CN113103706A - Electrochromic photonic crystal film and preparation method and application thereof - Google Patents

Electrochromic photonic crystal film and preparation method and application thereof Download PDF

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CN113103706A
CN113103706A CN202110325703.1A CN202110325703A CN113103706A CN 113103706 A CN113103706 A CN 113103706A CN 202110325703 A CN202110325703 A CN 202110325703A CN 113103706 A CN113103706 A CN 113103706A
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photonic crystal
crystal film
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CN113103706B (en
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田丰
赵国伟
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Phomera Technologies Zhuhai Co ltd
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Phomera Technologies Zhuhai Co ltd
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    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
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    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
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    • B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
    • B05D5/06—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain multicolour or other optical effects
    • B05D5/061—Special surface effect
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    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
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    • B32B27/00—Layered products comprising a layer of synthetic resin
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    • B32—LAYERED PRODUCTS
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    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
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    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60J—WINDOWS, WINDSCREENS, NON-FIXED ROOFS, DOORS, OR SIMILAR DEVICES FOR VEHICLES; REMOVABLE EXTERNAL PROTECTIVE COVERINGS SPECIALLY ADAPTED FOR VEHICLES
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
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    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
    • C09D151/003—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/63—Additives non-macromolecular organic
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
    • B32B37/24—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer not being coherent before laminating, e.g. made up from granular material sprinkled onto a substrate
    • B32B2037/243—Coating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/40—Symmetrical or sandwich layers, e.g. ABA, ABCBA, ABCCBA
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00—Coating on the layer surface
    • B32B2255/10—Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00—Coating on the layer surface
    • B32B2255/26—Polymeric coating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/402—Coloured
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2419/00—Buildings or parts thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2605/00—Vehicles
    • 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
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
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    • C08J2451/00—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
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    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
    • C08L2205/18—Spheres

Abstract

The invention provides an electrochromic photonic crystal film and a preparation method and application thereof, wherein the preparation method of the electrochromic photonic crystal film comprises the following steps: s1, preparing polymer nano microsphere emulsion; s2, drying the emulsion to obtain nano micro-aggregates; s3, uniformly dispersing the nanosphere aggregate into a solution of a viologen compound to form gel, coating the gel between an upper layer of ITO-PET substrate and a lower layer of ITO-PET substrate to form a sandwich structure, and then performing rolling treatment to obtain a composite film material; s4, subjecting the composite film to vibration shearing and arranging equipment to obtain the photonic crystal film with the nano microspheres arranged in a three-dimensional ordered manner between the upper layer of ITO-PET substrate and the lower layer of ITO-PET substrate, wherein the prepared electrochromic photonic crystal film comprises a periodic array of the nano microspheres, and organic viologen compounds with reversible electro-redox activity are filled between the nano microspheres in the array.

