CN113386437B - Flexible photonic crystal material with temperature/voltage response color change and preparation method thereof - Google Patents

Flexible photonic crystal material with temperature/voltage response color change and preparation method thereof Download PDF

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CN113386437B
CN113386437B CN202110613994.4A CN202110613994A CN113386437B CN 113386437 B CN113386437 B CN 113386437B CN 202110613994 A CN202110613994 A CN 202110613994A CN 113386437 B CN113386437 B CN 113386437B
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photonic crystal
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color
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CN113386437A (en
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汪长春
黄翰闻
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Zhongshan Fudan Joint Innovation Center
Zhongshan Lanhong Technology Co ltd
Fudan University
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Zhongshan Fudan Joint Innovation Center
Zhongshan Lanhong Technology Co ltd
Fudan University
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    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
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    • C08J2461/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
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    • C08K3/20—Oxides; Hydroxides
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
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    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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    • C08K3/20—Oxides; Hydroxides
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    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/10—Encapsulated ingredients

Abstract

The invention discloses a flexible photonic crystal material with temperature/voltage response color change and a preparation method thereof. The flexible photonic crystal material consists of a PET-ITO film, a temperature/voltage color-changing photonic crystal film and a PET-ITO film; the preparation method comprises the following steps: synthesizing an emulsion of monodisperse core-shell polymer microspheres, drying to obtain a microsphere solid, blending with a temperature-sensitive pigment, an electrochromic material and a dispersion medium, and shearing, inducing and regulating to enable the composite membrane to generate a bright structural color; the photonic crystal microsphere structure comprises a crosslinked hard core layer, an intermediate connecting layer and a soft shell layer; the temperature-sensitive pigment is microcapsule particles; the electrochromic material is an organic color-changing molecule and/or an inorganic color-changing material; the film of the invention can produce different color-changing effects under different temperatures and voltages, and has various color changes under different temperatures; the transmittance of the film can be changed after voltage is applied; is suitable for the next generation of intelligent color-changing window materials.

Description

Flexible photonic crystal material with temperature/voltage response color change and preparation method thereof
Technical Field
The invention belongs to the technical field of intelligent response materials, and particularly relates to a flexible photonic crystal material with temperature/voltage response color change and a preparation method thereof.
Background
Photonic crystal material is a dielectric material with periodically arranged refractive index, which can regulate the propagation of light, i.e. selectively reflect or transmit light with specific wavelength, and is applied in a plurality of fields of optical materials, such as reflective coatings of lenses, waveguides, mirrors, displays, etc. (Chemical Communications, 2018, 54, 3057-.
The color of photonic crystals can be intelligently controlled by changing the external environment, and therefore researchers have developed a series of mechanical force, temperature, solvent, humidity and photoresponsive photonic crystal materials.
The color change of the first photonic crystal is based on Bragg formula = 2d (Angewandte chemical International Edition, 2014, 53(13): 3318) -3335). The lattice spacing (d) of the photonic crystal can be changed by changing the temperature, so as to regulate and control the color reflected by the photonic crystal (Science, 1996,274, 959-. Similarly, the lattice spacing can be changed by applying an electric field to obtain photonic crystals with different structural colors (Advanced functional materials, 2017, 28(43): 1804628-; another photonic crystal color change is based on the change of pigment color, and a responsive photonic crystal film is obtained by compounding a series of temperature-sensitive and electric field response color-changing materials with the photonic crystal (Small, 2020, 16(34): 2002319).
At present, no photonic crystal film with temperature and electric field response is reported. Meanwhile, the existing temperature-sensitive photonic crystal also has the defects of complex preparation method, difficulty in large-area preparation and the like. In conclusion, there is an urgent need in the art to develop a photonic crystal material with low cost, flexibility, large area and temperature sensitivity and electrochromism, which can be used for preparing the next generation of intelligent windows. The intelligent window can respond to the ambient temperature, and shows different colors at different temperatures to be used as an indoor emotion regulator; and after an external voltage is applied, the transmissivity of the intelligent window is reduced, the transparency is reduced, and privacy is provided for indoor personnel.
Disclosure of Invention
Aiming at the defects of the existing technology in the field of the current temperature and voltage response photonic crystal material, the invention aims to provide a new generation of intelligent window material which has the advantages of quick response to the environmental temperature, quick color change after voltage is applied and transmittance reduction, namely a flexible photonic crystal material with temperature/voltage response color change and a preparation method thereof.
