CN113512177A - 一种红光聚合物及其制备方法 - Google Patents

一种红光聚合物及其制备方法 Download PDF

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CN113512177A
CN113512177A CN202110343496.2A CN202110343496A CN113512177A CN 113512177 A CN113512177 A CN 113512177A CN 202110343496 A CN202110343496 A CN 202110343496A CN 113512177 A CN113512177 A CN 113512177A
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樊嘉政
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Guangzhou All Things Internet Of Things Technology Co ltd
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Abstract

本发明属光电显示器件技术领域，具体涉及一种红光聚合物及其制备方法。本发明提供了一种红光聚合物，其化学式如式(I)所示：其中，x+y＝0.5，n＝1‑300，R为芳基、三苯胺基、碳原子数为1‑20的直链或支链烷基，或者碳原子数1～20的烷氧基。本发明还提供了一种红光聚合物的制备方法，包括将1－苯基－2－(4－(4，4，5，5－四甲基－1，3，2－二氧硼酯－2－基)苯基)－1H－菲并咪唑，式(IV)所示化合物，式(II)所示化合物，式(III)所示化合物通过Suzuki偶联反应制得式(I)所示聚合物。本发明提供了一种红光聚合物及其制备方法，解决了现有技术中缺少菲并咪唑类红色荧光光电材料，且器件效率低的技术问题。

Description

一种红光聚合物及其制备方法
技术领域
本发明属光电显示器件技术领域，具体涉及一种红光聚合物及其制备方法。
背景技术
在电致发光领域，高性能的红光材料不仅具有理论研究意义，而且影响着发光器件实用化和全色显示平板商业化的进展。通过将单分子材料与窄带隙单体共聚，尽管可以得到色纯度较高、分子量大、效率高的聚合物。但由于产生红光发射的化合物的能级差很小，并且红光材料体系中，存在较强的π-π相互作用或具有强的电荷转移特性，易产生荧光淬灭现象，导致荧光量子产率下降和电致发光效率较低。
发明内容
本发明提供了一种红光聚合物及其制备方法，解决了现有技术中红光荧光光电材料易产生荧光淬灭，荧光量子产率和电致发光效率较低的技术问题。
本发明提供了一种红光聚合物，其化学式如式(I)所示：
Figure BDA0002999981030000011
其中，x+y＝0.5，n＝1-300，R为芳基、三苯胺基、碳原子数为1-20的直链或支链烷基，或者碳原子数1～20的烷氧基。
优选的，其化学式为
Figure BDA0002999981030000021
本发明还提供了一种红光聚合物的制备方法，包括将1－苯基－2－(4－(4，4，5，5－四甲基－1，3，2－二氧硼酯－2－基)苯基)－1H－菲并咪唑，式(IV)所示化合物，式(II)所示化合物，式(III)所示化合物通过Suzuki偶联反应制得式(I)所示聚合物；
Figure BDA0002999981030000022
Figure BDA0002999981030000031
优选的，所述Suzuki偶联反应的温度为80℃。
优选的，所述Suzuki偶联反应的时间为20h-40h。
优选的，所述式(III)所示化合物的制备方法包括以下步骤：
步骤1：将3,4-乙撑二氧噻吩通过溴化反应制得式(V)所示化合物，
Figure BDA0002999981030000032
步骤2：将式(V)所示化合物与4-碘苯酚通过取代反应生成式(IV)所示化合物，
Figure BDA0002999981030000033
