CN115785668B - Light response dynamic liquid crystal elastomer driver material and preparation method thereof - Google Patents
Light response 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 94
- 239000000463 material Substances 0.000 title claims abstract description 52
- 230000004298 light response Effects 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title abstract description 12
- 229920000642 polymer Polymers 0.000 claims abstract description 52
- 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
- 239000002904 solvent Substances 0.000 claims description 28
- 239000000243 solution Substances 0.000 claims description 26
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 21
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 20
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 20
- 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
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 18
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 18
- -1 iron ion Chemical class 0.000 claims description 14
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 12
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 9
- 238000000746 purification Methods 0.000 claims description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 6
- 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
- 239000012670 alkaline solution Substances 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 239000004973 liquid crystal related substance Substances 0.000 claims description 5
- 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
- 239000002243 precursor Substances 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- 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
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 2
- 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
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 claims description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 2
- LCKIEQZJEYYRIY-UHFFFAOYSA-N Titanium ion Chemical compound [Ti+4] LCKIEQZJEYYRIY-UHFFFAOYSA-N 0.000 claims description 2
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims description 2
- 230000009471 action Effects 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
- 238000001035 drying Methods 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
- 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
- 238000003756 stirring Methods 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
- 230000002441 reversible effect Effects 0.000 abstract description 9
- 239000000654 additive Substances 0.000 abstract description 6
- 230000004044 response Effects 0.000 abstract description 4
- 230000000996 additive effect Effects 0.000 abstract description 2
- 239000007787 solid Substances 0.000 abstract description 2
- 238000007493 shaping process Methods 0.000 abstract 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical group OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 6
- 238000004090 dissolution Methods 0.000 description 5
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 5
- 239000012046 mixed solvent Substances 0.000 description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 5
- 239000004810 polytetrafluoroethylene Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- 238000005452 bending Methods 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000001237 Raman spectrum Methods 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation 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
- 230000007547 defect Effects 0.000 description 2
- 238000000113 differential scanning calorimetry Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 238000010146 3D printing Methods 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000001069 Raman spectroscopy Methods 0.000 description 1
- 239000012327 Ruthenium complex Substances 0.000 description 1
- 206010057040 Temperature intolerance Diseases 0.000 description 1
- 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
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000008543 heat sensitivity Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 231100000683 possible toxicity Toxicity 0.000 description 1
- CASUWPDYGGAUQV-UHFFFAOYSA-M potassium;methanol;hydroxide Chemical compound [OH-].[K+].OC CASUWPDYGGAUQV-UHFFFAOYSA-M 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000004043 responsiveness Effects 0.000 description 1
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
Landscapes
- Liquid Crystal Substances (AREA)
Abstract
The invention discloses a light response dynamic liquid crystal elastomer driver material and a preparation method thereof. The liquid crystal elastomer is prepared by coordination and crosslinking of a polymer and metal ions. The liquid crystal elastomer has the capability of low-temperature and high-temperature shaping, and the driving performance can be obtained after shaping. In addition, the resulting driver material has solid state plasticity, light or heat responsive driving characteristics, and good mechanical properties, and reversible driving strain is 1% -80%. The preparation method of the liquid crystal elastomer driver is simple and effective, and no photo-thermal response additive is needed to be added in the preparation process.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a light response dynamic liquid crystal elastomer driver material and a preparation method thereof.
Background
The liquid crystal elastomer driver is an intelligent high polymer material capable of responding to external stimulus and generating reversible deformation. Conventional liquid crystal elastomer drivers can only respond to changes in ambient temperature, which is clearly disadvantageous for their application. Light is a relatively green stimulus with the significant advantage of being able to operate controllably in both time and space. The liquid crystal elastomer driver can obtain light responsiveness after the inorganic light-heat conversion filler is introduced into the polymer network, so that the light control driving capability is obtained. However, the preparation method generally accompanies agglomeration of photo-thermal fillers, and influences the driving performance and mechanical performance of the driver. Although a relatively structurally uniform liquid crystal elastomeric polymer network can be prepared by developing and introducing organic light absorbing additives, exudation and potential toxicity of the organic light and heat additives impose large limitations on the application scenario of the driver. In addition, conventional liquid crystal elastomer drivers based on stable covalent cross-linking generally do not have shape plasticity, self-repairing property, reworkability and the like, which is also disadvantageous for their application prospects.