The flexible photonic crystal material with temperature/voltage response color change is a composite material consisting of three layers of film materials, wherein the three layers of film materials are a polyethylene terephthalate-indium tin oxide (PET-ITO) film layer, a temperature-sensitive/voltage multi-response photonic crystal film layer and a polyethylene terephthalate-indium tin oxide film layer in sequence; wherein:
the temperature-sensitive/voltage-multiple-response photonic crystal thin film layer is formed by blending temperature-sensitive microcapsules, electrochromic materials, a dispersion medium and polymer microspheres to obtain high-viscosity pasty solids, and implementing a shear induced regular processing technology on the high-viscosity pasty solids to regularly arrange the polymer microspheres and the temperature-sensitive microcapsules so as to form a three-dimensional opal photonic crystal structure, wherein the electrochromic materials are uniformly dispersed in the three-dimensional opal photonic crystal structure. By adjusting the particle size of the polymer microsphere building unit and mixing the temperature-sensitive microcapsules with different color changes, the electrochromic material can generate the superposition effect of different pigments and structural colors, so that the temperature-sensitive and voltage-responsive color-changing photonic crystal film has different color and brightness change effects at different temperatures and voltages.
In the invention, the polymer microsphere is a hard-core soft-shell microsphere, which comprises a crosslinked hard core layer with high glass transition temperature, a soft shell layer with low glass transition temperature and an intermediate layer for connecting the core layer and the shell layer; the hierarchical structure microsphere is prepared by a step-by-step emulsion polymerization method. Here, the high glass transition temperature and the low glass transition temperature are relative to each other.
In the invention, the hard core soft shell polymer microsphere for constructing the photonic crystal is characterized in that the hard core layer is formed by copolymerizing styrene and 1, 4-butanediol diacrylate monomers; the shell layer is formed by copolymerizing acrylate monomers; wherein the comonomer is one or more of methyl acrylate, ethyl acrylate, butyl acrylate, isobutyl acrylate, tert-butyl acrylate, 2-ethyl acrylate, isooctyl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, decyl acrylate, isobutyl methacrylate and tert-butyl methacrylate; the shell layer and the hard core layer are connected by an intermediate layer, the intermediate layer is formed by copolymerizing acrylate monomers and a cross-linking agent, wherein the acrylate monomers are one or more of ethyl acrylate, ethyl methacrylate, n-butyl methacrylate and isobutyl methacrylate, and the cross-linking agent is one or more of divinylbenzene, butyl acrylate, dipropylene glycol diacrylate, 1, 6-hexanediol diacrylate, isobutyl acrylate, methyl methacrylate, allyl methacrylate, trimethylolpropane triacrylate, tripropylene glycol diacrylate and 1, 4-butanediol diacrylate.
In the invention, the particle size of the polymer microsphere is 20-600 nm; the monodispersity of the polymer microspheres in each synthesis stage is 0-5%, preferably 0.5-5%.
In the invention, in order to obtain excellent optical properties, the particle size of the polymer nano-microsphere is 20-600 nm; preferably, the average particle size is 50-400 nm; more preferably, the average particle diameter is 100 nm to 300 nm.
In the invention, the temperature-sensitive microcapsule is a substance with good response to temperature, and the color change comprises the following components: white-red, white-green, white-yellow, etc.
In the invention, the particle size of the temperature-sensitive microcapsule pigment particles is 0.1-100 microns; preferably, the particle size of the temperature-sensitive microcapsule pigment particles is between 0.5 and 50 microns; more preferably, the particle size of the particles is between 0.5 and 30 microns.
In the invention, the temperature-sensitive microcapsule pigment is preferably a compound consisting of melamine formaldehyde resin, a solvent and corresponding thermochromic organic molecules. Wherein the thermochromic molecules are one or more of spiropyrans, spirooxazines, benzopyrans and fulgides.
In the invention, the electrochromic material is a substance with good response to voltage, and the color change comprises the following steps: colorless-red, colorless-yellow, colorless-green, colorless-purple, colorless-blue.
In the invention, the electrochromic material is WO3、NiO、 IrO2、 MnO2、Co3O4One or more of prussian blue and viologen derivatives.
In the invention, the amount of the temperature-sensitive microcapsule pigment is 0.01-70% of the solid mass of the polymer microsphere; preferably, the amount of the civilized microcapsule pigment is 0.1% -50% of the solid mass of the polymer microspheres; more preferably, the amount of the temperature-sensitive microcapsule pigment is 5-15% of the solid mass of the polymer microsphere.
