CN117430784A - 一种电致变色阴极材料以及电致变色溶液及其制备方法 - Google Patents
一种电致变色阴极材料以及电致变色溶液及其制备方法 Download PDFInfo
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Abstract
本发明公开了一种电致变色阴极材料,其为组分①、组分②、组分③反应生成的聚合物基嵌段式聚合物,其中,组分①为一种侧链接枝改性的联吡啶盐类材料。一种电致变色溶液的制备方法为将0.5‑2.5份组分①、0.02‑0.2份组分②、2‑10份组分③与电致变色溶液阳极材料一同溶解于100份溶剂中,分散均匀后,将滤液灌注进器件的空盒中,封口后将器件空盒放入烘箱中在60‑120℃温度下处理3至10小时,制得电致变色阴极材料。其优点在于:通过原位聚合的方式,使之变成一种聚合物凝胶态,降低了向负极迁移的速度,在长时间加电过程中,仍然较好地分散在溶液中而不会过度向一侧集结,保证了器件的变色效果。
Description
技术领域
本发明涉及电致变色材料制备技术领域,具体地说是一种电致变色阴极材料以及电致变色溶液及其制备方法。
背景技术
电致变色是指材料的光学属性(反射率、透过率、吸收率等)在外加电场的作用下发生稳定、可逆的颜色变化的现象,在外观上表现为颜色和透明度的可逆变化。具有电致变色性能的材料称为电致变色材料,用电致变色材料做成的器件称为电致变色器件。
电致变色过程中,电致变色溶液中含有阴极变色材料与阳极变色材料,这两种材料在溶液中正常情况下都是无色的,当给器件加直流电,阴极材料往负极迁移得到电子,阳极材料往正极迁移失去电子,此时材料的颜色或者说是吸收峰发生很大的变化,使溶液显色,即所谓的电致变色。
现有技术的电致变色材料中,小分子阴极变色材料因为相对分子量小,在变色过程中,小分子阴极变色材料在电场的作用下,容易向电极两侧迁移,以至于加电时间较长时,褪色过程中容易发生褪色过程不均匀的现象,更有甚者加电时间太长时,小分子阴极变色材料因为过度迁移,导致褪色时间很长或者不能褪色的情况出现。
如联吡啶类材料作为一种阴极电致变色材料,有着很好的着色效果。但是在其变色过程中,如遇到长时间加电,阴极变色材料的离子因为得到电子容易往正极迁移,阳极变色材料因为失去电子容易往负极迁移,从而发生两端极化现象,使得两者在正负极两侧发生聚集,在褪色过程中使得正负极两端过度聚集的离子无法快速恢复原状,甚至会导致变色的不可逆,严重影响产品的性能。因此,现有的电致变色阴极材料需要进一步改进。
发明内容
本发明之目的是弥补上述之不足,向社会公开能够避免变色材料过度迁移而导致变色不可逆现象产生的一种电致变色阴极材料以及电致变色溶液及其制备方法。
本发明的技术方案是这样实现的:
一种电致变色阴极材料,所述的电致变色阴极材料为组分①、组分②、组分③反应生成的聚合物基嵌段式聚合物,
其中,组分①为一种侧链接枝改性的联吡啶盐类材料,其结构式为:
其+2价为无色状态,+1价为显色状态,其中:R1、R2为吸电子基团或给电子基团,R3、R4为烷基,X为BF4或PF6;
组分②的结构式为:;
组分③的结构式为:。
作为改进,所述的R1、R2为吸电子基团,R1、R2分别为叔胺正离子、硝基、三卤烷基、氰基、磺酸基、甲酰基、酰基中的一种。
作为改进,所述的R1、R2为给电子基团,R1、R2分别为二烷基氨基、烷基氨基、氨基、羟基、烷氧基、烷基、苯基中的一种。
作为改进,所述的R3、R4中,烷基的C原子为2-20个,R3、R4分别为直链烷基伯烷、仲烷、叔烷或环烷基中的一种。
作为改进,所述的组分②为异佛尔酮二异氰酸酯。
作为改进,所述的组分③为聚甲基丙烯酸羟乙酯,聚合度n在10-1000之间,对应的相对分子质量在280-28000之间。
