CN108318943B - A kind of Responsive photonic crystals elastomeric film material, its preparation and application - Google Patents
A kind of Responsive photonic crystals elastomeric film material, its preparation and application Download PDFInfo
- Publication number
- CN108318943B CN108318943B CN201810216897.XA CN201810216897A CN108318943B CN 108318943 B CN108318943 B CN 108318943B CN 201810216897 A CN201810216897 A CN 201810216897A CN 108318943 B CN108318943 B CN 108318943B
- Authority
- CN
- China
- Prior art keywords
- polymer
- cross
- photonic crystal
- linked polymer
- preparation
- 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
Classifications
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/002—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of materials engineered to provide properties not available in nature, e.g. metamaterials
- G02B1/005—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of materials engineered to provide properties not available in nature, e.g. metamaterials made of photonic crystals or photonic band gap materials
Landscapes
- Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention belongs to Functionally structure field, more particularly to a kind of responsiveness, can selfreparing, display non-angular rely on photonic crystal elastomer film, preparation method and application.Responsive photonic crystals elastomeric film material of the invention, including cross-linked polymer matrix material, modified Nano particle and extinction nano material；The molar ratio of the cross-linked polymer, modified Nano particle and extinction nano material is (1~200): 100:(0~5)；The modified Nano particle and extinction nano material are dispersed in the cross-linked polymer matrix material with the structural arrangement of shortrange order, the color of the photonic crystal elastomeric film material does not change with viewing angle, it can be automatically repaired mechanical damage occurs, there is elasticity during stretching.
Description
Technical field
The invention belongs to the invention in Functionally structure field, relate more specifically to a kind of responsiveness, can selfreparing, aobvious
Show that non-angular relies on photonic crystal elastomer film, preparation method and application.
Background technique
Photonic crystal is a kind of material with periodic nano-structure, in sensing, display, detection, nano impression, intelligence
The fields such as material have a good application prospect.Photonic crystal has long range ordered structure, so that crystal film with photon generally has
Dependence of angle, and require its colour stable in use in order to observe and detect, therefore prepare non-angular and rely on
Photonic crystal membrane material have important application value.Meanwhile photonic crystal membrane material will not only have when in use convenient for seeing
The color examined also needs to have certain elasticity and has responsiveness to environmental stimuli, be just able to achieve in this way to light, heat, electricity, magnetic, from
The response of son etc., to widen its use scope.Traditional Responsive photonic crystals film mainly using basis material or is received
The property of rice corpuscles itself realizes its response to environmental stimuli；Be difficult to reach restore after response, duplicate responses and recovery
Purpose.Side particularly important to the practical application of photonic crystal membrane material, and traditional at present is replied and recycled to stimuli responsive
Method is also unable to satisfy the requirement.
Although selfreparing crystal film with photon is it has been reported that but in the photonic crystal of processing machinery (as stretched) responsiveness
It is low, frangible using the most intensity of photonic crystal membrane material of prior art preparation in terms of film, it is unable to satisfy the need of practical application
It asks.In addition, the crystal film with photon preparation process of conventional method preparation is complicated, stretching is difficult to reuse, and cannot achieve selfreparing
With the purpose of reuse.The defect of the above photonic crystal membrane material and the insufficient practical application for strongly limiting the material.
Summary of the invention
Aiming at the above defects or improvement requirements of the prior art, the present invention provides a kind of responsiveness, can selfreparing, display
Non-angular relies on photonic crystal elastomer film, preparation method and application, sufficiently combines photonic crystal elastomeric film material
Feature and demand, specific aim carry out again the polymer material type and nanoparticle type of photon crystal material assembling weight
Selection, and the other parameters such as key parameter such as component proportion, component dissolubility are designed, correspondingly obtain a kind of sound
Ying Xing, can selfreparing, display non-angular rely on photonic crystal elastomer film, thus solve the prior art photonic crystal membrane material
Most intensity is low, frangible, and demand and the preparation process for being unable to satisfy practical application are complicated, and stretching is difficult to reuse, can not
The technical issues of purpose of realization selfreparing and reuse.
To achieve the above object, according to one aspect of the present invention, a kind of Responsive photonic crystals elastomer film is provided
Material, including cross-linked polymer matrix material, modified Nano particle and extinction nano material；The cross-linked polymer, modification are received
The molar ratio of rice corpuscles and extinction nano material is (1~200): 100:(0~5)；The modified Nano particle and the extinction
Nano material is dispersed in the cross-linked polymer matrix material with the structural arrangement of shortrange order, the photonic crystal elastomer film
The color of material does not change with viewing angle, can be automatically repaired after mechanical damage occurs, and has elasticity during stretching.
Preferably, the size of the modified Nano particle is 100~500nm；The size of the extinction nano material is 10
~100nm.
Preferably, the cross-linked polymer is between crosslinking agent and the functional group of polymer by the way that coordination, host-guest occurs
Interaction, hydrogen bond or chemical crosslink reaction and the cross-linked polymer with network structure formed, the polymer for it is transparent,
Flexible functionalized polymer, the refraction index of the polymer are 1.2~2.0；The functionalized polymer contains
At least one of amino, pyridine groups, imidazoles, azobenzene, cyclodextrin, hydroxyl, sulfydryl, boric acid or adamantane double bond, it is described
The glass transition temperature of polymer is lower than 25 DEG C；The molar ratio of the polymer and the crosslinking agent is 0.05:1~6:1.
Preferably, the polymer is functionalized dimethyl silicone polymer (PDMS) or functionalized polyacrylic acid fourth
Ester.
Preferably, the crosslinking agent is selected from metal ion, cyclodextrin, boric acid, polyalcohol, multi-thiol and diolefin.
Preferably, the metal ion is alkaline-earth metal ions, transition metal ions or rare earth metal with unoccupied orbital
Ion.
Preferably, the metal ion is Ce3+、Zn2+、Cu2+、Ni2+Or Co2+One or more of.
Preferably, the nanoparticle of the modification carries out cross-linking modified obtain by nanoparticle under the action of modifying agent
It arrives, the nanoparticle is does not dissolve in organic solvent, and medicine ball or nucleocapsid knot of the size within the scope of 100-500nm
Structure spheroidal particle；The modifying agent is the oil-soluble polymers that molecular weight is less than 40000g/mol.
Preferably, the nanoparticle is SiO2Nanoparticle, polystyrene nanoparticle or polymethylacrylic acid nanometer
Particle.
Preferably, the modifying agent is the oil-soluble polymers that molecular weight is 600~30000g/mol.
Preferably, the modified Nano particle has the degree of cross linking greater than 40%.
Preferably, the extinction nano material is selected from carbon black, CNT, graphene, fullerene, PbS and CuS.
Other side according to the invention provides a kind of preparation side of Responsive photonic crystals elastomeric film material
Method includes the following steps:
(1) nanoparticle the preparation of modified Nano particle: is passed through into sol-gal process under the action of modifying agent
Learn and be modified, then in organic solvent by modified nanoparticle dispersion, wherein the mass concentration of modified Nano particle be 1%~
50%；The nanoparticle is will not dissolve in organic solvent, and medicine ball or nucleocapsid of the size within the scope of 100-500nm
Structure spheroidal particle；The modifying agent is the oil-soluble polymers that molecular weight is less than 40000g/mol；
(2) it the preparation of cross-linked polymer: obtains after transparent, elastic functionalized polymer is dissolved or melted containing poly-
Close the organic solution of object, then crosslinking agent be added dropwise in the organic solution containing polymer, the polymer with it is described
The molar ratio of crosslinking agent is 0.05:1~6:1；Be coordinated between the crosslinking agent and the functional group of the polymer by generation,
Host-guest interactions, hydrogen bond or chemical crosslink reaction and to form the crosslinking with self-repair function with network structure poly-
Close object；The cross-linked polymer is colorless and transparent, and refraction index is 1.2~2.0；The functionalized polymer contain amino,
At least one of pyridine groups, imidazoles, azobenzene, cyclodextrin, hydroxyl, sulfydryl, boric acid or adamantane double bond；The polymer
Glass transition temperature be lower than room temperature (25 DEG C)；The crosslinking agent is selected from metal ion, cyclodextrin, boric acid, polyalcohol, polynary
Mercaptan and diolefin；In organic solvent by the cross-linked polymer prepared dispersion, wherein the mass concentration of cross-linked polymer is
1%~65%；
(3) preparation of photonic crystal elastic film material: by the modified Nano grain of step (1) dispersion in organic solvent
Son and extinction nano material and step (2) the dispersion cross-linked polymer in organic solvent according to mass ratio 100:(0~
5): (1~200), preferred mass ratio are 100:(0~2): (1~200), in hydrophobic and organic solvent-resistant material surface or appearance
Device internal mix obtains Hybrid assembling body, and organic solvent under the conditions of 20~70 DEG C in Hybrid assembling body described in fast eliminating obtains
To photonic crystal elastic film material, wherein the removing rate of the organic solvent is greater than 0.4ml/min；Or by the mixing group
Dress body is placed in spraying container, is sprayed into the hydrophobic material surface and is obtained photonic crystal elastic film material；
Wherein, the Flory-Huggin of step (1) modifying agent and step (2) described cross-linked polymer interacts
Parameter is not more than 0.5, it is ensured that modified Nano particle described in step (3) can dissolve each other with the cross-linked polymer.
