CN108586711A - 一种侧链含有空穴传输基团的聚螺芴及其制备方法与应用 - Google Patents
一种侧链含有空穴传输基团的聚螺芴及其制备方法与应用 Download PDFInfo
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Abstract
本发明属于有机发光材料制备技术领域,具体涉及一种侧链含有空穴传输基团的聚螺芴及其制备方法与应用。该聚螺芴的侧链含有空穴传输基团,可以提高聚螺芴的HOMO能级,降低空穴注入势垒,有利于实现空穴和电子注入的平衡。此外,该聚螺芴发光材料具有较好的溶解性,采用常见有机溶剂溶解后,通过旋涂、喷墨打印或印刷即可成膜,制备得到发光二极管的发光层。基于该聚合物的发光层在制备发光器件时不需要添加空穴传输层,使得器件制备工艺更简单。将该聚螺芴发光材料用于单层电致发光器件,其最大电流效率(LEmax)为0.67cd/A,器件的最大亮度(Lmax)为3484cd/m2,器件的开启电压(Von)仅为2.7v。
Description
技术领域
本发明属于有机发光材料制备技术领域,具体涉及一种侧链含有空穴传输基团的聚螺芴及其制备方法与应用。
背景技术
1990年英国剑桥大学的科学家将共轭高分子聚对苯撑乙烯(PPV)引入有机电致发光器件中,开拓了聚合物有机发光二极管的研究。聚合物发光二极管因其具有可溶液加工、材料的利用率高、成本较低和大面积制备等优点,引起了学术界和产业界的广泛关注,在全彩显示和固态照明领域有很好的应用前景。聚合物发光二极管无论用于全彩显示还是白光照明,均具有高稳定性、高色纯度和高效率的红、蓝、绿三基色发光的优点。但是,与聚合物红、绿光材料相比相比,聚合物蓝光材料在效率、寿命和色纯度方面还面临着很大的挑战。
聚芴具有较高的固态光致荧光量子产率和良好的溶解性,其化学结构易于修饰,被认为是最有潜力的聚合物蓝光材料。然而,聚芴薄膜在聚合物发光二极管中工作一段时间后,会观察到长波方向出现新的发射峰,这是由于聚集/激基缔合物或芴酮造成的,导致聚芴的光谱不稳定,且色纯度较低。相对而言,聚螺芴是一种更有潜力的聚合物深蓝光材料。聚螺芴的基本单元是螺二芴。螺二芴是由两个芴通过9位碳原子连接,因此避免了芴酮结构的产生。聚螺芴的主链和侧链之间十字交叉的构象产生较大的空间位阻效应,可以抑制分子在薄膜状态下发生π-π堆积,进而抑制荧光淬灭现象。聚螺芴的刚性结构,使其具有良好的化学和热稳定性。但是,聚螺芴与聚芴一样具有较深的HOMO能级,使PEDOT:PSS和发光层之间有很大的空穴注入势垒,降低了器件的发光效率。该问题可通过在器件制作中加入空穴传输层来解决。然而,空穴传输层的加入增加了器件制作的复杂性,不利于制备大面积的PLED,并且溶液加工多层有机层器件时,很容易发生层间的互溶,破坏界面的表面形貌,导致器件性能下降。
发明内容
为克服现有技术的缺点和不足,本发明的首要目的在于提供一种侧链含有空穴传输基团的聚螺芴。
本发明的另一目的是提供上述侧链含有空穴传输基团的聚螺芴的制备方法。
本发明的再一目的是提供上述侧链含有空穴传输基团的聚螺芴的应用。
为实现上述目的,本发明采用的技术方案如下。
一种侧链含有空穴传输基团的聚螺芴,具有以下结构通式:
其中,Hole为空穴传输基团,n为1~1000的自然数。
优选地,所述空穴传输基团具有以下任一种结构式:
其中,R1和R2表示相同或不相同的H或C1~C20的烷基或烷氧基,但R1和R2不同时为H;
波浪线表示C1~C20的烷基或烷氧基;
所述的空穴传输基团通过R1或R2中的烷基或烷氧基、或空穴传输基团中的N原子或芳基与螺芴相连。
更优选地,所述的侧链含有空穴传输基团的聚螺芴具有以下任一项所述的结构式:
