CN103524678A - Liquid crystal elastomer composite material for optical actuator and preparation method thereof - Google Patents
Liquid crystal elastomer composite material for optical actuator and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a liquid crystal elastomer composite material for an optical actuator and a preparation method thereof. The composite material is prepared by in-situ polymerization of a nano carbon material as a filler and a thermotropic liquid crystal elastomer as a matrix, wherein the weight ratio of the nano carbon material to the thermotropic liquid crystal elastomer is 0.02-3:100, and the nano carbon material is graphene, graphene oxide or carbon nanotubes. The composite material can efficiently absorb near infrared lasers; optical energy is converted into heat energy so as to trigger the liquid crystal elastomer to generate phase transition, so that the liquid crystal elastomer which has no light stimulus response in intrinsic performance can be used in the optical actuator; at the same time, the carbon nanotube reinforced liquid crystal elastomer can increase output force of the actuator; moreover, the carbon nanotubes shrink when being irradiated by the near infrared lasers, the shrinkage behavior is consistent to a liquid crystal elastomer thermal shrinkage behavior in the deformation direction, and synergistic effect of the carbon nanotubes and the liquid crystal elastomer improves the response rate and the deformation quantity of the actuator.
Description
Technical field
The present invention relates to intelligent material and polymer based nanocomposites field, refer to particularly a kind of liquid crystal elastic body matrix material for optical actuator and preparation method thereof.
Background technology
Actuator refers under the outfields such as electricity, light and heat stimulate, and electric energy, heat energy and luminous energy etc. is converted to the executive device of mechanical energy.Wherein, take light as drive source build polymer actuator have remote controlled, mechanism simplifying is easy of integration, cost is low, quality is light and the outstanding advantage such as easy machine-shaping.The intelligent material that structure actuator is used requires to have concurrently responsiveness and driven nature feature, and the Deformation Mechanisms of polymkeric substance optical actuator comes from photic molecule isomery and light triggers physical deformation.Be mainly in the minority polymkeric substance intrinsics such as azobenzene, to show photo-deformable at present, but azobenzene polymkeric substance is confined to produce mechanical response under ultraviolet lighting condition, the power output of straight polymer material construction actuator is little simultaneously, and its application is restricted.
Graphene and carbon nanotube have excellent electricity, light, heat and mechanical property and anisotropy feature, for building high performance actuator, have opened new thinking and approach.The electric actuator and the optical actuator that with Graphene and carbon nanotube, build can produce larger power output.Yet the cost of pure Graphene and carbon nanotube actuator is high, poor in processability and coupling efficiency low.Scientists discovery, Graphene and carbon nanotube can absorb near-infrared laser efficiently, be that heat energy forms " molecule well heater ", and then trigger polymers elastic composite produce mechanical response by transform light energy.Yet macroscopical mechanical response of polymer composites comes from nano-carbon material and the elastically-deformable vector of polymeric matrix, but deformation quantity and the power output of photo-thermal effect induction traditional polymer material production are less, and the speed of response is slower.
Summary of the invention
The object of the invention is to overcome actuator that existing single-material builds and have that the speed of response is slow, deformation quantity is little and the defect of difficult Long-distance Control, a kind of liquid crystal elastic body matrix material for optical actuator and preparation method thereof is provided, and to realize, the structure speed of response is fast, deformation quantity large and the optical actuator of High power output.
For achieving the above object, liquid crystal elastic body matrix material for optical actuator provided by the present invention, by the nano-carbon material as filler, form as the thermotropic liquid crystal elastomerics in-situ polymerization of matrix, the elastomeric weight ratio of described nano-carbon material and thermotropic liquid crystal is 0.02～3:100, and described nano-carbon material is Graphene, graphene oxide or carbon nanotube.
Preferably, the elastomeric weight ratio of described nano-carbon material and thermotropic liquid crystal is 0.05～1:100.
More preferably, the elastomeric weight ratio of described nano-carbon material and thermotropic liquid crystal is 0.1～0.5:100.
Preferably, described thermotropic liquid crystal elastomerics forms by esters of acrylic acid liquid crystal monomer, vinyl aromatic ester liquid crystal monomer, vinyl azobenzene liquid crystal monomer or Vinylbiphenyl liquid crystal monomer are crosslinked.
Described esters of acrylic acid liquid crystal monomer is preferably waist and connects type esters of acrylic acid liquid crystal monomer, as 2 ', 5 '-bis-(4 " alkoxy benzene methanoyl)-4-benzoyloxy-1-acrylate liquid crystal monomer, 2 ', 5 '-bis-(4 " alkyl-cyclohexyl methanoyl)-4-benzoyloxy-1-acrylate liquid crystal monomer.
