CN115785668A - Photoresponse dynamic liquid crystal elastomer driver material and preparation method thereof - Google Patents
Photoresponse dynamic liquid crystal elastomer driver material and preparation method thereof Download PDFInfo
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- 239000004997 Liquid crystal elastomers (LCEs) Substances 0.000 title claims abstract description 96
- 239000000463 material Substances 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title abstract description 14
- 229920000642 polymer Polymers 0.000 claims abstract description 55
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 17
- 238000004132 cross linking Methods 0.000 claims abstract description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 78
- 239000000243 solution Substances 0.000 claims description 28
- 239000002904 solvent Substances 0.000 claims description 27
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 21
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 21
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 21
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 18
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 18
- -1 iron ions Chemical class 0.000 claims description 18
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 12
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- 238000000746 purification Methods 0.000 claims description 7
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- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
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- 238000001035 drying Methods 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
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- GQHTUMJGOHRCHB-UHFFFAOYSA-N 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepine Chemical compound C1CCCCN2CCCN=C21 GQHTUMJGOHRCHB-UHFFFAOYSA-N 0.000 claims description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 4
- 230000009471 action Effects 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 239000002243 precursor Substances 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 3
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- FVKFHMNJTHKMRX-UHFFFAOYSA-N 3,4,6,7,8,9-hexahydro-2H-pyrimido[1,2-a]pyrimidine Chemical compound C1CCN2CCCNC2=N1 FVKFHMNJTHKMRX-UHFFFAOYSA-N 0.000 claims description 2
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 2
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- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 2
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 claims description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 2
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 claims description 2
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 229910001424 calcium ion Inorganic materials 0.000 claims description 2
- 229910001429 cobalt ion Inorganic materials 0.000 claims description 2
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 claims description 2
- 229910001431 copper ion Inorganic materials 0.000 claims description 2
- 229910001448 ferrous ion Inorganic materials 0.000 claims description 2
- 229910001425 magnesium ion Inorganic materials 0.000 claims description 2
- 229910001437 manganese ion Inorganic materials 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 229910001453 nickel ion Inorganic materials 0.000 claims description 2
- BDAWXSQJJCIFIK-UHFFFAOYSA-N potassium methoxide Chemical compound [K+].[O-]C BDAWXSQJJCIFIK-UHFFFAOYSA-N 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 229910001456 vanadium ion Inorganic materials 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 229960001701 chloroform Drugs 0.000 claims 3
- 230000002441 reversible effect Effects 0.000 abstract description 9
- 239000000654 additive Substances 0.000 abstract description 6
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- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 5
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- 230000002776 aggregation Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- LHBUQXJBITZGBJ-UHFFFAOYSA-N benzene-1,2-diol;cobalt Chemical compound [Co].OC1=CC=CC=C1O LHBUQXJBITZGBJ-UHFFFAOYSA-N 0.000 description 2
- OQRLVNFTCUZFSJ-UHFFFAOYSA-N benzene-1,2-diol;iron Chemical compound [Fe].OC1=CC=CC=C1O OQRLVNFTCUZFSJ-UHFFFAOYSA-N 0.000 description 2
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- 238000001069 Raman spectroscopy Methods 0.000 description 1
- 239000012327 Ruthenium complex Substances 0.000 description 1
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- ISSYGWIDLYOJEN-UHFFFAOYSA-N [3-methyl-4-[4-(3-prop-2-enoyloxypropoxy)benzoyl]oxyphenyl] 4-(3-prop-2-enoyloxypropoxy)benzoate Chemical compound C=1C=C(OC(=O)C=2C=CC(OCCCOC(=O)C=C)=CC=2)C(C)=CC=1OC(=O)C1=CC=C(OCCCOC(=O)C=C)C=C1 ISSYGWIDLYOJEN-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
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- Liquid Crystal Substances (AREA)
Abstract
The invention discloses a photoresponse dynamic liquid crystal elastomer driver material and a preparation method thereof. The liquid crystal elastomer is prepared by coordination crosslinking of a polymer and metal ions. The liquid crystal elastomer obtained by the invention has the capacity of low-temperature and high-temperature shaping, and can obtain the driving performance after shaping. In addition, the resulting driver material has solid state plasticity, optically or thermally responsive driving characteristics, and good mechanical properties, with a reversible driving strain of 1-80%. The preparation method of the liquid crystal elastomer driver is simple and effective, and any photo-thermal response additive is not required to be added in the preparation process.
