CN101341190A - 聚合物4,4′-联吡啶结构、用于电致变色活性层的制剂及用于后者的用途 - Google Patents
聚合物4,4′-联吡啶结构、用于电致变色活性层的制剂及用于后者的用途 Download PDFInfo
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/0622—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms
- C08G73/0627—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms with only one nitrogen atom in the ring
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- C09K9/00—Tenebrescent materials, i.e. materials for which the range of wavelengths for energy absorption is changed as a result of excitation by some form of energy
- C09K9/02—Organic tenebrescent materials
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect
- G02F1/1503—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect caused by oxidation-reduction reactions in organic liquid solutions, e.g. viologen solutions
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
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- C09K2211/1466—Heterocyclic containing nitrogen as the only heteroatom
Abstract
本发明涉及一种材料体系,其中由于稳定化的结构改变使得电化学和/或光化学平行反应被完全避免或由于结构改变被抑制了几个数量级。本发明也涉及聚合物4,4′-联吡啶结构,基于该结构并应用于电致变色活性层的配方和4,4′-联吡啶结构用于生产有机电致变色显示器的用途。
Description
[0001]本发明涉及新型的聚合物4,4′-联吡啶鎓结构,基于该结构并应用于电致变色活性层的配方和4,4′-联吡啶鎓结构用于生产有机电致变色显示器的用途。
[0002]基于有机材料的电致变色显示器通常包含活性电致变色层,在显示器中其位于相互垂直安置的两个电极之间。该活性层的主要组成部分是氧化还原体系和pH活性染料。通过施加电压,材料中氧化还原配对物的彼此浓度比发生迁移。通过该反应,材料中质子和/或离子被释放或被束缚,其会对pH值产生影响。当对材料施加电压时,在两个电极上的氧化还原配对物的平衡向相反的方向迁移。由此会导致其中一个电极上的pH值上升,而对电极上的pH值下降。通过pH染料,pH值的变化被转换为材料颜色的变化并且使得电压的施加可视。
[0003]由WO 02/075441A2和WO 02/075442A1已知的是,在电极之间存在为电致变色体系的糊状制剂。电致变色系统的组成作为必要组分包含作为固体电解质的聚合物、导电盐、氧化还原系统、作为白色颜料的TiO2、溶剂和染料。所述染料通常是pH指示剂。
[0004]实现电致变色显示器的另一个原理在于,颜色的改变不是通过显示器中的pH值的改变而导致的,而是使用本来发生的氧化还原过程,通过在合适的材料中还原态和/或氧化态的形成来产生反差明显的颜色变化。而且首先作为材料种类已知的是所谓的紫精和聚噻吩。
[0005]在文献M.O.M.Edwards,Appl.Phys.Lett.2005,86(7)和Helmut W.Heuer,Rolf Wehrmann,Stephan Kirchmeyer Adv.Funct.Mater.2002,89中有实例。
[0006]迄今为止的发明中最大的缺点是这类电致变色显示器相对较短的使用寿命。在pH值调节的(实现通过离子,尤其是质子的电荷传递)显示器中,组分的多样性特别被视为制剂的缺陷,因为开始时仅有潜在的,也即附加的动力学或热动力学上抑制的电化学反应平行进行,但随时间的推移,会由于大范围的对比度退化(massive Verschlechterung des Kontraste)而凸现。此外作为质子活性的结果透明电极会劣化。
[0007]就以纯氧化还原材料为基础的显示器来说,如提到的基于紫精的体系,首先会由于还原物质的Pi(∏)异构(Merisation)(通过∏电子能级形成芳环堆叠)而发生颜色对比度退化,其导致由蓝色至紫色(因此称为紫精)的颜色迁移和极度的难溶性。
[0008]在这种情况下初始物质不再完全被电氧化(再次转变回无色的状态),以至于颜色改变时的对比越来越小。
[0009]本发明的任务在于,提出一种用于电致变色制剂的材料,其在不含其它的添加物(只有溶剂和染料)情况下在显示器中具有提高的长期稳定性。
[0011]本发明的主题和任务的解决方法是聚合物4,4′-联吡啶鎓结构,其通过亚烷基间隔基(C10至C20)彼此分开,以及其在用于电致变色活性层的制剂中的用途,以及电致变色活性层,其具有至少一种含4,4′-联吡啶鎓结构的组分,其中,4,4′-联吡啶鎓结构通过亚烷基间隔基分开。
[0012]作为亚烷基间隔基指的是以非共轭的直链C10至C20链,其与单独的联吡啶鎓单元彼此连接。
[0013]其中必要的是,当聚合物精确按照实施例中所述的规定制造时,形成的聚合物就具有提高的性能。特别重要的是反应要在80℃-120℃进行,优选85℃(乙腈)。由此可以确保在反应产物中除了聚合物之外还有低聚物,以及单官能的4,4′-联吡啶鎓-吡啶。
