CN113234193A - 一种自支撑液晶膜及其制备方法 - Google Patents
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Abstract
本发明属于液晶领域,具体涉及一种自支撑液晶膜及其制备方法,所示制备方法,包括以下步骤,将液晶分子、手性掺杂剂和光引发剂在溶剂I中溶解混合后注入水面,通过紫外光照射,制得所述自支撑液晶膜。本发明是在水面制作液晶膜,不需要其他基底,易获得液晶膜;所采用的丙烯酸酯的液晶化合物,通过光聚合分子本身就可以交联,不需要外加交联剂,最后得到结构有序的手性向列相液晶聚合物薄膜;所得材料可以用于反射紫外、可见以及近红外光。
Description
技术领域
本发明属于液晶领域,具体涉及一种自支撑液晶膜及其制备方法。
背景技术
液晶是各向异性的流体,它结合了普通液体的流动特性和一般只有晶体才有的各向异性。它们的有序程度不同,代表了位于普通各向同性液体和结晶固体之间的热力学稳定相。液晶分为热致液晶和溶致液晶,热致液晶仅通过温度变化观察到,并且只能在一定温度范围内存在;溶致液晶是通过加入一个各向同性溶剂而形成的。热致液晶可分为近晶相,向列相和胆甾相(又称手性向列相)。胆甾相液晶(CLC)或手性向列相聚合物是一种一维光子材料,因其易于制备成响应性材料而备受关注,为了制作聚合物液晶膜,一般液晶与光反应双功能单体以约按照一定浓度比例混合,并加入手性掺杂剂和少量的光引发剂,将这种混合物填充到由氧化铟(ITO)涂层玻璃基板中;然后,通过表面相互作用或电场或磁场的应用,将材料带入所需的取向,并通过用紫外光照射样品来诱导光聚合,得到具有结构色的液晶薄膜。其工序复杂,制作成本高。
发明内容
本发明旨在提供一种自支撑液晶膜及其制备方法,能够简化加工工序,降低制作成本。
安装本发明的技术方案,所述自支撑液晶膜的制备方法,包括以下步骤,将液晶分子、手性掺杂剂和光引发剂在溶剂I中溶解混合后注入水面,通过紫外光照射,制得所述自支撑液晶膜。
进一步的,所述液晶分子为端基为丙烯酸酯的向列相液晶分子。
进一步的,所述液晶分子的通式为:
其中,n为3-12中任一整数,M为如下基团中的一种:
进一步的,所述液晶分子的制备方法如下:将化合物A、化合物B、二环己基碳二亚胺或三苯基膦、催化剂在溶剂II中混合,搅拌反应后重结晶得到所述液晶分子,所述化合物A的通式如下:
其中,n为3-12中任一整数;所述化合物B为如下任一一种:
进一步的,所述催化剂为4-二甲氨基吡啶或偶氮二甲酸二乙酯,所述溶剂II为四氢呋喃或二氯甲烷。具体的,当加入脱水剂二环己基碳二亚胺时,催化剂为4-二甲氨基吡啶;当加入三苯基膦时,催化剂为偶氮二甲酸二乙酯。
进一步的,所述化合物A与化合物B、脱水剂和催化剂的摩尔比为20~60:10~30:40~90:1.5~5。
进一步的,所述液晶分子的制备方法可以如下:称取4-(6-(丙烯酰氧基)己氧基)苯甲酸(20.0~60.0mmol),对苯二酚(10.0~30.0mmol),二环己基碳二亚胺(DCC)或三苯基膦(40.0~90.0mmol),4-二甲氨基吡啶或(DMAP)或偶氮二甲酸二乙酯(DEAD)(1.5~5.0mmol),放入250mL圆底烧瓶中,加入THF(100mL);将反应混合物在0℃搅拌2-5h,然后在室温搅拌40-60h;过滤后,通过在甲醇中重结晶来得到产物。合成通式如下:
其中,n为3-12中任一整数。
进一步的,所述溶剂I为乙酸乙酯、四氢呋喃、二氯甲烷或碳酸二乙酯。
进一步的,所述紫外光的波长为280~365nm nm。
进一步的,所述自支撑液晶膜的制备方法可以如下:称取液晶分子(0.01~0.5mmol),手性掺杂剂(0.005~0.1mmol),光引发剂(0.001~0.1mmol),将其用足够溶解量的乙酸乙酯(或四氢呋喃、二氯甲烷、碳酸二乙酯)溶解混匀后,用注射器吸取液晶混合物于盛有去离子水的烧杯中,将烧杯放入60~90℃的烘箱中,待溶剂完全挥发后取出,经波长为280~365nm的紫外光照射聚合,即可从水面上取得液晶膜。
本发明的第二方面提供了上述任一制备方法制得的自支撑液晶膜。
