CN103524678B - Liquid crystal elastic body composite for optical actuator and preparation method thereof - Google Patents
Liquid crystal elastic body composite for optical actuator and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of liquid crystal elastic body composite for optical actuator and preparation method thereof, this composite is formed by the nano-carbon material as filler, thermotropic liquid crystal elastomer in-situ polymerization as matrix, described nano-carbon material is 0.02～3:100 with the weight ratio of thermotropic liquid crystal elastomer, and described nano-carbon material is Graphene, graphene oxide or CNT.The composite of the present invention can be efficiently absorbed near-infrared laser, convert light energy into heat energy and trigger liquid crystal elastic body generation phase in version, the liquid crystal elastic body not possessing light stimulus response in intrinsic is made to can be used for optical actuator, CNT strengthens liquid crystal elastic body and can improve the power output of actuator simultaneously, and shrink when CNT is by near-infrared laser irradiation, heat-induced shrinkage behavior with liquid crystal elastic body is consistent on deformation direction, and both cooperative effects improve the speed of response and the deformation quantity of actuator.
Description
Technical field
The present invention relates to intellectual material and polymer based nanocomposites field, in particular to
A kind of liquid crystal elastic body composite for optical actuator and preparation method thereof.
Background technology
Actuator refers under the outfields such as electricity, light and heat stimulate, by electric energy, heat energy and luminous energy
Etc. the execution device being converted to mechanical energy.Wherein, polymer actuated with light for driving source to build
Utensil have remote controlled, mechanism simplifying is easy of integration, low cost, light weight and be easily processed into
The outstanding advantages such as type.The intellectual material building actuator requires to have response and driven nature concurrently
Feature, the Deformation Mechanisms of polymer light actuator comes from photic molecule isomery and light triggers physics
Deformation.It is presently mainly on the minority polymer inherent such as azobenzene and shows photo-deformable,
But azobenzene polymer is confined under ultraviolet irradiation condition produce mechanical response, the purest poly-
The power output that laminate material builds actuator is little, and its application is restricted.
Graphene and CNT have excellence electricity, light, heat and mechanical property and each to
Opposite sex feature, opens new thinking and approach for building high performance actuator.With graphite
Electric actuator and optical actuator that alkene and CNT build can produce bigger power output.
But, cost height, poor in processability and the coupling efficiency of pure Graphene and CNT actuator
Low.Scientists finds, Graphene and CNT can be efficiently absorbed near-infrared laser,
Convert light energy into heat energy and form " molecular heater ", and then trigger polymers elastomer composite
Material produces mechanical response.But, the macro-mechanical response of polymer composites comes to be received
Rice material with carbon element and the elastically-deformable vector of polymeric matrix, but photo-thermal effect induction tradition is poly-
Deformation quantity and power output that laminate material produces are less, and the speed of response is slower.
Summary of the invention
There is response in the actuator that it is an object of the invention to overcome existing homogenous material to build
Speed is slow, deformation quantity is little and the defect of difficult long-range control, it is provided that a kind of for optical actuator
Liquid crystal elastic body composite and preparation method thereof, to realize building, the speed of response is fast, shape
Variable is big and the optical actuator of High power output.
For achieving the above object, the liquid crystal elastic body for optical actuator provided by the present invention
Composite, by the nano-carbon material as filler, the elasticity of the thermotropic liquid crystal as matrix
Body in-situ polymerization forms, and described nano-carbon material with the weight ratio of thermotropic liquid crystal elastomer is
0.02～3:100, described nano-carbon material is Graphene, graphene oxide or CNT.
Preferably, described nano-carbon material with the weight ratio of thermotropic liquid crystal elastomer is
0.05～1:100.
It is highly preferred that the weight ratio of described nano-carbon material and thermotropic liquid crystal elastomer is
0.1～0.5:100.
Preferably, described thermotropic liquid crystal elastomer is by esters of acrylic acid liquid crystal monomer, ethene
Base aromatic ester liquid crystal monomer, vinylazonan benzene class liquid crystal monomer or Vinylbiphenyl liquid
Crystalline substance is monomer crosslinked to be formed.
Described esters of acrylic acid liquid crystal monomer is preferably waist direct type esters of acrylic acid liquid crystal monomer,
Such as 2 ', 5 '-two (4 "-alkoxy benzene formyloxy)-4-benzoyloxy-1-acrylate liquid crystal
Monomer, 2 ', 5 '-two (4 "-alkyl-cyclohexyl formyloxy)-4-benzoyloxy-1-acrylic acid
Ester liquid crystal monomer.
