研究生: |
林瑋翔 Wei-Hsiang Lin |
---|---|
論文名稱: |
含三氟甲基及非共面結構之新型聚甲亞胺的合成與性質探討 Novel Organosoluble Polyazomethines Containing Trifluoromethyl Biphenyl and Non-coplanar Structures: Synthesis, Thermal, Optical, and Electrochemical Properties |
指導教授: |
陳志堅
Jyh-Chien Chen |
口試委員: |
李宗銘
Tzong-ming Lee 王英靖 Ing-Jing Wang 游進陽 Chin-Yang Yu |
學位類別: |
碩士 Master |
系所名稱: |
工程學院 - 材料科學與工程系 Department of Materials Science and Engineering |
論文出版年: | 2011 |
畢業學年度: | 99 |
語文別: | 中文 |
論文頁數: | 59 |
中文關鍵詞: | 三氟甲基 、聚甲亞胺 |
外文關鍵詞: | trifluoromethyl, polyazomethine |
相關次數: | 點閱:147 下載:1 |
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本研究以2-aminobenzotrifluoride和1-bromo-3-nitrobenzene作為起始物,利用Sandmeyer reaction、Ullmann coupling reaction,再進一步還原得到的二醛(6)。以及利用Suzuki coupling reaction後的產物,還原而成的四組二胺(12a~12d)。將二醛單體(6)分別與四組二胺單體(12a~12d),在減壓條件下,於m-cresol中進行溶液聚合,合成新型聚甲亞胺(13a~13d)。這些聚甲亞胺的固有黏度(inherent viscosity)為0.38~0.50 dL/g(0.5 g/dL, NMP, 30℃)。此系列聚甲亞胺在進行溶液聚合後皆可得到均勻的聚甲亞胺溶液,展現良好的溶解度。這些聚甲亞胺在一般常見的有機溶劑當中(如m-cresol、DMF、THF、Chloroform等),展現了良好的溶解度。因為巨大三氟甲基苯的導入,主鏈兩個苯環處於非平面的狀態,高分子鏈無法緊密的堆積,自由體積增大。聚甲亞胺(13a~13d)亦展現出良好的熱穩定性。熱裂解溫度(T5%)由熱重分析儀(TGA)測得皆高於438℃。利用熱示差掃描儀(DSC)測量聚甲亞胺的玻璃轉移溫度(Tg),在350℃的測量範圍皆未觀察到玻璃轉移現象。導入巨大的三氟甲基苯增加了分子主鏈的空間位阻,造成分子鏈柔性降低,亦導致玻璃轉移溫度超過量測範圍。以紫外吸收光譜及螢光放射光譜對此系列聚甲亞胺進行測量(5x10-5 M, THF),並進一步計算其量子效率。聚甲亞胺的吸收波長介於351~358 nm,而量子效率則介在0.3~1.6%。其中,聚甲亞胺(13d) 則是因為放光效率過低,無法計算。根據循環伏安法所測得的CV圖譜,這些聚甲亞胺的起始氧化電位介在1.00~1.10 eV之間,而起始還原電位則是介在-1.45~-1.60 eV之間。掃描過程中,皆顯示為不可逆循環。
Four new aromatic diamines,2,2’-Bis[o-(trifluoromethyl)phenyl]-4,4’-diaminobiphenyl (12a), 2,2’-Bis[m-(trifluoromethyl)phenyl]-4,4’-diaminobiphenyl (12b), 2,2’-Bis[p-(trifluoromethyl)phenyl]-4,4’-diaminobiphenyl (12c), 2,2’-Bis{[3,5-bis(trifluoromethyl)]phenyl}-4,4’-diaminobiphenyl (12d), were synthesized by using 2-Amino-5-bromobenzotrifluoride as a starting material. Novel polyazomethines 13a~13d were prepared from these diamines with dialdehyde (6) via a room-temperature solution polycondensation in m-cresol under reduced pressure. These polyazomethines, containing twist-biphenyl structure and bulky trifluoromethyl substitutents, were highly soluble in common organic solvents such as dimethylformamide (DMF), tetrahydrofuran (THF), Chloroform and m-cresol at room temperature. These polyazomethines had inherent viscosities from 0.38 to 0.50 dLg-1 in NMP at 30 °C. These polyazomethines had the UV cut-off wavelengths in the range of 351-358 nm. Their quantum efficiency were in range of 0.3~1.6%. These polyazomethines had no glass transition temperatures. They exhibited good thermal stability, without any significant weight loss up to 400 ℃. The decomposition temperatures of these polyazomethines at 5% weight loss under nitrogen were in the ranges of 438-460 °C. These polyazomethines were observed irreversible.
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