臺灣博碩士論文加值系統

本研究以四乙基矽氧烷（Tetraethoxysilane, TEOS）為無機成分之單體原料，聚乙烯醇（Polyvinyl alcohol, PVA）及聚醋酸乙烯（Polyvinyl acetate, PVAc）等乙烯系樹脂（Vinyl polymer）為有機高分子原料，以鹽酸為催化劑，利用溶膠-凝膠法（Sol-gel method）使TEOS形成三次元網狀之無機矽氧烷高分子結構，並與有機高分子混成製備Vinyl polymer/Silica之有機-無機混成材料（Organic-Inorganic hybrid），探討不同Vinyl polymer種類、Vinyl polymer/TEOS混成比例及催化劑濃度等混成條件對所製備Vinyl polymer/Silica混成材料性質之影響，並進一步探討有機-無機混成材料應用於膠合劑之可行性。由結果得知，在酸性催化劑之反應條件下，有機相與無機相間相容性良好，所製備之Vinyl polymer/Silica混成材料均呈透明狀。由FT-IR及29Si Solid-state NMR分析結果顯示，Vinyl polymer/Silica 混成材料中TEOS於Vinyl polymer有機相中所形成之無機相結構主要以Si-O-Si為主，有機相與無機相間則無共價鍵結形成，而隨TEOS及酸催化劑添加量增加，其無機相Sol-gel反應程度增加。Vinyl polymer/Silica混成材料之耐溶劑性明顯較原PVA及PVAc提升。由應力應變曲線顯示混成材料可提升有機高分子之抗拉強度，且隨TEOS添加量增加其抗拉強度提高，破壞伸長率則下降。由TGA分析結果顯示，混成材料之熱重保留率提高且各階段熱降解溫度向高溫側偏移，顯示無機相的加入使得有機高分子熱降解過程趨於緩和。以完全皂化型PVA製備之PVA/Silica混成材料，其膨潤性低於部分皂化者；以高聚合度PVA 所製備混成材料之抗拉強度大於低聚合度者。以丙酮為溶劑合成之PVAc所製備PVAc/Silica混成材料抗拉性質明顯出現硬而脆之性質，以乙酸乙酯與甲醇為溶劑製備者，其抗拉性質較為軟韌。在膠合性能上，PVA/TEOS溶液為膠合劑者對牛皮紙之膠合力大於紙力，紙張破壞率均達100%。PVAc/TEOS混成溶液為膠合劑者對實木-實木、實木-玻璃之膠合強度均較單獨使用PVAc者為佳，耐水膠合強度獲得提昇，且由被膠材之破壞情形顯示以混成材料膠合者，其對玻璃之親和性優於PVAc者。三種溶劑合成之PVAc所製備PVAc/TEOS混成溶液之膠合強度，其中以乙酸乙酯為溶劑製備者最高。PVAc/TEOS混成溶液可應用於稻殼粉熱壓成型物之製造，其耐溶劑性及耐水性隨TEOS及酸催化劑添加量增加而提高。

In this study, the three-dimensional net structure of inorganic polysiloxane was formed by the sol-gel reaction of tetraethoxysilane (TEOS) and was made with vinyl polymer to form the vinyl polymer/silica hybrids. The purpose of this study was to discuss the properties of vinyl polymer/silica hybrids by kinds of vinyl polymer, various blending ratios and catalyst concentrations. Further, this study was to investigate the organic-inorganic hybrid‘s feasibility to apply the adhesive. The films of vinyl polymer/silica hybrids prepared in this study had good transparency, indicating there had good compatibility between the organic phase and inorganic phase in the hybrids. The solvent resistance of vinyl polymer/silica hybrids was better than pure PVA and PVAc, and the more TEOS content the higher solvent resistance would be. The tensile strength of vinyl polymer/silica hybrids was higher than pure PVA and PVAc, and it would be increased significantly with increasing the TEOS content. By the results of FT-IR and 29Si solid-state NMR, the inorganic bonding was Si-O-Si in the vinyl polymer/silica hybrid which by the sol-gel reaction of TEOS under acid condition and no covalent bonding was formed between organic phase and inorganic phase. By the results of TG and DTG analysis, the percent of weight retention of vinyl polymer/silica hybrids was higher than pure vinyl polymer. With increasing the TEOS content, the weight retention of hybrids would be increased and the thermal degradation would shifted