Therefore, it is an urgent problem to prepare a light-responsive liquid crystal elastomer driver having uniform structure and dynamic characteristics by a simple and effective means.
Disclosure of Invention
In order to solve the defects in the prior art, the invention provides a light response dynamic liquid crystal elastomer driver material and a preparation method thereof. The preparation method of the driver material is simple, and the driver material has a dynamic polymer network with uniform structure, excellent light response driving performance and excellent mechanical performance.
The technical scheme adopted by the invention is as follows:
1. Light response dynamic liquid crystal elastomer driver material
The liquid crystal elastomer driver material is prepared by coordination and crosslinking of a polymer shown in a formula (I) and metal ions;
The polymer was catechol-terminated 1, 4-bis- [4- (3-acryloxypropoxy) benzoyloxy ] -2-methylbenzene and 3, 6-dioxa-1, 8-octanedithiol copolymer, designated RM257-Dopa.
The chemical structure of the polymer is shown as a formula (I):
the number average molecular weight of the polymer is 1000-50000.
The coordination mode of the polymer and the metal ion in the polymer network is one or two of double coordination mode and triple coordination mode.
The mass portion of the polymer is 90-99.9 portions and the mass portion of the metal ion is 0.1-10 portions.
The metal ion is one or more of iron ion, ferrous ion, ruthenium ion, aluminum ion, copper ion, nickel ion, zinc ion, titanium ion, calcium ion, magnesium ion, vanadium ion, manganese ion and cobalt ion.
The liquid crystal elastomer driver material has solid state plasticity, light or heat response driving characteristics and good mechanical property, and reversible driving strain is 1% -80%.
2. Preparation method of light response 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 uniformly stirring and mixing to obtain a liquid crystal elastomer solution;
3) Injecting the liquid crystal elastomer solution into moulds with different shapes, and demoulding after the solvent is volatilized to obtain an initial liquid crystal elastomer;
4) Sequentially placing the initial liquid crystal elastomer in a first solvent and a second solvent for purification, and then drying completely to obtain a purified liquid crystal elastomer;
5) The purified liquid crystal elastomer is endowed with any preset shape through the action of external force, and then is placed at 20-250 ℃ for 30 seconds-10 days, so as to obtain a pre-liquid crystal elastomer;
6) After cooling the pre-liquid crystal elastomer, a liquid crystal elastomer driver material is obtained.
In the step 1), the mass portion of the polymer is 90-99.9 portions, the mass portion of the metal ion is 0.1-10 portions, and the mass portion of the alkaline solution is 0.1-20 portions.
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 used 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 used for preparing the metal ion-containing solution is one or more of methanol, ethanol, isopropanol, N-butanol, glycerol, ethylene glycol, tetrahydrofuran, N-dimethylformamide, N-dimethylacetamide and water;
In the step 2), alkaline substances for preparing alkaline solution are 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, methylene dichloride, chloroform and tetrahydrofuran.
3. Soft robot
The liquid crystal elastomer driver material is prepared or obtained by the method.
The liquid crystal elastomer driver has a polymer network with uniform structure, and can show better light response 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 direct coordination crosslinking of a linear polymer with specific functional groups (i.e. catechol groups) and metal ions, and the preparation process is simple and easy to control, and does not involve high temperature, high pressure or other harsh reaction conditions. Structurally, the repeating units of the linear polymer used comprise liquid crystal units capable of producing ordered-disordered transitions and flexible chain extending molecules, while the polymer ends are capped with catechol groups. Catechol groups may form coordination structures with metal ions, especially iron ions. The catechol-iron complex, catechol-ruthenium complex, catechol-cobalt complex and the like formed have stronger absorption in the visible light and near infrared light regions, and endow a 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, so that a polymer network is rearranged under the direct heating or photo-thermal effect, and performances such as plasticity, self-repairing property, processability and the like are shown.
The beneficial effects of the invention are as follows:
1. the liquid crystal elastomer driver material provided by the invention has a polymer network with a uniform structure, can show light response drivability, plasticity, self-repairing property and reworkability under the condition of not containing additional photo-thermal additives, overcomes the defects of agglomeration, toxicity, high exudation risk and the like caused by using the photo-thermal additives of most of the light response liquid crystal elastomer materials reported at present, and has obvious advantages compared with most of the liquid crystal elastomer drivers reported at present.
