Please use this identifier to cite or link to this item: http://hdl.handle.net/11455/65875
標題: 聚醋酸乙烯樹脂性質改良之研究-架橋反應及無機矽氧化合物混成之應用
Study on the Modifications of Poly(vinyl acetate) Resin-- the Application of Crosslinking and Hybrids with Inorganic Siloxane
作者: 林正勛
Lin, Cheng-Hsun
關鍵字: Polyvinyl alcohol;聚乙烯醇;Polyvinyl acetate;Crosslinked PVAc resin;Tetraethoxysilane;Sol-gel reaction;Bonding strength;聚醋酸乙烯樹脂;架橋型PVAc樹脂;四乙基矽氧烷;溶膠-凝膠反應;膠合強度
出版社: 森林學系所
引用: 參考文獻 1. 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。台北。pp.22-35。 2. 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。 3. 馬振基 (1995) 高分子複合材料上冊。國立編譯館。pp.3、pp.649~674。 4. 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。 5. 劉正字,陳基聰 (1981) 耐水性木工膠合劑之研究,中華林學季刊,14(3):9-20。 6. 劉正字,劉昭吟 (1994) 聚醋酸乙烯乳膠性質改良之研究(第一報)-- 合成條件對聚醋酸乙烯乳膠性質之影響,中興大學實驗林研究報告,16(1):29-40。 7. 劉正字,劉昭吟 (1996) 聚醋酸乙烯乳膠性質改良之研究(Ⅱ)-- 共聚合型聚醋酸乙烯乳膠之合成及其應用,中興大學實驗林研究彙刊,18(2):19-31。 8. 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。 9. 蔡信行 編著 (1978) 聚合物化學。文京圖書公司。台北。pp.269-287。 10. 大北熊一、井上幸彥 (1959) ゴム‧接著劑。森北出版株式會社。 11. 新倉正治 (1971) 接著劑技術入門第10回,Vol. 15, No. 2, pp.30-37。 12. Aelion, R., A. Loebel and F. Eirich (1950) Hydrolysis of ethyl silicate. J. Am. Chem. Soc. 72(12): 5705-5712. 13. 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. 14. Brinker, C. J. (1988) Hydrolysis and condensation of silicates: Effects on structure. J. Non-Cryst. Solids. 100(1-3): 31-50. 15. Brinker, C.F. and G. W. Scherer (1990) Sol-Gel-science. Academic, San Diego. 16. Cai, Y. (1997) Synthesis of melamine-formaldehyde resin modified poly (VAc-MMA) emulsion. China Adhesives 6(2): 43-45. 17. Carrà, S., A. Sliepcevich, A. Canevarolo and S. Carrà (2005) Grafting and adsorption of poly(vinyl) alcohol in vinyl acetate emulsion polymerization. Polymer 46: 1379-1384. 18. Chen, Y. (1996) Researchs of wood adhesives with high strength, water and creep resistance. Nianjie 17(1): 25-27. 19. 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. 20. Comyn, J. (1997) Adhesion Science, The royal socirty of chemistry, pp. 36-39. 21. 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. 22. Craig, D. H. (1989) Effect of hydroxyethyl cellulose molecular weight and hydroxyethyl content on grafting reaction of vinyl monomers during latex manufacture. J. Coatings Technol. 10(779): 49-53. 23. Ghosh, S. (1996) Protective colloids and their sffects on poly(vinyl acetate) emulsion. Pigment & Ink International. pp. 19-21. 24. Hajji, P., L. David, J. F. Gerard, J. P. Pascault and G. Vigier (1999) Synthesis, structure, morphology of polymer-silica hybrid nanocomposities based on hydroxyethyl methacrylate. J. Polym. Sci. B: Polymer physics. 37(22): 3159-3255. 25. Jirgensons, B. and M. E. Straumanis (1962) A Short Textbook of Colloid. Chemistry (2nd reviseden). The Macmillan Co. New York. 26. Kioul, A. and L. Mascia (1994) Compatibility of polyimide-silicate creamers induced by alkoxysilane silian coupling agent. J. Non-Cryst. Solids. 175(2-3): 169-186. 27. Klevn, L. C. (1985) Sol-Gel process of silicate. Ann. Rev. Master. Sci. 15: 227-248. 28. Komarneni, S., R. Roy and D. M. Roy (1983) Evaluation of SrMoO4 in repository simulating tests. Nucl. Tech. 62: 71-74. 29. Lu, G. (1996) Improvement of polyvinyl acetate emulsion. Huagong Shikab 10(6): 17. 30. Liu, C. T. and C. Y. Liu (1998) Effect of the addition of free radical initiators on the water-resistance of heat-setting PVAc emulsion adhesive. Bulletin of the Experimental Forest of National Chung Hsing University 20(2): 65-70. 31. Loy, D. A. and K. J. Shea (1995) Bridged polysilsesquioxanes. Highly porous hybrid organic-inorganic materials. Chem. Rev. 95(5): 1431-1442.31. 32. Magallanes, G. S. (1996) Characterization of poly(vinyl alcohol) during the emulsion polymerization of vinyl acetate using poly(vinyl alcohol) as emulsifier. J. Polymer Sci., Part A 34: 849-862. 33. 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. 