Crosslinked Side-chain Polyurethane with Shape-memory Effect

本論文藉由MDI及CAPAR2303 (Mn=3000)為主體，導入反應性的小分子雙醇、DEG、樹枝狀分子及交聯化，來製備具有形狀記憶材料之聚胺酯。利用側鏈上具反應性的azetidine-2,4-dione官能基作為交聯點，直接加入交聯劑diamine或接枝3-amino-propyltriethoxysilane (APS) 後經由水解縮合過程產生有機/無機混成材料，以達到物性強化和改善形狀記憶的效果。比較傳統線性、側鏈樹枝狀(物理交聯型)、化學鍵結交聯及有機/無機混成交聯四系統，探討硬鏈段比例、化學鍵結、交聯密度及有機/無機混成等分子間作用力效應。 從WXRD及DSC可發現材料結晶度隨著交聯密度提高而降低，玻璃轉移溫度(Tg)、Tanδ溫度及機械性質則因交聯密度及APS含量的增加而提高。DMA可發現到儲存模數隨導入化學交聯及APS都能有效提升機械性質，而損失模數中亦觀察到材料的交聯點增加，使相變化不容易而導致相變化溫度明顯增大，Tanδ數值之降低顯示材料剛性因導入交聯而增大。在高與低溫的儲存模數比中，較高的比值造成低溫下較好的形狀維持特性，高溫下快速的形狀回復速度及能力。此外，軟硬鏈段相分離情形可藉由AFM來分析其特徵。 在形狀記憶測試方面，隨著物理交聯、化學交聯及有機/無機混成導入，可得到具有優良形狀回復能力的聚胺酯材料，提高硬鏈段比例、交聯密度及無機物混成比例皆能提升形狀記憶效果，其化學交聯回復率最高可達99.5%，且形狀回復能在6秒內完成，而有機/無機混成材料中回復率更能達到99.8%，形狀回復時間縮短在3秒內完成，並且經由3次循環測試後仍可保有99.4%的回復率。因此在本實驗中已成功製備出具優良形狀記憶效應聚胺酯材料。A hydroxyl group-containing [3-(4-(4-(3,3-dimethyl-2,4- dioxoazetidin-1-yl)benzyl)phenyl)-1,1-bis(2-hydroxyethyl)urea] with reactive azetidine-2,4-dione group was prepared and introduced into polyurethane backbone. The polyurethanes with reactive pendent azetidine-2,4-dione groups were further crosslinked by short-chain aliphatic diamine or modified by silane coupling agent (3-aminopropyltriethoxysilane; APS) following by a sol-gel reaction to bring about Si–O–Si crosslinked organic/inorganic hybrid polyurethanes with shape memory function. X-ray diffraction (WXRD) and differential scanning calorimeter (DSC) showed that the crystallinity of polyurethane decreased with the increase of crosslinking density. The glass transition temperatures (Tg), tensile strength and storage modulus increased with increasing crosslinking density and hard-segment rigidity. Dynamic mechanical analysis (DMA) and shape recovery tests revealed the close relationship between shape memory behaviors and polymeric structures. The high ratio of storage moduli below and above transition temperature accounted for excellent temporary shape fixing at low temperatures and faster shape recovery speed at high temperatures. In addition, phase separation was characterized by atomic force microscopy (AFM). By introducing the chemically crosslinked structures, the deformed samples completely recovered to their original shape in less than 6 second without any deficiency during shape recovery tests. Shape recovery went up to 99% during cyclic thermomechanical tensile tests, indicating that the polyurethanes with chemical crosslinking effects exhibited higher impact than did the linear and dendritic side-chain polyurethanes. Consequently, these novel crosslinked polyurethanes with excellent shape-memory effect have been successfully developed in this work.誌謝.. i 中文摘要 ii 英文摘要 iii 圖目錄 vi 表目錄 ix 壹、緒論 1 貳、文獻回顧 2 2.1形狀記憶材料之簡介 2 2.1.1形狀記憶材料的原理 3 2.1.2熱感應型(thermo-responsive)形狀記憶高分子 4 2.2聚胺酯樹脂之簡介 7 2.2.1聚胺酯之原料及特性 8 2.3規則樹枝狀分子(dendrimer)簡介 11 2.3.1 Dendrimer合成路徑 13 2.3.2規則樹枝狀衍生物 14 2.4有機無機混成奈米複合材料 15 2.5形狀記憶高分子之應用 17 2.6研究動機 19 参、實驗內容 20 3.1藥品及溶劑 20 3.2實驗儀器 24 3.3實驗流程圖 27 3.4合成步驟 28 3.4.1 IDD之製備 28 3.4.2反應型單體之合成 30 3.4.3規則樹枝狀聚合物之合成 31 3.4.4規則樹枝狀聚合物鏈延長劑之合成 33 3.4.5線性聚胺酯材料之製備 34 3.4.6側鏈樹枝狀聚胺酯材料之製備 34 3.4.7側鏈交聯型聚胺酯材料之製備 36 3.4.8側鏈交聯型聚胺酯有機/無機混成材料之製備 36 肆、結果與討論 39 4.1具反應選擇性單體IDD之製備 39 4.2 IDD反應選擇性之監控 44 4.3 DEA-diol之合成與鑑定 45 4.4 Polyurethane/malonamide dendrons之合成 47 4.5 [G-1.5]-OH之合成與結構鑑定 55 4.6形狀記憶型有機奈米聚胺酯材料之製備 58 4.7 FT-IR光譜之比較 60 4.8 29Si-NMR光譜比較圖 64 4.9熱性質比較 65 4.10機械性質分析 73 4.11 DMA熱動態分析 78 4.12型態學分析 85 4.13形狀記憶效應測試及分析 90 伍、結論 102 陸、參考文獻 10