WO2020107614A1 - 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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WO2020107614A1
WO2020107614A1 PCT/CN2018/124575 CN2018124575W WO2020107614A1 WO 2020107614 A1 WO2020107614 A1 WO 2020107614A1 CN 2018124575 W CN2018124575 W CN 2018124575W WO 2020107614 A1 WO2020107614 A1 WO 2020107614A1
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water
polymer network
interpenetrating polymer
responsive
liquid crystal
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PCT/CN2018/124575
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English (en)
French (fr)
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德·哈恩劳伦斯
邓子轩
周国富
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华南师范大学
深圳市国华光电科技有限公司
深圳市国华光电研究院
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Priority to US16/498,727 priority Critical patent/US11498989B2/en
Publication of WO2020107614A1 publication Critical patent/WO2020107614A1/zh

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Definitions

  • the present invention relates to water-responsive materials, in particular to a water-responsive interpenetrating polymer network.
  • the materials commonly used in liquid crystal displays are generally composed of rod-shaped molecules that point in one direction. This characteristic makes these materials have an ordered phase, but can also flow like a liquid.
  • cholesteric liquid crystals are used to prepare various photons. The system is very important.
  • a nematic material or mixture is partially or entirely composed of molecules with a chiral center, a cholesteric phase is formed.
  • the director axis is continuously twisted, resulting in the formation of a spiral structure of the molecule.
  • This phase has the ability to be based on a complete spiral Distance (that is, pitch) reflects the special properties of light in a specific wavelength band.
  • the reflection occurs.
  • the type and number of chiral molecules in the cholesteric phase material determine the pitch. And the reflected wavelength, the more chiral molecules, the shorter the pitch, the shorter the reflected wavelength, this characteristic can be used to adjust the wavelength of light reflected by the material.
  • Water-responsive cholesteric material is a special type of cholesteric liquid crystal system, which usually contains some hydrophilic groups, interacting with water molecules can expand the material, increase the pitch of the cholesteric phase, and thus increase the reflection wavelength. The material can be restored to its original state when it is dried again, and its interaction with water molecules is usually reversible.
  • water-responsive cholesteric materials contain carboxyl groups as hydrophilic groups.
  • the strong hydrogen bonding between the carboxyl groups facilitates hydrogen bonding with water, and these groups are not initially water-responsive. In order to make these materials have water resistance In response, they need to be activated with high pH solutions, such as aqueous solutions of sodium hydroxide (NaOH) or potassium hydroxide (KOH). This converts the carboxylic acid group into a hygroscopic carboxylate (when NaOH or KOH are used, respectively, to obtain the corresponding sodium or potassium carboxylate), which no longer forms hydrogen bonds but can interact ionicly with water molecules .
  • This kind of material that can interact with water molecules has great potential commercial value. For example, Moirangthem et al. developed a printable blue CLC polymer coating. Inkjet printing using Ca(NO 3 ) 2 solution will The coating is patterned, which suppresses water swelling by replacing potassium ions with stronger ion-bonded calcium ions. The final product showed full color camouflage when exposed to water or simply by exhalation.
  • Interpenetrating polymer networks are polymer blends composed of two or more polymer networks that are each cross-linked and interpenetrating.
  • a water-responsive film can be obtained by establishing an interpenetrating polymer network (IPN), such as an interpenetrating polymer formed by the combination of cholesteric liquid crystal and poly(acrylic acid)
  • IPN interpenetrating polymer network
  • the physical network polymerizes a cholesteric mixture of polymerizable liquid crystals and non-polymerizable liquid crystals, and removes the non-polymerizable compounds by heating, where the non-polymerizable liquid crystals are called porogens, and then uses the free space generated by removing the non-polymerizable compounds to make acrylic acid Penetrate into the membrane and conduct a second polymerization to lock the acrylic, so that you get an interpenetrating network.
  • IPN interpenetrating polymer network
  • the technical problem to be solved by the present invention is to provide a water-responsive interpenetrating polymer network and a preparation method, a light-reflecting coating, and a reflective device. Alkali activation process, and water responsiveness will not be lost when used for a long time, and has high commercial value.
  • the invention provides a water-responsive interpenetrating polymer network, including an interpenetrating polymer network formed by a cholesteric liquid crystal polymer and a polyionic liquid; wherein, the cholesteric liquid crystal polymer is formed by polymerization of a liquid crystal mixture;
