本文探討添加氧化石墨烯(GO)、低接枝密度之矽烷接枝氧化石墨烯(LD-sg-GO)、高接枝密度之矽烷接枝氧化石墨烯(HD-sg-GO)、熱脫層氧化石墨烯(TRGO)以及矽烷接枝之熱脫層氧化石墨烯(sg-TRGO)等數種特用添加劑的合成及其對苯乙烯(St)/乙烯基酯(VER)/特用添加劑三成份系統於120 oC恆溫固化之微觀型態結構、體積收縮特性及機械性質的影響。
熱脫層氧化石墨烯(TRGO)是將氧化石墨烯(GO)置於1050 oC的高溫爐中30 sec合成而得；後者，則是將平均粒徑為2至15微米的天然石墨粉以改良的Hummers法製得。矽烷接枝氧化石墨烯(sg-GO)係以帶有壓克力不飽和C=C雙鍵的矽烷偶合劑，即甲基丙烯酰氧丙基三甲氧基矽烷(MPS)，做為表面改質劑，在GO/MPS/溶劑三者的重量比於1:5:94下，並在不同反應溫度(60 oC-100 oC)及時間(1.5 hr-48 hr)、不同使用溶劑(如甲苯、乙醇以及二甲基甲醯胺)及不同反應次數下(一或三次反應，以進行GO之表面處理)，對氧化石墨烯(GO)進行表面處理而得。兩種矽烷接枝氧化石墨烯，包刮低接枝密度(LD-sg-GO)及高接枝密度(HD-sg-GO)。吾人以傅立葉轉換紅外光分析儀(FTIR)的定量測得之接枝密度分別為112 mmole MPS/100 g GO及492 mmole MPS/100 g GO。至於矽烷接枝熱脫層氧化石墨烯(sg-TRGO)，吾人以FTIR所測得之接枝密度為83 mmole MPS/ 100 g TRGO。
視GO的種類及添加量(GO及sg-GO之添加量為0.5 wt%-5.0 wt%，而TRGO及sg-TRGO之添加劑為0.5 wt%-1.0 wt%)，添加GO於VER樹脂中，其聚合固化後之體積收縮會有不同程度的降低效果。通常，添加GO量愈大，聚合固化後之體積收縮亦愈小。在本研究的四種不同添加劑中，包括GO、sg-GO、TRGO以及sg-TRGO，在固定的添加量下，以sg-TRGO及TRGO為添加劑的抗體積收縮效果最好，sg-GO系次之，GO系則是最差。5.0 wt% GO系及0.5 wt% sg-GO系，其抗體積收縮的表現相近，而0.5 wt% sg-TRGO系及0.5 wt% TRGO系，其抗體積收縮效果較0.5 wt% sg-GO系為佳。本研究中，吾人發現添加0.5 wt% TRGO、0.5 wt% sg-TRGO或1.0 wt% sg-TRGO這三個系統，其在St/VER(n=2)/添加劑三成份係於120 oC聚合固化之體積收縮控制的效果最佳。而這三個系統中，以添加1.0 wt% sg-TRGO三成份系的機械性質表現最佳，其楊氏模數與純VER(n=2)樹脂系相較，增加10%，抗張強度僅減小5%，而耐衝擊強度大增100%。

The effects of graphene oxide (GO), low grafting density silane-grafted graphene oxide (LD-sg-GO), high grafting density silane-grafted graphene oxide (HD-sg-GO), thermally reduced graphene oxide (TRGO), and silane-grafted thermally reduced graphene oxide (sg-TRGO) as special addities on the cured sample morphologies, volume shrinkage characteristics and mechanical properties for low-shrink vinyl ester resins (VER) cured at 120 oC were investigated.
The TRGO was produced by placing the GO in a high-temperature furnace kept at 1050 oC for 30 s, which was synthesized from natural graphites with average particle size of 2 to 15 μm by a modified Hummers method. The sg-GO was synthesized by using the silane coupling agent bearing acrylic C=C bonds, namely, γ-methacryloxy propyl trimethoxy silane (MPS), as a surface modifier for the surface treatment of GO at varied reaction temperatures (60 oC-100 oC) and reaction times (1.5 hr-48 hr), with different times of reaction for surface treatment between GO and MPS (n=1 or 3), using different reagents, such as toluene, ethanol and dimethyl formamide, as the solvent and with a fixed weight ratio of GO/MPS/solvent at 1:5:94, where the grafting density was 112 mmole MPS/100 g GO and 492 mmole MPS/100 g GO for low grafting density of silane-grafted GO (LD-sg-GO) and high grafting density of silane-grafted GO (HD-sg-GO), respectively, as measured by FTIR. As for the silane-grafted TRGO (sg-TRGO), the grafting density was 83 mmole MPS/100 g TRGO, as measured by FTIR.