Described vinyl aromatic ester liquid crystal monomer is preferably waist and connects type vinyl aromatic ester liquid crystal monomer, as 1-vinyl-3-alkyl-2, and 5-bis-(4 '-alkylbenzene methanoyl) benzoic ether liquid crystal monomer.
Preferably, described carbon nanotube is hydroxylation carbon nanotube.
The present invention also provides a kind of preparation method of above-mentioned liquid crystal elastic body matrix material, comprises the following steps:
1) nano-carbon material is joined to organic solvent for ultrasonic ripple and process, dispersion concentration is 0.01～1mg/mL, then liquid crystal monomer, linking agent and light trigger are added 90:5～10:0.2～1 in molar ratio, continues to stir to obtain dispersion liquid;
2) dispersion liquid is spin-coated on glass or polytetrafluoroethylsubstrate substrate plate, then under lucifuge and nitrogen atmosphere environment, be slowly warming up to 90～130 ℃, after insulation 5～20min, be cooled to 75～100 ℃, use immediately 250～800nm photoirradiation, 5～20min, after being warming up to 85～110 ℃, again irradiate 5～20min, reacted the liquid crystal elastic body matrix material that obtains film like;
Described liquid crystal monomer is esters of acrylic acid liquid crystal monomer, vinyl aromatic ester liquid crystal monomer, vinyl azobenzene liquid crystal monomer or Vinylbiphenyl liquid crystal monomer.
Preferably, described linking agent is diacrylate class or divinyl alkoxy benzene class linking agent, can select 1,6-hexanediyl ester, 1,6-hexanediol dimethacrylate, 4-acryloxy alkoxyl group-1-(4 '-ethene alkoxyl group phenoxy group)-benzoic ether or Isosorbide-5-Nitrae-bis-(1-vinyl)-alkoxy benzene.
Preferably; described light trigger is 2-benzyl-2-dimethylamino-1-(4-morpholinyl phenyl) butanone (Irgacure369), 2-methyl isophthalic acid-(4-methylthio group phenyl)-2-morpholinyl acetone, 2-hydroxy-2-methyl-1-phenyl-acetone, 1-hydroxy-cyclohexyl phenyl ketone, 2; 4; 6-trimethylbenzoyl-diphenyl phosphine oxide, 2; 4,6-trimethylbenzoyl phenyl-phosphonic acid ethyl ester, 2-benzyl-2-dimethylamino-1-(4-morpholinyl phenyl) butanone or 2-hydroxy-2-methyl-1-[4-(2-hydroxyl-oxethyl) phenyl] acetone.
Preferably, described organic solvent is acetone, ethanol, tetrahydrofuran (THF), DMF or N-Methyl pyrrolidone.
Preferably, described nano-carbon material is hydroxylation carbon nanotube, and its preparation method is as follows:
A) by carbon nanotube reflow treatment 8～12h in salpeter solution, liquid to be mixed is cooled to filtration under diminished pressure after room temperature, and deionized water wash is to neutral, and vacuum-drying obtains black powder;
B) black powder ultrasonic wave is dispersed in solvent; concentration is 0.5～2mg/mL; add again hydroxylation reagent; the weight ratio of carbon nanotube and hydroxylation reagent is 1/10～1/30; then stirring and refluxing 8～12h under the condition of nitrogen protection; then be cooled to room temperature, elimination liquid, deionized water wash precipitation, vacuum-drying obtains hydroxylation carbon nanotube.
Preferably, solvent described in the preparation method's of described hydroxylation carbon nanotube step a) is water, DMF, acetone or N-Methyl pyrrolidone.
Preferably, hydroxylation reagent described in the preparation method's of described hydroxylation carbon nanotube step b) is the two methylol hydroxyethyl propionic acid amides, 2 of azo dimethyl N-, 2'-azo [2-methyl-N-(2-hydroxyethyl) propionic acid amide], 4,4'-azo two (4-cyano group amylalcohol) or 1-azido-alkyl primary alconols.
Preferably, described liquid crystal monomer is 2 ', 5 '-bis-(4 " alkoxy benzene methanoyl)-4-benzoyloxy-1-acrylate, 2 '; 5 '-bis-(4 " alkyl-cyclohexyl methanoyl)-4-benzoyloxy-1-acrylate or 1-vinyl-3-alkyl-2,5-bis-(4 '-alkylbenzene methanoyl) benzoic ether.
