CN107286291A - 一种高偏振荧光薄膜及其制备方法 - Google Patents
一种高偏振荧光薄膜及其制备方法 Download PDFInfo
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- SXGBREZGMJVYRL-UHFFFAOYSA-N butan-1-amine;hydrobromide Chemical compound [Br-].CCCC[NH3+] SXGBREZGMJVYRL-UHFFFAOYSA-N 0.000 description 1
- QNEFNFIKZWUAEQ-UHFFFAOYSA-N carbonic acid;potassium Chemical compound [K].OC(O)=O QNEFNFIKZWUAEQ-UHFFFAOYSA-N 0.000 description 1
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- GQPLMRYTRLFLPF-UHFFFAOYSA-N nitrous oxide Inorganic materials [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
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- 235000010288 sodium nitrite Nutrition 0.000 description 1
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Abstract
本发明公开了一种高偏振荧光薄膜的制备方法,将荧光二色性染料和一种可聚合的具有高度有序的近晶B相的液晶材料混合,得到二色性混合物,将二色性混合物在5µm反平行摩擦的液晶盒于近晶B相实现分子有序取向,进而在45℃下进行聚合制备成膜,实现高线偏振度。基于此,此类使分子取向制备高偏振薄膜的技术在光学和液晶显示领域具有广阔的应用前景。
Description
技术领域
本发明属于偏振光学领域,具体涉及一种高偏振荧光薄膜及其制备方法。
背景技术
偏振光在光学存储、信号传输和显示领域等具有广泛的应用。单一的发光分子具有偏振性,而聚集态的发光分子由于排列的无序性不具有偏振性。此外,一般的发光分子的偶极矩与分子长轴存在一定的夹角,所以很难通过诱导分子有序取向来实现高偏振度。而液晶材料易于在外界刺激下实现分子有序取向。因此,将一种分子长轴与偶极矩方向平行的二色性染料和一种具有高度有序性液晶相的液晶材料在有序排列下制备成薄膜是目前急需解决的问题
发明内容
本发明旨在提供一种将荧光二色性染料和液晶材料聚合成网络制成高偏振薄膜的方法,此方法将一种分子长轴与偶极矩方向平行的荧光二色性染料和一种具有高度有序的液晶相态的液晶材料混合,并制备了高偏振荧光薄膜。
本发明所采用的技术方案为:
一种高偏振荧光薄膜的制备方法,其特征在于:将一种荧光二色性染料和一种可聚合的具有高度有序的近晶B相的液晶材料,通过365nm紫外光引发聚合形成薄膜,具有高偏振荧光,具体操作如下:
(1)按照液晶材料:荧光二色性染料:光引发剂:抑制剂=1:(0.015-0.025):(0.009-0.011):0.001的比例,分别称取液晶材料、荧光二色性染料、光引发剂和抑制剂,然后将称取的所有原料混合,得到二色性混合物;
(2)将步骤(1)制得的二色性混合物在118-122℃的温度下灌入4-6μm反平行摩擦的液晶盒中,在摩擦方向的诱导下,分子发生取向,待材料灌满液晶盒后,再降温至44-46℃时,使用365nm的紫外灯光照引发聚合,使液晶分子和荧光二色性染料分子在高度有序排列下聚合成网络制成薄膜,实现高偏振荧光。
所述的高偏振荧光薄膜的制备方法,其特征在于:所述的荧光二色性染料的结构通式如下所示:
其中n=6,7,8,9,10,11,12。
