CN101481440A - Liquid crystal polymer material and composite material realizing photo-induced deformation by visible light irradiation - Google Patents

Liquid crystal polymer material and composite material realizing photo-induced deformation by visible light irradiation Download PDF

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CN101481440A
CN101481440A CN 200910045903 CN200910045903A CN101481440A CN 101481440 A CN101481440 A CN 101481440A CN 200910045903 CN200910045903 CN 200910045903 CN 200910045903 A CN200910045903 A CN 200910045903A CN 101481440 A CN101481440 A CN 101481440A
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liquid crystal
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material
crystal polymer
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CN 200910045903
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俞燕蕾
尹若元
徐婉娴
程伏涛
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复旦大学
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Abstract

The invention provides a novel photo-induced deformation liquid crystal polymer material and a compound material; the polymer material is deformed under the irradiation of visible light at the room temperature and heating or the visible light irradiation is carried out for restoring the original shape. The polymer material and the compound material are used in the fields of micro-actuators, artificial muscles, and the like.

Description

一种由可见光照射实现光致形变的液晶高分子材料及复合材料 A liquid crystal photo-polymer material and a composite material deformable realized by irradiation with visible light

[0001] 技术领域 [0001] Technical Field

[0002] 本发明属于液晶高分子材料领域,具体涉及一种新的光致形变液晶高分子材料及复合材料,该高分子材料在室温下经可见光的照射实现形变,再经加热或是可见光的照射又可恢复形变。 [0002] The present invention belongs to the field of liquid crystal polymer, particularly relates to a novel light-induced deformation of the liquid crystal polymer materials and composite materials, deformation of the polymer material by irradiation with visible light is achieved at room temperature, or heated visible deformation can be back illuminated.

[0003] 背景技术 [0003] BACKGROUND OF THE INVENTION

[0004] 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。 [0004] The deformation of the liquid crystal photo-polymer material is a material deformation smart controlled by the light. 具体表现为:当材料受到光照射时(通常为紫外光),其内部结构发生异构化反应而降低液晶分子的有序性,再通过交联液晶网络中高分子链段的协同运动,使高分子链的状态发生显著变化,材料在宏观上产生光致形变,从而实现从光能到机械能的直接转化。 Specifically as follows: when the material is irradiated by light (usually ultraviolet light), the internal structure of the isomerization reaction and reduce the ordering of the liquid crystal molecules, and then through the coordinated movement crosslinked polymer network liquid crystal segments, the high- significant change in the state of the molecular chain occurs, the deformation induced in a material generates light macro in order to achieve direct conversion from light energy to mechanical energy. 当光照停止后改用其他波长的光照射或者加热,材料又会恢复原状。 When the irradiation of light is stopped to switch to other wavelengths of light or heat, the material will be restitution. 因此从光致形变到恢复的整个过程是一个可逆的循环过程,材料可以反复利用而不会出现明显的疲劳现象。 Thus the entire process from deformation to recover the photoluminescence is a reversible cycle, the material can be without significant fatigue repeated use. 光是一种清洁的能源,容易实现快速、精确和远程控制,所以光致形变材料成为人们研究的新热点,可用于制造智能传感器和驱动器,在人工肌肉、微型传感器、光控开关以及航空领域都有着广泛的应用前景。 Light is a clean energy, easy to implement fast, accurate and remote control, the photo-deformable material become a new hot research, may be used to manufacture smart sensors and actuators, the artificial muscle, micro-sensors, optical switch and aviation We have a wide range of applications.

[0005] 光致形变液晶高分子材料的化学结构需要具有光响应性的有机发色团,因此一般将诸如偶氮苯、苯并螺吡喃、俘精酸酐、1,2-二苯乙烯等光致变色分子引入到液晶体系中。 [0005] The chemical structures of light-induced deformation of the liquid crystal polymer material is required to have light-responsive organic chromophore, and therefore generally such as azobenzene, benzo spiropyrans, fulgides, stilbene and the like the photochromic molecules incorporated into the liquid crystal system. 以偶氮苯为例,当体系中棒状的反式偶氮苯受到紫外光照射时会发生顺反异构变化形成V字形的顺式结构,从而打乱液晶分子的有序排列。 In azobenzene example, when trans-azobenzene systems rod-exposure to ultraviolet light change occurs cis-trans isomerization of cis form a V-shaped configuration, thereby disrupting the orderly arrangement of the liquid crystal molecules. 当偶氮苯发色团接到高分子链上后,其顺反异构变化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, which will cause cis-trans isomerization changes conformational change in the polymer main chain and side chain, while accompanied by a change of physical properties of the polymer solution and a solid chemical properties . 在这个体系中偶氮苯基团因其棒状的结构特征符合液晶性分子要求,所以同时扮演介晶基元的角色。 In this system, the liquid crystal molecules due to its structural characteristics azobenzene groups to meet the requirements of the rod-shaped, so while the role of the mesogen. 由于液晶的有序排列特性,使偶氮苯介晶基元在特定波长的光作用下,发生较为一致的形态变化,再通过与高分子链的耦合,从而实现微观到宏观上的材料形变。 Since the alignment characteristics of the liquid crystal, azobenzene mesogenic under the action of light of a specific wavelength, more consistent morphology changes, then the polymer chain via a coupling, in order to achieve the microstructure to macroscopic deformation of the material.

[0006] 在过去有关含有偶氮苯发色团的液晶弹性体的研究中,人们已经发现该材料具有一种特殊的光响应性能,在吸收光能后可以发生一维、二维的收缩甚至三维的弯曲形变。 [0006] In the past the study elastomer azobenzene chromophore-containing liquid crystal, it has been found that a special material having a light-responsive properties, a one-dimensional, two-dimensional shrinkage may occur even after absorption of light energy a three-dimensional bending deformation. 由于液晶弹性体兼有弹性体和液晶的双重特性(即弹性和有序性),与非交联型液晶高分子相比具有许多独特的性质,具有良好的外场响应性和分子协同作用,包括自发地可逆形变特性即“软弹性”等,而且这种可逆形变具有形变量大、可逆性好等优点,因而液晶弹性体在智能材料领域有着诱人的发展前景。 Since the liquid crystal elastomer, and the elastomer both the dual characteristics of liquid crystal (i.e., elasticity and ordering), and non-crosslinked polymer liquid crystal as compared with many unique properties, have good responsiveness and field synergy molecule, comprising spontaneously reversible deformation characteristic known as "soft-elastic" and so on, and this has a large reversible deformation deformation, and good reversibility, and thus liquid crystal elastomer has attractive prospects for development in the field of smart materials.