Described vinyl aromatic ester liquid crystal monomer is preferably waist direct type vinyl aromatic esters
Liquid crystal monomer, such as 1-vinyl-3-alkyl-2,5-bis-(4 '-alkylbenzene formyloxy) benzene first
Acid esters liquid crystal monomer.
Preferably, described CNT is hydroxylating CNT.
Present invention also offers the preparation method of a kind of above-mentioned liquid crystal elastic body composite, bag
Include following steps:
1) nano-carbon material joining organic solvent for ultrasonic ripple process, dispersion concentration is
0.01～1mg/mL, then by liquid crystal monomer, crosslinking agent and light trigger in molar ratio
90:5～10:0.2～1 adds, and continues to be uniformly mixing to obtain dispersion liquid；
2) dispersion liquid is spin-coated on glass or polytetrafluoroethylsubstrate substrate plate, then in lucifuge
Be to slowly warm up to 90～130 DEG C under nitrogen atmosphere environment, insulation 5～20min after be cooled to
75～100 DEG C, immediately with 250～800nm light irradiation 5～20min, it is warming up to 85～110 DEG C
After again irradiate 5～20min, reacted the liquid crystal elastic body composite obtaining film-form；
Described liquid crystal monomer is esters of acrylic acid liquid crystal monomer, vinyl aromatic ester liquid crystal list
Body, vinylazonan benzene class liquid crystal monomer or Vinylbiphenyl liquid crystal monomer.
Preferably, described crosslinking agent is diacrylate esters or the friendship of divinyl alkoxy benzene class
Connection agent, can be selected for 1,6-hexanediyl ester, HDDMA,
4-acryloxy alkoxyl-1-(4 '-vinyl alkoxy phenoxy group)-benzoic ether or 1,4-
Two (1-vinyl)-alkoxy benzene.
Preferably, described light trigger is 2-benzyl-2-dimethylamino-1-(4-morpholine
Phenyl) butanone (Irgacure369), 2-methyl isophthalic acid-(4-methyl mercapto phenyl)-2-morpholinyl
Acetone, 2-hydroxy-2-methyl-1-phenylacetone, 1-hydroxycyclohexyl phenyl ketone, 2,4,6-
Trimethylbenzoy-dipheny phosphine oxide, 2,4,6-trimethylbenzoyl phenyl phosphonic acids second
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, oxolane, N, N-dimethyl
Formamide or 1-METHYLPYRROLIDONE.
Preferably, described nano-carbon material is hydroxylating CNT, and its preparation method is as follows:
A) by CNT reflow treatment 8～12h in salpeter solution, liquid to be mixed is cooled to
Filtration under diminished pressure after room temperature, deionized water washing is to neutral, and vacuum drying obtains black powder；
B) being disperseed in a solvent by black powder ultrasonic wave, concentration is 0.5～2mg/mL, then
Adding hydroxylating agent, CNT is 1/10～1/30 with the weight ratio of hydroxylating agent,
Then under conditions of nitrogen is protected, it is stirred at reflux 8～12h, is then cooled to room temperature, filters off
Liquid, deionized water washing precipitation, vacuum drying obtains hydroxylating CNT.
Preferably, molten described in the step a) of the preparation method of described hydroxylating CNT
Agent is water, N,N-dimethylformamide, acetone or 1-METHYLPYRROLIDONE.
Preferably, hydroxyl described in the step b) of the preparation method of described hydroxylating CNT
Base reagent is azo dimethyl N-double hydroxymethylhydroxyethyl propionamide, 2,2'-azo [2-first
Base-N-(2-hydroxyethyl) propionamide], 4,4'-azo double (4-cyano group amylalcohol) or 1-fold
Nitrogen base alkyl primary alcohol.
Preferably, described liquid crystal monomer (4 "-alkoxy benzene formyloxy)-4-that is 2 ', 5 '-two
Benzoyloxy-1-acrylate, 2 ', 5 '-two (4 "-alkyl-cyclohexyl formyloxy)-4-benzene
Formyloxy-1-acrylate or 1-vinyl-3-alkyl-2,5-two (4 '-alkylbenzene methanoyl
Base) benzoic ether.
