CN106635060B - 一种具有近晶相—胆甾相转变的液晶组合物 - Google Patents
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Abstract
本发明公开了一种具有近晶相—胆甾相转变的液晶组合物。本发明将联苯氰类液晶化合物与适合的苯基环己烷类液晶化合物和双环己烷类液晶化合物进行共混,并在混合物中添加适量的手性化合物,得到了SmA~N*转变温度可在12℃~35℃任意调节的具有近晶相—胆甾相转变的液晶组合物。
Description
技术领域
本发明属于液晶材料领域,具体涉及一种具有近晶相—胆甾相转变的液晶组合物,其可以用于制备智能温控调光膜。
背景技术
能源是国民经济的基础产业,对经济持续稳定发展和人民生活质量的改善具有十分重要的保障作用。随着全球不可再生能源资源日益枯竭预期的强化,能源供需矛盾突现。提高能源使用效率是解决能源紧缺问题最为有效的途径之一。其中,新型高效节能材料的开发使用是一种从根本上大幅减少能耗的有效途径,具有极大的节能潜力。液晶材料可以对温度、电场、磁场等外界变化进行相应,因此,在智能节能材料领域有着非常广阔的应用空间。
根据分子排列的方式和有序性的不同,液晶可分为近晶相、向列相和胆甾相。近晶相液晶分子排列成层,在层内,分子长轴相互平行,其方向可垂直或倾斜与层面,因为分子排列整齐,其规整性接近晶体。但分子质心位置在层内无序,可以自由平移,从而有流动性,然而粘度很大。在向列相液晶分子结构中,如果没有外部取向(即表面边界和场)的影响,分子长轴基本上保持平行,但质心位置比近晶相更混乱,具有相当大的流动性。胆甾相液晶实际上是向列相液晶的一种特殊状态,也叫做手性向列相液晶,这类液晶分子呈扁平形状,排列成层,层内分子相互平行,分子长轴平行于层平面;不同层的分子长轴方向稍有变化,相邻两层分子,其长轴彼此有一轻微的扭曲角,多层分子的排列方向逐渐扭转成螺旋线,并沿着层的法线方向排列成螺旋状结构。
利用液晶分子在不同温度范围内呈现出不同的相态这一特点,可以制备出智能温控调光材料,这种材料不需要外界能量的输入,可以自身感应外界温度的变化,从而在光透过和光散射两种状态之间进行可逆的转变,因此是一种新型高效节能材料,并可广泛应用于建筑薄膜材料,汽车贴膜材料等领域。文献(Liq.Cryst.,2000;27[12];1695)中采用将液晶S6与液晶E48进行共混,得到了具有SmA~N*相转变的液晶组合物,并将该液晶组合物与液晶性可聚合单体、手性化合物SLI-4572、光引发剂组成混合物,制备出在低温时光透过,高温时光散射的液晶薄膜,但是该文献中所使用的液晶组合物转变温度较高,液晶相温度范围窄,不适合实际应用;中国专利文献CN101362949B采用联苯氰类液晶与向列相小分子混晶SLC1717进行共混,并添加适量的手性化合物,在一定程度上拓宽了液晶相的温度范围,但是该液晶组合物的相转变温度依然高于35℃,清亮点约为55℃,依然无法实际应用,而且SLC1717为商用类液晶,成本较高;中国专利文献CN104130783A采用联苯氰类液晶与二苯乙炔类液晶、含氟类液晶等进行共混,得到了具有SmA~N*相转变的液晶组合物,但是该液晶组合物的相转变温度高于24℃,用该液晶组合物制备的智能温控调光膜依然无法适用于一些环境温度较低的地区。总体而言,目前多种液晶材料的混配方法依然无章可循,为得到具有SmA~N*相转变的液晶材料,一般都是通过将具有近晶相的小分子液晶单体与具有向列相的小分子液晶单体进行共混,通过大量的实验,控制相应液晶单体的组分,来或得各方面性能都比较优异的液晶材料,如较低的相转变温度,高介电常数、低粘度等。
发明内容
本发明目的之一在于提供一种具有近晶相—胆甾相转变的液晶组合物,该液晶组合物具有相转变温度低,相变温度可任意调节,材料体系成本较低等优点。
本发明提供了一种具有近晶相—胆甾相转变的液晶组合物,所述液晶组合物包含第一组份,所述液晶组合物还包含第二组份、第三组份、第四组份、第五组份中的一种或多种;
所述第一组份为下列组A和组B中任意一组液晶化合物中的一种或几种,或为包括组A中一种或几种与组B中一种或几种组成的混合物;组A为式(1-a)所示的液晶化合物,组B为式(1-b)所示的液晶化合物,式中Ra是含有8~12个碳原子的烷基,Rb是含有8~10个碳原子的烷基;
所述第二组份为包括组C和组D中任意一组液晶化合物中的一种或几种,或为包括组C中一种或几种与组D中一种或几种组成的混合物;其中,Rc是含有6~7个碳原子的烷基,Rd是含有5~7个碳原子的烷基;组C为式(2-c)所示的液晶化合物,组D为式(2-d)所示的液晶化合物;
所述第三组份具有如式(3)所组成的液晶化合物;其中,R3是含有5~7个碳原子的烷基;
所述第四组份为下列组E、组F和组G中任意一组液晶化合物中的一种或几种,或为包括组E中一种或几种、组F中一种或几种、组G中一种或几种组成的混合物;其中,R4是含有5~7个碳原子的烷基;组E为式(4-e)所示的液晶化合物,组F为式(4-f)所示的液晶化合物,组G为式(4-g)所示的液晶化合物;
