CN106905551A - A kind of counter opal structure temperature-sensitive material and preparation method thereof - Google Patents

Abstract

The invention relates to an inverse opal structure temperature sensing material and a preparation method thereof. Using the porous microstructure of the inverse opal photonic crystal, the temperature-sensing material is selectively filled in the porous microstructure of the inverse opal and encapsulated, and then the temperature-sensing material is obtained. According to the different temperature-sensing substances filled, the temperature-sensing material displays different colors at different temperatures. The inverse opal temperature sensing material prepared by the invention has high flexibility and high sensitivity, simple preparation process, strong controllability and easy industrial production.

Description

A kind of inverse opal structure temperature sensing material and preparation method thereof

Technical field:

The invention relates to an inverse opal structure temperature sensing material and a preparation method thereof, belonging to the field of inverse opal structure photonic crystal materials and temperature sensitive materials.

Background technique:

Photonic crystals are structures in which materials with different dielectric constants are periodically arranged in space. By using the periodic change of the refractive index of photonic crystals, the prohibition of light of a certain wavelength can be adjusted, that is, the photonic band gap. Inverse opal is obtained by filling the gaps of the three-dimensional ordered self-assembled opal structure of photonic crystals with another material, and then using chemical etching or calcination to remove the original photonic crystal template.

Due to the nanoscale pore structure, the porous material has high specific surface area, uniform and adjustable pore size and ordered dimensions, and has important applications in the fields of biocatalysis, functional polymer composite assembly, chemical sensing, adsorption separation, and microdevices. prospect. As an ultra-high specific surface area material, inverse opal photonic crystal has a wide range of applications, and has been continuously developed as a new catalyst and its carrier, biosensor and other applications. Patent CN101870866A modified the surface of silicon dioxide inverse opal photonic crystal with fluorescein FITC, and successfully prepared an inverse opal structure silicon dioxide fluorescent film that recognizes TNT vapor, forming a nanostructure with high selectivity, high sensitivity and molecular recognition performance probe. Patent CN103257123A modified heavy metal sensing groups to the surface of inverse opal photonic crystals, and prepared a photonic crystal thin film heavy metal sensor with multi-level structure, which can greatly improve the sensitivity, selectivity and scope of application for the analysis and detection of specific substances. Patent CN102193213B uses hydrogel as the framework of inverse opal photonic crystals, and fills the holes with standard thermosolid liquid for contact lenses to obtain colorful contact lenses. Compared with other colored contact lenses, the dazzling colored contact lenses are more elegant in appearance, have good biocompatibility, and have good practicability. A variety of materials have been used to modify inverse opal photonic crystals, so that inverse opal photonic crystals exhibit various properties. However, in the previous application of inverse opal structures, there has not been any report of filling temperature-sensitive substances as temperature-sensing materials. Traditional thermometers are made of mercury and glass, which are easily damaged, causing mercury volatilization and leakage, and causing harm to the human body and the environment; the thermometer has a fixed shape and cannot be bent, so it cannot meet temperature measurement under complex conditions. Since the thin-film liquid crystal thermometer is in the form of fluid, it is easy to leak and cause losses. In order to solve the lack of temperature-sensing materials in complex environments, a temperature-sensing material with an inverse opal structure was obtained by encapsulating temperature-sensitive substances in it by using the porous characteristics of the inverse opal structure.

Invention content:

The invention relates to a novel inverse opal structure temperature-sensing material and a preparation method thereof. Using the porous microstructure of the inverse opal photonic crystal, the temperature-sensing material is selectively filled in the porous microstructure of the inverse opal and encapsulated to obtain temperature sensitive material.

An inverse opal-structured temperature-sensing material provided by the invention: vertically sedimentation of silicon dioxide microspheres is assembled into a silicon dioxide photonic crystal-embedded polymer film, and the polymer film embedded in a silicon dioxide photonic crystal is selectively etched to form an inverse opal In the region, the inverse opal region formed after etching is filled with a temperature-sensing substance, and encapsulated to form an inverse-opal structure temperature-sensing material.

The temperature-sensitive substance is a cholesteric liquid crystal; one or a mixture thereof selected from the following liquid crystals: cholesteryl oleyl carbonate, cholesteryl nonanoate, cholesteryl benzoate, chlorinated cholesterol, Cholesteryl carbonate or cholestenyl p-nonylphenyl carbonate.

A method for preparing an inverse opal structure temperature sensing material provided by the present invention, the specific steps and conditions are as follows:

(1) Preparation of silica microspheres

Using the optimized Stober method, mix ethanol and ammonia water with a mass concentration of 25% according to the volume ratio of 45:1-3:1, take 100 parts by mass, add dropwise 3-30 Parts by mass of tetraethyl orthosilicate. After 6-48 hours of reaction, the product is washed and dried to obtain silica microspheres with uniform particle size, which are ready for use.