The design principle of the present invention:
Liquid crystal elastic body has anisotropy and the entropic elasticity of crosslinked polymer network of liquid crystal concurrently,
Heat energy is converted light energy into after absorbing near-infrared laser by nano-carbon material, elastic to liquid crystal
Body intramolecule heats, and makes internal liquid crystal unit ordered orientation reduce, makes liquid crystal bullet
Gonosome generation thermal induced phase transition, is changed into isotropism state from liquid crystal state, and along director orientation
Produce large deformation.On the other hand, also produce deformation during nano-carbon material self Stimulated Light irradiation,
Thus combine nano-carbon material and can give the response of polymeric material opto-mechanical and liquid crystal elastic body
Produce the feature of large deformation when thermal induced phase transition, finally make liquid crystal elastic body composite material exhibits
Go out macroscopic view large deformation.It is simultaneously based on nano-carbon material activating in performance with liquid crystal elastic body
Concertedness on complementary and deformation direction, is expected to construct that the speed of response is fast, deformation quantity is big
Optical actuator with High power output.
Beneficial effects of the present invention:
The liquid crystal elastic composite for optical actuator provided is to near-infrared laser spoke
Fast according to response, deformation big, High power output, can be efficiently absorbed near-infrared laser, by luminous energy
Be converted to heat energy and trigger liquid crystal elastic body generation phase in version, make not possess in intrinsic light stimulus
The liquid crystal elastic body of response can be used for optical actuator, and nano-carbon material strengthens liquid crystal bullet simultaneously
Gonosome can improve the power output of actuator, and nano-carbon material by near-infrared laser irradiation time
Shrinking, the heat-induced shrinkage behavior with liquid crystal elastic body is consistent on deformation direction, both associations
The speed of response and the deformation quantity of actuator is improved with effect.
Accompanying drawing explanation
Fig. 1 is the graphene oxide/liquid crystal elastic body THIN COMPOSITE of the embodiment of the present invention 1 preparation
The scanning electron microscope image of film section.
Fig. 2 is that the hydroxylating CNT/liquid crystal elastic body of the embodiment of the present invention 4 preparation is multiple
Close the scanning electron microscope image of thin-membrane section.
Fig. 3 is with near-infrared laser (wavelength 808nm, power 2W) irradiation nano-carbon material
Filling liquid crystal elastomer composite film produces the time m-strain curve of mechanical response；Figure acceptance of the bid
The liquid crystal elastic body composite of numbers 1～4 the most corresponding embodiments 1～4, label X is comparison
Example.
Fig. 4 receives with near-infrared laser (wavelength 808nm, power 2W) irradiation hydroxylating carbon
Mitron/liquid crystal elastic body laminated film produces the time m-strain curve of mechanical response；Figure acceptance of the bid
Numbers 1～6 it is corresponding in turn to embodiment 11, embodiment 5, embodiment 9, embodiment 8, implements
Example 7, the liquid crystal elastic body composite of embodiment 4, label X is reference examples.
Detailed description of the invention
Below in conjunction with the drawings and specific embodiments, the present invention is described in further detail.
The liquid crystal monomer used in each embodiment following is 2 ', 5 '-two (4 "-butyl phenyl ether first
Acyloxy)-4-benzoyloxy-1-butyl acrylate, its preparation method is as follows:
1. joining in DMF by P-hydroxybenzoic acid, being made into concentration is
The solution of 1g/mL, adding with DHB mol ratio is the bicarbonate of 3:1
Sodium, stirs 1h at 70 DEG C, obtains solution A；
2. add and the equimolar benzyl bromide a-bromotoluene of P-hydroxybenzoic acid in solution A, continue
Stirring reaction 7h at 70 DEG C, after question response mixed liquor is cooled to room temperature, adds N, N-diformazan
The water dilution of 3 times of volumes of base formamide, then extract by the hexane/ethyl acetate that volume ratio is 1:1
Take twice, separate organic phase and obtain solution B；