[0007] 然而,在以往的研究工作中所使用的交联液晶高分子材料的玻璃化转变温度较高(大于50℃),光致弯曲行为需要在材料被加热的条件下才能发生,所以,不利于器件的小型化,而且,光致形变的激发光源多采用小于380nm的紫外光(200710038100.3、200810032771.3),对人体有一定的伤害等等,这些不足之处直接影响到材料的应用。 [0007] However, the glass of the liquid crystal polymer material crosslinked in previous studies used a higher transition temperatures (greater than 50 deg.] C), light-induced bending behavior needs to take place at the material is heated, so that, is not conducive to miniaturization of the device, and, the excitation light source of UV-induced deformation of the multi-use (200710038100.3,200810032771.3) of less than 380nm, the human body has some damage, etc., these deficiencies directly affect the application of the material. 鉴于这些原因,本发明提供一种能够在室温下通过可见光的照射来实现形变及在可见光的照射或是加热条件下恢复形变的交联液晶高分子材料及其复合料,它克服了现有材料玻璃化转变温材度较高以及激发光使用紫外光的缺点。 For these reasons, the present invention provides a recovery strain and deformation is achieved at the irradiation of visible light or heating the crosslinked polymer liquid crystal material and a composite material by irradiation with visible light at room temperature, which overcomes the existing materials high glass transition temperature of the material used and ultraviolet light excitation disadvantages. 本发明还进一步的提供了所述液晶高分子材料的合成方法及其复合材料的制备方法。 The present invention further provides a method of synthesizing a composite material and a preparation method of the liquid crystal polymer material. 所述的液晶高分子材料及其复合材料可用于微执行器、人工肌肉等领域。 The liquid crystal polymer materials and composites may be used microactuators, artificial muscles, and other fields.

[0008] 发明内容 [0008] SUMMARY OF THE INVENTION

[0009] 本发明的目的之一是提供一种能够在室温下通过可见光的照射来实现形变及在可见光照射或是加热的条件下恢复的交联液晶高分子材料,其特征是,首先有机合成出单体X和交联剂Y,然后再与一定量的光引发剂或者热引发剂混合,放入反应器中,选择合适的光强或是反应温度,通过光聚合反应或者热聚合反应生成液晶高分子材料; [0009] One object of the present invention to be achieved is to provide a liquid crystal strain and the crosslinked polymer material recovered at the visible light irradiation or heating by irradiation with visible light at room temperature, characterized in that the first organic synthesis the crosslinker monomer X and Y, then the light amount of initiator or a thermal initiator mixed agent, into a reactor, select the appropriate light intensity or reaction temperature, reaction by photopolymerization or thermal polymerization reaction liquid crystal polymer material;

[0010] 其中,所述单体X的通式为: [0010] wherein X is a monomer of the formula:

[0011] D1——A1——R [0011] D1 - A1 - R

[0012] 所述交联剂Y的通式为: [0012] Y is the crosslinking agent of the general formula:

[0013] D2——A2——D3 [0013] D2 - A2 - D3

[0014] 其中R是H,或者是C1-C20的取代或未取代的烃基或者烷氧基,或者是具有极性的端基;A1、A2选自如下结构中的一种基团或是两种以对应的结构键链接而成的基团或是三种以对应的结构键链接起来而成的基团, [0014] wherein R is H, or a substituted or unsubstituted hydrocarbon group or a C1-C20 alkoxy group, or having a polar terminal group; A1, A2 structure selected from a group of one or two species corresponding key link structure formed by three kinds of group or bond to the corresponding linked structure formed by a group

[0015] [0015]

—CH=CH— —C≡C— —N=N— —B— -CH = CH- -C≡C- -N = N- -B-

[0016] [0016]

—B—CH=CH— —B—C≡C— -B-CH = CH- -B-C≡C-

[0017] —B1—C≡C—B2— —B1—CH=CH—B2— —B1—N=N—B2— [0017] -B1-C≡C-B2- -B1-CH = CH-B2- -B1-N = N-B2-

[0018] A1、A2的结构相同或者不同,在上述基团中,B、B1、B2是取代或未取代的脂肪族环、芳环、稠环、杂环,或者是它们相应的衍生物,B、B1、B2的结构相同或者不同,但A1、A2其中之一至少含有偶氮苯的共轭结构,不限于以下结构, The same as [0018] A1, A2, or different structures, in the above-mentioned groups, B, B1, B2 is a substituted or unsubstituted aliphatic ring, an aromatic ring, a condensed ring, heterocyclic ring, or corresponding derivatives thereof, B, B1, B2 of the same structure or different, A1, A2 comprising at least one conjugated structure of azobenzene is not limited to the following structure,

[0019] [0019]

[0020] 其中,D1~D3是含有能进行聚合的碳碳双键结构的基团,它们独立选自如下结构中的一种,D1~D3结构相同或者不同, [0020] wherein, D1 ~ D3 is a group containing a carbon-carbon double bond structures can be polymerized, they are independently selected from one of the following structures, the same or different structure D1 ~ D3,

[0021] [0021]

[0022] 其中R1是H或是CH3;R2是H,或者在单体通式中不出现,或是C1-C20的取代或未取代的烃基或烷氧基、烷硫基、烷氨基、二烷氨基、烷酰基、烷酰氧基、烷酰胺基、烷磺酰基,或者是它们相应的衍生物。 [0022] wherein R1 is H or CH3; R2 is H, or is not present in the monomer of formula, or a substituted or unsubstituted C1-C20 hydrocarbon group or an alkoxy group, an alkylthio group, an alkylamino group, di alkylamino, alkanoyl, alkanoyloxy, alkanoylamino group, an alkylsulfonyl group, or their corresponding derivatives.

[0023] 在一个优选的技术方案中,R优选的是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,所述具有极性的端基优选自F、Cl、Br、I或酯基。 [0023] In a preferred aspect, R is preferably a C1 ~ C12 hydrocarbon group or a substituted or unsubstituted alkoxy group, or a polar group having a terminal, said terminal having a polar group is preferably selected from F , Cl, Br, I or an ester group.

[0024] 在一个优选的技术方案中,R2优选的是C1~C12的取代或未取代的烃基,所述的烃基可以是饱和的或不饱和的,或选自烷氧基。 [0024] In a preferred aspect, R2 is preferably C1 ~ C12 substituted or unsubstituted hydrocarbon group, the hydrocarbon group may be saturated or unsaturated, or selected from alkoxy.