Preferably, the nanoparticle is SiO2Nanoparticle, polystyrene nanoparticle or polymethylacrylic acid nanometer
Particle.
Preferably, the modifying agent is the oil-soluble polymers that molecular weight is 600~30000g/mol.
Preferably, the modified Nano particle has the degree of cross linking greater than 40%.
Preferably, the organic solvent is selected from tetrahydrofuran, chloroform, methylene chloride, hexamethylene, DMSO, DMF, benzene, first
Alcohol, ethyl alcohol, isopropanol, pyridine, toluene, ethyl acetate and acetone.
Preferably, the molecular weight of step (2) described polymer is 5000~1,000,000g/mol
Other side according to the invention provides the application of photonic crystal elastic membrane described in one kind, is applied to anti-
Pseudo-, wearable, fingerprint recognition, sensor, coating or paint field.
In general, through the invention it is contemplated above technical scheme is compared with the prior art, can obtain down and show
Beneficial effect:
(1) present invention realizes the preparation of cross-linked polymer by selecting particular kind of polymer and crosslinking agent.The present invention
The polymer for selecting elasticity and modulus with higher regulates and controls cross-linked polymer by the molar ratio of regulation polymer and crosslinking agent
The degree of cross linking, to be adjusted to obtain film strength according to use demand.
(2) cross-linked polymer that the present invention uses contains reversible crosslink structure, is the selfreparing of photonic crystal elastomer film
Provide a good platform, after the film is destroyed in use can the selfreparing within the regular hour, be convenient for material
Material is used for multiple times.
(3) the present invention provides a kind of preparation methods of photonic crystal elastomer film, real by quickly volatilizing or spraying
The preparation of non-angular dependence crystal film with photon is showed, preparation time is short, and easy to operate, repeatability is strong, convenient for extensive system
It is standby.
(4) present invention introduces the extinctions nano material such as carbon black in photonic crystal elastomer film preparation process, is conducive to
It stretches or observes its color when compressing, be conducive to it in context of detection application.
(5) the schemochrome non-angular dependence of photonic crystal elastomer provided by the invention has preferable elasticity and has
Standby self-healing properties.This photonic crystal elastomer is interacted with functionalized polymer and additional third substance, that is, crosslinking agent
Cross-linked structure is formed, then the modified nanoparticle of oleophylic and extinction nano material are dispersed in cross-linked polymer ultrasonic mixing
In specific solvent, after control the preparation of solvent evaporation rate by modes such as spraying, spin coatings and form a film.This method is easy to operate, at
This is low and is convenient for large scale preparation.Obtained photonic crystal elastomer film also has one other than with specific schemochrome
Fixed fluorescent characteristic can be used for anti-fake, wearable device, fingerprint recognition, sensor, selfreparing colour-wash, intelligent toy etc.
Field.
(6) it is provided by the invention can photonic crystal elastomer film its area of selfreparing and display non-angular dependence can root
According to arbitrarily adjustment is needed, the spraying technology used provides advantage for the large area preparation of the film.Can meet it is anti-fake, can wear
It wears, the size requirement in the application such as fingerprint recognition, sensor or even coating, paint to photonic crystal elastomer, is expected to realize light
Practical application of the sub- crystal film in above-mentioned field.
Detailed description of the invention
Fig. 1 is the scanning electricity for four kinds of various sizes of Nano particles of silicon dioxide that embodiment 1 is synthesized according to the method
Mirror picture.Fig. 1 (a) prepare blue photons film thus improved silica nanoparticle；Fig. 1 (b) prepares green photon film institute
With improved silica nanoparticle；Fig. 1 (c) prepare the sub- film of yellow colour thus improved silica nanoparticle；Fig. 1
(d) prepare yellow photons film thus improved silica nanoparticle the case where dispersing in PDMS.
Fig. 2 is four kinds of various sizes of improved silica nanoparticles and the crosslinking of embodiment 2-6 the method synthesis
The digital photograph (Fig. 2 (a)) and spectrogram (Fig. 2 (b)) for the crystal film with photon that polymer is prepared after being blended.The sample exists
Shown in the variation relation such as Fig. 2 (c) of the maximum absorption band of different angle with angle, this illustrates that the sample does not have dependence of angle.
Fig. 2 (d) is cross-linked polymer and the drawing for adding the crystal film with photon prepared after four kinds of various sizes of Nano particles of silicon dioxide
Stretch curve.
Fig. 3 be embodiment 1-6 preparation four kinds of different colours photonic crystal elastomer films different angle (0 °, 15 °,
30 °, 45 °, 60 °, 75 °) observation when obtained spectrogram: Fig. 3 (a) blue photons crystal film, Fig. 3 (b) green photon crystal film,
Fig. 3 (c) yellow photons crystal film, Fig. 3 (d) red photon crystal film.
Fig. 4 be embodiment 2 prepare crystal film with photon, surface have scratch (blade is scratched) afterwards (Fig. 4 (a)) at 60 DEG C
The digital photograph of (Fig. 4 (b)) after lower placement 48h.
Fig. 5 is that embodiment 2 is the crystal film with photon after being scratched with knife, and 60 DEG C of reparation certain times (6 h, for 24 hours, 48h)
Extension test data afterwards.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to the accompanying drawings and embodiments, right
The present invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, and
It is not used in the restriction present invention.As long as in addition, technical characteristic involved in the various embodiments of the present invention described below
Not constituting a conflict with each other can be combined with each other.
The photon crystal material of the prior art cannot meet simultaneously responsiveness, can selfreparing, reuse, display non-angular
Dependence and sufficient intensity, the present invention provides a kind of Responsive photonic crystals elastomeric film materials, including cross-linked polymer base
Body material, modified Nano particle and extinction nano material；The cross-linked polymer, modified Nano particle and extinction nano material
Molar ratio is (1~200): 100:(0~5)；The modified Nano particle and extinction nano material are arranged with the structure of shortrange order
Column are dispersed in the cross-linked polymer matrix material, and the color of the photonic crystal elastomeric film material does not become with viewing angle
Change, can be automatically repaired mechanical damage occurs, there is elasticity during stretching.The size of the modified Nano particle is
100-500nm；The size 10-100nm of the extinction nano material.
Wherein, cross-linked polymer is mutual by generation coordination, master-object between crosslinking agent and the functional group of polymer
Effect, hydrogen bond or chemical crosslink reaction and the cross-linked polymer with network structure formed, the polymer and the crosslinking
The molar ratio of agent is 0.05:1~6:1；The cross-linked polymer is colorless and transparent, and refraction index is 1.2~2.0；It is wherein described
Polymer is transparent, elastic functionalized polymer, and the glass transition temperature of the polymer is lower than room temperature (25 DEG C), institute
It states functionalized polymer and preferably comprises amino, pyridine groups, imidazoles, azobenzene, cyclodextrin, hydroxyl, sulfydryl, boric acid or Buddha's warrior attendant
At least one of alkane double bond；The polymer is preferably functionalized dimethyl silicone polymer (PDMS) or functionalized poly-
Butyl acrylate；The crosslinking agent is preferably selected from metal ion, cyclodextrin, boric acid, polyalcohol, multi-thiol and diolefin.Gold
Belonging to ion is alkaline-earth metal ions, transition metal ions or rare earth ion with unoccupied orbital, preferably Ce3+、Zn2+、Cu2 +、Ni2+Or Co2+One or more of.
When polymer is the polymer containing amino, pyridine groups or imidazole group, crosslinking agent is metal ion.Polymerization
The cross-linked polymer that object and crosslinking agent have network structure by the way that coordination formation occurs.The selection gist of metal ion is to guarantee
Polymer after crosslinking does not influence the colour developing of photonic crystal without deeper color.
