CN105623174B - Polyaniline/liquid crystal elastic body composite film material and preparation method thereof - Google Patents
Polyaniline/liquid crystal elastic body composite film material and preparation method thereof Download PDFInfo
- Publication number
- CN105623174B CN105623174B CN201610178999.8A CN201610178999A CN105623174B CN 105623174 B CN105623174 B CN 105623174B CN 201610178999 A CN201610178999 A CN 201610178999A CN 105623174 B CN105623174 B CN 105623174B
- Authority
- CN
- China
- Prior art keywords
- liquid crystal
- polyaniline
- elastic body
- crystal elastic
- film material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 0 CC[Si](C)(CCCCOc(cc1)ccc1C(Oc(cc1)ccc1OC)=O)OC(C)C(C)[Si](C)(C*C*Oc(cc1)ccc1O*C*C**)OC Chemical compound CC[Si](C)(CCCCOc(cc1)ccc1C(Oc(cc1)ccc1OC)=O)OC(C)C(C)[Si](C)(C*C*Oc(cc1)ccc1O*C*C**)OC 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/08—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/12—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes
- C08F283/128—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes on to reaction products of polysiloxanes having at least one Si-H bond and compounds having carbon-to-carbon double bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/02—Polyamines
- C08G73/026—Wholly aromatic polyamines
- C08G73/0266—Polyanilines or derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2250/00—Compositions for preparing crystalline polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2351/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2351/08—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2479/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2461/00 - C08J2477/00
- C08J2479/02—Polyamines
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/16—Applications used for films
Abstract
The invention discloses a kind of polyaniline/liquid crystal elastic body composite film material and preparation method thereof, the material is the liquid crystal elastic body polymer for being doped with conjugation polyaniline, the liquid crystal elastic body polymer selects polysiloxanes as main chain, select the crosslinking agent of single monomer of the end with ethylene linkage and double terminal olefinic links, add a certain amount of catalyst, two step crosslinkings prepare liquid crystal elastomeric film material under heating conditions, and the conjugation polyaniline of different proportion is adulterated during preparation.It is that a kind of photothermal conversion is efficient, stability is good, no biotoxicity photo-thermal conjugated polymer to be conjugated polyaniline, has strong absworption peak near the 800nm of near infrared region, there is very strong absorption near infrared light.Material of the present invention can be applied to the fields such as solar energy hot-cast socket, shape-memory material, biology sensor, medical treatment.
Description
Technical field
The invention belongs to photo-thermal filed of functional, be related to it is a kind of have the function of the conjugation polyaniline of photothermal conversion and its
The method for preparing liquid crystal elastomer composite film.
Background technology
Since Finkelmann synthesized polysiloxanes side-chain liquid crystal elastomer first in 1981, liquid crystal elastic body
Research becomes an emerging branch of liquid crystal polymer research field in the past 30 years.Polysiloxane Liquid Crystal Polymer is with poly-
Type siloxane oligomer or high polymer are as main chain, macromolecular with liquid crystal characteristic of the liquid crystalline small molecules as rigid nuclear.Greatly
The main chain of most Polysiloxane Liquid Crystal Polymers is Si-O-Si keys, and side chain is Si-C or C-C keys, therefore, has organic polymer concurrently
The characteristic of thing and inorganic material, such as good heat resistance, ozone resistance, resistance to UV aging, nonlinear optical properties.It is poly-
These characteristics of type siloxane liquid crystal polymer make it in chromatography column, medical treatment, electronic apparatus, optical engineering and artificial-muscle
There is important application prospect Deng field.Liquid crystal elastic body (LCE) refers to non-crosslinked type liquid crystal polymer through appropriately crosslinked, and
The polymer of isotropism state or liquid crystal state display elasticity, have concurrently elastomer and liquid crystal double grading (i.e. elastic, order and
Mobility).Liquid crystal elastic body has good thermoelasticity, i.e., liquid crystal elastic body is along mesomorphic during thermally-induced phase in version
The orientation of primitive is shunk and expansion.But heat cannot control when being used as stimuli responsive in time in actual application, because
Such a property is combined the photo-deformable for being achieved that liquid crystal elastic body by this with photochemistry phase in version.Because just one kind can be fast
Speed, the accurate, clean energy resource of remote control, so photo-deformable liquid crystal elastomer becomes the new hot spot of people's research.
