CN114350002B - Deformation reconfigurable liquid crystal polymer film driver and preparation method thereof - Google Patents
Deformation reconfigurable liquid crystal polymer film driver and preparation method thereof Download PDFInfo
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Abstract
A deformation reconfigurable liquid crystal polymer thin film driver and a preparation method thereof are provided, wherein the preparation method comprises the following steps: taking polymerizable monofunctional liquid crystal monomers, polymerizable bifunctional liquid crystal monomers and non-polymerizable liquid crystal monomers to mix to obtain mixed liquid crystal; coating the mixed liquid crystal into a film, and performing ultraviolet polymerization to obtain a liquid crystal polymer film; soaking one side of the liquid crystal polymer film in a KOH aqueous solution, cleaning with deionized water and drying; then partially soaking in CaCl 2 In the water solution, washing with deionized water and drying; and finally, completely soaking the film in an EDTA-2K aqueous solution, cleaning the film by using deionized water, and drying the film to obtain the liquid crystal polymer film driver which is reconfigurable and is based on humidity response. The preparation method adopts a non-destructive modification mode to prepare the responsive liquid crystal elastomer, can realize repeated processing and utilization by treating, eliminating, retreating and retreating the surface of the film, and is a very cheap and environment-friendly process.
Description
Technical Field
The invention relates to the field of high polymer materials, in particular to a liquid crystal polymer film driver with reconfigurable deformation and a preparation method thereof.
Background
For the photoresponsive liquid crystal polymer, the photoresponsive liquid crystal polymer cannot operate in a dark environment, so that the photoresponsive liquid crystal polymer is not suitable for some dark environments and can not manipulate photodegradable substances, and thus, the development of liquid crystal polymer materials with other stimulus responsiveness is required. Plants in nature perform physiological activities by sensing changes in factors such as sunlight, air flow, and ambient humidity. Under the development of nature, material scientists hope to prepare novel bionic devices capable of simulating animals and plants in nature by using non-toxic and harmless control modes such as environmental humidity and the like. The environmental humidity is dynamically changed, and the humidity is used as a stimulus source, so that the energy-saving and efficient driving mode is realized. The humidity of the environment is dynamically changed, and how to use the humidity as a stimulus to obtain an energy-saving and efficient driving mode is an important issue to be researched urgently.
Disclosure of Invention
Based on the above, the invention provides a liquid crystal polymer film driver with reconfigurable deformation and a preparation method thereof, wherein the preparation method adopts a non-destructive modification mode to prepare a responsive liquid crystal elastomer, and the mode can realize repeated processing and utilization through treatment, elimination, retreatment and reelimination of the film surface, so that the liquid crystal polymer film driver is a very cheap and environment-friendly process.
In order to achieve the above object, the present invention provides a method for preparing a deformable reconfigurable liquid crystal polymer thin film driver, comprising the steps of:
1) taking a polymerizable monofunctional liquid crystal monomer, a polymerizable bifunctional liquid crystal monomer and a non-polymerizable liquid crystal monomer to mix to obtain a mixed liquid crystal;
2) coating the mixed liquid crystal obtained in the step 1) into a film, and then polymerizing within a preset temperature range to obtain a parallel-oriented liquid crystal polymer film;
3) soaking one side of the liquid crystal polymer film obtained in the step 2) in a solution with the pH value of 11.0-13.0 and the concentration of 0.06-0.08 mol.L -1 Soaking in KOH aqueous solution for 0.1-12.0 h;
4) cleaning the liquid crystal polymer film treated in the step 3) by using deionized water, and drying;
5) soaking the part of the liquid crystal polymer film treated in the step 4) in a solution with the concentration of 0.04-0.06 mol.L -1 In (C) is 2 Soaking in water solution for 0.1-12.0 hr;
6) cleaning the liquid crystal polymer film treated in the step 5) by using deionized water, and drying;
7) the liquid crystal polymer film treated in the step 6) is treatedSoaking in water at a concentration of 0.08-0.10 mol.L -1 Soaking in EDTA-2K water solution for 0.1-12.0 hr;
8) and (3) cleaning the liquid crystal polymer film treated in the step 7) by using deionized water, and drying to finally obtain the liquid crystal polymer film driver with reconfigurable deformation and based on humidity response.