一种电致变色溶液,所述的电致变色溶液包含组分①、组分②、组分③以及电致变色溶液所需的阳极材料。
一种电致变色溶液的制备方法,将0.5-2.5份组分①、0.02-0.2份组分②、2-10份组分③与电致变色溶液所需的阳极材料一同溶解于100份溶剂中,分散均匀后,将所得滤液灌注进器件的空盒中,封口后将器件空盒放入烘箱中在60-120℃温度下处理3至10小时,制得聚合物阴极变色材料基的电致变色溶液,上述的份数均为质量份数。
作为改进,所述的组分①的制备方法,包括以下步骤:
步骤a、在三口烧瓶中依次加入60mmol2-丙羟基-4-溴吡啶、88mmol2-丙羟基-4-硼酸吡啶、1.12mmol Pd2(DBA)3、2.56mmol P(Cy)3、160ml二氧六环,氮气保护下用注射器,将用160ml脱氧水溶解的152mmol碳酸钾加入三口烧瓶中;待分散均匀,然后将其置于60℃油浴中,然后缓慢升温至100℃回流,保温搅拌18小时,再冷却至室温;将反应物倒入分液漏斗中分层,收集有机相后过滤,将滤液进行旋转蒸发将二氧六环挥发去除,所得残余固体在300ml乙酸乙酯中溶解,再用活性炭和无水硫酸钠进行处理,搅拌下加热回流10min,过滤,所得滤液再进行旋转蒸发将溶剂挥发掉,得到目标产物2,2-丙羟基-4,4-联吡啶;
步骤b、将38.6克溴庚烷和97.6克2,2-丙羟基-4,4-联吡啶和1.0L乙腈装入到安装有回流冷凝器、机械搅拌器和加热套的2L三口圆底烧瓶中,在正氮气压下搅拌的同时,将反应浆液加热回流;144小时后将反应冷却至室温,经由真空过滤得到粗制产品,然后用乙醇洗涤,再用丙酮进行洗涤,将得到的产物在真空干燥箱中60℃加热4h,得到纯化后的二溴化物盐;
步骤c、将二溴化物盐与200ml丙酮、500ml去离子水和500ml50%的六氟磷酸铵水溶液一起加入到2L的圆底烧瓶总,将得到的化合物加热至回流以溶解,然后室温冷却,期间目标产物1,1-二庚基-2,2-丙羟基-4,4-联吡啶二六氟磷酸盐形成沉淀,经过滤将产物收集,再用去离子水进行洗涤,然后用甲醇进行重结晶,将结晶的产物放入真空干燥箱中60℃处理8小时,即得到组分①。
作为改进,所述的组分③的制备方法,包括以下步骤:采用甲基丙烯酸羟乙酯100克、无水乙醇120克、偶氮二异丁腈0.5克、装入500ml三口烧瓶中分散均匀,通氮气30min将瓶内的氧气清除干净,再放入60℃油浴中加热反应12h,此时瓶内呈现胶状透明物质,将其倒出至器皿中,冷却后呈固态状态;将其用搅碎机分散呈细小颗粒,再放入真空干燥箱中100℃进行干燥处理5h,即得到组分③。
本发明与现有技术相比的优点是:
本发明通过将阴极变色材料进行原位聚合的方式,使之变成一种聚合物凝胶态,使其得到电子的同时,由于分子体积过大,降低了其向负极迁移的速度,从而使其在长时间加电过程中,仍然可以较好地分散在溶液中而不会过度向一侧集结,保证了器件的变色效果。
附图说明
图1为本发明的变色阴极材料器件两极加不同电压后的透光率光谱图。
具体实施方式
下面结合附图进一步详细描述本发明:
一种电致变色阴极材料,所述的电致变色阴极材料为组分①、组分②、组分③反应生成的聚合物基嵌段式聚合物,
其中,组分①为一种侧链接枝改性的联吡啶盐类材料,其结构式为:
其+2价为无色状态,+1价为显色状态,值得注意的是:其0价虽然显色,但是其可逆性差,也就是说,一旦到达0价时,器件就容易产生不可逆的破坏。
其中:R1、R2为吸电子基团或给电子基团,R3、R4为烷基,X为BF4或PF6;
组分②的结构式为:;
组分③的结构式为:。
所述的R1、R2为吸电子基团,R1、R2分别为叔胺正离子(-N+R3)、硝基(-NO2)、三卤烷基(-RX3,X=F、Cl)、氰基(-CN)、磺酸基(-SO3H)、甲酰基(-CHO)、酰基(-COR)中的一种。