In the invention, the amount of the electrochromic material is 0.01-20% of the solid mass of the polymer microsphere; preferably, the amount of the electrochromic material is 0.1-10% of the solid mass of the polymer microsphere; more preferably, the amount of electrochromic material is 0.1% to 5% of the solid mass of the polymer microspheres.
In the invention, the driving voltage of the electrochromic material is 0.1V-100V; preferably, the driving voltage is 0.5V-50V; more preferably, the driving voltage is 1V to 1.5V.
In the invention, the dispersion medium is one or more of ethyl acrylate, butyl acrylate, isobutyl acrylate, methyl methacrylate, n-butyl methacrylate, isobutyl methacrylate and ethyl methacrylate.
The invention also provides a preparation method of the flexible photonic crystal material with temperature/voltage response color change, which comprises the following specific steps:
(1) and (3) freeze drying: carrying out freeze-drying and dewatering on hard-core soft-shell particles synthesized by stepwise emulsion polymerization in a freeze dryer;
(2) blending: blending the photonic crystal particle powder obtained by freeze-drying with a temperature-sensitive microcapsule, an electrochromic material and a dispersion medium, and rapidly stirring and hot-pressing to obtain a uniform high-viscosity photonic crystal solid blend;
(3) and (3) normalization: the obtained composite film is placed on a regular device, the composite film is sheared by utilizing shearing force provided by the rotation of the double rods at a certain temperature, microspheres and temperature-sensitive microcapsules in the film are induced to be arranged in order, so that the microspheres and the temperature-sensitive microcapsules are arranged in a matrix formed by microsphere shell layers in a close-packed mode to form a photonic crystal structure, and meanwhile, electrochromic materials are uniformly dispersed in the matrix, so that the pigment color and the structural color are uniformly compounded.
The invention has the beneficial effects that:
by compounding the photonic crystal with electrochromic and temperature-sensitive color-changing materials, an intelligent window device capable of responding to an applied electric field and ambient temperature simultaneously is obtained. Different color changing effects can be generated under different temperatures and voltages, and various colors can be changed under different temperatures; the transmittance of the film changes after voltage is applied. The device realizes the regulation and control of various colors and brightness through active regulation and control (electric field) and passive regulation and control (environment temperature). The method can be used for simply and efficiently preparing large-area intelligent window materials, the intelligent window can provide privacy protection for indoor personnel by applying voltage, and the window color is regulated and controlled based on the environmental temperature, so that indoor atmosphere regulation and control are provided.
Drawings
FIG. 1 is a structural diagram of a multi-response flexible photonic crystal material with temperature-sensitive and electrochromic effects prepared by the invention.
Fig. 2 shows the color change of the temperature-sensitive electrochromic material. Fig. 3 is a schematic view of a use scene of the vehicle-mounted smart window.
Detailed Description
The foregoing aspects are further described below in connection with non-limiting examples to provide a more complete understanding of the invention to those skilled in the art. It should be noted that the protection scope of the present invention should not be limited by the above-mentioned embodiments, and those skilled in the art can make various modifications and changes without departing from the principle of the present invention, and such modifications and changes should also be covered by the protection scope of the embodiments of the present invention.
Example 1
A flexible photonic crystal film with temperature-sensitive/electrochromic multi-response comprises a polyethylene terephthalate-indium tin oxide (PET-ITO) film layer, a temperature-sensitive/electrochromic multi-response photonic crystal layer and a polyethylene terephthalate-indium tin oxide (PET-ITO) film layer as shown in figure 1.
Wherein the thickness of the polyethylene glycol terephthalate-indium tin oxide (PET-ITO) film layer is 100-150 microns, and the resistance is 1-10 omega/Sq; the temperature-sensitive/electrochromic multi-response photonic crystal layer is composed of hard-core soft-shell microspheres with the particle size of 100-300 nanometers, temperature-sensitive microcapsule particles with the particle size of 1-10 micrometers and an electrochromic material, and the thickness of the temperature-sensitive/electrochromic multi-response photonic crystal layer is 100-160 micrometers.
The mixture of the polymer microspheres, the temperature-sensitive pigment and the electrochromic material is placed between two layers of PET-ITO films, and shearing induction is conducted through an open mill for regularization, so that the temperature-sensitive and electrochromic photonic crystal is obtained.
Example 2
(1) And (3) preparing a monodisperse hard-core soft-shell core-shell polymer microsphere emulsion.
