研究生: |
陳彥廷 YEN-TING CHEN |
---|---|
論文名稱: |
由元素矽水解法合成無機二氧化矽奈米顆粒及以RAFT 活自由基聚合法合成用於不飽和聚酯、乙烯基酯及環氧樹脂之奈米級無機二氧化矽/有機高分子核殼型顆粒添加劑 Synthesis of nano-scale colloidal silica from elemental silicon by hydrolysis, and synthesis of nano-scale inorganic silica/organic polymer core-shell particle as additives by RAFT living free radical polymerizations for unsaturated polyester, vinyl ester, and epoxy resins. |
指導教授: |
黃延吉
Yan-Jyi Huang |
口試委員: |
陳崇賢
Chorng-Shyan Chern 邱文英 Wen-Yen Chiu |
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: | 2012 |
畢業學年度: | 100 |
語文別: | 中文 |
論文頁數: | 101 |
中文關鍵詞: | 表面改質劑 、無機/有機核殼型顆粒(CSP) 、可逆加成-斷裂鏈轉移RAFT 、不飽和聚酯 、乙烯基酯 、環氧樹脂 、抗體積收縮性 、活高分子 、二氧化矽 |
外文關鍵詞: | Silica, modifier, Reversible Addition-Fragmentation Chain Transfer, inorganic/organic core-shell particle (CSP), unsaturated polyester (UP), vinyl ester resins (VER), epoxy (EP), low-profile additives, living polymer |
相關次數: | 點閱:632 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 |
本文以元素矽水解法合成不同奈米粒徑的二氧化矽當作擔體,經由表面改質劑( 4-(Chloromethyl)phenyltrimethoxysilane )改質之後,再利用可逆加成-斷裂鏈轉移之活自由基聚合作用(RAFT),在二氧化矽表面接枝高分子,形成無機/有機核殼型顆粒(CSP),可當成不飽和聚酯、乙烯基酯及環氧樹酯的特殊添加劑,以改善熱固性樹脂基材之物性,如抗體積收縮性質及機械性質。
CSP的合成是以二氧化矽當做核心,再以具化學結構Z-C(=S)-S-R之RAFT鏈轉移劑3-Benzylsulfanylthiocarbonylsufanylpropionic Acid (BSPA),接枝於先經苯甲氯表面改質後的二氧化矽(即Si-Cl),形成接枝鏈轉移劑之二氧化矽(Si-BSPA),再以 Si-BSPA 為鏈轉移劑,經由RAFT 溶液聚合途徑聚合有機之丙烯酸甲酯、丙烯酸丁酯單體,形成無機/有機核殼型顆粒(Si-PMA, Si-PBA-b-PMA)。反應中的鏈轉移劑(BSPA)在RAFT聚合作用過程中會形成休眠基團,緩慢的進行聚合作用,可以控制接枝聚合物的分子量及分子量分佈,所得到之核殼顆粒之高分子外殼,並具活高分子(living polymer)之特性。
In the synthesis of the Si-PMA and Si-PBA-b-PMA, the nano-scale colloidal silica was obtained by the hydrolysis of elemental silicon. Then silica was reacted with 4-(chloromethyl)phenyltrimethoxysilane to produce benzyl chloride functionalized silica(Si-Cl) first, followed by reacting with BSPA to make BSPA-grafted silica particle (Si-BSPA). Later, Si-BSPA can be used as a RAFT agent to make Si-poly(methyl acrylate) (i.e. Si-PMA) and Si-PBA-b-PMA via Reversible Addition -Fragmentation Chain Transfer (RAFT) polymerization.
During RAFT polymerization, the CTA chain transfer agent would become a dormant specimen, which may slow down the polymerization rate, and the molecular weight and molecular weight distribution can then be controlled. The Si-PMA has a characteristic of living polymer. By characteristic of living polymer, Si-PMA was utilized as a macro-CTA to mediate chain extension polymerization of butyl acrylate(BA) monomers, and diblock copolymer grafted silica (i.e Si-PBA-b-PMA) was prepared.
The synthesized Si-PMA and Si-PBA-b-PMA, namely, inorganic/ organic core-shell particle (CSP) can be employed as low-profile additives (LPA) for low-shrink unsaturated polyester (UP), vinyl ester resins (VER), and Epoxy (EP) resin.
