聚对苯撑乙炔类共聚物的设计合成及光谱性能研究
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摘要
有机电致发光材料是有机电致发光器件的物质基础,是影响其器件性能的关键因素。同小分子材料相比,聚合物电致发光材料因其分子量大,分子链长,成膜性好,容易实现大面积显示;同时由于其高的量子效率,工艺简单,热稳定好等特点,在彩色大屏幕平板显示技术领域显示出了广阔的应用前景。
本文在系统研究聚合物电子发光材料及其器件进展的基础上,从改善聚合物的溶解性、热稳定性和改变发光颜色出发,设计合成了主链含有腈基乙烯,咔唑和苯并噻唑及吡唑啉基团的三类新型聚对苯撑乙炔聚合物类电子发光材料。并对它们的热稳定性、聚合物结构以及紫外-可见吸收和荧光光谱特征进行了系统的研究。
研究结果表明,所合成的主链含有腈基乙烯,咔唑和苯并噻唑及吡唑啉基团的烷氧基聚对苯撑乙炔类共聚物具有较好的溶解性和成膜性;DSC和TGA的研究结果表明,共聚物具有较好的热稳定性;光谱性能的研究结果表明,它们均具有其较强的光致发光性质,实现了对聚合物发光颜色的改变。
As the foundation of organic light-emitting diode,organic electroluminescent materials are one of the key factors influencing the device performance.Compared with small molecule organic eletroluminescent materials, polymer materials can be applicated in large-area flat panel displays because of their high molecular weight, long molecular chain and good film-forming ability. Polymer light-emitting materials have attracted much interest all over the world because of their high photoluminescence quantum efficiency, easily fabrication, good thermal stability.
In this dissertation, the development of polymer electroluminescent materials and their applications in polymer Light-emitting diode was systematic studied. Based on improving solubility, thermal stability and altering luminescence color, three types of novel copolymers containing phenylenecyanovinylene, carbazole and benzothiazole and pyrazoline units based on phenylenebisethynylene were designed and synthesized. Their thermal stability, structure and optical properties were also studied. The research results indicated that all of the copolymers have excellent solubility and film-forming property. The DSC and TGA results indicated that all of the copolymers possess satisfactory thermal stabilities. As to their Luminescence properties, all these materials exhibit good fluorescence and emit in different colours.
本文在系统研究聚合物电子发光材料及其器件进展的基础上,从改善聚合物的溶解性、热稳定性和改变发光颜色出发,设计合成了主链含有腈基乙烯,咔唑和苯并噻唑及吡唑啉基团的三类新型聚对苯撑乙炔聚合物类电子发光材料。并对它们的热稳定性、聚合物结构以及紫外-可见吸收和荧光光谱特征进行了系统的研究。
研究结果表明,所合成的主链含有腈基乙烯,咔唑和苯并噻唑及吡唑啉基团的烷氧基聚对苯撑乙炔类共聚物具有较好的溶解性和成膜性;DSC和TGA的研究结果表明,共聚物具有较好的热稳定性;光谱性能的研究结果表明,它们均具有其较强的光致发光性质,实现了对聚合物发光颜色的改变。
As the foundation of organic light-emitting diode,organic electroluminescent materials are one of the key factors influencing the device performance.Compared with small molecule organic eletroluminescent materials, polymer materials can be applicated in large-area flat panel displays because of their high molecular weight, long molecular chain and good film-forming ability. Polymer light-emitting materials have attracted much interest all over the world because of their high photoluminescence quantum efficiency, easily fabrication, good thermal stability.
In this dissertation, the development of polymer electroluminescent materials and their applications in polymer Light-emitting diode was systematic studied. Based on improving solubility, thermal stability and altering luminescence color, three types of novel copolymers containing phenylenecyanovinylene, carbazole and benzothiazole and pyrazoline units based on phenylenebisethynylene were designed and synthesized. Their thermal stability, structure and optical properties were also studied. The research results indicated that all of the copolymers have excellent solubility and film-forming property. The DSC and TGA results indicated that all of the copolymers possess satisfactory thermal stabilities. As to their Luminescence properties, all these materials exhibit good fluorescence and emit in different colours.
引文
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2.N.Holonyak S.F.Bevacqua.Appl.Phys.Lett,1962,1,82.
3.Rainer E et al. Physicochimie/Physical chemistry,2000,4(1):447-470.
4.Leni Akcelrud. Electroluminescent polymers. Prog Polym Sci, 2003, 28:875-962.
5.M,Pope,H.P.Kallmann,P,Magnante,J,Chem.Phys,1963,28,2042
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7.D.F.Williams,M.Schadt,Proc.IEEE,1970,58,476.
8.P.S.Vincett,W.A.Barlow,R.A.Hann,et,al.Thin Solid Films,1982,94,171.
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14.刘青宜,张志峰. 有机电致发光的研究及进展,现代显示,2005,06,30
15.赵洪池,刘贤豪,信息记录材料,2005,06,17
16.钟志有,蒋亚东,王涛,等.现代显示.2005,5:27-31.
17.D.Braun,A.J.Heeger,Appl.Phys.Lett,1991,58,1982.
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27.G.J.Mpallas,K.I.Spilipoulos,J A.Mikroyannidis, Journal of Polymer Science: PartA:polymer Cemistry,2003,41,1091.
28.S,H Wu,C.H Shen,J.H.Chen,R.C.Chao.Journal of Polymer Science: PartA:polymer Cemistry, 2004,42,3954.
29.J H Kim and H Lee,Chem.Mater.2002,14,2270.
