Please use this identifier to cite or link to this item: http://hdl.handle.net/11455/3676
標題: 合成AB2型中間體應用於製備分歧狀聚亞醯胺高分子
Synthesis of AB2 Type Intermediate for Use in Preparation of Hyperbranched Polyimide
作者: 施君儒
Shih, Chun-Ju
關鍵字: AB2
AB2
Hyperbranched Polyimide
分歧狀
聚亞醯胺
出版社: 化學工程學系所
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摘要: 本研究以3,4-二甲苯胺及4-氟硝基苯為原料,經一步驟縮合反應得到產率為84 % 之4,4’-二硝基-3”,4”-二甲基三苯胺(1),由(1)經自氧化法後再以氫化法還原硝基,成功地製備出帶有二胺基與一羧基的三官能基之AB2型三苯胺中間體(AB2型PI中間體),自氧化反應與氫化法的產率各為81%及90%。因此,此簡便的合成之途徑首次能大量合成分歧狀聚亞醯胺之重要單體(AB2型PI中間體)。 由製備之AB2型PI中間體以下列三種不同反應條件下進行自身聚縮合的反應: (1)常溫/DBOP-三乙基胺 (2) 100℃/三苯亞磷酸-砒碇 及(3) 200oC,製得三類型性質各異分歧狀聚亞醯胺。所得聚亞醯胺皆具如下相同之優點如: 熱性質上具高穩定性,其TGA在氮氣5 wt %重量損失(Td)測定可高達460 ~ 540℃玻璃轉移溫度(Tg)亦達315℃在溶解度方面,它們在反應條件在(1)和(2)下時皆具極佳之溶解性,不只可溶解於高極性有機溶劑如: NMP、DMSO、DMF,亦可溶於中極性之溶劑如CHCl3、m-cresol。同時發現在反應條件(3)時,它們的熱穩定性質增加,但溶解性也相對降低了。這個趨勢顯示出隨著反應溫度的增加,聚合物的分子量也隨著增加,並且在高溫反應下可能會有些許的交鏈。 此AB2對稱型與前實驗室製作之ABB’不對稱型單體合成之聚亞醯胺做各項性質上的分析和比較時,發現由合成之聚亞醯胺從TGA和DSC數據顯示相對於由ABB’中間體合成之聚亞醯胺,有較好的熱性質表現。有這個結果可能是因為AB2中間體對稱的結構及含有較高芳香環含量的緣故。然而,至目前為止,由於缺乏軔度之故,二者皆難成膜。 我們以常見的合成路徑成功的製備出AB2型和ABB’型分歧狀聚亞醯胺,其製備單體之程序均可採取巳被廣泛應用的工業製程法,有助益於未來擴大生產及應用。
We have synthesized 4,4'-dinitro-3” 4''-dimethyl triphenylamine, (1), in 84% yield in an one-step condensation process between 3,4-dimethyl aniline and 4-fluoro-nitrobenzene. After the auto-oxidation of (1) and the subsequent hydrogenation of the nitro-groups, an AB2 type triphenylamine polyimide (PI) intermediate bearing two amine groups and one acid-anhydride group each on individual phenyl ring, {AB2 PI Intermediate}, was prepared successfully. The yields of the autoxidation and the hydrogenation steps are 81% and 90% respectively. Thus, for the first time, {AB2 PI intermediate} suitable for synthesis of hyper-branch PIs has been accomplished by our short synthetic scheme. We have carried out the self-condensation of the prepared {AB2 PI Intermediate} by the following three different reaction conditions: (1) DBOP-TEA promoted reaction at room temperature, (2) TPP-Pyridine promoted reaction at 100 ℃, and (3) thermolysis of the intermediate directly at 200 ℃. After imidation of amine groups in all self condensation PI products, three hyperbranch PI polymers with slightly different properties were obtained. All of them show excellent thermal stabilities with Tds of between 460 ~ 540 ℃ and Tgs of above 315 ℃. The solubility study on the hyperbranch PI polymers showed that those made from condition (1) and (2) have excellent solubility characteristics in NMP, DMSO, and DMF as well as in less polar solvents such as chloroform and cresol. We have also observed an increased thermal stability and worsen solubility with the PI made from the condition (3). This trend implies that there is an increased molecular built-up and perhaps some low-degree of crosslinkings with the heightened reaction temperature. In further comparison of hyperbrach PIs from different approach (using a ABB' intermediate) made previously in our laboratory, the hyperbranch PI made form AB2 intermediate of this study shows a better thermal stability as indicated in TGA and DSC data than those made from ABB'. This may be due to the hyperbrach PI made from AB2 are more symmetrical structure with higher aromatic content per connecting atoms. However, both types of PIs failed to make good films because of lack of toughness. Since our successful development of this general synthetic scheme for preparing AB2 and ABB' hydperbranch PI intermediates with low-cost materials and straightforward reactions, our research will be of use in future scaling-up of the materials for more application study.
URI: http://hdl.handle.net/11455/3676
其他識別: U0005-1108200819064800
文章連結: http://www.airitilibrary.com/Publication/alDetailedMesh1?DocID=U0005-1108200819064800
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