本发明的第三方面提供了上述自支撑液晶膜在制备液晶器件中的应用。
本发明的技术方案相比现有技术具有以下优点:
1、本发明是在水面制作液晶膜,不需要其他基底,易获得液晶膜;
2、本发明所采用的丙烯酸酯的液晶化合物,通过光聚合分子本身就可以交联,不需要外加交联剂,最后得到结构有序的手性向列相液晶聚合物薄膜;
3、本发明主要通过控制手性添加剂浓度进行光照聚合,固定其手性液晶相结构调整其结构色,这些材料可以用于反射紫外、可见以及近红外光。
附图说明
图1为液晶分子1的偏光显微镜照片(标尺长度50μm)。
图2为液晶分子2的偏光显微镜照片(标尺长度100μm)。
图3为液晶分子3的偏光显微镜照片(标尺长度100μm)。
图4为水面液晶膜2制作示意图。
图5为制备的液晶膜2图。
具体实施方式
下面结合附图和具体实施例对本发明作进一步说明,以使本领域的技术人员可以更好地理解本发明并能予以实施,但所举实施例不作为对本发明的限定。
实施例一
制备包含如下结构的液晶材料1:
液晶分子1
手性掺杂剂1
光引发剂1
(1)液晶分子1的合成
称取4-(6-(丙烯酰氧基)己氧基)苯甲酸(16.73g,57.22mmol),2-甲基对苯二酚(3.00g,27.25mmol),二环己基碳二亚胺(DCC)(16.53g,80.11mmol),4-二甲氨基吡啶(DMAP)(0.47g,3.9mmol)放入250mL圆底烧瓶中,加入重蒸过的四氢呋喃(THF)(100mL);将反应混合物在0℃搅拌3h,然后在室温搅拌48h;过滤后,在甲醇中重结晶,得到的白色固体即为液晶分子1,产率为63%,偏光显微镜照片如图1所示。
(2)液晶材料的制备
称取液晶分子1(50mg)、手性掺杂剂1(1.1mg)和光引发剂1(3mg),用乙酸乙酯溶解混合均匀,用注射器吸取液晶混合物于盛有去离子水的烧杯中,将烧杯放入90℃的烘箱中,待溶剂完全挥发后取出,经波长为365nm的紫外光照射聚合,即可从水面上取得红色液晶膜1。
实施例二
制备包含如下组分的液晶材料2
液晶分子2
手性掺杂剂2
光引发剂1
(1)液晶分子2的合成
称取4-(6-(丙烯酰氧基)己氧基)苯甲酸(16.73g,57.22mmol),2-甲基对苯二酚(3.38g,27.25mmol),二环己基碳二亚胺(DCC)(16.53g,80.11mmol),4-二甲氨基吡啶(DMAP)(0.47g,3.9mmol)放入250mL圆底烧瓶中,加入重蒸过的四氢呋喃(THF)(100mL);将反应混合物在0℃搅拌3h,然后在室温搅拌48h;过滤后,在甲醇中重结晶,得到的白色固体即为液晶分子2,产率为62%,偏光显微镜照片如图2所示。
(2)液晶材料2的制备
称取液晶分子2(50mg)、手性掺杂剂2(1.55mg)和光引发剂1(3mg),用乙酸乙酯溶解混合均匀,如图4所示,用注射器吸取液晶混合物于盛有去离子水的烧杯中,将烧杯放入90℃的烘箱中,待溶剂完全挥发后取出,经波长为365nm的紫外光照射聚合,即可从水面上取得紫色液晶膜2,其图片如图5所示。
实施例三
制备包含如下组分的液晶材料3
液晶分子3
手性掺杂剂3
光引发剂1
(1)液晶分子3的合成
称取4-(6-(丙烯酰氧基)己氧基)苯甲酸(16.73g,57.22mmol),2-氯对苯二酚(3.94g,27.25mmol),二环己基碳二亚胺(DCC)(16.53g,80.11mmol),4-二甲氨基吡啶(DMAP)(0.47g,3.9mmol)放入250mL圆底烧瓶中,加入重蒸过的四氢呋喃(THF)(100mL);将反应混合物在0℃搅拌3h,然后在室温搅拌48h;过滤后,在甲醇中重结晶,得到的白色固体即为液晶分子3,产率为54%,偏光显微镜照片如图3所示。
(2)液晶材料3的制备
称取液晶分子3(50mg)、手性掺杂剂3(1.55mg)和光引发剂1(3mg),用乙酸乙酯溶解混合均匀,用注射器吸取液晶混合物于盛有去离子水的烧杯中,将烧杯放入90℃的烘箱中,待溶剂完全挥发后取出,经波长为365nm的紫外光照射聚合,即可从水面上取得紫色液晶膜3。
实施例四
制备包含如下组分的液晶材料4
液晶分子4
手性掺杂剂2
光引发剂2
(1)液晶分子4的合成