Principle of design of the present invention:
Liquid crystal elastic body has the anisotropy of liquid crystal and the entropy-elasticity of crosslinked polymer network concurrently, after absorbing near-infrared laser by nano-carbon material, by transform light energy, be heat energy, liquid crystal elastic body intramolecule is heated, inner liquid crystal unit ordered orientation is reduced, make liquid crystal elastic body generation thermal induced phase transition, from liquid crystal state, change isotropy state into, and produce large deformation along director orientation.On the other hand, during nano-carbon material self Stimulated Light irradiation, also produce deformation, thereby combining nano carbon material can be given the response of polymer materials opto-mechanical and liquid crystal elastic body produces the feature of large deformation when thermal induced phase transition, finally makes liquid crystal elastic body matrix material show macroscopical large deformation.Simultaneously based on nano-carbon material and liquid crystal elastic body, activating complementarity in performance and the synergetic property in deformation direction, be expected to construct that the speed of response is fast, deformation quantity greatly and the optical actuator of High power output.
Beneficial effect of the present invention:
The liquid crystal elastic composite for optical actuator providing is fast to near-infrared laser irradiation response, deformation is large, High power output, can absorb efficiently near-infrared laser, by transform light energy, be that heat energy triggers liquid crystal elastic body generation transformation mutually, make the liquid crystal elastic body that does not possess light stimulus responsiveness in intrinsic can be used for optical actuator, nano-carbon material strengthens the power output that liquid crystal elastic body can improve actuator simultaneously, and nano-carbon material shrinks while being subject to near-infrared laser irradiation, consistent in deformation direction with the heat-induced shrinkage behavior of liquid crystal elastic body, both synergistic effects improve the speed of response and the deformation quantity of actuator.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope image of graphene oxide/liquid crystal elastic body laminated film section of the embodiment of the present invention 1 preparation.
Fig. 2 is the scanning electron microscope image of hydroxylation carbon nanotube/liquid crystal elastic body laminated film section of the embodiment of the present invention 4 preparations.
Fig. 3 produces the time m-strain curve of mechanical response with near-infrared laser (wavelength 808nm, power 2W) irradiation nano-carbon material filling liquid crystal elastomer composite film; Number in the figure 1～4 is the liquid crystal elastic body matrix material of corresponding embodiment 1～4 respectively, and label X is reference examples.
Fig. 4 produces the time m-strain curve of mechanical response with near-infrared laser (wavelength 808nm, power 2W) irradiation hydroxylation carbon nanotube/liquid crystal elastic body laminated film; Number in the figure 1～6 is the liquid crystal elastic body matrix material of corresponding embodiment 11, embodiment 5, embodiment 9, embodiment 8, embodiment 7, embodiment 4 successively, and label X is reference examples.
Embodiment
Below in conjunction with the drawings and specific embodiments, the present invention is described in further detail.
The liquid crystal monomer adopting in following each embodiment is 2 ', 5 '-bis-(4 " butyl phenyl ether methanoyl)-4-benzoyloxy-1-butyl acrylate, its preparation method is as follows:
1. P-hydroxybenzoic acid is joined in DMF, be made into the solution that concentration is 1g/mL, then the sodium bicarbonate that to add with DHB mol ratio be 3:1, at 70 ℃, stir 1h, obtain solution A;
2. in solution A, add and the equimolar bromotoluene of P-hydroxybenzoic acid, continuation is stirring reaction 7h at 70 ℃, question response mixed solution is cooled to after room temperature, add N, the water dilution of 3 times of volumes of dinethylformamide, the hexane/ethyl acetate extracting twice that is 1:1 by volume ratio again, separated organic phase obtains solution B;
3. solution B is washed with water 3 times, then add anhydrous sodium sulfate drying, except desolventizing obtains brown solid, finally take ether as eluent, with 100-200 object silica gel column chromatography, purify, remove ether and obtain yellow crystals P-hydroxybenzoic acid benzene methyl;
4. by the P-hydroxybenzoic acid benzene methyl of gained and to butyl phenyl ether formic acid, N, N-bicyclic ethyl carbodiimide and tetramethyleneimine pyridine successively in molar ratio 5:10:10:1 be dissolved in methylene dichloride, mole total concn of four kinds of reactants is 3M, and stirring at room reaction 12h, refilters and obtain liquor C;
5. liquor C is respectively extracted once with acetic acid and the deionized water of deionized water, mass concentration 5% successively, in separating obtained organic phase, add anhydrous sodium sulphate, standing water suction 12h, evaporation obtains faint yellow product except after desolventizing, the ethanol/toluene mixed solvent recrystallization that is 4:1 by volume ratio again three times, obtains white needle-like crystals D;
6. by crystal D and palladium-carbon catalyst (10wt%, Pd/C) solution in mass ratio 10:1 join in ethyl acetate, be mixed with the solution that concentration is 50mg/mL, stirring at room reaction 10h under hydrogen atmosphere, filter and collect filtrate, evaporation, except desolventizing, obtains flakey white crystal E;
7. by crystal E, to hydroxyl butylacrylic acid ester, N, N-bicyclic ethyl carbodiimide and tetramethyleneimine pyridine successively in molar ratio 9:10:10:1 be dissolved in methylene dichloride, mole total concn of four kinds of reactants is 0.2M, after stirring at room reaction 12h, reaction mixture is filtered, collect filtrate F;
8. filtrate F is respectively extracted once with acetic acid and the deionized water of deionized water, mass concentration 5% successively, in separating obtained organic phase, add anhydrous sodium sulphate, standing water suction 12h, evaporation obtains faint yellow product except after desolventizing, the ethanol/toluene mixed solvent recrystallization that is 4:1 by volume ratio again three times, last gained white crystal is liquid crystal monomer.