Seed synthesis: taking a certain mass of sodium dodecyl sulfate, deionized water, 1, 4-butanediol diacrylate and styrene monomer, placing the mixture in a beaker, carrying out ultrasonic treatment until the mixture is uniformly dispersed, adding the mixture into a reaction kettle, starting stirring, and heating the emulsion to 85 ℃. Sodium persulfate aqueous solution is added into the reaction kettle to initiate polymerization reaction. Blue opalescence appeared in about 1-2 minutes, indicating that particles were formed and the reaction was initiated. The reaction is continued for 20 minutes to prepare the styrene seed emulsion.
Synthesis of the core: preparing a pre-emulsion from sodium dodecyl sulfate, deionized water, Dowfax 2A1, potassium hydroxide, 1, 4-butanediol diacrylate and a styrene monomer with certain mass, adding a sodium persulfate aqueous solution into the pre-emulsion, adding the pre-emulsion into a polystyrene seed emulsion at a certain dropping rate by using a peristaltic pump, keeping the reaction temperature unchanged after dropping is finished, and continuously reacting for 30 minutes to obtain the nuclear microsphere emulsion.
And (3) synthesizing the core-middle layer, namely repeating the steps, preparing a pre-emulsion from sodium dodecyl sulfate, deionized water, Dowfax 2A1 and ethyl acrylate, and adding a sodium persulfate aqueous solution into the pre-emulsion. And (3) dropwise adding the pre-emulsion at the same speed, and after dropwise adding, keeping the temperature for 15 minutes to obtain the emulsion containing the intermediate layer.
Core-intermediate layer-shell synthesis, firstly, preparing pre-emulsion, which consists of sodium dodecyl sulfate, potassium hydroxide, Dowfax 2A1, deionized water, ethyl acrylate and sodium persulfate aqueous solution. After the dropwise addition, the reaction is continued for 1 hour, and then the monodisperse hard-core soft-shell polymer microsphere can be obtained after filtering with 325-mesh filter cloth.
(2) And (3) preparing solid polymer microspheres. Filtering the prepared emulsion with a filter bag, and freeze-drying the filtered product for 48 hours to obtain the polymer solid microspheres which can be used for preparing temperature-sensitive and electrochromic photonic crystals.
(3) Preparation of temperature-sensitive/electrochromic mixture. The polymer microsphere solid and the temperature-sensitive microcapsule (white-red; white-yellow) and electrochromic material are dispersed in a dispersion medium together, and are quickly stirred to obtain a temperature-sensitive and electrochromic mixture, and the mixture is a high-viscosity pasty solid.
(4) And (3) preparing the flexible photonic crystal with temperature-sensitive/electrochromic multi-response. 2 g of temperature-sensitive electrochromic mixture is placed between two PET-ITO films, and shearing induction is carried out by an open mill for regularity.
The specific color change effect is shown in fig. 2.
Example 3
In the preparation of the monodisperse core-shell polymer microsphere emulsion, ethyl acrylate was replaced with a mixture of isobutyl methacrylate, ethyl acrylate and isooctyl acrylate in the synthesis of the shell, and the other conditions were kept the same as in example 2.
Example 4
In the preparation of the temperature-sensitive color-changing material, white-red, white-yellow temperature-sensitive color-changing pigments are replaced by white-lemon yellow, white-raspberry red, white-violet, white-dark blue, white-orange red, white-tea flower red and white-lake blue. Other conditions were kept the same as in example 2.
Example 5
In the preparation of the electrochromic material, the electrochromic material with colorless-purple change is replaced by colorless-green, colorless-blue and colorless-red. Other conditions were kept the same as in example 2.

Claims (9)

1. A flexible photonic crystal material with temperature/voltage response color change is characterized by being a composite material consisting of three layers of film materials, wherein the three layers of film materials are a polyethylene glycol terephthalate-indium tin oxide film layer, a temperature-sensitive/voltage multi-response photonic crystal film layer and a polyethylene glycol terephthalate-indium tin oxide film layer in sequence; wherein:
the temperature-sensitive/voltage-multiple-response photonic crystal thin film layer is a high-viscosity pasty solid obtained by blending temperature-sensitive microcapsules, electrochromic materials, a dispersion medium and polymer microspheres, and the polymer microspheres and the temperature-sensitive microcapsules are regularly arranged by implementing a shear induction regular processing technology on the high-viscosity pasty solid, so that a three-dimensional opal photonic crystal structure is formed; wherein the electrochromic material is uniformly dispersed therein; by adjusting the particle size of the polymer microsphere construction unit and mixing temperature-sensitive microcapsules with different color changes, the electrochromic material generates the superposition effect of different pigments and structural colors, so that the temperature-sensitive and voltage-responsive color-changing photonic crystal film has different color and brightness change effects at different temperatures and voltages;
wherein the polymer microsphere is a hard-core soft-shell microsphere, comprising a crosslinked hard core layer with high glass transition temperature, a soft shell layer with low glass transition temperature and an intermediate layer connecting the core layer and the shell layer; the three-layer structure microsphere is prepared by a gradual emulsion polymerization method.
2. The flexible photonic crystal material of claim 1, wherein the crosslinked hard core layer is formed by copolymerizing styrene and 1, 4-butanediol diacrylate monomers; the soft shell layer is formed by copolymerizing acrylate monomers; wherein the comonomer is one or more of methyl acrylate, ethyl acrylate, butyl acrylate, isobutyl acrylate, tert-butyl acrylate, 2-ethyl acrylate, isooctyl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, decyl acrylate, isobutyl methacrylate and tert-butyl methacrylate; the soft shell layer and the crosslinking hard core layer are connected by an intermediate layer, and the intermediate layer is made of acrylate monomers and a crosslinking agent through copolymerization; wherein, the acrylate monomer is one or more of ethyl acrylate, ethyl methacrylate, n-butyl methacrylate and isobutyl methacrylate, and the cross-linking agent is one or more of divinylbenzene, butyl acrylate, dipropylene glycol diacrylate, 1, 6-hexanediol diacrylate, isobutyl acrylate, methyl methacrylate, allyl methacrylate, trimethylolpropane triacrylate, tripropylene glycol diacrylate and 1, 4-butanediol diacrylate.
3. The flexible photonic crystal material of claim 2, wherein the polymer microspheres have a particle size of 20 nm to 600 nm; the monodispersity of the polymer microspheres in each synthesis stage is 0.5-5%.
4. The flexible photonic crystal material according to any one of claims 1 to 3, wherein the temperature-sensitive microcapsules are a substance having a good response to temperature, and the color change comprises: white-red, white-green or white-yellow.
5. The flexible photonic crystal material of claim 4, wherein the particle size of the temperature-sensitive microcapsule is between 0.1 micron and 100 microns;
the temperature-sensitive microcapsule pigment is a compound consisting of melamine formaldehyde resin, a solvent and corresponding thermochromic organic molecules; wherein the thermochromic organic molecules are one or more of spiropyrans, spirooxazines, benzopyrans and fulgides.
6. The flexible photonic crystal material of claim 5, wherein the electrochromic material is a substance of a type having good response to voltage, and the color change comprises: colorless-red, colorless-yellow, colorless-green, colorless-purple, colorless-blue; the electrochromic material is WO3、NiO、 IrO2、 MnO2、Co3O4One or more of prussian blue and viologen derivatives.
7. The flexible photonic crystal material of claim 6, wherein:
the amount of the temperature-sensitive microcapsule pigment is 0.01-70% of the solid mass of the polymer microspheres;
the amount of the electrochromic material is 0.01-20% of the solid mass of the polymer microsphere;
the driving voltage of the electrochromic material is 0.1-100V.
8. The flexible photonic crystal material of claim 1, wherein the dispersion medium is one or more of ethyl acrylate, butyl acrylate, isobutyl acrylate, methyl methacrylate, n-butyl methacrylate, isobutyl methacrylate and ethyl methacrylate.
9. A method for preparing a flexible photonic crystal material according to any one of claims 1 to 8, comprising the following specific steps:
(1) and (3) freeze drying: carrying out freeze-drying and dewatering on hard-core soft-shell particles synthesized by stepwise emulsion polymerization in a freeze dryer;
(2) blending: blending the photonic crystal particle powder obtained by freeze-drying with a temperature-sensitive microcapsule, an electrochromic material and a dispersion medium, and rapidly stirring and hot-pressing to obtain a uniform high-viscosity photonic crystal solid blend;
(3) and (3) normalization: the obtained composite film is placed on a regular device, the composite film is sheared by utilizing shearing force provided by rotation of double rollers at a certain temperature, microspheres and temperature-sensitive microcapsules in the film are induced to be orderly arranged, so that the microspheres and the temperature-sensitive microcapsules are arranged in a matrix formed by microsphere shell layers in a close-packed mode to form a photonic crystal structure, and meanwhile, electrochromic materials are uniformly dispersed in the matrix, so that pigment colors and structural colors are uniformly compounded.
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