研究生: |
張庭豐 Ting-Feng Chang |
---|---|
論文名稱: |
以 RAFT活自由基溶液聚合法合成高分子接枝之氧化石墨烯及熱脫層氧化石墨烯及探討其對乙烯基酯樹脂之聚合固化樣品微觀型態結構、體積收縮、機械性質、熱傳導及導電性質的影響 Synthesis of polymer-grafted graphene oxide and thermally reduced graphene oxide by RAFT free radical solution polymerizations, and their effects on volume shrinkage, mechanical properties, and thermal and electrical conductivities for vinyl ester resins |
指導教授: |
黃延吉
Yan-Jyi Huang |
口試委員: |
邱文英
WUN-YING CIOU 陳崇賢 CHONG-SIAN CHEN |
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: | 2019 |
畢業學年度: | 107 |
語文別: | 中文 |
論文頁數: | 203 |
中文關鍵詞: | 高分子接枝之氧化石墨烯 、抗收縮劑 、增韌劑 、可逆加成-斷裂鏈轉移聚合法 、乙烯基酯樹脂 、氧化石墨烯 、熱還原氧化石墨烯 、聚合固化 、體積收縮 、機械性質 、熱傳導性質 、導電性質 |
外文關鍵詞: | graphite oxide, thermal reduced graphite oxide |
相關次數: | 點閱:444 下載:1 |
分享至: |
查詢本校圖書館目錄 查詢臺灣博碩士論文知識加值系統 勘誤回報 |
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)高分子接枝之熱還原氧化石墨烯的合成,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、體積收縮特性、機械性質及導熱導電的影響。
這些核殼型結構(CSS),以TRGO-polymer標示之,係以氧化石墨烯(GO)經由熱還原形成之熱還原氧化石墨烯(TRGO)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,氧化石墨烯(GO)是以modified Hummers 方法將天然石墨氧化合成。熱還原氧化石墨烯(TRGO)則是將氧化石墨烯放入高溫爐中,在1050℃下,以熱還原法製備而得。TRGO -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(BA)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))。
BTPT、GO、TRGO及TRGO-Polymer的結構,吾人以FTIR、1H-NMR、GPC、TGA及XRD鑑定之。本文中,吾人亦探討TRGO-Polymer對苯乙烯(St)/乙烯基酯(VER)/TRGO-Polymer之三成分系統於120℃恆溫聚合固化後之微觀型態結構(以SEM、TEM鑑定)、體積收縮、機械性質、導熱及導電性質。
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 and thermal and electrical conductivities for low-shrink vinyl ester resins (VER) during the cure were investigated.
These CSS designated as TRGO-polymer, which contained thermal reduced graphene oxide(TRGO) 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. Thermal reduced graphene oxide (TRGO) was obtained by placing the graphene oxide in a high temperature furnace at 1050 ° C by a thermal reduction method.The grafted polymer as the shell structure of the TRGO-polymer was made from copolymer of MA and glycidyl methacrylate (poly(MA-co-GMA)), and poly(butylacrylate)-block- poly(methylacrylate-co-glycidyl methacrylate) (PBA-block-poly(MA-co-GMA)).
Structure characterizations of BTPT, GO, TRGO,and TRGO-polymer have been performed by using FTIR, 1H-NMR, 13C-NMR, GPC, TGA and XRD. In this work, the effects of TRGO-polymer on the volume shrinkage characteristics and mechanical properties and thermal and electrical conductivities of the styrene(St)/ vinyl ester(VER)/ TRGO-polymer ternary systems during the cure have also been explored.
[1] H. Kim, A. A. Abdala, C. W. Macosko, Macromolecules 2010, 43, 6515.
[2] M. Eizenberg; J. M. Blakely, Surf. Sci. 1970, 82, 228–236.
[3] K.S.Novoselov;A.K.Geim;S.V.Morozov;D.Jiang;Y.Zhang;S.V.Dubonos;I. V.Grigorieva,; A. A.Firsov, Science 2004, 306, 666–669.
[4] K.Hu,D.D.Kulkarni,I.Choi,Vladimir V.Tsukruk. Progress in Polymer Science. 2014,39,1934
[5] R. B. Burns, "Polyester molding compounds", Marcel Dekker, New York, 1982
[6] The B.F. Goodriche Co, WO93/21274, Oct. 28.1993.
[7] E. Martuscelli, P. Musto, G. Ragosta, G. Scarinzi, E. Bertotti, Journal of Polymer Science Part B: Polymer Physics 1993, 31, 619.
[8] S. B. Pandit, V. M. Nadkarni, Industrial & Engineering Chemistry Research 1994, 33, 2778.
[9] D. S. Kim, K. Cho, J. H. An, C. E. Park, Journal of Materials Science 1994, 29, 1854.
[10] J. S. Ullett, R. P. Chartoff, Polymer Engineering & Science 1995, 35, 1086.
[11] M. Abbate, E. Martuscelli, P. Musto, G. Ragosta, G. Scarinzi, Journal of Applied Polymer Science 1995, 58, 1825.
