本研究利用4,4’-oxydianiline (ODA)為起始物，經過氧化、控制溴化劑N-bromosuccinamid (NBS)的當量數進行溴化與還原後，得到兩個含溴且具非對稱結構的新型芳香族二胺，2-Bromo-4,4’-oxydianiline (Br-ODA 6)與2,2’,6-tribromo-4,4’-oxydianiline (TrB-ODA 7)。將Br-ODA (6)與TrB-ODA (7)分別與三種不同的二酸酐pyromellitic dianhydride (PMDA)、3,3',4,4'-biphenyl tetracarboxylic dianhydride (BPDA)與2,2'-bis-(3,4-dicarboxyphenyl) hexafluoropropane dianhydride (6FDA)用一步法合成出新型的芳香族聚醯亞胺PI 10與PI 11系列。這些聚醯亞胺的固有黏度(inherent viscosity)約為0.50∼0.96 dL/g (0.5 g/dL, NMP, 30℃)。除了Br-ODA/PMDA之外，其餘的聚醯亞胺在m-cresol中以一步法反應皆可得到均勻的聚醯亞胺溶液，展現了良好的溶解性。而TrB-ODA所合成出的聚醯亞胺其溶解度比對稱型更為優異，即使和結構較剛硬的Pyromellitic dianhydride (PMDA)或3,3',4,4'-biphenyl tetracarboxylic dianhydride (BPDA)反應，所形成的聚醯亞胺仍在常溫下溶於NMP、DMAc與m-cresol中，展現了極佳的溶解特性。這是因為不對稱的構型會造成高分子鏈重覆單元的異構，破壞高分子鏈間的作用和堆疊能力，使溶解度提升。這些聚醯亞胺亦展現出良好的熱穩定性。使用熱機械分析儀(TMA)測得玻璃轉移溫度介於297∼333℃之間，熱膨脹係數27∼56μm/(m℃)。熱裂解溫度(Td 5%)由熱重分析儀(TGA)測得皆高於475℃，展現了此新型聚醯亞胺良好的尺寸安定性和熱穩定性。除此之外，本研究將利用鈴木偶合反應，將Br-ODA與TrB-ODA上的溴基置換成苯基，得到另外兩個含不對稱苯基結構的新型二胺。

Two new asymmetric and aromatic diamines, 2-bromo-4,4’-oxydianiline (Br-ODA 6) and 2,2’,6-tribromo-oxydianiline (TrB-ODA 7), have been synthesized by oxidation, bromination in the presence of different amount of N-Bromosuccinimide (NBS) then reduction of 4,4’-oxydianiline (4,4’-ODA). Based on diamine (6) and (7), a series of asymmetric polyimides (PI 10 and PI 11) were prepared by three different dianhydrides in refluxing m-cresol containing a catalytic amount of isoquinoline, respectively. The resulting polyimides, except Br-ODA/PMDA, are soluble in the m-cresol without precipitated during polymerization. These polyimides, especially PI 11, showed enhanced solubilities compared to those derived from 4,4’-ODA and corresponding dianhydride. The PI 11a derived from the very rigid pyromellitic dianhydride (PMDA) and TrB-ODA (7) can be soluble in THF, DMF, DMAc, DMSO and NMP in ambient temperature. In the 1H-NMR spectrum of the PI 11a, the protons of pyromellitic moiety shows three different chemical shifts are attributed to the fact that there are three different repeating unit isomers. The incorporation of the asymmetric bromide substituents is an effective way to increase the interchain distance and decrease in the intermolecular force and packing ability of resulting polymers. Thus, these polyimides also exhibited good thermal stability. Their glass transition temperatures were ranged from 297 to 333℃ and coefficient of thermal expansion were 27∼56μm/(m℃) measured by thermal mechanical analysis (TMA). The temperature at 5% weight loss (Td 5%), determined by thermal gravimetric analysis (TGA) in nitrogen atmosphere, were in the range of 467 to 529℃. In addition, another two diamines containing asymmetric phenyl groups were synthesized by using Suzuki coupling based on asymmetric bromide diamines. The preliminary results on the properties of polyimides derived from these two phenyl substituted asymmetric diamines were also reported.

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