to higher temperature, indicating that the inorganic phase would improve the thermal stability of vinyl polymer. The water resistance of PVA/silica hybrids with PVA containing higher degree of polymerization was higher than that of the lower degree one. The swelling coefficient of PVA/silica hybrids with partially hydrolyzed PVA higher than fully hydrolyzed. The tensile strength of PVA/silica hybrids was higher than pure PVA, and it would be impressionable significantly with the higher degree of polymerization of PVA. The tensile property of PVAc/silica hybrids which prepared in acetone was hard and brittle. The hybrids prepared in methanol ethyl acetate were soft and tough. The adhesive force of Kraft papers bonded with PVA/TEOS solution was higher than the strength of Kraft paper. The bonding strengths of wood-wood and wood-glass substrates which glued with PVAc/TEOS solution were higher than those with PVAc solution. Among the three kinds of solvents, the bonding strength of wood glued with PVAc/TEOS solution prepared in ethyl acetate had the highest one. The solvent and water resistance performance of moldings which combined PVAc/TEOS solution with rice husk powder were obtained, and it would be increased with increasing the TEOS content and acid catalyst content.

目 錄
目錄 ………………………………………………………………………..I
圖目次.…………………………………………………………………… III
表目次.……………………………………………………………………XI
摘要 ………………………………………………………………………1
SUMMARY ………………………………………………………….……3
第一章 前言………………………………………………………….…...5
第二章 文獻回顧....………………………………………………………9
第三章 PVA/silica混成材料製造及性質……………………………...31
一、試驗材料 ………………………………………………………..31
二、試驗方法 ……………………………………………………..…33
（一）PVA水溶液之製備…………………………………………33
（二）TEOS預聚物之製備………………………………………..33
（三）PVA/silica混成材料之製備………………………………..33
（四）PVA/silica混成溶液性質測定...……………………...……35
（五）PVA/silica混成材料薄膜之性質測定…………………..…35
三、結果與討論……………………………………………………………..…39
（一）TEOS預聚物成分對Sol-Gel反應之影響…………….…..39
（二）組成份對PVA/silica混成材料性質之影響………..………43
（三）PVA皂化度及聚合度對PVA/silica混成材料性質之影響.66
第四章 PVAc/silica混成材料製造及性質…………………………….86
一、試驗材料………………………………………………………….86
二、試驗方法………………………………………………..………..88
（一）溶劑型PVAc之合成………………………………………..88
（二）溶劑型PVAc溶液性質測定………………………………..90
（三）TEOS預聚物之製備………………………………………..91
（四）PVAc/silica混成材料之製備………………………………91
（五）PVAc/silica混成溶液性質測定……………………………91
（六）PVAc/silica混成材料性質測定……………………………92
三、結果與討論………………………………………………….……93
（一）溶劑型PVAc之製備………………………………………..93
（二）PVAc/silica組成條件對其混成材料性質之影響………..115
（三）各合成條件PVAc對PVAc/silica混成材料性質之影響..136
第五章 有機-無機混成材料之膠合應用……………………………...149
一、試驗材料………………………………………………………..149
二、試驗方法………………………………………………………..150
（一）膠合劑製備…………………………………………………150
（二）被膠合材前處理……………………………………………150
（三）膠合作業……………………………………………………151
（四）膠合強度測定………………………………………………154
（五）PVAc/silica混成溶液與稻殼粉成型物製作………….….156