步骤3：将4-(2,7-二溴咔唑-9-基)苯胺，式(IV)所示化合物和1,10-菲咯啉通过取代反应制得式(III)所示化合物。
优选的，式(II)所示化合物通过以下步骤制备：
步骤1：将2,7-二溴芴通过反应制得2,7-二溴芴酮；
步骤2：将所述2,7-二溴芴酮通过反应制得2,7-二溴-9,9-双(4-羟基苯基)芴；
步骤3：将所述2,7-二溴-9,9-双(4-羟基苯基)芴与3-(6-溴己基甲基)-3-乙基氧杂环丁烷通过反应制得式(II)所示化合物。
本发明的有益效果如下：
本发明实施例中启亮电压最低为3.6V，本发明最大流明效率可达2.12cd/A，最大亮度也达到了10056cd/m2，外量子效率可达76％，从色坐标上看，所有聚合物的色坐标均表示为红光。
附图说明
图1为本发明实施例制得的聚合物在甲苯溶液中的紫外-可见吸收和光致发光光谱；
图2为本发明实施例制得的聚合物在薄膜状态下的紫外-可见吸收光谱和光致发光光谱；
图3为本发明实施例制得的聚合物的单层器件的电流效率-电流密度(LE-J)曲线。
具体实施方式
下面结合具体实施例对本发明做进一步详细说明，但实施例并不对本发明做任何形式的限定。除非特别说明，本发明采用的试剂、方法和设备为本技术领域常规试剂、方法和设备。
实施例1
在0-5℃下，向250ml的单口瓶内加入3，4-乙撑二氧噻吩(5mL，27.86mmol)，冰醋酸(50ml)及浓硫酸(50ml)，避光搅拌。然后分三次加(12.3g，180mmol)N-溴代丁二酰亚胺(NBS)，再逐渐升至室温，反应过夜。用大量水稀释反应液，分离出固体，然后反复用NaHCO3水溶液和甲醇洗涤数次，晾干后用热氯苯溶剂纯化，制得式(V)所示化合物(4.3g，产率70％)，其化学反应方程式为：
Figure BDA0002999981030000051
实施例2
将150mlDMF与式(V)所示化合物(39.7g，180mmol)，4-碘苯酚(25.36g，115.27mmol)和碳酸钾(31.74g，229.65mmol)中。将反应混合物在氮气下加热至80℃回流过夜。然后将混合物冷却至室温，并加入200ml冷水。随后将混合物用500ml二氯甲烷萃取。合并有机相，并用500ml饱和盐水洗涤，用硫酸镁干燥并蒸发溶剂。将取得的粗产物通过柱色谱法(石油醚)纯化，得到式(IV)所示化合物(46.6g，72％),其化学反应方程式为：
Figure BDA0002999981030000052
实施例3
在4-(2,7-二溴咔唑-9-基)苯胺(6.24g，15mmol)，式(IV)所示化合物(10.08g，28mmol)，氯化铜(0.05g，0.51mmol)和氢氧化钾(4g，71.3mmol)中加入50ml甲苯，然后在氩气下回流反应48小时。然后将反应混合物冷却至室温并加入200ml水，再用200ml二氯甲烷萃取3次，合并有机相用水洗涤并且硫酸镁干燥，将溶剂蒸发，将粗产物以石油醚：三乙胺＝20:1为洗脱剂进行硅胶柱色谱纯化，得到式(III)所示化合物(11.6g，88％)，其化学反应方程式为：
Figure BDA0002999981030000061
实施例4
将9,10－菲醌(21g，100mmol)，苯胺(36.6ml，200mmol)，溴苯甲醛(18.5g，100mmol)和醋酸铵(38.5g，500mmol)加入到500ml圆底烧瓶中，再用300ml冰醋酸溶解。氮气保护下，110℃下搅拌回流4小时。将反应物倒入100ml冰水中，抽滤。将抽滤所得固体以石油醚：二氯甲烷＝1:1为洗脱剂经柱层析分离，乙醇重结晶，真空烘箱烘干，得到2－(4－溴苯基)－1－苯基－1H－菲并咪唑(34g，产率75％)，其化学反应方程式为：
Figure BDA0002999981030000062
实施例5
将2－(4－溴苯基)－1－苯基－1H－菲并咪唑(3.73g，10mmol)，联硼酸频哪醇酯(7.62g，30mmol)，醋酸钾(2.94g，30mmol)，[1,1’-双(二苯基膦基)二茂铁]二氯化钯(0.2g，1mmol)加入到500ml圆底烧瓶中，并溶解于50ml二氧六环中，在氮气保护，90℃下搅拌回流72小时。反应结束后，用二氯甲烧萃取，以石油醚：二氯甲烷＝1:2为洗脱剂通过硅胶柱层析分离，旋转蒸发浓缩萃取液，真空烘箱烘干，得到1－苯基－2－(4－(4，4，5，5－四甲基－1，3，2－二氧硼酯－2－基)苯基)－1H－菲并咪唑(3.48g，产率62％)，其化学反应方程式为：