本发明进一步提供上述侧链含有空穴传输基团的聚螺芴的制备方法,包括以下步骤:将2-溴-4'-Hole-1,1'-联苯与正丁基锂和二溴芴酮反应,得到芴醇;然后在冰乙酸和盐酸的作用下闭环,得到侧链带有空穴传输基团的2,7-二溴螺芴单体;然后将侧链带有空穴传输基团的二溴螺芴单体与双联频哪醇硼酸酯反应,得到侧链带有空穴传输基团的2,7-螺芴硼酸酯单体;最后将两个单体通过Suzuki偶联反应进行聚合,得到侧链含有空穴传输基团的聚螺芴。
本发明进一步提供上述侧链含有空穴传输基团的聚螺芴的应用,将所述的聚螺芴用于电致发光器件、光伏电池、非线性光学器件或传感器件中。
本发明与现有技术相比,具有如下优点和有益效果:
(1)本发明的聚螺芴发光材料在聚螺芴的侧链上引入空穴传输基团,与传 统聚螺芴相比,该聚螺芴发光材料具有较高的HOMO能级,因此有利于空穴的注入和传输,实现空穴和电子注入的平衡,从而获得更高的器件效率和更低的启动电压。此外,在聚螺芴的侧链上引入空穴传输基团可避免多层有机器件的复杂制备,因此该聚螺芴在单层电致发光器件领域有很好的应用前景。
(2)本发明的聚螺芴发光材料因侧基上带有长链的取代基团而可溶于各种常见溶剂,适合旋涂或者打印成膜,从而可在电致发光、光伏电池、非线性光学和传感领域得到应用。将该聚螺芴用于单层电致发光器件,其最大电流效率(LEmax)为0.67cd/A,器件的最大亮度(Lmax)为3484cd/m2,器件的开启电压(Von)仅为2.7v。
附图说明
图1为实施例1中制备的2',7'-二溴-N,N-双(4-辛基苯基)-9,9'-螺二芴-2-胺的1H谱图。
图2为实施例1中制备的2',7'-二溴-N,N-双(4-辛基苯基)-9,9'-螺二芴-2-胺的13C谱图;
图3为实施例1中制备的N,N-双(4-辛基苯基)-2',7'-二(4,4,5,5-四甲基-1,3,2-二氧硼杂环戊烷-2-基)-9,9'-螺二芴-2-胺的1H谱图。
图4为实施例1中制备的N,N-双(4-辛基苯基)-2',7'-二(4,4,5,5-四甲基-1,3,2-二氧硼杂环戊烷-2-基)-9,9'-螺二芴-2-胺的13C谱图。
图5为实施例1中制备的聚合物P(C8TPA-SF)的1H谱图。
图6为实施例2中制备的2,7-二溴-2'-(2-乙基己氧基)-9,9'-螺二芴的1H谱图。
图7为实施例2中制备的2,7-二(4,4,5,5-四甲基-1,3,2-二氧硼杂环戊烷-2-基)-2'-(2-乙基己氧基)-9,9'-螺二芴的1H谱图。
图8为实施例3中聚合物P(C8TPA-SF)的在薄膜状态下的紫外-可见吸收光谱谱图。
图9为实施例3中聚合物P(C8TPA-SF)的在薄膜状态下的光致发光光谱谱图。
图10为实施例3中基于聚合物P(C8TPA-SF)的单层电致发光器件电流效率-电流密度图。
具体实施方式
下面结合实施例及附图对本发明作进一步详细的描述,但本发明的实施方式不限于此。对于未特别注明的工艺参数,可参照常规技术进行。
实施例1
本实施例提供一种侧链含有空穴传输基团的聚螺芴P(C8TPA-SF)的制备方法。
(1)4-溴-N,N-二(4-辛基苯)苯胺的制备
称取1-碘-4-N-辛基苯(22g,70mmol),4-溴苯胺(5.16g,30mmol),1,10-菲啰啉(0.632g,3.5mmol),碘化亚铜(0.636g,3.5mmol),氢氧化钾(0.7mol,39.2g)于250ml单口瓶中,然后加入84ml二甲苯和56ml甲苯。在冷冻液(-40℃左右的无水乙醇)的保护下,换氩气三次,加热到135℃,回流反应24h。降到室温,在砂芯漏斗上铺一层硅胶抽滤,用二氯甲烷洗三次滤饼。旋干,抽干,称重,用二氯甲烷溶解,加入1~2倍的硅胶,旋干,硅胶层析色谱柱提纯,旋干,抽干,最后得到无色液体产物6.8g,产率=41%。化学反应方程式如下所示:
(2)4-(双(4-辛基苯基)氨基)苯基)硼酸的制备
