CN109593424B - 水响应的互穿聚合物网络及其制备方法和应用 - Google Patents

水响应的互穿聚合物网络及其制备方法和应用 Download PDF

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CN109593424B
CN109593424B CN201811418185.2A CN201811418185A CN109593424B CN 109593424 B CN109593424 B CN 109593424B CN 201811418185 A CN201811418185 A CN 201811418185A CN 109593424 B CN109593424 B CN 109593424B
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water
polymer network
interpenetrating polymer
liquid crystal
responsive
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CN109593424A (zh
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劳伦斯·德·哈恩
邓子轩
周国富
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South China Normal University
Shenzhen Guohua Optoelectronics Co Ltd
Academy of Shenzhen Guohua Optoelectronics
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South China Normal University
Shenzhen Guohua Optoelectronics Co Ltd
Academy of Shenzhen Guohua Optoelectronics
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Priority to PCT/CN2018/124575 priority patent/WO2020107614A1/zh
Priority to US16/498,727 priority patent/US11498989B2/en
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Abstract

本发明公开了水响应的互穿聚合物网络及其制备方法和应用，所述水响应的互穿聚合物网络包括胆甾型液晶聚合物和聚离子液体形成的互穿聚合物网络；其中，所述胆甾型液晶聚合物由液晶混合物经聚合形成；所述聚离子液体含有亲水性基团或为亲水性的盐。本发明的互穿聚合物网络无需进行碱性溶液活化便具有水响应性，简化了制备过程，在长时间和/或重复暴露于水后响应性能稳定，本发明的水响应的互穿聚合物网络能够用于制备光反射涂层和反射器件，具有较高的商业价值。