称取4-(6-(丙烯酰氧基)己氧基)苯甲酸(16.73g,57.22mmol),2,3-二甲基对苯二酚(3.77g,27.25mmol),二环己基碳二亚胺(DCC)(16.53g,80.11mmol),4-二甲氨基吡啶(DMAP)(0.47g,3.9mmol)放入250mL圆底烧瓶中,加入重蒸过的四氢呋喃(THF)(100mL);将反应混合物在0℃搅拌3h,然后在室温搅拌48h;过滤后,在甲醇中重结晶,得到的白色固体即为液晶分子4,产率为64%。
液晶分子4的基础表征:
M.p.87℃.FT-IR(KBr,cm-1)υmax:2943,2860,1756,1604,1510,1388,1216,1078,1040,982,845,811and 762.1H NMR(400MHz,CDCl3;TMS):δ(ppm)1.44–1.57(m,8H,aliphatic hydrogens),1.73(m,4H,aliphatic hydrogens),1.85(m,4H,aliphatichydrogens),2.16(s,6H,-CH3),4.06(t,J=6.5Hz,4H,ArOCH2-),4.19(t,J=6.6Hz,4H,-COOCH2-),5.83(d,J=10.0Hz,2H,-CH=CH2),6.15(dd,J=17.3,10.4Hz,2H,-CH=CH2),6.41(d,J=17.3Hz,2H,-CH=CH2),6.98(d,J=6.8Hz,4H,ArH),7.04(d,2H,ArH),8.17(d,J=6.8Hz,4H,ArH).MS m/z(rel.int.):709(M++Na,100).Elemental analysis:calculated(for C40H46O10),C 69.95,H 6.75%;found,C 69.94,H 6.75%.
(2)液晶材料的制备
称取液晶分子4(50mg)、手性掺杂剂2(1.25mg)和光引发剂2(3mg),用乙酸乙酯溶解混合均匀,用注射器吸取液晶混合物于盛有去离子水的烧杯中,将烧杯放入90℃的烘箱中,待溶剂完全挥发后取出,经波长为365nm的紫外光照射聚合,即可从水面上取得绿色液晶膜4。
实施例五
制备包含如下组分的液晶材料5
液晶分子5
手性掺杂剂3
光引发剂2
(1)液晶分子5的合成
称取4-(6-(丙烯酰氧基)己氧基)苯甲酸(16.73g,57.22mmol),2,6-二甲基对苯二酚(3.77g,27.25mmol),二环己基碳二亚胺(DCC)(16.53g,80.11mmol),4-二甲氨基吡啶(DMAP)(0.47g,3.9mmol)放入250mL圆底烧瓶中,加入重蒸过的四氢呋喃(THF)(100mL);将反应混合物在0℃搅拌3h,然后在室温搅拌48h;过滤后,在甲醇中重结晶,得到的白色固体即为产物,产率为56%。
液晶分子5的基础表征:
M.p.87℃.FT-IR(KBr,cm-1)υmax:2943,2860,1756,1604,1510,1388,1216,1078,1040,982,845,811and 762.1H NMR(400MHz,CDCl3;TMS):δ(ppm)1.44–1.57(m,8H,aliphatic hydrogens),1.73(m,4H,aliphatic hydrogens),1.85(m,4H,aliphatichydrogens),2.16(s,6H,-CH3),4.06(t,J=6.5Hz,4H,ArOCH2-),4.19(t,J=6.6Hz,4H,-COOCH2-),5.83(d,J=10.0Hz,2H,-CH=CH2),6.15(dd,J=17.3,10.4Hz,2H,-CH=CH2),6.41(d,J=17.3Hz,2H,-CH=CH2),6.98(d,J=6.8Hz,4H,ArH),7.04(d,2H,ArH),8.17(d,J=6.8Hz,4H,ArH).MS m/z(rel.int.):709(M++Na,100).Elemental analysis:calculated(for C40H46O10),C 69.95,H 6.75%;found,C 69.94,H 6.75%.
(2)液晶材料的制备
称取液晶分子5(50mg)、手性掺杂剂3(1.5mg)和光引发剂2(3mg),用乙酸乙酯溶解混合均匀,用注射器吸取液晶混合物于盛有去离子水的烧杯中,将烧杯放入80℃的烘箱中,待溶剂完全挥发后取出,经波长为365nm的紫外光照射聚合,即可从水面上取得紫色液晶膜5。
实施例六
制备包含如下组分的液晶材料6
液晶分子6
手性掺杂剂1
光引发剂2
(1)液晶分子6的合成
称取4-(6-(丙烯酰氧基)己氧基)苯甲酸(16.73g,57.22mmol),2,3,5,6-四氟对苯二酚(4.96g,27.25mmol),二环己基碳二亚胺(DCC)(16.53g,80.11mmol),4-二甲氨基吡啶(DMAP)(0.47g,3.9mmol)放入250mL圆底烧瓶中,加入重蒸过的四氢呋喃(THF)(100mL);将反应混合物在0℃搅拌3h,然后在室温搅拌48h;过滤后,在甲醇中重结晶,得到的白色固体即为液晶分子6,产率为62%。
液晶分子6的基础表征:
M.p.88℃.FT-IR(KBr,cm-1)υmax:2935,2857,1753,1604,1512,1244,1195,1052,982,863,809,755,731and 688.1H NMR(400MHz,CDCl3;TMS):δ(ppm)1.49–1.35(m,8H,aliphatic hydrogens),1.72–1.59(m,4H,aliphatic hydrogens),1.87–1.73(m,4H,aliphatic hydrogens),4.00(t,J=6.3Hz,4H,ArOCH 2-),4.12(t,J=6.6Hz,4H,-COOCH 2-),5.76(d,J=10.4Hz,2H,-CH=CH 2),6.06(dd,J=17.3,10.4Hz,2H,-CH=CH2),6.34(d,J=17.3Hz,2H,-CH=CH 2),6.93(d,J=8.7Hz,4H,ArH),8.09(d,J=8.7Hz,4H,ArH).MS m/z(rel.int.):753(M++Na,100).Elemental analysis:calculated(for C38H38F4O10),C62.46,H 5.24%;found,C 62.48,H 5.25%.
(2)液晶材料6的制备
称取液晶分子6(50mg)、手性掺杂剂1(3.0mg)和光引发剂2(3mg),用乙酸乙酯溶解混合均匀,用注射器吸取液晶混合物于盛有去离子水的烧杯中,将烧杯放入90℃的烘箱中,待溶剂完全挥发后取出,经波长为365nm的紫外光照射聚合,即可从水面上取得液晶膜。
显然,上述实施例仅仅是为清楚地说明所作的举例,并非对实施方式的限定。对于所属领域的普通技术人员来说,在上述说明的基础上还可以做出其它不同形式变化或变动。这里无需也无法对所有的实施方式予以穷举。而由此所引申出的显而易见的变化或变动仍处于本发明创造的保护范围之中。
Claims (10)
1.一种自支撑液晶膜的制备方法,其特征在于,包括以下步骤,将液晶分子、手性掺杂剂和光引发剂在溶剂I中溶解混合后注入水面,通过紫外光照射,制得所述自支撑液晶膜。
4.如权利要求3所述的自支撑液晶膜的制备方法,其特征在于,所述催化剂为4-二甲氨基吡啶或偶氮二甲酸二乙酯,所述溶剂II为四氢呋喃或二氯甲烷。
7.如权利要求1所述的自支撑液晶膜的制备方法,其特征在于,所述溶剂I为乙酸乙酯、四氢呋喃、二氯甲烷或碳酸二乙酯。
8.如权利要求1所述的自支撑液晶膜的制备方法,其特征在于,所述紫外光的波长为280~365nm。
9.如权利要求1-8任一所述制备方法制得的自支撑液晶膜。
10.如权利要求9所述的自支撑液晶膜在制备液晶器件中的应用。
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