Description
Technical Field
The invention belongs to a liquid crystal elastomer driver material in the technical field of high polymer materials, and particularly relates to a photoresponse dynamic liquid crystal elastomer driver material and a preparation method thereof.
Background
The liquid crystal elastomer driver is an intelligent high polymer material which can respond to external stimulation and generate reversible deformation. The conventional liquid crystal elastomer driver can only respond to the external temperature change, which is obviously not favorable for the application. Light is a relatively green stimulus, with the significant advantage of being able to operate controllably in time as well as space at the same time. The liquid crystal elastomer actuator can obtain photoresponsiveness after inorganic photothermal conversion filler is introduced into the polymer network, so that the capability of light control actuation is obtained. However, the preparation method is usually accompanied with agglomeration of the photo-thermal filler, and influences the driving performance and the mechanical performance of the driver. While relatively structurally uniform liquid crystalline elastomeric polymer networks can be prepared by developing and incorporating organic light absorbing additives, the exudation and potential toxicity of organic photo-thermal additives impose significant limitations on the application scenarios of the actuators. Furthermore, conventional liquid crystal elastomer actuators based on stable covalent crosslinking generally do not have shape plasticity, self-healing properties, reworkability, etc., which is likewise disadvantageous for their application prospects.
Therefore, it is an urgent problem to prepare a photoresponsive liquid crystal elastomer driver with uniform structure and dynamic characteristics by a simple and effective means.
Disclosure of Invention
In order to solve the defects of the prior art, the invention provides a photoresponse dynamic liquid crystal elastomer driver material and a preparation method thereof. The driver material is simple in preparation method, and has a dynamic polymer network with a uniform structure and excellent photoresponse driving performance and mechanical performance.
The technical scheme adopted by the invention is as follows:
1. optical response dynamic liquid crystal elastomer driver material
The liquid crystal elastomer driver material is prepared by the coordination crosslinking of the polymer and metal ions in the formula (I);
the polymer is catechol terminated 1, 4-bis- [4- (3-acryloxypropoxy) benzoyloxy ] -2-methylbenzene and 3, 6-dioxa-1, 8-octane dithiol copolymer, which is recorded as RM257-Dopa.
The chemical structure of the polymer is shown as the formula (I):
the number average molecular weight of the polymer is 1000-50000.
The coordination mode of the polymer and the metal ions in the polymer network is one or two of a double coordination mode and a triple coordination mode.
The polymer is 90-99.9 parts by mass, and the metal ion is 0.1-10 parts by mass.
The metal ions are one or more of iron ions, ferrous ions, ruthenium ions, aluminum ions, copper ions, nickel ions, zinc ions, titanium ions, calcium ions, magnesium ions, vanadium ions, manganese ions and cobalt ions.
The liquid crystal elastomer driver material has solid plasticity, light or heat response driving characteristics and good mechanical properties, and reversible driving strain is 1-80%.
2. Preparation method of photoresponse dynamic liquid crystal elastomer driver material
1) Dissolving a polymer in a solvent, and then adding a solution containing metal ions to obtain a precursor solution;
2) Adding an alkaline solution into the precursor solution, and stirring and mixing uniformly to obtain a liquid crystal elastomer solution;
3) Injecting the liquid crystal elastomer solution into molds of different shapes, and demolding after the solvent is volatilized to obtain an initial liquid crystal elastomer;
4) Sequentially placing the initial liquid crystal elastomer into a first solvent and a second solvent for purification, and then completely drying to obtain a purified liquid crystal elastomer;
5) Endowing the purified liquid crystal elastomer with any preset shape under the action of external force, and standing at the temperature of 20-250 ℃ for 30 seconds-10 days to obtain a pre-liquid crystal elastomer;
6) And cooling the pre-liquid crystal elastomer to obtain the liquid crystal elastomer driver material.
In the step 1), the mass parts of the polymer are 90-99.9 parts, the mass parts of the metal ions are 0.1-10 parts, and the mass parts of the alkaline solution are 0.1-20 parts.
In the step 1), the mass part ratio of the solvent to the polymer is 1:1-40:1.
