CN106519733B - 一类含3位取代基的苯绕蒽酮液晶染料,其制备方法及应用 - Google Patents
一类含3位取代基的苯绕蒽酮液晶染料,其制备方法及应用 Download PDFInfo
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Abstract
本发明公开了一类含3位取代基的苯绕蒽酮液晶染料,其制备方法及应用。本发明以3‑溴苯绕蒽酮为母体在3‑位引入不同的乙炔基增加分子在液晶中的溶解度,增强分子的线性结构进而改善液晶化合物的二向色性;利用苯环上高度离域的电子与母体形成大共轭体系。本发明合成一类苯绕蒽酮类荧光二向性液晶染料最大吸收波长集中在可见光区,发射波长集中在500nm左右,液晶染料化合物结构新颖,原料易得,合成方法简单;在液晶中具有较好的二向色比以及有序参数,可用于制造液晶显示产品,尤其在宾主型液晶显示器具有高的二向色性。
Description
技术领域
本发明涉及一种含有3位不同取代的新型苯绕蒽酮类液晶染料化合物及其应用,属于显示材料领域。
背景技术
信息化的高速发展带动了液晶平板技术和产业的发展,传统的阴极射线管(CRT)技术已经被平板显示所取代,平板显示器给人们的生活带来了革命性的变化。
“宾-主”显示是近些年来兴起的新型显示模式。“宾-主”(GH)模式是显示有色变化的工作模式,是由G.Heilmeier等与DS模式几乎同时提出来的。在向列相液晶主材料中掺杂一些二向色性染料构成一对“宾-主”材料,对其施加电场,液晶分子发生取向而变化。“宾-主”(GH)模式就是利用改变分子取向的二色性染料光吸收来实现显示。
荧光“宾-主”型显示器是传统“宾-主”型显示器的改进,它是将荧光二向性染料应用于液晶显示中,这样不仅吸收光的强度,而且发射光的强度也可以通过电场来控制,从而将发射型显示器的优点和传统液晶显示器的特点集于一体,制成更加便携的低功耗电子器件。纯的液晶材料已经不能满足液晶材料的各种特性,如光、电、热等。于是利用液晶化合物或染料来复配液晶材料借以获得性能更加优越的液晶材料成为一个很明显的趋势。复配的液晶染料可以获得更高更稳定的液晶相温度范围、更高的清亮点以及调节折射率的功能。
发明内容
为解决现有技术中存在的缺少性能良好的荧光二向色性染料的问题,本发明提供的液晶染料,可作为荧光二向性染料适用于液晶显示产品。
本发明的技术目的之一在于提供一类新型的液晶染料。
本发明的另一技术目的在于提供上述液晶染料化合物的制备方法,包括以下步骤:
分别将4’-乙炔基-4-烷基联苯、对正丁氧基苯乙炔、1-正癸炔、对乙炔基苯甲酸乙酯与3-溴苯绕蒽酮偶联得到所述液晶染料化合物;
所述4’-乙炔基-4-烷基联苯的制备方法为:4’-溴-4-烷基联苯与2-甲基-3-丁炔-2-醇偶联,经过碱处理得到4’-乙炔基-4-烷基联苯;
所述4’-溴-4-烷基联苯选自4’-溴-4-乙基联苯、4’-溴-4-正戊基联苯。
具体的合成线路如下:
进一步地,将4’-溴-4-正戊基联苯或4’-溴-4-乙基联苯与2-甲基-3-丁炔-2-醇进行反应时,二者的最佳混合摩尔比为1:1,以干燥三乙胺作为反应溶剂,加入催化量的三苯基膦氯化钯、三苯基膦和碘化亚铜催化剂,在氮气保护条件下磁力搅拌加热至回流。反应8h后TLC跟踪监测至反应完全减压除去多余溶剂,固体产物过硅胶柱层析,得固体(化合物1)。