所述的R1、R2为给电子基团,R1、R2分别为二烷基氨基(-NR2)、烷基氨基(-NHR)、氨基(-NH2)、羟基(-OH)、烷氧基(-OR)、烷基(-R)、苯基(-Ph)中的一种。
所述的R3、R4中,烷基的C原子为2-20个,R3、R4分别为直链烷基伯烷、仲烷、叔烷或环烷基中的一种。
所述的组分②为异佛尔酮二异氰酸酯。
所述的组分③为聚甲基丙烯酸羟乙酯,聚合度n在10-1000之间,对应的相对分子质量在280-28000之间。
一种电致变色溶液,所述的电致变色溶液包含组分①、组分②、组分③以及电致变色溶液所需的阳极材料。
一种电致变色溶液的制备方法,将0.5-2.5份组分①、0.02-0.2份组分②、2-10份组分③与电致变色溶液所需的阳极材料一同溶解于100份溶剂中,分散均匀后,将所得滤液灌注进器件的空盒中,封口后将器件空盒放入烘箱中在60-120℃温度下处理3至10小时,制得聚合物阴极变色材料基的电致变色溶液,上述的份数均为质量份数。
上述的溶剂为γ-丁内酯、碳酸丙烯酯、碳酸乙烯酯、N-甲基吡咯烷酮中的一种或两种的混合。
所述的组分①的制备方法,包括以下步骤:
步骤a、在三口烧瓶中依次加入60mmol2-丙羟基-4-溴吡啶、88mmol2-丙羟基-4-硼酸吡啶、1.12mmol Pd2(DBA)3、2.56mmol P(Cy)3、160ml二氧六环,氮气保护下用注射器,将用160ml脱氧水溶解的152mmol碳酸钾加入三口烧瓶中;待分散均匀,然后将其置于60℃油浴中,然后缓慢升温至100℃回流,保温搅拌18小时,再冷却至室温;将反应物倒入分液漏斗中分层,收集有机相后过滤,将滤液进行旋转蒸发将二氧六环挥发去除,所得残余固体在300ml乙酸乙酯中溶解,再用活性炭和无水硫酸钠进行处理,搅拌下加热回流10min,过滤,所得滤液再进行旋转蒸发将溶剂挥发掉,得到目标产物2,2-丙羟基-4,4-联吡啶;
步骤b、将38.6克溴庚烷和97.6克2,2-丙羟基-4,4-联吡啶和1.0L乙腈装入到安装有回流冷凝器、机械搅拌器和加热套的2L三口圆底烧瓶中,在正氮气压下搅拌的同时,将反应浆液加热回流;144小时后将反应冷却至室温,经由真空过滤得到粗制产品,然后用乙醇洗涤,再用丙酮进行洗涤,将得到的产物在真空干燥箱中60℃加热4h,得到纯化后的二溴化物盐;
步骤c、将二溴化物盐与200ml丙酮、500ml去离子水和500ml50%的六氟磷酸铵水溶液一起加入到2L的圆底烧瓶总,将得到的化合物加热至回流以溶解,然后室温冷却,期间目标产物1,1-二庚基-2,2-丙羟基-4,4-联吡啶二六氟磷酸盐形成沉淀,经过滤将产物收集,再用去离子水进行洗涤,然后用甲醇进行重结晶,将结晶的产物放入真空干燥箱中60℃处理8小时,即得到组分①。
所述的组分③的制备方法,包括以下步骤:采用甲基丙烯酸羟乙酯100克、无水乙醇120克、偶氮二异丁腈0.5克、装入500ml三口烧瓶中分散均匀,通氮气30min将瓶内的氧气清除干净,再放入60℃油浴中加热反应12h,此时瓶内呈现胶状透明物质,将其倒出至器皿中,冷却后呈固态状态;将其用搅碎机分散呈细小颗粒,再放入真空干燥箱中100℃进行干燥处理5h,即得到组分③。
将本发明的电致变色阴极材料器件的两极加0.8-1.5V电压,并测试其在不同电压下的透过率,测试结果如图1所示,图1中,横坐标为波长,纵坐标为透过率。本发明的电致变色材料分为褪色态和着色态两种状态,图1中从上至下分别为线1、线2、线3和线4,线1为褪色态的光谱曲线,线2为加0.8V电压下的着色态的光谱曲线,线3为加1.0V电压下的着色态的光谱曲线,线4为加1.2V电压下的着色态的光谱曲线。本发明的电致变色材料在不同电压下着色效果不同,电压越大,着色越深,透过率越低。