[0014]提出了含有至少一种下述结构的组分的下面的电致变色制剂:
n=10-20;
m=10-200;
X=任意阴离子,优选卤化物和/或三氟甲基磺酸盐,此外根据所述的规定所描述制造的材料也含有单官能团物质的部分。本发明材料的主要部分是基于4,4′-联吡啶鎓离子的结构,其由于结构性质不再具有紫精的性能。尤其标记n=10至20导致通过芳环堆叠的形成引起的π异构的发生几率如此之低,以至于预计到经多个循环之后均匀的可逆还原。在来自已知紫精的聚合物情况下发生聚合,该聚合物由具有短于C10的亚烷基间隔基的4,4′-联吡啶鎓结构制备。非聚合4,4′-联吡啶鎓盐也发生聚合,尽管其不会总是同样剧烈。
[0015]紫精是4,4′-联吡啶鎓结构,其在还原时另外发生∏异构(Pimerisieren),这以浅色位移(hypsochromen Farbshift)(从蓝色到紫色)可见,并以完全不溶解的聚合物化合物为特征。∏异构体(Pimer)的极端不溶性随时间的推移造成电致变色组件(EC-Bauelement)的残余变色,因为氧化还原不再是100%的可逆。该组件的另一个缺点是色移(Farbshift)依赖于浓度。
[0016]本发明的不具有紫精的性能的4,4′-联吡啶鎓离子的结构是相应的聚合物4,4′-联吡啶鎓结构,其通过亚烷基间隔基(C10至C20)相互分开。
[0017]该间隔基(Spacer)赋予聚合物在有机溶剂中好的溶解性并且避免了∏异构(Pimerisation),以至于4,4′-联吡啶鎓单元不会通过堆叠达到近程有序。还原态的颜色保持稳定的蓝色(分光光度计验证),而还原态中的聚合物在对质子惰性的极性(polar)和双极性(dipolar)溶剂(如碳酸丙二酯、丁内酯、醇,二醇)中有很好的溶解性。特别有利的是亚十二烷基间隔基,其不再容许紫精的性能并且仍允许有好的材料导电性。
[0018]单官能4,4′-联吡啶鎓-吡啶物质的含量在本发明制剂中起电子供体作用,并且由此造成电子传递,且该物质同时确保了阳极反应。此外通过单烷基化反应得到一种材料,其由于端基的极性,有改善的溶解性并导致了电致变色单元内部制剂稳定性提高。
[0019]此外通过本发明材料获得了纯蓝色的颜色外观(Farbeindruck),而不是如由聚合物得到的紫色或者蓝绿色的颜色外观。其中,这类化合物(紫精)就是以紫色外观得名。
此外令人惊奇的是通过本发明材料,该制剂可以在环境条件下生产和加工。
[0020]使用包含聚合物4,4′-联吡啶鎓盐的制剂,使得允许边缘锐利的对比明显的像素图像,在1V电压作用下不使用导电盐却有高的转换速度和提高的图像复现以及较长的使用寿命。
[0021]通过这种方式,本发明4,4′-联吡啶鎓盐可以在电场中一再回复到在阴极“蓝色”的联吡啶鎓盐和阳极无色(白色)联吡啶鎓盐。
[0022]实施例:
[0023]a)聚-亚十二烷基-4,4′-联吡啶鎓-二溴化物。
[0024]0.1mol 4,4′-联吡啶和0.1mol亚十二烷基二溴化物在500ml乙腈中搅拌升温至沸腾达10小时。冷却后,所述反应混合物用混入的200ml醚抽吸(absaugen),并用添加5%的甲醇的醚彻底清洗。产率为95%。
[0025]b)聚-亚十二烷基-4,4′-联吡啶鎓-三氟甲磺酸盐:
[0026]0.1mol 4,4′-联吡啶和0.1mol亚十二烷基二溴化物在500ml乙腈中搅拌升温至沸腾达10小时。冷却后,所述反应混合物用混入的200ml醚抽吸,并用添加了5%甲醇的醚彻底清洗。然后将经抽吸的产物溶于100ml甲醇并用0.2mol三氟甲磺酸银在50ml甲醇中的溶液处理。由此沉淀下来的溴化银被抽吸出,滤液被浓缩并最后用醚沉淀和洗涤。产率为75%
[0027]c)电致变色配方的制备:
0.6g本发明电致变色聚合物a)同6g TiO2和2g二甘醇在高速搅拌机下剧烈搅拌。
[0028]d)电致变色组件的制备:
[0029]制剂c)被施加到两个透明的导电基材间,其可用胶粘框粘结。通过施加大约1V的等电压,阴极均从白色转变为蓝色。
[0030]通过本发明首次给出一种材料体系,其中由于稳定化的结构改变使得电化学和/或光化学平行反应被完全避免或由于结构改变被抑制了几个数量级。本发明也涉及聚合物4,4′-联吡啶鎓结构,基于该结构并应用于电致变色活性层的制剂和4,4′-联吡啶鎓结构用于生产有机电致变色显示器的用途。
Claims (6)
1.通过亚烷基间隔基互相隔开的聚合物4,4′-联吡啶鎓结构,其特征在于,亚烷基间隔基包含10至20个碳原子。
2.按照权利要求1的4,4′-联吡啶鎓结构,其中亚烷基间隔基包含12至16个碳原子。
3.按照权利要求1或2的4,4′-联吡啶鎓结构,其中亚烷基间隔基包含12个碳原子。
4.用于电致变色活性层的制剂,其特征在于,其包含至少一种按照权利要求1至3任一项的含……的4,4′-联吡啶鎓结构的组分。
5.按照权利要求1至4任一项的含……的聚合物4,4′-联吡啶鎓结构用于制备电致变色活性层的用途。
6.按照权利要求1至4任一项的含……的聚合物4,4′-联吡啶鎓结构用于制备有机基电致变色显示器的用途。
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WO2008083861A1 (de) * | 2007-01-11 | 2008-07-17 | Siemens Aktiengesellschaft | Transparente organisch basierte elektrochrome formulierung, herstellung eines transparenten elektrochromen bauteils und verwendungen dazu |
DE102007023747A1 (de) | 2007-05-22 | 2008-11-27 | Siemens Ag | Organisches elektrochromes Bauelement für Daueranzeigen |
