CN116535569A - 一种无侧基丙烯酸酯液晶化合物及其制备方法 - Google Patents
一种无侧基丙烯酸酯液晶化合物及其制备方法 Download PDFInfo
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Abstract
本发明公开了一种无侧基丙烯酸酯液晶化合物及其制备方法。原料包括液晶分子、光引发剂、阻聚剂、交联剂、手性添加剂,其质量比为89.8‑78.4:3‑5:0.1‑0.3:3‑8:4‑8。制备方法是S1:原料溶于有机溶剂中,于40℃下搅拌混合;S2:用OSP10#线棒,控制湿膜厚度为6μm均匀涂布在PET上;S3:涂布完成后,将湿膜放到烘箱锡纸或铁板上,于60℃下烘烤15秒至1min,除去溶剂;S4:将膜取出经过40mj/cm2‑800mj/cm2的UV固化机,固定螺距梯度,得到炫彩液晶薄膜。本发明所制备的化合物消除了液晶分子之间的联锁,从而提升了分子构象随温度变化的能力。
Description
技术领域
本发明涉及液晶技术领域,尤其涉及一种无侧基丙烯酸酯液晶化合物及其制备方法。
背景技术
CLC因为具有温度依赖而发生颜色变化的这种热特性而被用于热致变色材料。这是因为CLC中P的大小受温度的影响,而P与反射波长有直接的相关性,因此温度变化,颜色发生变化。
Timothy J.Bunning等人将层状CLC薄膜与对温度有响应的CLC相结合,制备了具有可用温度调节反射波长的多反射带CLC薄膜,这是目前唯一将层状CLC薄膜与响应性CLC结合起来制备的可调的多反射带CLC器件。
上述制备层状胆甾相液晶材料的方法,虽然可以制备具有多个反射波带的CLC薄膜,但这一方法存在一个在实际中无可避免的问题,即层与层之间的界面会影响到薄膜整体的透过率。因此,制备具有多个反射波带的单层CLC薄膜成为一种需求,目前,只有两种方法实现了该功能,一是杨槐教授研究小组的洗出灌入法,二是Michel Mitov教授研究小组的聚合物稳定液晶的降温手性翻转法。李丽等在PET基材上分别制备了三层单一螺距叠加和单层梯度螺距分布的胆甾相液晶聚合物薄膜,薄膜厚度均匀,具有良好的膜基结合力,反射波宽均达200nm。李发胜等通过聚合物稳定胆甾相液晶制备了螺旋结构的高分子网络,然后灌入具有不同螺距的可聚合的胆甾相小分子液晶单体混合物,经紫外光照射聚合后获得了能够反射可见光区(450~780nm)覆盖红蓝绿三色光的胆甾相液晶固体薄膜。
发明内容
针对现有技术的不足,本发明提供一种无侧基丙烯酸酯液晶化合物及其制备方法。
为了实现上述目的,本发明的技术方案是:
一种无侧基丙烯酸酯液晶化合物,其原料至少包括液晶分子、光引发剂、阻聚剂、交联剂、手性添加剂,所述液晶分子、光引发剂、阻聚剂、交联剂和手性添加剂质量比为89.8-78.4:3-5:0.1-0.3:3-8:4-8;其中,所述液晶分子为液晶分子A和/或液晶分子B;
所述液晶分子A结构式为:
所述液晶分子B结构式为:
其中m为3-6;
作为对上述技术方案的改进,所述无侧基丙烯酸酯液晶化合物还包括流平剂,所述液晶分子、光引发剂、流平剂、阻聚剂、交联剂和手性添加剂质量比为89.8-78.4:3-5:0.1-0.3:0.1-0.3:3-8:4-8。
作为对上述技术方案的改进,本发明并提供了一种无侧基丙烯酸酯液晶化合物的制备方法,其特征在于:该制备方法包括以下步骤:
S1:将液晶分子、光引发剂、流平剂、阻聚剂、交联剂、手性添加剂溶于混合有机溶剂中,于40℃下搅拌混合;
S2:将上述制备好的液晶材料,用OSP10#线棒(湿膜间隙10μm),控制湿膜厚度为6μm均匀涂布在50μm的没有任何HC或primer的PET上;
S3:涂布完成后,将湿膜放到烘箱锡纸或铁板上,于60℃下烘烤15秒至1min,除去溶剂;最后将膜取出经过40mj/cm2-800 mj/cm2的UV固化机,固定螺距梯度,得到炫彩液晶薄膜;
作为对上述技术方案的改进,所述光引发剂为光引发剂184、907或MBZ中的一种或多种以任意比混合的混合物。
作为对上述技术方案的改进,所述流平剂为EFKA-3600、BYK355或BYK359。
作为对上述技术方案的改进,所述阻聚剂为对苯二酚或2,6二叔丁基对甲基苯酚。
