臺灣博碩士論文加值系統

本研究以聚四甲基醚二醇 (Polytetramethylene ether glycol; PTMG) 、六亞甲基二異氰酸酯 (1,6-Hexamethylene diisocyanate; HDI) 及1,4-丁二醇 (1,4-Butanediol; 1,4-BD) 為原料，合成兩種不同硬鏈段含量之熱塑型聚胺基甲酸酯樹脂 (Thermoplastic polyurethane; TPU) ，並將其與四乙基矽氧烷 (Tetraethoxysilane; TEOS) 混合後藉由溶膠-凝膠法 (Sol-gel process) 製備有機-無機混成材料，進一步則利用多元醇液化柳杉取代部分PTMG合成液化木材改質TPU樹脂 (LTPU) ，另於樹脂合成階段添加3-(三乙氧矽基)丙胺 (3-Aminopropyltriethoxysilane; APTES) 製備含矽氧烷分子團之矽氧烷改質TPU樹脂，並探討經不同改質處理之TPU樹脂與TEOS所製作混成材料之性質。由試驗結果得知硬鏈段含量為23.5%之TPU-A-0具有較佳之拉伸性質，而硬鏈段含量為27.5%之TPU-B-0則有較佳之耐溶劑性及熱穩定性；將TPU與TEOS混合製作TPU/矽氧混成材料時，隨TEOS添加量增加，混成材料薄膜具備較高之儲存模數及加熱至600℃之重量保留率。而於TPU樹脂結構中導入多元醇液化柳杉或矽氧烷分子團可提高TPU樹脂薄膜之拉伸強度、儲存模數及熱穩定性，其所製作之矽氧混成材料薄膜亦隨TEOS添加量增加，耐溶劑性及熱穩定性提高。

In this study, two kinds of thermoplastic polyurethane resin (TPU) with different hard segment contents were synthesized from polytetramethylene ether glycol (PTMG) , 1,6-hexamethylene diisocyanate (HDI) and 1,4-butanediol (1,4-BD) . These TPU resins were blended with tetraethoxysilane (TEOS) to prepare organic-inorganic hybrids by sol-gel process. Furthermore, the liquefied wood-modified TPU were prepared by replacing part of PTMG with polyol-liquefied Cryptomeria japonica and the alkoxysilane-modified TPU that containing alkoxysilane groups were prepared by adding 3-aminopropyltriethoxysilane (APTES) during resin synthesis. The properties of hybrids made by blending the modified TPU resins and TEOS were investigated. The results show that TPU-A-0 with 23.5% of hard segment content had better tensile properties and TPU-B-0 that contained 27.5% of hard segment content possess better solvent resistance and thermal stability. When mixed TPU with TEOS to prepare TPU/silica hybrids, increment of TEOS content would lead hybrids with higher storage modulus and more char yield at 600℃. Incorporating liquefied Cryptomeria japonica or alkoxysilane groups into the molecular structure of TPU resins, the tensile strength, storage modulus and thermal stability of TPU films could be advanced. The solvent resistance and thermal stability of hybrids made with modified TPU would raise as the content of TEOS increased.

摘要 i
Summary ii
目錄 iii
圖目次 vi
表目次 xi
第一章　前言 1
第二章　文獻回顧 3
一、TPU樹脂之製備與性質 3
(一) PU樹脂之發展 3
(二) PU樹脂之反應機制 3
(三) TPU樹脂之製備 5
(四) TPU樹脂之兩相性質 6
(五) TPU樹脂之單體原料組成對兩相結構之影響 8
二、生物質材料於PU樹脂製備之應用 10
(一) 多元醇液化條件 10
(二) 多元醇液化產物製備PU樹脂之性質 10
三、PU/矽氧有機-無機混成材料之製備 11
(一) 有機-無機混成材料之製備 11
(二) 溶膠-凝膠反應 13
(三) 溶膠-凝膠法製備TPU/矽氧混成材料之性質 14
第三章　TPU與TPU/矽氧混成材料之製備與性質 17
一、材料與方法 17
(一) 試驗材料 17
(二) 試驗方法 17
二、結果與討論 21
(一) TPU樹脂之性質 21
(二) TEOS預聚物組成條件對TPU/矽氧混成材料薄膜性質之影響 21
(三) TPU/矽氧混成材料薄膜之分子結構分析 23
(四) TPU/矽氧混成材料薄膜之形態分析 24
(五) TPU/矽氧混成材料薄膜之耐水及耐溶劑性 26
(六) TPU/矽氧混成材料薄膜之機械性質 27
(七) TPU/矽氧混成材料薄膜之熱性質 28
第四章　液化木材改質TPU/矽氧混成材料之製備與性質 35
一、材料與方法 35
(一) 試驗材料 35
(二) 試驗方法 36
二、結果與討論 39
(一) 多元醇液化柳杉之性質 39
(二) LTPU樹脂之性質 39
(三) 混成材料薄膜之機械性質 40
(四) 不同LTPU及LTPU/矽氧混成材料薄膜之分子結構分析 42
(五) 不同LTPU及LTPU/矽氧混成材料薄膜之耐水及耐溶劑性 46
(六) 不同LTPU及LTPU/矽氧混成材料薄膜之形態分析 47
(七) 不同LTPU及LTPU/矽氧混成材料薄膜之熱性質 48
第五章　矽氧烷改質TPU/矽氧混成材料之製備與性質 55
一、材料與方法 55
(一) 試驗材料 55
(二) 試驗方法 55
二、結果與討論 58
(一) ATPU及ALTPU樹脂之性質 58
(二) 矽氧烷改質TPU/矽氧混成材料薄膜之機械性質 58
(三) 矽氧烷改質TPU/矽氧混成材料薄膜之分子結構分析 60
(四) 矽氧烷改質TPU/矽氧混成材料薄膜之耐水與耐溶劑性 62
(五) 矽氧烷改質TPU/矽氧混成材料薄膜之形態分析 63
(六) 矽氧烷改質TPU/矽氧混成材料薄膜之熱性質 65
第六章　結論 70
參考文獻 72

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