(1) R.K. Ilen, Ed., The chemistry of silica: Solubility, Polymerization, Colloid and Surface Properties, and Biochemistry, Wiley, New York, 1979.
(2) R. B. Burns, Ed., Polyester Molding Compounds, Marcel Dekker, New York, 1982.
(3) K.E. Atkins, H.G. Kia, Eds., Sheet Molding Compounds: Science and Technology, Ch.4, H.G. Kia, Hanser, New York, 1993.
(4) Y.J. Huang, C.M. Liang, Polymer 37, 401 (1996).
(5) Y.J. Huang, C.J. Chu, J.P. Dong, J.Appl. Polym. Sci. 78, 543 (2000).
(6) Y.J. Huang, T.S. Chen, J.G. Huang, F.H. Lee, Polym. Mater. Sci. Eng. 83, 493 (2000).
(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. Goodrich Co., WO93/21274, (Oct.28.1993).
(9) E. Martuscelli, P. Musto, G. Ragosta, G. Scarinzi, E. Bertotti, J.Polym. Sci., PartB: Polym. Phys. 31, 619 (1993).
(10) S.B. Pandit, V.M. Nadkarni, Ind. Eng. Chem. Res. 33, 2778 (1994).
(11) D.S. Kim, K. Cho, J.H. An, C.E. Park, J. Mater. Sci. 29, 1854 (1994).
(12) J.S. Ullett, R.P. Chartoff, Polym. Eng. Sci. 35, 1086 (1995).
(13) M. Abbate, E. Mrtuscelli, P. Musto, G. Ragosta, G. Scatinzi, J. Appl. Polym. Sci. 58, 1825 (1995).
(14) M.L.L. Maspoch, A.B. Martinez, Polym. Eng. Sci. 38, 2909 (1998).
(15) (a)N.A. Miller, C.D. Stirling, Polym. Polym. Comps. 9, 31 (2001).(b)R.E. Young, in “Usaturated Polyester Technology ,”ed. P.F. Bruins, Gordon and Breach Science Publishers, New York, 1976.(c)M.E. Kelly, in “Unsarurated Polyester Technology,”Ed.P.F. Bruins, Gordon and Breach Science Publishers, New York,1976,p.370. (d)F. Fekete, in” Unsaturated Polyester Technology,” ed. P.F. Bruins, Gordon and Science Publishers, New York,1976,p.28
(16) Bryan Ellis. Chemistry and Technology of Epoxy Resin. 1993, London: Blackie Academic & Professional.
(17) 陳東課, 環氧樹脂在積層板之應用, 化工技術第四卷第五期, 1996.
(18) 賴耿陽, 環氧樹脂應用實務, 復漢出版社, 台灣 1999.
(19) 賴家聲, 環氧樹脂與硬化劑(上), 復漢出版社, 台灣 1999.
(20) S. V. Levchik, G. Camino, M. P. Luda, L. Costa, G. Mullerm, and B. Costes, Polym. Deg. Stab., 1998. 60, 169.
(21) 黃滄閔, 碩士論文 國立成功大學 2001.
(22) T. Mitani, H. Shiraish, K. Honda, G. E. Owen. 44th Annual conference compositie institute, SP1, session RF(Reb3-9,1989).
(23) W. Li, L. J. Lee, Polymer 39, 5677 (1998).
(24) M. Kinkelaar, S. Muzumdar, L. J. Lee, Polym. Eng. Sci. 35, 823 (1995).
(25) R. R. Hill, S. Muzumdar, L. J. Lee, Polym. Eng. Sci. 35, 852 (1995).
(26) E.Martuscelli,P.Musto,G.Scarinzi,andE.Rertotti,J.Polm.Sci.,PartB:Polym.Phys.,31,619(1993)
(27) S.B. Pandit, and V.M. Nadkarni, Ind. Eng. Chem.Res.,33,2778(1994)
(28) W. Crc for Polymers Pty. Ltd., WO97,43339(Nov 20,1997)
(29) J.Chiefari,U.K.Chong,F.Ercole,J.Krstina,K,J.Jeffery,T.P.TLe,R.T.A. Mayadunne, G.F.Meijs, C.L. Moad. G. Moad, E. Rizzardo, and S. H.Thong, Macromolecule, 31, 5559(1998).