Document Soft Matter.2011,7,7511-7516 report a kind of doped carbon near infrared light with response
The liquid crystal elastic body membrane material of nanotube, carbon nanotubes have absorption in visible ray and near-infrared region, it can be used as one kind
Photothermal reagent is entrained in liquid crystal elastic body membrane material, so that absorbing near infrared light is converted into thermal energy.But carbon nanotubes conduct
A kind of inorganic material, with high-molecular organic material poor compatibility, the stability of material of preparation is poor, meanwhile, carbon nanotubes biology
Poor compatibility, has certain physiological-toxicity, limits its application in terms of biomaterial.
Document Angew.Chem., Int.Ed., 2011,50,441-444 report a kind of water solubility of polyvinyl alcohol cladding
The photo-thermal therapy that Nano particles of polyaniline is used for tumour is conjugated, which has good heat endurance, biology
Toxicity is low, and has good photothermal conversion efficiency, can absorb infrared light and be converted into heat so as to kill cancer cell.But water
The Nano particles of polyaniline of dissolubility limits its application in organic phase.
The content of the invention
Technical problem：In order to solve traditional liquid crystal elastic body composite film material and inorganic material poor compatibility, stability
The problems such as not high, the present invention provide the polyphenyl that a kind of photothermal conversion is efficient, bio-toxicity is low, compatibility is good and stability is high
Amine/liquid crystal elastic body composite film material, while a kind of preparation method of the material is provided.
Technical solution：Polyaniline of the present invention/liquid crystal elastic body composite film material, to be doped with the liquid crystal bullet of conjugation polyaniline
Elastomer polymer, the liquid crystal elastic body polymer are formed by molecular backbone along film stretching direction ordered arrangement, the molecule master
Connected between chain by crosslinking agent, each equal pendant of molecular backbone has tail direct type liquid crystal moleculeThe structure of the conjugation polyaniline is as follows：
Further, in material of the present invention, the structure of the liquid crystal elastic body polymer is as follows：
X: y=5: 1, wherein,For main chain；
The crosslinking agent is Isosorbide-5-Nitrae-bis- (10- hendecenes epoxides) benzene, and structural formula is：
Further, in material of the present invention, the mass ratio of the conjugation polyaniline and liquid crystal elastic body polymer is
0.5%-10%.
The method for preparing above-mentioned polyaniline/liquid crystal elastic body composite film material of the present invention, comprises the following steps：
(1) aniline liquid is added in hydrochloric acid solution, ice bath stirring is lower to be added dropwise ammonium persulfate liquid oxidizer, keeps temperature
Between 0 to 5 DEG C, stirring 6 to 12 it is small when after, filter, be washed with deionized water, by obtained solid vacuum drying 24 it is small when, be made
It is conjugated polyaniline；
(2) by polymethyl siloxane, liquid crystal monomer, crosslinking agent and conjugation polyaniline according to 36: 150: 21: (1~20)
Mass ratio is dissolved in toluene, at room temperature ultrasonic disperse 5~10 minutes, is transferred in polytetrafluoroethylene (PTFE) groove, ultrasonic disperse is equal
Pt (COD) Cl is added after even2Catalyst, ultrasonic disperse again, until the bubble in solution is divided；
(3) by tetrafluoroethene groove be put into 60 to 65 DEG C of precrosslink 2 to 4 of baking oven it is small when, after in groove solvent volatilization completely after
Take out film, stretching orientation after be crosslinked again at 60 to 65 DEG C 24 to 48 it is small when, that is, be made polyaniline/liquid crystal elastic body composite membrane
Material.