所述的高偏振荧光薄膜的制备方法,其特征在于,所述的荧光二色性染料的合成方法:以4,7-二溴-2,1,3-苯并噻二唑、对甲氧基苯硼酸为原料,采用铃木反应、水解反应、取代反应得到荧光二色性染料。
所述的高偏振荧光薄膜的制备方法,其特征在于,所述的荧光二色性染料的合成反应路线为:
所述的高偏振荧光薄膜的制备方法,其特征在于,所述的荧光二色性染料的具体合成步骤如下:
(1)中间体1的制备
称取11.7-11.8g 4,7-二溴-2,1,3-苯并噻二唑和15.1-15.2g对甲氧基苯硼酸,用210-220mL 1,4-二氧六环溶解,氮气环境保护,再称取16.5-16.6g K2CO3配成 2M水溶液加入烧瓶中搅拌,再加入3.4-3.5g Pd(PPh3)4,控制反应温度103-105℃,回流反应24h,反应结束后冷却至室温,经抽滤、真空干燥后得到中间体1;
(2)中间体2的制备
称取4.5-4.7g步骤(1)制得的中间体1,加入100-120mL溴化氢醋酸溶液,再加入4.5-4.7g四正丁基溴化铵,控制反应温度70-72℃,回流反应24h,反应结束后冷却至室温,滤出固体,用水洗涤3-4次,用甲醇、二氯甲烷冲洗,真空干燥后得到中间体2;
(3)中间体3的制备
称取5.0-5.1g溴代烷烃,用50mL二氯甲烷溶解,加入3.5-3.7mL三乙胺,再滴加1.7-1.8mL丙烯酰氯,冰浴下搅拌30min后恢复室温搅拌过夜,反应结束后加入30mL水,摇匀后分液萃取,有机层干燥后得中间体3;
(4)目标产物T的制备
称取1.2-1.3g步骤(2)制得的中间体2和1.3-1.4g K2CO3,加入25mL DMF 使其溶解,加热搅拌30min后加入2.0-2.1g步骤(3)制得的中间体3,控制反应温度90-92℃,回流反应24h,反应结束后冷却至室温,将体系倒入300mL水中稀释,经二氯甲烷萃取、硅胶柱层析得到目标产物T。
所述的新型荧光二色性染料,其特征在于:所述荧光二色性染料在液体和固体状态下均具有高的荧光量子效率ρ=0.85和高的二色性比DR=10。
所述的高偏振荧光薄膜的制备方法,其特征在于:所述含有高度有序的近晶B相的液晶材料的结构通式如下所示:
所述的高偏振荧光薄膜的制备方法,其特征在于:所述的可聚合的具有高度有序的近晶B相的液晶材料的制备方法如下:以对羟基苯甲酸乙酯、4,4'-二氨基联苄和6-溴己醇为原料,采用取代反应、水解反应、重氮化反应和酯化反应得到含有高度有序的近晶B相的液晶材料,合成反应路线为:
具体合成步骤如下:
(1)中间体4的制备
称取9.9-10.0g对羟基苯甲酸乙酯,加入80mL DMF使其溶解,加入9.9-10.2g 碳酸钾,加热搅拌半小时后加入10.8-10.9g 6-溴己醇,控制反应温度90-92℃,回流反应24h,反应结束后冷却至室温,将体系倒入600mL水中稀释,经乙醚萃取、干燥、旋蒸得到中间体4;
(2)中间体5的制备
称取12.0-12.2g步骤(1)制得的中间体4,加入100mL THF使其溶解,再加入4.8-4.9g NaOH水溶液50mL,控制反应温度85-90℃,回流反应24h,反应结束后冷却至室温,抽滤,加入溶解,调pH使产物析出,抽滤、真空干燥得中间体5;
(3)中间体6的制备
称取5.0-5.1g步骤(2)制得的中间体5,加入500mL THF使其溶解,加入 7.1-7.2mL三乙胺,在冰浴下滴加1.5mL丙烯酰氯,0℃下搅拌30min后恢复室温搅拌过夜,反应结束后,将体系浓缩,加水稀释,经萃取、硅胶柱层析得中间体6;
(4)中间体7的制备
称取10.5-10.6g 4,4'-二氨基联苄,加入200mL水和32mL浓盐酸,冰浴下滴加7.5-7.6g亚硝酸钠水溶液50mL,0℃下搅拌30min后加入三勺尿素,控制反应温度100-105℃,回流反应30min,反应结束后冷却至室温,抽滤、水洗,滤饼用 12.0-12.1g NaOH水溶液300mL溶解,加五勺活性炭脱色,调pH使产物析出,经萃取、干燥得到中间体7;
(5)中间体8的制备
