臺灣博碩士論文加值系統

本研究利用異佛爾酮二異氰酸酯(Isophorone diisocyanate; IPDI)與經多元醇液化木質素(Liquefied lignin; LL)部分取代之聚四亞甲基醚二醇(Polytetramethylene ether glycol; PTMG)反應製備水性PU樹脂，並比較乙二胺(Ethylenediamine; EDA)和1,4-丁二醇(1,4-Butanediol; 1,4-BD)兩種鏈延長劑所製備水性PU樹脂之性質，進一步則於合成時添加3-(三乙氧矽基)丙胺(3-Aminopropyltriethoxysilane; APTES)製備含矽氧烷基之改質水性PU樹脂，並比較未改質及矽氧烷改質水性PU樹脂混合四乙基矽氧烷(Tetraethoxysilane; TEOS)所製作有機-無機混成薄膜之性能。試驗結果顯示，LL可應用於水性PU樹脂之製備，隨LL取代量增加，水性PU樹脂液之黏度及粒徑增大，添加LL可提高PU樹脂薄膜之拉伸模數及熱安定性，然耐水性、耐溶劑、拉伸強度及拉伸破壞伸長率則降低；含LL之水性PU樹脂對木材及PVC塑膠具備良好膠合性，而塗裝性方面各塗膜抗彎曲性良好，添加LL者硬度提高，惟耐磨耗性及附著性降低。兩種鏈延長劑比較，以EDA為鏈延長劑者，其樹脂薄膜之耐水性、耐溶劑性、拉伸強度及熱抵抗性較佳，以1,4-BD為鏈延長劑者則具備較大之拉伸伸長率。水性PU樹脂添加TEOS形成PU樹脂/矽氧混成薄膜時，在SiO2 含量1%及3%時可提高PU樹脂薄膜之耐水性、耐溶劑性、拉伸強度、韌性及室溫時之儲存模數，但過多的SiO2則降低其耐水性及耐溶劑性。經APTES改質之水性PU樹脂對其PU樹脂/矽氧混成薄膜之耐溶劑性無改善效果，但可提高樹脂薄膜之機械性質及熱安定性，矽氧結構主要限制PU樹脂中軟鏈段之熱活動性，對硬鏈段則無明顯影響。

In this study, waterborne polyurethane (PU) resins were prepared by reacting isophorone diisocyanate (IPDI) with polyol that polyhydric alcohol liquefied lignin (LL) was being substituted for partial polytetramethylene ether glycol (PTMG). In addition, the performance of waterborne PU resins those prepared with ethylenediamine (EDA) and 1,4-butanediol (1,4-BD) as chain extender was compared. Furthermore, the modified waterborne PU resin that containing alkoxysilane groups was prepared by adding 3-aminopropyltriethoxysilane (APTES) during resins synthesis. The performance of organic-inorganic hybrids prepared by mixing waterborne PU resin (unmodified and alkoxysilane-modified) with tetraethoxysilane (TEOS) was also investigated. The result shows that LL can be used in preparing waterborne PU resins. The viscosity and particle size of waterborne PU resins increased with increasing the content of LL. The tensile modulus and thermal stability of PU films can be enhanced by adding LL, but the water- and solvent-resistance, tensile strength and elongation at break are decreased. Waterborne PU resins containing LL have good bonding performance for wood and PVC. In addition, they have well bending resistance and high hardness for coatings. However, the abrasion resistance and adhesion are decreased. Comparison between two chain extenders, films with EDA as chain extender have better water- and solvent-resistance, tensile strength and thermal resistance. On the other hand, films with 1,4-BD have higher tensile elongation. The water resistance, solvent resistance, tensile strength, toughness and room temperature storage modulus of PU/silica hybrid films those made by adding TEOS into waterborne PU resins are increased for which containing 1% and 3% of SiO2. However, the water and solvent resistance decreased when too much of SiO2 existed. Modification waterborne PU resins with APTES is noneffective for improving the solvent resistance of PU silica hybrids films, but can enhance the mechanical properties and thermal stability. The effect of silica structure is mainly restricted the thermal action of soft segment in PU resins, but this effect is unobvious for hard segment.

摘要 i
Summary ii
目錄 iv
表目次 vii
圖目次 xi
第一章　前言 1
第二章　文獻回顧 3
一、PU樹脂簡介 3
二、水性PU樹脂之製備原理及性質 5
三、水性PU樹脂/矽氧有機-無機混成材料 11
四、生物質材料於PU樹脂製備之應用 15
五、木質纖維之液化處理及液化產物在合成樹脂之製備及應用 16
第三章　含液化木質素水性PU樹脂之製備及其性質 17
一、材料與方法 17
(一) 試驗材料 17
(二) 試驗方法 18
二、結果與討論 26
(一) 液化木質素之性質 26
(二) 水性PU樹脂之性質 28
(三) PU樹脂薄膜之性質 34
(四) PU樹脂之膠合及塗裝性質 44
第四章　不同鏈延長劑之水性PU樹脂/矽氧混成材料 46
一、材料與方法 46
(一) 試驗材料 46
(二) 試驗方法 46
二、結果與討論 47
(一) 不同鏈延長劑水性PU樹脂之基本性質 47
(二) 不同鏈延長劑PU樹脂薄膜之FT-IR分析 50
(三) 不同鏈延長劑PU樹脂薄膜之耐水性及耐溶劑性 53
(四) 不同鏈延長劑PU樹脂薄膜之機械性質 53
(五) 不同鏈延長劑PU樹脂薄膜之TGA熱性質 55
(六) 不同鏈延長劑PU樹脂薄膜之DMA熱分析 57
第五章　TEOS/水性PU樹脂製備PU/矽氧混成材料之性質 60
一、材料與方法 60
(一) 試驗材料 60
(二) 試驗方法 60
二、結果與討論 61
(一) PU樹脂/矽氧混成薄膜之顯微結構 61
(二) PU樹脂/矽氧混成薄膜之FT-IR分析 63
(三) PU樹脂/矽氧混成薄膜之耐水性及耐溶劑性 66
(四) PU樹脂/矽氧混成薄膜之機械性質 68
(五) PU樹脂/矽氧混成薄膜之TGA熱性質 71
(六) PU樹脂/矽氧混成薄膜之DMA熱分析 75
第六章　APTES改質水性PU樹脂/矽氧混成材料之製備與性質 80
一、材料與方法 80
(一) 試驗材料 80
(二) 試驗方法 80
二、結果與討論 81
(一) 矽氧烷改質水性PU樹脂之基本性質 81
(二) 矽氧烷改質水性 PU樹脂/矽氧混成薄膜之顯微結構 82
(三) 矽氧烷改質水性PU樹脂/矽氧混成薄膜之FT-IR分析 84
(四) 矽氧烷改質水性PU樹脂/矽氧混成薄膜之耐水性及耐溶劑性 88
(五) 矽氧烷改質水性PU樹脂/矽氧混成薄膜之機械性質 90
(六) 矽氧烷改質水性PU樹脂/矽氧混成薄膜之TGA熱性質 93
(七) 矽氧烷改質水性PU樹脂/矽氧混成薄膜之DMA熱分析 97
第七章　結論 101
參考文獻 103

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