2013-01-222024-05-16https://scholars.lib.ntu.edu.tw/handle/123456789/666721摘要：智慧材料(Intelligent material)為一種能感應外界刺激，且自我判斷及回應的新型功能性材料，近年受到相當廣泛的研究及具備潛在應用價值，從日常生活、資訊科技，甚至於國防工業都可窺見其蹤跡。常見智慧材料為形狀記憶材料(Shape-memory material)，可細分為三類：(一)合金材料(Metal alloy)、(二)陶瓷材料(Ceramic material)、(三)高分子材料(Polymer)。以高分子材料最具備應用及發展的潛力，其優勢為價格便宜、加工性佳、多變化易改質等。聚胺酯(Polyurethane；PU)高分子具有獨特的物性及功能，如高彈性、高伸長率、抗溶劑、抗酸與耐磨損等，軟硬鏈段造成的微相分離及物理交聯，能增加分子間作用力(氫鍵、偶極力以及凡得瓦力)，能有效的提升形狀記憶之效果。文獻中一般藉由：(1)混摻無機材料、(2)導入物理或化學交聯系統、(3)改變軟硬鏈段比例等方式來達成。 本研究利用實驗室開發的反應選擇性單體4-isocyanat-4′(3,3-dimethyl-2,4-dioxo-azetidino) diphenylmethane (IDD)與diethanolamine (DEA)反應成DEA-diol，並導入PU鏈段中形成具有側鏈反應性聚胺酯，分別完成傳統線性、側鏈樹枝狀(物理性交聯)、化學性交聯及有機/無機混成系統四個部分並進行差異比較：(一)線性硬鏈段組成為MDI與線性鏈延長劑diethylene glycol (DEG)，軟鏈段組成為CAPA&reg;2303 (Mn=3000)。(二)物理性交聯則導入具反應選擇性官能基(azetidine-2,4-dione)為基礎的樹枝狀dendrimer，利用dendrimer來補強其硬鏈段之物理性質。(三)化學性交聯則製備具有側鏈反應性官能基的PU，利用diamine形成化學性交聯，進而提升物理性質。(四)有機/無機混成乃透過側鏈azetidine-2,4-dione官能基與3-aminopropyl triethoxysilane(APTES)的改質，透過APTES之sol-gel水解縮合產生Si-O-Si交聯鍵結與無機domain，以達到物性及形狀記憶效果的整體提升。 <br> Abstract: A short-chain diol with reactive azetidine-2,4-dione group was prepared and introduced into polyurethane backbone. The polyurethane with reactive pendent azetidine-2,4-dione groups were further crosslinked by short-chain aliphatic diamine or modified by silicane 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) shows that crystallinity of polyurethane decreased with the increase of crosslinking density. The glass transition temperatures (Tg), tensile strength and storage modulus increased with crosslinking density and hard-segment rigidity. Dynamic mechanical analysis (DMA) and shape recovery tests revealed the relationship between shape memory behaviors and polymeric structures. The high ratio of storage modulus below and above transition temperature accounted for excellent temporary shape fixing at low temperature and faster shape recovery speed at high temperature. By introducing the chemically crosslinked structures, the deformed samples completely recovered their original shape in less than 10 second without any deficiency during shape recovery tests. Shape recovery went up to 99%, indicating the chemical crosslinking effects exhibited higher impact than that of linear and dendritic side-chain polyurethane. Consequently, these novel crosslinked polyurethanes with excellent shape-memory effect will be successfully developed in this project.聚胺酯交聯型形狀記憶有機/無機混成材料polyurethanecrosslinkshape-memory effectorganic/inorganic hybrid