CN100439470C - 一类显蓝光的聚合物材料及制备方法 - Google Patents
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Abstract
一类可显蓝光的聚合物材料及制备方法,将两端含芴醇结构的单体a与三苯胺类化合物TPD或TPA聚合反应,得到在紫外光照射下可显蓝光的聚合物材料,其玻璃化转变温度100℃-240℃,5%热分解温度430℃-440℃,固体膜的光致发光效率40%-50%。
Description
(一)技术领域
本发明属于有机、高分子化学合成领域。利用芳环的亲电取代反应,发明了一种新的缩聚方法,用来制备具有新颖空间结构的蓝光材料。
(二)背景技术
烷基取代的聚芴是一类典型的蓝光材料,其突出优点是蓝光效率高、热稳定性好、易于溶解,适合喷涂作业制备大面积器件,然而研究发现,传统的聚芴材料热稳定性不高,特别是在器件使用时发热,聚芴材料分子链发生聚集,导致分子链(18)ππ叠加而发出黄光,致使蓝光不纯,同时发光效率降低。Setayesh S.等在芴的9位上引入体积很大的多个苯环结构(J.Am.Chem.Soc.2001,123,946,分子结构式1),用以防止聚芴分子的聚集,起到了遏制黄光的作用,但分子刚性大,不易溶解。Yu W.L.等合成带螺旋芴的聚合物(Adv.Mater.2000,12,No.11,830,分子结构式2),由于螺旋芴的空间结构,起到了遏制产生黄光的作用。Shu Ching-Fong等在聚芴上引入三苯胺等基团(Macromolecules,2003,Vol.36,No.18,6698,分子结构式3),目的是扩大聚芴分子间距的同时,同时提高材料的导空穴能力,以上的聚合都通过传统的Suziki反应进行。
分子结构式1 分子结构式2
分子结构式3
有机合成中的Friedel-Krafts烷基化反应是一种芳环亲电取代反应的合成方法,当卤烷上有稳定碳正离子基团时(如叔丁基、苯基),有助于提高产率。Yu W.L.等利用9-(2’-双苯基)-9-羟基芴的分子内三苯甲醇结构(Adv.Mater.2000,12,No.11,830),来合成螺旋芴,使用的催化剂为盐酸和醋酸,产率达到80%(化学反应式1)。Wong K.T.等利用9-苯基-9-羟基-芴与甲苯的反应来合成9,9-二苯基芴(Org.Lett.,2001,Vol.3,2286),使用的催化剂为甲磺酸(化学反应式2)。
(三)发明内容
本发明制备的新型聚芴蓝光材料摈弃了采用大体积取代基团来防止分子链聚集的途径,而是利用分子本身空间结构的位阻来阻止分子间ππ叠加现象的发生。聚合方法利用了上面的Friedel-Krafts烷基化反应机理,将有机小分子芳环亲电取代反应拓展为高分子缩聚反应。
本发明合成了芴醇结构的芴类齐聚物(单体a,见化学反应式3)。首先利用对溴甲苯与2-溴芴酮加成反应,得到中间体;而后中间体与硼酸封端的齐聚芴进行Suzuki偶合反应得到单体a。单体a的两端含芴醇结构,中间是1-8个芴的齐聚物(即m为1-8),侧链是脂肪链的取代基(n为2-15)。单体b是通用的三苯胺类化合物,如N,N′-二苯基-N,N′-双(4-甲基苯基)-(1,1-二苯基)-4,4′-二胺(简称TPD),N-(4-甲基)二苯基胺(简称TPA)等。
本发明利用芴醇与三苯胺类化合物反应而得到高分子,其中芴类齐聚物是可显蓝光的基体材料。在这个缩聚反应中,一个反应基团是氮原子取代苯对位的氢原子,另一个基团可以看作三苯基取代的甲醇。氮原子的富电子效应,活化了苯对位氢原子的亲电加成能力,同时芴醇是高活性的烷基化试剂,这使Friedel-Crafts小分子取代反应扩展为高分子缩聚反应成为可能。在酸性催化剂作用下,高反应活性的官能团相互间能发生定量的芳环亲电取代反应,单体间相互脱水缩合成二聚体,然后二聚体继续发生芳环亲电取代反应,继续缩合,逐步聚合成高分子。
聚合时,将等摩尔的单体a和单体b溶解在溶剂中,加入单体a 5-20%的摩尔酸作催化剂。脱氧充氮3次后,加热到50-120℃反应数小时以上,有机小分子单体即缩聚成高分子。合成过程见化学反应式4。聚合度x为2-100,其中聚合度超过10为佳。
由于芴的平面结构,在9位上的取代基团扭曲于芴平面。通过取代基团间发生的聚合反应,使得该聚合物具有空间扭曲结构,就象一根根硬棒支开了聚芴分子链,从而避免发生分子链ππ聚集而导致器件黄光现象的产生,制备出了一类稳定的蓝光材料,而且分子的空间结构性有利于提高聚合物的溶解性。