[12] M. L. L. Maspoch, A. B. Martinez, Polymer Engineering & Science 1998, 38, 290.
[13] N. A. Miller, C. D. Stirling, Polym. Polym. Comps. 2001 , 9, 31.
[14] R. E. Young, in "Unsaturated Polyester Technology" ed. P.F. Bruins, Gordon and Breach Science Publishers, New York 1976.
[15] M. E. Kelly, in "Unsaturated Polyester Technology" ed. P.F. Bruins, Gordon and Breach Science Publishers, New York 1976, 370.
[16] F. Fekete, in "Unsaturated Polyester Technology" ed. P.F. Bruins, Gordon and Breach Science Publishers, New York 1976, 28.
[17] B. Ellis, "Chemistry and Technology of Epoxy Resins", London: Blackie Academic and Professional 1993.
[18] 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.
[19] 賴耿陽, 環氧樹脂應用實務, 復漢出版社, 台灣, 1999.
[20] 賴家聲, 環氧樹脂與硬化劑(上), 復漢出版社, 台灣, 1999.
[21] S. V. Levchik, G. Camino, M. P. Luda, L. Costa, G. Muller, B. Costes, Polymer degradation and stability 1998, 60, 169.
[22] 黃滄閔,碩士論文,國立成功大學,2001.
[23] Y. J. Huang, C. M. Liang, Polymer 1996, 37, 401.
[24] 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.
[25] W. Li, L. J. Lee, Polymer 1998, 39, 5677.
[26] M. Kinkelaar, S. Muzumdar, L. J. Lee, Polymer Engineering & Science 1995, 35, 823.
[27] R. R. Hill, S. V. Muzumdar, L. J. Lee, Polymer Engineering & Science 1995, 35, 852.
[28] W. Crc for Polymers Pty. Ltd., WO97,43339 Nov 20,1997.
[29] 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.
[30] G. M. T. P. Le, S. H. T. E. Rizzardo, PCT Int. Appl. WO9801478 A1980115 1998.
[31] D. J. Keddie, G. Moad, E. Rizzardo, S. H. Thang, Macromolecules 2012, 45, 5321.
[32] Y. Zhao and S. Perrier," Macromolecules, 2007, 40, 9116-9124.
[33] H. Kim, Y. Miura, C. W. Macosko, Chemistry of Materials 2010, 22, 3441.
[34] H. Kim, C. W. Macosko, Macromolecules 2008, 41, 3317.
[35] W. Huang, X. Ouyang, L. J. Lee, ACS Nano, 6, 10178, 2012.
[36] J. Z. Xu, C. Chen, Y. Wang, H. Tang, Z. M. Li, B. S. Hsiao, Macromolecules, 2011, 44, 2808.
[37] J.R.Potts, O.Shankar, L. Du, and R.S. Ruoff, Macromolecules 2012, 45, 6045.
[38] S. Wang, M. Tambraparni, J. Qiu, J. Tipton, D. Dean, Macromolecules, 2009, 42, 5251.
[39] S. Ganguli, A. K. Roy, D. P. Anderson, Carbon 2008, 46, 806.
[40] M. Martin-Gallego, R. Verdejo, M. A. Lopez-Manchado, M. Sangermano, Polymer 2011, 52, 4664.
[41] 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.
[42] S.Stankovich; D. A.Dikin; G. H. B.Dommett; K. M.Kohlhaas; E. J.Zimney; E. A. Stach; R. D.Piner; S. T.Nguyen; R. S.Ruoff, Nature 2006, 442, 282–286.
[43] P.Steurer; R.Wissert; R.Thomann; R.Muelhaupt, Macromol. Rapid Commun. 2009, 30, 316–327.
[44] H.Kim; C. W.Macosko, Polymer 2009, 50, 3797–3809.
[45] H. Kim, Y. Miura, and C. W. Macosko, Chem. Mater. 2010, 22, 3441–3450 3441
[46] S.Ahmed, H.S.Wajid, A.Tanvir, S.D.F. Irin, F.Alan, M.J.Jankowski, Green, Macromol.Mater.Eng.2013,298,339–347
[47] W. S. Hummers, R. E. Offeman, J. Am. Chem. Soc., 1958, 80, 1339.
[48] 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.
[49] Y. Yang, J. Wang, J. Zhang, J. Liu, X. Yang, H. Zhao, Langmuir 2009, 25, 11808
[50] F.Beckert,C.Friedrich, R.Thomann, R.Mulhaupt , Macromolecules 2012, 45, 1346
[51] 彭俊昇,碩士論文,國立台灣科技大學,2000.
[52] H. R. Allcock, F. W. Lampe, "Contemporary Polymer Chemistry, "2nd Ed." , Prentice-Hall, New Jersey, 1990, p.50.
[53] C.S.Brazel and S.L. Rosen, "Fundamental Principles of Polymeric Materials, 3rd Ed." Wiley, New York, 2012.
[54] 張容瑋,碩士論文,國立台灣科技大學, 2008.
[55] M. Szwarc, Nature, 178, 1168, London, 1956.
[56] T. Otsu, M. Yoshida, Makromol Chem Rapid Commun. 1982, 3, 127, 542.
[57] K. Matyjaszewski, J. Xia, Chemical Reviews 2001, 101, 2921.
[58] J. S. Wang, K. Matyjaszewski, Journal of the American Chemical Society 1995, 117, 5614.
[59] M. Kamigaito, T. Ando, M. Sawamoto, Chemical Reviews 2001, 101, 3689.
[60] D. H. Solomon, E. Rizzardo, P. Cacioli, US Patent, 4, 581, 429, 1985.
[61] M. K. Georges, R. P. N. Veregin, P. M. Kazmaier, G. K. Hamer, Macromolecules 1993, 26, 2987.
[62] R. Francis, D. Taton, J. L. Logan, P. Masse, Y. Gnanou, R. S. Duran, Macromolecules 2003, 36, 8253.
[63] P. Takolpuckdee, C. A. Mars, S. Perrier, Organic letters 2005, 7, 3449.
[64] 盧天智, 碩士論文,台灣科技大學, 1991
[65] Y. J. Huang, C. C. Su, J. Appl. Polym. Sci. 1995, 55, 305.
[66] Y. J. Huang, C.C. Su, Polym. 1994, 35, 2397.
[67] J.P. Dong, J.G. Huang, F.U. Lee, J.W. Roan, and Y.J. Huang, J. Appl. Polym. Sci. 2004, 91, 3369
[68] E. J. Bartkus, C. H Kroekel, Appl. Polym. Symp. 1970, 15, 113.
[69] V. A. Pattison, R. R. Hindersinn, W. T. Schwartz, J. Appl. Polym. Sci. 1974, 18, 2763.
[70] V. A. Pattison, R. R. Hindersinn, W. T. Schwartz, J. Appl. Polym. Sci. 1975, 19 3045.
[71] Y. J. Huang, T. S. Chen, J. G. Huang, F. H. Lee, J. Appl. Polym. Sci. 2003, 89, 3336
[72] K. E. Atkins, in “Sheet Molding Compound :Science and Technology” Ed., H.G. Kia, Hanser Publishers, 1993, Ch4.
[73] C. B. Bucknall, I. K. Partridge, M. J. Phillips, Polym. 1991, 32, 786.
[74] T. Mitani, H. Shiraishi, K. Honda, G.E. Owen, 44th Annual Conference Composite Institute, SPI, Session 12-F, 1989.
[75] Y. J. Huang, J. C. Horng, Polym. 1998, 39, 3683.
[76] W. D. Cook, O. Delatycki, J. Polym. Sci. Polym. Phys. Ed. 1974, 12, 2111.
[77] W. D. Cook, O. Delatycki, J. Polym. Sci. Polym. Phys. Ed. 1974, 12, 1925.
[78] J. P. Dong , J. H. Lee, D. H. Lai, Y. J. Huang, Appl. Polym. Sci. 2005, 98, 264
[79] Y. J. Huang, S. C. Lee, J. P. Dong, J. Appl. Polym. Sci. 2000, 78, 558.
[80] Y. J. Huang, T. S. Chen, J. G. Huang, F. H. Lee, J. Appl. Polym. Sci. 2003, 89, 3347.
[81] Y. Tsujii, M. Ejaz, K. Sato, A. Goto, T. Fukuda, Macromolecules 2001, 34, 8872.
[82] R. Narain, S. P. Armes, Macromolecules 2003, 36, 4675.
[83] Y. S. Yang, L. J. Lee, Polymer 1988, 29, 1793.
[84] K. Horie, I. Mita, H. Kambe, Journal of Polymer Science Part A: Polymer Chemistry 1969, 7, 2561.
[85] 江文慶,碩士論文,國立台灣科技大學,1996.
[86] Y. Zhao, and S. Perrier, Macromolecules 2006, 39, 8603.
[87] K. Jiang, C. Ye, P. Zhuang, X. Wang, and Y. Zhao, Macromolecules 2012, 45, 1346.
[88] 陳彥博,碩士論文,國立臺灣科技大學,2019
[89] 林暐靜,碩士論文,國立臺灣科技大學,2019
[90] 江義駿,碩士論文,國立臺灣科技大學,2018.
[91] 粘純嫣,碩士論文,國立臺灣科技大學,2017
[92] S.R. Wang, J. J. Qiu, Composites:Part B 41(2010)533-536
[93] L. Yusriah, S.M. Sapuan, E.S. Zainudin, M. Mariatti, M. Jawaid, POLYM.
COMPOS., 37:2008–2017, 2016.
[94] O. Eksik, S.F. Bartolucci, T. Gupta, H. Fard, T. Borca-Tasciuc, N. Koratkar, Carbon
101 (2016) 239-244.
[95] S. Ganguli, A.K. Roy, D.P. Anderson, Carbon 46 (2008) 806-817.