CN101041779A - Photo-induced deformation liquid crystal macromolecular material and preparation method thereof - Google Patents

Photo-induced deformation liquid crystal macromolecular material and preparation method thereof Download PDF

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CN101041779A
CN101041779A CN 200710038100 CN200710038100A CN101041779A CN 101041779 A CN101041779 A CN 101041779A CN 200710038100 CN200710038100 CN 200710038100 CN 200710038100 A CN200710038100 A CN 200710038100A CN 101041779 A CN101041779 A CN 101041779A
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liquid crystal
group
light
photo
cationic
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CN 200710038100
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CN100567455C (en )
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俞燕蕾
林里
王蔚茹
徐吉翔
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复旦大学
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Abstract

The invention discloses a new photo-induced deforming liquid crystal macromolecular material in liquid crystal macromolecular material technical domain, which is characterized by the following: choosing ethoxyl group as main chain and azo-benzene derivant as lateral chain with part crosslinking; choosing azo-benzene derivant of monocyclic oxygen group and bicycle oxygen group as monomer; mixing finite quantity light trigger and trigger of positive ion; putting into reactor; choosing proper reacting temperature; copolymerizing the light trigger positive ion under the function of wavelength light; getting the product. This material is a controlled photo-inducer flexural deformation material, which can be used to study driver and artificial muscle.

Description

一种光致形变液晶高分子材料及其制备方法 A light-induced deformation of the liquid crystal polymer material and its preparation method

技术领域 FIELD

本发明属液晶高分子材料技术领域,具体涉及一种新的光致形变液晶高分子材料(乙氧基为主链的重复单元,偶氮苯衍生物为侧链,并有部分交联的液晶高分子)及其制备方法。 The present invention belongs to the field of the liquid crystal polymer material, particularly relates to a novel light-induced deformation of the liquid crystal polymer material (ethoxy repeating units in the main chain, a side chain azobenzene derivative, and a liquid crystal partially crosslinked polymer) and its preparation method.

背景技术 Background technique

光致形变液晶高分子材料是一种由光控制的智能形变材料,具体表现为:当材料受到光照射时(通常为紫外光),其内部发生光异构化反应引起相应部分的尺寸变化,并通过液晶分子间以及高分子链段间的协同作用把这种微观变化传递给分子链,使分子链的状态发生显著性变化,材料在宏观上表现为光致形变。 Photo-deformable material is a liquid crystal polymer by the intelligent control of light deformable material, specifically as follows: when the material is irradiated with light to cause changes in the size of the respective portion (usually ultraviolet), optical isomerization reaction occurs therein, significant change state and the liquid crystal molecules by the synergy between and among the polymer chain to pass this microscopic changes to the molecular chain, molecular chain occurs, photocurable material behaves as deformation macroscopically. 当光照停止后,材料又发生可逆的光异构化反应,分子链的形态相应地复原,材料则恢复原状,当然也可通过加热或用其他波长的光照射(通常为可见光)加速其恢复过程。 When the light is stopped, and the material of the photo-isomerization reaction is reversible, morphogenesis of the molecular chain restoring Accordingly, the material restitution, of course, can accelerate the recovery of other wavelengths is irradiated with light (usually visible light) or by heating . 从光致形变到恢复整个过程,可以不断实现,且材料不出现明显的疲劳现象。 From deformation to recover the entire photo process can continue to achieve, and the material no appreciable fatigue. 光是一种清洁能源,环保安全,通过光致形变可以实现光能到机械能的直接转化,避免能量经多次转化造成的损耗,提高了光能的利用效率。 Light is a clean energy, environmental safety, energy can be achieved directly converted to mechanical energy by a photo deformation, avoiding the energy loss caused by the multiple conversions, improving the light use efficiency. 光致形变液晶高分子材料应用广泛,在人工肌肉,光感应装置,微型器械领域,以及在航空上都具有相当的应用潜力和发展前景。 Photocurable material is applied widely deformation of the liquid crystal polymer, the artificial muscle, an optical sensing device, a micro device field, and have considerable potential applications in aviation and Prospects.