Depending on the type of GO and their contents (0.5 wt% to 5.0 wt% for GO and sg-GO, and 0.5 wt% to 1.0 wt% for TRGO and sg-TRGO) added, the GO could lead to a reduction of volume shrinkage after the cure to differing degrees. In general, a higher content of GO may result in a lower volume shrinkage after cured. Among the four additives studied in this work, namely, GO, sg-GO, TRGO, and sg-TRGO at a fixed content of additive, sg-TRGO and TRGO would result in the best volume shrinkage control, followed by sg-GO and GO. The performance of volume shrinkage control was quite close to each other for the 5.0 wt% GO and the 0.5 wt% sg-GO systems, whereas the 0.5 wt% sg-TRGO system and 0.5 wt% TRGO system could lead to a better volume shrinkage control than the 0.5 wt% sg-GO system. In this work, it has been found that adding 0.5 wt% of TRGO, 0.5 wt% of sg-TRGO or 1.0 wt% sg-TRGO as the LPA for the St/VER(n=2)/additive ternary system during the cure at 120 oC is the best recipe for a good volume shrinkage control, which exhibited a fractional volume shrinkage of 2.6%, about one half of that for the neat VER cured system. However, the 1.0 wt% sg-TRGO ternary system would possess the best mechanical properties, exhibiting a slight increase of 10% in Young’s modulus, and a slight decrease of 5% in tensile strength, and a 100% increase in impact strength, when compared with that of neat VER(n=2) cured system.

[1] A. Almagableh, P. R.Mantena, A. Alostaz, W. Liu, L. T. Drzal, eXPRESS Polym. Lett. 2009, 11, 724-723.
[2] Z. Guo, K. Lei, Y. Li, W. Liu, H. W. Ng, P. Sergy, H. Thomas, Compos. Sci. Technol. 2008, 68, 1513-1520.
[3] L. Liao, X. Wang, P. Fang, M. Kim, C. Pan, Appl. Mater. & Interfaces. 2011, 3 534-538.
[4] S. DUA, R. L. McCULLOUGH, G. R. PALMESE, Polym. Compos. 1999, 20 379-391.
[5] J. Changwoon, S. Nouranian, E. L. Thomas, S. R. Gwaltney, H. Toghiani, C. H. Pittman, Carbon. 2012, 50, 748-760.
[6] W. Posthumus, P.C.M.M. Magusin, J.C.M. Brokken-Zijp, A.H.A. Tinnemans, R. van der Linde, J. Colloid and Interface Sci. 2004, 269, 109-116.
[7] R. B. Burns, "Polyester molding compounds", Marcel Dekker, New York, 1982.
[8] 鍾宛倫, 碩士論文, 台灣科技大學, 2014.
[9] W. H. Liao, H. W. Tien, S.T. Hsiao, S. M. Li, Y. S. Wang, Y. L. Huang, S. Y. Yang, C. C. M. Ma, Y. F. Wu, Appl. Mater. & Interfaces. 2013, 5, 3975-3982.
[10] R. E. Young, in “Unsaturated Polyester Technology”, Ed. P.F. Bruins, Gordon and Breach Science Publishers, 1976.
[11] M.E. Kelly, in “Unsaturated Polyester Technology”, Ed. P.F. Bruins, Gordon and Breach Science Publishers, 1976, P.370.
[12] 黃智偉, 碩士論文, 台灣科技大學, 2014
[13] F. Fekete, in “Unsaturated Polyester Technology”, Ed. P.F. Bruins, Gordon and Breach Science Publishers, 1976, P.28.
[14] R.B. Burn, “Polyester Molding Compounds”, Marcel Dekker, Inc, New York, 1982.
[15] E. J. Bartkus, C. H Kroekel, Appl. Polym. Symp. 1970, 15, 113.
[16] K. E. Atkins, in “Sheet Molding Compound :Science and Technology” Ed., H.G. Kia, Hanser Publishers, 1993, Ch4.
[17] V. A. Pattison, R. R. Hindersinn, W. T. Schwartz, J. Appl. Polym. Sci. 1974, 18, 2763.
[18] V. A. Pattison, R. R. Hindersinn, W. T. Schwartz, J. Appl. Polym. Sci. 1975, 19 3045.
[19] Y. J. Huang, C. C. Su, J. Appl. Polym. Sci. 1995, 55, 305.
[20] Y. J. Huang, J. C. Horng, Polym. 1998, 39, 3683.
[21] Y. J. Huang, L. D. Chen, Polym. 1998, 39, 7049.
[22] L. Suspene, D. Fourquier, Y. S. Yang, Polym. 1991, 32, 1593.
[23] Y. J. Huang, C. M. Liang, Polym. 1996, 37, 401.
[24] L. J. Lee, W. Li, K. H. Hsu, Polym. 2000, 41, 711.
[25] C. B. Bucknall, I. K. Partridge, M. J. Phillips, Polym. 1991, 32, 636.
[26] Y. J. Huang, T. S. Chen, J. G. Huang, F. H. Lee, J. Appl. Polym. Sci. 2003, 89, 3336.
[27] J. P. Dong , J. H. Lee, D. H. Lai, Y. J. Huang, Appl. Polym. Sci. 2005, 98, 264.