(30) G. M. T.P. Le, E. Rizzardo, S.H. Thang, PCT Int.Appl.WO9801478 A1980115 (1998).
(31) J. Guo. X. Liu, Y. Li, G. Xu, and P.ui, Journal of Colloid and Interface Science 326, 138 (2008).
(32) M. H. Stenzel, T. P. Davis, A. G. Fane, J. Mater. Chem. 13, 2090 (2003).
(33) M. H. Stenzel, T. P. Davis, J. Polym. Sci., Part A: Polym. Chem. 40, 4498 (2002)
(34) D. L. Patton and R. C. Advincula, Macromolecules. 39, 8674 (2006)
(35) 彭俊昇, 碩士論文 國立台灣科技大學 2000.
(36) H. R. Allcock, F. W. Lampe., “Contemporary Polymer Chemistry,” 2nd Ed., Prentice Hall, Englewood Cliffs,, New Jersey, 1990,p50.
(37) S.L. Rosen., Ed.,”Fumdamental Priciples of polymeric Materials”, 2nd Ed., Wiley, New York,1993
(38) 張容瑋, 碩士論文 國立台灣科技大學 2008.
(39) M. Szwarc., Nature 178, 1168 (London 1956).
(40) T. Otsu, M. Yoshida, Makromol Chem, Rapid Commun. 3, 127 (1982).
(41) K. Matyjaszewski, J. Xia, Chem. Rev. 101, 2921 (2001).
(42) J.S. Wang, K. Matyjaszewski, J. Am. Chem. Soc. 117, 5614 (1995).
(43) M. Kamigaito, T. Ando, M. Sawamoto, Chem. Rev. 101, 3689 (2001).
(44) D. H. Solomon, E. Rizzardo, P. Cacioli, US Patent 4, 581, 429, (1985).
(45) M. K. Georges, R. P. N. Veregin, P. M. Kazmaier, G. K. Hamer, Macromolecules, 26, 2987 (1993).
(46) R. Francis et al., Macromolecules 86, 8253 (2003).
(47) P. Takolpuckdee, C. A. Mars, S. Perrier, Org. Lett. 7, 3449 (2005).
(48) Y. Tsujii, M. Ejaz, K. Sato, A. Goto, T. Fukuda, Macromolecules 34, 8872 (2001).
(49) R. Narain, S.P. Armes, Macromolecules 36, 4675 (2003).
(50) M.H. Stenzel, T.P. Davis,and A.G. Fance, J Mater Chem,13,2090(2003)
(51) Silica gel and Bonded Phases. , (Raymond P.W. Scott ).
(52) K. Ohno, T. Morinaga, K. Koh, Y. Tsujii, T. Fukuda, Macromolecules 38, 2137 (2005).
(53) W. Stober, A. Fink, and E. Bohn, Journal of colloid and interface science 26, 62 (1968).
(54) 合成二氧化矽的特性與用途 高分子工業 1998.
(55) Y. S. Yang, L. J. Lee, Polymer 29, 1793 (1988).
(56) K. Horie, I. Mita, H. Kambe, J. Polym. Sci. PartA-1: Polym. Chem. 7, 2561(1969).
(57) 江文慶, 碩士論文 國立台灣科技大學 1996.
(58) J.L. Zhu et al., J.Polym. Sci., Part A : Polym.chem.,45,5354 (2007).
(59) 謝宇軒, 碩士論文 國立台灣科技大學 2009.
(60) 林建辰, 碩士論文 國立台灣科技大學 2010.
(61) H. Zheng et al., Microchim Acta 157, 7 (2007).
(62) Y. Zhao and S. Perrier, Macromolecules, 40,9116 (2007)
(63) X.Jiang, W.Tian, C.Zhao, H.Zhang, M.Liu, Talanta 72, 119 (2007).
(64) Y. Zhao, S. Perrier, Macromolecules 39, 8603 (2006).
(65) R. K. Sharma, S. Das, A. Maitra, Journal of Colloid and Interface Science 277,342 (2004).
(66) Se. Perrier, P. Takolpuckdee, and C. A. Mars, Macromolecules,38, 6770 (2005)