光致形变液晶高分子材料,化学结构上应该具有能发生可逆的光异构化反应的基团,有通过顺反异构反应的,如偶氮苯、二苯乙烯;有通过偶极离子生成反应的,如苯并螺吡喃;有通过环化反应的,如俘精酸酐;有通过离子对生成反应的,如三芳基甲烷衍生物;还有通过其他一些反应来实现的。 Photo-polymer material deformation of the liquid crystal, should have the chemical structure of a group capable of undergoing a photo-isomerization reaction is reversible, it is by cis-trans isomerization reaction, such as azobenzene, stilbene; the dipolar ion produced by reaction, such as benzotriazole spiropyran; there through cyclization, as fulgide; have through ion pair, such as a triarylmethane derivative forming reaction; there by some other reaction achieved. 同时材料还必须具有液晶性,介晶基元可在主链上,也可在侧链上。 While the material must also exhibit liquid mesogenic, on the side chain may be in the main chain. 由于液晶的有序排列特性,使介晶基元在特定波长的光作用下,发生较为一致的变化,再通过与高分子链的偶合,从而实现微观到宏观上的形变。 Since the liquid crystal alignment characteristics to the mesogen at a specific wavelength of light action, more consistent changes, and then by coupling to the polymer chain, in order to achieve the microstructure to macroscopic deformation.

在过去有关非液晶体系的光致形变研究中,人们就已经发现由于偶氮苯生色团具有一种特殊的光响应性能,能够在吸收光能后发生分子的顺反异构。 In the past studies of non-liquid crystal light-induced strain in the system, it has been found that as azobenzene chromophore having a particular optical response properties, can occur along the molecule absorbs light energy in the trans isomer. 当偶氮苯生色团接到高分子链上后,顺反异构会引起高分子主链和侧链的构象变化,同时伴随着高分子溶液和固体的物理性能与化学性能的改变。 When the azobenzene chromophore to the polymer chain, cis and trans isomers can cause a conformational change in the polymer main chain and a side chain, while accompanied by a change of physical properties of the polymer solution and a solid chemical properties. 其中,弹性交联网络和凝胶的光致伸缩因为能够产生可逆的光机械效应(光能直接转化为机械能),可应用于驱动器和人工肌肉的研究。 Wherein the elastic gel crosslinked network and can generate light because light electrostrictive reversible mechanical effect (energy directly into mechanical energy), and the human muscle Driving may be applied. 然而,在过去的研究工作中,不足10%的形变率限制了这一效应的实际应用。 However, past research work, less than 10% of the deformation rate limits the practical application of this effect. 所以近年来,研究人员开始采用一种新的高分子体系-含偶氮苯等生色团的高分子液晶弹性体,即轻度交联的液晶高分子,进行光致形变的研究,获得了形变率达20%的光致伸缩。 So in recent years, researchers have started using a new polymer systems - an elastomeric polymer liquid crystal-containing azobenzene chromophores, i.e., slightly cross-linked liquid crystal polymer, light-induced deformation study, obtain strain rate of 20% of the light electrostriction. 高分子液晶弹性体既具有液晶材料的各种优异性能又具有高分子交联网络的特征,因此具有良好的外场响应性、分子协同作用和弹性。 Excellent properties of the liquid crystal polymer elastomer having both a liquid crystal material and a polymer having a crosslinked network characteristic, it has good responsiveness field, elastic molecules and synergy.

但是,目前人们所采用的偶氮苯液晶弹性体的主链为丙烯酸酯型结构,急需开发其他类型主链结构的材料。 However, at present the main chain liquid crystalline elastomer azobenzene people employed an acrylate structure, urgent need to develop other types of material backbone structure. 并且现在常用的偶氮苯液晶弹性体是通过自由基热聚合或光聚合的方法制备的,由于光引发自由基聚合存在易被氧气阻聚、固化过程收缩率高、内应力大等缺点,直接影响到材料的性能。 Prepared by the method now commonly used and azobenzene liquid crystal elastomer is thermally by free radical polymerization or photopolymerization, since the presence of a radical polymerization photoinitiator susceptible to oxygen polymerization, curing shrinkage rate, stress and other shortcomings, directly affect the properties of the material. 此外,目前的光致形变局限于一维、二维方向上,主要表现为伸缩行为,形变率有限。 Further, the present light-induced deformation localized on one-dimensional, two-dimensional direction, mainly for stretching behavior, limited deformation rate. 以上有关偶氮苯液晶弹性体光致形变的许多方面都有待提高。 For many aspects of the above light-induced deformation of azobenzene liquid crystalline elastomer to be improved.

发明内容 SUMMARY

本发明的目的在于提出一种具有新的主链结构,可发生三维形变-光致弯曲,且能够通过光精确控制可实现材料定向弯曲形变的液晶高分子材料及其制备方法。 Object of the present invention is to propose a new kind of backbone structure, three-dimensional distortion may occur - photo-bent, and can be achieved by a light material, precise control of directional bending deformation of the liquid crystal polymer material and its preparation method.