  • the polyionic liquid contains a hydrophilic group or a hydrophilic salt.
  • the hydrophilic group includes at least one of a hydroxyl group, an amide group, a carboxyl group, and a pyrrole group;
  • the hydrophilic salt is preferably a carboxylate, ammonium salt, sulfonate, imidazole salt, pyridine salt .
  • the polyionic liquid is formed by polymerizing a polymerizable salt, and the polymerizable salt is generated by reacting ionic liquid monomer one and ionic liquid monomer two.
  • the second monomer of ionic liquid is: Wherein, R 1 and R 2 are each independently selected from hydrogen, C1-C10 alkyl groups, halogen groups, C1-C10 alkoxy groups, R 3 is selected from C1-C10 alkylene groups, R 4 and R 5 Each is independently selected from C1-C10 alkyl groups.
  • the halogen group includes Cl, Br and the like.
  • R 1 is selected from hydrogen or methyl
  • R 2 is selected from hydrogen or methyl
  • R 3 is selected from C1-C6 alkylene
  • R 4 and R 5 are each independently selected from hydrogen, methyl, and ethyl One of the bases.
  • the first ionic liquid monomer is an unsaturated carboxylic acid derivative, in which the carboxyl group can be combined with the second ionic liquid monomer to form a carboxylate.
  • preferred compounds according to the present invention are shown in Table 1:
  • the liquid crystal mixture contains a polymerizable liquid crystal monomer, a chiral dopant and a photoinitiator.
  • the polymerizable liquid crystal monomer may be all or part of the chiral liquid crystal monomer, the purpose is to polymerize the liquid crystal mixture to form a cholesteric liquid crystal polymer.
  • the liquid crystal mixture further contains a surfactant to improve the arrangement of molecules.
  • the invention also provides a method for preparing the above water-responsive interpenetrating polymer network, including the following steps:
  • the porogen selected in the present invention does not participate in the reaction when the liquid crystal mixture is polymerized to form a cholesteric polymer, and can be removed by heating and evaporation or solvent washing.
  • the porogen is a non-photopolymerizable liquid crystal monomer.
  • a water-responsive interpenetrating polymer network is preferably prepared on the substrate.
  • the liquid crystal mixture and the porogen are mixed and coated on the substrate.
  • the substrate used may be a hard substrate such as Glass can also be a soft substrate such as a plastic film.
  • the coating process can use one of blade coating, bar coating, spin coating, inkjet printing and spray coating.
  • the substrate can have an orientation layer to improve the arrangement of molecules. Although this may not always be necessary, because shear forces can also cause alignment during the coating process in many cases.
  • irradiation with ultraviolet light activates the photoinitiator and initiates the polymerization of the liquid crystal monomer.
  • the invention also provides a light reflective coating comprising the water-responsive interpenetrating polymer network described above.
  • the present invention also provides a reflective device comprising the above water-responsive light reflective coating.
  • the invention provides a water-responsive interpenetrating polymer network formed by interpenetrating cholesteric liquid crystal polymer and polyionic liquid, using polyionic liquid instead of traditional polyacrylic acid as the second polymer, and forming the ionic liquid monomer by polymerization
  • the polyionic liquid has a hydrophilic group or a hydrophilic salt, so it is hygroscopic so that the interpenetrating polymer network can absorb moisture and swell, increasing the pitch of the cholesteric polymer in the interpenetrating polymer network.
  • the length causes the reflection wavelength of the interpenetrating polymer network material to increase, thereby exhibiting water responsiveness.
  • the water-responsive interpenetrating polymer network of the present invention does not require alkaline solution activation, which simplifies the preparation process. At the same time, since positive ions and negative ions are both part of the polyionic liquid, when captured in the interpenetrating polymer network, no Ions can escape from the network without losing the water-responsive performance of the material. The response performance is stable after prolonged and/or repeated exposure to water.
  • the water-responsive interpenetrating polymer network of the present invention can be used to prepare light reflective coatings Layers and reflective devices have high commercial value.
  • FIG. 1 is a test result diagram of the water response stability of the interpenetrating polymer network in Comparative Example 1.
  • FIG. 2 is a test result diagram of the water response stability of the interpenetrating polymer network of Example 1.
  • nematic liquid crystal monomer HCM-002 used in the following examples purchased from Hecheng, Jiangsu, has the structure:
  • the non-polymerizable liquid crystal element 5CB purchased from Jiangsu Chuangtuo, has the structure:
  • the structure of the photoinitiator is:
  • the structure of the surfactant is:
  • nematic liquid crystal monomer HCM-002 Take 48.6 parts by mass of nematic liquid crystal monomer HCM-002, 6.8 parts by mass of chiral dopant HCM-006, 2 parts by mass of photoinitiator, 2 parts by mass of surfactant and 40.6 parts by mass of non-polymerizable liquid crystal Primitive 5CB, mixed to form a mixture, coated with a squeegee coating on a methacrylate-functionalized glass substrate, orienting the molecules using shear force, using ultraviolet irradiation immediately after coating, and illuminating under a nitrogen atmosphere The oriented coating was polymerized, in which the non-polymerizable liquid crystal cell 5CB was present as a porogen, and then placed at 140°C and heated for 10 min to remove 5CB to obtain a cholesteric polymer coating.
  • the polymerizable salt generated by the reaction is placed on the above cholesteric polymer coating, covered with a quick glass plate, heated to allow the polymerizable salt to penetrate better and quickly, and then subjected to the second ultraviolet light irradiation to make Polymerizable salts polymerize to form polyionic liquids and form interpenetrating polymer networks with cholesteric polymers.
  • the polymerizable salt used to form the polyionic liquid in this embodiment is a carboxylate formed by the reaction of acrylic acid and 2-(dimethylamino)ethyl methacrylate.
  • the polyionic liquid includes but is not limited to carboxylic acid groups Ionic liquids, sulfonic acid-based ionic liquids such as 4-vinylbenzenesulfonic acid-tetrabutyl quaternary phosphine salt polymer (PTPSS), amide-based ionic liquids such as N-isopropylacrylamide polymer (PNIPAM), etc.
  • the polyionic liquid has a hydrophilic group or a hydrophilic salt, so it is hygroscopic so that the interpenetrating polymer network can absorb water and swell, increasing the length of the pitch of the cholesteric polymer in the interpenetrating polymer network.
  • Comparative Example 1 provides a cholesteric interpenetrating polymer network. The preparation process is the same as in Example 1, except that acrylic acid is used instead of the polymerizable salt in Example 1 and is formed with the cholesteric polymer Interpenetrating polymer networks and using KOH for activation.
  • Example 1 and Comparative Example 1 were taken and subjected to a water response stability test.
  • the specific process is as follows: Both types of interpenetrating polymer networks were immersed in deionized water, using UV-Vis/IR spectroscopy The method determines the reflection band of the two interpenetrating polymer networks in a wet state after being immersed at different times. The results are shown in FIGS. 1 and 2, wherein FIG. 1 represents Comparative Example 1, and FIG. 2 represents Example 1. It can be seen from Fig.
  • the reflection band blue shifts with the increase of immersion time, which is reflected by 563nm at 5 minutes immersion With the immersion time, the position of the reflection band continues to blue shift.
  • the reflection band is at 436nm, which is basically the same as the reflection band position during drying. With prolongation, positive ions continuously escape from the network and the water responsiveness gradually disappears. It can be seen from FIG.
  • the measured reflection band positions remain substantially the same
  • the approximate position is at 513nm
  • the reflection band curve measured by immersion for 5min and 30min is basically the same
  • the reflection band curve measured by immersion for 3h and 1d is basically the same, which also illustrates the interpenetrating polymer network of the present invention from the side
  • the water response performance is quite stable. Therefore, it can be concluded that the interpenetrating polymer network of the present invention has a more stable response performance after prolonged and/or repeated exposure to water, as compared to the interpenetrating polymer network formed by conventional polyacrylic acid.
  • nematic liquid crystal monomer HCM-002 Take 48.6 parts by mass of nematic liquid crystal monomer HCM-002, 6.8 parts by mass of chiral dopant HCM-006, 2 parts by mass of photoinitiator, 2 parts by mass of surfactant and 40.6 parts by mass of non-polymerizable liquid crystal Primitive 5CB, mixed to form a mixture, coated with a squeegee coating on a methacrylate-functionalized glass substrate, orienting the molecules using shear force, using ultraviolet irradiation immediately after coating, and illuminating under a nitrogen atmosphere The oriented coating was polymerized, in which the non-polymerizable liquid crystal cell 5CB was present as a porogen, and then placed at 140°C and heated for 10 min to remove 5CB to obtain a cholesteric polymer coating.
  • a polymer of 4-vinylbenzenesulfonic acid-tetrabutyl quaternary phosphine salt is obtained.
  • the polymerizable salt generated by the reaction is placed on the above cholesteric polymer coating, covered with a quick glass plate, heated to allow the polymerizable salt to penetrate better and quickly, and then subjected to the second ultraviolet light irradiation to make
  • the polymerizable salt polymerizes to form a polyionic liquid and forms an interpenetrating polymer network with the cholesteric polymer.
  • the prepared interpenetrating polymer network has been determined to have stable water responsiveness.