Figure BDA0002999981030000071
实施例6
向500ml的单口瓶中加入2,7-二溴芴(12.94g,40mmol)和240mL乙酸，冰浴下使反应体系的温度维持在0～3℃，分批加入CrO3(2.99g，30mmol)。然后在室温下机械搅拌反应过夜，体系由黑变绿。反应结束后，将反应混合物倒入大量水中，抽滤出固体，并用稀盐酸洗涤三次，除去未反应的三氧化铬，然后用水洗涤几次，直至产物变黄色，然后干燥，最后用异丙醇重结晶得产物2,7-二溴芴酮(11.88g，产率74％)，其化学反应方程式为
Figure BDA0002999981030000072
实施例7
在150ml的二颈瓶中加入2,7-二溴芴酮(0.604g，25mmol)、苯酚(9.4g,100mmol)以及60ml四氯化碳，向二颈瓶中通氮气搅拌并加热至85℃，待体系溶解时，加入甲烷磺酸(11.93g,50mmol)，回流反应过夜，在反应过程中大量的白色固体析出，液相为淡红褐色。反应结束后，冷却至室温，抽滤，再用二氯甲烷洗几次至白色，干燥得到产物2,7-二溴-9,9-双(4-羟基苯基)芴(7.3g，产率65％)，其化学反应方程式为：
Figure BDA0002999981030000081
实施例8
在100mlSchlenk瓶中将2,7-二溴-9,9-双(4-羟基苯基)芴(2.54g，5mmol)溶解在30ml二甲基亚砜(DMSO)中，抽换氮气三次。在搅拌下分批加入3-(6-溴己基甲基)-3-乙基氧杂环丁烷(4.16g，15mmol)。将该混合物脱气3次。再加入细KOH(0.98，15mmol)。反应在60±8℃下进行，6小时后，将混合物冷却至室温，并用30ml水稀释。用乙醚萃取水相。收集有机相并用无水硫酸镁干燥。除去溶剂后，将所得油状物通过硅胶柱色谱法纯化，并以甲苯/乙酸乙酯(3∶2)作为洗脱剂，得到产物式(II)所示化合物(3.39g，产率75％)，其化学反应方程式为：
Figure BDA0002999981030000082
实施例9
将1－苯基－2－(4－(4，4，5，5－四甲基－1，3，2－二氧硼酯－2－基)苯基)－1H－菲并咪唑(0.105g，0.25mmol)，式(IV)所示化合物(0.16g,0.25mmol)和式(III)所示化合物(0.2g,0.25mmol)，式(II)所示化合物(0.226g，0.25mmol)加入到20ml精制甲苯和10ml四氢呋喃的混合溶液中，氩气气氛中加热搅拌，10min后加入10mg四(三苯基膦)钯，温度稳定在80℃时加入1mL浓度为20％的四乙基羟氨水溶液，30min后停止通气，氩气气氛中反应20h。之后加入苯硼酸(50mg，0.4mmol)封端并反应12h，接着加入溴苯(125mg，0.8mmol)封端并继续反应6h。将反应停止并冷却到室温，沉析到250mL甲醇中，过滤干燥后索氏提取(先后用甲醇，丙酮和正己烷各抽提12h)。之后将聚合物干燥，用甲苯溶解，以200-300目硅胶为固定相，石油醚：二氯甲烷＝4:1为洗脱剂进行柱层析，将溶液浓缩后再次沉析到甲醇中，固体过滤后放入真空干燥箱干燥，得到聚合物P1(0.85g，产率78％)，其化学反应方程式为：
Figure BDA0002999981030000091
实施例10
本实施例与实施例9的区别为：本实施例在氩气气氛中反应时间为30h，而实施例9在氩气气氛中的反应时间为20h，最终制得聚合物P2(0.98g，产率76％)。
实施例11
本实施例与实施例9的区别为：本实施例在氩气气氛中反应时间为40h，而实施例9在氩气气氛中的反应时间为20h，最终制得聚合物P3(1.04g，产率76％)。
本发明实施例的紫外-可见吸收光谱(UV-Vis)通过日本Shimadzu UV-2600分光光度计测定；荧光发射光谱(PL)通过美国Perkin-Elmer LS45X和日立F-4600荧光分光光度计测定。图1为本发明实施例制得的聚合物在甲苯溶液中的紫外-可见吸收(左)和光致发光光谱(右)；由于咔唑主链的π-π*跃迁，本发明在450nm附近均出现明显的吸收峰。所有聚合物均在610nm和630nm附近出现主峰和肩峰的特征发射。随着反应温度的提高，本发明实施例制得的聚合物的吸收和发射光谱有轻微的红移和宽化，这是由于聚合物中的D-A作用引起分子内电荷转移(ICT)导致的。
