2921.
[54] J. S. Wang, K. Matyjaszewski, Journal of the American Chemical Society 1995, 117, 5614.
[55] M. Kamigaito, T. Ando, M. Sawamoto, Chemical Reviews 2001, 101, 3689.
[56] D. H. Solomon, E. Rizzardo, P. Cacioli, US Patent, 4, 581, 429, 1985.
[57] M. K. Georges, R. P. N. Veregin, P. M. Kazmaier, G. K. Hamer, Macromolecules 1993, 26, 2987.
[58] R. Francis, D. Taton, J. L. Logan, P. Masse, Y. Gnanou, R. S. Duran, Macromolecules 2003, 36, 8253.
[59] P. Takolpuckdee, C. A. Mars, S. Perrier, Organic letters 2005, 7, 3449.
[60] Y. Tsujii, M. Ejaz, K. Sato, A. Goto, T. Fukuda, Macromolecules 2001, 34, 8872.
[61] R. Narain, S. P. Armes, Macromolecules 2003, 36, 4675.
[62] Y. S. Yang, L. J. Lee, Polymer 1988, 29, 1793.
[63] K. Horie, I. Mita, H. Kambe, Journal of Polymer Science Part A: Polymer Chemistry 1969, 7, 2561.
[64] 江文慶,碩士論文,國立台灣科技大學,1996.
[65] Y. Zhao, and S. Perrier, Macromolecules 2006, 39, 8603.
[66] K. Jiang, C. Ye, P. Zhuang, X. Wang, and Y. Zhao, Macromolecules 2012, 45, 1346.
[67] 林怡均,碩士論文,國立台灣科技大學,2016.
[68] 王妤榛,碩士論文,國立台灣科技大學,2016.
[69] 鍾宛倫,碩士論文,國立台灣科技大學,2014.
[70] L. Hlalele, and B. Klumperman, Macromolecules 2011, 44, 7100.