30.John A.Mikroyannidis,Ioakim K.Spiliopoulos,et al.Jourunal of Polymer Science:Part A:Polymer Chemistry,2004,42,2112.
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36.Baughman R H,Chance R R.J Appl Phys,1976,47,4295.
37.J A Joke,M W L Bea,K Joop,et al.Adv.Mater,2000,12,908-911.
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41.Y.Yang,Q.Pei,A.J.Heeger,J.Appl.Phys,1996,79,834.
42.佟拉嘎,荣华,等,发光学报,2006,27,526.
43.M.Fukuda,K.Sawaka,K.Yoshino,Journal of Polymer Science,Polymer Chemistry, 1993, 31,2465.
44.M.Fukuda,K.Sawaka, K.Yoshino,Japananses Journal of Applied Physics,1989,28, 1433.
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47.Shu H H, Lin H C. Wu F I. Macromolecules,2003,36,6698.
48.Sonar P, Zhang J Y, Grimsdale A C, et al, Macromolecules,2004,37,709.
49.Kong X X,Abhishek P,Kulkarni,Samson A,Jenekhe.Macromolecules, 2003, 36,8992.
50.Q.Peng,M.G.Xie, Y,Hang, et al,Journal of Polymer Science:Part A: Polymer Chemistry,2004,42,2985.
51.P. Sonar, J. Y. Zhang, A. C. Grimstafe, et al., Macromolecules,2004,37,709.
52.B, Liu. W. L. Yu. W. Huang,Macromolecules, 2000,33,8945.
53.E. Lim, B. J. Jung,H. K. Sim,Macrmolecules,2003,36,4288.
54.R. Q. Yang, R. Y. Tian, J. G.Yan,et al. Macromolecules,2005,38,244.
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56.Pei J,Liu X L,Yu W L,et al.Macromolecules,2002,35:7274-7280.
57.Peng Q, Lu Z Y, Huang Y,et al. Macromolecules,2004,37,260.
58.Chen M X, Perzon E,Robisson N,et al. Synth Met,2004,146:233.
59.Zhatg,Q.T.;TOUR,J.M.J.Am.Chem.Soc.1998,120(22),5355.
60.Dhanabalan,A;Van Dongen,J.L.J.;Van Duren,J.K.J.;Janssen,H.M.;Van Hal,P.A.; Janssen, R.A.J. Macromolecules,2001,34,2495.
61.Egbe,D.A.M.;Tillmann,H.;Birckner,E.;Klemm,E.Macromol.Chem.Phys.2001,202, 2712.
62.Egbe,D.A.M.; Birckner,E.;Klemm,E.J.Polym.Sci.,Part A: Polym. Chem. 2002,40, 2670.
63.Weder,C.;Wrighton,M.S.Macromolecules 1996,29,5157.
64.Hirohata, M. Tada, K. Kawai, T. Synth. Metal.,1997,85,1273.
65.Woo,H,S;Gtaham,S.C;Hallidey,D,A;Bradley,D.D.C;Feiend,R.H,Phys.Rev.,1992,B46, 7379.
66.Christopfel W C,Miller L L.J Org Chem,1986,51:4169-4175.
67.Cervini R,Homlmes A B,Moratti S C,et al.Synthesis of new conjugated thiophene polymers , Synth Met,1996,76:169-171.
68.牛俊峰,杨志祥,等,浙江科技学院学报,2006,18(2):90-93.
69.Xiaowei Zhan;Yanqi Liu;Xia Wu;Shuai Wang;Daoben Zhu. Macromolecules, 2002,35, 2529.
70.Egbe,D.A.M;Tillmann,H;Birckner,E;Klemm,E.Macromol.Chem.Phys.2001,202,2712.
71.牛俊峰,赵子军,李惠,等.化学学报.2005,63:1220-1224.
72.彭强,四川大学博士学位论文,2004,73.
73.李耀华,陈兵,徐寿颐,等,西北民族学院学报(自然科学版),2001,42:1-4.
74.Wang Y,Quick R P.Macromolecules,1995,28:3495-3501.
75.Yang Y,Pei Q,Heeger A J.J Appl Phys,1996,79:934-939.
76.Campbell T W,Mcdonald R N,J Org.Chem.,1959,24:1246-1281.
77.Yang Z,Sokolik I,Karasz F E, et al.J Appl Phys,1993,74:3584-3586.
78.Oberski J,Festag R,Schmidt C,et al.Macromolecules,1995,28:8676-8682.
79.Christ T,Glusen B,Greiner A,et al.Adv Mater,1997,9:48-52
80.李武,牛俊峰,赵子军,等。功能高分子学报,2004,17,479-482.
81.Konig, B,Pelka M,Zieg H, et al.J Am Chen Soc,1999,121(8),1681.
82.Dalton L R,Sapochak L S.J Phys Chem,1993,97(12),2871.
83.Bailey N,The future of organic light-emitting diodes. Information Display,2000(3),12
84.Romero D B,Schaer M, Zuppiroli L,et al. Synth.Met., 1996,80(3):271-277.
85.Z.L.Yan,G.W.Hu,S.K.Wu,Acta.Chim.Sin,1995,53,227.
86.Zhang X H,Wu S K,Gao Z Q,et al.Thin Solid Films,2000,371:40.
87.Yuning Li,Jianfu Ding,Michael Day,Ye Tao,Jianping Lu,Marie Diorio . Chem. Mater, 2004, 16,2165.
88.冼远芳,李东风,吴臣,吉林工学院学报,1996,17,37.
89.Lu Z Y,Zhu W G,Jiang Q,et al.Chin Chem Lett,1999,10:679.
90.张华西,四川大学博士学位论文,2006,66.