三、結果與討論……………………………………………………..158
（一） PVA/TEOS混成溶液之黏度及對紙張之膠合性………..158
（二）PVAc/TEOS混成溶液對木材之膠合性…………………160
（三） PVAc/TEOS混成溶液對玻璃-玻璃、木材-玻璃膠合性...163
（四）PVAc/TEOS混成溶液對木材-鋁板之膠合性 .…………165
（五）PVAc/silica乾燥薄膜對木材之貼面膠合性……………..166
（六）PVAc/TEOS混成溶液應用於成型物之製備及其性質…167
第六章 結論..……………………………………………………….… 171
參考文獻..………………………………………………………………173

林建中 (1998) 高分子材料性質與應用。高立圖書公司。台北。pp.76-172
宋憶青、李文昭、劉正字 (2005) 溶膠-凝膠法製備不同混成比例及催化劑濃度之PVA/Silica混成材料。林產工業 24(2)：
馬振基 (1995) 高分子複合材料。上冊 國立編譯館 p3、pp.649~674。
馬振基、林佳民、陳致源 (2001) 酚醛樹脂／二氧化矽混成防火複合材料之熱劣化性質研究。化工 48(1)：1-12
陳載永、翁瀅植、陳合進、徐俊雄 (2003) 木材-低密度聚乙烯塑膠複合材之耐候性探討。林產工業 22(1)：63-70。
葉世傑、鄭如忠 (2000) 三聚氰胺樹脂與矽氧烷類所形成之有機--無機複合材料。興大工程學刊11(1):37-44
薛敬和編 (1985)黏著劑全書-材料與技術。高立圖書公司 台北 pp.759-783
Seymour, R. B. and C.E. Carraher著 薛敬和譯 (1994) 高分子化學。高立圖書公司 台北
Silverstein著、賀孝雍譯 (1998) 有機化合物之光譜鑑別法。眾光文化事業有限公司。台北。
井本三郎著、廖明隆譯 (1979) 醋酸乙烯系塑膠。台灣文源書局有限公司pp.77-126。
Aelion, R., A. Loebel and F. Eirich (1950) Hydrolysis of ethyl silicate. J. Am. Chem. Soc. 72(12):5705-5712.
Abdul, A.B. and R. A. Pethrick (1982) Ultrasonic studies of aqueous solutions of polyvinyl alcohol. Polymer 23(10):1446-1450
Brinker, C. J., K. D. Keefer, D. W. Schaefer, R. A. Assink, B. D. Kay and C. S. Ashley (1984) Sol-gel transition in simple silicates II. J. Non-Cryst. Solids. 63(1-2)：45-49
Brinker, C. J. (1988) Hydrolysis and condensation of silicates: Effects on structure. J. Non-Cryst. Solids. 100(1-3):31-50.
Brink, C.J. and G.W. Scherer (1990) Sol-Gel science. Academic Press. Boston
Chetri, P. and N. N. Dass (1996) Synthesis of poly(vinyl benzal) from poly(vinyl alcohol) in nonaqueous medium. J. Appl. Polym. Sci. 62(12): 2139-2145.
Chu, L., M.I. Tejedo and M.A. Anderson (1997) Particulate sol-gel route for microporous silica gels. Microporous Material. 8(5-6):207-213
Costa, L., M. Avataneo, P. Bracco and V. Brunella (2002) Char formation in polyvinyl polymers I. polyvinyl acetate polymer. Degradation and Stability. 77:503–510
Chou, K.S. and C.C. Chen (2003) Preparation and characterization of monodispersed silica colloid. Adv. Tech. of Mater. & Mater. Processing. 5(1):31-35
Dislich, H. (1971) Darstellung von mehrkomponentengläsern ohne durchlaufen der schmelzphase. Glastechn. Ber. 44:1
Dal S. M. A., A. C. Antunes, C. Ribeiro, C. P. F. Borges, S. R. M. Antunes, A. J. Zara and S. A. Pianaro (2003) Electric and morphologic properties of SnO2 films prepared by modified sol–gel process. Mater. Lett. 57(28):4378-4381
Ellsworth M. W., B. M. Novak (1991) Mutually interpenetrating inorganic-organic networks. New routes into nonshrinking sol-gel composite materials. J. Am. Chem. Soc. 113(7):2756-2758.
Fyfe, C.A. (1983) Solid state NMR for chemists. C.F.C. Press. Canada.