作为对上述技术方案的改进,所述交联剂为二季戊四醇六丙烯酸酯或三丙烯酸丙烷三甲醇酯。
作为对上述技术方案的改进,所述手性添加剂为:
作为对上述技术方案的改进,所述混合有机溶剂为:环己酮、环戊酮和乙酸丁酯中的任意两种以任意比混合的混合物。
与现有技术相比,本发明具有的优点和积极效果是:1、本发明制备的无侧基丙烯酸酯液晶化合物,液晶核上无侧基,可以消除了液晶分子之间的联锁,从而提升了分子构象随温度变化的能力。2、通过不同化合物的配比应用于薄膜上可达到50%的反射,使得本发明的无侧基丙烯酸酯液晶化合物可应用于装饰、防伪等诸多领域。
附图说明
为了更清楚地说明本发明实施例或现有技术中的技术方案,下面将对实施例或现有技术描述中所需要使用的附图作简单地介绍,显而易见地,下面描述中的附图仅仅是本发明的一些实施例,对于本领域普通技术人员来讲,在不付出创造性劳动性的前提下,还可以根据这些附图获得其他的附图。
图1为A1的红外光谱图;
图2为B1的红外光谱图;
图3为实施例5的薄膜透过率曲线图;
图4为实施例6制得的薄膜在偏光显微镜下的液晶分子取向。
具体实施方式
下面将结合本发明实施例中的附图,对本发明实施例中的技术方案进行清楚、完整地描述,显然,所描述的实施例仅仅是本发明一部分实施例,而不是全部的实施例。基于本发明中的实施例,本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例,都属于本发明保护的范围。
本申请先用表一将下述五个实施例的配方比例给以展示。
表一:配方表
实施例1
制备包含如下结构的材料1:
液晶分子A1,其红外光谱如图1所示。
引发剂184
手性添加剂
(1)液晶分子A1的合成
将14.6g(0.05mol)4-(6-丙烯酰氧基己氧基)苯甲酸、12.5g(0.06mol)的N,N-二环己基碳二亚胺(DCC)和40mL二氯甲烷和添加到200mL的单口烧瓶中,室温搅拌并滴加含有3.3g(0.03mol)对苯二酚和0.7g(0.005mol)4-二甲胺基吡啶(DMAP)的二氯甲烷溶液100mL,搅拌反应48h之后抽滤除去不溶物,再用5%稀盐酸和5%碳酸氢钠水溶液分别洗涤,后用去离子水洗涤三遍,无水硫酸镁干燥过夜。抽滤除去硫酸镁,再配制二氯甲烷:乙酸丁酯=6:1的混合溶剂作为洗脱剂,通过柱层析法分离提纯得到的产物,真空干燥后得到白色晶体11.8g。
(2)薄膜材料的制备
称取液晶分子A1(8.98)与光引发剂184(0.3g),流平剂EFKA-3600(0.01g),阻聚剂对苯二酚(0.01g),二季戊四醇六丙烯酸酯(0.3g),手性添加剂S811(0.4g)溶于环己酮和环戊酮(4:1)(30g)混合溶剂中,制成固含量为25%的混合溶液。用OSP10#线棒(湿膜间隙10μm),控制湿膜厚度为6μm均匀涂布在50μm的没有任何HC或primer的PET上。u0℃烘烤15秒至1min,进行紫外固化,得到液晶薄膜。
将不同质量比例的液晶分子、光引发剂、流平剂、阻聚剂、交联剂、手性添加剂用以上方法混合,制得不同颜色的液晶薄膜,配方如表1所示。
实施例2
制备包含如下结构的材料2:
液晶分子A1
液晶分子B1,其红外光谱如图2所示。
引发剂907
手性添加剂
(1)液晶分子A1的合成
与实施例1中相同
(2)液晶分子B1的合成
29.2(0.1mol)4-(6-丙烯酰氧基己氧基)苯甲酸、16.74g(0.135mol)4-甲氧基酚13.5g(0.066mol)DCC、0.66g(0.006mol)DMAP溶于适量二氯甲烷中,在常温搅拌2天。反应结束后,将沉淀过滤除去,将体系浓缩,倒入正己烷中沉淀,并用正己烷重结晶,得到37.81g4-(6-丙烯酰氧基)己基苯甲酸-4’-甲氧基苯酚酯。
(3)薄膜材料的制备
称取液晶分子A1(4.49g)、B1(4.49g)与光引发剂907(0.3g),流平剂BYK355(0.01g),阻聚剂2,6二叔丁基对甲基苯酚(0.01g),交联剂三丙烯酸丙烷三甲醇酯,手性添加剂(0.4g)溶于环己酮和乙酸丁酯(4:1)(30g)混合溶剂中,制成固含量为25%的混合溶液。用OSP10#线棒(湿膜间隙10μm),控制湿膜厚度为6μm均匀涂布在50μm的没有任何HC或primer的PET上。60℃烘烤15秒至1min,进行紫外固化,得到液晶薄膜。