2. The liquid crystal elastomer driver material provided by the invention has the advantages that the preparation process is simple, the process of forming a crosslinked network does not involve harsh reaction conditions, the liquid crystal elastomer driver material is suitable for various production and processing modes, such as pouring, 3D printing and the like, and the liquid crystal elastomer driver material has a relatively high application prospect.
Drawings
FIG. 1 is a hydrogen nuclear magnetic resonance (1 H NMR) chart of the polymer used in example 1.
FIG. 2 is a Differential Scanning Calorimetry (DSC) ramp up and ramp down graph of 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) element distribution image of the fracture surface of the liquid crystal elastomer material prepared in example 1.
Fig. 5 is a tensile stress-strain curve of the liquid crystal elastomer material prepared in example 1.
FIG. 6 is a photo-thermal response chart 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 an exhibition view of the liquid crystal elastomer driver prepared in example 1.
Detailed Description
The present invention will be described in more detail with reference to the following specific examples, but the embodiments of the present invention are not limited thereto.
Embodiments of the invention are as follows:
Example 1
0.5G of a polymer having a number average molecular weight of 5360 was weighed and dissolved in 12ml of chloroform, and after sufficient dissolution, 625. Mu.l of a 0.1mol/l methanol solution of ferric trichloride was added and mixed uniformly. Subsequently, 935. Mu.l of 0.2mol/l potassium hydroxide in methanol was slowly added to the above solution and thoroughly mixed. The resulting liquid crystal elastomer solution was poured into a polytetrafluoroethylene mold and the solvent was evaporated to dryness at 30 ℃. The resulting coordination crosslinked initial liquid crystal elastomer was purified by placing it in 50ml of an N, N-dimethylformamide/methanol mixed solvent at a volume ratio of 7/3, followed by taking out and placing it in 50ml of methanol for secondary purification. Finally, the obtained liquid crystal elastomer material is dried completely in vacuum at 30 ℃, and the purified liquid crystal elastomer which has the light response dynamic state can be obtained. And (3) axially stretching the obtained purified liquid crystal elastomer to 150% strain, then standing at 120 ℃ for 5min, and then slowly cooling to room temperature to obtain the liquid crystal elastomer driver material with light response shrinkage/extension driving, wherein the final liquid crystal elastomer driver material has driving characteristics.
FIG. 1 is a 1 H NMR chart of the polymer used in this example. FIG. 2 is a DSC heating and cooling profile of the polymer used in this example, showing that the ordered to disordered phase transition temperature of the polymer is 42.3℃during the heating process. FIG. 3 is a Raman spectrum of the liquid crystal elastomer material prepared in the present example, wherein characteristic peaks at the Raman shifts 530, 585 and 634cm -1 indicate that catechol groups on the polymer coordinate with iron ions, and the catechol groups are used as crosslinking points to construct a polymer network. Fig. 4 (a) and (b) are SEM and EDS element distribution diagrams, respectively, of the fracture surface of the liquid crystal elastomer material prepared in this example, and it is 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 tensile stress-strain curve of the liquid crystal elastomer driver material prepared in this example, wherein the polymer can exhibit excellent mechanical properties, and the tensile strength is 6.25.+ -. 0.13MPa and the breaking strain is 325.+ -. 10% at room temperature. FIG. 6 is a photo-thermal response chart of the liquid crystal elastomer material prepared in this example, which shows that the surface of the polymer can be rapidly heated up under the irradiation of near infrared light of 0.8W/cm 2 nm, and the temperature can exceed 100 ℃ within 5 seconds, and the photo-thermal conversion performance is excellent. The dynamic characteristics of the polymer network are characterized by its stress relaxation behavior. Fig. 7 is a graph showing stress relaxation 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 coordination bond exchange of the polymer network is significantly accelerated, so that the stress relaxation degree and the stress relaxation speed of the polymer in the test time are rapidly increased, which indicates that the polymer network has good dynamic characteristics. Fig. 8 is a graph showing the reversible driving curve and the display of the liquid crystal elastomer driver prepared in this example, and it can be seen that the polymer exhibits significant shrinkage and elongation driving with a driving strain of about 33% when the temperature is cyclically raised and lowered between 0 ℃ and 80 ℃. As can be seen from the inset in FIG. 8, the lengths of the bar drives were 3.3cm and 2.5cm at 0deg.C and 80deg.C, respectively.