称取4-溴-N,N-二(4-辛基苯)苯胺(12.2g,22.2mmol)于250ml三口瓶中,换氩气三次,注入60ml干燥过的THF溶解,用液氮降温到-78℃,向恒压滴液漏斗中注入正丁基锂(12.5ml,31mmol),缓慢滴加,滴加完毕后,用10ml干燥过的THF洗恒压滴液漏斗。在-78℃下反应2h,然后用注射器取硼酸三甲酯(11ml,92mmol),注入到恒压滴液漏斗中,一次性加入到反应液中,在-60℃左右反应2h,自然升温,搅拌反应过夜。第二天,降温到0℃左右,加入200ml1mol/L的稀盐酸,搅拌0.5h。用氯仿萃取三次,合并有机层,水洗,饱和食盐水洗,无水硫酸镁干燥,抽滤,滤液为棕色,上层泛蓝色,在40℃水浴旋干,抽干得到淡黄色固体10g,二氯甲烷溶解,加入15g硅胶旋干,旋干,硅胶层析色谱柱提纯,旋干,抽干,最后得到无色液体产物6g,产率=52%。化学反应方程式如下所示:
(3)2'-溴-N,N-二(4-辛基苯基)-[1,1'-联苯基]-4-胺的制备
称取1,2-二溴代苯(9.44g,40mmol),4-(双(4-辛基苯基)氨基)苯基)硼酸(5.14g,10mmol),碳酸钠水溶液(15ml,2mol/L),醋酸钯(0.006g,0.025mmol),三(邻甲基苯基)磷(0.031g,0.1mmol),3滴三辛基甲基氯化铵(Aliquat336),30ml甲苯于100ml单口瓶中,在冷冻液(-40℃左右的无水乙醇)的保护下,换氩气五次,升温到室温,油浴加热到90℃,在90℃下反应48h。反应结束后,降温到室温,甲苯萃取三次,合并有机层,饱和食盐水洗三次,无水硫酸镁干燥,抽滤,旋干,减压蒸馏,除去前馏分1,2-二溴代苯,石油醚溶解,硅胶层析色谱柱提纯,洗脱剂为石油醚,最后得到无色液体粗产物8g,粗产率=55%。化学反应方程式如下所示:
(4)9-(4'-(双(4-辛基苯基)氨基)-[1,1'-联苯]-2-基)-2,7-二溴-9H-芴-9-醇的制备
称取2'-溴-N,N-二(4-辛基苯基)-[1,1'-联苯基]-4-胺(7.5g,12mmol)于250ml三口瓶中,抽真空,松香石蜡封口,接口处缠石蜡膜,换氩气三次,注入150ml干燥过的THF溶解,用液氮降温到-78℃,向恒压滴液漏斗中注入正丁基锂(7.5ml,18.75mmol),缓慢滴加,大约1h滴完,滴加完毕后,用10ml干燥过的THF洗恒压滴液漏斗。在-78℃下反应2h,称取二溴芴酮(4.1g,12mmol),快速加入到三口瓶中,并注入20ml干燥过的四氢呋喃洗瓶壁,在-60℃左右反应2h,自然升温,搅拌反应过夜。第二天,向反应液中加入10g氯化铵和100ml水淬灭,搅拌0.5h。用乙酸乙酯萃取三次,合并有机层,水洗,饱和食盐水洗,无水硫酸镁干燥,抽滤,滤液为淡黄色,旋干,抽干,硅胶层析色谱柱提纯,最后得到棕黄色粘稠液体粗产物9g,粗产率=85%。化学反应方程式如下所示:
(5)2',7'-二溴-N,N-双(4-辛基苯基)-9,9'-螺二芴-2-胺的制备
称取9-(4'-(双(4-辛基苯基)氨基)-[1,1'-联苯]-2-基)-2,7-二溴-9H-芴-9-醇(8.84g,10mmol),冰乙酸200ml于500ml单口瓶中,油浴加热100℃回流,等到粘稠液体完全溶解时,向溶液中滴加30ml浓盐酸,滴加到4ml时,溶液变浑浊,搅拌时溶液底部有大量的棕色油状物,回流4h,降温至常温,搅拌反应过夜。第二天,直接用水泵旋干,抽干,得到8.56g粘液,二氯甲烷溶解,加入15g硅胶,旋干,抽干,硅胶层析色谱柱提纯,洗脱剂为石油醚:二氯甲烷=4:1,旋干,抽干,无水乙醇重结晶三次,最后得到白色固体产物4g,熔点104-106℃,产率=46%。
所得产物的1H谱图和13C谱图分别如图1和图2所示。