将不同质量比例的液晶分子、光引发剂、流平剂、阻聚剂、交联剂、手性添加剂用以上方法混合,制得不同颜色的液晶薄膜,配方如表1所示。
实施例3
制备包含如下结构的材料3:
液晶分子A2
引发剂BDK
手性添加剂
(1)液晶分子A2的合成
将14.6g(0.05mol)4-(6-丙烯酰氧基己氧基)苯甲酸、12.5g(0.06mol)的N,N-二环己基碳二亚胺(DCC)和40mL二氯甲烷和添加到200mL的单口烧瓶中,室温搅拌并滴加含有3.3g(0.03mol)邻苯二酚和0.7g(0.005mol)4-二甲胺基吡啶(DMAP)的二氯甲烷溶液100mL,搅拌反应48h之后抽滤除去不溶物,再用5%稀盐酸和5%碳酸氢钠水溶液分别洗涤,后用去离子水洗涤三遍,无水硫酸镁干燥过夜。抽滤除去硫酸镁,再配制二氯甲烷:乙酸丁酯=6:1的混合溶剂作为洗脱剂,通过柱层析法分离提纯得到的产物,真空干燥后得到白色晶体9.85g。
(2)薄膜材料的制备
称取液晶分子A2(8.98)与光引发剂BDK(0.3g),流平剂BYK359(0.01g),阻聚剂对苯二酚(0.01g),交联剂三丙烯酸丙烷三甲醇酯(0.3g),手性添加剂(0.4g)溶于环戊酮和乙酸丁酯(4:1)(30g)混合溶剂中,制成固含量为25%的混合溶液。用OSP10#线棒(湿膜间隙10μm),控制湿膜厚度为6μm均匀涂布在50μm的没有任何HC或primer的PET上。60℃烘烤15秒至1min,进行紫外固化,得到液晶薄膜。
将不同质量比例的液晶分子、光引发剂、流平剂、阻聚剂、交联剂、手性添加剂用以上方法混合,制得不同颜色的液晶薄膜,配方如表1所示。
实施例4
制备包含如下结构的材料4:
液晶分子A2
液晶分子B2
引发剂BDK
手性添加剂
(1)液晶分子A2的合成
与实施例3中相同
(2)液晶分子B2的合成
将26.4g(0.1mol)4-(4-丙烯酰氧基丁氧基)苯甲酸、16.74g(0.135mol)4-甲氧基酚13.5g(0.066mol)DCC、0.66g(0.006mol)DMAP溶于适量二氯甲烷中,在常温搅拌2天。反应结束后,将沉淀过滤除去,将体系浓缩,倒入正己烷中沉淀,并用正己烷重结晶,得到35.15g白色晶体。
(3)薄膜材料的制备
称取液晶分子A2(4.64g)、B2(4.64g)与光引发剂BDK(0.3g),流平剂BYK359(0.01g),阻聚剂2,6二叔丁基对甲基苯酚(0.01g),二季戊四醇六丙烯酸酯(0.3g),手性添加剂(0.4g)溶于环己酮和环戊酮(4:1)(30g)混合溶剂中,制成固含量为25%的混合溶液。用OSP10#线棒(湿膜间隙10μm),控制湿膜厚度为6μm均匀涂布在50μm的没有任何HC或primer的PET上。60℃烘烤15秒至1min,进行紫外固化,得到液晶薄膜。
将不同质量比例的液晶分子、光引发剂、流平剂、阻聚剂、交联剂、手性添加剂用以上方法混合,制得不同颜色的液晶薄膜,配方如表1所示。
实施例5
制备包含如下结构的材料5:
液晶分子A3
液晶分子B1
引发剂184
手性添加剂
(1)液晶分子A3的合成
将26.4g(0.1mol)4-(4-丙烯酰氧基丁氧基)苯甲酸、25.0g(0.12mol)的N,N-二环己基碳二亚胺(DCC)和80mL二氯甲烷和添加到200mL的单口烧瓶中,室温搅拌并滴加含有6.6g(0.06mol)对苯二酚和1.4g(0.01mol)4-二甲胺基吡啶(DMAP)的二氯甲烷溶液100mL,搅拌反应48h之后抽滤除去不溶物,再用5%稀盐酸和5%碳酸氢钠水溶液分别洗涤,后用去离子水洗涤三遍,无水硫酸镁干燥过夜。抽滤除去硫酸镁,再配制二氯甲烷:乙酸丁酯=6:1的混合溶剂作为洗脱剂,通过柱层析法分离提纯得到的产物,真空干燥后得到白色晶体17.4g。
(2)液晶分子B1的合成
与实施例2中相同
(3)薄膜材料的制备
称取液晶分子A3(4.3g)、B1(4.3g)与光引发剂184(0.4g),流平剂BYK359(0.02g),阻聚剂对苯二酚(0.02g),二季戊四醇六丙烯酸酯(0.7g),手性添加剂(0.8g)溶于环戊酮和乙酸丁酯(4:1)(30g)混合溶剂中,制成固含量为25%的混合溶液。用OSP10#线棒(湿膜间隙10μm),控制湿膜厚度为6μm均匀涂布在50μm的没有任何HC或primer的PET上。60℃烘烤15秒至1min,进行紫外固化,得到液晶薄膜。薄膜透过率曲线如图3所示。