When polymer is polymer containing groups such as polyalcohol, multi-thiol, amido bonds, crosslinking agent be polyalcohol,
Polyacid, amido bond form cross-linked polymer between polymer and crosslinking agent with hydrogen bond action.
When polymer and crosslinking agent are polymer isostructural containing azobenzene, crosslinking agent is that cyclodextrin etc. can be by master-
Object interacts and forms the cross-linked polymer with network structure.
When polymer be containing hydroxyl, polyol structure polymer when, crosslinking agent is boric acid, and polymer and crosslinking agent are logical
It crosses chemical crosslink reaction and forms the cross-linked polymer with network structure.
The present invention polymerize species to obtain the photonic crystal that the cross-linked polymer of clear, colorless obtains clear, colorless in turn
The selection of class and the selection of type of crosslinking agent are most important, and polymer and crosslinking agent are both preferably clear, colorless, at least want
Ask its refraction index of the cross-linked polymer to be formed in 1.2~2.0 ranges.On the other hand, in order to have after obtaining mechanical damage
Can restore deformation realization cycling and reutilization after self-repair function, stretching repairs photonic crystal, by especially selecting to have
Certain functionalized polymer of elasticity is crosslinked with suitable crosslinking agent, and the cross-linked polymer of formation is because of its framework material
There is the polymer compared with low Tg for polysiloxanes, butyl polyacrylate etc., polymer chain has preferable flexibility, gathers
The effect closed between object and crosslinking agent is reversible action, when connection (coordinate bond, host-guest phase between polymer and crosslinking agent
The corresponding chemical bond of interaction, hydrogen bond or the corresponding chemical bond of chemical crosslinking) disconnect after, and can be again coupled to, i.e., it is of the invention
Cross-linked polymer contain reversible crosslink structure, restore deformation after tension failure or when surface abrasion, realize that circulation is sharp again
With.
Modified nanoparticle by nanoparticle carried out under the action of modifying agent it is cross-linking modified obtain, the nanoparticle
Son is does not dissolve in organic solvent, and medicine ball or core-shell structure spheroidal particle of the size within the scope of 100-500nm, described
Nanoparticle is preferably SiO2Nanoparticle, polystyrene nanoparticle or polymethylacrylic acid nanoparticle；It is preferred that nanoparticle
Son is SiO2Nanoparticle, preferred size range 170-270nm；Modifying agent is that molecular weight is molten less than the oil of 40000g/mol
Property polymer, preferably molecular weight be 600~30000g/mol oil-soluble polymers；By using small molecule oil-soluble polymerization
Object is cross-linking modified to nanoparticle progress, and its object is to enhance modified Nano particle and the crosslinking with supramolecular network structure
The compatibility of polymer.Modified Nano particle preferably has greater than 40% degree of cross linking, correspondingly, modified Nano particle and crosslinking
Polymer has better compatibility.Nanoparticle is modified using modifying agent, makes modified nanoparticle and crosslinking
Polymer has good dissolution compatibility, should by selecting the Flory-Huggin interaction parameter with cross-linked polymer
What parameter mainly characterized two kinds of polymer is mutually dissolved performance, can pass through solubility meter of the two kinds of polymer in same solvent
It calculates, when value is not more than 0.5, modified Nano particle and cross-linked polymer have well mutually when being mixed with photon crystal film
It is molten, it is not in macro when realizing that the specific requirement well dissolved each other mixes for the two with cross-linked polymer to modified Nano particle here
See mutually separation when rheology testing (i.e., the frequency scanning curve under different temperatures meets time temperature equivalence principle of stacking).
Extinction nano material is selected from carbon black, CNT, graphene, fullerene, PbS and CuS.
The present invention provides the preparation methods of above-mentioned Responsive photonic crystals elastomeric film material, include the following steps:
(1) preparation of modified Nano particle: nanoparticle is handed under the action of modifying agent by sol-gal process
Connection is modified, method particularly includes: and then in organic solvent by modified nanoparticle dispersion, the wherein quality of modified Nano particle
Concentration is 1%~50%；The nanoparticle is that will not dissolve in organic solvent, and size is within the scope of 100-500nm
Medicine ball or core-shell structure spheroidal particle；The nanoparticle is preferably SiO2Nanoparticle, polystyrene nanoparticle or poly-
Methacrylic acid nanoparticle；The modifying agent is molecular weight less than 40000, and preferred molecular weight is 600~30000g/mol's
Oil-soluble polymers, the modified Nano particle preferably have greater than 40% degree of cross linking.
(2) preparation of cross-linked polymer: by transparent, elastic functionalized polymer using organic solvent carry out dissolution or
The organic solution containing polymer is obtained after melting, and then crosslinking agent is added dropwise in the organic solution containing polymer,
The molar ratio of the polymer and the crosslinking agent is 0.05:1~6:1；Being crosslinked for polymer is controlled by controlling the molar ratio
Degree, and the degree of cross linking should not it is too high can not be too low, too high crystal film with photon elasticity is too low, the too low photonic crystal film-strength of the degree of cross linking
Not enough.By the way that coordination, host-guest interactions or chemical crosslinking occurs between the crosslinking agent and the functional group of the polymer
It reacts and forms the cross-linked polymer with self-repair function with network structure；The cross-linked polymer is colorless and transparent, folding
Optical index is 1.3~1.8；The functionalized polymer preferably comprise amino, pyridine groups, imidazoles, azobenzene, cyclodextrin,
The glass transition temperature of at least one of hydroxyl, sulfydryl, boric acid or adamantane double bond, the polymer is lower than room temperature (25
℃)；The crosslinking agent is preferably selected from metal ion, cyclodextrin, boric acid, polyalcohol, multi-thiol and diolefin；Point of polymer
Son amount is 5000~1,000,000g/mol.The cross-linked polymer prepared is dispersed in organic solvent, wherein cross-linked polymeric
The mass concentration of object is 1%~65%；The concentration of cross-linked polymer cannot be too high, otherwise assembling prepare photonic crystal be cannot
The defect sturcture of shortrange order is formed, on the other hand, concentration is too high, and spraying may be blocked when preparing photonic crystal using spray coating method
Rifle.The polymer is preferably functionalized dimethyl silicone polymer (PDMS) or functionalized butyl polyacrylate；The friendship
Connection agent is preferably selected from metal ion, cyclodextrin, boric acid, polyalcohol, multi-thiol and diolefin.Metal ion is with unoccupied orbital
Alkaline-earth metal ions, transition metal ions or rare earth ion, preferably Ce3+、Zn2+、Cu2+、Ni2+Or Co2+In one
Kind is a variety of.
(3) preparation of photonic crystal elastic film material: by the modified Nano grain of step (1) dispersion in organic solvent
Son and extinction nano material and step (2) the dispersion cross-linked polymer in organic solvent according to mass ratio 100:(0~
5): (1~200), preferred mass ratio are 100:(0~2): (1~200), in hydrophobic and organic solvent-resistant material surface or appearance
Device internal mix obtains Hybrid assembling body, and organic solvent under the conditions of 20~70 DEG C in Hybrid assembling body described in fast eliminating obtains
To photonic crystal elastic film material, wherein the removing rate of the organic solvent is greater than 0.4mL/min；Or by the mixing group
Dress body is placed in spraying container, is sprayed into the hydrophobic material surface and is obtained photonic crystal elastic film material.Extinction nano material
It can first mix with modified Nano particle, then be mixed with the organic solution of cross-linked polymer, three can also be mixed simultaneously.
Wherein, the Flory-Huggin of step (1) modifying agent and step (2) described cross-linked polymer interacts
Parameter is not more than 0.5, it is ensured that modified Nano particle described in step (3) can dissolve each other with the cross-linked polymer.Organic solvent
Selected from tetrahydrofuran, chloroform, methylene chloride, hexamethylene, DMSO, DMF, benzene, methanol, ethyl alcohol, isopropanol, pyridine, toluene, second
Acetoacetic ester and acetone.