鉴定数据如下:1H NMR(600MHz,CDCl3)δ7.71(d,J=7.6Hz,1H),7.63(d,J=8.3Hz,1H),7.56(d,J=8.2Hz,2H),7.44(dd,J=8.2,1.8Hz,2H),7.35(td,J=7.6,0.8Hz,1H),7.09–7.01(m,1H),7.01–6.83(m,11H),6.65(d,J=7.6Hz,1H),6.45(d,J=2.0Hz,1H),2.53–2.44(m,41H),1.56–1.52(m,4H),1.29(t,J=10.3Hz,20H),0.89(t,J=7.0Hz,6H)。
13C NMR(151MHz,CDCl3)δ150.77,148.35,146.95,145.17,141.72,139.59,137.56,135.55,130.97,128.99,128.24,127.27,126.96,124.07,123.87,123.20,121.76,121.38,120.73,119.51,118.75,65.61,35.32,31.94,31.43,29.51,29.37,29.29,22.71,14.13;MALDI-TOF MS:m/z,865.11。
化学反应方程式如下所示:
(6)N,N-双(4-辛基苯基)-2',7'-二(4,4,5,5-四甲基-1,3,2-二氧硼杂环戊烷-2-基)-9,9'-螺二芴-2-胺的制备
称取1.35g醋酸钾于100ml单口瓶中,在135℃下抽真空1h,冷却到室温。称取2',7'-二溴-N,N-双(4-辛基苯基)-9,9'-螺二[芴]-2-胺(1.73g,2mmol),双联频哪醇硼酸酯(1.53g,6mmol),[1,1'-双(二苯基膦)二茂铁]二氯化钯二氯甲烷络合物(0.1g,0.12mmol),快速加入到单口瓶中,换氩气三次,用注射器注入40ml蒸过的二氧六环,油浴80℃下避光反应24h。反应结束后,降至室温,砂芯漏斗铺硅胶抽滤,用二氯甲烷润洗三次,在70℃下旋干,抽干,二氯甲烷溶解,湿法过柱,二氯甲烷为洗脱剂,3.5cm*25cm快速过柱,旋干,抽干,2ml二氯甲烷溶解,加入120ml甲醇,空旋,直到溶液变浑浊,放到冰箱下层(-15℃左右)过夜。第二天,抽滤,抽干,重结晶三次,得到白色粉末固体0.5g,产率=52%。
所得产物的1H谱图和13C谱图分别如图3和图4所示。
鉴定数据如下:1H NMR(600MHz,CDCl3)δ7.84–7.74(m,4H),7.73–7.68(m,1H),7.64(d,J=8.3Hz,1H),7.34–7.26(m,1H),7.22(s,2H),7.03–6.93(m,2H),6.90–6.78(m,8H),6.62(d,J=7.6Hz,1H),6.45(dd,J=14.1,1.8Hz,1H),2.50–2.41(m,4H),1.53(dd,J=14.7,7.3Hz,4H),1.30(t,J=7.6Hz,44H),0.89(t,J=7.0Hz,6H);
13C NMR(151MHz,CDCl3)δ148.76,148.45,144.40,137.02,134.62,130.13,128.80,127.51,126.71,124.04,123.78,119.67,119.36,83.70,67.97,65.90,35.30,31.94,31.44,29.50,29.37,29.29,25.64,24.88,24.81,22.70,14.13;MALDI-TOFMS:m/z,959.47。
化学反应方程式如下所示:
(7)P(C8TPA-SF)的聚合