3. solution B is washed with water 3 times, be subsequently adding anhydrous sodium sulfate and be dried, remove solvent
Obtain brown solid, finally with ether as eluant, eluent, with the silica gel column chromatography of 100-200 mesh
Method purifies, and removes ether and obtains yellow crystals P-hydroxybenzoic acid benzene methyl；
4. by the P-hydroxybenzoic acid benzene methyl of gained and to butoxybenzoic acid, N, N-bis-ring
Ethyl carbodiimide and pyrrolidines pyridine 5:10:10:1 the most in molar ratio are dissolved in dichloromethane
In alkane, mole total concentration of four kinds of reactants is 3M, and reaction 12h is stirred at room temperature, after
Filter obtains liquor C；
5. by liquor C successively by deionized water, the acetic acid of mass concentration 5% and deionized water
Each extraction once, adds anhydrous sodium sulfate in separating obtained organic phase, stands water suction
12h, obtains faint yellow product after evaporation of solvent, then with the ethanol that volume ratio is 4:1/
Toluene Mixed Solvent recrystallizes three times, obtains white needle-like crystals D；
6. by crystal D and palladium-carbon catalyst (10wt%, Pd/C) solution 10:1 in mass ratio
Join in ethyl acetate, be configured to the solution that concentration is 50mg/mL, under hydrogen atmosphere
Reaction 10h is stirred at room temperature, filtrate, evaporation of solvent is collected by filtration, obtains flakey white
Look crystal E；
7. by crystal E, to hydroxyl butyl propyleneglycol acid esters, N, N-bicyclic ethyl carbodiimide and pyrrole
In coughing up alkane pyridine 9:10:10:1 being dissolved in dichloromethane the most in molar ratio, four kinds of reactants
Mole total concentration be 0.2M, be stirred at room temperature reaction 12h after, reactant mixture is carried out
Filter, collect filtrate F；
8. by filtrate F successively by deionized water, the acetic acid of mass concentration 5% and deionized water
Each extraction once, adds anhydrous sodium sulfate in separating obtained organic phase, stand water suction 12h,
Obtain faint yellow product after evaporation of solvent, then mix by the ethanol/toluene that volume ratio is 4:1
Bonding solvent recrystallizes three times, and last gained white crystal is liquid crystal monomer.
Reference examples
By 2 ', 5 '-two (4 "-butyl phenyl ether formyloxy)-4-benzoyloxy-1-acrylic acid fourth
Ester liquid crystal monomer (0.1g), 1,6 hexanediol diacrylate (4mg) and Irgacure369
(0.32mg) it is dissolved in 5mL acetone, is spin-coated on smooth surface after stirring smooth
Teflon plate on, then under lucifuge and nitrogen atmosphere, be to slowly warm up to 100 DEG C,
After insulation 10min, slow cooling is to 80 DEG C, immediately with 365nm light irradiation 15min, then
It is warming up to 90 DEG C of irradiation 15min, has reacted and obtained pure liquid crystal elastic body laminated film.
Embodiment 1
1) graphene oxide (0.31mg) is joined in 5mL acetone ultrasonically treated, then
Add 2,5-bis-(4 '-butyl phenyl ether formyloxy)-4 "-benzoyloxy butyl-1-acrylic acid
Ester liquid crystal monomer (0.1g), 1,6 hexanediol diacrylate crosslinking agent (4mg) and Irgacure
369 light triggers (0.32mg), continue to be uniformly mixing to obtain the dispersion liquid of black；
2) dispersion liquid is spin-coated in the teflon plate that smooth surface is smooth, then exists
Being to slowly warm up to 100 DEG C under lucifuge and nitrogen atmosphere, after insulation 10min, slow cooling is extremely
80 DEG C, immediately with 365nm light irradiation 15min, then it is warming up to 90 DEG C of irradiation 15min, instead
Should complete to obtain the liquid crystal elastic body laminated film containing 0.3wt% graphene oxide.
Embodiment 2
1) Graphene (0.31mg) is joined in 5mL acetone ultrasonically treated, add
2,5-bis-(4 '-butyl phenyl ether formyloxy)-4 "-benzoyloxy butyl-1-acrylate liquid
Brilliant monomer (0.1g), 1,6 hexanediol diacrylate crosslinking agent (4mg) and Irgacure369
Light trigger (0.32mg), continues to be uniformly mixing to obtain the dispersion liquid of black；
2) dispersion liquid is spin-coated in the teflon plate that smooth surface is smooth, then exists
Being to slowly warm up to 100 DEG C under lucifuge and nitrogen atmosphere, after insulation 10min, slow cooling is extremely
80 DEG C, immediately with 365nm light irradiation 15min, then it is warming up to 90 DEG C of irradiation 15min, instead
Should complete to obtain the liquid crystal elastic body laminated film containing 0.3wt% Graphene.