In the step 1), the solvent for dissolving the polymer is one or more of dichloromethane, chloroform, tetrahydrofuran, ethyl acetate, dioxane, toluene, N-dimethylformamide, N-dimethylacetamide and dimethyl sulfoxide; the solvent for preparing the solution containing the metal ions is one or more of methanol, ethanol, isopropanol, N-butanol, glycerol, ethylene glycol, tetrahydrofuran, N-dimethylformamide, N-dimethylacetamide and water;
in the step 2), the alkaline substance for preparing the alkaline solution is one or more of triethylamine, potassium hydroxide, sodium methoxide, potassium methoxide, pyridine, 1, 8-diazabicyclo [5.4.0] undec-7-ene and 1,5, 7-triazabicyclo [4.4.0] dec-5-ene;
4) Wherein the first solvent and the second solvent are one or more of methanol, ethanol, isopropanol, ethyl acetate, dichloromethane, chloroform, tetrahydrofuran, N-dimethylformamide and N, N-dimethylacetamide; the solvent 2 is one or more of methanol, ethanol, isopropanol, ethyl acetate, dichloromethane, chloroform and tetrahydrofuran.
3. Software robot
The liquid crystal elastomer driver material is obtained by preparation or the liquid crystal elastomer driver material prepared by the method is obtained by preparation.
The liquid crystal elastomer driver has a polymer network with a uniform structure, and can show better photoresponse driving performance, plasticity, self-repairing performance and reworkability under the condition of not using any photo-thermal additive and reversible bond exchange catalyst.
The liquid crystal elastomer material is prepared by directly coordinating and crosslinking a linear polymer with a specific functional group (namely a catechol group) and metal ions, the preparation process is simple and easy to control, and high temperature, high pressure or other harsh reaction conditions are not involved. Structurally, the repeating units of the linear polymer used comprise liquid crystal units capable of producing order-disorder transition and flexible chain-extending molecules, and meanwhile, the two ends of the polymer are terminated by catechol groups. The catechol group may form a coordination structure with a metal ion (particularly, an iron ion). The formed catechol-iron complex, catechol-ruthenium complex, catechol-cobalt complex and the like have strong absorption in visible light and near infrared light regions, and endow the polymer network with better photo-thermal effect. In addition, coordination bonds such as catechol-iron, catechol-ruthenium, catechol-cobalt and the like have heat sensitivity, can cause rearrangement of a polymer network under the action of direct heating or photo-thermal action, and show performances such as plasticity, self-repairability, processability and the like.
The invention has the following beneficial effects:
1. the liquid crystal elastomer driver material provided by the invention has a polymer network with a uniform structure, can show photoresponse drivability, plasticity, self-repairability and reworkability under the condition that the liquid crystal elastomer driver material does not contain an additional photo-thermal additive, overcomes the defects of high risk of agglomeration, toxicity and exudation and the like caused by the photo-thermal additive used in most of the currently reported photoresponse liquid crystal elastomer materials, and has obvious advantages compared with most of the currently reported liquid crystal elastomer drivers.
2. The liquid crystal elastomer driver material provided by the invention has a simple preparation process, does not involve harsh reaction conditions in the process of forming a cross-linked network, is suitable for various production and processing modes such as pouring, 3D printing and the like, and has a high application prospect.
Drawings
FIG. 1 shows the hydrogen nuclear magnetic resonance of the polymer used in example 1: ( 1 H NMR) figure.
FIG. 2 is a graph of Differential Scanning Calorimetry (DSC) rise and fall in temperature for the polymer used in example 1.
Fig. 3 is a raman spectrum of the liquid crystal elastomer material prepared in example 1.
FIG. 4 is a Scanning Electron Microscope (SEM) and X-ray energy spectrum (EDS) elemental distribution image of a fracture surface of the liquid crystal elastomer material prepared in example 1.
FIG. 5 is a tensile stress-strain graph of the liquid crystal elastomer material prepared in example 1.
FIG. 6 is a graph showing a photo-thermal response of the liquid crystal elastomer material prepared in example 1.
FIG. 7 is a graph showing stress relaxation curves of the liquid crystal elastomer material prepared in example 1 at different temperatures.
Fig. 8 is a reversible driving curve and a display diagram of the liquid crystal elastomer actuator prepared in example 1.
Detailed Description
The present invention will be described in more detail with reference to specific examples, but the embodiments of the present invention are not limited thereto.