[28] 盧天智, 碩士論文,台灣科技大學, 1991
[29] H. R. Allcock, F. W. Lampe, “Contemporary Polymer Chemistry”, 2nd Ed.,
Prentice Hall, Englewood Cliffs, (1990), P.50.
[30] Y. S. Yang, L. J. Lee, Polym. 1988, 29, 1793.
[31] K. Horie, I. Mita, H. Kambe, J. Polym. Sci. PartA-1:Polym. Chem. 1969, 7 2561.
[32] 江文慶, 碩士論文,台灣科技大學, 1996.
[33] Y. J. Huang, C. C. Su, J. Appl. Polym. Sci. 1995, 55, 323.
[34] Y. J. Huang, C. C. Su, J. Appl. Polym. Sci. 1995, 55, 305.
[35] Y. J. Huang, C.C. Su, Polym. 1994, 35, 2397.
[36] C. B. Bucknall, I. K. Partridge, M. J. Phillips, Polym. 1991, 32, 786.
[37] T. Mitani, H. Shiraishi, K. Honda, G.E. Owen, 44th Annual Conference
Composite Institute, SPI, Session 12-F, 1989.
[38] W. D. Cook, O. Delatycki, J. Polym. Sci. Polym. Phys. Ed. 1974, 12, 2111.
[39] W. D. Cook, O. Delatycki, J. Polym. Sci. Polym. Phys. Ed. 1974, 12, 1925.
[40] J. P. Dong, J. G. Huang, F. H. Lee, J. W. Roan, Y. J. Huang, J. Appl. Polym. Sci. 2004, 91, 3388.
[41] Y. J. Huang, S. C. Lee, J. P. Dong, J. Appl. Polym. Sci. 2000, 78, 558.
[42] Y. J. Huang, T. S. Chen, J. G. Huang, F. H. Lee, J. Appl. Polym. Sci. 2003, 89, 3347.
[43] H. Kim, A. A. Abdala, C. W. Macosko, Macromol. 2010, 43, 6515-6530.
[44] Y. J. Wan, L. X. Gong, L. C. Tang, L. B. Wu, J. B. Jiang, Composites: Part A. 2014, 64, 79-89.
[45] Y. J. Wan, L. C. Tang, L. X. Gong, Y. D. Yan, Y. B. Li, L. B. Wu, J. X. Jiang, G. Q. Lai, Carbon. 2014, 69, 467-480.
[46] C. Botas, P. A´lvarez, C. Blanco, R. Santamarı´a, M. Granda, M. Gutie´rrez, F. R. Reinoso, R. Mene´ndez, Carbon. 2013, 52, 476-485.
[47] H. Kim, Y. Miura, C. W. Macosko, Chem. Mater. 2010, 22, 3441-3450.
[48] J. Zang, Y. J. Wan, Li. Zhao, L. C. Tang, Macromol. Mater. Eng. 2015, 300, 737-749.
[49] R. Thomann, R. Mülhaupt, A. K. Appel, Polym. 2012, 53, 4931-4939.
[50] G. H. Yeoh, X. Wang, W. Xing, L. Song, B. Yu, Y. Hu, Reactive & Functional Polym. 2013, 73, 854-858.
[51] A. Chaturvedi, A. Tiwari, A. Tiwari, Adv. Mat. Lett. 2013, 4, 656-661.
[52] O. Eksik, S. F. Bartolucci, T. Gupta, H. Fard, T. B. Tasciuc, N. Koratkar, Carbon. 2016, 101, 239-244.
[53] JR. Hummers, R. E. Offeman, J. Americ. Chem. Soc. 1958, 80, 1339.
[54] C. H. Schniepp, J. L. Li, M. J. McAllister, H. Sai, H. A. Margarita, D. H. Adamson, R. K. Prud’homme, R. Car, D. A. Saville, I. A. Aksay, J. Phys. Chem. B. 2006, 17, 8535.
[55] Y. Yang, J. Wang, J. Zhang, J. Liu, X. Yang, H,. Zhao, Langmuir, 2009, 25, 118.
[56] F. Beckert, C. Friedrich, R. Thomann, R. Mulhaupt, Macromol. 2012, 45, 7083.
[57] Y. J. Wan, L. X. Gong, L. C. Tang, L. B. Wu, J. B. Jiang, Composites: Part A. 2014, 64, 79-89.
[58] J. Michael, J. L. McAllister, H. A. Douglas, C. Hannes, Chem. Mater. 2007, 19 4396-4400.
[59] R.-M. Hossein, H.-A. Vahid, K. Khezrollah, Z. Elnaz, S. K. Mehdi, J. Polym. Res. 2014, 16, 333.
[60] C. Hontoria-Lucas, A. Lopez-Peinado, D. Lopez-Gonzalez, M. L. Rojas-Cervantes, R. M. Martin-Ara nda, Carbon. 1995, 33, 1585-1592.
[61] H. Kim, Y. Miura, C. W. Macosko, Chem. Mater. 2010, 22, 3441-3450.