Further, in the method for the present invention, the structure of the conjugation polyaniline is as follows：
Further, in the method for the present invention, the liquid crystal monomer in the step (2) is 4- (3- butylene oxo) benzoic acid 4-
Methoxy, structure are as follows：
Further, in the method for the present invention, the crosslinking agent in the step (2) is the alkene crosslinking containing terminal double bond
Agent.
Further, in the method for the present invention, the crosslinking agent is Isosorbide-5-Nitrae-bis- (10- hendecenes epoxides) benzene, and structural formula is：
Beneficial effect：Compared with prior art, the present invention has the following advantages：
The present invention provides a kind of polyaniline/liquid crystal elastic body composite film material.Liquid crystal elastic body membrane material is studied at present
Most is doping inorganic material and some organic small molecule materials to realize its response to environmental stimuli, the inorganic material of doping
Material is concentrated mainly on the novel metal nano particle based on gold, silver, palladium, graphene and carbon nanotubes based on carbon
Deng organic small molecule material is then concentrated mainly on some compounds with azo structure.Under normal conditions, inorganic material is with having
Machine material compatibility is poor, biological metabolism is bad and long term toxicity.The main problem that presently, there are is shown as：1. inorganic material has
Certain physiological-toxicity, limits the application of liquid crystal elastic body film, and inorganic material poor compatibility, in liquid crystal elastic body membrane material
Middle time length can separate out, and stability is poor.2. some organic small molecule materials with azo structure are exposed to long-term in air
Illumination, molecular structure can be destroyed, and cause liquid crystal elastic body to respond the stimulation in the external world, the phenomenon is mainly by molecule and light
Generation oxidation reaction causes.
Compared with prior art, the present invention has the following advantages：1. polyaniline is commonly used to as conductive polymeric material
Material, present invention discover that conjugation polyaniline can be dispersed in organic solvent by ultrasound, survey is ultraviolet to find it in near-infrared
There is strong absorption in light area, and polyaniline/liquid crystal elastic body composite film material prepared by present invention invention is under Infrared irradiation
Quick obvious contraction, and the composite membrane prepared has liquid crystal property.2. conjugation polyaniline prepared by the present invention and liquid crystal bullet
Property body film compatibility is good, and polyaniline/liquid crystal elastic body composite film material light heat/chemical stability of preparation is good, service life
It is long.3. polyaniline/liquid crystal elastic body composite film material load-bearing capacity prepared by the present invention is big, 200 times of own wt can be reached,
It may be used as load-bearing material.4. polyaniline/liquid crystal elastic body composite film material prepared by the present invention is under illumination and heating condition
It is repeatedly reversible flexible, it may be used as shape-memory material.5. polyaniline/liquid crystal elastic body composite film material for preparing of the present invention without
Physiological-toxicity, can be used for artificial skin and field of biosensors.
Brief description of the drawings
Fig. 1 is the uv absorption spectra of concentration 0.1mg/mL polyanilines；
Fig. 2 (A) is polyaniline/liquid crystal elastic body composite membrane polarisation picture in the horizontal direction, and Fig. 2 (B) is polyaniline/liquid
Brilliant elastomer composite film rotates clockwise 45 degree of polarisation picture.
Embodiment
With reference to embodiment and Figure of description, the present invention is further illustrated.
The preparation of I polyanilines/liquid crystal elastic body composite film material
By polymethyl siloxane, liquid crystal monomer, the alkene crosslinking agent containing terminal double bond and polyaniline 36: 150: 21: (1
~20) mass ratio is dissolved in toluene, at room temperature ultrasonic disperse 5~10 minutes, is transferred in polytetrafluoroethylene (PTFE) groove, is added
45 parts of platinum catalyst solution, continues ultrasound and removes bubble in 10~20 minutes.Polytetrafluoroethylene (PTFE) groove is put into 60 to 65 DEG C of baking
When heat cross-linking 2~4 is small in case, when toluene solvant, all volatilization is complete, and a small amount of n-hexane leaching is added in polytetrafluoroethylene (PTFE) groove
Bubble, removes film and carries out stretching orientation.Be reentered into 60 to 65 DEG C of baking ovens continue heat cross-linkings 24~48 it is small when, obtain polyaniline/liquid
Brilliant elastomer composite membrane material.
