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標題: 液化纖維素合成水性PU樹脂及其應用於有機-無機混成材料之研究
Waterborne Polyurethane Resins Synthesized from Liquefied Cellulose and Their Application in Organic-Inorganic Hybrid Materials
作者: 林均憲
Chun-Hsien Lin
關鍵字: 塗膜性質;液化纖維素;有機-無機混成材料;溶膠凝膠法;水性聚胺基甲酸酯;Coating properties;Liquefied cellulose;Organic-inorganic hybrids;Sol-gel process;Waterborne polyurethane
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Synthesis and molecular characterization of chitosan based polyurethane elastomers using aromatic diisocyanate. International Journal of Biological Macromolecules 66: 26-32.
有鑑於化石原料日漸枯竭,本研究以液化反應轉化生質物(Biomass)取代部分傳統化學品。第一部分以微晶纖維素(Microcrystalline cellulose;MC)及Whatman 1號濾紙(Whatman No.1 filter paper;WH)為原料,聚乙二醇(Polyethylene glycol;PEG-400)及丙三醇為液化溶劑,硫酸為催化劑進行液化處理,探討液化產物性質之經時變化;第二部分以液化MC與WH取代部分多元醇與異佛爾酮二異氰酸酯(Isophorone diisocyanate;IPDI)以預聚合法合成水性聚胺基甲酸酯(Waterborne polyurethane;WPU)樹脂,並探討合成樹脂及其應用於塗料之性質;第三部分則於水性PU樹脂添加四乙基矽氧烷(Tetraethoxysilane;TEOS),以溶膠凝膠法(Sol-gel process)製備水性PU/矽氧有機-無機混成材料,並探討不同TEOS添加量對混成材薄膜性質之影響。研究結果顯示液化纖維素之殘渣率隨液化時間增加而降低,液化處理90 min後MC和WH之羥價為294和286 mg KOH/g,重量平均分子量為998和1153 g/mol,顯微影像證實液化處理之殘渣尺寸較原料小且分布較窄,XRD分析證明液化產物殘渣維持纖維素Ⅰβ型結晶結構。液化纖維素為原料可成功製備水性PU樹脂,隨液化纖維素取代比例增加,樹脂液之黏度及粒徑增大,其樹脂薄膜之拉伸模數及儲存模數增加,液化纖維素基質者於紫外光波段之穿透率降低,然熱安定性、拉伸強度及破壞伸長率則降低。塗裝性質則顯示各條件樹脂塗膜附著性、耐衝擊性、耐冷及耐熱性佳,添加液化纖維素者顏色偏黃且硬度增加,惟耐磨耗性降低。添加TEOS製備之水性PU/矽氧混成材所形成之SiO2三次元網狀結構會增加材料間之交互作用,並限制水性PU樹脂分子鏈之活動性,提高水性PU/矽氧混成材之熱穩定性,但過量SiO2影響水性PU樹脂分子鏈排列之規則性,降低樹脂薄膜之耐水性、耐溶劑性及機械性質,惟液化纖維素取代比例50%者,添加TEOS之薄膜拉伸強度及拉伸模數顯著增加。

In this study, biomass was liquefied to substitute partial chemicals due to the depletion of fossil fuels. In the first section, microcrystalline cellulose (MC) and Whatman No.1 filter paper (WH) were liquefied using PEG400-glycerol co-solvent with sulfuric acid as a catalyst. The properties of liquefied MC and WH at various liquefaction time intervals were investigated. In the second section, waterborne polyurethane (PU) resins were prepared from polyol that partial polyhydric alcohol was substituted by liquefied cellulose and isophorone diisocyanate (IPDI) by prepolymer mixing process. The properties of waterborne PU resin solution, films and coatings were studied. In the third section, waterborne PU/silica organic-inorganic hybrids were prepared by mixing waterborne PU resins with tetraethoxysilane (TEOS) through sol-gel process. The performance of prepared hybrid films was discussed. The result shows that residual content of liquefied cellulose gradually decreased with prolonged liquefaction time. The hydroxyl values of liquefied MC and WH are 294 and 286 mg KOH/g. The weight average molecular weight of liquefied MC and WH are 998 and 1153 g/mol. Microscopy images show that residues of liquefied cellulose have smaller particle size and narrower distribution than unliquefied ones. X-ray diffraction analysis confirms that residues of liquefied MC and WH maintain cellulose type Ⅰβ crystal structure. Liquefied cellulose can be successfully used in preparing waterborne PU resins. Viscosity and particle size of synthetic resins increases with increased the substitution ratio of liquefied cellulose. Waterborne PU resin films contain liquefied cellulose have lower ultraviolet (UV) transmittance than conventional PU film. With the content of liquefied cellulose increasing, the Young's modulus and storage modulus of PU film increase while the tensile strength, elongation at break and thermal stability decrease. PU resin coatings prepared with various content of liquefied cellulose show good performance of adhesion, impact resistance, cold and heat resistance for wood. With the content of liquefied cellulose increasing, the color of waterborne PU coatings turns yellow and the hardness increase. However, the abrasion resistance of liquefied cellulose-based waterborne PU decreases. Waterborne PU/silica organic-inorganic hybrids can be successfully prepared by mixing waterborne PU resins with TEOS. The network structure of SiO2 increases the interaction between materials and limits the activity of the molecular chains of waterborne PU resin. Thus, the thermal stability of waterborne PU/silica hybrids can be improved. The water resistance, solvent resistance and mechanical properties of PU/silica hybrid films are reduced since excessive SiO2 affect the regular arrangement of the molecular chains of waterborne PU resin. Notably, the tensile strength and Young's modulus of waterborne PU resin films containing 50% liquefied cellulose increase after adding TEOS.
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