Example 2
0.3G of a polymer having a number average molecular weight of 5360 was weighed and dissolved in 12ml of chloroform, and after complete dissolution, 850. Mu.l of a methanol solution of 0.1mol/l of ferric trichloride was added and mixed uniformly. Subsequently, 1180. Mu.l of 0.2mol/l potassium hydroxide in methanol was slowly added to the above solution and thoroughly mixed. The obtained liquid crystal elastomer is poured into a polytetrafluoroethylene mould, and then the solvent is volatilized at 30 ℃ until the solvent is completely dried. The resulting coordination crosslinked initial liquid crystal elastomer was purified by placing it in 50ml of an N, N-dimethylformamide/methanol mixed solvent at a volume ratio of 7/3, followed by taking out and placing it in 50ml of methanol for secondary purification. Finally, the obtained liquid crystal elastomer material is dried completely in vacuum at 30 ℃ to obtain the purified liquid crystal elastomer. And (3) axially stretching the obtained purified liquid crystal elastomer to 150% strain, then standing at 120 ℃ for 10min, and slowly cooling to room temperature to obtain the liquid crystal elastomer driver material with light response shrinkage/extension driving. The driving strain of the resulting driver was about 28%.
Example 3
0.5G of a polymer having a number average molecular weight 8380 was weighed and dissolved in 12ml of chloroform, and after complete dissolution, 380. Mu.l of a methanol solution of 0.1mol/l of ferric trichloride and 160. Mu.l of a methanol solution of 0.1mol/l of aluminum trichloride were added and mixed uniformly. Subsequently, 745. Mu.l of a 0.2mol/l potassium hydroxide methanol solution was slowly added to the above solution and thoroughly mixed. The obtained liquid crystal elastomer is poured into a polytetrafluoroethylene mould, and then the solvent is volatilized at 30 ℃ until the solvent is completely dried. The resulting coordination crosslinked initial liquid crystal elastomer was purified by placing it in 50ml of an N, N-dimethylformamide/methanol mixed solvent at a volume ratio of 7/3, followed by taking out and placing it in 50ml of methanol for secondary purification. Finally, the obtained liquid crystal elastomer material is dried completely in vacuum at 30 ℃ to obtain the purified liquid crystal elastomer. The obtained purified liquid crystal elastomer is folded and bent, and then is stood for 3 days at 30 ℃ to prepare the liquid crystal elastomer driver material with light response reversible bending driving, wherein the driving strain is about 46%.
Example 4
1.0G of a polymer having a number average molecular weight of 46200 was weighed and dissolved in 15ml of chloroform, and after sufficient dissolution, 50. Mu.l of a methanol solution of 0.1mol/l of ferric trichloride and 10. Mu.l of a methanol solution of 0.1mol/l of ruthenium trichloride were added and mixed uniformly. Subsequently, 90. Mu.l of 0.2mol/l potassium hydroxide in methanol was slowly added to the above solution and thoroughly mixed. The obtained liquid crystal elastomer is poured into a polytetrafluoroethylene mould, and then the solvent is volatilized at 30 ℃ until the solvent is completely dried. The resulting coordination crosslinked initial liquid crystal elastomer was purified by placing it in 50ml of an N, N-dimethylformamide/methanol mixed solvent at a volume ratio of 7/3, followed by taking out and placing it in 50ml of methanol for secondary purification. Finally, the obtained liquid crystal elastomer material is dried completely in vacuum at 30 ℃ to obtain the purified liquid crystal elastomer. The obtained purified liquid crystal elastomer is folded and bent, and then is stood for 3 days at 30 ℃ to prepare the liquid crystal elastomer driver material with light response reversible bending driving, and the driving strain is about 76%.
