臺灣博碩士論文加值系統

本論文利用具有反應選擇性的雙官能基單體 (4-isocyanato-4’(3,3-dimethyl-2,4-azetidino)diphenylmethan) (IDD)，以收歛法製備出一系列以金剛烷為末端基團的poly(urea/malonamide)規則樹枝狀分子，探討其應用在形狀記憶聚胺酯的效果。
以IDD和構築單元交替反應，isocyanate和一級胺在低溫下反應成urea鍵結，再以azetidine-2,4-dione和一級胺在高溫下形成malonamide鍵結，可免除催化劑添加、活化、去保護等步驟，逐步得到一系列具有窄分子量分布特性的樹枝狀分子，urea/malonamide的分子設計賦予樹枝狀分子豐富的氫鍵。將規則樹枝狀分子改質成聚胺酯的雙醇鏈延長劑接在側鏈，或單醇封端劑接在主鏈，經由豐富的urea/malonamide鍵結增加硬鏈段氫鍵密度，加強材料性質。
由IR、NMR、Mass、EA分析poly(urea/malonamide)，證實確實製備出樹枝狀分子，並以GPC確認規則樹枝狀分子擁有窄分子量分佈。TGA與DSC分析poly(urea/malonamide)與聚胺酯的熱性質，確認poly(urea/malonamide)的玻璃轉移溫度隨代數而上升，並由DSC了解聚胺酯的相轉變行為。由萬能拉力機、DMA分析聚胺酯，萬能拉力機顯示聚胺酯在室溫下的機械性質，發現結晶與硬鏈段含量皆對聚胺酯的機械性質有影響。DMA觀察聚胺酯在不同溫度下的儲存模數，發現高溫儲存模數會隨著物理交聯密度的增加而提高，低溫則受到材料結晶能力的影響。形狀記憶能力同樣以DMA量測，發現擁有高代數側鏈的聚胺酯具有較穩定氫鍵物理交聯，因此在多次拉伸後仍擁有良好的形狀記憶能力，本實驗以SPU35-G2.5、SPU40-G2.5、SPU45-G2.5的性質最佳，擁有97%以上的高形狀維持率，且經過多次拉伸，形狀回復率維持在94%以上，並在手拉測試中可在瞬間完成形狀回復。

A series of poly(urea/malonamide) dendrons with peripheral adamantyl groups were incoporated into polyurethanes to investigate their shape memory behavior. The dual functional (4-isocyanato-4’(3,3-dimethyl-2,4-azetidino)diphenylmethan) (IDD) was used to synthesize a series of hydrogen bond-rich poly(urea/malonamide) dendrons via convergent route. With high reactivity of isocyanate and reaction selectivity of azetidine-2,4-dione, a sequential method to prepare dendrons without protection-deprotection process was developed under mild condition The dendrons were further introduced into polyurethanes, providing physical crosslinking interactions to polyurethanes.
Well-defined poly(urea/malonamide) dendrons were successfully prepared as evidenced by analyses of IR, NMR, and Mass spectroscopy, and EA. GPC analysis showed that the molecular weights of dendrons in this study are mono-dispersed. Differential scanning calorimeter (DSC) revealed that with the increasing generation of dendritic poly (urea/malonamide), the glass transition temperature rose as a result of increasing hydrogen bonding interactions.
Universal tensile machine (UTM) and dynamic mechanical analysis (DMA) were utilized for evaluating mechanical and shape memory properties of side-chain dendritic polyurethanes (SPUs) and end-capped polyurethanes (EPUs). A series of linear polyurethanes (LPUs) were prepared for comparison. All the EPUs were fragile under room temperature, which were not available for mechanical testing. UTM shows that SPUs are more rigid than LPUs under room temperature due to better crystallinity or stronger physical crosslinking interactions. DMA shows that SPUs exhibited higher storage modulus than did LPU at low temperatures owing to higher crystallinity. This would further enhance shape retention properties. On the other hand, the higher density of physical crosslinks in SPU-G2.5 than those in SPU-G1.5 and LPU would also enhance storage modulus of SPUs-G2.5 at high temperatures. This would improve shape recovery properties. The result of cyclic shape memory test shows that shape memory process of SPUs took less than 3 seconds. Furthermore, SPUs with high soft segment content exhibited excellent shape retention over 97%, and the SPU40-G2.5 sample exhibit shape recovery over 95% even after 3 rounds of cyclic shape memory test. It is concluded that the enhanced physical crosslinking interactions improved shape memory effect in polyurethanes, along with a proper tuning of hard segment content. A series of PUs with excellent shape-memory effect have been successfully developed in this work.