Wherein methyl polysilicone alkyl structure isLiquid crystal monomer MBB structures are
Crosslinking agent 11UB structures are
The structure of the Optical Conjugated Polymer Polyaniline of polyaniline/liquid crystal elastic body composite film material doping is as follows：
Platinum catalyst is dichloro (1,5- cyclo-octadiene) platinum, and structure is as follows：
The UV absorption test of II conjugated polymers：
UV absorption is tested：Using the ultraviolet-uisible spectrophotometer of Japanese Shimadzu Corporation, ripple is set in parameter setting
Long scope is 400-1000nm, detects photothermal conversion materiat UV absorption, draws curve.1mg polyanilines are dissolved in before detection
Wiring solution-forming in 10mL tetrahydrofurans, using tetrahydrofuran solution as blank sample, sweeps baseline, is put into prepare liquid after clearing, detects it
UV absorption, by related data, with origin Software on Drawing absorption curves.
The elongation measure and maximum capacity measure of III polyanilines/liquid crystal elastic body composite film material：
(1) during polyaniline/liquid crystal elastic body composite film material is prepared, heat cross-linking 2 in 60 to 65 DEG C of baking oven
~4 it is small when after, take out film carry out stretching orientation, measure its elongation.
(2) weight of the film prepared, measure film maximum multiple that can stretch own wt under Infrared irradiation are weighed.
Embodiment 1：PolyanilinePreparation
18.9g (0.2mol) aniline liquid is added in the aqueous hydrochloric acid solution that 300mL concentration is 1mol/L, is stirred under ice bath
30 minutes.The 200mL 1mol/L HCl solutions for being added dropwise 11.41g (0.05mol) ammonium persulfate molten.Keep temperature always
Less than 5 DEG C, when magnetic agitation 6 is small.Reaction terminates, and stops stirring, reaction solution is filtered, is washed, most after 40 DEG C of vacuum
6.5g polyaniline solids powder, yield 34.4% are obtained after when drying 24 is small.
Embodiment 2：The preparation of conjugated polymer/liquid crystal elastic body photothermal conversion membrane material and its elongation measure and maximum
Load-bearing measures：
By the polymethyl siloxane of 36mg (0.6mmol)150mg (0.5mmol) monomer21mg (0.05mmol) crosslinking agent
With 1mg polyanilinesInput contains 2mL first together
In the brown vial of benzene, it is 0.48% that conjugation polyaniline, which accounts for the mass fraction always to feed intake,.Ultrasound is uniformly dispersed for 10 minutes, is transferred to
In the polytetrafluoroethylene (PTFE) groove of 2cm × 2cm × 2cm, Pt (COD) Cl of 45 μ L is added2Catalyst solution, it is ultrasonic again to remove within 15 minutes
Remove the bubble in toluene solution.Be put into 60 to 65 DEG C baking oven precrosslink 2~4 it is small when.When toluene solvant, all volatilization is complete
Polytetrafluoroethylene (PTFE) groove is taken out afterwards, is cooled to room temperature, a small amount of n-hexane is added in groove and is soaked 2 minutes, is removed film and is carried out stretching and takes
To the elongation of film is 50%.Be reentered into 60 to 65 DEG C of baking ovens continue heat cross-linkings 24~48 it is small when, obtain polyaniline/liquid crystal
Elastomer composite membrane material.The film that length is 2.5cm, width 0.5cm, weight are 50mg is taken, it is maximum under Infrared irradiation
The weight of 10000mg can be stretched, it is 200 times of its own weight that its maximum load-bearing, which is calculated,.