Description

水响应的互穿聚合物网络及其制备方法和应用
技术领域
本发明涉及水响应材料，尤其是涉及一种水响应的互穿聚合物网络。
背景技术
液晶显示中通常使用的材料一般由棒状分子组成，这些分子都指向一个方向，这种特性使得这些材料具有有序的相，但是也能像液体一样流动，其中胆甾型液晶对于制备各种光子系统具有非常重要的意义。当向列型材料或者混合物部分或全部由具有手性中心的分子组成时会形成胆甾相，在这种相中指向矢轴不断扭曲，导致分子形成螺旋结构，该相具有能够基于一个完整螺旋距离(即螺距)反射特定波段的光的特殊属性，当光的偏振手性和胆甾相螺距结构的手性相同时会发生反射，胆甾相材料中手性分子的种类和数量决定着螺距和反射的波长，手性分子越多，螺距越短，反射波长越短，这种特性可以用来调整材料反射光的波长。
在一些胆甾型材料中，外部刺激可以改变螺距进而改变反射光的波长，利用此特性能够应用在一些如温度计、情绪环、智能红外反射器、水响应彩色图案、传感器、成像、防伪措施等应用上。水响应胆甾型材料是一种特殊类型的胆甾型液晶系统，其通常含有一些亲水基团，与水分子相互作用能够使材料膨胀，增加胆甾相的螺距，进而增加反射波长，当材料再次干燥时能够恢复初始状态，其与水分子作用的过程通常是可逆的。通常，水响应性胆甾醇材料含有羧基作为亲水基团，羧基之间的强氢键有利于与水的氢键合，而这些基团最初不是水响应性的，为了使这些材料对水有响应，它们需要用高pH溶液活化，例如氢氧化钠(NaOH)或氢氧化钾(KOH)的水溶液。这将羧酸基团转化为吸湿性羧酸盐(当分别使用NaOH或KOH时，分别得到对应的羧酸钠或羧酸钾)，其不再形成氢键但可以与水分子发生离子相互作用。而这种能够与水分子发生相互作用的材料具有较大的潜在商业价值，例如Moirangthem等人开发出可印刷的蓝色CLC聚合物涂层，使用Ca(NO3)2溶液的喷墨印刷将该涂层图案化，其通过用更强离子键合的钙离子代替钾离子来抑制水溶胀。最终产品在暴露于水中或仅仅通过呼气时显示出全彩色伪装。
互穿聚合物网络是由两种或多种各自交联和互相穿透的聚合物网络组成的高分子共混物。作为在没有内置吸湿基团的液晶网络中获得水响应性的方法，可以通过建立互穿聚合物网络(IPN)获得水响应膜，例如胆甾型液晶和聚(丙烯酸)结合形成的互穿聚合物网络，将可聚合液晶和不可聚合液晶的胆甾型混合物聚合，并通过加热除去不可聚合化合物，其中不可聚合液晶被称为致孔剂，然后利用通过除去不可聚合化合物产生的自由空间使丙烯酸渗透到膜中，并进行第二次聚合锁住丙烯酸，这样，就得到了一个互穿网络。这种基于羧酸基团的具有水响应的所有胆甾型系统，均需要用碱性溶液活化以破坏氢键并使材料具有吸湿性以诱导水响应。此外这种基于碱活化羧基的水响应性胆甾型聚合物反射器的水响应性的稳定性都不理想，这是由于反应阳离子在浸入水中时很容易从网络中逸出，因此激活过程将迅速逆转，导致响应性消失，从而使得这些器件的寿命较短，无法应用于商业产品，只具有作为一次性实验室演示的价值。
发明内容
针对现有技术的不足，本发明所要解决的技术问题是提供一种水响应的互穿聚合物网络及制备方法、光反射涂层和反射器件，所述水响应的互穿聚合物网络无须经过碱活化过程，并且在长时间使用时水响应性不会丧失，具有较高的商业价值。
本发明所采取的技术方案是：
本发明提供一种水响应的互穿聚合物网络，包括胆甾型液晶聚合物和聚离子液体形成的互穿聚合物网络；其中，所述胆甾型液晶聚合物由液晶混合物经聚合形成；所述聚离子液体含有亲水性基团或为亲水性的盐。
优选地，所述亲水性基团包括羟基、酰胺基、羧基、吡咯基中的至少一种；所述亲水性的盐优选羧酸盐、铵盐、磺酸盐、咪唑盐、吡啶盐。
优选地，所述聚离子液体由可聚合盐经聚合形成，所述可聚合盐由离子液体单体一和离子液体单体二反应生成，所述离子液体单体一为：
Figure BDA0001879969750000031
离子液体单体二为：
Figure BDA0001879969750000032
其中，R1、R2各自独立地选自氢、C1～C10的烷基、卤素基团、C1～C10的烷氧基，R3选自C1～C10的亚烷基，R4、R5各自独立地选自C1～C10的烷基。所述卤素基团包括Cl、Br等。
进一步优选地，R1选自氢或甲基，R2选自氢或甲基，R3选自C1～C6的亚烷基，R4、R5各自独立地选自氢、甲基、乙基中的一种。
上述离子液体单体一和离子液体单体二生成可聚合盐的反应过程如下所示：
Figure BDA0001879969750000041
离子液体单体一为不饱和羧酸衍生物，其中羧基可与离子液体单体二结合生成羧酸盐。作为形成可聚合盐所使用的分子，根据本发明的优选化合物，如表1所示：
表1形成可聚合盐的分子的优选化合物
Figure BDA0001879969750000042
优选地，所述液晶混合物包含可聚合的液晶单体、手性掺杂剂和光引发剂。其中，可聚合的液晶单体可以全部或部分是手性液晶单体，目的是为了使液晶混合物聚合形成胆甾型液晶聚合物。
进一步优选地，所述液晶混合物中还包含表面活性剂，用以改善分子的排列。
本发明还提供一种上述的水响应的互穿聚合物网络的制备方法，包括以下步骤：
S1、取液晶混合物和致孔剂混合，聚合，然后除去致孔剂；
S2、加入离子液体单体，再次聚合，形成互穿聚合物网络。
本发明选择的致孔剂在液晶混合物聚合形成胆甾型聚合物时不参与反应，并且能够通过加热蒸发或溶剂洗涤的方式去除，优选所述致孔剂为不可光聚合的液晶单体。
以下为使用的液晶单体和致孔剂的优选化合物，如表2和表3所示。
表2液晶单体的优选化合物
Figure BDA0001879969750000051
Figure BDA0001879969750000061
表3使用的致孔剂的优选化合物
Figure BDA0001879969750000062
根据本发明的制备方法，优选在基板上制备水响应的互穿聚合物网络，具体而言，将液晶混合物和致孔剂混合后涂覆于基板上，所采用的基板可以为硬质基板如玻璃，也可以是软质基板如塑料薄膜，涂覆的工艺可以采用刮刀涂布、棒涂、旋涂、喷墨打印和喷涂中的一种，基板可以带有取向层以改善分子的排列，尽管这可能并不总是必要的，因为在涂覆过程中剪切力在许多情况下也可以引起排列。涂覆后，用紫外光照射以活化光引发剂并引发液晶单体的聚合。此时得到的是固体薄膜，其中仍存在致孔剂，通过加热蒸发或溶剂洗涤除去致孔剂，得到具有自由空间的胆甾型聚合物，然后在自由空间中填充可聚合盐，再次聚合后形成互穿聚合物网络。