所述第五组份为具有相同手性构型的手性化合物。
作为上述技术方案一种较好的选择,所述液晶组合物内包括第一组份15%~40%,第二组份35%~60%,第三组份1%~10%,第四组分5%~25%,第五组份1%~20%。
作为上述技术方案一种较好的选择,所述的液晶组合物包括式(1-a)、式(1-b)、式(2-c)、式(2-d)、式(3)、式(4-e)、式(4-f)、式(4-g)所示的化合物和第五组份。
作为上述技术方案一种较好的选择,式(1-a)所示液晶化合物质量分数为15%~40%,式(1-b)所示液晶化合物质量分数为0%~8%,式(2-c)所示液晶化合物质量分数为16%~45%,式(2-d)所示液晶化合物质量分数为15%~28%,式(3)所示液晶化合物质量分数为1%~10%,式(4-e)所示液晶化合物质量分数为5%~25%,式(4-f)所示液晶化合物质量分数为0%~6%,式(4-g)所示液晶化合物质量分数为0%~5%,(5)所示液晶化合物质量分数为1%~20%。
本发明将联苯氰类液晶化合物与适合的苯基环己烷类液晶化合物和双环己烷类液晶化合物进行共混,并在混合物中添加适量的手性化合物,得到了SmA~N*转变温度可在12℃~35℃任意调节的具有近晶相—胆甾相转变的液晶组合物。该液晶组合物的最大优点在于可通过适当改变或增加相应的液晶化合物,使其相变温度可在12℃~35℃之间进行任意调节;同时兼具原料易得、成本低廉、性能稳定等优点。这意味着用该液晶组合物为主要原料制备的智能温控调光膜可通过调节SmA~N*的相转变温度从而可适用于全球不同气候条件的地区,使智能温控调光膜走向实用化迈出了重要的一步,使其在建筑节能等领域可发挥更广泛的作用。
具体实施方式
如下实施例仅用于说明本发明的技术方案,其并不能用于限制本发明的保护范围。
如下实施例中所涉及的符号及意义如下:
Cr~SmA表示结晶态到近晶A相的转变温度;
SmA~N*表示近晶A相到胆甾相的转变温度;
CP表示清亮点。
实施例1
按表1所示的液晶化合物及其对应的质量分数进行液晶组合物的混配;
表1实施例1的近晶相到胆甾相转变的液晶组合物的组份配比
上述液晶组合物的各相态之间的转变温度如表2所示。
表2实施例1中液晶组合物各相态之间的转变温度
实施例2
按表3所示的液晶化合物及其对应的质量分数进行液晶组合物的混配;
表3实施例2的近晶相到胆甾相转变的液晶组合物的组份配比
上述液晶组合物的各相态之间的转变温度如表4所示。
表4实施例2中液晶组合物各相态之间的转变温度
实施例3
按表5所示的液晶化合物及其对应的质量分数进行液晶组合物的混配;
表5实施例3的近晶相到胆甾相转变的液晶组合物的组份配比
上述液晶组合物的各相态之间的转变温度如表6所示。
表6实施例3中液晶组合物各相态之间的转变温度
Claims (3)
1.一种具有近晶相-胆甾相转变的液晶组合物,其特征在于所述液晶组合物内包括第一组份15%~40%,第二组份35%~60%,第三组份1%~10%,第四组分5%~25%,第五组份1%~20%;
所述第一组份为下列组A或组B中任意一组液晶化合物中的一种或几种,或包括组A中一种或几种与组B中一种或几种组成的混合物;组A为式(1-a)所示的液晶化合物,组B为式(1-b)所示的液晶化合物,式中Ra是含有8~12个碳原子的烷基,Rb是含有8~10个碳原子的烷基;
所述第二组份为包括组C和组D中任意一组液晶化合物中的一种或几种,或为组C中一种或几种与组D中一种或几种组成的混合物;其中,Rc是含有6~7个碳原子的烷基,Rd是含有5~7个碳原子的烷基;组C为式(2-c)所示的液晶化合物,组D为式(2-d)所示的液晶化合物;
所述第三组份具有如式(3)所组成的液晶化合物;其中,R3是含有5~7个碳原子的烷基;
所述第四组份为下列组E、组F和组G中任意一组液晶化合物中的一种或几种,或包括组E中一种或几种、组F中一种或几种、组G中一种或几种组成的混合物;其中,R4是含有5~7个碳原子的烷基;组E为式(4-e)所示的液晶化合物,组F为式(4-f)所示的液晶化合物,组G为式(4-g)所示的液晶化合物;
所述第五组份为具有相同手性构型的手性化合物;
所述液晶组合物的近晶A相到胆甾相的转变温度为12-24.8℃。
2.根据权利要求1所述的液晶组合物,其特征在于,所述的液晶组合物包括如式(1-a)、式(1-b)、式(2-c)、式(2-d)、式(3)、式(4-e)、式(4-f)、式(4-g)所示的化合物和第五组份。
3.根据权利要求1所述的液晶组合物,其特征在于,式(1-a)所示液晶化合物质量分数为15%~40%,式(1-b)所示液晶化合物质量分数为0%~8%,式(2-c)所示液晶化合物质量分数为16%~45%,式(2-d)所示液晶化合物质量分数为15%~28%,式(3)所示液晶化合物质量分数为1%~10%,式(4-e)所示液晶化合物质量分数为5%~25%,式(4-f)所示液晶化合物质量分数为0%~6%,式(4-g)所示液晶化合物质量分数为0%~5%,第五组份的质量分数为1%~20%。
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