臺灣博碩士論文加值系統

本實驗以含有碳酸酯官能基的多元醇(聚碳酸酯醚型(PCE-based)及聚碳酸酯型(PCDL)) 與4,4-二異氰酸二苯甲烷(MDI)及1,4-丁二醇透過一步法合成熱塑性聚氨酯(TPU)。
以DSC測試熱塑性聚氨酯的玻璃轉移點(Tg)，發現聚碳酸酯醚基的(Tg)，會因PCE多元醇中CO2含量越高其Tg也隨之提升，當多元醇中CO2含量為30%其Tg為47.8℃，而CO2含量為40%其Tg為55.0℃，而PCDL的Tg則為12.4℃。PCE的5%裂解點為216.1℃，相較PCDL的裂解點為302℃，可知PCE的熱塑性聚氨酯熱穩定性較差。
將熱塑性聚氨酯以溶劑成膜後，進行80℃退火(Annealing)不同時間，可發現PCE隨著退火時間的增加，Tg會由14.6℃上升至59.6℃，這是因PCE的多元醇含有侧支甲基，由於自由體積旋轉障礙大導致Tg提升。另一原因為重複單元中含有碳酸酯基中的三個氧原子帶著六對孤電子對，孤電子對會相互排斥導致構型會受影響。從PCDL中也可發現，因結構中有三個氧原子導致Tg由-3.6℃上升至5.5℃。
將溶劑成膜後的TPU薄膜測試其形狀記憶性質，發現其固定性皆能達97%以上，且回復性皆在第3輪能達到91%以上，因此PCE的薄膜可應用於高溫(50-60℃)微形狀記憶膜材，而PCDL可應用於低溫(20℃)微形狀記憶膜材中，期許在未來能與織物結合成為新的複材。

This work is use poly carbonate-ether based polyol (PCE-based) and poly carbonate-based polyol(PCDL) with 4,4-Methylene diphenyl diisocyanate (MDI) and 1,4-Butane diol to synthesis thermoplastic polyurethane (TPU) by one-step method.
Use DSC to test thermoplastic polyurethane's glass transition temperature (Tg), and
We Observe when CO2 ratio increase in the poly carbonate-ether based polyol and Tg will increase too, when CO2 ratio is 30 % , Tg is 47.8 ℃ and CO2 ratio is 40 %, Tg is 55.0 ℃ and PCDL's Tg is 12.4 ℃
Td,5% of PCE-based TPU is 216.1 ℃, compare with Td,5% PCDL-TPU is 302 ℃. It is known that the thermoplastic polyurethane of PCE has poor thermal stability.
After the thermoplastic polyurethane to from film by solvent casting and annealing the film at 80 ℃ with different time, it's observe that PCE that the Tg of PCE increased from 14.6 °C to 59.6 °C with increasing annealing time. because the PCE-Polyol has side methyl group,result in free volume rotation obstacle is high, so the Tg will increase. Another factor is the PCE-polyol include three oxygen atoms that bring six long pairs, and the lone pairs will mutually repel each other and the configuration will be affected. It can be observe from PCDL that bring three oxygen atoms in the structure which will result in Tg increased from -3.6 °C to 5.5 °C.
After the thermoplastic polyurethane to from film by solvent casting,and tset shape memory property.It’s fixing ratio is over 97 %,at third round the recovery ratio will over 91 %. Therefore, the film of PCE can be applied to high temperature (50-60 °C) shape memory film, and PCDL can be applied to low temperature (20 °C) shape memory film, and hope to utilized in fabric to form a new composite in the future.

摘要 i
Abstract iii
致謝 v
目錄 viii
表目錄 xi
圖目錄 xii
第一章 緒論 1
1.1前言 1
1.2研究動機 2
第二章 文獻回顧 3
2.1 聚氨酯 3
2.1.1 聚氨酯歷史 3
2.2 多元醇 (Polyol) 4
2.3 異氰酸酯 (Isocyanate) 6
2.4 擴鏈劑 (Chain extender) 7
2.5 聚氨酯化學反應 8
2.5.1 一步法聚合 8
2.5.2 二步法聚合 (預聚法) 8
2.5.3 異氰酸酯基團的基礎反應 9
2.5.4 異氰酸酯親核性加成反應 9
2.5.5 OH基與異氰酸酯反應 9
2.6 以二氧化碳開環的多元醇其反應活性 10
2.7 CO2-based水性聚氨酯有抗水解及抗氧化性質 12
2.8 溫感型形狀記憶聚氨酯 15
第三章 實驗 16
3.1實驗材料 16
3.2實驗設備 19
3.2.1 真空烘箱 19
3.2.2 熱風烘箱 19
3.2.3 熱壓機 20
3.3 測試與分析儀器 21
3.3.1 傅立葉轉換紅外線光譜儀(FT-IR) 21
3.3.2 凝膠滲透分析儀(GPC) 21
3.3.3 動態熱機械分析儀(DMA) 22
3.3.4 示差掃描熱分析儀(DSC) 23
3.3.5 熱重量分析儀(TGA) 23
3.3.6 Shore-D硬度計 24
3.3.7 萬能拉伸試驗機 24
3.4 實驗流程 25
3.4.1 形狀記憶熱塑性聚氨酯合成 25
3.4.2 形狀記憶熱塑性聚氨酯檢測項目 26
3.5 實驗方法 27
3.5.1 形狀記憶熱塑性聚氨酯合成配比 27
3.5.2 形狀記憶熱塑性聚氨酯合成 27
3.5.3熱塑性聚氨酯薄膜製備 28
3.6 測試方法 29
3.6.1 傅立葉轉換紅外線光譜分析 29
3.6.2 凝膠透層析分析 29
3.6.3 動態熱機械分析 29
3.6.4 差示掃描熱量分析 29
3.6.5 熱重量分析 29
3.6.6 形狀記憶效果測試 30
3.6.7 硬度測試 31
3.6.8 拉伸測試 31
第四章 結果與討論 32
4.1 傅立葉轉換紅外線光譜分析 32
4.2 凝膠滲透層析分析 35
4.3 差示掃描熱量分析 38
4.4 熱重量分析 40
4.5 硬度測試 43
4.6 拉伸測試 44
4.7 動態熱機械分析 47
4.8 形狀記憶效果測試 53
第五章 結論 58
參考文獻 60

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