Reference examples
By 2 ', 5 '-bis-(4 " butyl phenyl ether methanoyl)-4-benzoyloxy-1-butyl acrylate liquid crystal monomer (0.1g), 1; 6-hexanediyl ester (4mg) and Irgacure369(0.32mg) be dissolved in 5mL acetone; be spin-coated on after stirring in the smooth teflon plate of smooth surface; be then slowly warming up to 100 ℃ under lucifuge and nitrogen atmosphere; slow cooling to 80 ℃ after insulation 10min; use immediately 365nm photoirradiation 15min, be warming up to again 90 ℃ of irradiation 15min, reacted and obtained pure liquid crystal elastic body laminated film.
Embodiment 1
1) graphene oxide (0.31mg) is joined to supersound process in 5mL acetone, add again 2,5-bis-(4 '-butyl phenyl ether methanoyl)-4 " benzoyloxy butyl-1-acrylate liquid crystal monomer (0.1g), 1; 6-hexanediyl ester linking agent (4mg) and Irgacure369 light trigger (0.32mg), continuing to stir obtains the dispersion liquid of black;
2) dispersion liquid is spin-coated in the smooth teflon plate of smooth surface, then under lucifuge and nitrogen atmosphere, be slowly warming up to 100 ℃, slow cooling to 80 ℃ after insulation 10min, use immediately 365nm photoirradiation 15min, be warming up to again 90 ℃ of irradiation 15min, reacted the liquid crystal elastic body laminated film obtaining containing 0.3wt% graphene oxide.
Embodiment 2
1) Graphene (0.31mg) is joined to supersound process in 5mL acetone, add again 2,5-bis-(4 '-butyl phenyl ether methanoyl)-4 " benzoyloxy butyl-1-acrylate liquid crystal monomer (0.1g), 1; 6-hexanediyl ester linking agent (4mg) and Irgacure369 light trigger (0.32mg), continuing to stir obtains the dispersion liquid of black;
2) dispersion liquid is spin-coated in the smooth teflon plate of smooth surface, then under lucifuge and nitrogen atmosphere, be slowly warming up to 100 ℃, slow cooling to 80 ℃ after insulation 10min, use immediately 365nm photoirradiation 15min, be warming up to again 90 ℃ of irradiation 15min, reacted the liquid crystal elastic body laminated film obtaining containing 0.3wt% Graphene.
Embodiment 3
1) carbon nanotube (0.31mg) is joined to supersound process in 5mL acetone, add again 2,5-bis-(4 '-butyl phenyl ether methanoyl)-4 " benzoyloxy butyl-1-acrylate liquid crystal monomer (0.1g), 1; 6-hexanediyl ester linking agent (4mg) and Irgacure369 light trigger (0.32mg), continuing to stir obtains the dispersion liquid of black;
2) dispersion liquid is spin-coated in the smooth teflon plate of smooth surface, then under lucifuge and nitrogen atmosphere, be slowly warming up to 100 ℃, slow cooling to 80 ℃ after insulation 10min, use immediately 365nm photoirradiation 15min, be warming up to again 90 ℃ of irradiation 15min, reacted the liquid crystal elastic body laminated film obtaining containing 0.3wt% carbon nanotube.
Step 1: preparation hydroxylation carbon nanotube
A) 2g carbon nanotube is joined in the salpeter solution that 300mL concentration is 3M, at 100 ℃, stir after 12h, mixed solution is cooled to room temperature, then filtration under diminished pressure, with deionized water repetitive scrubbing, to neutral, then vacuum-drying obtains black powder at 100 ℃;
B) carbon nanotube of 50mg nitric acid treatment is added in 80mL water; after supersound process 30min; join again in the aqueous solution (20mL) containing the two methylol hydroxyethyl propionic acid amides of 0.5g azo dimethyl N-; at nitrogen protection and 100 ℃, react after 12h; be cooled to room temperature; filtration under diminished pressure, deionized water wash, vacuum-drying, obtain hydroxylation carbon nanotube.