称取2',7'-二溴-N,N-双(4-辛基苯基)-9,9'-螺二芴-2-胺(M2)(0.1515g,0.175mmol),N,N-双(4-辛基苯基)-2',7'-二(4,4,5,5-四甲基-1,3,2-二氧硼杂环戊烷-2-基)-9,9'-螺二[芴]-2-胺(M3)(0.168g,0.175mmol)于聚合管中,然后 取醋酸钯(1mg,0.0044mmol),三(邻甲基苯基)磷(6.5mg,0.0212mmol)于1ml离心管中,向其中加入1ml甲苯使其完全溶解,取出0.5ml溶液,在剩余的溶液中再加入0.5ml甲苯混合均匀,然后取出0.5ml溶液加入到聚合管中,然后在取四乙基氢氧化铵(其中有片状白色固体析出)(1ml,25%的水溶液),甲苯4.5ml,蒸过的二氧六环0.5ml于聚合管中,在冷冻液(-40℃左右的无水乙醇)的保护下,换氩气五次。然后开始加热,加热到50℃,用止水夹夹住乳胶管,在90℃下反应72h。然后冷却到室温,称取4-甲基苯硼酸(30mg,0.22mmol)溶于1ml蒸过的二氧六环中,用注射器注入到聚合管中封端,然后在90℃下反应12h。然后冷却到室温,取溴苯0.5ml溶解于1ml甲苯中,注入到聚合管中封端,然后在90℃下反应12h。冷却至室温,划断聚合管,倒入加入10ml 10%稀盐酸溶液中,搅拌4h,甲苯萃取三次,水洗三次,旋干,用3ml甲苯溶解,用200ml甲醇沉淀,滤纸过滤。取滤饼,三聚硫氰酸(8mg,0.045mmol)于50ml单口瓶中,换氩气三次,注入20ml蒸过的四氢呋喃,在75℃下回流12h,冷却至室温,旋干溶剂,用3ml甲苯溶解,用200ml甲醇沉淀,滤纸过滤。滤饼依次用甲醇、石油醚和丙酮进行索氏抽提,每次抽提12h。抽提完毕后,用甲苯溶解过硅胶层析色谱柱提纯,旋干,用3ml甲苯溶解,用200ml甲醇沉淀,析出大量淡黄色长纤维状固体,过滤,抽干,得到淡黄色长纤维状固体80mg,产率=56%。采用聚苯乙烯为标准物,以THF(四氢呋喃)为流动相,通过GPC测得P(C8TPA-SF)的数均分子量(Mn)为44878,重均分子量(Mw)为83251,聚合物分散性指数(PDI)为1.86。
所得产物的1H谱图如图5。
鉴定数据如下:1H NMR(600MHz,CDCl3,ppm):7.64~6.40(aromatic H),2.13~0.88(aliphatic H)。
化学反应方程式如下所示:
实施例2
本实施例提供一种侧链不含有空穴传输基团的聚螺芴sPF的制备方法。
(1)2,7-二溴-2'-(2-乙基己氧基)-9,9'-螺二芴的制备
称取2-溴-4'-((2-乙基己基)氧基)-1,1'-联苯(4.33g,12mmol)于250ml三口瓶中,换氩气三次,注入150ml干燥过的THF溶解,降温到-78℃,向恒压滴液漏斗中注入正丁基锂(7.5ml,18.75mmol),缓慢滴加。在-78℃下反应2h,称取二溴芴酮(4.1g,12mmol),快速加入到三口瓶中,在-60℃左右反应2h,自然升温,搅拌反应过夜。第二天,向反应液中加入10g氯化铵和100ml水淬灭。用乙酸乙酯萃取三次,合并有机层,水洗,饱和食盐水洗,无水硫酸镁干燥,抽滤,滤液为淡黄色,旋干,抽干。加入200ml冰乙酸,油浴加热100℃回流,向溶液中滴加30ml浓盐酸,回流4h,降温至常温,搅拌反应过夜。,旋干,抽干,硅胶层析色谱柱提纯,无水乙醇重结晶三次。产物为白色粉末,熔点为183-186℃,产率=50%。
所得产物的1H谱图如图6
鉴定数据如下:1H NMR(600MHz,CDCl3)δ7.73(dd,J=8.0,4.5Hz,2H),7.69–7.61(m,2H),7.49(dd,J=8.2,1.8Hz,2H),7.36(td,J=7.5,1.0Hz,1H),7.06(tt,J=7.5,3.6Hz,1H),6.94(dd,J=8.4,2.3Hz,1H),6.86(d,J=1.7Hz,2H),6.65(d,J=7.5Hz,1H),6.22(d,J=2.3Hz,1H),3.73–3.65(m,2H),1.63–1.57(m,1H)1.46–1.19(m,8H),0.85(t,J=7.4Hz,6H).
