臺灣博碩士論文加值系統

本研究進行不同鏈段長酯/醚混合PU block copolymer之合成與物性探討。本研究先以4,4-Methylenebis(cyclohexyl isocyanate)（H12MDI）為硬鏈節、polytetramethylene glycol (PTMG1000)為軟鏈節及1,4 Butane diol（1,4 BD）合成末端含diol不同鏈段長之醚型軟鏈段；並以H12MDI及Polycaprolactone diol (PCL1000)合成不同鏈段長的酯型鏈段且末端含-NCO基團，接著再將兩者依所定比例進行不同鏈段長酯/醚混合型PU block copolymer之合成。探討酯/醚混合型PU block copolymer之熱性質與加工布織物物性，並與傳統的PU random copolymer作比較。
研究結果發現，就Tg,s方面，random型PU之Tg,s遠低於block型PU。同一醚型軟鏈長度下酯型軟鏈段增大時其Tgs大幅上升在下降。酯/醚軟鏈鏈段比相同時，軟鏈段愈長者其block型PU之Tg,s愈低。在PU之熱重量損失方面，PU之起始分解溫度以酯/醚混合軟鏈block型PU遠高於純PCL酯型PU(All C)與純PTMG醚型PU(All T) ；PU耐熱性均隨C/T莫耳比的提高而增加；在酯/醚軟鏈節莫耳比相同之下，軟鏈節鏈段長愈長耐熱性愈高。而在軟鏈斷裂解溫度下，random型PU遠低於block型PU；隨酯/醚軟鏈節C/T莫耳比的增加，軟鏈裂解溫度愈高；在酯/醚軟鏈節莫耳比相同之下，軟鏈節鏈段長愈長耐熱性愈高。在耐隆塗佈加工布方面，抗張強度以block型PU強度大於random型PU；另外抗張強度隨著酯/醚軟鏈節C/T莫耳比的增加而提高；在相同酯/醚軟鏈莫耳比下，軟鏈節鏈長愈長者抗張強度愈小。最後就透濕度而言，block型PU(B-1T1C)之透濕度小於random型PU (R-1T)；透濕度隨酯/醚軟鏈節C/T莫耳比愈大而下降；在相同酯/醚軟鏈莫耳比下，軟鏈節鏈長愈長者透濕度愈大。

In this study, first, we synthesized the hydroxyl-terminated ether segment and isocyanate-terminated ester segment with different chain length, respecility. The former procedures by using 4,4-methylenebis(cyclohexyl isocyanate, H12MDI), as hard chain , polytetramethylene glycol with molecule weight of 1000 as soft chain and 1,4-Butane diol. The later was synthesized by polycaprolactone with molecule weight of 1000 and H12MDI. The ether-soft segment and ester-soft segment proceed the polymerization of the polyurethane (PU) to from block copolymer of different length ester-ether segment. The thermal properties of regular PU(block PU) and random PU were compared. In addition, using polymer to coating on nylon fabric,and the tensile strength and the water vapor permeability (WVP) were investigated.
The result showed : The glass transition temperature (Tg,s) of block PUs are lower than random PUs, in the same composition. Within block PUs of low ester /ether molar ratio (C/T molar ratio), Tg,s enhance as decrease of ester-soft segment content. The PUs containing long ester/ether segment have low Tg,s . The block and random type of PUs have higher thermal decompose initiation (Tdi) than PU with single PCL or PTMG soft segment. In addition, block PUs have higher Tdi and thermal decompose of soft segment (Tds) than random PUs. The Tdi and Tds rise up as increase of C/T molar ratio. The PU containing long ester /ether segment has higher Tdi and Tds. Within the properties of coated fabric, tensile strength of fabric treated by the block PUs are higher then random PUs. Tensile strength increase following C/T molar ratio. The low tensile strength as showed while PUs contain short soft segment. The WVP of fabric treated by random PUs are higher then block PUs . The WVP decrease as increase of C/T molar ratio and decrease of long soft segment content.

中文摘要 Ⅰ
ABSTRACT Ⅱ
致謝 Ⅲ
目錄 Ⅳ
圖表索引 Ⅴ
一、 前言 1
1-1 序言 1
1-2 過去相關研究 3
1-2-1 軟鏈種類對物性影響之相關研究 3
1-2-2 酯/醚掺混軟鏈節種類與物性之相關研究 8
1-3 本研究之目的 12
二、 實驗方法 13
2-1 實驗材料 13
2-2 實驗設備及儀器 14
2-3 酯/醚混合軟鏈PU block copolymer之合成 17
2-3-1 酯/醚混合軟鏈段PU block copolymer之合成 17
2-3-2 酯/醚混合型PU random copolymer之合成 18
2-4 合成PU之構造與熱性質分析 21
2-4-1 NCO(%)末端基含量滴定 21
2-4-2 FT-IR光譜 22
2-4-3 掃描式微差熱分析測試 22
2-4-4 熱重量損失分析儀 22
2-5 PU薄膜製備與織物塗佈 23
2-6 耐隆加工織物物性測試 24
2-6-1 耐隆加工織物之抗張強度 24
2-6-2 耐隆加工織物之透濕度測試 24
三、 結果與討論 25
3-1 酯/醚混合軟鏈型PU block copolymer之合成與鑑定 25
3-1-1 軟鏈段各聚合時其合成反應過程中之NCO殘留率分析 25
3-1-2 合成PU之FT-IR分析 48
3-2 合成PU之熱性質 40
3-2-1 PU之DSC分析 40
3-2-2 PU之TGA分析 49
3-3 合成PU耐隆塗佈加工織物之抗張強度 61
3-4 合成PU耐隆塗佈加工織物之透濕性 69
四、 結論 78
參考文獻 80
作者簡介 86

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