本发明提出的液晶高分子材料,其化学结构以乙氧基为主链的重复单元,偶氮苯衍生物为侧链,并有部分交联的液晶高分子,它由单环氧基取代的偶氮苯衍生物和双环氧基取代的偶氮苯衍生物,通过阳离子光聚合反应得到。 Liquid crystal polymer material by the present invention, repeating ethoxy units in the chemical structure of the main chain, a side chain azobenzene derivative, and a partially crosslinked liquid crystal polymer, an epoxy group which is substituted by a single azobenzene derivatives and bicyclic-substituted azobenzene derivative, obtained by the cationic photopolymerization reaction. 阳离子光聚合体系具有固化过程体积收缩率小、光固化过程不被氧气阻聚、固化反应不易终止和适于厚膜光固化等优点。 Cationic photopolymerization system having a small volume shrinkage during curing, photocuring polymerization process is not oxygen, the curing reaction is easily adapted to thick photocurable termination and other advantages. 本发明选择单环氧基的偶氮苯衍生物(EAB)和双环氧基的偶氮苯衍生物(DEAB)为单体,来制备液晶高分子材料,其中DEAB具有双官能团,是起到交联剂的作用,它们的化学结构式为: The present invention is selected monoepoxy azobenzene derivative (the EAB) and azobenzene derivatives bicyclic group (DEAB) monomer, to prepare a liquid crystal polymer material, wherein DEAB having difunctional, is played a crosslinking agent, as their chemical structural formula: 其中R是H,或者是C1~C12的取代或未取代的烃基(可以是饱和的或不饱和)或烷氧基,或者是具有极性的端基,可选择的有氰基,异氰基,羟基,卤素(F、Cl、Br、I),酯基,羧基,硝基,氨基或酰胺基。 Wherein R is H, or a substituted or unsubstituted C1 ~ C12 hydrocarbon group (which may be saturated or unsaturated) or an alkoxy group, or a polar end groups, are optionally cyano, isocyano , hydroxy, halo (F, Cl, Br, I), an ester group, a carboxyl group, a nitro group, an amino group or an amide group. R1,R2和R3可独立选自于C1~C16的取代或未取代的烃基或烷氧基。 R1, R2 and R3 may be independently selected from a substituted or unsubstituted C1 ~ C16 hydrocarbon group or an alkoxy group. EAB与DEAB的摩尔比为99∶1-1∶99。 And the molar ratio of DEAB was 99:1-1:99 EAB.

本发明首先有机合成EAB和DEAB这两种单体,然后再与一定量的自由基光引发剂和阳离子引发剂混合,放入反应器中,选择合适的反应温度,在一定波长的光作用下,通过光引发阳离子共聚合生成液晶高分子薄膜材料。 The present invention first organic synthesis and DEAB EAB two monomers, and then with an amount of a free radical photoinitiator and a cationic initiator mixture, placed in a reactor, to select a suitable reaction temperature, under the action of light of a certain wavelength , by copolymerizing a cationic photoinitiator generates a liquid crystal polymer film material. DEAB是具有双官能团的单体,聚合过程同时发生交联反应,其与EAB的配比不同,材料的交联度也不一样,从而直接影响到对所合成的液晶高分子薄膜材料的性能。 DEAB is a difunctional monomer having polymerization crosslinking reactions occur simultaneously, EAB differ from the ratio of the degree of crosslinking is not the same material, which directly affect the performance of the liquid crystal polymer film of synthetic material. 本发明控制的EAB与DEAB的摩尔比值为99∶1----1∶99,优选95/5-50/50。 EAB DEAB and the molar ratio of the present invention to control ---- 99 99, preferably 95 / 5-50 / 50.

用于本发明的光引发剂的摩尔分数为0.5%-5%,阳离子引发剂的摩尔分数为0.5%-5%,引发剂和单体总摩尔分数为100%。 Mole fraction for the photoinitiator according to the present invention is from 0.5% to 5%, a cationic initiator molar fraction of 0.5% to 5%, the total mole fraction of initiator and monomers to 100%. 进行光引发阳离子聚合所选择的光波长在200nm-600nm,强度在1mW/cm2-20mW/cm2,优选为2mW/cm2-14mW/cm2。 Optical cationic polymerization initiator selected wavelengths of light in the 200nm-600nm, strength of 1mW / cm2-20mW / cm2, preferably from 2mW / cm2-14mW / cm2. 聚合时间在0.5h-20h,优选为2h-14h,反应温度在25℃-250℃。 The polymerization time 0.5h-20h, preferably for the 2h-14h, the reaction temperature at 25 ℃ -250 ℃.

本发明涉及的自由基光引发剂选自具有发色团的有机羰基类化合物、过氧化物、偶氮化合物、硫化物、卤代物和有机金属类化合物中的一种或多种,优选为有机羰基类化合物和有机金属类化合物。 The present invention relates to free-radical photoinitiator is selected from organic carbonyl compounds having a chromophore, peroxides, azo compounds, sulfide, halide and the organic metal compound of one or more, preferably an organic carbonyl compound and an organic metal compound. 阳离子引发剂选自阳离子光引发剂,优选为鎓盐类和茂铁盐类,更优选为鎓盐类。 Cationic initiator selected from cationic photoinitiators, preferably onium salts and ferrocenium salt, more preferably an onium salt.