进一步地,将化合物1加入双口瓶中加入无水乙醇磁力搅拌加热使之溶解,加入过量的氢氧化钾,加热至回流,氢氧化钾逐渐溶解,跟踪监测反应的进行程度,不断补加KOH。持续回流数小时后停止反应,此时反应溶液呈褐色。冷却至室温,将反应产物倒入水里,用盐酸溶液调节pH值到中性析出大量黄色沉淀,抽滤、洗涤后干燥得黄白色固体,粗产物过硅胶柱层析,得到固体4’-乙炔基-4-乙基联苯、4’-乙炔基-4-正戊基联苯(化合物2)
进一步地,分别将4’-乙炔基-4-乙基联苯、4’-乙炔基-4-正戊基联苯、对正丁氧基苯乙炔、1-正癸炔、对乙炔基苯甲酸乙酯与3-溴苯绕蒽酮进行反应时,二者的最佳混合摩尔比为1:1,以干燥三乙胺作为反应溶剂,加入催化量的三苯基膦氯化钯、三苯基膦和碘化亚铜催化剂,在氮气保护条件下磁力搅拌加热至回流。反应8h后TLC跟踪监测至反应完全减压除去多余溶剂,固体产物过硅胶柱层析,得橙黄色固体(F)液晶染料。
本发明另一方面提供上述液晶染料化合物作为荧光二向色性染料在制造液晶显示产品中的应用。所述的液晶显示产品是宾主型液晶显示器。具体地,是用作宾体液晶染料,应用于制备宾主型液晶显示器。
本发明提供一类宾主型液晶显示器,所述的液晶显示器以本发明所述的液晶染料化合物作为宾体液晶染料。
此外,本发明的液晶化合物还具有液晶相,所述的液晶主体为近晶相液晶、向列相液晶或者胆甾相液晶。
本发明的化合物具有液晶相,可与液晶E7混合应用于液晶显示器。
发明有益效果
第一、本发明以苯绕蒽酮为母体,在3-位引入不同取代的乙炔基,增强分子的线性结构进而改善染料的二向色性,液晶化合物结构新颖,原料易得,合成方法简单;
第二、本发明合成5个苯绕蒽酮类荧光二向性液晶染料最大吸收波长集中在可见光区,发射波长集中在500nm左右,发射鲜艳的黄绿色荧光,在二氯甲烷以及不同溶剂中摩尔消光系数均超过104。在液晶E7中表现出较好的二向色比以及有序参数,可用于制造液晶显示产品,尤其是宾主型液晶显示器,作为宾体液晶染料;
第三、本发明的液晶化合物还具有液晶相,此外,它还可以作为液晶添加组分,添加至液晶主体中提高液晶主体的光电性能。
附图说明
图1为实施例1制备的F1的差热扫描量热图。
具体实施方式
下述非限制性实施例可以使本领域的普通技术人员更全面地理解本发明,但不以任何方式限制本发明。
其中,对正丁氧基苯乙炔、1-正癸炔、对乙炔基苯甲酸乙酯原料为购买所得。
实施例1
液晶染料F1的合成
(1)2-甲基-4-(4’-乙基联苯)3-丁炔-2-甲醇(化合物1)的合成
将302mg(1mmol)4’-溴-4-乙基联苯和100μL(1mmol)2-甲基-3-丁炔-2-醇以及7mg二三苯基膦二氯化钯、15mg三苯基膦、8mgCuI作为催化剂分别加入50mL双口圆底烧瓶中,用15mL干燥三乙胺作为缚酸剂和溶剂。氮气保护条件下搅拌,加热至回流使之反应完全。减压除去三乙胺,粗产物过硅胶层析柱(洗脱剂:二氯甲烷),减压除去溶剂得281.7mg白色固体,产率92%。熔点:48.4-49.7℃。
1H-NMR(400MHz,CDCl3):δ=7.54(s,4H),7.50(d,J=8.0Hz,2H),7.25(d,J=3.2Hz,2H),3.12(s,1H),2.68-2.61(m,2H),1.69-1.60(m,2H),1.38-1.31(m,4H),0.90(t,J=6.8Hz,3H).