34. Menczel, J. D., M. Jaffe and W. E. Bessey (1997) Films. In "Thermal characterization of polymer materials, Vol. 2" Ed. Tari, E. A. Academic Press. Inc. San Digego. pp. 2047-2050. 35. Nakamae, M., K. Yuki, T. Sato and H. Maruyama (1999) Preparation of polymer emulsions using a poly(vinyl alcohol) as protective colloid. Colloid and Surfaces A : Physiochemical and Engineering Aspects 153: 367-372. 36. Novak, B. M. (1993) Hybrid nanocomposite materials-between inorganic glasses and organic polymers. Adv. Mater. 5(6): 422-433. 37. 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. 38. 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. 39. 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. 40. Qiao, L., A. F. Easteal, C. F. Bolt, P. K. Coveny and R. A. Franich (2000) Improvement of the water resistance of poly(vinyl acetate) emulsion wood adhesives. Pigment & Resin Technology 29(3): 152-158. 41. Qiao, L. and A. F. Easteal (2001) Aspects of the performance of PVAc adhesives in wood joints. Pigment & Resin Technology 30(2): 79-87. 42. Qiao, L., P. K. Coveny and A. F. Easteal (2002) Modifications of poly(vinyl alcohol) for use in poly(vinyl acetate) emulsion wood adhesives. Pigment & Resin Technology 31(2): 88-95. 43. Schmidt, H. (1985) New type of non-crystalline solids between inorganic and organic materials. J. Non-Cryst. Solids 73: 681-691. 44. Shaw, D. J. (1966) Introduction to Colloid and Surface Chemistry. pp. 79-84; 210-243. 45. Shi, L. (1996) Preparation of new water resistance PVAc emulsion adhesives. China Adhesives 153(1-3): 367-372. 46. 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. 47. 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. 48. Silveria, K. F., I. V. P. Yoshida and S. P. Nunes (1995) Phase separation in PMMA/silica sol-gel systems. Polym. 36(7): 1425-1434. 49. 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. 50. Sperling, L. H. (1992) Molecular weights and sizes. In. “Introduction to physical polymer science 2nd.” John wiley & Sons co. New York. pp. 68~71. 51. Tai, H., A. Sergienko and M. S. (2001) Organic-inorganic networks in forms from high internal phase emulsion polymerizations. Polym. 42(10): 4473-4482. 52. 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. 53. 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. 54. Wang, J. (1999) Study on improving properties of polyvinyl acetate emulsion. Zhanjie, 20(3): 16-19. 55. Wright, J. D. and N. A. J. M. Sommerdijk (2001) Sol-gel materials : chemistry and applications. Taylor & Francis co. London. pp. 1-52. 56. Yano, S. (1994) Preparation and characterizaton of hydroxypropyl cellulose/silica micro-hybrids. Polymer 35(25):5565-5570. 57. Yano, S., K. Iwata and K. Kurita (1998) Physical properities and structure of organic-inorganic hybrid materials produced by sol-gel process. Materials Science & Engineering-C 6(2-3): 75-90. 58. Ye, Q. (1999) Adhesives. China Materials Management Publishing House. 59. Zhou, H. (1991) Research on the improvement of water resistance of polyvinyl acetate emulsion. Nianjie, 12(4): 11-12.
摘要: 
本研究以不同皂化度及聚合度之聚乙烯醇(Polyvinyl alcohol; PVA)做為保護膠體合成聚醋酸乙烯樹脂(Polyvinyl acetate resin; PVAc),並嘗試在PVAc樹脂中添加過氧化二苯甲醯(Benzoyl peroxide; BPO)及偶氮二異丁基腈(2,2''-Azo-bis-isobutyronitrile; AIBN)作為自由基架橋起始劑,藉由其生成之自由基促使PVAc分子鏈之間產生架橋連結而形成三次元結構;另於PVAc樹脂合成時添加四乙基矽氧烷(Tetraethoxysilane; TEOS),使其於PVAc樹脂合成反應過程中進行溶膠-凝膠(Sol-gel)反應,形成-Si-O-Si-之三次元網狀無機矽氧高分子,並與PVAc之長鏈狀高分子形成PVAc/Silica混成材料,期藉此兩種方式改善PVAc樹脂之耐水性及耐熱性。由研究結果顯示,採用完全皂化型PVA做為保護膠體之PVAc樹脂之薄膜浸水時之膨潤係數皆低於部分皂化型者; DSC熱示差掃描分析顯示PVAc樹脂熱分析過程先出現PVAc側掛乙醯基斷裂之吸熱峰及其隨後立即出現主鏈結構斷裂之吸熱峰;而由膠合試驗顯示PVAc缺乏耐水膠合強度。添加BPO及AIBN為架橋起始劑可使PVAc分子間產生架橋反應而形成較安定之網狀結構,進而增加PVAc樹脂之耐水性及耐熱性。於PVAc樹脂合成時添加TEOS單體,其經由Sol-gel反應形成之無機相網狀結構可有效限制PVAc分子於高濕環境中的分子移動,且使PVAc/Silica混成材料之熱解過程漸趨於緩和,並提高其加熱至700℃時之重量保留率,顯示藉由添加TEOS於PVAc中所形成之無機相網狀結構可增進其耐水性及耐熱性,而PVAc/Silica混成樹脂溶液之常態膠合強度皆可達CNS之11031號標準之要求,並改善PVAc之耐水膠合力。