将本发明经过聚合处理的电致变色阴极材料器件与未经聚合处理的电致变色阴极材料器件进行对比实验。实验中,采用在不同电压下,并对器件持续加电压1h/2h/4h/8h/16h处理,对比器件褪色过程,未经聚合处理的电致变色阴极材料器件在加电1h后褪色有明显的黄蓝分离现象;而本发明的电致变色阴极材料经过聚合反应,通电2h后褪色均一性都非常好,均没有明显的黄蓝分离现象出现,通电4h以上,开始褪色时有轻微的黄蓝分离,但是10s内可以快速复原至正常褪色状态。
本发明的电致变色阴极材料通过将小分子阴极材料接枝到聚合物分子链上,使其保持变色性能的同时,通过与聚合物大分子形成一个整体,使其难以往一个方向迁移,从而减少了极化现象,降低了长时间加电后褪色不均匀的问题。通过原位聚合的方式,使之变成一种聚合物凝胶态,使其得到电子的同时,由于分子体积过大,降低了其向负极迁移的速度,从而使其在长时间加电过程中,仍然可以较好地分散在溶液中而不会过度向一侧集结,保证了器件的变色效果。本发明的电致变色阴极材料可广泛应用于电致变色领域,比如汽车防炫目后视镜,智能调光眼镜,智能调光摄像头,电致变色智能窗,汽车玻璃等领域。
电致变色溶液中,组分①含量的多少将直接影响器件的透光率,组分①的含量越多,透光率越低,相反,组分①的含量越少,透光率越高。
下表为不同组分①含量下透过率的光谱数据分析表:
其中,第1列对应不同波光,第2列至第9列对应不同组分①含量下(组1至组8,从组1至组8,组分①含量逐渐增加)对应的透光率,得到8组透光率数据。
对比实验:器件准备:采用两片30*30mm的方形导电玻璃,单边错位2mm,导电面贴合导电面用胶水沿边缘点胶贴合,且留一个单开口的孔用于灌液,中间用100微米的微球隔开形成一个空腔,制作好备用。
(1)将0.95份组分①、0.12份组分②、3.5份组分③与电致变色溶液所需的阳极材料一同溶解于100份γ-丁内酯中,分散均匀后,将所得滤液灌注进器件的空盒中,封口后将器件空盒放入烘箱中在90℃温度下处理6小时,制得一种含聚合物阴极材料的电致变色溶液。所测得的数据对应上述表格中第3组数据。
(2)将1.85份组分①、0.06份组分②、5.13份组分③与电致变色溶液所需的阳极材料一同溶解于100份碳酸丙烯酯中,分散均匀后,将所得滤液灌注进器件的空盒中,封口后将器件空盒放入烘箱中在100℃温度下处理4小时,制得一种含聚合物阴极材料的电致变色溶液。所测得的数据对应上述表格中第7组数据。
作为拓展,器件准备中的中间spacer盒厚可以50-300微米之间任意设定。组分①、组分②、组分③的含量可以做适当调整,其中组分①:0.5-2.5份,组分②:0.02-0.2份,组分③:2-10份,溶剂可以是γ-丁内酯、碳酸丙烯酯、碳酸乙烯酯、N-甲基吡咯烷酮中的任意一种或两种的任意比例组合,烘箱处理温度可以60-120℃之间,时间可以3-10小时之间任意设定。根据自身设定组成的器件性能光谱曲线,可从光谱数据中的组1-组8中数据中选取,根据组分①的浓度越高,着色越深,透过率越低,越靠近第8组数据的原则进行即可。
本发明的最佳实施例已被阐明,由本领域普通技术人员做出的各种变化或改型都不会脱离本发明的范围。
Claims (10)
1.一种电致变色阴极材料,其特征是:所述的电致变色阴极材料为组分①、组分②、组分③反应生成的聚合物基嵌段式聚合物,
其中,组分①为一种侧链接枝改性的联吡啶盐类材料,其结构式为:
其+2价为无色状态,+1价为显色状态,其中:R1、R2为吸电子基团或给电子基团,R3、R4为烷基,X为BF4或PF6;
组分②的结构式为:
组分③的结构式为:
2.根据权利要求1所述的一种电致变色阴极材料,其特征是:所述的R1、R2为吸电子基团,R1、R2分别为叔胺正离子、硝基、三卤烷基、氰基、磺酸基、甲酰基、酰基中的一种。
3.根据权利要求1所述的一种电致变色阴极材料,其特征是:所述的R1、R2为给电子基团,R1、R2分别为二烷基氨基、烷基氨基、氨基、羟基、烷氧基、烷基、苯基中的一种。
4.根据权利要求1所述的一种电致变色阴极材料,其特征是:所述的R3、R4中,烷基的C原子为2-20个,R3、R4分别为直链烷基伯烷、仲烷、叔烷或环烷基中的一种。
5.根据权利要求1所述的一种电致变色阴极材料,其特征是:所述的组分②为异佛尔酮二异氰酸酯。
6.根据权利要求1所述的一种电致变色阴极材料,其特征是:所述的组分③为聚甲基丙烯酸羟乙酯,聚合度n在10-1000之间,对应的相对分子质量在280-28000之间。
7.一种电致变色溶液,其特征是:所述的电致变色溶液包含如权利要求1中所述的组分①、组分②、组分③以及电致变色溶液所需的阳极材料。
8.根据权利要求7所述的一种电致变色溶液的制备方法,其特征是:将0.5-2.5份组分①、0.02-0.2份组分②、2-10份组分③与电致变色溶液所需的阳极材料一同溶解于100份溶剂中,分散均匀后,将所得滤液灌注进器件的空盒中,封口后将器件空盒放入烘箱中在60-120℃温度下处理3至10小时,制得聚合物阴极变色材料基的电致变色溶液,上述的份数均为质量份数。
9.根据权利要求8所述的一种电致变色溶液的制备方法,其特征是:所述的组分①的制备方法,包括以下步骤:
步骤a、在三口烧瓶中依次加入60mmol2-丙羟基-4-溴吡啶、88mmol2-丙羟基-4-硼酸吡啶、1.12mmol Pd2(DBA)3、2.56mmol P(Cy)3、160ml二氧六环,氮气保护下用注射器,将用160ml脱氧水溶解的152mmol碳酸钾加入三口烧瓶中;待分散均匀,然后将其置于60℃油浴中,然后缓慢升温至100℃回流,保温搅拌18小时,再冷却至室温;将反应物倒入分液漏斗中分层,收集有机相后过滤,将滤液进行旋转蒸发将二氧六环挥发去除,所得残余固体在300ml乙酸乙酯中溶解,再用活性炭和无水硫酸钠进行处理,搅拌下加热回流10min,过滤,所得滤液再进行旋转蒸发将溶剂挥发掉,得到目标产物2,2-丙羟基-4,4-联吡啶;
步骤b、将38.6克溴庚烷和97.6克2,2-丙羟基-4,4-联吡啶和1.0L乙腈装入到安装有回流冷凝器、机械搅拌器和加热套的2L三口圆底烧瓶中,在正氮气压下搅拌的同时,将反应浆液加热回流;144小时后将反应冷却至室温,经由真空过滤得到粗制产品,然后用乙醇洗涤,再用丙酮进行洗涤,将得到的产物在真空干燥箱中60℃加热4h,得到纯化后的二溴化物盐;
步骤c、将二溴化物盐与200ml丙酮、500ml去离子水和500ml50%的六氟磷酸铵水溶液一起加入到2L的圆底烧瓶总,将得到的化合物加热至回流以溶解,然后室温冷却,期间目标产物1,1-二庚基-2,2-丙羟基-4,4-联吡啶二六氟磷酸盐形成沉淀,经过滤将产物收集,再用去离子水进行洗涤,然后用甲醇进行重结晶,将结晶的产物放入真空干燥箱中60℃处理8小时,即得到组分①。
10.根据权利要求8所述的一种电致变色溶液的制备方法,其特征是:所述的组分③的制备方法,包括以下步骤:采用甲基丙烯酸羟乙酯100克、无水乙醇120克、偶氮二异丁腈0.5克、装入500ml三口烧瓶中分散均匀,通氮气30min将瓶内的氧气清除干净,再放入60℃油浴中加热反应12h,此时瓶内呈现胶状透明物质,将其倒出至器皿中,冷却后呈固态状态;将其用搅碎机分散呈细小颗粒,再放入真空干燥箱中100℃进行干燥处理5h,即得到组分③。
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