熔点:113.4-114.7℃。TOF MS EI+:计算值:[C19H20]+(m/z)=248.1565,实测值:[C19H20]+(m/z)=248.1574。
(2)4’-乙炔基-4-乙基联苯(化合物2)的合成
将上步反应所制得的281.7mg白色固体加入50mL双口瓶中加入20mL无水乙醇磁力搅拌加热使之溶解,加入过量的氢氧化钾,加热至回流,氢氧化钾逐渐溶解,跟踪监测反应的进行程度,不断补加KOH。持续回流数小时后停止反应,此时反应溶液呈褐色。冷却至室温,将反应产物倒入100mL水里,用盐酸溶液调节pH值到中性析出大量黄色飘絮,抽滤、洗涤后干燥得187.1mg黄白色固体,粗产物过硅胶柱层析,洗脱剂PE,产率82%。
(3)目标产物F1的合成
将1mmol 3-溴苯绕蒽酮309mg加入两口烧瓶中,分别将14mg三苯基膦氯化钯、52mg三苯基膦、16mg碘化亚铜、20mL干燥三乙胺加入两口烧瓶中,氮气保护下加入206mg 4’-乙炔基-4-乙基联苯,磁力搅拌下回流反应8h TLC跟踪监测反应完全,将混合物冷却至室温减压除去溶剂,硅胶柱层析提纯,洗脱剂是二氯甲烷和石油醚比例是1:1,收集橙黄色荧光谱带,得到橙黄色固体357.5mg,产率82%。
1H NMR(500MHz,CDCl3)δ8.83(ddd,J=8.4,7.7,1.1Hz,2H),8.51(dd,J=7.9,1.2Hz,1H),8.42(d,J=7.9Hz,1H),8.33(d,J=8.1Hz,1H),7.93(d,J=7.8Hz,1H),7.90–7.86(m,1H),7.75(dd,J=13.7,7.6Hz,3H),7.65(d,J=8.3Hz,2H),7.60–7.54(m,3H),7.31(d,J=8.1Hz,2H),2.72(q,J=7.6Hz,2H),1.30(t,J=7.6Hz,3H).
13C NMR(126MHz,CDCl3)δ183.51(d,J=45.0Hz),144.14(s),141.64(s),137.54(s),135.74(s),135.59(s),134.26(s),133.64(s),133.56(d,J=21.3Hz),133.48(s),132.18(s),130.78–130.51(m),130.26(s),128.69(s),128.49(s),128.22(d,J=3.0Hz),127.73(s),127.01(d,J=5.0Hz),124.24(s),123.26(s),123.07(s),97.20(s),87.67(s),58.43(s),28.57(s),18.43(s).
熔点:253.5℃。TOF MS EI+(m/z):计算值:[C33H22O]+(m/z)=434.5272,实测值:[C33H22O]+(m/z)=434.1667。
实施例2
液晶染料F2的合成
合成方法同F1,把步骤(1)中的4’-溴-4-乙基联苯换成4’-溴-4-正戊基联苯。把步骤(3)中展开剂是DCM:PE=2:1,得到终产物黄色固体406.3mg,产率85%。
1H NMR(500MHz,CDCl3)δ8.84(dd,J=19.2,7.7Hz,2H),8.51(d,J=7.9Hz,1H),8.43(d,J=7.8Hz,1H),8.33(d,J=8.1Hz,1H),7.96–7.84(m,2H),7.75(dd,J=15.9,8.1Hz,3H),7.66(d,J=8.3Hz,2H),7.57(t,J=8.3Hz,3H),7.29(d,J=8.1Hz,2H),2.70–2.63(m,2H),1.72–1.62(m,2H),1.42–1.32(m,4H),0.95–0.88(m,3H).
13C NMR(126MHz,CDCl3)δ153.46(s),144.11(s),141.40–141.13(m),137.51(s),137.03(s),136.10(s),132.44(s),132.26(s),131.43(s),130.23(s),129.71(s),129.61(d,J=5.4Hz),129.43(d,J=4.1Hz),128.76(s),128.47(s),128.13(s),128.13(s),126.96(s),125.10(s),123.67(s),122.52(s),122.30(d,J=5.7Hz),97.13(s),87.39(s),58.41(s),29.71(s),28.56(s),18.46(s),15.56(s).
熔点:157.3-158.6℃。TOF MS EI+(m/z):计算值:[C36H28O]+(m/z)=476.6069,实测值:[C36H28O]+(m/z)=476.2149。
实施例3
液晶染料F3的合成
合成方法同F1中步骤(3),不同在于,把步骤(3)中的4’-乙炔基-4-乙基联苯换成对正丁氧基苯乙炔。展开剂是DCM:PE=1:2,得到橙黄色的终产物313.6mg,产率78%。
1H NMR(500MHz,CDCl3)δ8.82(dd,J=15.1,7.7Hz,2H),8.50(d,J=7.9Hz,1H),8.41(d,J=7.7Hz,1H),8.33(d,J=8.1Hz,1H),7.88(dd,J=16.2,8.0Hz,2H),7.75(t,J=7.6Hz,1H),7.64–7.52(m,3H),6.94(d,J=8.7Hz,2H),4.02(t,J=6.5Hz,2H),1.84–1.76(m,2H),1.57–1.48(m,2H),1.00(t,J=7.4Hz,3H).