Step 2: preparation hydroxylation carbon nanotube/liquid crystal elastic body matrix material
1) hydroxylation carbon nanotube (0.31mg) is joined to supersound process in 5mL acetone, add again 2,5-bis-(4 '-butyl phenyl ether methanoyl)-4 " benzoyloxy butyl-1-acrylate liquid crystal monomer (0.1g), 1; 6-hexanediyl ester linking agent (4mg) and Irgacure369 light trigger (0.32mg), continuing to stir obtains the dispersion liquid of black;
2) dispersion liquid is spin-coated in the smooth teflon plate of smooth surface, then under lucifuge and nitrogen atmosphere, be slowly warming up to 100 ℃, slow cooling to 80 ℃ after insulation 10min, use immediately 365nm photoirradiation 15min, be warming up to again 90 ℃ of irradiation 15min, reacted the liquid crystal elastic body laminated film obtaining containing 0.3wt% hydroxylation carbon nanotube.
Embodiment 5
Step 1: the preparation of hydroxylation carbon nanotube is with embodiment 4
Step 2: preparation hydroxylation carbon nanotube/liquid crystal elastic body matrix material
1) hydroxylation carbon nanotube (0.21mg) is joined to supersound process in 10mL acetone, add again 2,5-bis-(4 '-butyl phenyl ether methanoyl)-4 " benzoyloxy butyl-1-acrylate liquid crystal monomer (1g), 1; 6-hexanediyl ester (40mg) and Irgacure369(3.2mg), continuing to stir obtains the dispersion liquid of black;
2) dispersion liquid is spin-coated in the smooth teflon plate of smooth surface, then under lucifuge and nitrogen atmosphere, be slowly warming up to 100 ℃, slow cooling to 80 ℃ after insulation 10min, use immediately 365nm photoirradiation 15min, be warming up to again 90 ℃ of irradiation 15min, reacted the liquid crystal elastic body laminated film obtaining containing 0.02wt% hydroxylation carbon nanotube.
Step 1: the preparation of hydroxylation carbon nanotube is with embodiment 4
Step 2: preparation hydroxylation carbon nanotube/liquid crystal elastic body matrix material
1) hydroxylation carbon nanotube (0.13mg) is joined to supersound process in 5mL acetone, add again 2,5-bis-(4 '-butyl phenyl ether methanoyl)-4 " benzoyloxy butyl-1-acrylate liquid crystal monomer (0.25g), 1; 6-hexanediyl ester (10mg) and Irgacure369(0.8mg), continuing to stir obtains the dispersion liquid of black;
2) dispersion liquid is spin-coated in the smooth teflon plate of smooth surface, then under lucifuge and nitrogen atmosphere, be slowly warming up to 100 ℃, slow cooling to 80 ℃ after insulation 10min, use immediately 365nm photoirradiation 15min, be warming up to again 90 ℃ of irradiation 15min, reacted the liquid crystal elastic body laminated film obtaining containing 0.05wt% hydroxylation carbon nanotube.
Embodiment 7
Step 1: the preparation of hydroxylation carbon nanotube is with embodiment 4
Step 2: preparation hydroxylation carbon nanotube/liquid crystal elastic body matrix material
1) hydroxylation carbon nanotube (0.26mg) is joined to supersound process in 10mL acetone, add again 2,5-bis-(4 '-butyl phenyl ether methanoyl)-4 " benzoyloxy butyl-1-acrylate liquid crystal monomer (0.25g), 1; 6-hexanediyl ester (10mg) and Irgacure369(0.8mg), continuing to stir obtains the dispersion liquid of black;
2) dispersion liquid is spin-coated in the smooth teflon plate of smooth surface, then under lucifuge and nitrogen atmosphere, be slowly warming up to 100 ℃, slow cooling to 80 ℃ after insulation 10min, use immediately 365nm photoirradiation 15min, be warming up to again 90 ℃ of irradiation 15min, reacted the liquid crystal elastic body laminated film obtaining containing 0.1wt% hydroxylation carbon nanotube.
Embodiment 8
Step 1: the preparation of hydroxylation carbon nanotube is with embodiment 4
Step 2: prepare carbon nanotube/liquid crystal elastic body matrix material
1) hydroxylation carbon nanotube (0.52mg) is joined to supersound process in 10mL acetone, add again 2,5-bis-(4 '-butyl phenyl ether methanoyl)-4 " benzoyloxy butyl-1-acrylate liquid crystal monomer (0.1g), 1; 6-hexanediyl ester (4mg) and Irgacure369(0.32mg), continuing to stir obtains the dispersion liquid of black;
2) dispersion liquid is spin-coated in the smooth teflon plate of smooth surface, then under lucifuge and nitrogen atmosphere, be slowly warming up to 100 ℃, slow cooling to 80 ℃ after insulation 10min, use immediately 365nm photoirradiation 15min, be warming up to again 90 ℃ of irradiation 15min, reacted the liquid crystal elastic body laminated film obtaining containing 0.5wt% hydroxylation carbon nanotube.