摘要 I
Abstract II
目錄 IV
圖目錄 VII
表目錄 XI
壹、緒論 1
貳、 文獻回顧 3
2.1 形狀記憶材料之簡介 3
2.1.1形狀記憶高分子的原理 6
2.1.2熱感應型(thermo-responsive)形狀記憶高分子 8
2.2聚胺酯樹脂之簡介 11
2.2.1聚胺酯之原料及特性31 12
2.2.2 形狀記憶聚胺酯的設計 18
2.3規則樹枝狀分子(dendrimer)簡介 18
2.3.1 規則樹枝狀分子合成路徑 20
2.3.2規則樹枝狀衍生物 22
2.4 Poly(urea/malonamide)規則樹枝狀分子 23
2.4.1 Azetidine-2,4-dione反應選擇性 23
2.4.2 反應選擇性IDD製備poly(urea/malonamide)規則樹枝狀分子 24
2.4.3 Poly(urea/malonamide)規則樹枝狀分子應用於聚胺酯 25
2.4.4 poly(urea/malonamide)側鏈規則樹枝狀形狀記憶聚胺酯 26
2.5形狀記憶高分子之應用 26
2.6金剛烷補強高分子 30
2.7研究動機 31
参、實驗內容 33
3.1藥品及溶劑 33
3.2實驗儀器 36
3.3實驗流程圖 38
3.4合成步驟 40
3.4.1 IDD之製備 40
3.4.2 末端含金剛烷Poly(urea/malonamide) 規則樹枝狀分子之合成 41
3.4.3 末端含金剛烷poly(urea/malonamide)鏈延長劑之製備 46
3.4.4末端含金剛烷poly(urea/malonamide)封端劑之製備 49
3.4.5 線性聚胺酯 (LPU)之製備 51
3.4.6 含金剛烷之側鏈規則樹枝狀聚胺酯材料 (SPU)之製備 52
3.4.7 含金剛烷之封閉型末端規則樹枝狀聚胺酯材料 (EPU)之製備 53
肆、結果與討論 55
4.1合成具反應選擇性單體IDD 55
4.2 規則樹枝狀poly(urea/malonamide)分子之合成 58
4.2.1 G0.5-Ada之合成與結構鑑定 58
4.2.2 G1.0-Ada之合成與結構鑑定 61
4.2.3 G1.5-Ada之合成與結構鑑定 63
4.2.4 G2.0-Ada合成與結構鑑定 66
4.2.5 G2.5-Ada之合成與結構鑑定 68
4.3 金剛烷系列鏈延長劑之合成與鑑定 71
4.3.1 A-G0.5-Ada之合成與結構鑑定 71
4.3.2 A-G1.5-Ada之合成與結構鑑定 74
4.3.3 A-G2.5-Ada之合成與結構鑑定 76
4.3.4 E-G0.5-Ada之合成與結構鑑定 79
4.3.5 E-G1.5-Ada之合成與結構鑑定 82
4.3.6 E-G2.5-Ada之合成與結構鑑定 85
4.4 規則樹枝狀poly(urea/malonamide) 聚合物之熱性質分析 89
4.4.1 TGA熱重分析 89
4.4.2 DSC微差掃描熱分析 90
4.5 形狀記憶聚胺酯材料之合成與鑑定 92
4.5.1 線性聚胺酯 (LPU)之合成 92
4.5.1 側鏈含金剛烷形狀記憶聚胺酯 (SPU)之合成 93
4.5.2末端含金剛烷形狀記憶聚胺酯 (EPU)之合成 94
4.6聚胺酯之FT-IR光譜之比較 95
4.7聚胺酯之熱性質分析 99
4.7.1 TGA熱重分析 99
4.7.2 DSC微差掃描熱分析 100
4.8聚胺酯之機械性質分析 108
4.9聚胺酯之動態機械性質分析 (DMA) 112
4.10聚胺酯形狀記憶測試 117
4.10.1 LPU系列聚胺酯之形狀記憶測試 118
4.10.1 SPU系列聚胺酯之形狀記憶測試 119
伍、結論 123
陸、參考文獻 124

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