Embodiment 3
1) CNT (0.31mg) is joined in 5mL acetone ultrasonically treated, then add
Enter 2,5-bis-(4 '-butyl phenyl ether formyloxy)-4 "-benzoyloxy butyl-1-acrylate
Liquid crystal monomer (0.1g), 1,6 hexanediol diacrylate crosslinking agent (4mg) and Irgacure
369 light triggers (0.32mg), continue to be uniformly mixing to obtain the dispersion liquid of black；
2) dispersion liquid is spin-coated in the teflon plate that smooth surface is smooth, then exists
Being to slowly warm up to 100 DEG C under lucifuge and nitrogen atmosphere, after insulation 10min, slow cooling is extremely
80 DEG C, immediately with 365nm light irradiation 15min, then it is warming up to 90 DEG C of irradiation 15min, instead
Should complete to obtain the liquid crystal elastic body laminated film containing 0.3wt% CNT.
Embodiment 4
Step one: preparation hydroxylating CNT
A) 2g CNT is joined in the salpeter solution that 300mL concentration is 3M,
After 100 DEG C of stirring 12h, mixed liquor is cooled to room temperature, then filtration under diminished pressure, uses deionization
Water cyclic washing is to neutral, and then vacuum drying obtains black powder at 100 DEG C；
B) CNT of 50mg nitric acid treatment is added to 80mL water, ultrasonically treated
After 30min, it is then added to containing the double hydroxymethylhydroxyethyl propionamide of 0.5g azo dimethyl N-
The aqueous solution (20mL) in, react after 12h at nitrogen protection and 100 DEG C, be cooled to
Room temperature, the washing of filtration under diminished pressure, deionized water, vacuum drying, obtain hydroxylating CNT.
Step 2: preparation hydroxylating CNT/liquid crystal elastic body composite
1) hydroxylating CNT (0.31mg) is joined in 5mL acetone ultrasonically treated,
Add 2,5-bis-(4 '-butyl phenyl ether formyloxy)-4 "-benzoyloxy butyl-1-propylene
Acid esters liquid crystal monomer (0.1g), 1,6 hexanediol diacrylate crosslinking agent (4mg) and
Irgacure369 light trigger (0.32mg), continues to be uniformly mixing to obtain the dispersion liquid of black；
2) dispersion liquid is spin-coated in the teflon plate that smooth surface is smooth, then exists
Being to slowly warm up to 100 DEG C under lucifuge and nitrogen atmosphere, after insulation 10min, slow cooling is extremely
80 DEG C, immediately with 365nm light irradiation 15min, then it is warming up to 90 DEG C of irradiation 15min, instead
Should complete to obtain the liquid crystal elastic body laminated film containing 0.3wt% hydroxylating CNT.
Embodiment 5
Step one: the preparation of hydroxylating CNT is with embodiment 4
Step 2: preparation hydroxylating CNT/liquid crystal elastic body composite
1) hydroxylating CNT (0.21mg) is joined ultrasonic place in 10mL acetone
Reason, adds 2,5-bis-(4 '-butyl phenyl ether formyloxy)-4 "-benzoyloxy butyl-1-
Acrylate liquid crystal monomer (1g), 1,6 hexanediol diacrylate (40mg) and Irgacure
369(3.2mg), continue to be uniformly mixing to obtain the dispersion liquid of black；
2) dispersion liquid is spin-coated in the teflon plate that smooth surface is smooth, then exists
Being to slowly warm up to 100 DEG C under lucifuge and nitrogen atmosphere, after insulation 10min, slow cooling is extremely
80 DEG C, immediately with 365nm light irradiation 15min, then it is warming up to 90 DEG C of irradiation 15min, instead
Should complete to obtain the liquid crystal elastic body laminated film containing 0.02wt% hydroxylating CNT.
Embodiment 6
Step one: the preparation of hydroxylating CNT is with embodiment 4
Step 2: preparation hydroxylating CNT/liquid crystal elastic body composite
1) hydroxylating CNT (0.13mg) is joined in 5mL acetone ultrasonically treated,
Add 2,5-bis-(4 '-butyl phenyl ether formyloxy)-4 "-benzoyloxy butyl-1-propylene
Acid esters liquid crystal monomer (0.25g), 1,6 hexanediol diacrylate (10mg) and Irgacure
369(0.8mg), continue to be uniformly mixing to obtain the dispersion liquid of black；
2) dispersion liquid is spin-coated in the teflon plate that smooth surface is smooth, then exists
Being to slowly warm up to 100 DEG C under lucifuge and nitrogen atmosphere, after insulation 10min, slow cooling is extremely
80 DEG C, immediately with 365nm light irradiation 15min, then it is warming up to 90 DEG C of irradiation 15min, instead
Should complete to obtain the liquid crystal elastic body laminated film containing 0.05wt% hydroxylating CNT.