Fardad, M. A. and F. Horowitz (1995) Effects of H2O on structure of acid-catalyzed SiO2 sol-gel films. J. Non-Cryst. Solid.183:260-267.
Frings, S., H. A. Meinema, C. F. van Nostrum and R. van der Linde (1998) Organic–inorganic hybrid coatings for coil coating application based on polyesters and tetraethoxysilane. Progress in Organic Coatings. 33(2):126-130
Hajji,P., L. David, J.F. Gerard, J.P. Pascault and G. Vigier (1999) Synthesis, structure, and morphology of polymer–silica hybrid nanocomposites based on hydroxyethyl methacrylate. J. Polym. Sci. B: Polymer physics. 37(22):3159-3255
Hung, Z.H. and K. Y. Qiu, (1997) The effects of interactions on the properties of acrylic polymers/silica hybrid materials prepared by the in situ sol-gel process. Polymer. 38(3):521-526
Iler, R.K. (1979) The chemistry of silica from “Sol-Gel science: The physics and chemistry of sol-gel processing”, 1st Academic Press. U.S.A
Jirgensons, B. and M.E. Straumanis (1962) A Short Textbook of Colloid. Chemistry (2nd revisededn). The Macmillan Co. New York
Joly, C., S. Goizet, J.C. Schrotter, J. Sanchez, and M. Escoubes (1997) Sol-gel polyimide-silica composite membrane: gas transport properties. J. Memb. Sci. 130(1-2):63-74
Komarneni, S., R. Roy and D. M. Roy (1983) Evaluation of SrMoO4 in repository simulating tests. Nucl. Tech. 62:71-74
Klein, L.C. (1985) Sol-Gel Processing of Silicate. Ann. Rev. Mater. Sci. 15: 227-248
Kioul, A. and L. Mascia (1994) Compatibility of polyimide-silicate ceramers induced by alkoxysilane silane coupling agents. J. Non-Cryst. Solids. 175(2-3):169-186
Landry, C. J. T. and B. K. Coltrain, (1992) In situ polymerization of tetraethoxysilane in poly(methyl methacrylate):morphology and dynamic mechanical properties. Polym. 33(7):1486-1495.
Landry, C. J. T., B. K. Bradley., J. A. Wesson and N. Z. J. L. Lippert (1992) In situ polymerization of tetraethoxysilane in polymers: chemical nature of the interactions. Polym. 33(7):1496-1506.
Loy, D. A. and K. J. Shea (1995) Bridged polysilsesquioxanes. Highly porous hybrid organic-inorganic materials. Chem. Rev. 95(5):1431-1442
Liu, Y., R., W. Zhang and L. Y. Xi, (1999) New method for making porous SiO2 thin films” Thin Solid Films, 353(1-2):124-128
Mascia, L.,Z. Zhang and S.J. Shaw (1996) Carbon fibre composites based on polyimide/silica creamers:aspects of structure-properties relationship. Composites Part A: Appl. Sci. & Manu. 27(12): 1211-1221
Matthew, D.C. and A.E. Stiegman (1999) Morphology and pore structure of silica xerogels made at low pH. J. Non-Cryst. Solids. 249(1):62-68
Mansaray, K.G. and A.E. Ghaly (1999) Determination of kinetic parameters of rice husks in oxygen using thermogravimetric analysis. Biomass & Bioenergy. 17(1):19-31
Matsuura, Y., K. Matsukawa, R. Kawabata, N.Higashi and M.Niwa (2002) Synthesis of polysilane-acrylamide copolymers by photopolymerization and their application to polysilane-silica hybrid thin films. Polym. 43:1549-1553
Noell, J.L.W., G.L. Wilkes, D.K. Mohauty and J.E. McGrath, (1990) The preparation and characterization of new polyether ketone-tetraethylorthosilicate hybrid glasses by the sol-gel method. J.Appl. Polym. Sci. 40(7-8):1177-1194.
Novak, B. M. (1993) Hybrid nanocomposite materials - between inorganic glasses and organic polymers. Adv. Mater. 5(6): 422-433
Nakane, K., T. Yamashita, K. Iwakura and F. Suzuki (1999) Properties and structure of poly(vinyl alcohol)/silica composites. J. Appl. Polym. Sci. 74(1):133-138.
