CN106433689A - 一种含吡啶末端基炔类液晶化合物及其制备方法和应用 - Google Patents
一种含吡啶末端基炔类液晶化合物及其制备方法和应用 Download PDFInfo
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- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 title claims abstract description 12
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- C09K19/3441—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having nitrogen as hetero atom
- C09K19/3444—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having nitrogen as hetero atom the heterocyclic ring being a six-membered aromatic ring containing one nitrogen atom, e.g. pyridine
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Abstract
本发明公开了一种含吡啶末端基炔类液晶化合物及其制备方法和应用,该化合物的结构式为式中CnH2n+1代C2~C5直链烷基。该液晶化合物是通过吡啶基炔醇与芳香烃碘代物发生sonogashira偶联反应得到的,合成方法简单,成本较低,适用于工业化生产。本发明的液晶化合物具有正介电各向异性和一定的向列相液晶区间,具有较高清亮点,且与其他液晶性化合物相溶性优异,可作为染料敏化剂分子应用于染料敏化太阳能电池中,还可应用于IPS显示模式、TN显示模式。
Description
技术领域
本发明属于液晶化合物技术领域,具体涉及一种含吡啶末端基炔类液晶化合物,以及该液晶化合物的制备方法和应用。
背景技术
液晶材料发展至今,在液晶显示、液晶光学器件、高强度弹性材料、有机太阳能电池材料等众多领域中已经得到了应用。因而液晶材料作为交叉学科的研究热点,已经被研究者们广泛的研究。在能源危机与环境污染对全球可持续发展构成的挑战日益加剧的形势背景下,太阳能电池日渐被科学与工业界所高度重视。近两年来,液晶研究者们做了大量的尝试研究,期望能够将液晶材料应用于太阳能电池研究领域。如今,已有一些液晶材料成功应用于太阳能电池领域。例如,Agnieszka Iwan报道了一种手性光敏液晶分子(AZOX)掺杂到有机太阳能电池的活性层中,改善了器件的光伏性能(Liquid Crystals,2015,42(7),964-972)。
Fan Li报道了一种离子液晶(6CNBP-N)添加到体异质结聚合物太阳能电池的阳极缓冲层中,诱导了活性层的相分离、结晶度和有序结构,增加了聚合物太阳能电池的光伏性能(RSC Adv.2015,5,52874-52881)。
E.A.Soto-Bustamante报道了一种液晶(M6R8)纳米颗粒掺杂到二氧化钛纳米颗粒中,可以提高有机无机复合太阳能电池的光电流(J.Mater.Chem.C,2015,3,8566--8573)。
Kuan Sun报道了一种向列相液晶(BTR)非常适合可印刷的有机太阳能电池,掺杂到活性层中能够提高太阳能电池的效率(Nature Communications,2015,6,6013)。
Takashi Kato报道了一种液晶电解液(1/2-I2)应用在染料敏化太阳能电池中,可以使电池在高温下正常运行(Chem.Mater.2014,26,6496-6502)。
