Please use this identifier to cite or link to this item: http://hdl.handle.net/11455/3675
標題: 發散法合成聚亞醯胺樹枝狀高分子
Synthesis of Dendritic PI Nanomers via Divergent Scheme
作者: 蔡如伶
Tasi, Ru-Ling
關鍵字: Dendrimers
樹枝狀高分子
Divergent
Oxidation
Hydrogenation
Imidization
發散法
氧化
氫化
亞醯胺化
出版社: 化學工程學系所
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摘要: 本研究使用便宜又易取得的原料合成出獨特ABB''結構的單體(2)當做核心,再重覆進行氫化和亞醯胺反應,合成出第零代、一代和二代的芳香族聚亞醯胺樹枝狀高分子。 我們先利用3,4-二甲基苯酚和1-氯-2,4-二硝基苯酚合成出2,4-二硝基苯-3,4-二甲基苯醚(1)。再以冰醋酸當溶劑,MC觸媒作用下,自動氧化成3-(2,4-二硝基苯氧基)醋酸酐(2)。實驗中,我們發現當溶劑濃度在9.09%;醋酸鈷/醋酸錳/溴化鈉重量百分比比例在0.65/0.65/0.50及反應溫度在140℃時,(2)產率可以提高至84%-87%。 合成樹枝狀高分子時,先將產物(2)先和苯胺反應後,再進行亞醯胺化反應和氫化反應成為Di-amine-D0(4)和第零代聚亞醯胺樹枝狀高分子;(4)和二莫耳的(2)再進行亞醯胺化反應和氫化反應,成為tetra-amine-D1和第一代聚亞醯胺樹枝狀高分子;重覆進行亞醯胺化反應和氫化反應得到Octa-amine-D2和第二代聚亞醯胺樹枝狀高分子。 實驗中,我們發現氫化多硝基樹枝狀高分子時,1,4-環氧己烷是非常好的氫化溶劑。1,4-環氧己烷對於多硝基樹枝狀高分子的高溶解度,使得在氫化的過程中,具有不需要在高溫下就可以完成氫化反應,而且不會有副產物產生的優點。 第零代、一代和二代的聚亞醯胺樹枝狀高分子,主要特徵是在末端具有3個、5個和9個亞醯胺。熔點範圍在250℃-290℃而且可以快速溶解於一些有機溶劑,如NMP、THF或CHCl3等。這些聚亞醯胺樹枝狀高分子之熱性質及應用仍在繼續之中。
In this research, we developed a divergent scheme of synthesizing up to second generations of polyimide dendrimers (PI Dendrimers) based on one common ABB' Intermediate (2) as core through repetitive reactions of hydrogenation and imidization using low-cost reagents. The core of our overall scheme relied upon the synthesis of 3-(2,4-dinitrophenoxy) phthalic anhydride (2) .(2) was obtained by the autoxidation of 2,4-dinitrophenyl-3,4-dimethyl phenyl ether (1), which was readily accessible from 3,4-dimethyl phenol and 1-Chloro- 2,4-dinitrophenol by a base-initiated replacement reaction. The yield of autoxidation of (2) has been enhanced to 84~87% yield in this study by carefully adjusting cobalt acetate/manganes acetate/sodium bormide catalysts ratio in acetic acid. It was found that the optimal condition is to carry out the autoxidation at 140 ℃ with the concentration ration between Co(OAc)2/ Mn(OAc)2 /NaBr of 0.65:0.65:0.50 (wt%) in 9.09 % weight concentration. Imidization (2) of was carried out with aniline in the first step followed by hydrogenation to form the tri-imide-D0 bearing di-amine-D0 can then go through the same sequence of di-imidization with two moles of (2) and then hydrogenation of the tetra-nitro-D1, and this resulted in Penta-imide bearing tetra-amine-D1 (7). Finally, (7) went through the same sequences of imidization and hydrogenation to form the nonyl-imide-D2 bearing octa-amine-D2. Although this straight forward divergent synthesis could go on repeatedly in theory to form high PI dendrimers, we found that the hydrogenation of nitro-groups became sluggish in ethyl acetate solution as the generations of PI dendrimers grew. It was found that 1,4-dioxane on particularly a good solvent to use in hydrogenation of high generations of PI polynitro-dendrimers because of its solvating power, which allowed the hydrogenation to be done at low-temperature without other complications. All PI dendrimers synthesized show their melting points between 250℃-290℃and could be dissolved readily in solvents such as NMP, THF and CHCl3.The thermal characteristics and potential utilities of the dendrimers are still being investigate.
URI: http://hdl.handle.net/11455/3675
其他識別: U0005-1108200817293100
文章連結: http://www.airitilibrary.com/Publication/alDetailedMesh1?DocID=U0005-1108200817293100
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