Study On The Synthesis Of New Carbazole And Triarylamine V Type Hole-transport Materials

In this thesis,4-bromo-4’,4"-dimethyl aniline was synthesized by 4-iodotoluene and 4-bromoanilines via Ullmann coupling reaction at the condition of microwave irradiation. CuCl and 1,10-phenanthroline were used catalyst of the reaction and their ratio was 1:1.The optimum reaction conditions was determined by orthogonal experiments.The iodotoluene was 24mmol, n(iodotoluene):n(bromoaniline):n(CuCl)= 2.4:1.0:4.0.The reaction mixture was refluxed for 120 min at the teperature of 105℃in methylbenze when microwave power was 250W. The yield was 77.1%. And then 9-ethyl carbazole and 9-benzyl carbazole were synthesized by carbazole at room temperature. The cetyl trimethyl ammonium bromide could accelerate the reaction rate and shorten the reaction time in the N, N-dimethyl formamide solution.The 3,6 hydrogen atoms of the carbazole rings were more lively because of the 9-instead.And then a series of 3,6-dibromo-9-replace-9H-carbazole groups were synthesized by N-bromosuccinimide (NBS) and 9-substituted carbazoles. The optimum conditions was at the temperature of 35℃, n(9-substituted carbazole):n(DMF):n(NBS)= 10:25:21.New carbazole-based and triarylamine V-shaped hole transport materials named 4,4’-(9-ethyl-9H-carbazole-3,6-diyl)bis(N,N-dip-tolylaniline)、4,4’-(9-benzyl-9H-carbazole-3,6-diyl) bis(N,N-dip-tolylaniline) and 4,4’-(9-phenyl-9H-carbazole-3,6-diyl)bis(N,N-dip-tolylaniline) were synthetized by 4-bromo-4’,4"-dimethyl aniline and 3,6-dibromo-9-replace-9H-carbazole groups. Their yields were 75.1%,77.9% and 72.1%. The optimum conditions were that N, N-dimethyl formamide (DMF) as the solvent and cuprous chloride,1,10-phenanthroline, potassium iodide as the catalyst. The catalyst ratio of n (CuCl):n (1,10-phenanthroline):n (KI)= 1:1:1. The reaction mixture was refluxed for 8h at the temperature of 132℃.The products were identified by means of microscopic melting point apparatus,IR,1HNMR and so on.The structure of synthetic compounds were verify correct.The UV-visible absorption spectroscopy and fluorescence emission spectra of the target products were tested.The UV absorption wavelength range of measured product was 260-360nm and the largest solid fluorescence emission wavelength range was 415-420nm.The glass transition temperature was measured by differential scanning calorimetry (DSC).The target products were stydied by the electrochemical performance analysis. Then the HOMO energy levels and LUMO energy levels were calculated. These compounds have good hole injection and transmission performance. There will be a good potential value as hole transport materials in the future.In this paper, there are several shortcomings in the general Ullmann reaction.The reaction temperature is high.The reaction time is long and the separation is difficult and so on. Through improved version of the Ullmann reaction and under the condition of microwave irradiation that the reaction time is short.The process is easy to control and the yield of product is high.There will be a good application prospect in the future. This is also the innovation point of this paper.