然而关于显示用液晶材料应用于太阳能电池中的报道却没有。
发明内容
本发明所要解决的技术问题是提供一种只存在向列相且具有较大正介电各向异性的显示用液晶化合物,并为该显示用液晶化合物提供一种制备方法和应用。
解决上述技术问题所采用的技术方案是:该显示用液晶化合物为含吡啶末端基炔类液晶化合物,其结构式如下所示:
式中CnH2n+1代表C2~C5直链烷基。
上述含吡啶末端基炔类液晶化合物的制备方法为:首先,将对碘吡啶与2-甲基-3-丁炔-2-醇通过Heck偶联反应制备吡啶基炔醇1;然后,以甲苯与蒸馏水的体积比为3~5:1的混合物为溶剂,在惰性气体保护下,将吡啶基炔醇1、芳香烃碘代物nI、四正丁基溴化铵、四(三苯基)膦合钯、氢氧化钾按摩尔比为1:1~1.3:0.05~0.2:0.02~0.04:10~15,90~110℃搅拌反应12~24小时,分离纯化产物,得到含吡啶末端基炔类液晶化合物,其反应方程式如下:
上述含吡啶末端基炔类液晶化合物的制备方法中,优选吡啶基炔醇与芳香烃碘代物、四正丁基溴化铵、四(三苯基)膦合钯、氢氧化钾的摩尔比为1:1.2:0.1:0.03:12。
本发明的芳香烃碘代物根据公开号为CN 103805208A、发明名称为《双环己基乙撑基取代二苯炔液晶化合物及其制备方法》的中国发明专利申请中公开的方法合成。
本发明的含吡啶末端基炔类液晶化合物在制备染料敏化太阳能电池中的用途,其具体使用方法如下:
1、导电玻璃预处理
将导电玻璃依次在洗涤剂、乙醇、去离子水中用频率为40Hz、功率为100W的超声波清洗30分钟至1小时,110℃下烘干备用。
2、配制染料溶液
将含吡啶末端基炔类液晶化合物溶于乙腈与叔丁醇的体积比为1:1的混合溶剂中,配制成浓度为0.3mmol/L的染料溶液。
3、配制电解质溶液
将四丁基碘化铵、碘化锂、碘、对叔丁基吡啶加入乙腈中,配制成电解质溶液,电解质溶液中四丁基碘化铵、碘化锂、碘、对叔丁基吡啶的浓度分别为0.6mol/L、0.1mol/L、0.05mol/L、0.5mol/L。
4、制备光阳极
采用丝网印刷技术在预处理后的导电玻璃上制备面积为0.25cm2、厚度为12~20μm的纳米多孔TiO2薄膜,450℃烧结30分钟,自然降温至室温,制备成光阳极。
5、制备工作电极
将光阳极在染料溶液中浸渍12~24小时,得到敏化的工作电极。
6、制备对电极
采用丝网印刷技术在预处理后的导电玻璃上制备面积为0.25cm2、厚度为4~6μm的铂浆料,制备成对电极。
7、密封
在电极的周边位置,通过印刷喷涂把沙林热封膜均匀置于设定位置,工作电极和对电极合上并密封,电解质溶液通过真空倒吸灌注,密封,制得染料敏化太阳能电池。
本发明具有以下有益效果:
1、本发明液晶化合物以吡啶环为末端基,与传统的以柔性的烷基链为端基的液晶化合物相比,具有大的正介电各向异性,且具有一定的向列相液晶区间,可应用于TN显示模式和IPS显示模式。
2、本发明通过在反式环己烷与苯环之间插入能够自由旋转的乙撑桥键,且在分子结构中引入反式环己基、芳香基炔等结构,使该液晶化合物的相溶性较好。
3、本发明首次将含吡啶末端基炔类液晶化合物作为染料敏化剂,应用在染料敏化太阳能电池中。
附图说明
图1是实施例1制备的含吡啶末端基炔类液晶化合物制备的染料敏化太阳能电池的J-V曲线图。
具体实施方式
下面结合附图和实施例对本发明进一步详细说明,但本发明的保护范围不仅限于这些实施例。
实施例1
在氮气保护下,向500mL三口烧瓶中加入8.20g(40.00mmol)对碘吡啶、5.30g(60.00mmol)2-甲基-3-丁炔-2-醇、0.46g(0.40mmol)四三苯基膦合钯、0.38g(2.00mmol)碘化亚铜、0.84g(3.20mmol)三苯基膦和25g(250.00mmol)三乙胺、200mL DMF,在氮气保护下回流搅拌反应12小时,冷却至室温,用二氯甲烷萃取,有机相用氯化铵饱和溶液洗涤3次,合并有机相,水洗至中性,经无水硫酸镁干燥、浓缩后,得到黄褐色固体5.16g,即吡啶基炔醇1(HPLC>92%),其产率为80%,具体化学反应方程式如下:
在氮气保护下,将1.26g(7.8mmol)吡啶基炔醇1、0.25g(0.78mmol)四正丁基溴化铵、5.24g(93.6mmol)氢氧化钾、16mL甲苯和4mL蒸馏水加入到装有温度计、磁力搅拌子、冷凝管的三口烧瓶中,将三口烧瓶置于油浴锅中,并升温至60℃,待固体完全溶解后,加入3.33g(9.36mmol)的4-(反-(4-正丙基环己基)乙基)碘苯3I和0.27g(0.23mmol)四(三苯基)膦合钯,升温至100℃,恒温搅拌反应12小时,结束反应,将反应液冷却至室温,并用硅藻土过滤,滤液用乙酸乙酯萃取,分液后得到有机相水洗至中性,再用无水硫酸镁干燥后浓缩,浓缩液进行柱色谱分离纯化(以硅胶为固定相、以石油醚和乙酸乙酯的体积比为5:1的混合液为洗脱液),将分离纯化后的液体浓缩后用石油醚和乙酸乙酯的体积比为5:1的混合液重结晶,得到白色晶体——含吡啶末端基炔类液晶化合物3N,其收率为40%,化学命名为1-{4-[2-(4-正丙基环己基)乙基]苯基}-2-[4-吡啶基]乙炔,具体反应方程式如下:
所得含吡啶末端基炔类液晶化合物的结构表征数据如下:
13C-NMR(CDCl3为溶剂,内标为TMS,101MHz,ppm):149.73,144.88,131.85,131.69,128.55,125.48,119.17,94.39,86.16,39.77,39.02,37.52,37.50,33.40,33.23,33.20,20.04,14.4。
1H-NMR(CDCl3为溶剂,内标为TMS,400MHz,ppm):8.59(d,J=5.5Hz,2H),7.47(d,J=7.5Hz,2H),7.36(d,J=5.3Hz,2H),7.19(d,J=8.1Hz,2H),2.69-2.60(m,2H),1.85-1.69(m,4H),1.56-1.44(m,2H),1.39-1.25(m,2H),1.25-1.12(m,4H),1.01-0.81(m,7H)。
结合上述分析结果,证实得到的白色晶体确实是化合物1-{4-[2-(4-正丙基环己基)乙基]苯基}-2-[4-吡啶基]乙炔。
利用差式量热扫描仪、Leika DM2500P偏光显微镜和Linkam THMSE600冷热台测试合成的化合物1-{4-[2-(4-正丙基环己基)乙基]苯基}-2-[4-吡啶基]乙炔的热性能,结果表明该化合物具有液晶相,相变性质为Cr 82.3℃I 80.7℃N 48.3℃Cr,Cr表示晶体,N表示向列相,I表示各向同性液体。通过偏光显微镜测试,发现该化合物在降温过程中具有典型的向列相。测试合成的液晶化合物1-{4-[2-(4-正丙基环己基)乙基]苯基}-2-[4-吡啶基]乙炔的介电各向异性,所得的拟合参数为Δε=6.65。
实施例2
在实施例1中,所用的4-(反-(4-正丙基环己基)乙基)碘苯3I用等摩尔的4-(反-(4-正戊基环己基)乙基)碘苯5I替换,其他步骤与实施例1相同,得到白色晶体——含吡啶末端基炔类液晶分子5N,其收率为43%,化学命名为1-{4-[2-(4-正戊基环己基)乙基]苯基}-2-[4-吡啶基]乙炔,具体反应方程式如下:
所得含吡啶末端基炔类液晶化合物的结构表征数据如下:
13C-NMR(CDCl3为溶剂,内标为TMS,101MHz,ppm):149.73,144.88,131.85,131.69,128.55,125.48,119.17,94.40,86.16,39.02,37.82,37.51,37.44,33.41,33.24,33.24,32.26,26.68,22.73,14.14。