Embodiment 3：The preparation of conjugated polymer/liquid crystal elastic body photothermal conversion membrane material and its elongation measure and maximum
Load-bearing measures：
By the polymethyl siloxane of 36mg (0.6mmol)150mg (0.5mmol) monomer21mg (0.05mmol) crosslinking agent
With 2mg polyanilinesInput contains 2mL first together
In the brown vial of benzene, conjugation polyaniline accounts for the mass fraction always to feed intake and is uniformly dispersed within 10 minutes for 0.96% ultrasound, is transferred to
In the polytetrafluoroethylene (PTFE) groove of 2cm × 2cm × 2cm, Pt (COD) Cl of 45 μ L is added2Catalyst solution, it is ultrasonic again to remove within 15 minutes
Remove the bubble in toluene solution.Be put into 60 to 65 DEG C baking oven precrosslink 2~4 it is small when.When toluene solvant, all volatilization is complete
Polytetrafluoroethylene (PTFE) groove is taken out afterwards, is cooled to room temperature, a small amount of n-hexane is added in groove and is soaked 2 minutes, is removed film and is carried out stretching and takes
To the elongation of film is 30%.Be reentered into 60 to 65 DEG C of baking ovens continue heat cross-linkings 24~48 it is small when, obtain polyaniline/liquid crystal
Elastomer composite membrane material.The film that length is 2.5cm, width 0.5cm, weight are 50mg is taken, it is maximum under Infrared irradiation
The weight of 7500mg can be stretched, it is 150 times of its own weight that its maximum load-bearing, which is calculated,.
Embodiment 4：The preparation of conjugated polymer/liquid crystal elastic body photothermal conversion membrane material and its elongation measure and maximum
Load-bearing measures：
By the polymethyl siloxane of 36mg (0.6mmol)150mg (0.5mmol) monomer21mg (0.05mmol) crosslinking agent
With 5mg polyanilinesInput contains 2mL first together
In the brown vial of benzene, it is 2.36% that conjugation polyaniline, which accounts for the mass fraction always to feed intake,.Ultrasound is uniformly dispersed for 10 minutes, is transferred to
In the polytetrafluoroethylene (PTFE) groove of 2cm × 2cm × 2cm, Pt (COD) Cl of 45 μ L is added2Catalyst solution, it is ultrasonic again to remove within 15 minutes
Remove the bubble in toluene solution.Be put into 60 to 65 DEG C baking oven precrosslink 2~4 it is small when.When toluene solvant, all volatilization is complete
Polytetrafluoroethylene (PTFE) groove is taken out afterwards, is cooled to room temperature, a small amount of n-hexane is added in groove and is soaked 2 minutes, is removed film and is carried out stretching and takes
To the elongation of film is 25%.Be reentered into 60 to 65 DEG C of baking ovens continue heat cross-linkings 24~48 it is small when, obtain polyaniline/liquid crystal
Elastomer composite membrane material.The film that length is 2.5cm, width 0.5cm, weight are 50mg is taken, it is maximum under Infrared irradiation
The weight of 7500mg can be stretched, it is 150 times of its own weight that its maximum load-bearing, which is calculated,.
Embodiment 5：The preparation of conjugated polymer/liquid crystal elastic body photothermal conversion membrane material and its elongation measure and maximum
Load-bearing measures：
By the polymethyl siloxane of 36mg (0.6mmol)150mg (0.5mmol) monomer21mg (0.05mmol) crosslinking agent
With 10mg polyanilinesInput contains 2mL first together
In the brown vial of benzene, it is 4.61% that conjugation polyaniline, which accounts for the mass fraction always to feed intake,.Ultrasound is uniformly dispersed for 10 minutes, is transferred to
In the polytetrafluoroethylene (PTFE) groove of 2cm × 2cm × 2cm, Pt (COD) Cl of 45 μ L is added2Catalyst solution, it is ultrasonic again to remove within 15 minutes
Remove the bubble in toluene solution.Be put into 60 to 65 DEG C baking oven precrosslink 2~4 it is small when.When toluene solvant, all volatilization is complete
Polytetrafluoroethylene (PTFE) groove is taken out afterwards, is cooled to room temperature, a small amount of n-hexane is added in groove and is soaked 2 minutes, is removed film and is carried out stretching and takes
To the elongation of film is 20%.Be reentered into 60 to 65 DEG C of baking ovens continue heat cross-linkings 24~48 it is small when, obtain polyaniline/liquid crystal
Elastomer composite membrane material.The film that length is 2.5cm, width 0.5cm, weight are 50mg is taken, it is maximum under Infrared irradiation
The weight of 5000mg can be stretched, it is 100 times of its own weight that its maximum load-bearing, which is calculated,.