The embodiments of the invention are as follows:
example 1
0.5g of a polymer having a number average molecular weight of 5360 is weighed out and dissolved in 12ml of chloroform, and after sufficient dissolution, 625. Mu.l of a 0.1mol/l methanol solution of ferric trichloride is added and mixed uniformly. Subsequently, 935. Mu.l of a 0.2mol/l solution of potassium hydroxide in methanol was slowly added to the above solution and mixed well. And (3) pouring the obtained liquid crystal elastomer solution into a polytetrafluoroethylene mold, and volatilizing the solvent at 30 ℃ until the solvent is completely dried. The obtained initial liquid-crystalline coordination-crosslinked elastomer was purified by being placed in 50ml of a mixed solvent of N, N-dimethylformamide/methanol at a volume ratio of 7/3, and then taken out and placed in 50ml of methanol for secondary purification. Finally, the obtained liquid crystal elastomer material is completely dried in vacuum at 30 ℃, and then the purified liquid crystal elastomer which has light response dynamic is obtained. And axially stretching the obtained purified liquid crystal elastomer to 150% strain, standing at 120 ℃ for 5min, and slowly cooling to room temperature to obtain the liquid crystal elastomer actuator material with photoresponse contraction/extension drive, wherein the final liquid crystal elastomer actuator material has drive characteristics.
FIG. 1 shows the polymer used in this example 1 H NMR spectrum. FIG. 2 is a DSC temperature increase and decrease curve of the polymer used in this example, and it can be seen that the polymer has an ordered to disordered phase transition temperature of 42.3 ℃ during the temperature increase. FIG. 3 is a Raman spectrum of the liquid crystal elastomer material prepared in this example, in which Raman shifts are shown as 530, 585 and 634cm -1 The characteristic peak shows that the catechol group on the polymer is coordinated with iron ions and used as a crosslinking point to construct a polymer network. FIGS. 4 (a) and (b) are SEM and EDS elemental distribution diagrams of the fracture surface of the liquid crystal elastomer material prepared in this example, respectively, and it can be seen that the polymer network structure is uniform and iron ions are uniformly distributed in the polymer network. FIG. 5 is a graph showing the results of this exampleAs can be seen from the tensile stress-strain curve diagram of the prepared liquid crystal elastomer driver material, the polymer can show excellent mechanical properties, the tensile strength of the polymer is 6.25 +/-0.13 MPa at room temperature, and the breaking strain is 325 +/-10%. FIG. 6 is a photo-thermal response chart of the liquid crystal elastomer material prepared in this example, which can be seen at 0.8W/cm 2 Under near-infrared illumination of 808nm, the surface of the polymer can be rapidly heated to be more than 100 ℃ within 5s, and the polymer shows excellent photo-thermal conversion performance. The dynamic behavior of the network is characterized by the stress relaxation behavior of the polymer. Fig. 7 is a stress relaxation graph of the liquid crystal elastomer material prepared in this example at different temperatures, and it can be seen that when the temperature is increased from 90 ℃ to 140 ℃, the coordinate bond exchange of the polymer network is accelerated significantly, so that the stress relaxation degree and speed of the polymer are increased rapidly within the test time, indicating that the polymer network has good dynamic characteristics. Fig. 8 is a graph of the reversible drive curve and display of the liquid crystal elastomer actuator prepared in this example, and it can be seen that the polymer exhibits significant contraction and elongation drive with a drive strain of about 33% when heated and cooled between 0 c and 80 c cyclically. As can be seen from the inset in FIG. 8, the lengths of the strip drives at 0 deg.C and 80 deg.C are 3.3cm and 2.5cm, respectively.
Example 2
0.3g of a polymer having a number average molecular weight of 5360 is weighed and dissolved in 12ml of chloroform, and after sufficient dissolution, 850. Mu.l of a 0.1mol/l methanol solution of ferric trichloride is added and mixed uniformly. Subsequently, 1180. Mu.l of a 0.2mol/l solution of potassium hydroxide in methanol was slowly added to the above solution and mixed well. The obtained liquid crystal elastomer is poured into a polytetrafluoroethylene mould, and then the solvent is volatilized at 30 ℃ until the liquid crystal elastomer is completely dried. The obtained initial liquid-crystalline coordination-crosslinked elastomer was purified by being placed in 50ml of a mixed solvent of N, N-dimethylformamide/methanol at a volume ratio of 7/3, and then taken out and placed in 50ml of methanol for secondary purification. And finally, completely drying the obtained liquid crystal elastomer material at 30 ℃ in vacuum to obtain the purified liquid crystal elastomer. And axially stretching the obtained purified liquid crystal elastomer to 150% strain, standing at 120 ℃ for 10min, and slowly cooling to room temperature to obtain the liquid crystal elastomer driver material with photoresponse contraction/extension driving. The resulting drive strain of the actuator was about 28%.