As a further preferable embodiment of the present invention, the preparation method further comprises: repeating the steps 5) -8) while changing the dipping position of the liquid crystal polymer film in the step 5), so that the prepared liquid crystal polymer film driver has different shapes.
As a further preferred embodiment of the present invention, in the step 1), the polymerizable monofunctional liquid crystal monomer, the bifunctional liquid crystal monomer and the non-polymerizable liquid crystal monomer are mixed in a mass ratio of 49.0/35.0/15.0-15.0/35.0/49.0.
As a further preferable scheme of the invention, in the step 2), the thickness of the liquid crystal polymer film prepared by coating and mixing the liquid crystal is 10.0-40.0 μm, the length is 0.5-4.0cm, and the width is 0.5-2.0 cm.
As a further preferred embodiment of the present invention, the polymerizable monofunctional liquid crystal monomer and the polymerizable difunctional liquid crystal monomer each have an ability to undergo polymerization under ultraviolet light initiation, and both of the polymerizable monofunctional liquid crystal monomers include one or more of the following molecular structural formulae (1) to (4):
wherein n is a positive integer of 1 to 12, and R is selected from one of the following groups (1) to (4):
wherein n is a positive integer of 1 to 12.
As a further preferred embodiment of the present invention, when the photoinitiator is added during the preparation of the compounded liquid crystal in step 1), the compounded liquid crystal in step 2) undergoes a polymerization reaction under the irradiation of ultraviolet light.
In a further preferred embodiment of the present invention, the photoinitiator is benzil dimethyl ether.
As a further preferred embodiment of the present invention, the conditions for mixing the liquid crystal in the step 2) and performing the polymerization reaction are as follows: the illumination intensity is 2.0-3.0mW cm -2 Irradiating with 365nm ultraviolet at 70-100 deg.C for 30.0-60.0 min.
As a further preferable scheme of the invention, when the liquid crystal polymer film is soaked in the single side in the step 3), the ratio of the non-soaking length to the soaking length is 3.0/7.0-7.0/3.0.
The invention also provides a liquid crystal polymer film driver, which is prepared by any one of the preparation methods of the deformation reconfigurable liquid crystal polymer film driver.
By adopting the technical scheme, the liquid crystal polymer film driver with reconfigurable deformation and the preparation method thereof can achieve the following beneficial effects:
1) although the ethylene diamine tetraacetic acid dipotassium (EDTA-2K) used in the preparation method is a common biological anticoagulant, the ethylene diamine tetraacetic acid dipotassium (EDTA-2K) has the advantages of good biocompatibility, no toxicity, easy degradation and the like, and the preparation of the functionalized device by modifying and modifying the existing liquid crystal polymer by utilizing the EDTA-2K is beneficial to the preparation of the bionic material and has important significance for the research of the biological material;
2) the driving mode adopted in the invention is environment humidity which has the advantages of no toxicity, strong penetrability and the like, the energy density is low, and the defects of great damage to materials, harm to human bodies and the like existing in the traditional driving modes of light, heat and the like can be effectively solved;
3) compared with a chemical doping method in the traditional research, the preparation method adopts a nondestructive modification mode to prepare the responsive liquid crystal elastomer, and the mode can realize repeated processing and utilization by treating, eliminating, retreating and retreating the surface of the film, so that the preparation method is a very cheap and environment-friendly process.
Drawings
The present invention will be described in further detail with reference to the accompanying drawings and specific embodiments.
FIG. 1 shows ATR-FTIR test results of a liquid crystal polymer film treated with an aqueous KOH solution and a conventional untreated liquid crystal polymer film;
FIG. 2 is a test result of curvature of a liquid crystal polymer film after treatment with an aqueous KOH solution as a function of humidity;
FIG. 3 shows the use of CaCl 2 ATR-FTIR test results of the liquid crystal polymer film treated with the aqueous solution and the liquid crystal polymer film treated with the aqueous KOH solution;
FIG. 4 shows a liquid crystal polymer film treated with an aqueous EDTA-2K solution and treated with CaCl 2 ATR-FTIR test results of the liquid crystal polymer film treated by the aqueous solution;
fig. 5 is a deformation cycle process of the liquid crystal polymer thin film actuator prepared in example 2.
The objects, features and advantages of the present invention will be further explained with reference to the accompanying drawings.
Detailed Description
The invention will be further described with reference to the accompanying drawings and specific embodiments. In the preferred embodiments, the terms "upper", "lower", "left", "right", "middle" and "a" are used for clarity of description only, and are not used to limit the scope of the invention, and the relative relationship between the terms and the terms is not changed or modified substantially without changing the technical content of the invention.
Compared with humidity-responsive hydrogel, polymer composite materials and the like, the humidity-responsive liquid crystal polymer material has the advantages of adjustable deformation mode, outstanding mechanical properties and the like. The humidity response liquid crystal high polymer material has the advantages of adjustable deformation mode, outstanding mechanical property and the like. The humidity response deformation liquid crystal high polymer material is a material capable of realizing motion under the drive of humidity, and can directly convert chemical energy into mechanical energy of the material. The humidity is widely existed in various environments, has the advantages of simplicity, easy obtaining, non-contact remote control, good biocompatibility, strong penetrability and the like, is easy to control in time and space, and is an ideal driving mode.
Benzoic acid can form a rigid rod-shaped structure through the action of hydrogen bonds among carboxylic acids in a proper temperature range, a flexible chain is introduced into a benzene ring in a para position, the benzoic acid material can show liquid crystallinity, and a liquid crystal polymer network rich in the hydrogen bonds, namely a polymer network, can be constructed through benzoic acid hydrogen bond liquid crystal polymerization. Because the hydrogen bond of the polymer network can be broken under alkali treatment, the orderly collapse of the polymer network after the breakage forms a random polymer structure, and meanwhile, the carboxylate group on the polymer network can endow the network with hygroscopicity, and the polymer network can expand or contract through water absorption or water loss under different humidity environments. Based on the principle, the invention provides a preparation method of a deformation reconfigurable liquid crystal polymer film driver, which comprises the following steps:
1) taking polymerizable monofunctional liquid crystal monomers, polymerizable bifunctional liquid crystal monomers and non-polymerizable liquid crystal monomers to mix to obtain mixed liquid crystal;
2) coating the mixed liquid crystal obtained in the step 1) into a film, and then polymerizing the film by ultraviolet irradiation within a preset temperature range to obtain a parallel-oriented liquid crystal polymer film;
3) soaking one side of the liquid crystal polymer film obtained in the step 2) in a solution with the pH value of 11.0-13.0 and the concentration of 0.06-0.08 mol.L -1 Soaking in KOH aqueous solution for 0.1-12.0 h;
4) cleaning the liquid crystal polymer film treated in the step 3) by using deionized water, and drying;
5) soaking the part of the liquid crystal polymer film treated in the step 4) in a solution with the concentration of 0.04-0.06 mol.L -1 CaCl of 2 Soaking in water solution for 0.1-12.0 hr;
6) cleaning the liquid crystal polymer film treated in the step 5) by using deionized water, and drying;
7) completely soaking the liquid crystal polymer film treated in the step 6) in water at the concentration of 0.08-0.10mol ·L -1 Soaking in EDTA-2K water solution for 0.1-12.0 hr;
8) and (3) cleaning the liquid crystal polymer film treated in the step 7) by using deionized water, and drying to finally obtain the liquid crystal polymer film driver with reconfigurable deformation and based on humidity response.
Preferably, in order to obtain the liquid crystal polymer thin film driver having different shapes according to the manufacturing, the manufacturing method further includes: repeating the steps 5) -8) while changing the dipping position of the liquid crystal polymer film in the step 5), so that the prepared liquid crystal polymer film driver has a different shape. It should be noted that the previous steps 1) to 4) are the same, and the subsequent steps 5) to 8) can be adjusted according to requirements, so as to prepare liquid crystal polymer film drivers with different requirements.
According to the invention, the liquid crystal polymer film driven by humidity is prepared by treating one side of the liquid crystal polymer film with alkali, then the liquid crystal polymer film is locally soaked in calcium chloride aqueous solution to realize different deformations, and finally, EDTA-2K aqueous solution is used for recovering humidity response again.
The detailed principle of the preparation method of the invention is as follows: the single-side alkali treatment enables carboxylic acid in the local film thickness direction to react to generate hygroscopic carboxylate, and the difference of the hygroscopicity of the substrate and the treated part enables the liquid crystal polymer film in parallel orientation to be bent due to the uniform and ordered disturbance of liquid crystal elements; after the partial soaking treatment is carried out by using a calcium chloride aqueous solution, the carboxylate ions and the calcium ions of the treated part form covalent bonds, and the carboxylate loses hygroscopicity, so that the matrix and the treated part have no hygroscopicity difference, and the expansion performance is lost without deformation; finally, the film is soaked by EDTA-2K aqueous solution, and EDTA-2K can react with calcium ions to generate stable chelate calcium ethylene diamine tetraacetic acid, so that the treated part is changed back to the carboxylate with hygroscopicity. This state can be cycled back and forth so that the film can be specifically deformed, restored, re-deformed and re-restored in the presence of changes in ambient humidity.
The invention realizes the deformation of the liquid crystal polymer film driven by humidity, and the deformation amplitude and the deformation shape can be controlled by controlling the relative humidity and the liquid crystal polymerThe cutting angle of the compound film driver can be adjusted by CaCl 2 The liquid crystal film drivers with different performances are prepared by the local cross-linking treatment of the aqueous solution and the complexing treatment of the EDTA-2K aqueous solution. The preparation method has the advantages of low price, environmental protection and simplicity, and is expected to play a role in the fields of developing new generation humidity response intelligent materials, soft robots and the like. It is to be noted that the operation in the humid environment used in the present invention can be performed in a closed chamber filled with both dry and wet nitrogen gases.
The present invention will be described in further detail below by way of specific examples.
Example 1
step 2, weighing 0.45g of potassium hydroxide powder, dissolving the potassium hydroxide powder in 100.0mL of deionized water to obtain the solution with the concentration of 0.08 mol.L -1 The KOH aqueous solution of (1), one side of the prepared liquid crystal polymer film is soaked in the KOH aqueous solution for 30.0 seconds, and the ratio of the length of the liquid crystal polymer film which is not soaked to the length of the liquid crystal polymer film which is soaked is 3.0: 7.0;
step 3, taking out the soaked liquid crystal polymer film, washing the surface of the liquid crystal polymer film with deionized water for three times, wiping the surface of the liquid crystal polymer film with dust-free cloth, and drying the liquid crystal polymer film in a drying oven at 40.0 ℃;
step 4, weighing 0.67g of calcium chloride particles, dissolving the calcium chloride particles in 100.0mL of deionized water, and preparing to obtain the calcium chloride particles with the concentration of 0.06 mol.L -1 In (C) is 2 Aqueous solution, one end of the liquid crystal polymer film dried in the step 3 is stuck by an adhesive tape, the ratio of the length of the stuck adhesive tape to the length of the non-stuck adhesive tape is 1.0/1.0, and then the liquid crystal polymer stuck with the adhesive tape isFilm soaked CaCl 2 Soaking in water solution for 5.0 min;
step 5, taking out the soaked liquid crystal polymer film, tearing off the adhesive tape, washing the surface with deionized water for three times, wiping the surface with dust-free cloth, and drying in a drying oven at 40.0 ℃;
step 6, weighing 4.04g of ethylene diamine tetraacetic acid dipotassium powder, dissolving the powder in 100.0mL of deionized water, and preparing to obtain the solution with the concentration of 0.10 mol.L -1 Soaking the liquid crystal polymer film dried in the step 5 in the EDTA-2K aqueous solution for 10.0 minutes;
and 7, taking out the soaked liquid crystal polymer film, washing the surface with deionized water for three times, wiping the surface with dust-free cloth, and drying in a drying oven at 40.0 ℃ to obtain the liquid crystal polymer film driver with reconfigurable deformation and based on humidity response.
The following comparative tests were carried out on the intermediate product and the final product of example 1, respectively:
The results of comparing the alkali-treated liquid crystal polymer film with the ordinary liquid crystal polymer film by the ATR-FITR test and the curvature test at different relative humidities are shown in fig. 1, respectively, where the alkali-treated liquid crystal polymer film is the product of step 3 and the ordinary liquid crystal polymer film is the product of step 1.
As can be seen from the ATR-FTIR of FIG. 1, the untreated liquid crystal polymer film was found to be 1680cm -1 Shows a strong hydrogen bond absorption peak, and the absorption peak of the liquid crystal polymer film subjected to alkali treatment is obviously weakened. This is because the carboxyl groups on the treated side surface of the liquid crystal polymer film are neutralized to form carboxylate, and the hydrogen bonds between the carboxyl groups are broken. At the same time, at 1540cm -1 And 1395cm -1 The absorption peak shows the formation of hygroscopic carboxylate on the surface of the treated side, so that the hygroscopic carboxylate can be subjected to water absorption swelling and water loss shrinkage along with the change of relative humidity, thereby causing the three-dimensional deformation of the film.
In order to further study the performance of the liquid crystal polymer film with the curvature varying with the relative humidity, the curvature variation of the liquid crystal polymer film treated by KOH aqueous solutions with different concentrations under different relative humidities is tested, the influence of different relative humidities and different KOH aqueous solution concentrations on the humidity-responsive deformation of the film is analyzed, and the used liquid crystal polymer films are all prepared according to the step 1. Referring to fig. 2, it can be seen that the curvature of the liquid crystal polymer film treated with the KOH aqueous solution of the same concentration is significantly reduced with the increase of the relative humidity, and the larger the curvature of the liquid crystal polymer film at the same relative humidity, the more obvious the deformation is.
Test 2
The results of comparing the locally ionomer-treated liquid crystal polymer film with the alkali-treated liquid crystal polymer film by ATR-FITR test are shown in fig. 3, in which the locally ionomer-treated liquid crystal polymer film is the product of step 5 and the treated liquid crystal polymer film is the product of step 3.
As can be seen from ATR-FTIR in FIG. 3, the alkali-treated film was found to be 1680cm -1 Shows a weak hydrogen bond absorption peak, while the film subjected to the ionic crosslinking treatment has almost no absorption peak at this point. This is because the carboxylate and Ca on the surface of the liquid crystal polymer film subjected to the ion crosslinking treatment 2+ New ionic bonds are formed, and the original hydrogen bonds between carboxyl groups are all broken. At the same time, at 1540cm -1 And 1395cm -1 The position of the absorption peak is changed, which further proves that the carboxylate radical and Ca on the side surface of the treated material are 2+ The formation of the ionic bond results in the disappearance of the original hygroscopicity of the carboxylate, and the loss of the humidity-responsive deformation ability.
Test 3
Comparing the liquid crystal polymer film recovering humidity deformation response and the liquid crystal polymer film subjected to local ionic crosslinking by an ATR-FITR test, wherein the result is shown in FIG. 4, the liquid crystal polymer film recovering humidity deformation response is the final product of the step 7, and the liquid crystal polymer film subjected to local ionic crosslinking is the product of the step 5.
As can be seen from ATR-FTIR of FIG. 4The film treated with EDTA-2K aqueous solution was found to be 1680cm -1 The absorption peak of the hydrogen bond at which partial strength is restored, compared to the film subjected to the ionic crosslinking treatment, which has almost no absorption peak at this point. This is because Ca on the surface of the liquid crystal polymer film after the treatment with the aqueous EDTA-2K solution 2+ Generates a stable chelate EDTA-Ca by the complexation reaction with EDTA-2K, destroys carboxylate ions and Ca 2+ The ionic bond formed regenerates the carboxylate. At the same time, at 1540cm -1 And 1395cm -1 Again, the absorption peak intensity becomes large, which further proves that the treated side surface carboxylate radicals and Ca are present 2+ The ionic bonds formed in the bond are broken, where in turn hygroscopic carboxylate salts are formed, so that the film regains humidity-responsive driveability.
Example 2
The raw materials and the proportions of the raw materials used in the example 2 and the example 1 are the same, except that CaCl is adopted 2 And (4) repeatedly soaking the aqueous solution and the EDTA-2K aqueous solution for multiple times to verify that the liquid crystal polymer film driver has corresponding deformation reconfigurability based on humidity.
step 2, preparing to obtain the product with the concentration of 0.08 mol.L -1 The KOH aqueous solution of (3), one side of the prepared small strip is soaked in the KOH aqueous solution for 30 seconds, and the ratio of the length of the small strip which is not soaked to the length of the small strip which is soaked is 3.0: 7.0;
step 3, taking out the soaked strips, washing the surfaces of the strips with deionized water for three times, wiping the surfaces of the strips with dust-free cloth, and drying the strips in a drying oven at 40.0 ℃;
step 4, sticking the part with the middle length of 1.0cm of the small strip dried in the step 3 by using an adhesive tape, and then soaking the small strip in the adhesive tape at the concentration of 0.06 mol.L -1 CaCl of 2 Soaking in water solution for 5.0 min;
step 5, taking out the small strips soaked in the step 4, tearing off the adhesive tape, washing the surface with deionized water for three times, wiping the surface with dust-free cloth, and then drying in an oven at 40.0 ℃, wherein the dried small strips show U-shaped deformation in the environment humidity;
step 6, soaking the small strips dried in the step 5 in water at the concentration of 0.10 mol.L -1 Soaking in EDTA-2K water solution for 10.0 min;
step 7, taking out the small strips soaked in the step 6, washing the surfaces of the small strips with deionized water for three times, wiping the surfaces of the small strips with dust-free cloth, then drying the small strips in an oven at 40.0 ℃, and recovering the deformation capacity of the dried small strips before treatment in the environment humidity;
step 8, respectively sticking the left and right sides of the small strip dried in the step 5 with the length of 0.5cm by using adhesive tapes, wherein the ratio of the length of the adhesive tapes to the length of the adhesive tapes is 1.0/1.0, and then soaking the small strip in the solution with the concentration of 0.06 mol.L -1 In (C) is 2 Soaking in water solution for 5 min;
and 9, taking out the small strips soaked in the step 8, tearing off the adhesive tape, washing the surface with deionized water for three times, wiping the surface with dust-free cloth, and drying in a drying oven at 40.0 ℃. The dried bars exhibited a "C" deformation at ambient humidity.
and 11, taking out the small strips soaked in the step 10, washing the surface of the small strips with deionized water for three times, wiping the surface of the small strips with dust-free cloth, and drying the small strips in an oven at 40.0 ℃. The dried small strips recover the deformation capacity before treatment in the environment humidity;
step 12, the small strips obtained in the step 11 are arranged from the leftAdhering 0.3cm long part with adhesive tape at intervals of 0.3cm from side, wherein the ratio of the length of the adhesive tape to the length of the non-adhesive tape is 1.1/0.9, and soaking the small strip in water at a concentration of 0.06 mol.L -1 In (C) is 2 Soaking in water solution for 5.0 min;
step 13, taking out the small strips soaked in the step 12, tearing off the adhesive tape, washing the surface with deionized water for three times, wiping the surface with dust-free cloth, and drying in an oven at 40.0 ℃, wherein the dried small strips show W deformation in the environment humidity;
step 14, soaking the small strips obtained in step 13 in water at a concentration of 0.10 mol.L -1 Soaking in EDTA-2K water solution for 10.0 min;
step 15, taking out the small strips soaked in the step 14, washing the surfaces of the small strips with deionized water for three times, wiping the surfaces of the small strips with dust-free cloth, then drying the small strips in an oven at 40.0 ℃, and recovering the deformation capacity of the dried small strips before treatment in the environment humidity;
step 16, sticking the 0.4cm long part of the small strip at the position 0.5cm away from the left side and the right side by using an adhesive tape, wherein the ratio of the length of the adhesive tape to the length of the non-adhesive tape is 0.8/1.2, and soaking the small strip in water at the concentration of 0.06 mol.L -1 CaCl of 2 Soaking in water solution for 5.0 min;
and step 17, taking out the soaked strips, tearing off the adhesive tapes, washing the surfaces of the strips with deionized water for three times, wiping the surfaces of the strips with dust-free cloth, and drying the strips in an oven at 40.0 ℃, wherein the dried strips show W-shaped deformation in the environment humidity.
Step 18, soaking the small strips obtained in the step 15 in water at a concentration of 0.10 mol.L -1 Soaking in EDTA-2K water solution for 10.0 min;
and 19, taking out the soaked strips, washing the surfaces of the strips with deionized water for three times, wiping the surfaces of the strips with dust-free cloth, then drying the strips in an oven at 40.0 ℃, and recovering the deformation capacity of the dried strips before treatment in the environment humidity.
And 20, repeating the steps 4-19 to realize the deformation circulation of the small strips, wherein the deformation circulation process of the small strips when the steps 4-19 are repeated is shown in figure 5.
In the specific preparation process, CaCl is added 2 Repeatedly soaking the small strips in aqueous solution and EDTA-2K aqueous solution for multiple times while changing CaCl 2 The liquid crystal polymer film drivers with different functions and different shapes can be manufactured at the soaking position of the small strips by the aqueous solution, so that different use requirements can be met.
Although specific embodiments of the present invention have been described above, it will be appreciated by those skilled in the art that these are merely examples and that many variations or modifications may be made to the embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims.
Claims (10)
1. A method for preparing a deformation reconfigurable liquid crystal polymer film driver is characterized by comprising the following steps:
1) taking polymerizable monofunctional liquid crystal monomers, polymerizable bifunctional liquid crystal monomers and non-polymerizable liquid crystal monomers to mix to obtain mixed liquid crystal;
2) coating the mixed liquid crystal obtained in the step 1) into a film, and then polymerizing within a preset temperature range to obtain a parallel-oriented liquid crystal polymer film;
3) soaking one side of the liquid crystal polymer film obtained in the step 2) in a solution with the pH value of 11.0-13.0 and the concentration of 0.06-0.08 mol.L -1 Soaking in KOH aqueous solution for 0.1-12.0 h;
4) cleaning the liquid crystal polymer film treated in the step 3) by using deionized water, and drying;
5) soaking the part of the liquid crystal polymer film treated in the step 4) in the solution with the concentration of 0.04-0.06 mol.L -1 In (C) is 2 Soaking in water solution for 0.1-12.0 hr;
6) cleaning the liquid crystal polymer film treated in the step 5) by using deionized water, and drying;
7) completely soaking the liquid crystal polymer film treated in the step 6) in water at the concentration of 0.08-0.10 mol.L -1 Soaking in EDTA-2K water solution for 0.1-12.0 hr;
8) cleaning the liquid crystal polymer film treated in the step 7) by using deionized water, and drying to finally obtain a liquid crystal polymer film driver with reconfigurable deformation and based on humidity response;
wherein: the polymerizable monofunctional liquid crystal monomer and the polymerizable difunctional liquid crystal monomer both have R groups as shown below:
wherein n is a positive integer of 1 to 12.
2. A method of making a shape-changing reconfigurable liquid crystal polymer film actuator of claim 1, further comprising: repeating the steps 5) -8) while changing the dipping position of the liquid crystal polymer film in the step 5), so that the prepared liquid crystal polymer film driver has a different shape.
3. The method of manufacturing a shape-changing reconfigurable liquid crystal polymer film actuator according to claim 1, wherein in the step 1), the polymerizable monofunctional liquid crystal monomer, the difunctional liquid crystal monomer and the non-polymerizable liquid crystal monomer are mixed in a mass ratio of 49.0/35.0/15.0-15.0/35.0/49.0.
4. The method for preparing a shape-changing reconfigurable liquid crystal polymer film actuator according to claim 1, wherein in the step 2), the liquid crystal polymer film prepared by coating and compounding the liquid crystal has a thickness of 10.0 to 40.0 μm, a length of 0.5 to 4.0cm and a width of 0.5 to 2.0 cm.
5. The method of claim 1, wherein the polymerizable monofunctional liquid crystal monomer and the polymerizable difunctional liquid crystal monomer each have a polymerization ability under ultraviolet light initiation, and both of the polymerizable monofunctional liquid crystal monomers include one or more of the following molecular structural formulas (1) to (4):
wherein n is a positive integer of 1 to 12.
6. The method for preparing a shape-changing reconfigurable liquid crystal polymer film driver according to claim 5, wherein when a photoinitiator is added during the preparation of the compounded liquid crystal in the step 1), the compounded liquid crystal in the step 2) is polymerized under the irradiation of ultraviolet light.
7. The method for preparing a shape-changing reconfigurable liquid crystal polymer film actuator according to claim 6, wherein the photoinitiator is benzil dimethyl ether.
8. The method for preparing a shape-changing reconfigurable liquid crystal polymer film driver according to claim 7, wherein the conditions for mixing liquid crystal in the step 2) and carrying out polymerization reaction are as follows: the illumination intensity is 2.0-3.0mW cm -2 Irradiating with 365nm ultraviolet at 70-100 deg.C for 30.0-60.0 min.
9. The method for manufacturing a shape-changing reconfigurable liquid crystal polymer film driver according to claim 1, wherein when the liquid crystal polymer film is soaked in one side in step 3), the ratio of the length of the soaked liquid crystal polymer film to the length of the soaked liquid crystal polymer film is 3.0/7.0-7.0/3.0.
10. A liquid crystal polymer film actuator, which is prepared by the method for preparing a shape-changing reconfigurable liquid crystal polymer film actuator according to any one of claims 1 to 9.
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| CN106084135A (en) * | 2016-06-01 | 2016-11-09 | 上海交通大学 | Humidity based on Cellulose nanocrystal response photon crystal material and preparation method thereof |
| CN108727544A (en) * | 2018-05-21 | 2018-11-02 | 北京航空航天大学 | One kind can repair multiple response deformation liquid crystal elastic body film and the preparation method and application thereof |
| CN110527118A (en) * | 2019-07-11 | 2019-12-03 | 宁波大学 | A kind of humidity fluorescent color responsive polymer elastomer thin film material and preparation method thereof |
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2022
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106084135A (en) * | 2016-06-01 | 2016-11-09 | 上海交通大学 | Humidity based on Cellulose nanocrystal response photon crystal material and preparation method thereof |
| CN108727544A (en) * | 2018-05-21 | 2018-11-02 | 北京航空航天大学 | One kind can repair multiple response deformation liquid crystal elastic body film and the preparation method and application thereof |
| CN110527118A (en) * | 2019-07-11 | 2019-12-03 | 宁波大学 | A kind of humidity fluorescent color responsive polymer elastomer thin film material and preparation method thereof |
Non-Patent Citations (2)
| Title |
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| An Artificial Nocturnal Flower via Humidity-Gated Photoactuation in Liquid Crystal Networks;Wani, Owies M.;《ADVANCED MATERIALS》;20190122;第31卷(第2期);全文 * |
| Humidity-Induced Simultaneous Visible and Fluorescence Photonic Patterns Enabled by Integration of Covalent Bonds and Ionic Crosslinks;Lan, Ruochen;《ADVANCED FUNCTIONAL MATERIALS》;20210930;第31卷(第51期);全文 * |
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