Embodiment 6：The preparation of conjugated polymer/liquid crystal elastic body photothermal conversion membrane material and its elongation measure and maximum
Load-bearing measures：
By the polymethyl siloxane of 36mg (0.6mmol)150mg (0.5mmol) monomer21mg (0.05mmol) crosslinking agent
With 20mg polyanilinesInput contains 2mL first together
In the brown vial of benzene, it is 8.81% that conjugation polyaniline, which accounts for the mass fraction always to feed intake,.Ultrasound is uniformly dispersed for 10 minutes, is transferred to
In the polytetrafluoroethylene (PTFE) groove of 2cm × 2cm × 2cm, Pt (COD) Cl of 45 μ L is added2Catalyst solution, it is ultrasonic again to remove within 15 minutes
Remove the bubble in toluene solution.Be put into 60 to 65 DEG C baking oven precrosslink 2~4 it is small when.When toluene solvant, all volatilization is complete
Polytetrafluoroethylene (PTFE) groove is taken out afterwards, is cooled to room temperature, a small amount of n-hexane is added in groove and is soaked 2 minutes, is removed film and is carried out stretching and takes
To the elongation of film is 10%.Be reentered into 60 to 65 DEG C of baking ovens continue heat cross-linkings 24~48 it is small when, obtain polyaniline/liquid crystal
Elastomer composite membrane material.The film that length is 2.5cm, width 0.5cm, weight are 50mg is taken, it is maximum under Infrared irradiation
The weight of 5000mg can be stretched, it is 100 times of its own weight that its maximum load-bearing, which is calculated,.
Above-described embodiment is only the preferred embodiment of the present invention, it should be pointed out that：For the ordinary skill of the art
For personnel, without departing from the principle of the present invention, some improvement and equivalent substitution can also be made, these are to the present invention
Claim be improved with the technical solution after equivalent substitution, each fall within protection scope of the present invention.
Claims (8)
1. a kind of polyaniline/liquid crystal elastic body composite film material, it is characterised in that the material is to be doped with conjugation polyaniline
Liquid crystal elastic body polymer, the liquid crystal elastic body polymer by molecular backbone along film stretching direction ordered arrangement and
Into being connected between the molecular backbone by crosslinking agent, each equal pendant of molecular backbone has tail direct type liquid crystal moleculeThe structure of the conjugation polyaniline is as follows：
2. polyaniline according to claim 1/liquid crystal elastic body composite film material, it is characterised in that the liquid crystal elasticity
The structure of body polymer is as follows：
X: y=5: 1, wherein,For main chain；
The crosslinking agent is Isosorbide-5-Nitrae-bis- (10- hendecenes epoxides) benzene, and structural formula is：
3. polyaniline according to claim 1 or 2/liquid crystal elastic body composite film material, it is characterised in that the conjugation is poly-
The mass ratio of aniline and liquid crystal elastic body polymer is 0.5%-10%.
4. a kind of method of the polyaniline/liquid crystal elastic body composite film material prepared described in claim 1,2 or 3, its feature exist
In this method comprises the following steps：
(1) aniline liquid is added in hydrochloric acid solution, ice bath stirring is lower to be added dropwise ammonium persulfate liquid oxidizer, keeps temperature 0 to 5
Between DEG C, stirring 6 to 12 it is small when after, filter, be washed with deionized water, by obtained solid vacuum drying 24 it is small when, be made conjugation
Polyaniline；
(2) by polymethyl siloxane, liquid crystal monomer, crosslinking agent and conjugation polyaniline according to 36: 150: 21: the quality of (1~20)
Ratio is dissolved in toluene, at room temperature ultrasonic disperse 5~10 minutes, is transferred in polytetrafluoroethylene (PTFE) groove, after ultrasonic disperse is uniform
Add Pt (COD) Cl2Catalyst, ultrasonic disperse again, until the bubble in solution is divided；
(3) by tetrafluoroethene groove be put into 60 to 65 DEG C of precrosslink 2 to 4 of baking oven it is small when, after in groove solvent volatilization completely after take out
Film, stretching orientation after be crosslinked again at 60 to 65 DEG C 24 to 48 it is small when, that is, be made polyaniline/liquid crystal elastic body compound film material
Material.