Example 3
0.5g of a polymer having a number average molecular weight of 8380 was weighed and dissolved in 12ml of chloroform, and after sufficient dissolution, 380. Mu.l of a 0.1mol/l methanol solution of ferric trichloride and 160. Mu.l of a 0.1mol/l methanol solution of aluminum trichloride were added and mixed well. Then, 745. Mu.l of 0.2mol/l potassium hydroxide in methanol was slowly added to the above solution and mixed well. The obtained liquid crystal elastomer is poured into a polytetrafluoroethylene mould, and then the solvent is volatilized at 30 ℃ until the liquid crystal elastomer is completely dried. The resulting coordination-crosslinked initial liquid-crystalline elastomer was purified by being placed in 50ml of a mixed solvent of N, N-dimethylformamide/methanol at a volume ratio of 7/3, and then taken out and placed in 50ml of methanol for secondary purification. And finally, completely drying the obtained liquid crystal elastomer material at 30 ℃ in vacuum to obtain the purified liquid crystal elastomer. The obtained purified liquid crystal elastomer is folded and bent and then is kept stand for 3 days at 30 ℃ to prepare the liquid crystal elastomer driver material with photoresponse reversible bending driving, and the driving strain is about 46%.
Example 4
1.0g of a 46200 number-average molecular weight polymer was weighed and dissolved in 15ml of chloroform, and after sufficient dissolution, 50. Mu.l of a 0.1mol/l methanol solution of ferric trichloride and 10. Mu.l of a 0.1mol/l methanol solution of ruthenium trichloride were added and mixed well. Subsequently, 90. Mu.l of 0.2mol/l potassium hydroxide in methanol was slowly added to the above solution and mixed well. The obtained liquid crystal elastomer is poured into a polytetrafluoroethylene mould, and then the solvent is volatilized at 30 ℃ until the liquid crystal elastomer is completely dried. The obtained initial liquid-crystalline coordination-crosslinked elastomer was purified by being placed in 50ml of a mixed solvent of N, N-dimethylformamide/methanol at a volume ratio of 7/3, and then taken out and placed in 50ml of methanol for secondary purification. And finally, completely drying the obtained liquid crystal elastomer material at 30 ℃ in vacuum to obtain the purified liquid crystal elastomer. The obtained purified liquid crystal elastomer is folded and bent and then is kept stand for 3 days at 30 ℃ to prepare the liquid crystal elastomer driver material with photoresponse reversible bending drive, and the driving strain is about 76%.
Example 5
0.68g of a polymer having a number-average molecular weight of 1650 is weighed out and dissolved in 15ml of dichloromethane, and 4200. Mu.l of a 0.1mol/l solution of ferric chloride in tetrahydrofuran is added after sufficient dissolution and mixed well. Subsequently, 1810. Mu.l of a 0.6mol/l methanolic solution of potassium hydroxide was slowly added to the above solution and mixed well. And (3) pouring the obtained liquid crystal elastomer into a polytetrafluoroethylene mold, and volatilizing the solvent at 30 ℃ until the solvent is completely dried. The resulting coordination-crosslinked initial liquid-crystalline elastomer was purified by being placed in 50ml of a mixed solvent of N, N-dimethylformamide/methanol at a volume ratio of 7/3, and then taken out and placed in 50ml of methanol for secondary purification. And finally, completely drying the obtained liquid crystal elastomer material at 30 ℃ in vacuum to obtain the purified liquid crystal elastomer. The obtained purified liquid crystal elastomer is folded and bent and then stands for 20min at 110 ℃ to prepare the liquid crystal elastomer driver material with photoresponse reversible bending drive, and the driving strain is about 17%.
Claims (10)
1. A photoresponse dynamic liquid crystal elastomer driver material is characterized in that the material is prepared by coordination crosslinking of a polymer shown in a formula (I) and metal ions;
2. an optically responsive dynamic liquid crystal elastomer driver material as claimed in claim 1, wherein: the number average molecular weight of the polymer is 1000-50000.