将不同质量比例的液晶分子、光引发剂、流平剂、阻聚剂、交联剂、手性添加剂用以上方法混合,制得不同颜色的液晶薄膜,配方如表1所示。
实施例6
制备包含如下结构的材料6:
液晶分子A3
液晶分子B2
引发剂907
手性添加剂
(1)液晶分子A3的合成
与实施例5中相同
(2)液晶分子B2的合成
与实施例4中相同
(3)薄膜材料的制备
称取液晶分子A2(4.12g)、B1(4.12g)与光引发剂907(0.3g),流平剂BYK359(0.03g),阻聚剂对苯二酚(0.01g),三丙烯酸丙烷三甲醇酯(0.6g),手性添加剂(0.7g)溶于环己酮和乙酸丁酯(4:1)(30g)混合溶剂中,制成固含量为25%的混合溶液。用OSP10#线棒(湿膜间隙10μm),控制湿膜厚度为6μm均匀涂布在50μm的没有任何HC或primer的PET上。60℃烘烤15秒至1min,进行紫外固化,得到液晶薄膜。制得的薄膜在偏光显微镜下的液晶分子取向如图4所示。
将不同质量比例的液晶分子、光引发剂、流平剂、阻聚剂、交联剂、手性添加剂用以上方法混合,制得不同颜色的液晶薄膜,配方如表1所示。
基于本发明中的实施例,本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例,所作的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。
Claims (9)
1.一种无侧基丙烯酸酯液晶化合物,其特征在于:所述无侧基丙烯酸酯液晶化合物的原料至少包括液晶分子、光引发剂、阻聚剂、交联剂、手性添加剂,所述液晶分子、光引发剂、阻聚剂、交联剂和手性添加剂质量比为89.8-78.4:3-5:0.1-0.3:3-8:4-8;其中,所述液晶分子为液晶分子A和/或液晶分子B;
所述液晶分子A结构式为:
所述液晶分子B结构式为:
其中m为3-6且为整数。
2.如权利要求1所述无侧基丙烯酸酯液晶化合物,其特征在于:所述无侧基丙烯酸酯液晶化合物还包括流平剂,所述液晶分子、光引发剂、流平剂、阻聚剂、交联剂和手性添加剂质量比为89.8-78.4:3-5:0.1-0.3:0.1-0.3:3-8:4-8。
3.一种如权利要求2所述无侧基丙烯酸酯液晶化合物的制备方法,其特征在于:
S1:将液晶分子、光引发剂、流平剂、阻聚剂、交联剂、手性添加剂溶于混合有机溶剂中,于40℃下搅拌混合;
S2:将上述制备好的液晶材料,用OSP10#线棒,控制湿膜厚度为6μm均匀涂布在50μm的没有HC或primer的PET上;OSP10#线棒的湿膜间隙为10μm;
S3:涂布完成后,将湿膜放到烘箱锡纸或铁板上,于60℃下烘烤15秒至1min,除去溶剂;
S4:最后将膜取出经过40mj/cm2-800 mj/cm2的UV固化机,固定螺距梯度,得到炫彩液晶薄膜。
4.如权利要求3所述制备方法,其特征在于:所述光引发剂为光引发剂184、907或MBZ中的一种或多种以任意比混合的混合物。
5.如权利要求3所述制备方法,其特征在于:所述流平剂为EFKA-3600、BYK355或BYK359。
6.如权利要求3所述制备方法,其特征在于:所述阻聚剂为对苯二酚或2,6二叔丁基对甲基苯酚。
7.如权利要求3所述制备方法,其特征在于:所述交联剂为二季戊四醇六丙烯酸酯或三丙烯酸丙烷三甲醇酯。
8.如权利要求3所述制备方法,其特征在于:所述手性添加剂为
9.如权利要求3所述制备方法,其特征在于:所述混合有机溶剂为环己酮、环戊酮和乙酸丁酯中的任意两种以任意比混合的混合物。
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CN115322419A (zh) * | 2022-08-29 | 2022-11-11 | 华南师范大学 | 一种基于金纳米棒掺杂的偏振光响应型液晶聚合物网络薄膜的制备方法及其应用 |
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