Example 5
0.68G of a polymer having a number average molecular weight of 1650 was weighed and dissolved in 15ml of methylene chloride, and after sufficient dissolution, 4200. Mu.l of a 0.1mol/l solution of ferric trichloride in tetrahydrofuran was added and mixed well. Subsequently, 1810. Mu.l of 0.6mol/l potassium hydroxide in methanol was slowly added to the above solution and thoroughly mixed. The obtained liquid crystal elastomer is poured into a polytetrafluoroethylene mould, and then the solvent is volatilized at 30 ℃ until the solvent is completely dried. The resulting coordination crosslinked initial liquid crystal elastomer was purified by placing it in 50ml of an N, N-dimethylformamide/methanol mixed solvent at a volume ratio of 7/3, followed by taking out and placing it in 50ml of methanol for secondary purification. Finally, the obtained liquid crystal elastomer material is dried completely in vacuum at 30 ℃ to obtain the purified liquid crystal elastomer. The obtained purified liquid crystal elastomer is folded and bent, and then is kept stand for 20min at 110 ℃ to prepare the liquid crystal elastomer driver material with light response reversible bending driving, wherein the driving strain is about 17%.
Claims (8)
1. The light response dynamic liquid crystal elastomer driver material is characterized in that the light response dynamic liquid crystal elastomer driver material is prepared by coordination and crosslinking of a polymer shown in a formula (I) and metal ions;
（I）；
The mass portion of the polymer is 90-99.9 portions and the mass portion of the metal ion is 0.1-10 portions;
the number average molecular weight of the polymer is 1000-50000.
2. A light responsive dynamic liquid crystal elastomeric driver material as in claim 1, wherein: the coordination mode of the polymer and the metal ion in the polymer network is one or two of double coordination mode and triple coordination mode.
3. A light responsive dynamic liquid crystal elastomeric driver material as in claim 1, wherein: the metal ion is one or more of iron ion, ferrous ion, ruthenium ion, aluminum ion, copper ion, nickel ion, zinc ion, titanium ion, calcium ion, magnesium ion, vanadium ion, manganese ion and cobalt ion.
4. A method of preparing a light responsive dynamic liquid crystal elastomeric driver material as claimed in any one of claims 1 to 3, 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 uniformly stirring and mixing to obtain a liquid crystal elastomer solution;
3) Injecting the liquid crystal elastomer solution into moulds with different shapes, and demoulding after the solvent is volatilized to obtain an initial liquid crystal elastomer;
4) Sequentially placing the initial liquid crystal elastomer in a first solvent and a second solvent for purification, and then drying completely to obtain a purified liquid crystal elastomer;
5) The purified liquid crystal elastomer is endowed with any preset shape through the action of external force, and then is placed at 20-250 ℃ for 30 seconds-10 days, so as to obtain a pre-liquid crystal elastomer;
6) After cooling the pre-liquid crystal elastomer, a liquid crystal elastomer driver material is obtained.
5. The method for preparing a light-responsive dynamic liquid crystal elastomer driver material according to claim 4, wherein the polymer is 90-99.9 parts by mass, the metal ion is 0.1-10 parts by mass, and the alkaline solution is 0.1-20 parts by mass.
6. The method for preparing a light-responsive dynamic liquid crystal elastomer driver material according to claim 4, wherein in the step 1), the mass fraction ratio of the solvent to the polymer is 1:1-40:1.
7. The method for preparing a light-responsive dynamic liquid crystal elastomer driver material according to claim 4, wherein the solvent used for dissolving the polymer in 1) is one or more of dichloromethane, chloroform, tetrahydrofuran, ethyl acetate, dioxane, toluene, N-dimethylformamide, N-dimethylacetamide and dimethylsulfoxide; the solvent used for preparing the metal ion-containing solution is one or more of methanol, ethanol, isopropanol, N-butanol, glycerol, ethylene glycol, tetrahydrofuran, N-dimethylformamide, N-dimethylacetamide and water;
In the step 2), alkaline substances for preparing alkaline solution are 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 is one or more of methanol, ethanol, isopropanol, ethyl acetate, dichloromethane, chloroform, tetrahydrofuran, N-dimethylformamide and N, N-dimethylacetamide; the second solvent is one or more of methanol, ethanol, isopropanol, ethyl acetate, dichloromethane, chloroform and tetrahydrofuran.
8. A soft robot comprising the liquid crystal elastomer driver material of any one of claims 1-3 or the liquid crystal elastomer driver material of any one of claims 4-7.
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