DE102007037618A1 (de) | 2007-08-09 | 2009-02-12 | Siemens Ag | Elektrochrom aktive Formulierung mit verbesserter Lebensdauer und Verfahren zur Herstellung der Formulierung und von Displays auf Basis des elektrochromen Effekts |
DE102007037619A1 (de) | 2007-08-09 | 2009-02-12 | Siemens Ag | Elektrochrom aktive Formulierung mit verbesserter Lebensdauer und Verfahren zur Herstellung der Formulierung und von Displays auf Basis des elektrochromen Effekts |
DE102008024259A1 (de) | 2008-05-20 | 2009-12-31 | Siemens Aktiengesellschaft | Elektrochrome Formulierung und Verfahren zur Herstellung einer elektrochromen Formulierung; Verwendung der Formulierung und organisches elektronisches elektrochromes Bauteil |
DE102008024260B4 (de) | 2008-05-20 | 2010-04-15 | Siemens Aktiengesellschaft | Elektrochrome Formulierung und organisches elektrochrom schaltbares elektronisches Bauteil |
DE102008049546A1 (de) | 2008-09-30 | 2010-04-08 | Siemens Aktiengesellschaft | Elektrochrome Formulierung, Herstellungsverfahren dazu und elektrochromes organisches Bauelement |
DE102008049543A1 (de) | 2008-09-30 | 2010-04-01 | Siemens Aktiengesellschaft | Elektrochrome Formulierung und elektrochromes organisches Bauelement |
DE102009023309A1 (de) * | 2009-05-29 | 2010-12-16 | Siemens Aktiengesellschaft | Elektrochrome Formulierung, Herstellungsverfahren dazu und elektrochromes organisches Bauelement |
CN102942517A (zh) * | 2012-11-12 | 2013-02-27 | 西南大学 | 共轭扩展的紫精衍生物及其制备方法和应用 |
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US3856714A (en) * | 1973-09-07 | 1974-12-24 | Polaroid Corp | Polyviologens |
US4898923A (en) * | 1987-11-30 | 1990-02-06 | Minnesota Mining And Manufacturing Company | Polypyridinium copolymer |
US4841021A (en) * | 1987-11-30 | 1989-06-20 | Minnesota Mining And Manufacturing Company | Polypyridinium |
JPH0795170B2 (ja) * | 1990-08-21 | 1995-10-11 | ダイソー株式会社 | ポリビオロゲン修飾電極およびその用途 |
US5910854A (en) * | 1993-02-26 | 1999-06-08 | Donnelly Corporation | Electrochromic polymeric solid films, manufacturing electrochromic devices using such solid films, and processes for making such solid films and devices |
BR9811668A (pt) * | 1997-07-07 | 2000-09-19 | Bayer Ag | Sistemas eletrocrÈmicos de polìmero |
JPH11142891A (ja) * | 1997-11-05 | 1999-05-28 | Nippon Oil Co Ltd | エレクトロクロミックミラー |
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- 2006-07-10 JP JP2008520862A patent/JP2009500677A/ja active Pending
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ATE504616T1 (de) | 2011-04-15 |
DE502006009265D1 (de) | 2011-05-19 |
EP1907446B1 (de) | 2011-04-06 |
WO2007006767A8 (de) | 2007-04-19 |
US20090040589A1 (en) | 2009-02-12 |
EP1907446A1 (de) | 2008-04-09 |
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