称取9.0-9.2g步骤(4)制得的中间体7和3.2-3.3g碳酸钾,加入2.9-3.0g 6- 溴己醇,再加入50mL DMF,控制反应温度90-92℃,回流反应24h,反应结束后冷却至室温,将体系倒入300mL水中稀释,调pH至4-5,经抽滤、硅胶柱层析得到中间体8;
(6)中间体9的制备
称取5.0-5.2g步骤(5)制得的中间体8,加入80mL THF使其溶解,加入 4.5-4.6mL三乙胺,冰浴下滴加1.3-1.4mL丙烯酰氯,0℃下搅拌30min后恢复室温搅拌过夜,反应结束后,将体系浓缩,加水稀释,经萃取、硅胶柱层析得中间体9;
(7)目标产物AHPPAHB的制备
称取1.9-2.0g步骤(3)制得的中间体6和2.4-2.5g步骤(6)制得的中间体9,加入0.08g DMAP和50mL二氯甲烷,冰浴下搅拌15min后加入1.3-1.4g DCC, 0℃下搅拌30min后恢复室温搅拌过夜,反应结束后,经抽滤、重结晶得到目标产物AHPPAH。
所述的液晶材料的液晶相出现在30-106℃温度范围内,具有高度有序的近晶 B相和可聚合的末端。
所述的高偏振荧光薄膜的制备方法,其特征在于:所述的液晶材料的液晶相出现在30-106℃温度范围内,具有高度有序的近晶B相和可聚合的末端。
采用本发明方法制得的高偏振荧光薄膜。
本发明的有益效果:
本发明设计将液晶材料、荧光二色性染料、光引发剂和抑制剂掺杂得到二色性混合物,灌入到5μm反平行摩擦的液晶盒中通过紫外光引发聚合制成薄膜,实现高偏振荧光,简单易操作,可以应用于光学存储、信号传输和液晶显示技术中,为其带来进一步的发展。
附图说明
图1为本发明所使用的液晶材料降温过程中各个液晶相态的偏光图。
图2为本发明所制备的二色性混合物在5μm反平行摩擦的液晶盒中不同液晶相态下的偏振吸收图。
图3为本发明所制备的二色性混合物在5μm反平行摩擦的液晶盒中不同聚合时间下的对比度和有序参数值。
图4为本发明所制备的二色性混合物在5μm反平行摩擦的液晶盒中聚合成薄膜前后的偏振吸收图。
图5为发明所制备的二色性混合物在5μm反平行摩擦的液晶盒中聚合成薄膜与二色性混合物的热稳定性对比图。
具体实施方式
实施例1
近晶B相液晶材料的制备,合成路线为:
具体合成步骤如下:
1.1中间体4的制备
称取9.9g对羟基苯甲酸乙酯,加入80mL DMF使其溶解,加入10.0g碳酸钾,加热搅拌半小时后加入10.8g 6-溴己醇,控制反应温度90℃,回流反应24h,反应结束后冷却至室温,将体系倒入600mL水中稀释,经乙醚萃取、干燥、旋蒸得到中间体4(12.3g),产率77%。
1.2中间体5的制备
称取12.1g步骤(1)制得的中间体4,加入100mL THF使其溶解,再加入 4.8g NaOH水溶液50mL,控制反应温度90℃,回流反应24h,反应结束后冷却至室温,抽滤,加入溶解,调pH使产物析出,抽滤、真空干燥得中间体5(10.0g),产率93%。
1.3中间体6的制备
称取5.1g步骤(2)制得的中间体5,加入500mL THF使其溶解,加入7.2mL 三乙胺,在冰浴下滴加1.5mL丙烯酰氯,0℃下搅拌30min后恢复室温搅拌过夜,反应结束后,将体系浓缩,加水稀释,经萃取、硅胶柱层析得中间体6(5.5g),产率88%。
1.4中间体7的制备
称取10.6g 4,4'-二氨基联苄,加入200mL水和32mL浓盐酸,冰浴下滴加7. 6g亚硝酸钠水溶液50mL,0℃下搅拌30min后加入三勺尿素,控制反应温度 105℃,回流反应30min,反应结束后冷却至室温,抽滤、水洗,滤饼用12.0g NaOH 水溶液300mL溶解,加五勺活性炭脱色,调pH使产物析出,经萃取、干燥得到中间体7(8.5g),产率81%。
1.5中间体8的制备
称取9.1g步骤(4)制得的中间体7和3.2g碳酸钾,加入2.9g 6-溴己醇,再加入50mLDMF,控制反应温度90-92℃,回流反应24h,反应结束后冷却至室温,将体系倒入300mL水中稀释,调pH至4,经抽滤、硅胶柱层析得到中间体 8(9.6g),产率72%
1.6中间体9的制备