(2) Assembly of silica photonic crystals

The silica microspheres obtained in step (1) are configured into an ethanol dispersion with a mass concentration of 0.1-5%, preferably with a mass concentration of 1-3%, and the surface-hydrophilized glass substrate is put into the dispersion, and heated at a constant temperature. Under wet conditions, stand still for 24-96 hours to obtain silicon dioxide photonic crystals on the substrate surface (both sides).

The constant temperature and humidity conditions are as follows: temperature is 10-80°C, preferably 30-50°C; humidity is 5-80%, preferably 30-50%.

(3) Preparation of polymer films embedded with silica photonic crystals

The spacer is glued on both sides of the photonic crystal glass substrate, and another glass substrate is covered to form a cavity. The polymerizable monomer is filled into the cavity after adding a photoinitiator with a mass ratio of 1%-5%. Cured under ultraviolet light (intensity of ultraviolet light is 5-50mw/cm2, irradiation time is preferably 5-200 minutes), the cavity is placed in hot water at 60-95°C for 1-24 hours, and the formed polymer film Take it out of the cavity to get a polymer film embedded with silicon dioxide photonic crystals on one side.

The polymerizable monomer is selected from one of the following monomers or a mixture thereof: methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, methacrylic acid Hexyl methacrylate, hydroxypropyl methacrylate, glycidyl methacrylate, vinyl acetate, methyl acrylate, ethyl acrylate, hexyl acrylate, isooctyl acrylate, isodecyl acrylate, lauryl acrylate, hexanediol Diacrylate, polyethylene glycol diacrylate, trimethylolpropane triacrylate, A6OCB, AC-6CN, 6CB, 5CB, C3M, C4M, C6M.

The photoinitiator is selected from one of the following photoinitiators or their mixture: Irgacure 651, Irgacure 1717, Irgacure 1173, Irgacure 2959, Irgacure 184, Irgacure 907, Irgacure369, Irgacure 819, Irgacure 754, TPO, MBF .

(4) Selective etching to prepare patterns

Under the cover of the mask, the photonic crystal on the surface of the polymer film is etched with a dilute solution of hydrofluoric acid, and patterned flexible inverse opal structure voids are obtained on the surface of the photonic crystal of the polymer film. The mass concentration of the dilute hydrofluoric acid solution is 0.05-5%, preferably 1-3%, and the etching time is preferably 1-30 minutes.

(5) Filling and packaging of temperature-sensitive substances

Fill the temperature-sensitive substance into the gap of the etched inverse opal structure, and then spray the polymerizable encapsulation monomer added with photoinitiator on the surface of the film. After being cured by ultraviolet light, the temperature-sensitive substance is encapsulated in the inverse opal structure to obtain Inverse opal-structured temperature-sensing materials.

The temperature sensitive substance is preferably a liquid crystal mixture with the following mass ratio:

Cholesteryl p-nonylphenyl carbonate: cholesteryl nonanoate: cholesteryl benzoate: chlorinated cholesterol: cholestenyl carbonate = (20-30): (30-50): (0 -20):(0-10):(0-25)

Or cholesteryl oleyl carbonate: cholesteryl nonanoate: cholesteryl benzoate = (30-45): (45-60): 10

The polymerizable encapsulating monomer is a mixture of 1,6-hexanediol diacrylate (HDDA) with a mass ratio of 10:1 to 1:10 and one of the following monomers: methyl methacrylate, methyl methacrylate Ethyl acrylate, n-butyl methacrylate, isobutyl methacrylate, hexyl methacrylate, hydroxypropyl methacrylate, glycidyl methacrylate, vinyl acetate, methyl acrylate, ethyl acrylate , hexyl acrylate, isooctyl acrylate; the photoinitiator is selected from one of the following photoinitiators or their mixture: Irgacure 651, Irgacure 1717, Irgacure 1173, Irgacure 2959, Irgacure 184, TPO, photoinitiator The added amount is 1-4% of the total mass of monomers.

Effects of the present invention: the temperature sensing material prepared by the present invention has the characteristics of good biocompatibility, non-irritation, environmental friendliness, and high flexibility, which provides a material basis for designing a new type of temperature sensor. The present invention can also obtain sensing materials that sense different designated temperatures according to actual needs, and can be applied to various purposes according to the sensing temperature range, such as detecting human body temperature, wine product temperature and other narrow-range temperature detection fields. Compared with traditional mercury thermometers, inverse opal-structured temperature-sensing materials can be used in the preparation of flexible temperature measuring devices; compared with traditional mercury thermometers, they are more environmentally friendly and have more applicable scenarios; compared with electronic thermometers, they are cheaper.

detailed description:

Example 1:

Silica microspheres were synthesized by the optimized Stober method. First, 75 ml of ethanol and 7 ml of ammonia water with a mass concentration of 25% were mixed and added into the reactor, and heated to 30° C. in a water bath; mechanical stirring was performed at a speed of 300 rpm. The reaction temperature was controlled at 30°C, and 6ml of tetraethyl orthosilicate was added to the system at a rate of 1 drop/s. After the dropwise addition was completed, the reaction was carried out for 12h. After the product was centrifuged, it was repeatedly washed four times with ethanol and deionized water, and dried to obtain silica microspheres for use.