[0025] 本发明中单体和交联剂的摩尔比值为99:1—1:99。 [0025] In the present invention, the molar ratio of the monomers and the crosslinking agent is 99: 1-1: 99. 在一个优选的技术方案中,优选为95:5—50:50。 In a preferred aspect, preferably 95: 5-50: 50.

[0026] 其中,本发明涉及的光引发剂选自有机羰基类化合物和有机金属类化合物,优选自Irgacure 784、Irgacure 819,它们的结构式如下: [0026] However, the present invention relates to an optical initiator is selected from organic carbonyl compounds and organometallic compounds, preferably selected from Irgacure 784, Irgacure 819, whose structural formulas are as follows:

[0027] [0027]

[0028] 本发明涉及的热引发剂选自偶氮类化合物,优选自偶氮二异丁腈、偶氮二异庚腈。 [0028] The present invention relates to a thermal initiator selected from azo compounds, preferably selected from azobisisobutyronitrile, azobis iso-heptonitrile.

[0029] 其中,所选用的光引发剂或热引发剂的用量为单体与交联剂摩尔数之和的0.1%—10%,优选的是1%—5%。 [0029] wherein the chosen photoinitiator or thermal initiator is used in an amount of from 0.1% to 10% of monomer and crosslinking agent to the number of moles, preferably from 1% to 5%.

[0030] 其中,进行光聚合时所选择的波长范围是300nm—800nm,优选的是400nm-600nm;光的强度范围是0.1mW/cm2—20mW/cm2,优选的是1mW/cm2—10mW/cm2;进行光聚合的聚合时间范围是0.5h—20h,优选的是2h—10h;聚合温度范围是50℃—200℃,优选的是80℃—150℃。 [0030] wherein, when photopolymerization is selected wavelength range 300nm-800nm, preferably is 400nm-600nm; light intensity range is 0.1mW / cm2-20mW / cm2, preferably is 1mW / cm2-10mW / cm2 ; polymerization time is photopolymerizable 0.5h-20h, preferably the 2h-10h; the polymerization temperature in the range 50 ℃ -200 ℃, preferably is 80 ℃ -150 ℃.

[0031] 进行热聚合的聚合时间范围是1h—100h,优选的是3h—50h;聚合温度范围是20℃—200℃,优选的是40℃—150℃。 [0031] The polymerization is thermal polymerization time 1h-100h, are preferably 3h-50h; the polymerization temperature ranges from 20 ℃ -200 ℃, preferably is 40 ℃ -150 ℃.

[0032] 本发明另一个目的是提供一种使液晶高分子材料产生形变和恢复的方法,其特征是,在室温下通过可见光照射即能够使材料发生形变,再经过的可见光照射或加热又可回复到初始的状态。 [0032] Another object of the present invention is to provide a liquid crystal polymer material deforms and recovery method, characterized in that the material at room temperature can be made by irradiation of visible light is deformed, and then after the visible light irradiation or heating in turn return to the original state.

[0033] 在上述方法中,控制材料形变的可见光的波长为380nm—480nm,光强度在1mW/cm2—300mW/cm2,优选为5mW/cm2—50mW/cm2。 [0033] In the above method, the wavelength of visible light control material deformation is 380nm-480nm, the light intensity 1mW / cm2-300mW / cm2, preferably from 5mW / cm2-50mW / cm2. 使材料恢复初始状态的可见光的波长为500nm-800nm,强度为1mW/cm2—300mW/cm2,,优选为10mW/cm2-100mW/cm2。 Restore the initial state of the material of the wavelength of visible light is 500nm-800nm, intensity of 1mW / cm2-300mW / cm2 ,, preferably 10mW / cm2-100mW / cm2.

[0034] 本发明的再一目的是提供一种复合材料,所述的复合材料包括三层结构,第一层为交联液晶高分子材料,厚度为5μm—100μm;中间一层为复合用胶粘剂层,胶粘剂选自氰基丙烯酸酯类、聚氨酯类、丙烯酸类、聚丙烯酸类中的一种,其厚度为1μm—100μm;第三层为柔性基体材料,选自聚乙烯(PE)、聚丙烯(PP)、聚对苯二甲酸乙二醇酯(PET)、聚碳酸酯(PC)、天然橡胶(NR)中的一种,其厚度为5μm—5mm。 [0034] A further object of the present invention is to provide a composite material, said composite material comprising a three-layer structure, the first layer is a crosslinked liquid crystal polymer material, having a thickness of 5μm-100μm; intermediate adhesive layer of a composite layer, the adhesive selected from cyanoacrylate, urethane, acrylic, polyacrylic of one having a thickness of 1μm-100μm; the third layer is a flexible base material is selected from polyethylene (PE), polypropylene (PP), polyethylene terephthalate (PET), polycarbonate (PC), natural rubber (NR) of one having a thickness of 5μm-5mm.

[0035] 在一个优选的技术方案中,所述的交联液晶高分子材料的厚度为40μm—60μm,所述的胶粘剂层的厚度为5μm-30μm,所述的柔性基体材料的厚度为30μm-70μm。 [0035] In a preferred aspect, the thickness of the crosslinked polymer liquid crystal material is 40μm-60μm, the thickness of the adhesive layer is 5μm-30μm, the thickness of the flexible base material is 30μm- 70μm.

[0036] 本发明提供了一种新的光致形变液晶高分子材料及复合材料,该高分子材料在室温下经可见光的照射实现形变,再经加热或是可见光的照射又可恢复形变。 [0036] The present invention provides a new photochromic polymer materials and the deformation of the liquid crystal composite material, the polymer material is achieved by irradiation with visible light deformed at room temperature, and then heated or irradiated with visible light, but also to restore the deformation. 该高分子材料和复合材料可用于微执行器、人工肌肉等领域。 The polymer materials and composite materials can be used to micro-actuators, artificial muscles, and other fields.

[0037] 附图说明 [0037] BRIEF DESCRIPTION OF DRAWINGS

[0038] 图1为本发明实施例中合成交联液晶高分子材料的实验装置图,其中标记的含义是:1-光源,2-间隔材料,3-摩擦方向,4-加热台,5-基板,6-液晶盒; [0038] FIG 1 FIG experimental apparatus together with the liquid crystal polymer material turnover in the embodiments of the present invention, which is SYMBOLS: 1 - a light source, 2 the spacer material, the rubbing direction 3-, 4- heating stage, 5- substrate, 6 a liquid crystal cell;

[0039] 图2为本发明实施例中液晶高分子材料的光致形变和可逆回复过程示意图,其中标记的含义是:7-基板,8-交联液晶高分子材料,9-摩擦方向,10-可见光,11-发生形变的交联液晶高分子材料,12-可见光,13-回复初始状态的交联液晶高分子材料。 [0039] FIG. 2 and the reversible light-induced strain reverting process schematic diagram of the liquid crystal polymer material embodiment of the present invention, the meaning of which is labeled: a substrate 7-, 8-crosslinked polymer liquid crystal material, the rubbing direction 9-, 10 - visible, crosslinked liquid crystal polymer material is deformed 11-, 12- visible, 13 return the initial state of a crosslinked polymer liquid crystal material.