自由基光引发剂非限定例子是Irgacure 784,Irgacure 907和CQ,结构式如下: Free radical photoinitiator is a non-limiting example, Irgacure 784, Irgacure 907, and CQ, the following structural formula: 阳离子引发剂非限定例子是DiPhIPF6和TArSPF6,它们的结构式如下: Non-limiting examples of cationic initiators are DiPhIPF6 and TArSPF6, whose structural formulas are as follows:

本发明所合成的液晶高分子薄膜,在紫外光的照射下可观察到各向异性的弯曲行为,而且加热后可以恢复到初始平整状态。 Liquid crystal polymer film of the present invention synthesized in the UV irradiation can be observed anisotropy bending behavior, and after heating be restored to the original flat state. 而且,当液晶薄膜的上下两面分别置于紫外光下照射时,薄膜发生弯曲的方向正好相反,即表层介晶基元为平行取向的表面被紫外光照射时,因为沿着摩擦方向发生各向异性的表面收缩,整个液晶薄膜迎着紫外光的入射方向弯曲;而表层介晶基元为垂直取向的表面被紫外光照射时,则整个液晶薄膜朝着远离紫外光源的方向弯曲,这是因为薄膜表面呈现膨胀行为。 Further, when the upper and lower surfaces of the liquid crystal film were placed under ultraviolet light irradiation, the film is bent in the direction opposite occurs, i.e., the surface of the mesogenic oriented parallel to the surface is irradiated with ultraviolet light, since each place along the rubbing direction the surface of the opposite sex contraction, bending the entire liquid crystal film facing the UV light incident direction; the surface mesogen is oriented perpendicular to the surface is irradiated with ultraviolet light, the entire film liquid crystal is bent in the direction away from the ultraviolet light source, because swelling behavior of the film surface.

这种光致弯曲的实现主要是因为薄膜的表层分子对紫外光吸收大,使薄膜表面的偶氮苯介晶基元发生反式到顺式的光化学异构变化,并且进一步引起液晶相到各向同性相的转变,而薄膜本体部分的偶氮苯仍保持反式构象,这种表面和本体的形状上的差异使得整个薄膜宏观上呈现弯曲行为。 This photoisomerization achieved primarily because the curved surface of the molecular films large ultraviolet absorption, photochemical isomerization of cis-azobenzene-mediated changes in the surface of the crystal thin film cell type to occur, and further causing a liquid crystal phase to the respective to isotropic phase transition, the body portion azobenzene film remains the trans conformation, the shape of such a difference in the body so that the entire surface of the film and rendering the macro bending behavior. 此外,之所以当薄膜的正反两面分别置于紫外光下照射时薄膜的弯曲状态不同,主要是因为表层偶氮苯介晶基元的取向态不同,有垂直于底板的垂直取向和平行于底板的平行取向,此外薄膜的中间部分还有与底板成一定角度的扭转取向。 Further, when the curved state is distinctive both sides of the film were placed under ultraviolet light is irradiated films, mainly because of the different surface azobenzene mesogen alignment state, vertical alignment with a bottom plate and parallel to the vertical oriented parallel to the base plate, the intermediate portion of the film in addition there into the base plate at an angle of twist alignment.

附图说明 BRIEF DESCRIPTION

图1为合成高分子液晶薄膜的实验装置图,其中标记为1,2,3,4,5,6的依次是:辐射光源,空间间隔材料,摩擦方向,反应加热控制台,基板,聚合场所。 Figure 1 is the experimental apparatus of FIG synthetic polymer liquid crystal film, which in turn is marked 1,2,3,4,5,6: radiation source, spatial separation material, rubbing direction, the reaction was heated console, the substrate, the polymerization properties .

图2为高分子液晶薄膜材料中偶氮苯介晶基元的取向态,其中标记为7,8,9的依次是:平行取向液晶薄膜,垂直取向液晶薄膜,杂合取向液晶薄膜。 Figure 2 is a liquid crystalline polymer material azobenzene mesogen alignment state, wherein the labeled 7,8,9 are: parallel alignment liquid crystal film, the liquid crystal vertical alignment film, liquid crystal alignment film hybrid.