3. An optically responsive dynamic liquid crystal elastomer driver material as claimed in claim 1, wherein: the coordination mode of the polymer and the metal ions in the polymer network is one or two of a double coordination mode and a triple coordination mode.
4. An optically responsive dynamic liquid crystal elastomer driver material as claimed in claim 1, wherein: the polymer comprises, by mass, 90-99.9 parts of polymer and 0.1-10 parts of metal ions.
5. An optically responsive dynamic liquid crystal elastomer driver material as claimed in claim 1, wherein: the metal ions are one or more of iron ions, ferrous ions, ruthenium ions, aluminum ions, copper ions, nickel ions, zinc ions, titanium ions, calcium ions, magnesium ions, vanadium ions, manganese ions and cobalt ions.
6. A method of making an optically responsive dynamic liquid crystal elastomer actuator material as claimed in any one of claims 1 to 5, comprising the steps of:
1) Dissolving a polymer in a solvent, and then adding a solution containing metal ions to obtain a precursor solution;
2) Adding an alkaline solution into the precursor solution, and stirring and mixing uniformly to obtain a liquid crystal elastomer solution;
3) Injecting the liquid crystal elastomer solution into molds of different shapes, and demolding after the solvent is volatilized to obtain an initial liquid crystal elastomer;
4) Sequentially placing the initial liquid crystal elastomer into a first solvent and a second solvent for purification, and then completely drying to obtain a purified liquid crystal elastomer;
5) Endowing the purified liquid crystal elastomer with any preset shape under the action of external force, and standing at the temperature of 20-250 ℃ for 30 seconds-10 days to obtain a pre-liquid crystal elastomer;
6) And cooling the pre-liquid crystal elastomer to obtain the liquid crystal elastomer driver material.
7. The method for preparing a photoresponse dynamic liquid crystal elastomer driver material according to claim 6, wherein in the step 1), the mass parts of the polymer, the metal ions and the alkaline solution are respectively 90-99.9, 0.1-10 and 0.1-20.
8. The method for preparing an optically responsive dynamic liquid crystal elastomer driver material as claimed in claim 6, wherein in 1), the ratio of the solvent to the polymer in parts by mass is 1:1-40:1.
9. The method of claim 6, wherein the solvent used to dissolve the polymer in 1) is one or more of dichloromethane, chloroform, tetrahydrofuran, ethyl acetate, dioxane, toluene, N-dimethylformamide, N-dimethylacetamide, and dimethylsulfoxide; the solvent for preparing the solution containing the metal ions is one or more of methanol, ethanol, isopropanol, N-butanol, glycerol, ethylene glycol, tetrahydrofuran, N-dimethylformamide, N-dimethylacetamide and water;
in the step 2), the alkaline substance for preparing the alkaline solution is one or more of triethylamine, potassium hydroxide, sodium methoxide, potassium methoxide, pyridine, 1, 8-diazabicyclo [5.4.0] undec-7-ene and 1,5, 7-triazabicyclo [4.4.0] dec-5-ene;
4) The first solvent and the second solvent are one or more of methanol, ethanol, isopropanol, ethyl acetate, dichloromethane, trichloromethane, tetrahydrofuran, N-dimethylformamide and N, N-dimethylacetamide; the solvent 2 is one or more of methanol, ethanol, isopropanol, ethyl acetate, dichloromethane, chloroform and tetrahydrofuran.
10. A soft robot comprising the liquid crystal elastomer actuator material according to any one of claims 1 to 5 or the liquid crystal elastomer actuator material prepared by the method according to any one of claims 6 to 9.
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| 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 |
| CN112521798A (en) * | 2020-11-30 | 2021-03-19 | 常州大学 | Preparation method of 4D printing liquid crystal elastomer and application of elastomer in actuator |
| CN114316267A (en) * | 2022-01-10 | 2022-04-12 | 中国科学院兰州化学物理研究所 | Shape memory liquid crystal elastomer material with dynamically adjustable surface morphology and preparation method thereof |
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| 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 |
| CN112521798A (en) * | 2020-11-30 | 2021-03-19 | 常州大学 | Preparation method of 4D printing liquid crystal elastomer and application of elastomer in actuator |
| CN114316267A (en) * | 2022-01-10 | 2022-04-12 | 中国科学院兰州化学物理研究所 | Shape memory liquid crystal elastomer material with dynamically adjustable surface morphology and preparation method thereof |
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