上述的水响应的互穿聚合物网络在智能红外反射器、水响应彩色图案、传感器、成像和防伪措施中的应用。
发明还提供一种光反射涂层，包括上述的水响应的互穿聚合物网络。
本发明还提供一种反射器件，包括上述的水响应光反射涂层。
本发明的有益效果是：
本发明提供一种水响应的互穿聚合物网络，利用胆甾型液晶聚合物和聚离子液体互穿形成，使用聚离子液体代替传统的聚丙烯酸作为第二聚合物，离子液体单体聚合形成的聚离子液体由于具有亲水性基团或为亲水性盐，因而具有吸湿性能够使互穿聚合物网络吸收水分并膨胀，增加了互穿聚合物网络中胆甾型聚合物的螺距的长度，反过来导致互穿聚合物网络材料的反射波长的增加，从而表现出水响应性。本发明的水响应的互穿聚合物网络无需进行碱性溶液活化，简化了制备过程，同时由于正离子和负离子都是聚离子液体的一部分，因此被捕获在互穿聚合物网络中时，没有离子可以从网络中逸出，不会损失材料的水响应性能，在长时间和/或重复暴露于水后响应性能稳定，本发明的水响应的互穿聚合物网络能够用于制备光反射涂层和反射器件，具有较高的商业价值。
附图说明
图1为对比例1中的互穿聚合物网络的水响应稳定性的测试结果图；
图2为实施例1的互穿聚合物网络的水响应稳定性的测试结果图。
具体实施方式
以下将结合实施例对本发明的构思及产生的技术效果进行清楚、完整地描述，以充分地理解本发明的目的、特征和效果。显然，所描述的实施例只是本发明的一部分实施例，而不是全部实施例，基于本发明的实施例，本领域的技术人员在不付出创造性劳动的前提下所获得的其他实施例，均属于本发明保护的范围。
下述实施例中使用的向列型液晶单体HCM-002，购于江苏和成，结构为：
Figure BDA0001879969750000081
手性掺杂剂HCM-006，购于江苏和成，结构为：
Figure BDA0001879969750000082
不可聚合液晶基元5CB，购于江苏创拓，结构为：
Figure BDA0001879969750000083
光引发剂的结构为：
Figure BDA0001879969750000084
表面活性剂的结构为：
Figure BDA0001879969750000085
实施例1
取48.6质量份的向列型液晶单体HCM-002、6.8质量份的手性掺杂剂HCM-006、2质量份的光引发剂、2质量份表面活性剂和40.6质量份的不可聚合液晶基元5CB，混合形成混合物，使用刮刀涂布将其涂覆在甲基丙烯酸酯官能化的玻璃基板上，利用剪切力使分子取向，在涂覆后立即使用紫外照射，在氮气氛下光聚合已取向的涂层，其中不可聚合液晶基元5CB作为致孔剂存在，然后置于140℃下加热10min以除去5CB，得到胆甾型聚合物涂层。
取等摩尔的丙烯酸和甲基丙烯酸2-(二甲基氨基)乙酯中和反应产生可聚合盐，具体形成过程为：
Figure BDA0001879969750000091
取反应生成的可聚合盐置于上述胆甾型聚合物涂层上，用赶紧的玻璃板盖住，加热以使可聚合盐更好和快速地渗透，然后进行第二次紫外光照射以使可聚合盐聚合形成聚离子液体并与胆甾型聚合物形成互穿聚合物网络。
本实施例中形成聚离子液体所使用的可聚合盐为丙烯酸和甲基丙烯酸2-(二甲基氨基)乙酯反应生成的羧酸盐，本发明中聚离子液体包含但不限于羧酸基离子液体、磺酸基离子液体如4-乙烯基苯磺酸-四丁基季膦盐聚合物(PTPSS)、酰胺基离子液体如N-异丙基丙烯酰胺的聚合物(PNIPAM)等，由于聚离子液体具有亲水性基团或为亲水性盐，因而具有吸湿性能够使互穿聚合物网络吸收水分并膨胀，增加了互穿聚合物网络中胆甾型聚合物的螺距的长度，反过来导致互穿聚合物网络材料的反射波长的增加，从而表现出水响应性，同时由于正离子和负离子都是聚离子液体的一部分，因此被捕获在互穿聚合物网络中时，没有离子可以从网络中逸出，不会损失材料的水响应性能。
实施例2
对比例1：对比例1提供一种胆甾型互穿聚合物网络，制备过程与实施例1相同，不同之处在于使用丙烯酸代替实施例1中的可聚合盐并与胆甾型聚合物形成互穿聚合物网络，并使用KOH进行活化。
取实施例1和对比例1中的互穿聚合物网络，对其进行水响应稳定性测试，具体过程如下：将两种互穿聚合物网络均浸入去离子水中，利用UV-Vis/IR光谱法测定浸入不同时间后两种互穿聚合物网络在湿润状态下的反射带，结果如图1和图2所示，其中图1表示对比例1，图2表示实施例1。从图1中可以看出，对比例1中的对于经过活化的聚丙烯酸互穿的聚合物网络，其反射带随着浸入时间的增加发生蓝移，由浸泡5分钟时的在563nm处的反射带，随着浸泡的时间不断地延长反射带位置持续蓝移，当浸泡时间达到7天时，其反射带处于436nm的位置，基本上和干燥时的反射带位置一致，这表明随着浸泡时间的延长，正离子不断从网络中逸出并且水响应性逐渐消失。从图2中可以看出，对于实施例1中的聚离子液体与胆甾型液晶聚合物形成的互穿聚合物网络，随着浸入时间的增加，其测得的反射带位置均保持基本相同的值，大致位置处于513nm，浸泡5min和浸泡30min测得的反射带曲线基本一致，浸泡3h和浸泡1d测得的反射带曲线基本一致，从侧面也说明了本发明的互穿聚合物网络的水响应性能相当稳定。因此可以得出结论，与传统的聚丙烯酸形成的互穿聚合物网络相比，本发明的互穿聚合物网络在长时间和/或重复暴露于水后响应性能更稳定。
实施例3
取48.6质量份的向列型液晶单体HCM-002、6.8质量份的手性掺杂剂HCM-006、2质量份的光引发剂、2质量份表面活性剂和40.6质量份的不可聚合液晶基元5CB，混合形成混合物，使用刮刀涂布将其涂覆在甲基丙烯酸酯官能化的玻璃基板上，利用剪切力使分子取向，在涂覆后立即使用紫外照射，在氮气氛下光聚合已取向的涂层，其中不可聚合液晶基元5CB作为致孔剂存在，然后置于140℃下加热10min以除去5CB，得到胆甾型聚合物涂层。
取等摩尔的4-乙烯基苯磺酸和四丁基溴化膦反应产生可聚合盐，得到4-乙烯基苯磺酸-四丁基季膦盐的聚合物，其结构式为：
Figure BDA0001879969750000111
取反应生成的可聚合盐置于上述胆甾型聚合物涂层上，用赶紧的玻璃板盖住，加热以使可聚合盐更好和快速地渗透，然后进行第二次紫外光照射以使可聚合盐聚合形成聚离子液体并与胆甾型聚合物形成互穿聚合物网络，制备得到的互穿聚合物网络经测定具有稳定的水响应性。