13C NMR(126MHz,CDCl3)δ183.61(s),159.79(s),135.75(s),133.47(s),133.35(s),133.26(s),132.71(s),130.30(s),130.12(s),128.41(s),128.16(s),126.99(s),126.56(s),123.86(s),123.52(s),123.15(s),114.70(d,J=9.7Hz),97.48(s),85.90(s),67.87(s),31.26(s),19.25(s),13.86(s).
熔点:150.1-151.2℃。TOF MS EI+(m/z):计算值:[C29H22O2]+(m/z)=402.4838,实测值:[C29H22O2]+(m/z)=402.1627。
实施例4
液晶染料F4的合成
合成方法同F1中步骤(3),不同在于,把步骤(3)中的4’-乙炔基-4-乙基联苯换成1-正癸炔。展开剂是DCM:PE=1:1,得到黄色固体终产物263.5mg,产率72%。
1H NMR(400MHz,CDCl3)δ8.72(dd,J=19.1,7.7Hz,2H),8.47(d,J=7.1Hz,1H),8.28(dd,J=21.7,8.0Hz,2H),7.80(t,J=7.8Hz,1H),7.71(dd,J=15.0,7.4Hz,2H),7.53(t,J=7.4Hz,1H),2.60(t,J=7.1Hz,2H),1.80–1.68(m,2H),1.59–1.50(m,2H),1.34(d,J=21.2Hz,8H),0.90(t,J=6.7Hz,3H).
13C NMR(126MHz,CDCl3)δ183.58(s),135.75(s),135.75(s),133.49(s),132.99(s),130.77(s),130.34(s),129.96(s),128.58(s),128.26(s),128.04(s),127.64(s),126.79(s),126.14(s),124.37(s),123.42(s),123.05(s),98.71(s),78.38(s),31.88(s),29.27(s),29.17(s),29.12(s),28.82(s),22.70(s),19.91(s),14.14(s).
熔点:55.1-56.2℃。TOF MS EI+(m/z):计算值:[C27H26O]+(m/z)=366.4947,实测值:[C27H26O]+(m/z)=366.1913。
实施例5
液晶染料F5的合成
合成方法同F1中步骤(3),不同在于,,把步骤(3)中的4’-乙炔基-4-乙基联苯换成对乙炔基苯甲酸乙酯。展开剂是DCM:PE=4:1,得到黄色固体345.7mg,产率86%。
1H NMR(400MHz,CDCl3)δ8.84–8.74(m,2H),8.50(dd,J=7.9,1.2Hz,1H),8.39(d,J=7.9Hz,1H),8.30(d,J=8.1Hz,1H),8.12(d,J=8.4Hz,2H),7.89(dd,J=16.2,8.0Hz,2H),7.79–7.70(m,3H),7.57(dd,J=14.6,7.4Hz,1H),4.44(q,J=7.1Hz,2H),1.46(t,J=7.1Hz,3H).
13C NMR(126MHz,CDCl3)δ183.61(s),166.01(s),135.61(s),133.25(s),132.75(s),131.62(s),131.12(s),130.33(s),129.67(s),128.80(s),128.25(s),127.65(s),127.39(s),123.44(s),123.33(s),122.71(s),96.10(s),89.80(s),65.34(s),61.30(s),58.45(s),18.44(s).