Embodiment 9
Step 1: the preparation of hydroxylation carbon nanotube is with embodiment 4
Step 2: prepare carbon nanotube/liquid crystal elastic body matrix material
1) hydroxylation carbon nanotube (0.73mg) is joined to supersound process in 10mL acetone, add again 2,5-bis-(4 '-butyl phenyl ether methanoyl)-4 " benzoyloxy butyl-1-acrylate liquid crystal monomer (0.1g), 1; 6-hexanediyl ester (4mg) and Irgacure369(0.32mg), continuing to stir obtains the dispersion liquid of black;
2) dispersion liquid is spin-coated in the smooth teflon plate of smooth surface, then under lucifuge and nitrogen atmosphere, be slowly warming up to 100 ℃, slow cooling to 80 ℃ after insulation 10min, use immediately 365nm photoirradiation 15min, be warming up to again 90 ℃ of irradiation 15min, reacted the liquid crystal elastic body laminated film obtaining containing 0.7wt% hydroxylation carbon nanotube.
Step 1: preparation hydroxylation carbon nanotube
A) 2g carbon nanotube is joined in the salpeter solution that 300mL concentration is 3M, at 100 ℃, stir after 12h, mixed solution is cooled to room temperature, then filtration under diminished pressure, with deionized water repetitive scrubbing, to neutral, then vacuum-drying obtains black powder at 100 ℃;
B) carbon nanotube of 50mg nitric acid treatment is added in 80mL water; after supersound process 30min; add again containing 4 of 1.5g; in the aqueous solution (20mL) of 4'-azo two (4-cyano group amylalcohol); at nitrogen protection and 100 ℃, react after 12h; be cooled to room temperature, filtration under diminished pressure, deionized water wash purifying, vacuum-drying, obtain hydroxylation carbon nanotube.
Step 2: prepare carbon nanotube/liquid crystal elastic body matrix material
1) hydroxylation carbon nanotube (1.58mg) is joined to supersound process in 15mL acetone, add again 2,5-bis-(4 '-butyl phenyl ether methanoyl)-4 " benzoyloxy butyl-1-acrylate liquid crystal monomer (0.1g), 1; 6-hexanediol dimethacrylate (4.4mg) and 2-methyl isophthalic acid-(4-methylthio group phenyl)-2-morpholinyl acetone (0.24mg), continuing to stir obtains the dispersion liquid of black;
2) dispersion liquid is spin-coated in the smooth teflon plate of smooth surface, then under lucifuge and nitrogen atmosphere, be slowly warming up to 100 ℃, slow cooling to 80 ℃ after insulation 10min, use immediately 365nm photoirradiation 15min, be warming up to again 90 ℃ of irradiation 15min, reacted the liquid crystal elastic body laminated film obtaining containing 1.5wt% hydroxylation carbon nanotube.
Embodiment 11
Step 1: the preparation of hydroxylation carbon nanotube is with embodiment 10
Step 2: prepare carbon nanotube/liquid crystal elastic body matrix material
1) hydroxylation carbon nanotube (3.15mg) is joined to supersound process in 15mL acetone, add again 2,5-bis-(4 '-butyl phenyl ether methanoyl)-4 " benzoyloxy butyl-1-acrylate liquid crystal monomer (0.1g), 1; 6-hexanediol dimethacrylate (4.5mg) and 2-methyl isophthalic acid-(4-methylthio group phenyl)-2-morpholinyl acetone (0.25mg), continuing to stir obtains the dispersion liquid of black;
2) dispersion liquid is spin-coated in the smooth teflon plate of smooth surface, then under lucifuge and nitrogen atmosphere, be slowly warming up to 100 ℃, slow cooling to 80 ℃ after insulation 10min, use immediately 365nm photoirradiation 15min, be warming up to again 90 ℃ of irradiation 15min, reacted the liquid crystal elastic body laminated film obtaining containing 3wt% hydroxylation carbon nanotube.
Test example 1
The liquid crystal elastic body laminated film light obtaining in above-described embodiment is caused to mechanical response performance testing, and testing method is as follows:
Adopt dynamic thermal analysis instrument (DMA, TA Q800) stretch mode, the first fixing upper end of liquid crystal elastic body nano compound film, its lower end preload force 10mN, use again near-infrared laser (wavelength 808nm, power 2W) irradiation nano compound film in vertical direction, DMA instrument will record light application time and mechanical strain curve automatically, and then can calculate the speed of response and the deformation quantity of nano compound film.