5. the method for polyaniline/liquid crystal elastic body composite film material is prepared according to claim 4, it is characterised in that described
The structure for being conjugated polyaniline is as follows：
6. the method for polyaniline/liquid crystal elastic body composite film material is prepared according to claim 4, it is characterised in that described
Liquid crystal monomer in step (2) is 4- (3- butylene oxo) benzoic acid 4- methoxies, and structure is as follows：
7. according to the method for preparing polyaniline/liquid crystal elastic body composite film material of claim 4,5 or 6, it is characterised in that
Crosslinking agent in the step (2) is the alkene crosslinking agent containing terminal double bond.
8. the method for polyaniline/liquid crystal elastic body composite film material is prepared according to claim 7, it is characterised in that described
Crosslinking agent is Isosorbide-5-Nitrae-bis- (10- hendecenes epoxides) benzene, and structural formula is：
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610178999.8A CN105623174B (en) | 2016-03-25 | 2016-03-25 | Polyaniline/liquid crystal elastic body composite film material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610178999.8A CN105623174B (en) | 2016-03-25 | 2016-03-25 | Polyaniline/liquid crystal elastic body composite film material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105623174A CN105623174A (en) | 2016-06-01 |
| CN105623174B true CN105623174B (en) | 2018-04-24 |
Family
ID=56038546
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610178999.8A Active CN105623174B (en) | 2016-03-25 | 2016-03-25 | Polyaniline/liquid crystal elastic body composite film material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105623174B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106947042B (en) * | 2017-03-10 | 2020-04-21 | 清华大学 | Photothermal conversion element, and use of aniline oligomer and derivative thereof |
| CN107365401B (en) * | 2017-06-15 | 2019-09-10 | 东南大学 | A kind of near-infrared response backbone chain type liquid crystal elastomer and preparation method thereof |
| CN107556562A (en) * | 2017-09-04 | 2018-01-09 | 三维天工（北京）科技有限公司 | The preparation method of customizable optical-thermal conversion material and application |
| CN111718487B (en) * | 2020-06-28 | 2022-01-28 | 苏州美嘉写智能显示科技有限公司 | Preparation method of click-modified polysiloxane side chain liquid crystal polymer |
| CN115113388A (en) * | 2022-06-09 | 2022-09-27 | 西湖大学 | Light-driven micro mirror, preparation method and driving light path structure thereof |
| CN115055057B (en) * | 2022-06-27 | 2024-04-05 | 江苏久膜高科技股份有限公司 | Preparation method and application of white spirit aroma concentration composite membrane |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007270077A (en) * | 2006-03-31 | 2007-10-18 | Kagoshima Univ | Liquid crystal elastomer, liquid crystal film, liquid crystal gel and method for producing them |
| CN104479250A (en) * | 2014-12-18 | 2015-04-01 | 首都师范大学 | Multi-functional composite membrane with high photo-thermal conversion efficiency as well as preparation method and application of composite membrane |
-
2016
- 2016-03-25 CN CN201610178999.8A patent/CN105623174B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007270077A (en) * | 2006-03-31 | 2007-10-18 | Kagoshima Univ | Liquid crystal elastomer, liquid crystal film, liquid crystal gel and method for producing them |
| CN104479250A (en) * | 2014-12-18 | 2015-04-01 | 首都师范大学 | Multi-functional composite membrane with high photo-thermal conversion efficiency as well as preparation method and application of composite membrane |
Non-Patent Citations (3)
| Title |
|---|
| Near-infrared-responsive gold nanorod/liquid crystalline elastomer composites prepared by sequential thiol-click chemistry;Hong Yang等;《Chemical Communications》;20150622;第51卷;第12126-12129页，尤其涉及摘要、第12126页第1-3段 * |