In above-mentioned preparation method, cross-linked polymer, modified Nano particle and extinction nano material are being subjected to Hybrid assembling
When at photon crystal film material, the interaction of modified Nano particle and cross-linked polymer (guarantees modified Nano particle and gathers
Conjunction is mutually dissolved) and the evaporation rate of organic solvent be to directly influence the photon crystal film being finally prepared to develop the color
Two key factors, not requiring nothing more than cross-linked polymer and modified Nano particle has good compatibility, and compatibility is too poor to be led
Cause mutually separating and then the elastomer film of preparation being made not have color for larger size；And the evaporation rate of organic solvent is had to
Fastly, to guarantee that modified Nano particle forms the package assembly of shortrange order in the polymer.Extinction nano material is in Hybrid assembling
Mass fraction in body also should not be too high, and otherwise the color of light absorbent can cover the colour developing of photonic crystal.Using spraying legal system
When standby photon crystal film, spraying rate cannot be too high, and otherwise organic solvent has little time to volatilize, and leads to that photon crystalline substance cannot be formed
Body, reasonable spraying rate mainly pass through nitrogen pressure when spraying, control as 0.03MPa~0.5MPa.For the ease of that will make
Standby obtained photon crystal film is removed, is taken out from preparing in container, it should be noted that selection hydrophobicity is good and resistance to has
The material of solvent (not dissolving in organic solvent), adhesion polymer, the currently preferred container material quality for preparing is polytetrafluoroethyl-ne
Alkene, Kynoar, polypropylene, polyethylene or sheet glass, silicon wafer, the mica sheet of hydrophobically modified etc..
The application of above-mentioned photonic crystal elastic membrane provided by the invention, at the same have responsiveness, can selfreparing, repeat make
With, display non-angular rely on and sufficient intensity, can be widely applied to anti-fake, wearable, fingerprint recognition, sensor, coating or
Paint field.
The following are embodiments:
Embodiment 1
(1) synthesis and modification of Nano particles of silicon dioxide: by 8mL ammonium hydroxide, 4mL water is dissolved in the ethyl alcohol of 100mL,
Ten minutes later, the TEOS of 3mL is added dropwise in stirring, and quickly stirring 15min is added dropwise, reduces mixing speed, 30 DEG C of reaction 5- afterwards
6h is centrifuged after the reaction was completed with the revolving speed of 8 000rpm, is successively used ethanol solution hydrochloride, water and ethanol washing, is centrifuged
Nanoparticle is dried in vacuo at 50 DEG C and obtains white solid.Then by the Nano particles of silicon dioxide ultrasonic disperse of 1g 85
In mL ethyl alcohol, the lower ethanol solution 30mL (88mL ammonium hydroxide/320mL ethyl alcohol) that ammonium hydroxide is added dropwise, 40 stirring 1h are stirred, then by molecule
The ethanol solution for the PDMS that the triethoxy that amount is 600-900g/mol blocks is slowly dropped in above-mentioned solution, and addition finishes anti-
Should for 24 hours, product is centrifuged the silica for obtaining diameter as 170nm with the revolving speed of 7 000rpm, successively uses ethanol solution hydrochloride, water
And ethanol washing, white solid is obtained after centrifugal vacuum drying (50 DEG C).Finally, Nano particles of silicon dioxide ultrasonic disperse is existed
In tetrahydrofuran solution (10wt%), and suitable carbon black particle (0.5 wt%) is added in the solution, ultrasonic disperse is uniformly standby
With.
(2) preparation of cross-linked polymer solution: the PDMS that molecular weight is 5 000g/mol is dissolved in tetrahydrofuran, dense
Degree is 15wt%.In methyl alcohol (0.01-0.2g/mL) by cerium chloride dissolution, the methanol solution of cerium chloride is slowly dripped under stirring
It is added in polymer solution, is stirred overnight at room temperature, it is spare.
(3) cross-linked polymer and silica nanometer of certain volume the preparation of selfreparing photonic crystal elastomer film: are taken
Particle solution, with volume ratio 1:1 mix ultrasound 1h, using the black polypropylene plate of 8cm × 8cm as reception device, by polymer/
For silica/carbon black solution by the method for spray gun spraying, it is 0.03MPa that control, which sprays nitrogen pressure used, is quickly volatilized
Solvent, the crystal film with photon that preparation non-angular relies on.Its membrane area is by spraying the volume of solution used and spraying reception device
Size codetermines.
Embodiment 2
(1) synthesis and modification of Nano particles of silicon dioxide: by 8mL ammonium hydroxide, 4mL water is dissolved in the ethyl alcohol of 100mL,
Ten minutes later, the TEOS of 3mL is added dropwise in stirring, and quickly stirring 15min is added dropwise, reduces mixing speed, 30 DEG C of reaction 5- afterwards
6h is centrifuged after the reaction was completed with the revolving speed of 8 000rpm, is successively used ethanol solution hydrochloride, water and ethanol washing, is centrifuged
Nanoparticle obtains white solid after being dried in vacuo at 50 DEG C.Then by the Nano particles of silicon dioxide ultrasonic disperse of 1g 85
In mL ethyl alcohol, lower ethanol solution 30mL (88mL ammonium hydroxide/320mL ethyl alcohol), the 40 DEG C of stirring 1h that ammonium hydroxide is added dropwise are stirred, then will divide
The ethanol solution for the PDMS that the triethoxy that son amount is 600-900g/mol blocks is slowly dropped in above-mentioned solution, and addition finishes
Reaction for 24 hours, product is centrifuged the silica for obtaining diameter as 170nm with the revolving speed of 7 000rpm, successively with ethanol solution hydrochloride,
Water, ethanol washing, centrifugal vacuum dry (50 DEG C) obtain white solid.Finally by Nano particles of silicon dioxide ultrasonic disperse four
In hydrogen tetrahydrofuran solution (10wt%), and suitable carbon black particle (1wt%) is added in the solution, ultrasonic disperse is uniformly spare.
(2) preparation of cross-linked polymer solution: the PDMS that molecular weight is 50 000g/mol is dissolved in tetrahydrofuran,
Concentration is 10wt%.In methyl alcohol (0.01-0.2g/mL) by cerium chloride dissolution, under stirring that the methanol solution of cerium chloride is slow
It is added drop-wise in polymer solution, is stirred overnight at room temperature, it is spare.
(3) cross-linked polymer and silica nanometer of certain volume the preparation of selfreparing photonic crystal elastomer film: are taken
Particle solution, with volume ratio 1:1 mix ultrasound 1h, using the black polypropylene plate of 8cm*8cm as reception device, by polymer/
For silica/carbon black solution by the method for spray gun spraying, it is 0.08MPa that control, which sprays nitrogen pressure used, is quickly volatilized
Solvent, the crystal film with photon that preparation non-angular relies on.Its membrane area is by spraying the volume of solution used and spraying reception device
Size codetermines.
Embodiment 3
(1) synthesis and modification of Nano particles of silicon dioxide: by 8mL ammonium hydroxide, 2mL water is dissolved in the ethyl alcohol of 100mL,
Ten minutes later, the TEOS of 3mL is added dropwise in stirring, and quickly stirring 15min is added dropwise, reduces mixing speed, 30 DEG C of reaction 5- afterwards
6h is centrifuged after the reaction was completed with the revolving speed of 8 000rpm, successively uses ethanol solution hydrochloride, water, ethanol washing, what is be centrifuged receives
Rice corpuscles is dried in vacuo at 50 DEG C and obtains white solid.Afterwards by the Nano particles of silicon dioxide ultrasonic disperse of 1g in 85mL second
In alcohol, lower ethanol solution 30mL (88mL ammonium hydroxide/320mL ethyl alcohol), the 40 DEG C of stirring 1h that ammonium hydroxide is added dropwise are stirred, then by molecular weight
Ethanol solution for the PDMS of the triethoxy sealing end of 600-900g/mol is slowly dropped in above-mentioned solution, and addition finishes reaction
For 24 hours, product is centrifuged the silica for obtaining diameter as 200nm with the revolving speed of 7 000rpm, successively with ethanol solution hydrochloride, water,
Ethanol washing, centrifugal vacuum dry (50 DEG C) obtain white solid.Finally by Nano particles of silicon dioxide ultrasonic disperse in tetrahydro
In tetrahydrofuran solution (10wt%), and suitable carbon black particle (0.5wt%) is added in the solution, ultrasonic disperse is uniformly spare.
(2) preparation of cross-linked polymer solution: the PDMS that molecular weight is 100 000g/mol is dissolved in tetrahydrofuran,
Concentration is 5wt%.In methyl alcohol (0.01-0.2g/mL) by cerium chloride dissolution, the methanol solution of cerium chloride is slowly dripped under stirring
It is added in polymer solution, is stirred overnight at room temperature, it is spare.
(3) cross-linked polymer and silica nanometer of certain volume the preparation of selfreparing photonic crystal elastomer film: are taken
Particle solution, with volume ratio 1:1 mix ultrasound 1h, using the black polypropylene plate of 8cm × 8cm as reception device, by polymer/
Method of silica/carbon black solution by spray gun spraying, quick solvent flashing, control spray nitrogen pressure used and are
0.5MPa, the crystal film with photon that preparation non-angular relies on.Its membrane area is by spraying the volume of solution used and spraying reception device
Size codetermine.