Embodiment 7
Step one: the preparation of hydroxylating CNT is with embodiment 4
Step 2: preparation hydroxylating CNT/liquid crystal elastic body composite
1) hydroxylating CNT (0.26mg) is joined ultrasonic place in 10mL acetone
Reason, adds 2,5-bis-(4 '-butyl phenyl ether formyloxy)-4 "-benzoyloxy butyl-1-
Acrylate liquid crystal monomer (0.25g), 1,6 hexanediol diacrylate (10mg) and
Irgacure369(0.8mg), continue to be uniformly mixing to obtain the dispersion liquid of black；
2) dispersion liquid is spin-coated in the teflon plate that smooth surface is smooth, then exists
Being to slowly warm up to 100 DEG C under lucifuge and nitrogen atmosphere, after insulation 10min, slow cooling is extremely
80 DEG C, immediately with 365nm light irradiation 15min, then it is warming up to 90 DEG C of irradiation 15min, instead
Should complete to obtain the liquid crystal elastic body laminated film containing 0.1wt% hydroxylating CNT.
Embodiment 8
Step one: the preparation of hydroxylating CNT is with embodiment 4
Step 2: prepare CNT/liquid crystal elastic body composite
1) hydroxylating CNT (0.52mg) is joined ultrasonic place in 10mL acetone
Reason, adds 2,5-bis-(4 '-butyl phenyl ether formyloxy)-4 "-benzoyloxy butyl-1-
Acrylate liquid crystal monomer (0.1g), 1,6 hexanediol diacrylate (4mg) and Irgacure
369(0.32mg), continue to be uniformly mixing to obtain the dispersion liquid of black；
2) dispersion liquid is spin-coated in the teflon plate that smooth surface is smooth, then exists
Being to slowly warm up to 100 DEG C under lucifuge and nitrogen atmosphere, after insulation 10min, slow cooling is extremely
80 DEG C, immediately with 365nm light irradiation 15min, then it is warming up to 90 DEG C of irradiation 15min, instead
Should complete to obtain the liquid crystal elastic body laminated film containing 0.5wt% hydroxylating CNT.
Embodiment 9
Step one: the preparation of hydroxylating CNT is with embodiment 4
Step 2: prepare CNT/liquid crystal elastic body composite
1) hydroxylating CNT (0.73mg) is joined ultrasonic place in 10mL acetone
Reason, adds 2,5-bis-(4 '-butyl phenyl ether formyloxy)-4 "-benzoyloxy butyl-1-
Acrylate liquid crystal monomer (0.1g), 1,6 hexanediol diacrylate (4mg) and Irgacure
369(0.32mg), continue to be uniformly mixing to obtain the dispersion liquid of black；
2) dispersion liquid is spin-coated in the teflon plate that smooth surface is smooth, then exists
Being to slowly warm up to 100 DEG C under lucifuge and nitrogen atmosphere, after insulation 10min, slow cooling is extremely
80 DEG C, immediately with 365nm light irradiation 15min, then it is warming up to 90 DEG C of irradiation 15min, instead
Should complete to obtain the liquid crystal elastic body laminated film containing 0.7wt% hydroxylating CNT.
Embodiment 10
Step one: preparation hydroxylating CNT
A) 2g CNT is joined in the salpeter solution that 300mL concentration is 3M,
After 100 DEG C of stirring 12h, mixed liquor is cooled to room temperature, then filtration under diminished pressure, uses deionization
Water cyclic washing is to neutral, and then vacuum drying obtains black powder at 100 DEG C；
B) CNT of 50mg nitric acid treatment is added to 80mL water, ultrasonically treated
After 30min, add 4 containing 1.5g, the aqueous solution of 4'-azo double (4-cyano group amylalcohol)
(20mL), in, after reacting 12h at nitrogen protection and 100 DEG C, it is cooled to room temperature, subtracts
The washing of press filtration, deionized water purifies, vacuum drying, obtains hydroxylating CNT.