熔点:185.5-186.8℃。TOF MS EI+(m/z):计算值:[C28H18O3]+(m/z)=402.4407,实测值:[C28H18O3]+(m/z)=402.1262。
本发明的液晶染料化合物的性质测定:
(1)液晶染料化合物F在二氯甲烷中的光谱性质测试:
测试浓度:液晶化合物在不同溶剂中的浓度均为1.0×10-5mol/L。分别精确称取1.0×10-2mmol制备的液晶化合物(±0.1mg),放入体积为10mL容量瓶后用CH2Cl2定容,得到浓度为1.0×10-3mol/L备用溶液。移取备用溶液100μL于10mL容量瓶中,待溶剂挥发完全后用其他待测的溶剂定容,得到1.0×10-5mol/L的溶液,用于紫外吸收、荧光光谱测试。
液晶化合物荧光量子产率ΦF值的测定:以浓度1.0×10-5mol/L,ΦF值为0.55的硫酸喹咛溶液(5.0×10-2mol/L硫酸水溶液)为基准。为防止液晶化合物在高浓度条件下荧光猝灭,测试时液晶化合物溶液的吸光度控制在0.02-0.05范围内。所需参数在同一测试条件下测得,代入式(1)计算:
式中:Φ(sample)、Φ(standard)分别代表样品、标准物的ΦF值;Abs(standard)、Abs(sample)分别代表激发波长下标准物、样品的吸光度;Flu(sample)和Flu(standard)分别代表样品、标准物的荧光光谱积分面积。
F系列液晶染料的测试结果如下:
表1.液晶染料F3在不同溶剂中的光谱性质
表2.F系列染料在溶剂二氯甲烷中光谱特征
结论:苯绕蒽酮衍生物系列染料的最大吸收波长集中在400nm左右,F系列的最大发射波长在500nm左右,F系列的吸收半峰宽和发射半峰宽较大集中在70-80之间,色彩纯正,更有利于实现纯色显示。
(2)液晶染料F在液晶E7中的偏振光谱性质测试:
主体液晶:液晶E7具有较宽的、稳定的向列相范围(-10-60℃),好的化学稳定性,高的正介电各向异性作为主体液晶。
液晶盒:测试用液晶盒上下两基板的取向相互平行,盒厚度为15μm。
二向色比、有序参数的测定:将液晶染料F按照质量浓度为0.5%(w/w)的比例掺入到液晶中,在室温下混合均匀,然后将该混合物装入平行液晶盒,封住灌晶口。分别测试液晶化合物与液晶盒取向膜平行方向上的吸光度A‖和垂直方向上的吸光度A⊥、平行方向上的荧光强度F‖和垂直方向上的荧光强度F⊥;并按照下列公式(2)、(3)、(4)、(5)计算出液晶化合物F在液晶中的吸收有序参数SA、二向色比DA和荧光有序参数SF、二向色比DF:
液晶染料化合物F偏振光谱测试结果如下:
表3.液晶化合物F在液晶E7中的偏振紫外和偏振荧光数据
合成的目标产物F在液晶E7中表现出较好的二向色比以及有序参数。F1的SA和SF是最大的,分别达到0.66和0.55是具有实用价值的。二向色比为5.46。满足宾主显示实际应用要求。
(3)F系列在负性液晶BHR28000-300偏振光谱和光-电性质
液晶染料F1、F2和F3在负性液晶BHR28000-300测试外加不同电压(2、4、6、8、10V)的紫外偏振光谱,光谱测试数据如表4.所示。
表4.液晶染料F在负性液晶BHR28000-300中的偏振光谱性质
(4)液晶染料化合物F的液晶行为
对制备的液晶染料化合物F1进行差热扫描,得到其差热扫描量热图,如图1所示。
Claims (6)
1.含有3位炔基取代基的苯绕蒽酮类液晶染料,其特征在于:所述染料具有以下的化学分子结构通式:
2.权利要求1所述的苯绕蒽酮类液晶染料的制备方法,包括以下步骤:
分别将4’-乙炔基-4-烷基联苯、对正丁氧基苯乙炔、1-正癸炔、对乙炔基苯甲酸乙酯与3-溴苯绕蒽酮偶联得到所述液晶染料化合物;
所述4’-乙炔基-4-烷基联苯的制备方法为:4’-溴-4-烷基联苯与2-甲基-3-丁炔-2-醇偶联,经过碱处理得到4’-乙炔基-4-烷基联苯;
所述4’-溴-4-烷基联苯选自4’-溴-4-乙基联苯、4’-溴-4-正戊基联苯。
3.权利要求1所述的苯绕蒽酮类液晶染料作为荧光二向性液晶染料在制造液晶显示产品中的应用。
4.根据权利要求3所述的应用,其特征在于液晶显示器是宾主型液晶显示器。
5.一类宾主型液晶显示器,其特征在于以权利要求1所述的苯绕蒽酮类液晶染料作为宾体液晶染料。
6.权利要求1所述的苯绕蒽酮类液晶染料与液晶E7混合在液晶显示器中的应用。
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