图3为聚合前后偶氮苯介晶基元的取向态,其中标记为10,11,12,13,14,15,16,17,18的依次是:聚合前平行取向液晶薄膜材料,非偏振性的光照射,薄膜受光照的一个表面(图中以A表示),聚合后杂合取向液晶薄膜,薄膜的一个表面,薄膜的另一个表面(图中以B表示),摩擦取向方向,摩擦取向方向,薄膜的另一个表面。 FIG 3 is a longitudinal azobenzene polymerizable mesogen alignment state, wherein the labeled 10,11,12,13,14,15,16,17,18 are: polymerizable liquid crystal before the alignment film material in parallel, unpolarized irradiation of light, a light receiving surface of the film (in the figure indicated by a), after the polymerization hybrid alignment liquid crystal film (represented in figure B) a surface of the film, the other surface of the film, the rubbing direction, friction alignment direction, the other surface of the film.

图4为液晶薄膜材料的正反两面分别接受紫外光的照射时,液晶薄膜材料呈现不同的弯曲行为,其中标记为19,20,21,22,23,24,25的依次是:紫外光照射薄膜表面,薄膜垂直取向的一面(即上图的A面,图中也以A表示),紫外光照射后薄膜发生表面的膨胀致使材料弯曲,紫外光照射后薄膜发生表面的收缩致使材料弯曲,摩擦取向方向,薄膜的另一个表面(即上图的B面,图中也以B表示),紫外光照射薄膜表面。 Figure 4 is a front and back sides of the liquid crystal film material are irradiated with ultraviolet light, the liquid crystal film material exhibits different bending behavior, labeled 19,20,21,22,23,24,25 are: UV irradiation film surface, oriented perpendicular to the film surface (i.e., on the a side of FIG, also indicated in FIG. a), the expansion of the film surface occurs after UV irradiation resulting material is bent, the film shrinkage occurs after UV irradiation causes the surface material is bent, the rubbing direction of the other surface of the film (i.e. on the surface B of FIG, also indicated in FIG. B), ultraviolet irradiation of the surface of the film.

图5为在紫外光的作用下液晶薄膜材料的可出现的宏观形变行为示意图,其中标记为26,27,28,29的依次是:紫外光的作用,光作用前的薄膜状态,光作用后呈现的向下弯薄膜状态,光作用后呈现的向上弯薄膜状态。 FIG 5 is a macroscopic deformation behavior can occur in the liquid crystal film material under the action of ultraviolet light a schematic diagram which is marked as 26, 27 are: the role of ultraviolet light, a thin film state before the action of light, an optical effect after downturned state presentation film, showing the effect of the optical film upturned state.

具体实施方式 detailed description

实施例1本实施例说明了4-乙氧基-4'-羟基偶氮苯的合成方法。 EXAMPLE 1 This Example illustrates the synthesis of 4-ethoxy-4'-hydroxy-azobenzene. 首先把4-乙氧基苯胺(10g,73mmol)溶解在150mL盐酸(2mol/L)中,并将反应液置于烧杯中冷却至0℃,在搅拌下,再把含有5.05g(73mmol)亚硝酸钠的100mL水溶液滴加到反应液中,生成重氮盐。 First, the 4-ethoxy-aniline (10g, 73mmol) was dissolved in 150mL of hydrochloric acid (2mol / L), and the reaction was placed in a beaker cooled to 0 deg.] C, under stirring, then containing 5.05g (73mmol) alkylene 100mL aqueous solution of sodium nitrite was added dropwise to the reaction solution, the diazonium salt. 接着把6.9g(73mmol)的苯酚和8.8g(226mmol)氢氧化钠在水中预混合好,然后缓慢滴加到烧杯中,在搅拌下维持0℃反应2h,得到黄色固体沉淀。 Next to 6.9g (73mmol) of phenol and 8.8g (226mmol) of sodium hydroxide in water and pre-mixed well, and then slowly dropwise added to a beaker, maintained at 0 ℃ for 2h with stirring to give a yellow solid precipitate. 反应结束后,沉淀物用氯仿进行萃取,收集到的氯仿层用无水硫酸镁干燥,蒸去氯仿后得到的粗品再用硅胶填充的柱色谱行分离纯化,最后重结晶得到4-乙氧基-4'-羟基偶氮苯纯品。 After completion of the reaction, the precipitate was extracted with chloroform, the collected chloroform layer was dried over anhydrous magnesium sulfate, and purified by column chromatography separation to silica gel packed in chloroform was distilled off to obtain a crude product after then, finally recrystallized to give 4-ethoxy 4'-hydroxy-azobenzene-pure product.