称取5.1g步骤(5)制得的中间体8,加入80mL THF使其溶解,加入4.5mL 三乙胺,冰浴下滴加1.4mL丙烯酰氯,0℃下搅拌30min后恢复室温搅拌过夜,反应结束后,将体系浓缩,加水稀释,经萃取、硅胶柱层析得中间体9(4.5g),产率75%。
1.7目标产物AHPPAHB的制备
称取2.0g步骤(3)制得的中间体6和2.4g步骤(6)制得的中间体9,加入 0.08gDMAP和50mL二氯甲烷,冰浴下搅拌15min后加入1.4g DCC,0℃下搅拌30min后恢复室温搅拌过夜,反应结束后,经抽滤、重结晶得到目标产物液晶材料AHPPAH(2.7g),产率65%。
实施例2荧光二色性染料的合成
2.1合成路线为:
2.2具体合成步骤如下:
a、中间体1的制备
称取11.7g 4,7-二溴-2,1,3-苯并噻二唑和15.2g对甲氧基苯硼酸,用210mL 1,4-二氧六环溶解,氮气环境保护,再称取16.5g K2CO3配成2M水溶液加入烧瓶中搅拌,再加入3.5g Pd(PPh3)4,控制反应温度103-105℃,回流反应24h,反应结束后冷却至室温,经抽滤、真空干燥后得到中间体1(9.5g),产率68%;
b、中间体2的制备
称取4.6g步骤(1)制得的中间体1,加入100mL溴化氢醋酸溶液,再加入 4.6g四正丁基溴化铵,控制反应温度70℃,回流反应24h,反应结束后冷却至室温,滤出固体,用水洗涤3-4次,用甲醇、二氯甲烷冲洗,真空干燥后得到中间体2(3.8g),产率87%。
c、中间体3的制备
称取5.1g溴代烷烃,用50mL二氯甲烷溶解,加入3.6mL三乙胺,再滴加 1.8mL丙烯酰氯,冰浴下搅拌30min后恢复室温搅拌过夜。反应结束后加入30mL 水,摇匀后分液萃取,有机层干燥后得中间体3(4.5g),产率74%。
d、目标产物T的制备
称取1.2步骤(2)制得的中间体2和1.3g K2CO3,加入25mL DMF使其溶解,加热搅拌30min后加入2.1g步骤(3)制得的中间体3,控制反应温度90℃,回流反应24h,反应结束后冷却至室温,将体系倒入300mL水中稀释,经二氯甲烷萃取、硅胶柱层析得到目标产物荧光二色性染料T(4.2g),产率67%。
实施例3二色性混合物的制备
按照液晶材料AHPPAH:荧光二色性染料T:光引发剂:抑制剂=1:0.015:0.01:0.001的比例,分别称取配备浓度为1g/mL的液晶材料二氯甲烷溶液1mL,浓度为1.5mg/mL的荧光二色性染料二氯甲烷溶液1mL,浓度为1mg/mL 的光引发剂二氯甲烷溶液1mL,浓度为0.1mg/mL的光引发剂二氯甲烷溶液1mL。将所有溶液混合,除去溶剂后得到所需的二色性混合物。
实施例4高偏振薄膜的制备
将5μm反平行摩擦的液晶盒置于热台上,加热至120℃后预热10min后,将上述实施例2制备的二色性混合物在120℃利用虹吸作用灌入液晶盒中,在摩擦方向的诱导下,分子发生取向。待材料灌满液晶盒后,降温至45℃,使用365nm 的紫外灯光照引发聚合,聚合时间为30min。通过聚合成网络,荧光二色性染料分子和液晶材料在近晶B相的有序排列得以保存下来,实现高偏振荧光。
以上详细描述了本发明的较佳具体实施例。应当理解,本领域的普通技术无需创造性劳动就可以根据本发明的构思作出诸多修改和变化。因此,凡本技术领域中技术人员依本发明的构思在现有技术的基础上通过逻辑分析、推理或者有限的实验可以得到的技术方案,皆应在由权利要求书所确定的保护范围内。
Claims (8)
1.一种高偏振荧光薄膜的制备方法,其特征在于:将荧光二色性染料和可聚合的具有高度有序的近晶B相的液晶材料通过365nm紫外光引发聚合形成薄膜,具体操作如下:
(1)按照液晶材料:荧光二色性染料:光引发剂:抑制剂=1:(0.015-0.025):(0.009-0.011):0.001的比例,分别称取液晶材料、荧光二色性染料、光引发剂和抑制剂,然后将称取的所有原料混合,得到二色性混合物;
(2)将步骤(1)制得的二色性混合物在118-122℃的温度下灌入4-6μm反平行摩擦的液晶盒中,在摩擦方向的诱导下,分子发生取向,待材料灌满液晶盒后,再降温至44-46℃时,使用365nm的紫外灯光照引发聚合,使液晶分子和荧光二色性染料分子在高度有序排列下聚合成网络,制成薄膜,实现高偏振荧光。