Claims (12)

1.一种水响应的互穿聚合物网络，其特征在于，包括胆甾型液晶聚合物和聚离子液体形成的互穿聚合物网络；其中，所述胆甾型液晶聚合物由液晶混合物经聚合形成；所述聚离子液体为亲水性的盐，所述聚离子液体由可聚合盐经聚合形成，所述可聚合盐由离子液体单体一和离子液体单体二反应生成，所述离子液体单体一为：
Figure FDA0003028423850000011
离子液体单体二为：
Figure FDA0003028423850000012
其中，R1、R2各自独立地选自氢、C1～C10的烷基、卤素基团、C1～C10的烷氧基，R3选自C1～C10的亚烷基，R4、R5各自独立地选自C1～C10的烷基。
2.根据权利要求1所述的水响应的互穿聚合物网络，其特征在于，R1选自氢或甲基，R2选自氢或甲基，R3选自C1～C6的亚烷基，R4、R5各自独立地选自氢、甲基、乙基中的一种。
3.根据权利要求1-2任一项所述的水响应的互穿聚合物网络，其特征在于，所述液晶混合物包含可聚合的液晶单体、手性掺杂剂和光引发剂。
4.根据权利要求3所述的水响应的互穿聚合物网络，其特征在于，所述液晶混合物中还包含表面活性剂。
5.权利要求1-4任一项所述的水响应的互穿聚合物网络的制备方法，其特征在于，包括以下步骤：
S1、取液晶混合物和致孔剂混合，聚合，然后除去致孔剂；
S2、加入离子液体单体，再次聚合，形成互穿聚合物网络。
6.根据权利要求5所述的水响应的互穿聚合物网络的制备方法，其特征在于，所述致孔剂为不可光聚合的液晶单体。
7.根据权利要求5或6所述的水响应的互穿聚合物网络的制备方法，其特征在于，步骤S1具体为：取液晶混合物和致孔剂混合形成混合物，将所述混合物涂覆于基板上，光聚合后除去致孔剂。
8.根据权利要求7所述的水响应的互穿聚合物网络的制备方法，其特征在于，通过加热蒸发或溶剂洗涤除去致孔剂。
9.根据权利要求7所述的水响应的互穿聚合物网络的制备方法，其特征在于，所述基板上涂覆有取向层。
10.权利要求1-4任一项所述的水响应的互穿聚合物网络在智能红外反射器、水响应彩色图案、传感器、成像、防伪措施中的应用。
11.一种光反射涂层，其特征在于，包括权利要求1-4任一项所述的水响应的互穿聚合物网络。
12.一种反射器件，其特征在于，包括权利要求11所述的光反射涂层。
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