本发明聚合物(蓝光材料)分子通式为:
其中n=2-15,m=1-8,x=2-100,聚合物外观为白色或微黄色粉末固体,其玻璃化转变温度100℃-240℃,5%热分解温度430℃-440℃。紫外光照射下聚合物显蓝色,固体膜的光致发光效率40%-50%。本发明聚合物制备过程如下:
化学反应式3
化学反应式4
(四)发明实例
例1:
单体b是TPD,单体a1是两端含芴醇的芴类齐聚物。在硫酸的催化反应下,单体b和单体a1在对二甲苯溶剂中脱水缩聚成高分子。将反应后的溶液滴入10倍于溶剂的甲醇中,得到聚合物沉淀,产物为微黄色粉末固体,产率为85%。聚合物分子量3万,聚合分散度2.1。合成过程见化学反应式5。聚合物主要性能:玻璃化转变温度165℃。5%热分解温度430℃,在紫外光下呈蓝色,固体膜的光致发光效率49%。
化学反应式5
例2:
单体b是TPD,单体a2是两端含芴醇的芴类齐聚物。在甲磺酸的催化反应下,单体b和单体a2在均三甲苯溶剂中脱水缩聚成高分子。将反应后的溶液滴入10倍于溶剂的甲醇中,得到聚合物沉淀,产物为白色或微黄色粉末固体,产率为85%。聚合物分子量2.5万,聚合分散度1.8。合成过程见化学反应式6。聚合物主要性能:玻璃化转变温度234℃。5%热分解温度437℃,在紫外光下呈蓝色,固体膜的光致发光效率43%。
化学反应式6
例3:
单体b是TPA,单体a3是两端含芴醇的芴类齐聚物。在甲磺酸的催化反应下,单体b和单体a3在均三甲苯溶剂中脱水缩聚成高分子。将反应后的溶液滴入10倍于溶剂的甲醇中,得到聚合物沉淀,产物为白色或微黄色粉末固体,产率为80%。聚合物分子量2万,聚合分散度2.3。合成过程见化学反应式7。聚合物主要性能:玻璃化转变温度198℃。5%热分解温度435℃,在紫外光下呈蓝色,固体膜的光致发光效率42%。
化学反应式7
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US5708130A (en) * | 1995-07-28 | 1998-01-13 | The Dow Chemical Company | 2,7-aryl-9-substituted fluorenes and 9-substituted fluorene oligomers and polymers |
US20040110958A1 (en) * | 2002-09-20 | 2004-06-10 | Tosoh Corporation | Novel arylamine derivatives having fluorene skeleton, synthetic intermediates thereof, processes of producing those, and organic electrolumivescene devices |
CN1568303A (zh) * | 2002-03-27 | 2005-01-19 | 佳能株式会社 | 低聚芴化合物 |
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US5708130A (en) * | 1995-07-28 | 1998-01-13 | The Dow Chemical Company | 2,7-aryl-9-substituted fluorenes and 9-substituted fluorene oligomers and polymers |
CN1568303A (zh) * | 2002-03-27 | 2005-01-19 | 佳能株式会社 | 低聚芴化合物 |
US20040110958A1 (en) * | 2002-09-20 | 2004-06-10 | Tosoh Corporation | Novel arylamine derivatives having fluorene skeleton, synthetic intermediates thereof, processes of producing those, and organic electrolumivescene devices |
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