Embodiment 4
(1) synthesis and modification of Nano particles of silicon dioxide: by 8mL ammonium hydroxide, 2mL water is dissolved in the ethyl alcohol of 100mL,
Ten minutes later, the TEOS of 3mL is added dropwise in stirring, and quickly stirring 15min is added dropwise, reduces mixing speed, 30 DEG C of reaction 5- afterwards
6h is centrifuged after the reaction was completed with the revolving speed of 8 000rpm, successively uses ethanol solution hydrochloride, water, ethanol washing, what is be centrifuged receives
Rice corpuscles is dried in vacuo at 50 DEG C and obtains white solid.Then by the Nano particles of silicon dioxide ultrasonic disperse of 1g in 85 mL
In ethyl alcohol, lower ethanol solution 30mL (88mL ammonium hydroxide/320mL ethyl alcohol), the 40 DEG C of stirring 1h that ammonium hydroxide is added dropwise are stirred, then by molecule
The ethanol solution for the PDMS that the triethoxy that amount is 600-900g/mol blocks is slowly dropped in above-mentioned solution, and addition finishes anti-
Should for 24 hours, product is centrifuged the silica for obtaining diameter as 200nm with the revolving speed of 7 000rpm, successively uses ethanol solution hydrochloride, water
And ethanol washing, white solid is obtained after centrifugal vacuum drying (50 DEG C).Finally Nano particles of silicon dioxide ultrasonic disperse is existed
In tetrahydrofuran solution (10wt%), and suitable carbon black particle (1wt%) is added in the solution, ultrasonic disperse is uniformly spare.
(2) preparation of cross-linked polymer solution: the PDMS that molecular weight is 50 000g/mol is dissolved in tetrahydrofuran,
Concentration is 10wt%.In methyl alcohol (0.01-0.2g/mL) by zinc chloride dissolution, under stirring that the methanol solution of zinc chloride is slow
It is added drop-wise in polymer solution, is stirred overnight at room temperature, it is spare.
(3) cross-linked polymer and silica nanometer of certain volume the preparation of selfreparing photonic crystal elastomer film: are taken
Particle solution, with volume ratio 1:1 mix ultrasound 1h, using the black polypropylene plate of 8cm × 8cm as reception device, by polymer/
Method of silica/carbon black solution by spray gun spraying, quick solvent flashing, the photonic crystal that preparation non-angular relies on
Film.Its membrane area is codetermined by the size of the volume and spraying reception device that spray solution used.
Embodiment 5
(1) synthesis and modification of Nano particles of silicon dioxide: by 8mL ammonia solvent in the ethyl alcohol of 100mL, stirring is very
The TEOS of 3mL is added dropwise in Zhong Hou, and quickly stirring 15min is added dropwise, reduces mixing speed afterwards, 30 DEG C of reaction 5-6h have reacted
It is centrifuged after with the revolving speed of 8 000rpm, successively uses ethanol solution hydrochloride, water and ethanol washing, the nanoparticle being centrifuged exists
White solid is obtained after being dried in vacuo at 50 DEG C.Then by the Nano particles of silicon dioxide ultrasonic disperse of 1g in 85mL ethyl alcohol,
Lower ethanol solution 30mL (88mL ammonium hydroxide/320mL ethyl alcohol), the 40 DEG C of stirring 1h that ammonium hydroxide is added dropwise of stirring, then by molecular weight be 600-
The ethanol solution of the PDMS of the triethoxy sealing end of 900g/mol is slowly dropped in above-mentioned solution, and addition finishes reaction for 24 hours, produces
Object is centrifuged the silica for obtaining diameter as 270nm with the revolving speed of 7 000rpm, is successively washed with ethanol solution hydrochloride, water and ethyl alcohol
It washs, obtains white solid after centrifugal vacuum dry (50 DEG C).Finally by Nano particles of silicon dioxide ultrasonic disperse in tetrahydrofuran
In solution (10wt%), and suitable carbon black particle (2wt%) is added in the solution, ultrasonic disperse is uniformly spare.
(2) preparation of cross-linked polymer solution: the PDMS that molecular weight is 50 000g/mol is dissolved in tetrahydrofuran,
Concentration is 10wt%.In methyl alcohol by metal ion dissolution, metal ion is slowly dropped in polymer solution under stirring, room
Temperature is stirred overnight, spare.
(3) preparation of selfreparing crystal film with photon: take the cross-linked polymer of certain volume and Nano particles of silicon dioxide molten
Liquid mixes ultrasound 1h with volume ratio 1:1, using the black polypropylene plate of 8cm × 8cm as reception device, by polymer/titanium dioxide
Method of silicon/carbon black solution by spray gun spraying, quick solvent flashing, the crystal film with photon that preparation non-angular relies on.Its film
Area is codetermined by the size of the volume and spraying reception device that spray solution used.
Embodiment 6
(1) synthesis modification of polymer nano-particle: prepared by the method that polymer nano-particle mainly uses emulsion polymerization, with
Illustrate for the preparation of the polystyrene PHEMA ball of core-shell structure.First polypyrrole alkanone (6.5g) is dissolved in 135g water,
Styrene (6.5g) 1,4-butanediol diacrylate (BDDA) is added dropwise after stirring and dissolving, is heated to 90 DEG C, is then slowly added dropwise
A certain amount of potassium persulfate solution is added HEMA, double fork acrylamides, potassium peroxydisulfate after reaction 1.5 hours, reacts after being added dropwise
It two hours, finally adds and the PDMS containing allyl double bonds and KPS carries out oleophylic to nanoparticle surface and is modified.Reaction
It is centrifuged after the completion with the speed of 9000rpm, washing obtains polymer nano-particle drying.Finally nanoparticle ultrasonic disperse is existed
In tetrahydrofuran solution (10wt%), and suitable carbon black particle (2wt%) is added in the solution, ultrasonic disperse is uniformly spare.
(2) preparation of cross-linked polymer solution: the PDMS that molecular weight is 50 000g/mol is dissolved in tetrahydrofuran,
Concentration is 10wt%.In methyl alcohol by metal ion dissolution, metal ion is slowly dropped in polymer solution under stirring, room
Temperature is stirred overnight, spare.
(3) cross-linked polymer and silica nanometer of certain volume the preparation of selfreparing photonic crystal elastomer film: are taken
Particle solution, with volume ratio 1:1 mix ultrasound 1h, using the black polypropylene plate of 8cm × 8cm as reception device, by polymer/
Method of silica/carbon black solution by spray gun spraying, quick solvent flashing, the photonic crystal that preparation non-angular relies on
Film.Its membrane area is codetermined by the size of the volume and spraying reception device that spray solution used.
Embodiment 7
(1) synthesis and modification of Nano particles of silicon dioxide: by 8mL ammonia solvent in the ethyl alcohol of 100mL, stirring is very
The TEOS of 3mL is added dropwise in Zhong Hou, and quickly stirring 15min is added dropwise, reduces mixing speed afterwards, 30 DEG C of reaction 5-6h have reacted
It is centrifuged after with the revolving speed of 8 000rpm, successively uses ethanol solution hydrochloride, water, ethanol washing, the nanoparticle being centrifuged exists
Vacuum drying obtains white solid at 50 DEG C.Afterwards by the Nano particles of silicon dioxide ultrasonic disperse of 1g in 85mL ethyl alcohol, stirring
It is lower be added dropwise ammonium hydroxide ethanol solution 30mL (88mL ammonium hydroxide/320mL ethyl alcohol), 40 DEG C of stirring 1h, then by molecular weight be 600-
The ethanol solution of the PDMS of the triethoxy sealing end of 900g/mol is slowly dropped in above-mentioned solution, and addition finishes reaction for 24 hours, produces
Object is centrifuged the silica for obtaining diameter as 270nm with the revolving speed of 7 000rpm, is successively washed with ethanol solution hydrochloride, water, ethyl alcohol
It washs, obtains white solid after centrifugal vacuum dry (50 DEG C).Finally by Nano particles of silicon dioxide ultrasonic disperse in tetrahydrofuran
In solution (10wt%), and suitable graphene (2wt%) is added in the solution, ultrasonic disperse is uniformly spare.