实施例2本实施例说明了4-乙氧基-4'-缩水甘油醚氧基偶氮苯(E1AB2)单体的合成方法。 Example 2 This example illustrates the synthesis of 4-ethoxy-4'-glycidoxy azobenzene (E1AB2) monomer. 首先在三颈瓶中加入实施例1中所合成的4-乙氧基-4'-羟基偶氮苯纯品4.0g(17mmol),接着加入4.6g(50mmol)环氧氯丙烷,再加入含有0.6g苯基三丁基溴化铵和6.8g(50mmol)无水碳酸钾的50mL 2-丁酮溶液,在回流下加热反应4h后,将混合物倒入50mL冷的氢氧化钠水溶液(1.0mol/L)中,接着用氯仿进行洗涤萃取,收集到的氯仿层用无水硫酸镁干燥,蒸去氯仿后得到的粗品再用硅胶填充的柱色谱进行分离纯化,最后重结晶得到E1AB2纯品。 First Embodiment Example 1 was added in three-necked flask synthesized 4-ethoxy-4'-hydroxy-azobenzene-pure product 4.0g (17mmol), followed by 4.6g (50mmol) of epichlorohydrin, containing added after 0.6g phenyl tributyl ammonium bromide and 6.8g (50mmol) 50mL 2- butanone of anhydrous potassium carbonate, the reaction was heated at reflux for 4h, the mixture was poured into 50mL of cold aqueous sodium hydroxide solution (1.0 mol / L), followed by washing the extract with chloroform, the collected chloroform layer was dried over anhydrous magnesium sulfate, chloroform was distilled off to give the crude product by silica gel column chromatography packed separation and purification, and finally recrystallized E1AB2 pure product.

实施例3本实施例说明了4,4'-二羟基偶氮苯的合成方法。 Example 3 This example illustrates the synthesis of 4,4-dihydroxy-azobenzene. 首先把4-氨基苯酚(10.0g,92mmol)溶解在180mL盐酸(2mol/L)中,并将反应液置于烧杯中冷却至0℃,在搅拌下,再把含有6.3g(92mmol)亚硝酸钠的100mL水溶液滴加到反应液中,生成重氮盐。 First, the 4-aminophenol (10.0g, 92mmol) dissolved in 180mL of hydrochloric acid (2mol / L), and the reaction was placed in a beaker cooled to 0 deg.] C, under stirring, then containing 6.3g (92mmol) nitrite 100mL aqueous solution of sodium was added dropwise to the reaction solution, the diazonium salt. 接着把8.6g(92mmol)的苯酚和11.0g(275mmol)氢氧化钠在水中预混合好,然后缓慢滴加到烧杯中,在搅拌下维持0℃反应2h。 Next to 8.6g (92mmol) of phenol and 11.0g (275mmol) of sodium hydroxide in water and pre-mixed well, and then slowly dropwise added to a beaker, maintained at 0 ℃ for 2h with stirring. 得到的混合物溶液用氯仿进行萃取,收集到的氯仿层用无水硫酸镁干燥,蒸去氯仿后得到的粗品再用硅胶填充的柱色谱进行分离纯化,最后重结晶得到4,4'-二羟基偶氮苯纯品。 The resulting mixture was extracted with chloroform, the collected chloroform layer was dried over anhydrous magnesium sulfate, chloroform was distilled off to obtain a crude product of the packed silica gel column chromatography and then separated and purified, and finally recrystallized from 4,4'-dihydroxybiphenyl azobenzene-pure product.

实施例4本实施例说明了4,4'-二缩水甘油氧基偶氮苯(DE1AB)单体的合成方法。 Example 4 This example illustrates the synthesis of 4,4'-azobenzene glycidoxy (DE1AB) monomer. 首先在三颈瓶中加入实施例3中所合成的4,4'二羟基偶氮苯纯品2.1g(10mmol),接着加入9.3g(100mmol)环氧氯丙烷,再加入含有0.8g苯基三丁基溴化铵和13.8g(100mmol)无水碳酸钾的50mL 2-丁酮溶液,在回流下加热反应4h后,将混合物倒入50mL冷的氢氧化钠水溶液(1.0mol/L)中,接着用氯仿进行洗涤萃取,收集到的氯仿层用无水硫酸镁干燥,蒸去氯仿后得到的粗品再用硅胶填充的柱色谱进行分离纯化,最后重结晶得到DE1AB纯品。 First, three-necked flask in Example 3 Synthesis of 4,4 'dihydroxy-azobenzene-pure product 2.1g (10mmol), followed by addition of 9.3g (100mmol) of epichlorohydrin, was added 0.8g containing phenyl tributyl ammonium bromide and 13.8g 50mL 2- butanone (100 mmol) of anhydrous potassium carbonate, the reaction heated 4h, the mixture was poured into 50mL of cold aqueous sodium hydroxide solution (1.0mol / L) at reflux , then washed chloroform layer was extracted with chloroform, collected dried over anhydrous magnesium sulfate, chloroform was distilled off to give the crude product by silica gel column chromatography packed separation and purification, and finally recrystallized DE1AB pure product.

实施例5此实施例说明了根据本发明实施例2、4中得到的单体E1AB2和DE1AB进行液晶高分子材料的合成方法。 Example 5 This example illustrates the synthesis of a polymer material according to the liquid crystal monomer E1AB2 obtained in Examples 2 and 4 and the embodiment of the present invention DE1AB. 首先将单体E1AB2和DE1AB按摩尔数80/20配合,接着与2mol%的自由基光引发剂Irgacure 784和2mol%阳离子引发剂DiPhIPF6进行混合,熔融后注入两块基板制成的液晶盒中,控制反应温度130℃,并在波长大于545nm,光强为2mW/cm2的光辐射下反应2h,打开液晶盒后得到液晶高分子薄膜PE80D20。 The first monomer and DE1AB E1AB2 with 80/20 molar number, followed by reaction with 2mol% of a radical photoinitiator Irgacure 784 and 2mol% DiPhIPF6 cationic initiator were mixed, melted and injected into a liquid crystal cell made of two substrates, 130. deg.] C reaction temperature, and greater than 545nm in wavelength, the light intensity of 2mW / cm2 of irradiation at 2h, after opening the liquid crystal cell to obtain a liquid crystal polymer film PE80D20.

实施例本实施例中具体操作内容步骤同实施例5,但本实施例的反应单体E1AB2和DE1AB的摩尔数配比为50/50。 Example embodiments of the present embodiment in the specific operation contents the same procedure of Example 5 embodiment, but the reactive monomer E1AB2 present embodiment and the number of moles DE1AB ratio was 50/50. 最后得到液晶高分子薄膜PE50D50。 Finally obtain a liquid crystal polymer film PE50D50.

实施例7本实施例中具体操作内容步骤同实施例5,但本实施例所使用的自由基光引发剂为CQ,用量为4mol%,同时辐射光的波长变为436nm。 Example 7 This example content specific operation procedure of Example 5 the same embodiment, but the present embodiment used in Example radical photoinitiator wavelength agent is CQ, in an amount of 4mol%, while the radiated light becomes 436nm. 最后得到液晶高分子薄膜P'E80D20。 Finally obtain a liquid crystal polymer film P'E80D20.

实施例8-11本实施例中具体操作内容步骤同实施例7,但本实施例依次改变两种单体E1AB2和DE1AB的摩尔配比,分别为:95/5,90/10,80/20,50/50。 Examples 8-11 present in the specific embodiment with the operation of Step Example 7, but the present embodiment sequentially changing the molar ratio of two monomers E1AB2 DE1AB, namely: 95 / 5,90 / 10,80 / 20 50/50. 最后得到一组薄膜分别记为:P'E95D5,P'E90D10,P'E80D20,P'E50D50。 To obtain a final set of films were recorded as: P'E95D5, P'E90D10, P'E80D20, P'E50D50. 这些由不同单体配比得到的液晶高分子薄膜的相转变温度见表1。 The liquid crystal phase transition temperature of the polymer film obtained by a different monomer ratio shown in Table 1.

表1 不同单体配比的液晶高分子薄膜的相转变温度 Table 1 phase transition of the liquid crystal polymer film in a monomer ratio different temperatures

*K:晶相;N:向列相;I:各向同性相 * K: crystalline phase; N: nematic phase; I: isotropic phase

Claims (5)