The opto-mechanical respondent behavior of the nano-carbon material filling liquid crystal elastomer composite film that the pure liquid crystal elastic body of above-mentioned reference examples and each embodiment are obtained carries out simultaneous test, and its performance data is as shown in the table:
From accompanying drawing 3 and list data, carbon nanotube, graphene oxide or Graphene filling liquid crystal elastomerics are subject to near-infrared laser irradiation to produce mechanical response, and the undeformed generation while being subject to near-infrared laser irradiation of pure liquid crystal elastic body, and the speed of response of hydroxylation carbon nanotube/liquid crystal elastic body matrix material and deformation quantity maximum.
Test example 2
The opto-mechanical respondent behavior of hydroxylation carbon nanotube/liquid crystal elastic body laminated film that the pure liquid crystal elastic body of above-mentioned reference examples and each embodiment are obtained carries out simultaneous test, and its performance data is as shown in the table:
From Fig. 4 and list data, under identical near-infrared laser radiation parameter, the weight ratio of hydroxylation carbon nanotube and liquid crystal elastic body is when 0.1～0.5:100, the opto-mechanical speed of response of prepared liquid crystal elastic body matrix material and largest deformation amount are in optimum range, meet the application requiring of optical actuator, and too low (<0.05wt%) or too high (>1.0wt%) speed of response of liquid crystal elastic body matrix material of content of carbon nanotubes is slower, and deformation quantity is less.
Claims (11)
1. for a liquid crystal elastic body matrix material for optical actuator, it is characterized in that: it is by the nano-carbon material as filler, form as the thermotropic liquid crystal elastomerics in-situ polymerization of matrix; The elastomeric weight ratio of described nano-carbon material and thermotropic liquid crystal is 0.02～3:100, and described nano-carbon material is Graphene, graphene oxide or carbon nanotube.
2. according to claim 1 for the liquid crystal elastic body matrix material of optical actuator, it is characterized in that: the elastomeric weight ratio of described nano-carbon material and thermotropic liquid crystal is 0.05～1:100.
3. according to claim 2 for the liquid crystal elastic body matrix material of optical actuator, it is characterized in that: the elastomeric weight ratio of described nano-carbon material and thermotropic liquid crystal is 0.1～0.5:100.
4. according to claim 1 for the liquid crystal elastic body matrix material of optical actuator, it is characterized in that: described thermotropic liquid crystal elastomerics forms by esters of acrylic acid liquid crystal monomer, vinyl aromatic ester liquid crystal monomer, vinyl azobenzene monomer or Vinylbiphenyl liquid crystal monomer are crosslinked.
According to described in claim 1～4 any one for the liquid crystal elastic body matrix material of optical actuator, it is characterized in that: described carbon nanotube is hydroxylation carbon nanotube.
Described in claim 1 for a preparation method for the liquid crystal elastic body matrix material of optical actuator, comprise the following steps:
1) nano-carbon material is joined to organic solvent for ultrasonic ripple and process, dispersion concentration is 0.01～1mg/mL, then liquid crystal monomer, linking agent and light trigger are added 90:5～10:0.2～1 in molar ratio, continues to stir to obtain dispersion liquid;
2) dispersion liquid is spin-coated on glass or polytetrafluoroethylsubstrate substrate plate, then under lucifuge and nitrogen atmosphere environment, be slowly warming up to 90～130 ℃, after insulation 5～20min, be cooled to 75～100 ℃, use immediately 250～800nm photoirradiation, 5～20min, after being warming up to 85～110 ℃, again irradiate 5～20min, reacted the liquid crystal elastic body matrix material that obtains film like;
Described liquid crystal monomer is esters of acrylic acid liquid crystal monomer, vinyl aromatic ester liquid crystal monomer, vinyl azobenzene liquid crystal monomer or Vinylbiphenyl liquid crystal monomer.
7. according to claim 6 for the preparation method of the liquid crystal elastic body matrix material of optical actuator, it is characterized in that: described linking agent is diacrylate class or divinyl alkoxy benzene class linking agent.