(2) preparation of cross-linked polymer: the cross-linked polymer preparation method in preceding embodiment 1-6 is suitble to physical crosslinking poly-
The preparation for closing object, for then needing to realize under conditions of melting when chemical crosslinking, with the crosslinking of hydroxy-end capped PDMS and boric acid
For illustrate, reaction flask is dried before reactions, is heated after mixing PDMS and boric acid in certain proportion after sample drying
It melts, the viscosity of system significantly increases after stirring 6h, and polymer is dissolved in tetrahydrofuran after completion of the reaction, removes unreacted
Boric acid, the PDMS being chemically crosslinked, revolving remove tetrahydrofuran weighing after polymer is dissolved in it is spare in tetrahydrofuran.
(3) cross-linked polymer and silica nanometer of certain volume the preparation of selfreparing photonic crystal elastomer film: are taken
Particle solution, with volume ratio 1:1 mix ultrasound 1h, using the black polypropylene plate of 8cm × 8cm as reception device, by polymer/
Method of silica/carbon black solution by spray gun spraying, quick solvent flashing, the photonic crystal that preparation non-angular relies on
Film.Its membrane area is codetermined by the size of the volume and spraying reception device that spray solution used.
Embodiment 8
(1) synthesis and modification of Nano particles of silicon dioxide: by 8mL ammonia solvent in the ethyl alcohol of 100mL, stirring is very
The TEOS of 3mL is added dropwise in Zhong Hou, and quickly stirring 15min is added dropwise, reduces mixing speed afterwards, 30 DEG C of reaction 5-6h have reacted
It is centrifuged after with the revolving speed of 8 000rpm, successively uses ethanol solution hydrochloride, water, ethanol washing, the nanoparticle being centrifuged exists
Vacuum drying obtains white solid at 50 DEG C.Afterwards by the Nano particles of silicon dioxide ultrasonic disperse of 1g in 85mL ethyl alcohol, stirring
It is lower be added dropwise ammonium hydroxide ethanol solution 30mL (88mL ammonium hydroxide/320mL ethyl alcohol), 40 DEG C of stirring 1h, then by molecular weight be 600-
The ethanol solution of the PDMS of the triethoxy sealing end of 900g/mol is slowly dropped in above-mentioned solution, and addition finishes reaction for 24 hours, produces
Object is centrifuged the silica for obtaining diameter as 270nm with the revolving speed of 7 000rpm, is successively washed with ethanol solution hydrochloride, water, ethyl alcohol
It washs, obtains white solid after centrifugal vacuum dry (50 DEG C).Finally by Nano particles of silicon dioxide ultrasonic disperse in tetrahydrofuran
In solution (10wt%), and suitable carbon black particle (2wt%) is added in the solution, ultrasonic disperse is uniformly spare.
(2) preparation of cross-linked polymer: the cross-linked polymer preparation method in preceding embodiment 1-6 is suitble to physical crosslinking poly-
The preparation for closing object blocks PDMS and cyclodextrin for then needing to realize under conditions of melting when chemical crosslinking with azobenzene
Illustrate for crosslinking (host-guest interactions), the PDMS that the azobenzene that molecular weight is 50 000g/mol blocks is dissolved in four
In hydrogen furans, concentration is 10 wt%.Beta-cyclodextrin is dissolved in tetrahydrofuran, can suitably heat, stir to improve its dissolubility
Mix it is lower beta-cyclodextrin is slowly dropped in polymer solution, be stirred at room temperature 36h or more, both guarantee that sufficiently effect, solution are protected
It deposits spare.
(3) cross-linked polymer and silica nanometer of certain volume the preparation of selfreparing photonic crystal elastomer film: are taken
Particle solution, with volume ratio 1:1 mix ultrasound 1h, using the black polypropylene plate of 8cm × 8cm as reception device, by polymer/
Method of silica/carbon black solution by spray gun spraying, quick solvent flashing, the photonic crystal that preparation non-angular relies on
Film.Its membrane area is codetermined by the size of the volume and spraying reception device that spray solution used.
Embodiment 9
(1) synthesis and modification of Nano particles of silicon dioxide: by 8mL ammonia solvent in the ethyl alcohol of 100mL, stirring is very
The TEOS of 3mL is added dropwise in Zhong Hou, and quickly stirring 15min is added dropwise, reduces mixing speed afterwards, 30 DEG C of reaction 5-6h have reacted
It is centrifuged after with the revolving speed of 8 000rpm, successively uses ethanol solution hydrochloride, water, ethanol washing, the nanoparticle being centrifuged exists
Vacuum drying obtains white solid at 50 DEG C.Afterwards by the Nano particles of silicon dioxide ultrasonic disperse of 1g in 85mL ethyl alcohol, stirring
It is lower be added dropwise ammonium hydroxide ethanol solution 30mL (88mL ammonium hydroxide/320mL ethyl alcohol), 40 DEG C of stirring 1h, then by molecular weight be 600-
The ethanol solution of the PDMS of the triethoxy sealing end of 900g/mol is slowly dropped in above-mentioned solution, and addition finishes reaction for 24 hours, produces
Object is centrifuged the silica for obtaining diameter as 270nm with the revolving speed of 7 000rpm, is successively washed with ethanol solution hydrochloride, water, ethyl alcohol
It washs, obtains white solid after centrifugal vacuum dry (50 DEG C).Finally by Nano particles of silicon dioxide ultrasonic disperse in tetrahydrofuran
In solution (10wt%), and suitable carbon black particle (2wt%) is added in the solution, ultrasonic disperse is uniformly spare.
(2) preparation of cross-linked polymer: the cross-linked polymer preparation method in preceding embodiment 1-6 is suitble to physical crosslinking poly-
The preparation for closing object, for then needing to realize under conditions of melting when chemical crosslinking, with the friendship of hydroxy-end capped PDMS and polyalcohol
Illustrate for connection (interaction of hydrogen bond), the PDMS for the side chain hydroxyl that molecular weight is 50 000g/mol is dissolved in tetrahydro furan
In muttering, concentration 10wt%.Polyhydroxy small molecule is dissolved in tetrahydrofuran, is slowly dropped to polymer solution under stirring
In, it is stirred overnight at room temperature, solution saves backup.
(3) cross-linked polymer and silica nanometer of certain volume the preparation of selfreparing photonic crystal elastomer film: are taken
Particle solution, with volume ratio 1:1 mix ultrasound 1h, using the black polypropylene plate of 8cm × 8cm as reception device, by polymer/
Method of silica/carbon black solution by spray gun spraying, quick solvent flashing (solvent evaporation rate is greater than 20mL/h), system
The crystal film with photon that standby non-angular relies on.Its membrane area is common by the size for spraying the volume and spraying reception device of solution used
It determines.
Embodiment 10
(1) synthesis and modification of Nano particles of silicon dioxide: by 8mL ammonia solvent in the ethyl alcohol of 100mL, stirring is very
The TEOS of 3mL is added dropwise in Zhong Hou, and quickly stirring 15min is added dropwise, reduces mixing speed afterwards, 30 DEG C of reaction 5-6h have reacted
It is centrifuged after with the revolving speed of 8 000rpm, successively uses ethanol solution hydrochloride, water and ethanol washing, the nanoparticle being centrifuged exists
White solid is obtained after being dried in vacuo at 50 DEG C.Then by the Nano particles of silicon dioxide ultrasonic disperse of 1g in 85mL ethyl alcohol,
Lower ethanol solution 30mL (88mL ammonium hydroxide/320mL ethyl alcohol), the 40 DEG C of stirring 1h that ammonium hydroxide is added dropwise of stirring, then by molecular weight be 600-
The ethanol solution of the PDMS of the triethoxy sealing end of 900g/mol is slowly dropped in above-mentioned solution, and addition finishes reaction for 24 hours, produces
Object is centrifuged the silica for obtaining diameter as 270nm with the revolving speed of 7 000rpm, is successively washed with ethanol solution hydrochloride, water and ethyl alcohol
It washs, obtains white solid after centrifugal vacuum dry (50 DEG C).Finally by Nano particles of silicon dioxide ultrasonic disperse in tetrahydrofuran
In solution (10wt%), and suitable carbon black particle (2wt%) is added in the solution, ultrasonic disperse is uniformly spare.
(2) preparation of cross-linked polymer solution: molecular weight is molten for the amino-terminated butyl polyacrylate of 50 000g/mol
Solution is in tetrahydrofuran, concentration 10wt%.In methyl alcohol (0.05-2g/mL) by cerium chloride dissolution, by cerium chloride under stirring
Methanol solution is slowly dropped in polymer solution, is stirred overnight at room temperature, spare.
