臺灣博碩士論文加值系統

本研究利用4,4’-oxydianiline (4,4’-ODA)為起始物合成三種新型二胺，2,2’-diiodo-4,4’-oxydianiline (DI-ODA 3)、2,8-diaminodibenzofuran (DB-ODA 5)及2,2’-bis[p-(trifluoromethyl)phenyl]-4,4’-oxydianiline(BF-ODA 7)。分別與六種二酸以直接縮合聚合法合成新型的芳香族聚醯胺PA8a~8f、PA9a~9f及PA10a~10f。這些聚醯胺的固有黏度(Inherent viscosity)為 0.27~0.59 dL/g (0.5dL/g, NMP, 30℃)。由這三種二胺分別與4,4’-oxydibenzoic acid (OBA)、4,4’-sulfonyldibenzoic acid (SBA)及2,2-bis(4-carboxyphenyl)hexafluoropropane (6FA)所形成的聚醯胺，在濃度為20mg/mL時，皆可在室溫下溶於一般的有機溶劑，諸如DMAc、DMSO及NMP。其中聚醯胺PA10e及PA10d在室溫下亦可溶於Acetone、THF、DMF、DMAc、DMSO、m-Cresol及NMP，展現出良好的溶解度。這是因為在2,2’位置的巨大取代基三氟甲基苯，使高分子鏈堆疊不易所造成。這些聚醯胺亦展現出良好的熱穩定性，其玻璃轉移溫度(使用DSC測得)皆介於243~354℃之間；當使用相同二酸時，其玻璃轉移溫度為PA9系列＞PA8系列＞PA10系列。這些聚醯胺的5%熱重損失溫度Td5%(使用TGA測得)介於350~533℃之間，且PA9系列因為含有雜環且具平面結構，故熱裂解溫度比PA8及PA10系列都來的高，而PA8系列因為含有較弱的碳-碘鍵，其熱裂解溫度在聚醯胺系列之間為最低。以UV-visible光譜儀對聚醯胺的薄膜(厚度5~10 μm)進行量測穿透度，其截止波長(λcutoff)介於333~381 nm之間，而穿透度80%介於379~578 nm之間，顯示出聚醯胺具有淺色及良好的透光性。這些聚醯胺展現極佳的機械強度，由拉力試驗測得拉伸強度為21~88 MPa，伸長量為7~17 %，彈性模數為0.2~2.9 GPa。

Three aromatic diamines 2,2’-diiodo-4,4’-oxydianiline (DI-ODA 3), 2,8-diamino dibenzofuran (DADBF 5) and 2,2’-[bis(p-trifluoromethyl)phenyl]-4,4’-oxidianiline (BP-ODA 7) were synthesized by using 4,4’-oxydianiline (4,4’-ODA) as a starting material. Novel polyamides PA8a~f, PA9a~f, PA10a~f were prepared by the direct polycondensation of three diamines with various commercially available aromatic dicarboxylic acids. Inherent viscosities of the polyamides were in the range of 0.27-0.89 dL/g in N-methyl-2-pyrrolidinone (NMP) or concentrated sulfuric acid at 30 oC. The introduction of ether linkages and pendant groups (iodine and p-trifluoromethyphenyl) into polyamides led to an enhanced solubility in organic solvents such as N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAc), N,N-dimethylsulfoxide (DMSO) and NMP at room temperature or upon heating. Especially, polyamides 8a, 8b, 10a and 10b containing rigid p-phenylene and m-phenylene structures can be soluble in DMF, DMAc, DMSO, NMP and m-cresol at room temperature. The polyamides could be solution-cast into transparent films from their N,N-dimethylacetamide solution. These films had the UV onset wavelengths in the range of 333-381 nm and wave-lengths at 80% transmission of 379-578 nm, indicating high optical transparency. Wide angle X-ray diffraction patterns indicated that the polymers were essentially amorphous in nature. The glass transition temperature observed for the polyamides were in the range of 243-354 oC. The temperature at 5% weight loss (Td5%), determined by TGA in nitrogen atmosphere, were in the range of 350-533 oC, indicating their good thermal stability. Due to the weak carbon-iodine bond, polyamide 8 containing iodine substituents decomposed at lower temperatures then polyamides 9 and 10. High optical transparency combined with excellent solubility and high thermal stability makes these polyamides potential candidates for soft electronic applications.

摘要 I
Abstract II
誌謝 IV
目錄 V
Figure 索引 VI
Scheme 索引 VII
Table 索引 VIII
第一章緒論 1
1.1聚醯胺的簡介 1
1.2聚醯胺的合成方法 4
1.3聚醯胺的改質方法 11
1.4 研究動機 18
第二章實驗部分 19
2.1實驗藥品 19
2.2實驗儀器 21
2.3單體合成 22
2.4高分子合成 26
2.5高分子薄膜製備 26
第三章結果與討論 27
3.1單體的合成 27
3.2高分子的合成 39
3.3高分子分子量與溶解度 43
3.4高分子熱性質 47
3.5高分子機械特性和光學性質 52
第四章結論 57
參考文獻 58

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