Please use this identifier to cite or link to this item: http://hdl.handle.net/11455/65634
標題: 溶膠-凝膠法應用於乙烯系樹脂/聚矽氧烷混成材料之基礎研究及其利用
Fundamental Study on the Vinyl Polymer/Polysiloxane Hybridby Sol-Gel Method and Its Application
作者: 宋憶青
Sung, I-Ching
關鍵字: Organic-inorganic hybrids;有機-無機混成材料;Polyvinyl alcohol;Polyvinyl acetate;Sol-gel reaction;Tetraethoxysilane;聚乙烯醇;聚醋酸乙烯;溶膠-凝膠反應;四乙基矽氧烷
出版社: 森林學系
摘要: 
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.

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。
URI: http://hdl.handle.net/11455/65634
Appears in Collections:森林學系

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