(3) preparation of selfreparing crystal film with photon: take the cross-linked polymer of certain volume and Nano particles of silicon dioxide molten
Liquid mixes ultrasound 1h with volume ratio 1:1, using the black polypropylene plate of 8cm × 8cm as reception device, by polymer/titanium dioxide
Method of silicon/carbon black solution by spray gun spraying, quick solvent flashing, the crystal film with photon that preparation non-angular relies on.Its film
Area is codetermined by the size of the volume and spraying reception device that spray solution used.
Fig. 1 is the scanning electricity for four kinds of various sizes of Nano particles of silicon dioxide that embodiment 1 is synthesized according to the method
Mirror picture.Fig. 1 (a) prepare blue photons film thus improved silica nanoparticle；Fig. 1 (b) prepares green photon film institute
With improved silica nanoparticle；Fig. 1 (c) prepare the sub- film of yellow colour thus improved silica nanoparticle；Fig. 1
(d) prepare red photon film thus improved silica nanoparticle the case where dispersing in PDMS.As can be seen from the figure
Nanoparticle has apparent monodispersity, and forms shot-range ordered structure in the polymer.Embodiment only gives a kind of ruler
The synthetic method of very little nanoparticle, because the synthetic method of nanoparticle is identical, by changing the concentration of ammonium hydroxide and the amount of water
The size that nanoparticle can be changed, by regulate and control nanoparticle size can prepare the crystal film with photon of different colours with
Meet requirement.In addition from Fig. 1 (d) as can be seen that a part is in close when silica disperses in PDMS matrix
The structure of accumulation, and wherein also have biggish gap, this illustrates that Nano particles of silicon dioxide forms short distance in crystal film with photon
Ordered structure, this is also that crystal film with photon does not have the reason of dependence of angle.
Fig. 2 is four kinds of various sizes of improved silica nanoparticles and the crosslinking of embodiment 2-6 the method synthesis
The digital photograph (Fig. 2 (a)) and spectrogram (Fig. 2 (b)) for the crystal film with photon that polymer is prepared after being blended.The sample exists
Shown in the variation relation such as Fig. 2 (c) of the maximum absorption band of different angle with angle, this illustrates that the sample does not have dependence of angle.
Fig. 2 (d) is cross-linked polymer and the drawing for adding the crystal film with photon prepared after four kinds of various sizes of Nano particles of silicon dioxide
Curve is stretched, after adding various sizes of improved silica nanoparticle in cross-linked polymer as seen from the figure, is broken
It splits elongation to significantly improve, shows preferable tensile property, sample has preferable elasticity.
Fig. 3 is that four kinds of different colours photonic crystal elastomer films of embodiment 1-6 preparation are obtained in different angle observations
The spectrogram arrived: Fig. 3 (a) blue photons crystal film, Fig. 3 (b) green photon crystal film, Fig. 3 (c) yellow photons crystal film, Fig. 3
(d) red photon crystal film.Maximum absorption band when observing sample from different perspectives, in the spectrogram of obtained crystal film with photon
Position and viewing angle relational graph, find out that the position of maximum absorption band is basically unchanged from figure, spectrum peak is also shown well
Monochromaticjty, this further illustrates that the crystal film with photon does not have dependence of angle.
Fig. 4 be embodiment 2 prepare crystal film with photon, surface have scratch (blade is scratched) afterwards (Fig. 4 (a)) at 60 DEG C
The digital photograph of (Fig. 4 (b)) after lower placement 48h.Illustrating can the selfreparing within the regular hour after the film surface is impaired.
Fig. 5 be embodiment 2 be the crystal film with photon after being scratched with knife, 60 DEG C of reparation certain times (6h, for 24 hours,
Extension test data after 48h) have preferable tensile property repairing sample after a certain period of time, with the selfreparing time
Extend, the sample of (the most deep curve of color) before the closer reparation of the tensile property of sample.
As it will be easily appreciated by one skilled in the art that the foregoing is merely illustrative of the preferred embodiments of the present invention, not to
The limitation present invention, any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should all include
Within protection scope of the present invention.
Claims (12)
1. a kind of Responsive photonic crystals elastomeric film material, which is characterized in that received including cross-linked polymer matrix material, modification
Rice corpuscles and extinction nano material；Mole of the cross-linked polymer matrix material, modified Nano particle and extinction nano material
Than for (1~200): 100:(0~5)；The modified Nano particle and the extinction nano material are dispersed in the cross-linked polymeric
In object basis material, the color of the photonic crystal elastomeric film material does not change with viewing angle, the energy after mechanical damage occurs
It is enough automatically repaired, there is elasticity during stretching.
2. photonic crystal elastomeric film material as described in claim 1, which is characterized in that the size of the modified Nano particle
For 100~500nm；The size of the extinction nano material is 10~100nm.
3. photonic crystal elastomeric film material as described in claim 1, which is characterized in that the cross-linked polymer matrix material
By the way that coordination, host-guest interactions, hydrogen bond or chemical crosslink reaction occurs between crosslinking agent and the functional group of polymer
The cross-linked polymer with network structure formed, the polymer are transparent, flexible functionalized polymer, described poly-
The refraction index for closing object is 1.2~2.0；The functionalized polymer contains amino, pyridine groups, imidazoles, azobenzene, ring paste
At least one of essence, hydroxyl, sulfydryl, boric acid or adamantane double bond；The glass transition temperature of the polymer is lower than 25 DEG C；
The molar ratio of the polymer and the crosslinking agent is 0.05:1~6:1.
4. photonic crystal elastomeric film material as claimed in claim 3, which is characterized in that the crosslinking agent be selected from metal from
Son, cyclodextrin, boric acid, polyalcohol, multi-thiol and diolefin.
5. photonic crystal elastomeric film material as claimed in claim 4, which is characterized in that the metal ion is with empty rail
Alkaline-earth metal ions, transition metal ions or the rare earth ion in road.
6. photonic crystal elastomeric film material as described in claim 1, which is characterized in that the modified Nano particle is by receiving
Rice corpuscles carried out under the action of modifying agent it is cross-linking modified obtain, the nanoparticle is not dissolve in organic solvent, and ruler
Very little medicine ball or core-shell structure spheroidal particle within the scope of 100~500nm, the modifying agent are that molecular weight is less than 40000g/
The oil-soluble polymers of mol.
7. photonic crystal elastomeric film material as claimed in claim 6, which is characterized in that the nanoparticle is SiO2Nanometer
Particle, polystyrene nanoparticle or polymethylacrylic acid nanoparticle.
8. photonic crystal elastomeric film material as described in claim 1, which is characterized in that the extinction nano material is selected from charcoal
Black, CNT, graphene, fullerene, PbS and CuS.
9. a kind of preparation method of Responsive photonic crystals elastomeric film material, which comprises the steps of:
(1) preparation of modified Nano particle: nanoparticle is subjected to chemistry by sol-gal process under the action of modifying agent and is changed
Property, then in organic solvent by modified nanoparticle dispersion, wherein the mass concentration of modified Nano particle be 1%~
50%；The nanoparticle is will not dissolve in organic solvent, and medicine ball or core of the size within the scope of 100~500nm
Shell structure spheroidal particle；The modifying agent is the oil-soluble polymers that molecular weight is less than 40000g/mol；
(2) it the preparation of cross-linked polymer: obtains after transparent, elastic functionalized polymer is dissolved or melted containing polymer
Organic solution, then crosslinking agent is added dropwise in the organic solution containing polymer, the polymer and the crosslinking
The molar ratio of agent is 0.05:1~6:1；By the way that coordination, main-visitor occurs between the crosslinking agent and the functional group of the polymer
Body interaction, hydrogen bond or chemical crosslink reaction and form the cross-linked polymer with self-repair function with network structure；
The cross-linked polymer is colorless and transparent, and refraction index is 1.2~2.0；The functionalized polymer contains amino, pyridyl group
At least one of group, imidazoles, azobenzene, cyclodextrin, hydroxyl, sulfydryl, boric acid or adamantane double bond；The crosslinking agent is selected from gold
Belong to ion, cyclodextrin, boric acid, polyalcohol, multi-thiol and diolefin；The cross-linked polymer prepared is dispersed in organic solvent
In, wherein the mass concentration of cross-linked polymer is 1%~65%；
(3) preparation of photonic crystal elastic film material: by step (1) dispersion described modified Nano particle in organic solvent with
The cross-linked polymer of extinction nano material and step (2) dispersion in organic solvent is according to mass ratio 100:(0~5): (1
~200) Hybrid assembling body, is obtained in hydrophobic and organic solvent-resistant material surface or container internal mix, in 20~70 DEG C of items
Organic solvent under part in Hybrid assembling body described in fast eliminating obtains photonic crystal elastic film material, wherein the organic solvent
Removing rate be greater than 0.4ml/min；Or the Hybrid assembling body is placed in spraying container, it is sprayed into the hydrophobic material
Surface obtains photonic crystal elastic film material；
Wherein, the Flory-Huggin interaction parameter of step (1) modifying agent and step (2) described cross-linked polymer is not
Greater than 0.5, it is ensured that modified Nano particle described in step (3) can dissolve each other with the cross-linked polymer.