Description

Electrochromic photonic crystal film and preparation method and application thereof
Technical Field
The invention relates to the field of optical functional materials, in particular to an electrochromic photonic crystal film and a preparation method and application thereof.
Background
A material having electrochromic properties is referred to as an electrochromic material. The electrochromic property is a phenomenon that the optical properties (reflectivity, transmittance, absorptivity and the like) of the material generate stable and reversible color change under the action of an external electric field, and the material is represented as reversible change of color and transparency in appearance. The existing electrochromic materials comprise inorganic electrochromic materials and organic electrochromic materials, wherein the inorganic electrochromic materials are mostly transition metal oxides or derivatives thereof, such as: WO3 or NiO; the organic electrochromic material can be divided into organic micromolecule electrochromic material and conductive polymer electrochromic material, the organic micromolecule can be viologen compound, and the conductive polymer can be conductive polyacetylene. The existing electrochromic materials are numerous, but the existing electrochromic materials are subjected to single color change under the control of voltage within a certain range, so that the application range of the existing electrochromic materials is narrow.
The photonic crystal is an optical material with different dielectric constants and spatially and periodically distributed. The color development principle of the photonic crystal film is that light is modulated by Bragg diffraction of a periodic structure, and corresponding structural color can be obtained by reflecting, refracting and diffracting the light of the photonic crystal; that is, the characteristic of the periodic structure of the photonic crystal can correspond to different extensions of the angle of incident light and the observation angle, so that when the photonic crystal film is observed, the change of different colors of the photonic crystal can be observed along with the difference of the observation angle, and the current photonic crystal film can only display the colors which can be displayed by the photonic crystal film and cannot further display richer colors although the change of multiple colors can be realized.
Disclosure of Invention
The first purpose of the invention is to provide an electrochromic photonic crystal film with richer color development.
The second purpose of the invention is to provide a preparation method of the electrochromic photonic crystal film.
The third purpose of the invention is to provide the application of the electrochromic photonic crystal film.
In order to achieve the first object, the electrochromic photonic crystal film provided by the invention comprises a periodic array of nano microspheres, wherein the nano microspheres in the periodic array of nano microspheres are arranged in a three-dimensional order, and organic viologens with reversible electro-redox activity are filled between the nano microspheres.
According to the scheme, after the organic compound with reversible electro-redox activity is electrified, the organic compound can present different redox states and colors thereof at different voltages and reduction times; wherein the purple essence compound is named as 1,1 '-disubstituted-4, 4' -bipyridine, and strong electric transfer exists between purple essence compound molecules in the photonic crystal film after the photonic crystal film is electrified, so that monovalent cation (RV)+·) Coloring, wherein the lengths of substituent groups in the viologen compounds are different, so that the viologen compounds are in redox states with different colors; the refractive index difference between the continuous phase of photon crystal with electrically corresponding organic viologen compound as main body and the dispersed phase of photon crystal with nanometer microballoon as main body is also changed under the action of voltage, so that the color of the photon crystal film is changed under the same incident light and observation angle, and the color change of the photon crystal film is coupled with the two effects produced by the color change of the photon crystal of the non-electrically responsive nanometer microballoon periodic array photon crystal without changingOn the premise of changing the periodic array structure of the nano microspheres, brand new color and change completely different from the color of a non-electric-response photonic crystal structure are obtained by changing the state of the electric-response material through voltage, the color change degree of the photonic crystal film is further expanded, the photonic crystal film presents more different dynamic color development processes, and the application degree of the photonic crystal film is improved.
The further proposal is that the photonic crystal film has the response time of 300ms to 10s and the repetition period of 1,000 times to 100,000 times under the electrification of the response voltage interval of 0.3V to 3.0V and the static current interval of 0.1mA to 0.2 mA.
In a further scheme, the absorption wavelength of the photonic crystal film is changed between 470nm and 700 nm.
The further proposal is that the substituent of the viologen compound is alkyl, benzyl or cyano; the length of the substituent is a carbon chain or a side chain formed by connecting 1 to 12 carbon atoms.
In order to achieve the second object, the preparation method of the electrochromic photonic crystal film provided by the invention is used for preparing the photonic crystal film;
the preparation method comprises the following steps:
s1, preparing polymer nano microsphere emulsion;
s2, drying the polymer nano microsphere emulsion to obtain a nano micro-sphere polymer;
s3, uniformly dispersing the nanosphere aggregate into a solution of a viologen compound to form gel, coating the gel between an upper layer of ITO-PET substrate and a lower layer of ITO-PET substrate to form a sandwich structure, and then performing rolling treatment to obtain a composite film material;
s4, subjecting the composite film to vibration shearing and arranging equipment to obtain the photonic crystal film with the three-dimensional ordered arrangement of the nano microspheres between the upper layer of ITO-PET substrate and the lower layer of ITO-PET substrate.
According to the scheme, the nanometer microsphere emulsion is directly dried and then mixed with the viologen compound, the nanometer microsphere emulsion is directly dried after being prepared by an emulsion polymerization method or other methods, the steps of emulsion breaking, washing, dehydration and the like are not needed, the production process can be greatly simplified, and after the nanometer microsphere aggregate and the viologen compound are mixed to form gel, the gel is coated on the sheet in a coating mode, so that the coating is uniform, and the color change effect is better.
The further scheme is that the solvent in the solution of the viologen compound is acetonitrile, DMF or DMSO.
The further scheme is that the viologen compound is obtained by dissolving 4, 4' -bipyridine in a solvent to obtain a mixed solution, adding soluble salt into the mixed solution for reaction, wherein the negative ion in the soluble salt is PF6 -、AsF6 -、ClO4 -、CH3COO-、CH3(C6H4)SO3 -Or a halide ion.
In order to realize the third purpose of the invention, the invention provides an electrochromic photonic crystal film which is applied to the fields of architectural glass, vehicle-mounted glass and consumer electronic backboard glass.
Detailed Description