化学反应方程式如下所示:
(2)2,7-二(4,4,5,5-四甲基-1,3,2-二氧硼杂环戊烷-2-基)-2'-(2-乙基己氧基)-9,9'-螺二芴的制备
称取1.35g醋酸钾于100ml单口瓶中,在135℃下抽真空1h,冷却到室温。称取2,7-二溴-2'-(2-乙基己氧基)-9,9'-螺二芴(1.21g,2mmol),双联频哪醇硼酸酯(1.53g,6mmol),[1,1'-双(二苯基膦)二茂铁]二氯化钯二氯甲烷络合物(0.1g,0.12mmol),快速加入到单口瓶中,换氩气三次,用注射器注入40ml蒸过的二氧六环,油浴80℃下避光反应24h。反应结束后,降至室温,砂芯漏斗铺硅胶抽滤,用二氯甲烷润洗三次,硅胶层析色谱柱提纯,甲醇重结晶三次。产物为白色晶体状,产率75.5%。
所得产物的1H谱图如图7
鉴定数据如下:1H NMR(600MHz,CDCl3)δ7.91–7.80(m,4H),7.72(t,J=7.6Hz,2H),7.35–7.27(m,1H),7.17(d,J=12.2Hz,2H),7.04–6.94(m,1H),6.93–6.84(m,1H),6.63(dd,J=14.2,5.8Hz,1H),6.22(dd,J=10.0,2.2Hz,1H),3.68–3.61(m,2H),1.92–1.72(m,1H),1.43–1.11(m,32H),0.86–0.78(m,6H).
化学反应方程式如下所示:
(3)sPF的聚合
称取2,7-二溴-2'-(2-乙基己氧基)-9,9'-螺二芴(0.1054g,0.175mmol),2,7-二(4,4,5,5-四甲基-1,3,2-二氧硼杂环戊烷-2-基)-2'-(2-乙基己氧基)-9,9'-螺二芴(0.120g,0.175mmol)于聚合管中,然后取醋酸钯(1mg,0.0044mmol),三(邻甲基苯基)磷(6.5mg,0.0212mmol)于1ml离心管中,向其中加入1ml甲苯使其完全溶解,取出0.5ml溶液,在剩余的溶液中再加入0.5ml甲苯混合均匀,然后取出0.5ml溶液加入到聚合管中,然后在取四乙基氢氧化铵(其中有片状白色固体析出)(1ml,25%的水溶液),甲苯4.5ml,蒸过的二氧六环0.5ml于聚合管中,在冷冻液(-40℃左右的无水乙醇)的保护下,换氩气五次。在90℃下反应72h。然后冷却到室温,称取4-甲基苯硼酸(30mg,0.22mmol)溶于1ml蒸过的二氧六环中,用注射器注入到聚合管中封端,然后在90℃下反应12h。然后冷却到室温,取溴苯0.5ml溶解于1ml甲苯中,注入到聚合管中封端,然后在90℃下反应12h。冷却至室温,划断聚合管,倒入加入10ml 10%稀盐酸溶液中,搅拌4h,甲苯萃取三次,水洗三次,旋干,用3ml甲苯溶解,用200ml甲醇沉淀,滤纸过滤。取滤饼,三聚硫氰酸(8mg,0.045mmol)于50ml单口瓶中,换氩气三次,注入20ml蒸过的四氢呋喃,在75℃下回流12h,冷却至室温,旋干溶剂,用3ml甲苯溶解,用200ml甲醇沉淀,滤纸过滤。滤饼依次用甲醇、石油醚和丙酮进行索氏抽提,每次抽提12h。抽提完毕后,用甲苯溶解过硅胶层析色谱柱提纯,旋干,用3ml甲苯溶解,用200ml甲醇沉淀,析出大量淡黄色长纤维状固体,过滤,抽干,最后得到白色短纤维固体49mg,产率=58%。
化学反应方程式如下所示:
实施例3
本实施例提供实施例1中制备的侧链含有空穴传输基团的聚螺芴P(C8TPA-SF)和实施例2中制备的侧链不含有空穴传输基团的sPF在电致发光器件中的对比应用。
基于聚合物P(C8TPA-SF)和sPF的电致发光器件的制备
将预先做好的方块电阻≤12Ω/口的氧化铟锡(ITO)玻璃,先依次用去离子水、丙酮、洗涤剂、去离子水和异丙醇各超声清洗20分钟,在80℃烘箱里,烘干过夜。使用前用氧等离子处理4分钟;在ITO上旋涂PEDOT:PSS,旋涂转速为3000r,30s,厚度约为40nm。旋涂结束后,置于120℃的加热台上退火20min,除去溶剂;然后将16mg/ml的P(C8TPA-SF)的二甲苯溶液,或16mg/ml的sPF的二甲苯和四氢呋喃的混合溶液,旋涂到PEDOT:PSS上,厚度为75nm左右,作为发光层;最后在发光层上一次蒸镀1nm左右的CsF和100nm左右的金属铝。
