【作者】 徐业伟；

【导师】 张林；

【作者基本信息】 西南科技大学 ， 分析化学， 2010， 硕士

【摘要】 有机电致发光（OLED）显示技术因符合未来发展趋势而引起越来越多的关注和重视,因此有机电致发光材料的研究成为该领域的研究热点。苝类化合物,尤其是苝二酰亚胺化合物,因其具有极好的光稳定性、热稳定性、化学稳定性和极高的荧光量子效率等优点而受到广泛关注。然而,因为苝类有机小分子存在诸多缺点,所以研究者倾向于将苝高分子化。本文首先提出将可反应、可聚合的苯并环丁烯基团引入至苝二酰亚胺的bay位（1,6,7,12位）,增加其溶解性的同时,通过热聚合反应使其交联成高分子,使所得聚合物不仅具有良好的发光性能,而且具有良好的成膜特性,以解决小分子因溶解性差导致很难用溶液法成膜,最终使器件制作费用成本升高的问题。为了了解如何增加苝二酰亚胺的溶解性以及增加溶解性后对苝二酰亚胺性能的影响,我们首先对苝四甲酸酐的溴化反应过程进行了探索,同时合成了四种可溶性的苝二酰亚胺:N,N’-二（十二烷基）^-1,7-二溴-3,4,9,10-苝二酰亚胺（d）、N,N’-二（十二烷基）^-1,6,7,12-四溴-3,4,9,10-苝二酰亚胺（e）、N,N’-二（十二烷基）^-1,7-二（叔丁基苯氧基）-3,4,9,10-苝二酰亚胺（f）和N,N’-二（十二烷基）^-1,6,7,12-四（叔丁基苯氧基）-3,4,9,10-苝二酰亚胺（g）。利用1H NMR、FTIR和MS等手段确定了四种产物的结构,还研究了其紫外-可见吸收、荧光、循环伏安和热学等性能。实验结果表明:在酰亚胺的氮位置和bay位置引入基团能显著提高苝酰亚胺的溶解性,同时对其各方面性能也有一定影响。然后,对苯并环丁烯的聚合和成膜性能进行了研究。4-乙烯基苯并环丁烯（VBCB）首先与苯乙烯（St）发生自由基聚合反应,产物再与二乙烯基硅氧烷-双苯并环丁烯（DVSBCB）发生热聚合反应生成预聚体（VBCB-St-DVSBCB）,随后把预聚体溶解到甲苯中进行旋转涂膜,最后进行固化反应。实验发现,苯并环丁烯衍生物在200℃左右四元环容易开环发生聚合反应,同时其成膜性能非常好,并且膜平整度很高,polymer resin薄膜（1）的Ra、P-V和RMS分别为4.473×10^-1、3.475×101和7.801×10^-1 nm,而polymer resin薄膜（2）的Ra、P-V和RMS分别为7.807×10^-1、1.894×101和1.087 nm。最后,结合前两章内容合成了本文的目标产物,两种新型的苯并环丁烯-苝二酰亚胺化合物:N,N’-二（十二烷基）^-1,6,7,12-四（苯并环丁烯基氧基）-3,4,9,10-苝二酰亚胺（h）和N,N’-二（十二烷基）^-1,6,7,12-四（苯并环丁烯基）-3,4,9,10-苝二酰亚胺（i）,并利用各种分析手段确定了产物的结构,还研究了产物的紫外-可见吸收、荧光及其热学等性能。同时对产物h的热聚合和成膜性能做了研究。实验发现,产物h在225℃左右四元环容易开环发生交联反应。生成h预聚体后,其紫外可见吸收、荧光和循环伏安特性相对于产物h变化不大,同时,预聚体h可旋转涂膜,为实现大面积成膜奠定基础。更多还原

【Abstract】 OLED has been attracting increasing attentions and regards for its potential advantages in future display. So OLED materials have been a research hotspot. Perylene derivatives, especially perylene bisimides, have attracted intense investagation due to their high photo stability, chemical stability and thermal stability as well as high fluorescence quantum yield. However, small molecular perylene derivatives have many a shortcomings, so the researchers tend to make perylene derivatives polymerization. Hence, we want to induce benzocyclobutene which can polymerize through heating to the bay position of perylene bisimide to increase the solubility, and polymer perylene derivatives are prepared by thermal polymerization which not only posses luminescence properties, but also have good film forming ability. This process can account for the problem that is difficult to form in the solution which resulted in the cost increasing.In order to research on how to increase the solubility and the influence of performance of perylene bisimides after improving the solubility, The bromination reaction of perylene-3, 4, 9, 10-tetracarboxylic acid bisanhydride was first explored. And four soluble peyrlene bisimides [N,N’-didodecyl-1,7- dibromo-perylene-3,4,9,10-tetracar-boxylic acid diimide （d）, N,N’-didodecyl- 1,6,7,12-tetrabromo-perylene-3,4,9,10-tetracarboxylic acid diimide （e）, N,N’- didodecyl-1,7-di（4-t-butylphenoxy）perylene-3,4,9,10-tetra-carboxylic acid diimide （f） and N,N’-di-dodecyl-1,6,7,12- tetra（4-t-butylphenoxy）-3,4,9,10-tetra- carboxylic acid diimide （g） were synthesized. The structures were characterized by 1H NMR, FTIR and MS, and the UV-vis maximal absorption, fluorescence spectroscopy, electrochemical and thermal properties were investigated. The result indicated that the groups which were introduced into N and bay position can improve the solubility notability and can influence the performance of perylene bisimides.Subsequently, the polymerization and film forming ability of benzocyclobutene were investigated. Radical copolymerization of 4-vinyl-benzocyclobutene with styrene afforded the copolymer （4-vinylbenzocyclobutene-co-styrene） （VBCB-St）. Reaction of VBCB-St and divinyl tetramethyl disiloxane-bisbenzocyclobutene （DVSBCB） gave the oligomer （VBCB-St-DVSBCB）, which was subsequently subjected to the spin-coating and the cure reaction. It is found that benzocyclobutene opens the cyclobutene ring when heated to 200 oC and film forming ability is good, and the polymer resin possessed good film planarization. AFM images of polymer resin （1） shows that Ra, P-V and RMS are separately 4.473×10^-1, 3.475×101 and 7.801×10^-1 nm. Whereas Ra, P-V and RMS of polymer resin （2） are 7.807×10^-1, 1.894×101 and 1.087 nm.Finally, two novel benzocyclobutene-peyrlene derivatives [N,N’-didodecyl^-1,6,7,12-tetra（4-benzocyclobutenyloxy）perylene-3,4,9,10-tetracarboxy-lic acid diimide （h）, N,N’-didodecyl^-1,6,7,12-tetra- （4-benzocyclobutenyl）-3,4,9,10-tetra carboxylic acid diimide （i）] were synthesized. The structures were characterized by 1H NMR, FTIR and MS, and the UV-vis maximal absorption, fluorescence spectroscopy, thermal properties were also investigated. Meanwhile, the polymerization and film forming ability of compound i were investigated. It is found that compound h opens the cyclobutene ring to form polymers when heated to 225 oC, and UV-vis maximal absorption, fluorescence spectroscopy and electrochemical property of compound i change little after becoming oligomer i. At the same time, the film of oligomer h is received through spin-coating technique which provide the condition of achieving the large area film.更多还原