10. preparation method as claimed in claim 9, which is characterized in that the organic solvent is selected from tetrahydrofuran, chloroform, two
Chloromethanes, hexamethylene, DMSO, DMF, benzene, methanol, ethyl alcohol, isopropanol, pyridine, toluene, ethyl acetate and acetone.
11. preparation method as claimed in claim 9, which is characterized in that the molecular weight of step (2) described polymer be 5000~
1,000,000g/mol。
12. photonic crystal elastomer film made from the photonic crystal elastomeric film material as described in claim 1 to 8 any one
Application, which is characterized in that be applied to anti-fake, wearable, fingerprint recognition, sensor, coating or paint field.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810216897.XA CN108318943B (en) | 2018-03-16 | 2018-03-16 | A kind of Responsive photonic crystals elastomeric film material, its preparation and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810216897.XA CN108318943B (en) | 2018-03-16 | 2018-03-16 | A kind of Responsive photonic crystals elastomeric film material, its preparation and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108318943A CN108318943A (en) | 2018-07-24 |
| CN108318943B true CN108318943B (en) | 2019-07-19 |
Family
ID=62897836
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810216897.XA Active CN108318943B (en) | 2018-03-16 | 2018-03-16 | A kind of Responsive photonic crystals elastomeric film material, its preparation and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108318943B (en) |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109606002A (en) * | 2018-12-03 | 2019-04-12 | Oppo（重庆）智能科技有限公司 | Shell of electronic equipment and preparation method thereof, electronic equipment |
| CN111378182A (en) * | 2019-01-01 | 2020-07-07 | 翁秋梅 | Force-induced responsive polymer with single-hybrid network structure |
| CN110767075B (en) * | 2019-12-05 | 2022-04-08 | 南方科技大学 | Flexible anti-counterfeiting layer based on metal micro-nano network, and preparation method and application thereof |
| CN110908145B (en) * | 2019-12-13 | 2023-12-01 | 中国科学院深圳先进技术研究院 | Photonic crystal material with irreversible temperature responsiveness and preparation method thereof |
| CN111117263A (en) * | 2019-12-30 | 2020-05-08 | 武汉华星光电半导体显示技术有限公司 | Polyimide composite, preparation method and application thereof |
| CN111925723B (en) * | 2020-03-19 | 2021-10-08 | 华中科技大学 | Method for preparing structural color coating with photochromic capability |
| CN111349351B (en) * | 2020-04-17 | 2021-03-02 | 南京鼓楼医院 | Preparation method of photonic crystal microspheres based on multi-shell nanoparticles |
| CN111849260B (en) * | 2020-07-01 | 2021-11-16 | 武汉理工大学 | Preparation method of aging-resistant flame-retardant decorative photonic crystal structure color film |
| CN111904952A (en) * | 2020-08-20 | 2020-11-10 | 东南大学苏州医疗器械研究院 | Scar plaster and preparation method thereof |
| CN113739715B (en) * | 2021-08-26 | 2023-04-28 | 西安交通大学 | Flexible strain sensor based on fold structural color and preparation method thereof |
| CN114031946B (en) * | 2021-10-20 | 2023-04-07 | 安徽大学 | Photonic crystal film and preparation method and application thereof |
| CN115321829A (en) * | 2022-02-22 | 2022-11-11 | 江苏铁锚玻璃股份有限公司 | Fluoride-free and self-repairable super-hydrophobic glass and preparation method thereof |
| CN115232344A (en) * | 2022-07-22 | 2022-10-25 | 山东东辰瑞森新材料科技有限公司 | Coordination elastic photonic crystal structure color material and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104672485A (en) * | 2015-02-13 | 2015-06-03 | 华中科技大学 | Photonic crystal thin film as well as preparation method and application thereof |
| CN106040114A (en) * | 2016-05-24 | 2016-10-26 | 华中科技大学 | Hydrogel photonic crystal microspheres, and preparation method and application thereof |
| CN106547040A (en) * | 2016-11-23 | 2017-03-29 | 大连理工大学 | A kind of high intensity crystal film with photon and preparation method thereof |
| CN107121714A (en) * | 2017-04-28 | 2017-09-01 | 华南理工大学 | A kind of colour generation has free from flaw photonic crystal of low angle dependence and preparation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6158248B2 (en) * | 2014-05-27 | 2017-07-05 | ザ・ボード・オブ・トラスティーズ・オブ・ザ・ユニバーシティ・オブ・イリノイＴｈｅ Ｂｏａｒｄ Ｏｆ Ｔｒｕｓｔｅｅｓ Ｏｆ Ｔｈｅ Ｕｎｉｖｅｒｓｉｔｙ Ｏｆ Ｉｌｌｉｎｏｉｓ | Nanostructured material methods and devices |
-
2018
- 2018-03-16 CN CN201810216897.XA patent/CN108318943B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104672485A (en) * | 2015-02-13 | 2015-06-03 | 华中科技大学 | Photonic crystal thin film as well as preparation method and application thereof |
| CN106040114A (en) * | 2016-05-24 | 2016-10-26 | 华中科技大学 | Hydrogel photonic crystal microspheres, and preparation method and application thereof |
| CN106547040A (en) * | 2016-11-23 | 2017-03-29 | 大连理工大学 | A kind of high intensity crystal film with photon and preparation method thereof |
| CN107121714A (en) * | 2017-04-28 | 2017-09-01 | 华南理工大学 | A kind of colour generation has free from flaw photonic crystal of low angle dependence and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108318943A (en) | 2018-07-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108318943B (en) | A kind of Responsive photonic crystals elastomeric film material, its preparation and application | |
| Qiu et al. | Preparation, characterization and properties of UV-curable waterborne polyurethane acrylate/SiO 2 coating | |
| CN105102498B (en) | Copolymer and hydrophilic material comprising same | |
| CN105086726B (en) | Aqueous coating agent composition, water paint, film and coated articles | |
| KR102019707B1 (en) | Hollow particles, method for producing same, use thereof, and method for producing microcapsule particles | |
| Ribot et al. | New Photochromic Hybrid Organic–Inorganic Materials Built from Well‐Defined Nano‐Building Blocks | |
| CN102791826B (en) | Methods for producing photosensitive microparticles | |
| CN106574099A (en) | Hydrophilic material comprising sulfonate copolymer and amino resin | |
| CN105722940B (en) | Ultraviolet scattering diluent and application thereof | |
| CN103588955A (en) | Fluorine-containing epoxy resin and preparation method thereof, and double-super-hydrophobic surface preparing from fluorine-containing epoxy resin | |
| Shen et al. | Facile fabrication of mechanically stable non-iridescent structural color coatings | |
| CN111593492B (en) | Method for preparing liquid crystal display backlight film based on high-strength nanofiber film | |
| CN102464938B (en) | Plastic cement list is coated with painted UV radiation curable coating and production thereof, using method | |
| CN110272679B (en) | Ultraviolet light curing paint phenolic hyperbranched super-amphiphobic anticorrosive paint and preparation method thereof | |
| US11820853B2 (en) | Impact-resistant and aging-resistant reflective plastic applied to automobiles | |
| TW201734056A (en) | Hollow particle and use thereof | |
| CN109629326A (en) | A kind of preparation method and application obstructing hydrophobic paper base coating | |
| CN108355588A (en) | A method of synthesizing microballoon on super-double-hydrophobic surface | |
| KR101556837B1 (en) | Polyhydroxyurethane microparticles, and process for producing same | |
| CN105524551B (en) | Optical coating, the manufacture method of optical coating and antireflection film | |
| CN106590179A (en) | CNC/PEG composite coating and preparation method thereof | |
| CN107602792A (en) | A kind of preparation method of transparent polyurethane | |
| JP4022639B2 (en) | Organic / inorganic hybrid material and method for producing the same | |
| CN113980486B (en) | Preparation method of soap-free chemical crosslinking type copolymer nanoparticle coated organic pigment hybrid latex | |
| Sun et al. | Layer-by-layer fabrication of fluorescent microspheres using micelles as a spacer: simultaneously realizing fluorescence enhancement and introduction of bioconjugation sites |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |