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，其對不飽和聚酯樹脂在聚合固化後之樣品微觀型態結構、体積收縮特性、機械性質及導電導熱性質的影響。
此核殼型顆粒(CSS)以TRGO-polymer標示之，係以化石墨烯(GO)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)合成而得。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˚C下，以熱還原法製得。TRGO-polymer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))。
鏈轉移劑(BTPT)、氧化石墨烯(GO)、熱還原氧化石墨烯(TRGO)及接枝高分子之熱還原氧化石墨烯(TRGO-polymer)的結構，吾人用(_^1)H-NMR、GPC、拉曼、FTIR、TGA及XRD鑑定。
本文中，吾人亦探討不同TRGO-polymer添加量之苯乙烯(St)/不飽和聚脂樹脂(UP)/TRGO-polymer三成分系統於110˚C恆溫固化後之微觀結構型態(以SEM及TEM鑑定)、體積收縮、機械性質、導熱及導電性質。

Synthesis of polymer grafted thermal reduced graphene oxide with core-shell structure (CSS) as low-profile additives (LPA) and toughenors for thermoset resins, and their effects on the cured sample morphology, volume shrinkage characteristics and mechanical properties, and thermal and electrical conductivities for unsaturated polyester resins (UP) during the cure were investigated.
These CSP 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 rithio-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 graphene oxide in a high temperature furnance 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(butyl acrylate)-block-poly(methyl acrylate-co-glycidy methacrylate) (PBA-block-poly(MA-co-GMA)).
Structure characterizations of BTPT, GO, TRGO and TRGO-polymer have been performed by using (_^1)H-NMR, GPC, Raman, FTIR, TGA and XRD.
In this work, th effects of TRGO-polymer on the volume shrinkage characteristics and mechanical properties, thermal and electrical conductivities of the styrene(St)/unsaturated polyester resins(UP)/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.
2014,39,193.
[5] R. B. Burns, "Polyester molding compounds", Marcel Dekker, New York, 1982
[6] The B.F. Goodrich 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] Y. S. Yang and L. J. Lee, Polymer 1988, 29, 1793
[65] K. Horie, I. Mita, H. Kambe, Journal of Polymer Science Part A: Polymer Chemistry 1969, 7, 2561.
[66] 江文慶，碩士論文，國立台灣科技大學，1996.
[67] Y. J. Huang, C. C. Su, J. Appl. Polym. Sci. 1995, 55, 305.
[68] Y. J. Huang, C.C. Su, Polym. 1994, 35, 2397.
[69] Y. J. Huang, C.C. Su, J, Appl. Polym. Sci. 1995, 55, 323
[70] E. J. Bartkus, C. H Kroekel, Appl. Polym. Symp. 1970, 15, 113.
[71] V. A. Pattison, R. R. Hindersinn, W. T. Schwartz, J. Appl. Polym. Sci. 1974, 18, 2763.
[72] V. A. Pattison, R. R. Hindersinn, W. T. Schwartz, J. Appl. Polym. Sci. 1975, 19 3045.
[73] Y. J. Huang, T. S. Chen, J. G. Huang, F. H. Lee, J. Appl. Polym. Sci. 2003, 89, 3336
[74] J.P. Dong, J.G. Huang, F.U. Lee, J.W. Roan, and Y.J. Huang, J. Appl. Polym. Sci. 2004, 91, 3369
[75] K. E. Atkins, in “Sheet Molding Compound :Science and Technology” Ed., H.G. Kia, Hanser Publishers, 1993, Ch4.
[76] C. B. Bucknall, I. K. Partridge, M. J. Phillips, Polym. 1991, 32, 786.
[77] T. Mitani, H. Shiraishi, K. Honda, G.E. Owen, 44th Annual Conference Composite Institute, SPI, Session 12-F, 1989.
[78] Y. J. Huang, J. C. Horng, Polym. 1998, 39, 3683.
[79] W. D. Cook, O. Delatycki, J. Polym. Sci. Polym. Phys. Ed. 1974, 12, 2111.
[80] W. D. Cook, O. Delatycki, J. Polym. Sci. Polym. Phys. Ed. 1974, 12, 1925.
[81] J. P. Dong , J. H. Lee, D. H. Lai, Y. J. Huang, Appl. Polym. Sci. 2005, 98, 264
[82] Y. J. Huang, S. C. Lee, J. P. Dong, J. Appl. Polym. Sci. 2000, 78, 558.
[83] Y. J. Huang, T. S. Chen, J. G. Huang, F. H. Lee, J. Appl. Polym. Sci. 2003, 89, 3347.
[84] Y. Zhao, and S. Perrier, Macromolecules 2006, 39, 8603.
[85] K. Jiang, C. Ye, P. Zhuang, X. Wang, and Y. Zhao, Macromolecules 2012, 45, 1346.
[86] U. Khana, Arlene O’Neilla, Harshit Porwala, Peter Maya, Khalid Nawazb, Jonathan N. Colemana, Carbon, p.470-475, 2012.
[87] 張庭豐，碩士論文，國立台灣科技大學，2019.
[88] O. Eksik, S.F. Bartolucci, T. Gupta, H. Fard, T. Borca-Tasciuc, N. Koratkar,
Carbon 101 (2016) 239-244
[89] Tseng, I. H.; Chang, J. C.; Huang, S. L.; Tsai, M. H. Polym. Int. 2013, 62,
827−835.