Step 2: prepare CNT/liquid crystal elastic body composite
1) hydroxylating CNT (1.58mg) is joined ultrasonic place in 15mL acetone
Reason, adds 2,5-bis-(4 '-butyl phenyl ether formyloxy)-4 "-benzoyloxy butyl-1-
Acrylate liquid crystal monomer (0.1g), 1,6-HD dimethylacrylate (4.4mg)
With 2-methyl isophthalic acid-(4-methyl mercapto phenyl)-2-morpholinopropanone (0.24mg), continue stirring
Uniformly obtain the dispersion liquid of black；
2) dispersion liquid is spin-coated in the teflon plate that smooth surface is smooth, then exists
Being to slowly warm up to 100 DEG C under lucifuge and nitrogen atmosphere, after insulation 10min, slow cooling is extremely
80 DEG C, immediately with 365nm light irradiation 15min, then it is warming up to 90 DEG C of irradiation 15min, instead
Should complete to obtain the liquid crystal elastic body laminated film containing 1.5wt% hydroxylating CNT.
Embodiment 11
Step one: the preparation of hydroxylating CNT is with embodiment 10
Step 2: prepare CNT/liquid crystal elastic body composite
1) hydroxylating CNT (3.15mg) is joined ultrasonic place in 15mL acetone
Reason, adds 2,5-bis-(4 '-butyl phenyl ether formyloxy)-4 "-benzoyloxy butyl-1-
Acrylate liquid crystal monomer (0.1g), 1,6-HD dimethylacrylate (4.5mg)
With 2-methyl isophthalic acid-(4-methyl mercapto phenyl)-2-morpholinopropanone (0.25mg), continue stirring
Uniformly obtain the dispersion liquid of black；
2) dispersion liquid is spin-coated in the teflon plate that smooth surface is smooth, then exists
Being to slowly warm up to 100 DEG C under lucifuge and nitrogen atmosphere, after insulation 10min, slow cooling is extremely
80 DEG C, immediately with 365nm light irradiation 15min, then it is warming up to 90 DEG C of irradiation 15min, instead
Should complete to obtain the liquid crystal elastic body laminated film containing 3wt% hydroxylating CNT.
Test example 1
The liquid crystal elastic body laminated film light obtained in above-described embodiment causes machinery ring
Answering performance testing, method of testing is as follows:
Use dynamic thermal analysis instrument (DMA, TA Q800) stretch mode, first fix liquid crystal
The upper end of elastomer nano compound film, its lower end preload force 10mN, then use near-infrared
Irradiation nano compound film in laser (wavelength 808nm, power 2W) vertical direction, DMA
Instrument will record light application time and mechanical strain curve automatically, and then can calculate nano combined
The speed of response of film and deformation quantity.
The nano carbon material that the pure liquid crystal elastic body of above-mentioned reference examples and each embodiment are obtained
The opto-mechanical respondent behavior of material filling liquid crystal elastomer composite film carries out contrast test, its property
Energy data are as shown in the table:
From accompanying drawing 3 and list data, CNT, graphene oxide or Graphene are filled out
Fill liquid crystal elastic body and produced mechanical response by near-infrared laser irradiation, and pure liquid crystal elastic body is subject to
Undeformed generation during near-infrared laser irradiation, and hydroxylating CNT/liquid crystal elastic body
The speed of response of composite and deformation quantity are maximum.
Test example 2
The hydroxylating carbon that the pure liquid crystal elastic body of above-mentioned reference examples and each embodiment are obtained
The opto-mechanical respondent behavior of nanotube/liquid crystal elastic body laminated film carries out contrast test, its
Performance data is as shown in the table:
From Fig. 4 and list data, under identical near-infrared laser radiation parameter, hydroxyl
The weight ratio of carbon nano tube and liquid crystal elastic body when 0.1～0.5:100, prepared liquid crystal
The opto-mechanical speed of response and the largest deformation amount of elastic composite are in optimum range, full
The application requirement of foot optical actuator, and too low (<0.05wt%) or too high (>1.0wt%)
The speed of response of the liquid crystal elastic body composite of content of carbon nanotubes is relatively slow, and deformation quantity is relatively
Little.
Claims (7)
1. the liquid crystal elastic body composite for optical actuator, it is characterised in that:
It is the most poly-by the nano-carbon material as filler, thermotropic liquid crystal elastomer as matrix
Conjunction forms；Described nano-carbon material with the weight ratio of thermotropic liquid crystal elastomer is
0.1～0.5:100, described nano-carbon material is hydroxylating CNT.
