Please use this identifier to cite or link to this item: http://hdl.handle.net/11455/3063
標題: 側鏈交聯型聚胺酯在形狀記憶上之應用
Crosslinked Side-chain Polyurethane with Shape-memory Effect
作者: 劉信志
Liu, Hsin-Chih
關鍵字: 聚胺酯;polyurethane;化學交聯;形狀記憶效應;crosslink;shape-memory effect
出版社: 化學工程學系所
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摘要: 
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.
URI: http://hdl.handle.net/11455/3063
其他識別: U0005-3107201214574500
Appears in Collections:化學工程學系所

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