| Nematic liquid single crystal elastomers;Jurgen Kupfer等;《Die Makromolekulare Chemie Rapid Communications》;20030312;第12卷;第717-726页，尤其涉及第719页流程图1和第725页第6段 * |
| Spontaneous thermal expansion of nematic elastomers;A.R. Tajbakhsh等;《The European Physical Journal E》;20011031;第6卷;第181-188页，尤其涉及摘要，表1、3和图1 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105623174A (en) | 2016-06-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105623174B (en) | Polyaniline/liquid crystal elastic body composite film material and preparation method thereof | |
| Wei et al. | Near-infrared light-responsive electrochemical protein imprinting biosensor based on a shape memory conducting hydrogel | |
| Chen et al. | Polypyrrole-doped conductive supramolecular elastomer with stretchability, rapid self-healing, and adhesive property for flexible electronic sensors | |
| Lei et al. | Adaptable polyionic elastomers with multiple sensations and entropy-driven actuations for prosthetic skins and neuromuscular systems | |
| Daugaard et al. | Conductive polymer functionalization by click chemistry | |
| Cai et al. | Room-temperature self-healing ablative composites via dynamic covalent bonds for high-performance applications | |
| Ikura et al. | Supramolecular elastomers with movable cross-linkers showing high fracture energy based on stress dispersion | |
| Tang et al. | Superabsorbent conducting hydrogel from poly (acrylamide-aniline) with thermo-sensitivity and release properties | |
| Nguyen et al. | An acrylonitrile–butadiene–lignin renewable skin with programmable and switchable electrical conductivity for stress/strain-sensing applications | |
| Tang et al. | Two-steps synthesis of a poly (acrylate–aniline) conducting hydrogel with an interpenetrated networks structure | |
| He et al. | Highly stretchable and tough alginate-based cyclodextrin/Azo-polyacrylamide interpenetrating network hydrogel with self-healing properties | |
| CN107365401B (en) | A kind of near-infrared response backbone chain type liquid crystal elastomer and preparation method thereof | |
| CN102580633A (en) | Preparation method of graphene oxide/poly(N-isopropylacrylamide) composite hydrogel | |
| Dai et al. | Interfacial polymerization to high-quality polyacrylamide/polyaniline composite hydrogels | |
| CN110016148A (en) | Conductive polymer hydrogel material and preparation method thereof | |
| CN104762077B (en) | The polymer oil-displacing agent of high temperature resistant salt resistance | |
| CN102706929B (en) | A kind of preparation of Photocrosslinkable modified hyaluronic acid molecular engram sensor | |
| CN106496468A (en) | A kind of preparation method with self-healing and the silicone elastomer of shape-memory properties | |
| CN108939071B (en) | Preparation method of near-infrared photo-thermal response functionalized graphene oxide/hyaluronic acid composite hydrogel | |
| Wang et al. | Continuous meter-scale wet-spinning of cornlike composite fibers for eco-friendly multifunctional electronics | |
| Yang et al. | Hybrid organic-inorganic dyeionogels: Reversibly pH-responsive materials based dye-ionic liquids with improved structural stability and flexibility | |
| CN106908495A (en) | A kind of method that flexible molecule trace sensor is prepared based on carbon nanotube loaded polymer micelle | |
| CN109537083A (en) | A kind of preparation method and applications of graphene/polyaniline nano-composite fiber film | |
| Majstorovic et al. | Thermosensitive Fluorescence of an UCST-type Hybrid Functional Hydrogel | |
| CN105816881B (en) | Combined system, pharmaceutical carrier and preparation method based near infrared light thermit powder and temperature sensing polymer |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |