CN106831545B - 一种基于不同取代基的四元环吡啶多色彩的电致变色材料 - Google Patents
一种基于不同取代基的四元环吡啶多色彩的电致变色材料 Download PDFInfo
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Abstract
本发明公开了一种基于不同取代基的四元环吡啶多色彩的电致变色材料,以1,2‑双(4‑吡啶)乙烯为原料合成了1,2,3,4‑四‑(4‑吡啶)环丁烷,并通过氮烷基化反应合成了系列的N取代的盐,运用NMR检测了不同取代基化合物盐的结构,运用循环伏安法测试了化合物的电化学性能,紫外‑可见光谱测试了光谱性质,考察了由此做成的电致变色器件,不同取代基的电致变色性能的影响,施加不同的电压,显示不同的颜色,其电致变色的颜色可通过改变不同的取代基来实现,这类化合物在电致变色领域具有广阔的应用前景。
Description
技术领域
本发明属于功能材料制备领域中的电致变色材料技术范畴,尤其涉及一种基于不同取代基的四元环吡啶多色彩的电致变色材料,以及该类衍生物作为新型电致变色材料的应用。
背景技术
电致变色材料是指其在交替的正负外电场或高低电压的作用下,通过抽取或注入电荷(电子或离子),从而使材料在低透过率的着色态与高透过率的褪色态之间产生的一种稳定、可逆性变化的特殊现象,在外观上则表现为透明度和颜色的可逆性变化。利用电致变色材料制作而成的电致变色器件具有一些独特的特点,如材料光学性能在大范围内连续可调、可实现光调制、工作电压低、能耗低、易于集成电路匹配,工作温度范围宽、具有高反射率因而不需要外部光源等,在电子显示器、变色太阳镜、智能窗、汽车天窗光***、防眩后视镜等领域都有非常广泛的应用前景和巨大的商业价值。按照材料的化学性质,电致变色材料主要可以分为无机电致变色材料和有机电致变色材料两大类。按物质状态,可分为液态电致变色材料和固态电致变色材料。按照着色方式可分为阴极着色电致变色材料和阳极着色电致变色材料。无机电致变色材料包括过渡金属元素的氧化物(钨、镍、钼、钌、铱、钴、铑)络合物水合物以及普鲁士蓝等,无机电致变色材料由于显示颜色过于单调,难以制作成全色的电致变色器件,应用范围受到一定限制。有机电致变色材料以紫精、聚噻吩、聚吡咯、聚苯胺、四硫富瓦烯等分子结构中有共轭体系的分子为代表,具有原料易得,视角范围大,变色速度快,色彩丰富,对比度高,驱动电压低,耗能小等优点,因此受到科学家们的广泛青睐。其中,紫精类化合物由于具有成本低、颜色丰富、对比度高、响应时间短、使用寿命长等优点,已在电致变色器件,包括智能灵巧窗、汽车后视镜、电致变色数字显示屏以及光控分子器件中得到广泛应用。由于电致变色材料的性能在一定程度上决定着电致变色器件的性能,目前电致变色领域的主要研究方向之一就是开发性能稳定的新型电致变色材料,尤其是开发多种色彩显示的电致变色材料,以充分扩展电致变色材料的应用范围。然而紫精类有机化合物因为响应时间长、色彩变化比较单一,在实际的应用中受到极大的限制。
发明内容
本发明的目的在于提供一种基于不同取代基的四元环吡啶多色彩的电致变色材料,旨在解决紫精类有机化合物响应时间长、色彩变化单一的问题。
本发明是这样实现的,一种多色彩变化的四元环吡啶衍生物,所述多色彩变化的四元环吡啶衍生物具有式I所示结构:
式中,X1,X2,X3和X4任意地为Cl、Br或I;R1,R2,R3和R4任意地为脂链烃基或单环芳烃基取代烷烃,或者酯基。
进一步,R1,R2,R3和R4任意地为C1-C18烷基、C1-C18烯基、有单环芳烃基取代的C1-C18烷基、或有单环芳烃基取代的C1-C18烯基。
进一步,R1,R2,R3和R4任意地为C1-C8烷基、C1-C8烯基、或有苯基或取代苯基取代的C1-C8烷基,所述取代苯基为有C1-C8烷基或C1-C8烯基取代的苯基。
进一步,R1,R2,R3和R4任意地为甲基、乙基、丁基、辛基、烯丙基、异戊烯基、苄基、4-乙烯基苄基和三氟甲基苄基等。
005进一步,R1,R2,R3和R4任意地为CH2COOR5,R5任意地为甲基、乙基、丁基、辛基、烯丙基、异戊烯基、苄基、4-乙烯基苄基,三氟甲基苄基等。
本发明的另一目的在于提供一种利用所述多色彩变化的四元环吡啶衍生物制备的共轭扩展的四元环吡啶衍生物,所述共轭扩展的四元环吡啶衍生物的结构如下:
本发明的另一目的在于提供一种所述多色彩变化的四元环吡啶衍生物的制备方法,所述多色彩变化的四元环吡啶衍生物的制备方法如下:
在有机溶剂中加入式II所示1,2,3,4-四-(4-吡啶)环丁烷,再滴加式III所示卤代烃,1,2,3,4-四-(4-吡啶)环丁烷与卤代烃的摩尔比为1:4-4.5,然后80~90℃恒温搅拌反应,反应完毕后冷却至室温,加入三倍体积的***作沉淀剂,过滤,滤饼干燥,得式IV所示1,2,3,4-四-(4-吡啶)环丁烷吡啶盐,即R1、R2、R3和R4相同且X1、X2、X3和X4相同的式I化合物。
进一步,所述多色彩变化的四元环吡啶衍生物的制备方法化学反应式如下:
进一步,所述有机溶剂为甲醇,乙醇,THF,DMF,DMSO等。
本发明的另一目的在于提供一种利用所述多色彩变化的四元环吡啶衍生物制备的电致变色材料。
本发明的有益效果在于:本发明的有机电致变色材料——多色彩变化的四元环吡啶衍生物,该类化合物与紫精相似,是优良的阴极电致变色材料,具有良好的电致变色性能,尤其是调节取代基可以得到多种不同颜色的显示,从而扩展了有机电致变色材料的色彩选择范围,为彩色电致变色材料领域提供了一类新的多色彩变化的电致变色显示材料,在电致变色领域具有潜在、广阔的应用前景。此外,本发明还提供了该色彩变化的四元环吡啶衍生物的制备方法,具有反应条件温和、后处理方便、成本低等特点。
附图说明
图1是本发明实施例提供的基于不同取代基的四元环吡啶多色彩的电致变色材料的制备方法流程图。
图2是本发明实施例提供的四苄基-1,2,3,4-四(4-吡啶)环丁烷的循环伏安图。
图3是本发明实施例提供的四苄基-1,2,3,4-四(4-吡啶)环丁烷的紫外吸收图。
图4是本发明实施例提供的四苄基-1,2,3,4-四(4-吡啶)环丁烷的响应时间图。
具体实施方式
为了使本发明的目的、技术方案和优点更加清楚,下面对本发明的优选实施例进行详细的描述。
下面结合附图对本发明的应用原理作详细的描述。
本发明实施例提供的多色彩变化的四元环吡啶衍生物,所述多色彩变化的四元环吡啶衍生物具有式I所示结构:
式中,X1,X2,X3和X4任意地为Cl、Br或I;R1,R2,R3和R4任意地为脂链烃基或单环芳烃基取代烷烃,或者酯基。
进一步,R1,R2,R3和R4任意地为C1-C18烷基、C1-C18烯基、有单环芳烃基取代的C1-C18烷基、或有单环芳烃基取代的C1-C18烯基。
进一步,R1,R2,R3和R4任意地为C1-C8烷基、C1-C8烯基、或有苯基或取代苯基取代的C1-C8烷基,所述取代苯基为有C1-C8烷基或C1-C8烯基取代的苯基。
进一步,R1,R2,R3和R4任意地为甲基、乙基、丁基、辛基、烯丙基、异戊烯基、苄基或4-乙烯基苄基。
进一步,R1,R2,R3和R4任意地为CH2COOR5,R5任意地为甲基、乙基、丁基、辛基、烯丙基、异戊烯基、苄基或4-乙烯基苄基,三氟甲基苄基等。
利用多色彩变化的四元环吡啶衍生物制备的共轭扩展的四元环吡啶衍生物,所述共轭扩展的四元环吡啶衍生物的结构如下:
如图1所示,本发明实施例提供的多色彩变化的四元环吡啶衍生物的制备方法包括以下步骤:
S101:在有机溶剂中加入式II所示1,2,3,4-四-(4-吡啶)环丁烷,再滴加式III所示卤代烃,1,2,3,4-四-(4-吡啶)环丁烷与卤代烃的摩尔比为1:4-4.5;
S102:然后80~90℃恒温搅拌反应,反应完毕后冷却至室温,加入三倍体积的***作沉淀剂,过滤,滤饼干燥,得式IV所示1,2,3,4-四-(4-吡啶)环丁烷四吡啶盐,即R1、R2、R3和R4相同且X1、X2、X3和X4相同的式I化合物。
所述多色彩变化的四元环吡啶衍生物的制备方法化学反应式如下:
进一步,所述有机溶剂为甲醇,乙醇,THF,DMF,DMSO等。
下面结合具体实施例对本发明的应用原理作进一步的描述。
制备实施例1
将0.3g(0.82mmol)1,2,3,4-四-(4-吡啶)环丁烷加入8ml二甲基甲酰胺中,然后缓慢滴入2ml溶有0.58g(4.1mmol)碘甲烷的二甲基甲酰胺,80℃恒温搅拌反应36h,加入三倍体积的***作沉淀剂,过滤,滤饼用无水***洗涤,60℃烘干,即得N,N',N”,N”'-四甲基-1,2,3,4-四(4-吡啶基)环丁烷季铵盐碘化物1(黄黑色固体),收率86.0%;1HNMR(600MHz,DMSO-d6),δ(ppm):9.02(d,8H,J=6.60Hz),8.23(d,8H,J=6.60Hz),4.67(s,4H),4.34(s,12H);13CNMR(150MHz,DMSO-d6):156.28,145.99,127.19,48.05,48.02.产物结构经核磁测定与上述结构式1完全一致。
制备实施例2
将0.3g(0.82mmol)1,2,3,4-四-(4-吡啶)环丁烷加入8ml二甲基甲酰胺中,然后缓慢滴入2ml溶有0.79g(4.1mmol)溴代正辛烷的二甲基甲酰胺,80℃恒温搅拌反应36h,加入三倍体积的***作沉淀剂,过滤,滤饼用无水***洗涤,60℃烘干,即得N,N',N”,N”'-四正辛基-1,2,3,4-四(4-吡啶基)环丁烷吡啶盐溴化物2(浅棕色固体),收率56.1%;1HNMR(600MHz,DMSO-d6)δ(ppm)9.15(8H,d,J=66.0),8.36(8H,d,J=66.0),4.78(4H,s),4.59(8H,t,J=15),1.89(8H,m,J=6.0),1.24-1.29(40H,m,J=30.6),0.85(12H,t,J=15.2);13CNMR(150MHz,DMSO-d6)156.87,145.08,127.71,60.76,47.99,34.85,31.58,28.88,25.93,22.46,14.36.
产物结构经核磁测定与上述结构式2完全一致。
制备实施例3
将0.3g(0.82mmol)1,2,3,4-四-(4-吡啶)环丁烷加入8ml二甲基甲酰胺中,然后缓慢滴入2ml溶有0.70g(4.1mmol)溴化苄的二甲基甲酰胺中,80℃恒温搅拌反应36h,加入三倍体积的***作沉淀剂,过滤,滤饼用无水***洗涤,60℃烘干,即得N,N',N”,N”'-四苄基-1,2,3,4-四(4-吡啶基)环丁烷吡啶盐溴化物3白色固体),收率69.5%;1HNMR(600MHz,DMSO-d6)δ(ppm):9.30(d,8H,J=6Hz),8.36(d,8H,J=6Hz),7.59(d,8H,J=6.6Hz),7.43(d,12H,J=6.6Hz),5.87(s,8H),4.77(s,4H);13CNMR(150MHz,DMSO-d6):157.66,145.96,145.25,139.16,130.26,128.27,126.51,62.26,47.86.
产物结构经核磁测定与上述结构式3完全一致。
制备实施例4
将0.3g(0.82mmol)1,2,3,4-四-(4-吡啶)环丁烷加入8ml二甲基甲酰胺中,然后缓慢滴入2ml溶有0.50g(4.1mmol)丙烯基溴的二甲基甲酰胺,80℃恒温搅拌反应36h,加入三倍体积的***作沉淀剂,过滤,滤饼用无水***洗涤,60℃烘干,即得N,N',N”,N”'-四烯丙基-1,2,3,4-四(4-吡啶基)环丁烷吡啶盐溴化物4(棕色固体),收率71.6%;1HNMR(600MHz,DMSO-d6)δ(ppm):9.10(d,8H,J=6.6Hz),8.35(d,8H,J=6.6Hz),6.12-6.17(m,4H.J=27Hz),5.39-5.46(m,8H,J=37.8Hz),5.28(d,8H,J=6Hz),4.78(s,4H);13CNMR(150MHz,DMSO-d6):157.29,145.18,132.15,127.83,122.38,62.38,48.01.产物结构经核磁测定与上述结构式4完全一致。
制备实施例5
将0.3g(0.82mmol)1,2,3,4-四-(4-吡啶)环丁烷加入8ml二甲基甲酰胺中,然后缓慢滴入2ml溶有0.58g(4.1mmol)对甲基氯苄的二甲基甲酰胺,80℃恒温搅拌反应36h,加入三倍体积的***作沉淀剂,过滤,滤饼用无水***洗涤,60℃烘干,即得N,N',N”,N”'-四对甲基苄-1,2,3,4-四(4-吡啶基)环丁烷吡啶盐氯化物5(棕色固体),收率73.4%;1HNMR(600MHz,DMSO-d6)δ(ppm):9.27(8H,d,J=6.0),8.37(8H,d,J=6.6),7.48(8H,d,J=7.8),7.23(8H,d,J=7.8),5.79(8H,s),4.76(4H,s),2.29(12H,s);13CNMR(150MHz,DMSO-d6):157.45,144.91,139.51,131.86,130.17,129.43,128.10,62.99,47.96,21.18.
产物结构经核磁测定与上述结构式5完全一致。
制备实施例6
将0.3g(0.82mmol)1,2,3,4-四-(4-吡啶)环丁烷加入8ml二甲基甲酰胺中,然后缓慢滴入2ml溶有0.96g(4.1mmol)对三氟甲基苄溴的二甲基甲酰胺,80℃恒温搅拌反应36h,加入三倍体积的***作沉淀剂,过滤,滤饼用无水***洗涤,60℃烘干,即得N,N',N”,N”'-四对三氟甲基苄-1,2,3,4-四(4-吡啶基)环丁烷吡啶盐溴化物6(棕色固体),收率71.6%;1HNMR(600MHz,DMSO-d6)δ(ppm):9.30(8H,d,J=6.6),8.36(8H,d,J=6.6),7.79-7.83(16H,m,J=24.6),5.96(8H,s),4.76(4H,s);13CNMR(150MHz,DMSO-d6):157.67,145.25,139.17,130.24,128.25,126.54,126.52,62.32,47.84,34.83.产物结构经核磁测定与上述结构式6完全一致。
应用实施例1
取2片60×80mm的ITO导电玻璃,用框胶将2片玻璃的ITO面以面对面的方式贴合起来,形成60μm高的空腔,并留有一个灌注孔;从灌注孔向空腔中灌入制备实施例1制得的化合物1的DMSO溶液(将23mg化合物1、47mg二茂铁和85mg四丁基高氯酸铵溶于5ml DMSO中即得),然后用UV胶封口,制得电致变色器件。在驱动电压为1.3V的条件下,该电致变色器件的颜色由无色变为棕褐色,循环10000次后,电致变色器件的颜色及其色彩强度无明显改变。
按上述方法以化合物1的DMF或γ-丁内酯溶液制得的电致变色器件,其电致变色性能类似。
应用实施例2
取2片60×80mm的ITO导电玻璃,用框胶将2片玻璃的ITO面以面对面的方式贴合起来,形成60μm高的空腔,并留有一个灌注孔;从灌注孔向空腔中灌入制备实施例2制得的化合物2的DMSO溶液(将28mg化合物2、47mg二茂铁和85mg四丁基高氯酸铵溶于5ml DMSO中即得),然后用UV胶封口,制得电致变色器件。在驱动电压为1.4V的条件下,该电致变色器件的颜色由无色变为棕色,循环10000次后,电致变色器件的颜色及其色彩强度无明显改变。
按上述方法以化合物2的DMF或γ-丁内酯溶液制得的电致变色器件,其电致变色性能类似。
应用实施例3
取2片60×80mm的ITO导电玻璃,用框胶将2片玻璃的ITO面以面对面的方式贴合起来,形成60μm高的空腔,并留有一个灌注孔;从灌注孔向空腔中灌入制备实施例3制得的化合物3的DMSO溶液(将26mg化合物3、47mg二茂铁和85mg四丁基高氯酸铵溶于5ml DMSO中即得),然后用UV胶封口,制得电致变色器件。在驱动电压为1.2V的条件下,该电致变色器件的颜色由无色变为紫色;当电压调节到1.4V后该电致变色器件的颜色由无色变为棕色,循环10000次后,电致变色器件的颜色及其色彩强度无明显改变。
按上述方法以化合物3的DMF或γ-丁内酯溶液制得的电致变色器件,其电致变色性能类似。
应用实施例4
取2片60×80mm的ITO导电玻璃,用框胶将2片玻璃的ITO面以面对面的方式贴合起来,形成60μm高的空腔,并留有一个灌注孔;从灌注孔向空腔中灌入制备实施例4制得的化合物4的DMSO溶液(将21mg化合物4、47mg二茂铁和85mg四丁基高氯酸铵溶于5ml DMSO中即得),然后用UV胶封口,制得电致变色器件。在驱动电压为1.2V的条件下,该电致变色器件的颜色由无色变为粉红色;当电压调节到1.4V后该电致变色器件的颜色由无色变为棕色,循环10000次后,电致变色器件的颜色及其色彩强度无明显改变。
按上述方法以化合物4的DMF或γ-丁内酯溶液制得的电致变色器件,其电致变色性能类似。
应用实施例5
取2片60×80mm的ITO导电玻璃,用框胶将2片玻璃的ITO面以面对面的方式贴合起来,形成60μm高的空腔,并留有一个灌注孔;从灌注孔向空腔中灌入制备实施例5制得的化合物5的DMSO溶液(将23mg化合物5、47mg二茂铁和85mg四丁基高氯酸铵溶于5ml DMSO中即得),然后用UV胶封口,制得电致变色器件。在驱动电压为1.2V的条件下,该电致变色器件的颜色由无色变为浅紫色;当电压调节到1.4V后该电致变色器件的颜色由无色变为棕色,循环10000次后,电致变色器件的颜色及其色彩强度无明显改变。
按上述方法以化合物5的DMF或γ-丁内酯溶液制得的电致变色器件,其电致变色性能类似。
应用实施例6
取2片60×80mm的ITO导电玻璃,用框胶将2片玻璃的ITO面以面对面的方式贴合起来,形成60μm高的空腔,并留有一个灌注孔;从灌注孔向空腔中灌入制备实施例6制得的化合物6的DMSO溶液(将33mg化合物6、47mg二茂铁和85mg四丁基高氯酸铵溶于5ml DMSO中即得),然后用UV胶封口,制得电致变色器件。在驱动电压为1.2V的条件下,该电致变色器件的颜色由无色变为浅紫色;当电压调节到1.4V后该电致变色器件的颜色由无色变为棕色,循环10000次后,电致变色器件的颜色及其色彩强度无明显改变。
按上述方法以化合物6的DMF或γ-丁内酯溶液制得的电致变色器件,其电致变色性能类似。
最后说明的是,以上实施例仅用以说明本发明的技术方案而非限制,凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等,均应包含在本发明的保护范围之内。
Claims (6)
1.一种多色彩变化的四元环吡啶衍生物,其特征在于,所述多色彩变化的四元环吡啶衍生物具有式I所示结构:
式中,X1,X2,X3和X4相同且任意地为Cl、Br或I;
R1,R2,R3和R4相同且任意地为C1-C8烷基、C1-C8烯基、或有苯基或取代苯基取代的C1-C8烷基,所述取代苯基为有C1-C8烷基或C1-C8烯基取代的苯基;条件是式I不为CAS登记号为82649-99-8的化合物,即
2.如权利要求1所述的多色彩变化的四元环吡啶衍生物,其特征在于,R1,R2,R3和R4任意地为甲基、乙基、丁基、辛基、烯丙基、异戊烯基、苄基或4-乙烯基苄基和三氟甲基苄基。
3.如权利要求1所述的多色彩变化的四元环吡啶衍生物,其特征在于,所述多色彩变化的四元环吡啶衍生物为
4.一种如权利要求1所述多色彩变化的四元环吡啶衍生物的制备方法,其特征在于,所述多色彩变化的四元环吡啶衍生物的制备方法如下:
在有机溶剂中加入式II所示1,2,3,4-四-(4-吡啶基)环丁烷,再滴加式III所示卤代烃,1,2,3,4-四-(4-吡啶基)环丁烷与卤代烃的摩尔比为1∶4-4.5,然后80~90℃恒温搅拌反应,反应完毕后冷却至室温,加入三倍体积的***作沉淀剂,过滤,滤饼干燥,得式IV所示1,2,3,4-四-(4-吡啶基)环丁烷吡啶盐,即R1、R2、R3和R4相同且X1、X2、X3和X4相同的式I化合物;
所述多色彩变化的四元环吡啶衍生物的制备方法化学反应式如下:
5.如权利要求4所述的多色彩变化的四元环吡啶衍生物的制备方法,其特征在于,所述有机溶剂为乙腈,甲醇,乙醇,四氢呋喃,二甲基甲酰胺或二甲亚砜。
6.一种利用权利要求1所述多色彩变化的四元环吡啶衍生物制备的电致变色材料。
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Pyridylsubstituierte Cyclobutanderivate: Synthese und Redoxreaktionen von Cyaninen sowie Cyclobutenen und ihren Ringoffnungsprodukten;Michael Homer,等;《Liebigs Ann. Chem.》;19831231;642-657 |
Pyridylsubstituierte Cyclobutane durch Photodimerisierung von Azastilbenen;Michael Homer,等;《Liebigs Ann. Chem.》;19821231;1183-1210 |
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