The electrochromic photonic crystal film can be applied to building glass, vehicle window glass, consumer electronics backboard glass, intelligent wearing materials and anti-counterfeiting packages, and is arranged on glass or other carriers, so that privacy is protected, certain color vision is brought, and the use comfort is improved; after the power is switched on, the refractive index between the nano microspheres and the electric responsive material is changed, so that the photonic crystal film presents color change different from the periodic array of the nano microspheres in the photonic crystal film, and the color change of the periodic array of the nano microspheres is combined with the color change of the periodic array of the nano microspheres, so that the visual effect is richer.
Example 1
The electrochromic photonic crystal film in example 1 includes a periodic array of nano-microspheres, and viologen compounds are filled between the nano-microspheres in the array, and the viologen compounds are 1,1 '-diethyl-4, 4' -bipyridine;
the preparation method of the electrochromic photonic crystal film comprises the following steps:
s1, preparing polymer nano microsphere emulsion with solid content of 10-50%;
s2, drying the polymer nano microsphere emulsion to obtain a nano microsphere aggregate, wherein the specific preparation processes of the step S1 and the step S2 refer to the preparation of the nano microspheres in (1) in example 1 of the Chinese patent application CN 105949379A;
s3, preparing viologen compounds: dissolving 4, 4' -bipyridine in a solvent to obtain a mixed solution, adding a soluble salt into the mixed solution, and reacting to obtain a viologen compound, wherein the preparation process refers to the content of 2.1 small-molecule viologen in the page 2 in the preparation and mechanism of the viologen electrochromic material in the period 20, volume 9 of chemical evolution published in 2008, 9.9, wherein the dosage, the solvent type and the soluble salt type of each component are changed according to actual production; or purchased directly from the market, e.g. by means of the site Chemical Book, under the CAS number 46713-38-6;
s4, uniformly dispersing the nanosphere aggregate into a solution of a viologen compound to form gel, coating the gel on an upper layer of ITO-PET substrate and a lower layer of ITO-PET substrate to form a sandwich structure, and then performing rolling treatment to obtain a composite film material;
s5, subjecting the composite film to vibration shearing and arranging equipment to obtain 0.1-1000 m of photonic crystal film with three-dimensional ordered arrangement of nano microspheres between an upper layer of ITO-PET substrate and a lower layer of ITO-PET substrate.
The photonic crystal thin film in example 1 was electrified at a voltage of 3.0V and a static current of 0.1 mA.
Example 2
The preparation method of the photonic crystal thin film in the embodiment 2 is substantially the same, except that: at least one of the substituents on both sides of the viologen-based compound has a cyano group (-C.ident.N).
The photonic crystal thin film in example 2 was energized under the same energizing conditions as those in example 1.
Example 3
The preparation method of the photonic crystal thin film in the embodiment 3 is substantially the same, except that: counter ions in the viologen compounds are Br-Is replaced byPF6 -。
The photonic crystal thin film in example 3 was energized under the same energizing conditions as those in example 1.
Example 4
The preparation method of the photonic crystal thin film in example 4 is the same. The photonic crystal thin film in example 6 was energized under substantially the same energizing conditions as those in example 1, except that: the response voltage is 1V, and the power-on time is 2 min.
Example 5
The preparation method of the photonic crystal thin film in example 5 is the same. The photonic crystal thin film in example 7 was energized under substantially the same energizing conditions as those in example 1, except that: the response voltage was 5V.
Comparative example 1
The photonic crystal film in comparative example 1 is the same as that in example 1, but the photonic crystal film in comparative example 1 is not energized.
Comparative example 2
The method of manufacturing the photonic crystal thin film in comparative example 1 is substantially the same as the method of manufacturing the photonic crystal thin film in example 1 except that: the composite membrane material in the S6 does not pass through a vibration shearing and arranging device.
The photonic crystal thin film in comparative example 2 was energized under the same energizing conditions as those in example 1.
Comparative example 3
The method of manufacturing the photonic crystal thin film in comparative example 1 is substantially the same as the method of manufacturing the photonic crystal thin film in example 1 except that: the non-electric response material filled between the nanometer microspheres is polyurethane acrylate.
The photonic crystal thin film in comparative example 3 was energized under the same energizing conditions as those in example 1.
The finally obtained films of examples 1 to 5 and comparative examples 1 to 3 were respectively subjected to energization, the change in the position of the reflection peak and the corresponding time during energization were recorded, and the color change of the final film was observed by naked eyes, and the results are shown in table 1.
TABLE 1
Figure BDA0002994592830000061
As can be seen from table 1, the viologens used in the embodiments 1, 2 and 2 are different, so that the difference in refractive index between the electrically responsive material and the nanospheres is different, so that the colors of the photonic crystal films in the embodiments 1 to 3 before power-on are different, and after power-on, the viologens react to make the photonic crystal films show different colors, so that users can use different types of viologens according to their favorite color changes, and the photonic crystal films containing the electrically responsive material show different dynamic changes of color before and after power-on. The same photonic crystal thin film is electrified with different voltages in example 4 and example 5, and the electrifying pressure in example 4 is smaller, so that the electric response material reacts more slowly, and the response time of the final photonic crystal thin film is longer. Example 1 and comparative example 1 are compared, and under the condition of no electricity, the electric responsive material is not reacted, so that the color of the photonic crystal film is not changed. Example 1 corresponds to comparative example 2, because the nano microspheres in the film in comparative example 2 are not arranged in a three-dimensional order, the nano microsphere array cannot refract the color, and the color change in comparative example 2 is only the color change before and after the electric response material is electrified. Compared with the comparative example 3, in the comparative example 1, the photonic crystal film is added with the non-electric responsive material, so that the non-electric responsive material does not react after being electrified, and the photonic crystal film in the comparative example 1 does not generate color change and maintains dynamic color change before being electrified.
Finally, it should be emphasized that the above-described preferred embodiments of the present invention are merely examples of implementations, rather than limitations, and that many variations and modifications of the invention are possible to those skilled in the art, without departing from the spirit and scope of the invention.

Claims (8)

1. An electrochromic photonic crystal film, comprising: the nanometer microspheres in the nanometer microsphere periodic array are arranged in a three-dimensional order, and organic viologens compounds with reversible electro-redox activity are filled among the nanometer microspheres.
2. The electrochromic photonic crystal thin film of claim 1, wherein:
the photonic crystal film has a response time of 300ms to 10s and a repetition period of 1,000 times to 100,000 times under the electrification of a response voltage interval of 0.3V to 3.0V and a static current interval of 0.1mA to 0.2 mA.
3. The electrochromic photonic crystal thin film of claim 1, wherein:
the absorption wavelength of the photonic crystal film is changed between 470nm and 700 nm.
4. The electrochromic photonic crystal thin film of claim 1, wherein:
the substituent of the viologen compound is alkyl, benzyl or cyano; the length of the substituent is a carbon chain or a side chain formed by connecting 1 to 12 carbon atoms.
5. The preparation method of the electrochromic photonic crystal film is characterized by comprising the following steps: the preparation method prepares the photonic crystal film as described in any one of claims 1 to 4;
the preparation method comprises the following steps:
s1, preparing polymer nano microsphere emulsion;
s2, drying the polymer nano microsphere emulsion to obtain a nano microsphere aggregate;
s3, uniformly dispersing the nanosphere aggregate into a solution of a viologen compound to form gel, coating the gel between an upper layer of ITO-PET substrate and a lower layer of ITO-PET substrate to form a sandwich structure, and then performing rolling treatment to obtain a composite film material;
s4, subjecting the composite film to vibration shearing and arranging equipment to obtain the photonic crystal film with the nano microspheres arranged in a three-dimensional ordered manner, wherein the photonic crystal film is positioned between an upper layer and a lower layer of the ITO-PET base materials.
6. The method for preparing an electrochromic photonic crystal film according to claim 5, wherein:
the solvent in the solution of the viologen compound is acetonitrile, DMF or DMSO.
7. The method for preparing an electrochromic photonic crystal film according to claim 5, wherein:
the viologen compound is obtained by dissolving 4, 4' -bipyridine in a solvent to obtain a mixed solution, adding soluble salt into the mixed solution for reaction, wherein negative ions in the soluble salt are PF6 -、AsF6 -、ClO4 -、CH3COO-、CH3(C6H4)SO3 -Or a halide ion.
8. The application of the electrochromic photonic crystal film is characterized in that: the electrochromic photonic crystal film is the photonic crystal film as claimed in any one of claims 1 to 4, and the photonic crystal film is applied to architectural glass, vehicle-mounted glass and electronic equipment back panel glass.
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