新型全芳香族側鏈含二苯胺基團聚脲之合成、熱性質、光物理性質、電化學性質及電致變色性質之研究

Novel Aromatic Poly(aryl urea)s Bearing Pendent Diphenylamine Group: Synthesis, Thermal, Photophysical, Electrochemical, and Electrochromic Characteristics

江明哲(Ming-Che Chiang)

指導教授 ： 賴榮豊

國立暨南國際大學/科技學院/應用化學系/碩士(2009年)

https://doi.org/10.6837/NCNU.2009.00191

摘要

我們合成了兩新型骨架中含N,N,N’,N’-tetraphenyl-phenylenediamine (TPPA)之聚脲。N,N’-bis(4-aminophenyl)-N,N’-bis(4-methoxyphenyl)benzene-1,4-diamin由N,N’-bis(4-methoxyphenyl)benzene-1,4-diamine (1)與4-nitroaniline，CsF做催化劑的環境下進行反應而得到N,N’-bis(4-methoxyphenyl)-N,N’-bis(4-nitrophenyl)benzene-1,4-diamine，再將硝基還原成二胺分子，兩新型全芳香族聚脲PTPAMDI及PTPAPDI由二胺與methylenedi-p-phenyl diisocyanate (MDI) 或p-phenylene diisocyanate (PDI)經由低溫溶液加成聚合反應而製得。合成出之聚脲其黏度介於0.34~0.56 dL/g之間，重量平均分子量與數目平均分子量經由凝膠層析滲透儀(gel permeation chromatography; GPC)測得分別介於25,000~50,000之間。
所得之聚脲皆為非晶形之聚合物，可溶於一般有機溶劑例如：N,N-dimethylacetamide (DMAc)、N,N-dimethylformaide (DMF)、chloroform (CHCl3)且接展現良好的熱穩定性(裂解溫度介於340-360 oC)，以及高玻璃轉換溫度(glass-transition temperatures, Tgs; 139-138 oC)，PTPAMDI之量子效率為4.2 %，而此二系列之HOMO與LUMO可由循環伏安儀測得分別是4.73-4.78 eV對應至HOMO及1.53-1.57 eV對應至LUMO。而PTPAMDI之電洞、電子傳導特性在0.00~1.40 V電壓下展現出由無色中性態轉變為綠、藍色之氧化態。

關鍵字

聚脲三苯胺 ； 電致變色

並列摘要

We prepared two novel polyureas containing N,N,N’,N’-tetraphenyl-phenylenediamine (TPPA) in the backbone. N,N’-bis(4-aminophenyl)-N,N’-bis(4-methoxyphenyl)benzene-1,4-diamine was synthesized in two steps starting from N,N’-bis(4-methoxyphenyl)benzene-1,4-diamine, reaction with 4-nitroaniline, catalyzed by CsF, leads to N,N’-bis(4-methoxyphenyl)-N,N’-bis(4-nitrophenyl)benzene-1,4-diamine and reduced the nitro group to the diamine. Then, two novel polyureas (PTPAMDI and PTPAPDI) were prepared from low-temperature solution polyaddition polymerization with methylenedi-p-phenyl diisocyanate (MDI) or p-phenylene diisocyanate (PDI). These polyureas had inherent viscosities of 0.34-0.56 dL/g that corresponded to weight-average and number-average molecular weights (by gel permeation chromatography (GPC)) of 25,000-50,000.
Two polymers are amorphous and readily soluble in various organic solvents such as N,N-dimethylacetamide (DMAc), N,N-dimethylformamide (DMF), and chloroform (CHCl3). They exhibited good thermal stability (decomposition temperature around 340 and 360 °C) and relatively high glass transition temperature (139 and 183 °C). The fluorescence quantum efficiency of PTPAMDI with blue light was 4.2 %. The highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) energy levels of poly(aryl-urea)s can be determined from cyclic voltammograms as 4.73-4.78 and 1.53-1.57 eV, respectively. The hole-transporting, electron-transporting properties of PTPAMDI exhibited good electrochromic characteristics between 0.00 to 1.40 V with a color change from the original colorless neutral form to green and blue oxidized forms.

並列關鍵字

polyurea ； triphenylamine ； electrochromic

參考文獻

1. Platt, J. R. J. Chem. Phys. 1961, 34, 862-863.

2. Rosseinsky, D. R.; Mortimer, R. J. Adv. Mater. 2001, 13, 783-793.

3. (a) Granqvist, C. G.; Azens, A.; Isidorsson, J.; Kharrazi, M.; Cullman, L.; Lindstroem, T.; Niklasson, G. A.; Ribbing, C. G.; Roennow, D.; Stromme Mattsson, M.; Veszelei, M. J. Non-Cryst. Solids 1997, 218, 273-279. (b) Byker, H. J. Gentex Corporation, U.S. Patent No. 4902108. (c) Mortimer, R. G. Chem. Soc. ReV. 1997, 26, 147-156.

4. (a) Monk, P. M. S. J. Electroanal. Chem. 1997, 432, 175-179. (b) Bange, K. Sol. Energy Mater. Sol. Cells 1999, 58, 1-131.

5. (a) Granqvist, C. G.; Azens, A.; Hjelm, A.; Kullman, L.; Niklasson, G. A.; Ribbing, C. G.; Roennow, D.; Stromme Mattsson, M.; Veszelei, M.; Vaivars, G. Sol. Energy 1998, 63, 199-216. (b) Rauh, R. D. Electrochim. Acta 1999, 44, 3165-3176. (c) Tracy, C. E.; Zhang, J. G.; Benson, D. K.; Czanderna, A. W.; Deb, S. K. Electrochim. Acta 1999, 44, 3195-3202. (d) Pennisi, A.; Simone, F.; Barletta, G.; Di Marco, G.; Lanza, M. Electrochim. Acta 1999, 44, 3237-3243.