图2为本发明实施例制得的聚合物在薄膜状态下的紫外-可见吸收光谱(左)和光致发光光谱(右)，由图2可知，随着反应温度的提高，聚合物的吸收和发射光谱与在甲苯中的变化趋势相似，均表现出明显的红移和宽化，且聚合物无论在薄膜状态还是甲苯溶液中均位于红光区域。
图3为本发明实施例制得的聚合物的单层器件的电流效率-电流密度(LE-J)曲线，其中，电流效率-电流密度曲线采用Keithley 2420和Konica Minolta Chromameter CS-200测试，如图3所示，随着电流密度的增加，聚合物电流效率的滚降速度较缓，具有较好的电流效率稳定性。
表1本发明实施例制得聚合物的电致发光性能
实施例 V<sub>on</sub> L(cd/m<sup>2</sup>) LE(cd/A) CIE(x，y) PLQE(％)
实施例9 3.8 7896 1.38 (0.67,0.33) 64％
实施例10 3.8 10056 1.99 (0.66,0.34) 72％
实施例11 3.6 9875 2.12 (0.67,0.34) 76％
由表1可知，本发明实施例制得的聚合物的启亮电压有所降低，从表中数据可以看出，启亮电压最低为3.6V，本发明最大流明效率可达2.12cd/A，最大亮度也达到了10056cd/m2，荧光量子产率可达76％，从色坐标上看，所有聚合物的色坐标均表示为红光。
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，其他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 (7)

1.一种红光聚合物，其特征在于，其化学式如式(I)所示：
Figure FDA0002999981020000011
其中，x+y＝0.5，n＝1-300，R为芳基、三苯胺基、碳原子数为1-20的直链或支链烷基，或者碳原子数1～20的烷氧基。
2.根据权利要求1所述的一种红光聚合物，其特征在于，其化学式为
Figure FDA0002999981020000012
3.一种红光聚合物的制备方法，其特征在于，包括将1－苯基－2－(4－(4，4，5，5－四甲基－1，3，2－二氧硼酯－2－基)苯基)－1H－菲并咪唑，式(IV)所示化合物，式(II)所示化合物，式(III)所示化合物通过Suzuki偶联反应制得式(I)所示聚合物；
Figure FDA0002999981020000021
4.根据权利要求3所述的红光聚合物的制备方法，其特征在于，所述Suzuki偶联反应的温度为80℃。
5.根据权利要求3所述的红光聚合物的制备方法，其特征在于，所述Suzuki偶联反应的时间为20h-40h。
6.根据权利要求3所述的红光聚合物的制备方法，其特征在于，所述式(III)所示化合物的制备方法包括以下步骤：
步骤1：将3,4-乙撑二氧噻吩通过溴化反应制得式(V)所示化合物，
Figure FDA0002999981020000031
步骤2：将式(V)所示化合物与4-碘苯酚通过取代反应生成式(IV)所示化合物，
Figure FDA0002999981020000032
步骤3：将4-(2,7-二溴咔唑-9-基)苯胺，式(IV)所示化合物和1,10-菲咯啉通过取代反应制得式(III)所示化合物。
7.根据权利要求4所述的红光聚合物的制备方法，其特征在于，式(II)所示化合物通过以下步骤制备：
步骤1：将2,7-二溴芴通过反应制得2,7-二溴芴酮；
步骤2：将所述2,7-二溴芴酮通过反应制得2,7-二溴-9,9-双(4-羟基苯基)芴；
步骤3：将所述2,7-二溴-9,9-双(4-羟基苯基)芴与3-(6-溴己基甲基)-3-乙基氧杂环丁烷通过反应制得式(II)所示化合物。
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