1H-NMR(CDCl3为溶剂,内标为TMS,400MHz,ppm):8.59(d,J=5.4Hz,2H),7.47(d,J=8.3Hz,2H),7.36(d,J=5.6Hz,2H),7.18(d,J=7.7Hz,2H),2.70-2.58(m,2H),1.86-1.69(m,4H),1.57-1.45(m,2H),1.40-1.23(m,6H),1.21-1.12(m,4H),1.01-0.81(m,7H)。
结合上述分析结果,证实得到的白色晶体确实是化合物1-{4-[2-(4-正戊基环己基)乙基]苯基}-2-[4-吡啶基]乙炔。
利用差式量热扫描仪、Leika DM2500P偏光显微镜和Linkam THMSE600冷热台测试合成的化合物1-{4-[2-(4-正戊基环己基)乙基]苯基}-2-[4-吡啶基]乙炔的热性能,结果表明该化合物具有液晶相,相变性质为Cr 77.1℃N 85.9℃I 84.3℃N 45.3℃Cr,Cr表示晶体,N表示向列相,I表示各向同性液体。通过偏光显微镜观察,该化合物在升降温过程中都具有典型的向列相。测试合成的液晶化合物1-{4-[2-(4-正戊基环己基)乙基]苯基}-2-[4-吡啶基]乙炔的介电各向异性,所得的拟合参数为Δε=6.67。
实施例3
实施例1制备的含吡啶末端基炔类液晶化合物在制备染料敏化太阳能电池中的用途,其具体使用方法为:
1、导电玻璃预处理
将导电玻璃依次在洗涤剂、乙醇、去离子水中用频率为40Hz、功率为100W的超声波清洗30分钟至1小时,110℃下烘干备用。
2、配制染料溶液
将含吡啶末端基炔类液晶化合物溶于乙腈与叔丁醇的体积比为1:1的混合溶剂中,配制成浓度为0.3mmol/L的染料溶液。
3、配制电解质溶液
将四丁基碘化铵、碘化锂、碘、对叔丁基吡啶加入乙腈中,配制成电解质溶液,电解质溶液中四丁基碘化铵、碘化锂、碘、对叔丁基吡啶的浓度分别为0.6mol/L、0.1mol/L、0.05mol/L、0.5mol/L。
4、制备光阳极
采用丝网印刷技术在预处理后的导电玻璃上制备面积为0.25cm2、厚度为15μm的纳米多孔TiO2薄膜,450℃烧结30分钟,自然降温至室温,制备成光阳极。
5、制备工作电极
将光阳极在染料溶液中浸渍24小时,得到敏化的工作电极。
6、制备对电极
采用丝网印刷技术在预处理后的导电玻璃上制备面积为0.25cm2、厚度为6μm的铂浆料,制备成对电极。
7、密封
在电极的周边位置,通过印刷喷涂把沙林热封膜均匀置于设定位置,工作电极和对电极合上并密封,电解质溶液通过真空倒吸灌注,密封,制得染料敏化太阳能电池。
采用J-V特性测试系统(型号为IV Test Station2000,由美国CROWNTECH公司生产)对制备的太阳能电池进行测试,电池的短路电流密度为0.20mA/cm2、开路电压为438.05V、填充因子为0.54、光电转化效率0.05%。
Claims (4)
1.一种含吡啶末端基炔类液晶化合物,其特征在于该化合物的结构式如下所示:
式中CnH2n+1代表C2~C5直链烷基。
2.权利要求1所述的含吡啶末端基炔类液晶化合物的制备方法,其特征在于:将对碘吡啶与2-甲基-3-丁炔-2-醇通过Heck偶联反应制备吡啶基炔醇1;然后以甲苯与蒸馏水的体积比为3~5:1的混合物为溶剂,在惰性气体保护下,将吡啶基炔醇与芳香烃碘代物nI、四正丁基溴化铵、四(三苯基)膦合钯、氢氧化钾按摩尔比为1:1~1.3:0.05~0.2:0.02~0.04:10~15,90~110℃搅拌反应12~24小时,分离纯化产物,得到含吡啶末端基炔类液晶化合物;
3.根据权利要求2所述的含吡啶末端基炔类液晶化合物的制备方法,其特征在于:所述吡啶基炔醇与芳香烃碘代物、四正丁基溴化铵、四(三苯基)膦合钯、氢氧化钾的摩尔比为1:1.2:0.1:0.03:12。
4.权利要求1所述的含吡啶末端基炔类液晶化合物在制备染料敏化太阳能电池中的用途。
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