The most according to claim 1 for the liquid crystal elastic body composite of optical actuator,
It is characterized in that: described thermotropic liquid crystal elastomer is by esters of acrylic acid liquid crystal monomer, ethene
Base aromatic ester liquid crystal monomer, vinylazonan benzene class monomer or Vinylbiphenyl liquid crystal list
Body crosslinking forms.
3. for the liquid crystal elastic body composite of optical actuator described in a claim 1
Preparation method, comprise the following steps:
1) nano-carbon material joining organic solvent for ultrasonic ripple process, dispersion concentration is
0.01～1mg/mL, then by liquid crystal monomer, crosslinking agent and light trigger in molar ratio
90:5～10:0.2～1 adds, and continues to be uniformly mixing to obtain dispersion liquid；
2) dispersion liquid is spin-coated on glass or polytetrafluoroethylsubstrate substrate plate, then in lucifuge
Be to slowly warm up to 90～130 DEG C under nitrogen atmosphere environment, insulation 5～20min after be cooled to
75～100 DEG C, immediately with 250～800nm light irradiation 5～20min, it is warming up to 85～110 DEG C
After again irradiate 5～20min, reacted the liquid crystal elastic body composite obtaining film-form；
Described liquid crystal monomer is esters of acrylic acid liquid crystal monomer, vinyl aromatic ester liquid crystal list
Body, vinylazonan benzene class liquid crystal monomer or Vinylbiphenyl liquid crystal monomer；
Described nano-carbon material is hydroxylating CNT, and its preparation method is as follows:
A) CNT being blended in reflow treatment 8～12h in salpeter solution, liquid to be mixed is cold
But to filtration under diminished pressure after room temperature, deionized water washing is to neutral, and vacuum drying obtains black powder
End；
B) being disperseed in a solvent by black powder ultrasonic wave, concentration is 0.5～2mg/mL, then
Adding hydroxylating agent, CNT is 1/10～1/30 with the weight ratio of hydroxylating agent,
Then under conditions of nitrogen is protected, it is stirred at reflux 8～12h, is then cooled to room temperature, filters off
Liquid, deionized water washing precipitation, vacuum drying obtains hydroxylating CNT.
The most according to claim 3 for the liquid crystal elastic body composite of optical actuator
Preparation method, it is characterised in that: described crosslinking agent is diacrylate esters or divinyl
Alkoxy benzene class crosslinking agent.
The most according to claim 3 for the liquid crystal elastic body composite of optical actuator
Preparation method, it is characterised in that: described light trigger is 2-benzyl-2-dimethylamino
Base-1-(4-morpholinyl phenyl) butanone, 2-methyl isophthalic acid-(4-methyl mercapto phenyl)-2-morpholinyl third
Ketone, 2-hydroxy-2-methyl-1-phenylacetone, 1-hydroxycyclohexyl phenyl ketone, 2,4,6-tri-
Methyl benzoyl-diphenyl phosphine oxide, 2,4,6-trimethylbenzoyl phenyl phosphinic acid ethyl ester,
2-benzyl-2-dimethylamino-1-(4-morpholinyl phenyl) butanone or 2-hydroxy-2-methyl-1-[4-(2-
Hydroxyl-oxethyl) phenyl] acetone.
The most according to claim 3 for the liquid crystal elastic body composite of optical actuator
Preparation method, it is characterised in that: the step of the preparation method of described hydroxylating CNT
B) solvent described in is water, N,N-dimethylformamide, acetone or 1-METHYLPYRROLIDONE.
The most according to claim 3 for the liquid crystal elastic body composite of optical actuator
Preparation method, it is characterised in that: the step of the preparation method of described hydroxylating CNT
B) hydroxylating agent described in is azo dimethyl N-double hydroxymethylhydroxyethyl propionamide, 2,2'-
Azo [2-methyl-N-(2-hydroxyethyl) propionamide], 4,4'-azo are double (4-cyano group amylalcohol)
Or 1-azido alkyl primary alcohol.
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| CN105810830B (en) * | 2016-05-24 | 2018-10-30 | 中国科学院重庆绿色智能技术研究院 | A kind of flexible optoelectronic sensor and preparation method thereof based on three-dimensional conformal graphene |
| CN107201996B (en) * | 2017-06-07 | 2019-08-27 | 中国科学技术大学 | The preparation method of photic dynamic laminated film, photic dynamic laminated film and optical actuator |
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