含三苯胺結構之高分歧化聚醯胺的合成與性質

Synthesis and Properties of Hyperbranched Polyamides containing Triphenylamine Groups

黃國勛(Guo-Syun Huang)

指導教授 ： 汪昆立

國立臺北科技大學/工程學院/化學工程研究所/碩士(2007年)

摘要

合成4,4’-dintro-4’’-methyltriphenylamine為利用p-toluidine與1-fluoro-4-nitrobenzene進行CsF-芳香親核置換反應含有一甲基二硝基的三苯胺結構，隨後甲基氧化成羧基，更進一步將二硝基以Pd/C-聯胺還原後製得一新型三苯胺結構4-(bis(4-aminophenyl)amino)benzoic acid含有一羧基二胺基的單體。此高分歧化聚醯胺為含有大量的胺基末端基，其與acetyl chloride、benzoyl chloride、4-nitrobenzoyl chloride、3,5-dinitrobenzoyl chloride、phthalic anhydride進行末端基取代反應。
以FT-IR和NMR鑑定其結構；UV及PL光譜分析其光學性質；以TGA和DSC測定其熱性質；以雷射光散射測定高分子分子量。高分歧聚醯胺的DMAc溶液中在340~358nm有UV-vis吸收峰，而433~505nm有PL放射峰。其熱性質玻璃轉移溫度並無看出，在氮氣下的5％重量損失溫度為250~333℃，黏度為0.152~0.159 dL/g。其電化學性質是由循環伏安法所檢測，高分歧化聚醯胺的HOMO為5.29eV。

關鍵字

三苯胺 ； 高分歧化聚醯胺

並列摘要

The triphenylamine-containing monomer, 4,4’-dintro-4’’-methylttriphenylamine were synthesized via the cesium fluoride-mediated N-arylation reactions of p-toluidine with 1-fluoro-4-nitrobenzene, followed by oxidation reaction by potassium permanganate. Further palladium-catalyzed hydrazine reduction led to a new triphenylamine-based AB2 type monomer containing a carboxylic acid and two amino groups, 4-(bis(4-aminophenyl)amino)benzoic acid. The hyperbranched polyamide（HBP）posseses amine-terminated groups. The numerous amino end groups of the hyperbranched polyamide was modified by endcapping with acetyl chloride、benzoyl chloride、4-nitrobenzoyl chloride、3,5-dinitrobenzoyl chloride and phthalic anhydride.
The structures of hyperbranched polymers were confirmed by FT-IR and NMR. The optical properties were analyzed by UV-Vis and PL spectroscopy. The thermal properties were measured by TGA and DSC. The molecular weight of the amino-end hyperbranched polyamide was determined by laser light scattering measurement. The hyperbranched polyamide exhibited UV-Vis absorption band at 340~358 nm and showed PL maxium emission peak at 433~505nm in DMAc solution. The glass-transition temperature was not discernible and 5％ weight loss temperature was 250~333℃ under nitrogen. The inherent viscosity of the polymer were 0.152~0.159 dL/g. The electrochemical properties of the hyperbranched polyamide were investigated by cyclic voltammetry. The HOMO for HBP has been evaluated to be 5.29 eV .

並列關鍵字

Triphenylamine ； Hyperbranched Polyamide

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