Oyama, H. T., R. Sprycha, Y. Xie, R. E. Partch and E. Matijevic (1993) Coating of uniform inorganic particles with polymers, I . J. Colloid Interface Sci. 160(2):298~303
Olejniczak, Z., M. Leczka, K. Cholewa-Kowalska, K. Wojtach, M. Rokita and W. Mozgawa (2005) 29Si MAS NMR and FTIR study of inorganic–organic hybrid gels. J. Molecular Structure 744:465-471
Patel, M.A. and P. Prassnna (1987) Effect of thermal and chemical treatment on carbon and silica contents in rice husk. J. Mater. Sci. 20:4387
Piccaluga, G., E. Corradi, G. Ennas and A. Musinu (2000) In sol-gel preparation and characterization of metal-silica and metal oxide-silica nanocomposites. Material Science Foundations 13:4
Pereira, A. P. V., W. L. Vasconcelos and R. L. Oréfice (2000) Novel multicomponent silicate–poly(vinyl alcohol) hybrids with controlled reactivity. J. Non-Crystalline Solids. 273(1-3):180-185
Sarjeant, P. T. and R. Roy (1969) Experimental data on formation of new non- crystalline solid (NCS) phases.Reactivity of Solids. Ed. J.W. Mitchell, R.C. Devries, R.W. Roberts and P. Cannon. John Wiley & Sons, Inc. pp. 725-733.
Schmidt, H. (1985) New type of non-crystalline solids between inorganic and organic materials. J. Non-Cryst. Solids. 73:681-691
Shibayama M., M. Sato, Y. Kimura, H. Fujiwara and S. Nomura (1988) 11B n.m.r. study on the reaction of poly(vinyl alcohol) with boric acid. Polym. 29(2): 336-340
Sperling, L. H. (1992) Molecular weights and sizes. In. “Introduction to physical polymer science 2nd.” John wiley & Sons co. New York. pp.68~71.
Saegusa, T. (1995) Organic-inorganic polymers hybrids. Pure & Appl. Chem. 67(12):1965-1970
Silveira, K.F.,I.V.P. Yoshida and S. P. Nunes (1995) Phase separation in PMMA/silica sol-gel systems. Polym. 36(7):1425-1434
Silva, C.R. and C. Airoldi (1997) Acid and base catalysts in the hybrid silica sol–gel process. J. Colloid and Interface Science 195(2):381~387
Sivalingam, G.,R. Karthik, and G. Madras (2003) Effect of metal oxides on thermal degradation of poly(vinyl acetate) and poly(vinyl chloride) and their blends. Ind. Eng. Chem. Res. 42:3647-3653
Toki, M.,T.Y. Chow, T. Ohnaka, H. Samura and T. Saegusa (1992) Structure of poly(vinylpyrrolidone)-silica hybrid. Polym. Bull. 29(6):653-660
Tai, H., A. Sergienko and M.S. (2001) Organic-inorganic networks in forms from high internal phase emulsion polymerizations. Polym. 42(10):4473~4482
Yano, S. (1994) Preparation and characterizaton of hydroxypropyl cellulose/silica micro-hybrids. Polymer 35(25):5565-5570
Yano, S., K. Iwata and K. Kurita (1998) Physical properties and structure of organic-inorganic hybrid materials produced by sol-gel process. Materials Science & Engineering – C 6(2-3):75-90.
Wang, Y., N. H. Moller and T. Bein (1991) Three-dimensionally confined diluted magnetic semiconductor clusters: Zn−xMnxS . Solid State Communications 77(1):33-38
Wang, B., G. L. Wilkes, J. C. Hedrick, S. C. Liptak and J. E. McGrath (1991) New high-refractive-index organic/inorganic hybrid materials from sol-gel processing. Macromolecules. 24(11):3449-3450.
Wright. J.D.and N.A.J.M. Sommerdijk (2001) Sol-gel materials:chemistry and applications. Taylor & Francis co. London. pp.1-52