2.根据权利要求1所述的高偏振荧光薄膜的制备方法,其特征在于:所述的荧光二色性染料的结构通式如下所示:
其中n=6,7,8,9,10,11,12。
3.根据权利要求1所述的高偏振荧光薄膜的制备方法,其特征在于,所述的荧光二色性染料的合成方法:以4,7-二溴-2,1,3-苯并噻二唑、对甲氧基苯硼酸为原料,采用铃木反应、水解反应、取代反应得到荧光二色性染料。
4.根据权利要求3所述的高偏振荧光薄膜的制备方法,其特征在于,所述的荧光二色性染料的合成反应路线为:
5.根据权利要求4所述的高偏振荧光薄膜的制备方法,其特征在于,所述的荧光二色性染料的具体合成步骤如下:
(1)中间体1的制备
称取11.7-11.8g 4,7-二溴-2,1,3-苯并噻二唑和15.1-15.2g对甲氧基苯硼酸,用210-220mL 1,4-二氧六环溶解,氮气环境保护,再称取16.5-16.6g K2CO3配成2M水溶液加入烧瓶中搅拌,再加入3.4-3.5g Pd(PPh3)4,控制反应温度103-105℃,回流反应24h,反应结束后冷却至室温,经抽滤、真空干燥后得到中间体1;
(2)中间体2的制备
称取4.5-4.7g步骤(1)制得的中间体1,加入100-120mL溴化氢醋酸溶液,再加入4.5-4.7g四正丁基溴化铵,控制反应温度70-72℃,回流反应24h,反应结束后冷却至室温,滤出固体,用水洗涤3-4次,用甲醇、二氯甲烷冲洗,真空干燥后得到中间体2;
(3)中间体3的制备
称取5.0-5.1g溴代烷烃,用50mL二氯甲烷溶解,加入3.5-3.7mL三乙胺,再滴加1.7-1.8mL丙烯酰氯,冰浴下搅拌30min后恢复室温搅拌过夜,反应结束后加入30mL水,摇匀后分液萃取,有机层干燥后得中间体3;
(4)目标产物T的制备
称取1.2-1.3g步骤(2)制得的中间体2和1.3-1.4g K2CO3,加入25mL DMF使其溶解,加热搅拌30min后加入2.0-2.1g步骤(3)制得的中间体3,控制反应温度90-92℃,回流反应24h,反应结束后冷却至室温,将体系倒入300mL水中稀释,经二氯甲烷萃取、硅胶柱层析得到目标产物T。
6.根据权利要求1所述的新型荧光二色性染料,其特征在于:所述荧光二色性染料在液体和固体状态下均具有高的荧光量子效率ρ=0.85和高的二色性比DR=10。
7.根据权利要求1所述的高偏振荧光薄膜的制备方法,其特征在于:所述含有高度有序的近晶B相的液晶材料的结构通式如下所示:
8.如权利要求1所述的高偏振荧光薄膜的制备方法制得的高偏振荧光薄膜。
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Publication number | Priority date | Publication date | Assignee | Title |
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CN102338954A (zh) * | 2011-10-26 | 2012-02-01 | 合肥工业大学 | 电控彩色滤色液晶光阀 |
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CN103641742A (zh) * | 2013-11-14 | 2014-03-19 | 合肥工业大学 | 一种新型液晶发光材料及其制备方法 |
Cited By (1)
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---|---|---|---|---|
CN110456581A (zh) * | 2018-05-07 | 2019-11-15 | 青岛海信电器股份有限公司 | 一种显示面板以及显示设备 |
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