[0040] 具体实施方式 [0040] DETAILED DESCRIPTION

[0041] 现依据附图,对本行发明做进一步的描述。 [0041] Now according to the drawings, the Bank invention will be further described. 以单体丙烯酸-12-{4-[(4'-(4”-乙氧基苯基乙炔基)-2'-甲基)苯基偶氮]苯氧基}十二酯(A12ABT)和交联剂4,4'-二[12-(丙烯酰氧基)十二烷氧基]偶氮苯(DA12AB)的合成、聚合、聚合后的交联液晶高分子材料与聚乙烯的复合以及光致形变及恢复进行具体实施例说明。 Acrylate monomer -12- {4 - [(4 '- (4' - ethoxy-phenylethynyl) -2-methyl) phenyl azo] phenoxy} lauryl acrylate (A12ABT) and the crosslinking agent 4,4'-bis [12- (acryloyloxy) dodecyloxy] synthesis of azobenzene (DA12AB), polymeric, composite cross-linked polymer after polymerization of the liquid crystal material and polyethylene photo deformation and recovery will be specifically described embodiments.

[0042] [0042]

[0043] 实施例1 [0043] Example 1

[0044] 本实施例说明了2-甲基-4-溴-4'-羟基偶氮苯的合成方法。 [0044] This example illustrates the synthesis of 2-methyl-4-bromo-4'-hydroxy-azobenzene. 首先把5.0g 2-甲基-4-溴苯胺溶于30mL的HCl溶液(1mol/L)中,加入1.9g亚硝酸钠的水溶液12mL,在0℃~5℃下搅拌并加入3.7g碳酸钾和2.6g苯酚的混合水溶液12mL,反应3h,抽滤得到粗产物。 First, the HCl solution 5.0g 2- methyl-4-bromoaniline was dissolved in 30mL of (1mol / L) was added 1.9g of sodium nitrite in 12 mL aqueous solution, stirred at 0 ℃ ~ 5 ℃ and potassium carbonate was added 3.7g mixing an aqueous solution of 2.6 g of phenol and 12 mL of the reaction 3h, filtered by suction to give crude product. 经纯化后得到产物2-甲基-4-溴-4'-羟基偶氮苯5.6g。 After the product was purified to give methyl-4-bromo-4'-hydroxy-azobenzene 5.6g.

[0045] 实施例2 [0045] Example 2

[0046] 本实施例说明了2-甲基-4-溴-4'-(12-羟基十二烷氧基)偶氮苯的合成方法。 [0046] This example illustrates the 4 'methyl-4-bromo - synthesis of (12-hydroxy dodecyloxy) azobenzene. 将实施例1中合成的5.6g 2-甲基-4-溴-4'-羟基偶氮苯溶于100mL N,N-二甲基甲酰胺(DMF)中,加入5.2g碳酸钾,10.6g 12-溴-1-十二烷基醇,100℃加热搅拌反应3h。 Synthesis Example 1 in the embodiment of 5.6g 2- methyl-4-bromo-4'-hydroxy-azobenzene was dissolved in 100mL N, N- dimethylformamide (DMF) was added 5.2g of potassium carbonate, 10.6 g of 12- bromo-1-dodecanol, 100 ℃ reaction was heated and stirred 3h. 反应物结束后加入蒸馏水,抽滤得到粗产物。 After completion of the reaction was distilled water was added, to give a crude product was filtered off with suction. 经纯化后得到产物2-甲基-4-溴-4'-(12-羟基十二烷氧基)偶氮苯7.8g。 After the product was purified to give 2-methyl-4-bromo-4 '- (12-hydroxy dodecyloxy) azobenzene 7.8g.

[0047] 实施例3 [0047] Example 3

[0048] 本实施例说明了2-甲基-4-(三甲基硅乙炔基)-4'-(12-羟基十二烷氧基)偶氮苯的合成方法。 [0048] This example illustrates the preparation of 2-methyl-4- (trimethylsilyl-ethynyl) '- 4 - The method of (12-hydroxy dodecyloxy) azobenzene. 在一三颈瓶中,加入实施例2中合成的7.8g 2-甲基-4-溴-4'-(12-羟基十二烷氧基)偶氮苯,40g三甲基硅乙炔,1.5g三苯基磷,1.0g双三苯基磷二氯化钯(PdCl2(PPh3)2),3mL三乙胺在氮气保护下溶于四氢呋喃(THF)中,在50℃下搅拌6h。 A three-neck flask, was added Example 2 Synthesis of 7.8g 2- methyl-4-bromo-4 '- (12-hydroxy dodecyloxy) azobenzene, 4Og trimethylsilylacetylene, 1.5 g triphenylphosphine, 1.0 g of bis triphenylphosphine palladium (PdCl2 (PPh3) 2) chloride, 3 mL of triethylamine were dissolved in tetrahydrofuran (THF) under nitrogen and stirred for 6h at 50 ℃. 经萃取干燥后得到粗产物,再经纯化后得到产物2-甲基-4-(三甲基硅乙炔基)-4'-(12-羟基十二烷氧基)偶氮苯5.9g。 After extraction and drying to give a crude product was then purified to give the product 2-methyl-4- (trimethylsilyl-ethynyl) -4 '- (12-hydroxy dodecyloxy) azobenzene 5.9g.

[0049] 实施例4 [0049] Example 4

[0050] 本实施例说明了2-甲基-4-乙炔基-4'-(12-羟基十二烷氧基)偶氮苯的合成方法。 [0050] This example illustrates the preparation of 2-methyl-4-ethynyl-4 '- synthesis of (12-hydroxy dodecyloxy) azobenzene. 在500mL的烧瓶中,将实施例3中合成的5.9g 2-甲基-4-(三甲基硅乙炔基)-4'-(12-羟基十二烷氧基)偶氮苯和4.2g碳酸钾加入到500mL甲醇中,室温下反应10h。 5.9g 2- methyl-4- (trimethylsilyl-ethynyl) -4 'in a 500mL flask, synthesized in Example 3 - (12-hydroxy dodecyloxy) azobenzene and 4.2g of potassium carbonate was added to 500mL of methanol, at room temperature for 10h. 经萃取干燥后得到粗产物,再经纯化后得到产物2-甲基-4-乙炔基-4'-(12-羟基十二烷氧基)偶氮苯1.9g。 After extraction and drying to give a crude product was then purified to give the product 2-methyl-4-ethynyl-4 '- (12-hydroxy dodecyloxy) azobenzene 1.9g.

[0051] 实施例5 [0051] Example 5

[0052] 本实施例说明了2-甲基-4-(4”-乙氧基苯乙炔基)-4'-(12-羟基十二烷氧基)偶氮苯的合成方法。在一三颈瓶中,将实施例4中合成的1.9g 2-甲基-4-乙炔基-4'-(12-羟基十二烷氧基)偶氮苯,1.1g对乙氧基碘苯,0.5g三苯基磷,0.3gPdCl2(PPh3)2,0.5mL三乙胺在氮气保护下溶于THF中,在60℃下搅拌10h。经萃取干燥后得到粗产物,再经纯化后得到产物2-甲基-4-(4-乙氧基苯乙炔基)-4'-(12-羟基十二烷氧基)偶氮苯0.8g。 [0052] This example illustrates the preparation of 2-methyl-4- (4 '- ethoxy phenylethynyl)' - 4 - The method of (12-hydroxy dodecyloxy) azobenzene in thirteen. 1.9g 2- methyl-4-ethynyl-4 'necked flask, synthesized in Example 4 - (12-hydroxy dodecyloxy) azobenzene, 1.1 g of p-ethoxy-iodobenzene, 0.5 g triphenylphosphine, 0.3gPdCl2 (PPh3) 2,0.5mL triethylamine were dissolved in THF under nitrogen and stirred at 60 ℃ 10h. after extraction and drying to give a crude product was then purified to give the product 2- methyl-4- (4-ethoxy-phenylethynyl) -4 '- (12-hydroxy dodecyloxy) azobenzene 0.8g.

[0053] 实施例6 [0053] Example 6

[0054] 本实施例说明了丙烯酸-12-{4-[(4'-(4”-乙氧基苯基乙炔基)-2'-甲基)苯基偶氮]苯氧基}十二酯(A12ABT)的合成方法。在一三颈瓶中,将实施例5中合成的0.8g 2-甲基-4-(4”-乙氧基苯乙炔基)-4'-(12-羟基十二烷氧基)偶氮苯,0.3mL三乙胺溶于THF中,滴加0.2mL丙烯酰氯后,在室温下反应24h。 [0054] This example illustrates the acrylate -12- {4 - [(4 '- (4' - ethoxy-phenylethynyl) -2-methyl) phenyl azo] phenoxy} twelve 0.8g 2- methyl-4-ester method (A12ABT) is a three-necked flask, synthesized in Example 5 (4 '- ethoxy-phenylethynyl) -4' - (12-hydroxystearic dodecyloxy) azobenzene, 0.3 mL of triethylamine in THF, 0.2mL after the acrylic acid chloride was added dropwise, at room temperature for 24h. 经萃取干燥后得到粗产物,再经纯化后得到产物A12ABT0.5g。 After extraction and drying to give a crude product, and the product obtained after purification A12ABT0.5g.

[0055] 实施例7 [0055] Example 7

[0056] 本实施例说明了4-(12-羟基十二烷氧基)硝基苯的合成方法。 [0056] This example illustrates the synthesis of 4- (12-hydroxy dodecyloxy) nitrobenzene. 在一三颈瓶中,将1.7g对硝基苯酚溶于DMF中,加入1.7g碳酸钾,然后加入3.2g 12-溴-1-十二醇,回流反应3h。 A three-necked flask, 1.7g of p-nitrophenol dissolved in DMF, 1.7g of potassium carbonate was added, followed by addition of 3.2g 12- bromo-1-dodecanol, the reaction was refluxed for 3h. 反应后加入蒸馏水,抽滤得粗产物,再经纯化后得到产物4-(12-羟基十二烷氧基)硝基苯3.4g。 After the reaction, distilled water was added, the crude product is filtered off with suction to give, after further purification to afford the product 4- (12-hydroxy dodecyloxy) nitrobenzene 3.4g.

[0057] 实施例8 [0057] Example 8

[0058] 本实施例说明了4-(12-羟基十二烷氧基)苯胺的合成方法。 [0058] This example illustrates the synthesis of 4- (12-hydroxy dodecyloxy) aniline. 在一三颈瓶中,将3.4g(12-羟基十二烷氧基)硝基苯溶于THF中,加入0.5g 5%Pd/C和1.7g硼氢化钠后,搅拌反应2h,加入盐酸中和,经抽滤得粗产物,再经纯化后得到产物4-(12-羟基十二烷氧基)苯胺2.7g。 A three-necked flask, 3.4g (12- hydroxy dodecyloxy) nitrobenzene was dissolved in THF and, after addition of 0.5g 5% Pd / C and 1.7g of sodium borohydride, the reaction was stirred for 2h, hydrochloric acid was added and, the crude product by suction filtration, and then purified to give the product 4- (12-hydroxy dodecyloxy) aniline 2.7g.

[0059] 实施例9 [0059] Example 9

[0060] 本实施例说明了4'-羟基-4-(12-羟基十二烷氧基)偶氮苯的合成方法。 [0060] This example illustrates the synthesis of 4'-hydroxy-4- (12-hydroxy dodecyloxy) azobenzene. 在烧杯中,将2.7g 4-(12-羟基十二烷氧基)苯胺溶于HCl溶液中,在0℃~5℃的条件下加入亚硝酸钠0.6g的水溶液5mL,搅拌反应2h,加入苯酚0.9g、氢氧化钠0.4g的水溶液,搅拌反应3h,抽滤得到固体,纯化后得到产物4'-羟基-4-(12-羟基十二烷氧基)偶氮苯2.8g。 In the beaker, 2.7g 4- (12- hydroxy dodecyloxy) aniline was dissolved in HCl solution at 0 ℃ ~ 5 ℃ 5mL aqueous solution of 0.6g of sodium nitrite, the reaction was stirred for 2h, phenol 0.9g, 0.4g of aqueous sodium hydroxide, the reaction was stirred for 3h, suction filtered to give a solid product was obtained after purification of 4'-hydroxy-4- (12-hydroxy dodecyloxy) azobenzene 2.8g.

[0061] 实施例10 [0061] Example 10

[0062] 本实施例说明了4,4'-二(12-羟基十二烷氧基)偶氮苯的合成方法。 [0062] This example illustrates the synthesis of 4,4'-bis (12-hydroxy dodecyloxy) azobenzene. 在一三颈瓶中,将2.8g4'-羟基-4-(12-羟基十二烷氧基)偶氮苯溶于DMF中,加入0.5g碳酸钾和1.8g12-溴十二醇,100℃下搅拌反应4h。 A three-necked flask, 2.8g4'- hydroxy-4- (12-hydroxy dodecyloxy) azobenzene dissolved in DMF, was added 0.5g of potassium carbonate and 1.8g12- bromo-dodecanol, 100 ℃ the reaction was stirred at 4h. 反应结束后加入蒸馏水,抽滤得粗产物,纯化后得到产物4,4'-二(12-羟基十二烷氧基)偶氮苯3.1g。 After the reaction after addition of distilled water, filtered by suction to give crude product which was purified product to give 4,4'-bis (12-hydroxy dodecyloxy) azobenzene 3.1g.

[0063] 实施例11 [0063] Example 11

[0064] 本实施例说明了4,4'-二[12-(丙烯酰氧基)十二烷氧基]偶氮苯(DA12AB)的合成方法。 [0064] This example illustrates the 4,4'-bis [12- (acryloyloxy) dodecyloxy] azobenzene (DA12AB) synthesis method. 在一三颈瓶中,将3.1g 4,4'-二(12-羟基十二烷氧基)偶氮苯、1.1g三乙胺加入到THF中,搅拌条件下加入1.0g丙烯酰氯,室温下搅拌反应24h。 A three-necked flask, 3.1g 4,4'- bis (12-hydroxy dodecyloxy) azobenzene, 1.1 g of triethylamine were added to THF, 1.0g of acryloyl chloride was added with stirring, at room temperature the reaction was stirred 24h. 经萃取干燥后得到粗产物,再经纯化后得到产物4,4'-二[12-(丙烯酰氧基)十二烷氧基]偶氮苯(DA12AB)0.8g。 After extraction and drying to give a crude product, and the product was purified to give the 4,4'-bis [12- (acryloyloxy) dodecyloxy] azobenzene (DA12AB) 0.8g.

[0065] 实施例12 [0065] Example 12

[0066] 此实施例说明了根据本发明实施例6、11中得到的A12ABT和DA12AB进行光聚合制备液晶高分子材料的方法。 [0066] This example illustrates the A12ABT and DA12AB obtained in Example 6, 11 according to the embodiment of the present invention is a method for preparing the photopolymerizable liquid crystal polymer material. 请参见图1所示,首先将A12ABT和DA12AB按摩尔数90:10配比,然后加入A12ABT与DA12AB摩尔数之和5%的光引发剂Irgacure 784,熔融后注入两块基板5制成的液晶盒6中,两块基板5间放置了直径一定的间隔材料2使两基板5之间保持一定的间隔以控制所制得的交联液晶高分子材料的厚度,基板5的内表面被定向摩擦过,为的是使介晶基元沿着摩擦方向定向排列,摩擦方向3请见图中所示,接着用加热台4控制反应温度110℃,并在光源1所发出的波长大于545nm,光强为5mW/cm2的光照下反应6h,打开液晶盒6得到交联液晶高分子材料。 Referring to FIG. 1, first and DA12AB A12ABT by mole ratio of 90:10, and then added A12ABT DA12AB and 5% of the number of moles of the photoinitiator Irgacure 784, liquid crystal is injected after melting the substrate 5 is made of two the cartridge 6, the substrate 5 is placed between the two constant diameter spacer material 2 holding predetermined intervals between the two substrates to a thickness of 5 cross-linked polymer material obtained by controlling the liquid crystal, the inner surface of the substrate 5 is oriented friction too, in order that the mesogen alignment along the rubbing direction, the rubbing direction, as indicated on Figure 3, the stage 4 followed by heating control of the reaction temperature 110 ℃, and greater than 545nm wavelength emitted from the light source 1, light strong to 5mW / cm2 light reaction 6h, opening the liquid crystal cell 6 was crosslinked liquid crystal polymer material.

[0067] 实施例13 [0067] Example 13

[0068] 此实施例说明了根据本发明实施例6、11中得到的A12ABT和DA12AB进行热聚合制备液晶高分子材料的方法。 [0068] This example illustrates a method and DA12AB A12ABT obtained in Example 6, 11 thermally polymerized liquid crystal polymer material prepared according to the present embodiment of the invention. 首先将A12ABT和DA12AB按摩尔数90:10配比,然后加入A12ABT与DA12AB摩尔数之和1%的热引发剂偶氮二异庚腈,熔融后注入两块基板5制成的液晶盒6中,两块基板5间放置了直径一定的间隔材料2使两基板5之间保持一定的间隔以控制所制得的交联液晶高分子材料的厚度,基板5的内表面被定向摩擦过,为的是使介晶基元沿着摩擦方向定向排列,摩擦方向3请见图中所示,接着用加热台4控制反应温度100℃,反应12h,打开液晶盒6得到交联液晶高分子材料。 First and DA12AB A12ABT molar number ratio of 90:10, and then A12ABT DA12AB and 1% of the number of moles of added thermal initiator, azobis isobutyl nitrile heptyl, injecting the liquid crystal cell substrate 5 is made of two melt-6 , 5 is placed between the two substrates constant diameter of the holding spacer material 2 between two substrates predetermined intervals to control the thickness of the polymer material 5 is prepared by cross-linking the liquid crystal, the inner surface of the substrate 5 is oriented rubbed as is that the mesogen alignment along the rubbing direction, the rubbing direction, as indicated on Figure 3, the stage 4 followed by heating control of the reaction temperature 100 ℃, reaction 12h, opening the liquid crystal cell 6 was crosslinked liquid crystal polymer material.

[0069] 实施例14 [0069] Example 14

[0070] 此实施例说明了以上所制备的交联液晶高分子材料与聚乙烯材料进行复合的方法。 [0070] This example illustrates a liquid crystal polymer material with crosslinked polyethylene material composite prepared above method. 首先将50μm厚度的聚乙烯材料均匀地涂上约10μm厚度的胶粘剂层,然后取实施例13制备得到的交联液晶高分子材料加工成30μm的厚度后,将其平整地放在涂有胶粘剂层的聚乙烯上面,施加约0.05Kg/cm2的压力,待静压10min后,得到复合材料。 The first polyethylene material is evenly coated with a 50μm thickness of the adhesive layer thickness of about 10μm, then take embodiment postcrosslinking liquid crystal polymer obtained in Preparation Example 13 is processed to a thickness of 30μm, which is flat in the adhesive coated layer polyethylene above, applying a pressure of about 0.05Kg / cm2, the hydrostatic after 10min, to obtain a composite material.

[0071] 实施例15 [0071] Example 15

[0072] 本实施例说明了交联液晶高分子材料的光致形变的控制。 [0072] This example illustrates the controlled deformation of the photo-crosslinked polymer liquid crystal material. 请见图2所示,将实施例10或11中得到的交联液晶高分子材料8置于基板7上,然后在垂直于所述液晶高分子材料8上方启动波长为436nm,光强为20mW/cm2可见光10,此时可以观察到液晶高分子材料8沿着摩擦方向9弯向光源形成了发生形变的液晶高分子材料11。 See Figure 2, the cross-linked liquid crystal polymer obtained in Example 10 or 11 of the embodiment 8 is placed on the substrate 7, and then a vertical start to the liquid crystal polymer material 8 over a wavelength of 436 nm, the light intensity of 20mW / cm2 visible light 10, when the liquid crystal polymer material can be observed 8 9 bent along the rubbing direction of the light source is formed of a liquid crystal polymer 11 is deformed. 停止可见光10的照射后,启动波长大于545nm,光强为18mW/cm2的可见光12,又可观察到所述的发生形变的液晶高分子材料11变成了回复初始状态的液晶高分子材料13,此过程可以循环多次操作,而液晶高分子材料8本身不出现明显疲劳现象。 10 after stopping the irradiation with visible light, starting a wavelength greater than 545 nm, the light intensity of 18mW / cm2 visible light 12, can be observed in the liquid crystal polymer material 11 is deformed into a reply to the initial state of the liquid crystal polymer material 13, this process may loop multiple operations, the liquid crystal polymer material 8 itself is not significant fatigue.

Claims (12)

  1. 1、一种由可见光照射实现光致形变的液晶高分子材料,其特征是,首先有机合成出单体X和交联剂Y,然后再与一定量的光引发剂或者热引发剂混合,放入反应器中,选择合适的光强或是反应温度,通过光聚合反应或者热聚合反应生成液晶高分子材料; 1, the liquid crystal polymer material which is irradiated by a visible-light-induced deformation, wherein the first organic monomer X and a crosslinking agent synthesized Y, then the light amount of initiator or a thermal initiator mixed, put into the reactor, the light intensity or select the appropriate reaction temperature, reaction by photopolymerization or thermal polymerization reaction of the liquid crystal polymer material;
    其中,所述单体X的通式为: Wherein monomer X is of the general formula:
    D1—A1—R D1-A1-R
    所述交联剂Y的通式为: Y is the crosslinking agent of the general formula:
    D2—A2—D3 D2-A2-D3
    其中R是H,或者是C1-C20的取代或未取代的烃基或者烷氧基,或者是具有极性的端基;A1、A2选自如下结构中的一种基团或是两种以对应的结构键链接而成的基团或是三种以对应的结构键链接起来而成的基团, Wherein R is H, or a substituted or unsubstituted hydrocarbon group or a C1-C20 alkoxy group, or having a polar terminal group; A1, A2 selected from the structure of one or two kinds of groups to the corresponding the structure of the key links formed by three kinds of group or bond to link the corresponding structures formed by a group
    A1、A2的结构相同或者不同,在上述基团中,B、B1、B2是取代或未取代的脂肪族环、芳环、稠环、杂环,或者是它们相应的衍生物,B、B1、B2的结构相同或者不同,但A1、A2其中之一至少含有偶氮苯的共轭结构,不限于以下结构, A1, A2 are the same or different structures, in the above-mentioned groups, B, B1, B2 is a substituted or unsubstituted aliphatic ring, an aromatic ring, a condensed ring, heterocyclic ring, or the corresponding derivatives thereof, B, B1 , B2 is the same or different structures, but the A1, A2 comprising at least one azobenzene conjugated structure is not limited to the following structure,
    其中,D1~D3是含有能进行聚合的碳碳双键结构的基团,它们独立选自如下结构中的一种,D1~D3结构相同或者不同, Wherein, D1 ~ D3 is a group containing a carbon-carbon double bond structures can be polymerized, they are independently selected from one of the following structures, the same or different structure D1 ~ D3,
    其中R1是H或是CH3;R2是H,或者在单体通式中不出现,或是C1-C20的取代或未取代的烃基或烷氧基、烷硫基、烷氨基、二烷氨基、烷酰基、烷酰氧基、烷酰胺基、烷磺酰基,或者是它们相应的衍生物。 Wherein R1 is H or CH3; R2 is H, or is not present in the monomer of formula, or a substituted or unsubstituted C1-C20 hydrocarbon group or alkoxy, alkylthio, alkylamino, dialkylamino, alkanoyl, alkanoyloxy, alkanoylamino group, an alkylsulfonyl group, or their corresponding derivatives.
  2. 2、如权利要求1所述的液晶高分子材料,其特征是,R优选的是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,所述具有极性的端基优选自F、Cl、Br、I或酯基。 2, the liquid crystal polymer as claimed in claim 1, wherein, R is preferably a substituted or unsubstituted C1 ~ C12 alkoxy group or a hydrocarbon group, or a group having a polar end, said electrode having end group preferably selected from F, Cl, Br, I or an ester group.
  3. 3、如权利要求1所述的液晶高分子材料,其特征是,R2优选的是C1~C12的取代或未取代的烃基,所述的烃基可以是饱和的或不饱和的,或选自烷氧基。 3, a liquid crystal polymer as claimed in claim 1, wherein, R2 is preferably a substituted or unsubstituted C1 ~ C12 hydrocarbon group, the hydrocarbon group may be saturated or unsaturated, alkyl or selected from group.
  4. 4、如权利要求1所述的液晶高分子材料,其特征是,单体X和交联剂Y的摩尔比值为99∶1—1∶99,优选的比值为95∶5—50∶50。 4, a liquid crystal polymer as claimed in claim 1, characterized in that the molar ratio of monomer X and Y are 99:1-1:99 crosslinking agent, preferably the ratio 95:5-50:50.
  5. 5、如权利要求1所述的液晶高分子材料,其特征是,所述的光引发剂选自有机羰基类化合物和有机金属类化合物,优选自Irgacure 784、Irgacure 819,它们的结构式如下: 5, the liquid crystal polymer material as claimed in claim 1, wherein said photoinitiator is selected from the class of organic carbonyl compounds and organometallic compounds, preferably selected from Irgacure 784, Irgacure 819, whose structural formulas are as follows:
  6. 6、如权利要求1所述的液晶高分子材料,其特征是,所述的热引发剂选自偶氮类化合物,优选自偶氮二异丁腈、偶氮二异庚腈。 6, liquid crystal polymer as claimed in claim 1, wherein said thermal initiator is selected from azo compounds, preferably selected from azobisisobutyronitrile, azobis iso-heptonitrile.
  7. 7、如权利要求1所述的液晶高分子材料,其特征是,所选用的光引发剂或热引发剂的用量为单体与交联剂摩尔数之和的0.1%—10%,优选的是1%—5%。 7, a liquid crystal polymer as claimed in claim 1, characterized in that the chosen photoinitiator or a thermal initiator is used in an amount of 0.1% to 10% of monomer and crosslinking agent to the number of moles, preferably 1% to 5%.
  8. 8、如权利要求1所述的液晶高分子材料,其特征是,进行光聚合时所选择的波长范围是300nm—800nm,优选的是400nm-600nm;光的强度范围是0.1mW/cm2—20mW/cm2,优选的是1mW/cm2—10mW/cm2;进行光聚合的聚合时间范围是0.5h—20h,优选的是2h—10h;聚合温度范围是50℃—200℃,优选的是80℃—150℃。 8, a liquid crystal polymer as claimed in claim 1, characterized in that, when the photopolymerization is selected wavelength range 300nm-800nm, preferably is 400nm-600nm; light intensity range is 0.1mW / cm2-20mW / cm2, preferably is 1mW / cm2-10mW / cm2; photopolymerization polymerization time was 0.5h-20h, preferably the 2h-10h; the polymerization temperature in the range 50 ℃ -200 ℃, preferably is 80 ℃ - 150 ℃.
  9. 9、如权利要求1所述的液晶高分子材料,其特征是,进行热聚合的聚合时间范围是1h—100h,优选的是3h—50h;聚合温度范围是20℃—200℃,优选的是40℃—150℃。 9, a liquid crystal polymer as claimed in claim 1, characterized in that the polymerization is a thermal polymerization time 1h-100h, are preferably 3h-50h; the polymerization temperature ranges from 20 ℃ -200 ℃, is preferably 40 ℃ -150 ℃.
  10. 10、一种使液晶高分子材料产生形变和恢复的方法,其特征是,在室温下通过可见光照射即能够使材料发生形变,再经过的可见光照射或加热又可回复到初始的状态,其中控制材料形变的可见光的波长为380nm—480nm,光强度在1mW/cm2—300mW/cm2,优选为5mW/cm2—50mW/cm2,使材料恢复初始状态的可见光的波长为500nm-800nm,强度为1mW/cm2—300mW/cm2,,优选为10mW/cm2-100mW/cm2。 10. A liquid crystal polymer material deforms and recovery method, characterized in that the material at room temperature can be made by irradiation of visible light is deformed, and then after the irradiation with visible light or heating in turn return to the initial state, wherein the control wavelength of visible light wavelength of visible light for the deformation of the material of 380nm-480nm, the light intensity 1mW / cm2-300mW / cm2, preferably from 5mW / cm2-50mW / cm2, the material to restore the initial state of 500nm-800nm, intensity of 1mW / cm2-300mW / cm2 ,, preferably 10mW / cm2-100mW / cm2.
  11. 11、一种复合材料,其特征是,所述的复合材料包括三层结构,第一层为交联液晶高分子材料,厚度为5μm—100μm;中间一层为复合用胶粘剂层,胶粘剂选自氰基丙烯酸酯类、聚氨酯类、丙烯酸类、聚丙烯酸类中的一种,其厚度为1μm—100μm;第三层为柔性基体材料,选自聚乙烯、聚丙烯、聚对苯二甲酸乙二醇酯、聚碳酸酯、天然橡胶中的一种,其厚度为5μm—5mm。 11. A composite material, characterized in that said composite material comprises a three-layer structure, the first layer is a crosslinked liquid crystal polymer material, having a thickness of 5μm-100μm; intermediate layer is a composite adhesive layer, the adhesive is selected from cyanoacrylate, urethane, acrylic, polyacrylic of one having a thickness of 1μm-100μm; third layer is a flexible base material, selected from polyethylene, polypropylene, polyethylene terephthalate alcohol esters, polycarbonate, a natural rubber having a thickness of 5μm-5mm.
  12. 12、如权利要求11所述的复合材料,其特征是,所述的交联液晶高分子材料的厚度为40μm—60μm,所述的胶粘剂层的厚度为5μm-30μm,所述的柔性基体材料的厚度为30μm-70μm。 12. The composite of claim 11, wherein the flexible base material, characterized in that the thickness of the crosslinked polymer liquid crystal material is 40μm-60μm, the thickness of the adhesive layer is 5μm-30μm, the thickness of 30μm-70μm.
CN 200910045903 2009-01-22 2009-01-22 Liquid crystal polymer material and composite material realizing photo-induced deformation by visible light irradiation CN101481440A (en)

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CN101942058A (en) * 2010-08-26 2011-01-12 复旦大学 Infrared photodeformable liquid crystal high-polymer nano composite material and preparation method thereof
CN103087296A (en) * 2013-01-29 2013-05-08 复旦大学 Side chained linear azobenzene liquid crystal polymer material and preparation method thereof
CN103483495A (en) * 2013-09-16 2014-01-01 复旦大学 Photoinduced-deformation high polymer material based on triplet state-triplet state annihilation up-conversion luminescence
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CN101793243A (en) * 2010-03-12 2010-08-04 同济大学 Light-operated underwater scooter and boosting method
CN101942058A (en) * 2010-08-26 2011-01-12 复旦大学 Infrared photodeformable liquid crystal high-polymer nano composite material and preparation method thereof
CN101942058B (en) 2010-08-26 2012-11-28 复旦大学 Infrared photodeformable liquid crystal high-polymer nano composite material and preparation method thereof
CN103087296A (en) * 2013-01-29 2013-05-08 复旦大学 Side chained linear azobenzene liquid crystal polymer material and preparation method thereof
CN103087296B (en) * 2013-01-29 2015-07-29 复旦大学 One kind of a side chain-type linear polymer azobenzene liquid crystal material and method
CN103483495A (en) * 2013-09-16 2014-01-01 复旦大学 Photoinduced-deformation high polymer material based on triplet state-triplet state annihilation up-conversion luminescence
CN103483495B (en) * 2013-09-16 2016-08-17 复旦大学 Based triplet - converting the luminescent triplet annihilation photo polymer material deformation
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