对P(C8TPA-SF)或sPF的电致发光器件进行光电性能测试。
其中,采用日本岛津公司的UV-3600型紫外-可见光分光光度计进行测试,得到图8所示的P(C8TPA-SF)薄膜的紫外-可见吸收光谱谱图。
采用日本岛津公司的RF-5301PC型荧光光谱仪进行测试,得到图9所示的P(C8TPA-SF)薄膜的光致发光光谱谱图。
采用PR-705光谱仪进行测试,得到图10所示的P(C8TPA-SF)单层电致发光器件电流效率-电流密度图。
上述数据结果如表1所示。
可见,基于聚合物sPF的单层电致发光器件的最大电流效率(LEmax)为1.1cd/A,器件的最大亮度(Lmax)为2847cd/m2,器件的开启电压(Von)为3.3v。
基于聚合物P(C8TPA-SF)的单层电致发光器件的最大电流效率(LEmax)为0.67cd/A,器件的最大亮度(Lmax)为3484cd/m2,器件的开启电压(Von)仅为2.7v。与侧链不含有空穴传输基团的sPF相比,开启电压下降了0.6v。其中,CIEd为色度坐标,λEL为电致发光光谱发射峰的位置。
表1基于聚合物P(C8TPA-SF)和sPF的单层器件性能数据
a器件亮度为1cd/m2时的电压;b最大亮度;c最大电流效率;d色度坐标。
上述实施例为本发明较佳的实施方式,但本发明的实施方式并不受上述实施例的限制,其它的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化,均应为等效的置换方式,都包含在本发明的保护范围之内。
Claims (5)
1.一种侧链含有空穴传输基团的聚螺芴,其特征在于,具有以下结构通式:
其中,Hole为空穴传输基团,n为1~1000的自然数。
2.根据权利要求1所述的侧链含有空穴传输基团的聚螺芴,其特征在于,所述空穴传输基团具有以下任一种结构式:
其中,R1和R2表示相同或不相同的H或C1~C20的烷基或烷氧基,但R1和R2不同时为H;
波浪线表示C1~C20的烷基或烷氧基;
所述的空穴传输基团通过R1或R2中的烷基或烷氧基、或空穴传输基团中的N原子或芳基与螺芴相连。
3.根据权利要求2所述的侧链含有空穴传输基团的聚螺芴,其特征在于,具有以下任一项所述的结构式:
4.权利要求1~3任一项所述的侧链含有空穴传输基团的聚螺芴的制备方法,其特征在于,包括以下步骤:将2-溴-4'-Hole-1,1'-联苯与正丁基锂和二溴芴酮反应,得到芴醇;然后在冰乙酸和盐酸的作用下闭环,得到侧链带有空穴传输基团的2,7-二溴螺芴单体;然后将侧链带有空穴传输基团的二溴螺芴单体与双联频哪醇硼酸酯反应,得到侧链带有空穴传输基团的2,7-螺芴硼酸酯单体;最后将两个单体通过Suzuki偶联反应进行聚合,得到侧链含有空穴传输基团的聚螺芴。
5.权利要求1~3任一项所述的侧链含有空穴传输基团的聚螺芴的应用,其特征在于:将所述的聚螺芴用于电致发光器件、光伏电池、非线性光学器件或传感器件中。
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CN111378323A (zh) * | 2018-12-29 | 2020-07-07 | Tcl集团股份有限公司 | 油墨及量子点薄膜和量子点发光二极管 |
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CN112831221A (zh) * | 2019-11-22 | 2021-05-25 | Tcl集团股份有限公司 | 油墨及量子点薄膜和量子点发光二极管 |
CN113045930A (zh) * | 2019-12-28 | 2021-06-29 | Tcl集团股份有限公司 | 油墨及量子点薄膜和量子点发光二极管 |
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