8. according to claim 6 for the preparation method of the liquid crystal elastic body matrix material of optical actuator, it is characterized in that: described light trigger is 2-benzyl-2-dimethylamino-1-(4-morpholinyl phenyl) butanone, 2-methyl isophthalic acid-(4-methylthio group phenyl)-2-morpholinyl acetone, 2-hydroxy-2-methyl-1-phenyl-acetone, 1-hydroxy-cyclohexyl phenyl ketone, 2, 4, 6-trimethylbenzoyl-diphenyl phosphine oxide, 2, 4, 6-trimethylbenzoyl phenyl-phosphonic acid ethyl ester, 2-benzyl-2-dimethylamino-1-(4-morpholinyl phenyl) butanone or 2-hydroxy-2-methyl-1-[4-(2-hydroxyl-oxethyl) phenyl] acetone.
According to described in claim 6 or 7 or 8 for the preparation method of the liquid crystal elastic body matrix material of optical actuator, it is characterized in that: described carbon nanotube is hydroxylation carbon nanotube, and its preparation method is as follows:
A) carbon nanotube is blended in to reflow treatment 8～12h in salpeter solution, liquid to be mixed is cooled to filtration under diminished pressure after room temperature, and deionized water wash is to neutral, and vacuum-drying obtains black powder;
B) black powder ultrasonic wave is dispersed in solvent; concentration is 0.5～2mg/mL; add again hydroxylation reagent; the weight ratio of carbon nanotube and hydroxylation reagent is 1/10～1/30; then stirring and refluxing 8～12h under the condition of nitrogen protection; then be cooled to room temperature, elimination liquid, deionized water wash precipitation, vacuum-drying obtains hydroxylation carbon nanotube.
10. according to claim 9 for the preparation method of the liquid crystal elastic body matrix material of optical actuator, it is characterized in that: solvent described in the preparation method's of described hydroxylation carbon nanotube step a) is water, DMF, acetone or N-Methyl pyrrolidone.
11. according to claim 9 for the preparation method of the liquid crystal elastic body matrix material of optical actuator, it is characterized in that: hydroxylation reagent described in the preparation method's of described hydroxylation carbon nanotube step b) is the two methylol hydroxyethyl propionic acid amides, 2 of azo dimethyl N-, 2'-azo [2-methyl-N-(2-hydroxyethyl) propionic acid amide], 4,4'-azo two (4-cyano group amylalcohol) or 1-azido-alkyl primary alconols.
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105607170A (en) * | 2016-03-18 | 2016-05-25 | 西安交通大学 | Optical driving flexible adjustable grating and preparation method thereof |
| CN105810830A (en) * | 2016-05-24 | 2016-07-27 | 中国科学院重庆绿色智能技术研究院 | Flexible photoelectric sensor based on three-dimensional conformal graphene and manufacturing method thereof |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101372553A (en) * | 2008-10-24 | 2009-02-25 | 南开大学 | Functionalized single layer graphite and polyurethane photo-induced shape memory composite material and preparation thereof |
| CN101942058A (en) * | 2010-08-26 | 2011-01-12 | 复旦大学 | Infrared photodeformable liquid crystal high-polymer nano composite material and preparation method thereof |
| CN102615885A (en) * | 2012-03-23 | 2012-08-01 | 复旦大学 | Preparation method of reversible photoinduced deformation liquid crystal high polymer and carbon nano tube composite thin film |
| CN102993461A (en) * | 2012-12-28 | 2013-03-27 | 复旦大学 | Preparation method of oxidized grapheme/carapace-type liquid crystal macromolecule nanometer composite material |
-
2013
- 2013-10-10 CN CN201310469443.0A patent/CN103524678B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101372553A (en) * | 2008-10-24 | 2009-02-25 | 南开大学 | Functionalized single layer graphite and polyurethane photo-induced shape memory composite material and preparation thereof |
| CN101942058A (en) * | 2010-08-26 | 2011-01-12 | 复旦大学 | Infrared photodeformable liquid crystal high-polymer nano composite material and preparation method thereof |
| CN102615885A (en) * | 2012-03-23 | 2012-08-01 | 复旦大学 | Preparation method of reversible photoinduced deformation liquid crystal high polymer and carbon nano tube composite thin film |
| CN102993461A (en) * | 2012-12-28 | 2013-03-27 | 复旦大学 | Preparation method of oxidized grapheme/carapace-type liquid crystal macromolecule nanometer composite material |
Non-Patent Citations (2)
| Title |
|---|
| LIQIANG YANG，ET AL.: "Reversible Infrared Actuation of Carbon Nanotube–Liquid", 《ADVANCED MATERIALS》, vol. 20, no. 12, 18 June 2008 (2008-06-18), pages 2271 - 2275 * |
| YINGKUI YANG， ET AL.: "A fecile, green, and tunable method to functionalize carbon nanotubes with water-soluble azo initiators by one-step free radical addition", 《APPLIED SURFACE SCIENCE》, vol. 256, no. 10, 16 December 2009 (2009-12-16), pages 3286 - 3292 * |
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