In this study, polyvinyl alcohol (PVA) with various degrees of saponification and polymerization was used as the protective colloid in the preparation of polyvinyl acetate resin(PVAc). The benzoyl peroxide (BPO) and 2,2''-azo-bis-isobutyronitrile (AIBN) were added to PVAc resin as a free-radical crosslinking initiator to induce the crosslinking reaction among the linear molecular chain and to form the three dimensional structure of PVAc. Furthermore, the tetraethoxysilane (TEOS) was added to the synthesis system at the period of PVAc preparation to form the three dimensional networkwork structure of inorganic polysiloxane by sol-gel reaction, and blended with the linear PVAc polymer to form the PVAc/Silica hybrids. Both of this two ways were used to improve the water and heat resistance of PVAc resin. The results of this research showed that the PVAc prepared with fully saponification PVA as protective colloid had swelling coefficient lower than those with partial saponification PVA. DSC thermogram of PVAc showed two successive endothermic peaks, the frist peak was contributed to the pendant acetyl group breaking and the secondary peak was the main chain breaking of PVAc. The bonding strength of pure PVAc resin lacked for water resistance. Addition of BPO and AIBN into the PVAc as a free-radical initiator could crosslink the PVAc molecular chain and form a stable network structure and advanced the water and heat resistance of PVAc resin. TEOS monomer in the PVAc system could form inorganic network structure by sol-gel reaction and limited the molecular movement of PVAc under high moisture enviroment, and could relax the thermal degradation of PVAc and increased the percent of weight retention after heating to 700℃. This showed that the addition of TEOS into PVAc and formed the network structure of inorganic could increase the water and heat resistance of PVAc. PVAc/silica hybrid resin had the normal bonding strength that fitted the requests of CNS 11031 standard and improved the wet bonding strength of PVAc.
URI: http://hdl.handle.net/11455/65875
Appears in Collections:森林學系

Show full item record
 

Google ScholarTM

Check


Items in DSpace are protected by copyright, with all rights reserved, unless otherwise indicated.