  1. 1.一种光致形变液晶高分子材料,其特征在于化学结构是以乙氧基为主链的重复单元,偶氮苯衍生物为侧链,并有部分交联的液晶高分子,它由单体单环氧基的偶氮苯衍生物双环氧基的偶氮苯衍生物通过阳离子光聚合反应得到,前者单体记为EAB,后者单体记为DEAB,它们的化学结构具有如下通式: A liquid crystal photo-deformable polymer material, which is characterized in that the chemical structure of the main chain of repeating ethoxy units, is the side chain azobenzene derivative, and a partially crosslinked polymer liquid crystal, which consists of azobenzene derivative monomer monoepoxy bicyclic group azobenzene derivative obtained by reaction of cationic photopolymerization, the monomer denoted by the EAB former, the latter referred to as DEAB-monomer, which has the following chemical structure general formula: 式中R是H,或者是C1~C12的取代或未取代的烃基或烷氧基,或者是具有极性的端基,可选择的有氰基,异氰基,羟基,卤素,酯基,羧基,硝基,氨基或酰胺基;R1,R2和R3可独立选自于C1~C16的取代或未取代的烃基或烷氧基;所述的单环氧基的偶氮苯衍生物和双环氧基的偶氮苯衍生物按照摩尔比为99/1-1/99混合。 Wherein R is H, or a substituted or unsubstituted C1 ~ C12 hydrocarbon group or an alkoxy group, or having a polar end groups are optionally cyano, isocyano, hydroxy, halo, an ester group, a carboxyl group, a nitro group, an amino group or an amide group; R1, R2 and R3 may be independently selected from substituted or unsubstituted C1 ~ C16 hydrocarbon group or an alkoxy group; the azobenzene derivative and the bis monoepoxy azobenzene derivative molar ratio of epoxy groups of 99 / 1-1 / 99 hybrid.
  2. 2.一种如权利要求1所述的光致形变液晶高分子材料的制备方法,其特征在于先通过有机合成得单体EAB和DEAB,再与自由基光引发剂和阳离子引发剂混合,在反应器中在光作用下,通过光引发阳离子共聚生成液晶高分子材料,其中所使用的光引发剂选自具有发色团的有机羰基类化合物、过氧化物、偶氮化合物、硫化物、卤代物和有机金属类化合物中的一种或多种,阳离子引发剂选自阳离子光引发剂。 2. A method of preparing a photo-deformation of the liquid crystal polymer material as claimed in claim 1, wherein the first monomer obtained by organic synthesis and DEAB-EAB, then with a free radical photoinitiator and a cationic initiator mixture in reactor under the action of light, generated by copolymerizing cationic photoinitiator a liquid crystal polymer, wherein the optical initiator is used an organic carbonyl compound selected from having chromophore, peroxides, azo compounds, sulfur compounds, halogen Generation and organic metal compounds of one or more cationic initiator is selected from cationic photoinitiator.
  3. 3.根据权利要求2所述的光致形变液晶高分子材料的制备方法,其特征在于所用自由基光引发剂的摩尔分数为0.5%-5%,阳离子引发剂的摩尔分数为0.5%-5%,引发剂和单体总摩尔分数为100%。 The method of preparing a photo-deformation of the liquid crystal polymer material according to claim 2, characterized in that the free radical photoinitiator mole fraction of 0.5% to 5%, a cationic initiator molar fraction of 0.5% to 5 %, initiator and monomer mole fraction of the total 100%.
  4. 4.根据权利要求2所述的光致形变液晶高分子材料的制备方法,其特征在于进行光引发阳离子聚合所选择的光波长在200nm-600nm,强度在1mW/cm2-20mW/cm2。 The method of preparing a photo-deformation of the liquid crystal polymer material according to claim 2, characterized in that the optical cationic polymerization initiator selected wavelengths of light in the 200nm-600nm, strength of 1mW / cm2-20mW / cm2.
  5. 5.根据权利要求2所述的光致形变液晶高分子材料的制备方法,其特征在于聚合时间在0.5h-20h,反应温度在25℃-250℃。 The method of preparing the liquid crystal light-induced deformation of a polymer material according to claim 2, characterized in that the polymerization time of 0.5h-20h, the reaction temperature at 25 ℃ -250 ℃.
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CN101521030B (en) 2009-03-24 2011-02-16 中山大学 Azobenzol liquid crystal holography storage material and preparation method thereof
CN101709695B (en) 2009-11-19 2011-12-14 复旦大学 Photo film bending driven micropump
CN101656499B (en) 2008-08-19 2012-05-16 鸿富锦精密工业(深圳)有限公司 Photo-induced telescopic membrane and photo-induced telescopic driver with same
CN101574807B (en) 2009-06-16 2012-07-04 复旦大学 Photic driving robot and method for driving the robot
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CN101656499B (en) 2008-08-19 2012-05-16 鸿富锦精密工业(深圳)有限公司 Photo-induced telescopic membrane and photo-induced telescopic driver with same
CN101521030B (en) 2009-03-24 2011-02-16 中山大学 Azobenzol liquid crystal holography storage material and preparation method thereof
CN101574807B (en) 2009-06-16 2012-07-04 复旦大学 Photic driving robot and method for driving the robot
CN101579859B (en) 2009-06-16 2012-10-17 复旦大学 Photo gripping device and gripping method
CN101709695B (en) 2009-11-19 2011-12-14 复旦大学 Photo film bending driven micropump
CN101793243A (en) * 2010-03-12 2010-08-04 同济大学 Light-operated underwater scooter and boosting method
CN101964563B (en) 2010-08-13 2012-06-06 同济大学 Photic drive motor and driving method thereof
CN101964563A (en) * 2010-08-13 2011-02-02 同济大学 Photic drive motor and driving method thereof
CN105500857A (en) * 2015-12-18 2016-04-20 北京大学 Light-driven composite with double-layer-film structure and preparation method of light-driven composite

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