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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(NO 3) 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 PCTCN2018124575-appb-000001
离子液体单体二为：
Figure PCTCN2018124575-appb-000002
其中，R 1、R 2各自独立地选自氢、C1～C10的烷基、卤素基团、C1～C10的烷氧基，R 3选自C1～C10的亚烷基，R 4、R 5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，R 1选自氢或甲基，R 2选自氢或甲基，R 3选自C1～C6的亚烷基，R 4、R 5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 PCTCN2018124575-appb-000003
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 PCTCN2018124575-appb-000004
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 PCTCN2018124575-appb-000005
Figure PCTCN2018124575-appb-000006
表3使用的致孔剂的优选化合物
Figure PCTCN2018124575-appb-000007
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 PCTCN2018124575-appb-000008
手性掺杂剂HCM-006，购于江苏和成，结构为：
Figure PCTCN2018124575-appb-000009
不可聚合液晶基元5CB，购于江苏创拓，结构为：
Figure PCTCN2018124575-appb-000010
光引发剂的结构为：
Figure PCTCN2018124575-appb-000011
表面活性剂的结构为：
Figure PCTCN2018124575-appb-000012
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 PCTCN2018124575-appb-000013
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 PCTCN2018124575-appb-000014
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 (14)

  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；所述聚离子液体含有亲水性基团或为亲水性的盐。
  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，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。
  3. 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，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 PCTCN2018124575-appb-100001
    离子液体单体二为：
    Figure PCTCN2018124575-appb-100002
    其中，R 1、R 2各自独立地选自氢、C1～C10的烷基、卤素基团、C1～C10的烷氧基，R 3选自C1～C10的亚烷基，R 4、R 5各自独立地选自C1～C10的烷基。
  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，R 1选自氢或甲基，R 2选自氢或甲基，R 3选自C1～C6的亚烷基，R 4、R 5各自独立地选自氢、甲基、乙基中的一种。
  5. 根据权利要求1-4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。
  6. 根据权利要求5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。
  7. 权利要求1-6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。
  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，所述致孔剂为不可光聚合的液晶单体。
  9. 根据权利要求7或8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。
  10. 根据权利要求9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。
  11. 根据权利要求9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。
  12. 权利要求1-6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、成像和防伪措施中的应用。
  13. 一种光反射涂层，其特征在于，包括权利要求1-6任一项所述的水响应的互穿聚合物网络。
  14. 一种反射器件，其特征在于，包括权利要求13所述的水响应光反射涂层。
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11498989B2 (en) 2018-11-26 2022-11-15 South china normal university; Water-responsive interpenetrating polymer network, preparation method and use thereof

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Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107946641A (zh) * 2017-11-10 2018-04-20 南昌航空大学 离子液晶/聚咪唑半互穿网络聚合物电解质的制备方法

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010165868A (ja) * 2009-01-15 2010-07-29 Three M Innovative Properties Co ゲル状組成物
CN104793389B (zh) * 2015-05-06 2018-01-16 严锋 一种电控智能调光基材组件
EP3500650B8 (en) * 2016-08-17 2020-08-12 Shenzhen Guohua Optoelectronics Tech. Co. Ltd. Stimuli-responsive polymer film or coating, responsive device and process for preparing the same
CN108339410B (zh) * 2018-03-08 2021-01-01 华东师范大学 一种聚离子液体修饰的三维结构网膜及制备方法和应用
CN109593424B (zh) 2018-11-26 2021-08-03 华南师范大学 水响应的互穿聚合物网络及其制备方法和应用

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107946641A (zh) * 2017-11-10 2018-04-20 南昌航空大学 离子液晶/聚咪唑半互穿网络聚合物电解质的制备方法

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
GREGORY A BECHT ET AL: "Formation of a Liquid-Crystalline Interpenetrating Poly(ionic liquid) Network Hydrogel", MACROMOLECULES, vol. 44, no. 6, 21 February 2011 (2011-02-21), pages 1421 - 1428, XP055710539, ISSN: 0024-9297, DOI: 10.1021/ma102146r *
JELLE E STUMPEL. ET AL: "Stimuli-Responsive Materials Based on Interpenetrating Polymer Liquid Crystal Hydrogels", ADVANCED FUNCTIONAL MATERIALS, vol. 25, no. 22, 1 June 2015 (2015-06-01), pages 3314 - 3320, XP055635286, ISSN: 1616-301X, DOI: 10.1002/adfm.201500745 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11498989B2 (en) 2018-11-26 2022-11-15 South china normal university; Water-responsive interpenetrating polymer network, preparation method and use thereof

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