具有電子授受基團結構之芳香族高分歧聚醯胺合成與性質研究

Synthesis and Properties of Hyperbranched Aromatic Polyamides Containing Donor and Acceptor Groups

王鼎傑(Dean-Jay Wang)

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(2012年)

https://doi.org/10.6841/NTUT.2012.00069

摘要

利用一甲基二硝基的三苯胺1,3,4-噁二唑結構，將甲基氧化成羧基，更進一步將二硝基以Pd/C-聯胺還原後，合成具有一新型三苯胺1,3,4-噁二唑結構(6)含有一羧基二胺基AB2的單體進行自我縮聚反應形成具有多數末端胺基之官能基。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、pentanoyl chloride、1-(4-methoxyphenyl)ethanone進行末端基取代反應後,有較好的溶解性如DMSO,DMF,NMP,DMAc。
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。高分歧聚醯胺的NMP溶液在264~284nm和372~382nm有UV-vis吸收峰，而434~560nm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344~455℃，黏度為0.09~0.14 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和LUMO值可藉由氧化電位和吸收光譜的起始波長計算而得，分別是-5.34~ -5.2 eV and -2.82~ -2.73 eV。

關鍵字

高分歧化聚醯胺 ； 三苯胺 ； 1,3,4-噁二唑

並列摘要

4-Nitro-N-(4-nitrophenyl)-N-(4-(5-(p-tolyl)-1,3,4-oxadiazol-2-yl)phenyl)aniline were synthesized via the cesium fluoride-mediated N-arylation reactions of 4-(5-(p-tolyl)-1,3,4-oxadiazol-2-yl)aniline 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. The self-polycondensation of the AB2 monomer (6) afforded hyperbranched poly(triphenylamine-1,3,4-oxadiazole amide)s with amino end groups. The numerous amino end groups of the hyperbranched polyamide were modified by endcapping with acetyl chloride, benzoyl chloride, 4-nitrobenzoyl chloride,pentanoyl chloride and 1-(4-methoxyphenyl)ethanone.

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 hyperbranched polyamide exhibited UV-Vis absorption band at 264~284 nm and 372~384nm and showed PL maxium emission peaks at 434~560nm in NMP solution. The glass-transition temperatures were not discernible and 5％ weight loss temperature was 344~455℃ under nitrogen. The inherent viscosity of the polymer were 0.09~0.14 dL/g. The electrochemical properties of the hyperbranched polyamide were investigated by cyclic voltammetry. The energy levels of the HOMO and the LUMO wewe respectively estimated as -5.34~ -5.2 eV and -2.82~ -2.73 eV from the oxidation potential and the onset absorption wavelength of the UV-vis spectra.

並列關鍵字

Hyperbranched ； Polyamide ； Triphenylamine ； 1,3,4-oxadiazole

參考文獻

1 Zhou, Z.-H.; Zhou, P.-L.; Yang, S.-P.; Yu, X.-B.; Yang, L.-Z. Controllable synthesis of hydroxyapatite nanocrystals via a dendrimer-assisted hydrothermal process.Materials Research Bulletin 2007, 42, 1611-1618.

2 Aulenta, F.; Hayes, W.; Rannard, S. Dendrimers: a new class of nanoscopic containers and delivery devices.European Polymer Journal 2003, 39, 1741-1771.

3 Gao, C.; Yan, D. Hyperbranched polymers: from synthesis to applications.Progress in Polymer Science 2004, 29, 183-275.

4 Qin, H.; Mather, P. T.; Baek, J.-B.; Tan, L.-S. Modification of bisphenol-A based bismaleimide resin (BPA-BMI) with an allyl-terminated hyperbranched polyimide (AT-PAEKI).Polymer 2006, 47, 2813-2821.

5 Carlmark, A.; Hawker, C.; Hult, A.; Malkoch, M. New methodologies in the construction of dendritic materials.Chem Soc Rev 2009, 38, 352-362.