The silica microspheres were ultrasonically dispersed in ethanol at a mass concentration of 1.2%. Put the glass substrate treated with surface hydrophilicity (put the glass substrate in a mixed solution with a mass concentration of 37% hydrogen peroxide and 98% concentrated sulfuric acid at a volume ratio of 3:7 for 12 hours to enhance its surface hydrophilicity), and place it vertically Silica-ethanol dispersion in reservoir. Control the temperature at 35° C. and the humidity at 25%, let it stand for 48 hours, take it out, and obtain the silicon dioxide photonic crystal template after the ethanol evaporates completely.

Mix the polymerizable monomers C4M, C6M, and A6OCB at a mass ratio of 4:4:2, add 2% photoinitiator Irgacure651 to the total mass of the monomers, and fully stir and dissolve in dichloromethane. After removal of the solvent by evaporation under reduced pressure, a compounded polymerizable monomer was obtained. A spacer with a thickness of 20 microns is glued to both sides of the photonic crystal glass substrate, and another glass substrate is covered to form a cavity. After adding the photoinitiator to the polymerizable monomer (mass ratio of photoinitiator to polymerizable monomer is 1:50), it is filled into the cavity. Cured after 15 minutes of ultraviolet light irradiation with an intensity of 15mw/cm2, the cavity was placed in hot water at 80°C for 5 hours, and the formed polymer film was taken out of the cavity to obtain a photonic crystal embedded in silicon dioxide. polymer film.

Embed the photonic crystal polymer film on one side prepared in the previous step to cover the mask. Use a hydrofluoric acid solution with a mass concentration of 1% to evenly spread on the mask for partial etching. After 1 min, wash with deionized water. A patterned inverse opal template was obtained.

Cholesteryl oleyl carbonate, cholesteryl nonanoate, and cholesteryl benzoate were mixed in a mass ratio of 45:45:10, heated to 90°C, and added to the pattern of the patterned inverse opal template. Spray a layer of 1,6-hexanediol diacrylate and methyl methacrylate encapsulating monomer with a mass ratio of 1:1 on the surface of the film pattern (the mass ratio of the photoinitiator Irgacure651 is 2%). The package was cured under 25mw/cm ² UV light for 5min. Obtain the inverse opal structure temperature sensing material.

When the temperature is lower than 26.5°C, the film is in a colorless state as a whole. At 26.5°C, the film showed a red pattern; when heated from 26.5°C to 30.5°C, the color of the film changed to red, orange, green, and blue in turn. When the temperature is higher than 30.5°C, the film shows a colorless state again. The temperature-sensitive material with inverse opal structure can indicate the temperature range from 26.5°C to 30.5°C. The sensitivity is 1°C.

Example 2:

Silica microspheres were synthesized by the optimized Stober method. First, mix 75ml of ethanol and 8ml of ammonia water into the reactor with mechanical stirring, and heat it to 31°C in a water bath; control the mechanical stirring to 310rpm. After the temperature stabilized, 6ml of tetraethyl orthosilicate was added to the system at a rate of 1 drop/s. After the dropwise addition was completed, 12h, the reaction was stopped. After the product was centrifuged, it was repeatedly washed four times with ethanol and its deionized water respectively. Dry and set aside.

The silica microspheres were ultrasonically dispersed in ethanol at a mass concentration of 1.5%. Put the glass substrate with surface hydrophilic treatment (the surface hydrophilic treatment is the same as that in Example 1) vertically into the silica-ethanol dispersion liquid storage tank. Set the temperature at 30°C and the humidity at 35%. After standing still for 58 hours, the silicon dioxide photonic crystal template was obtained after the ethanol evaporated completely.

Mix the polymerizable monomers C4M and A6OCB at a mass ratio of 8:2, add 2% photoinitiator Irgacure1173 of the total mass of the monomers, and fully stir and dissolve in dichloromethane. After removal of the solvent by evaporation under reduced pressure, a compounded polymerizable monomer was obtained. Using the same method as in Example 1, a polymer film with one side embedded with silicon dioxide photonic crystals was obtained.

Cover the inverse opal film prepared in the previous step with a mask. Use a hydrofluoric acid solution with a mass concentration of 1.5% to evenly spread it on the mask for partial etching. After 1 min, wash with deionized water. A patterned inverse opal template was obtained.

Cholesteryl oleyl carbonate, cholesteryl nonanoate, and cholesteryl benzoate were mixed in a mass ratio of 44:46:10, heated to 95° C., and added to the pattern of the patterned inverse opal template. Encapsulate with 1,6-hexanediol diacrylate: acrylic acid mixed monomer with a mass ratio of 1:1 (photoinitiator Irgacure1173, accounting for 2% of the monomer mass), and other conditions are the same as in Example 1 to obtain an inverse opal structure. Material.

When the temperature is lower than 30°C, the film as a whole is in a colorless state. At 30°C, the film showed a red pattern; when heated from 30°C to 33°C, the color of the film changed to red, orange, green, and blue. When the temperature is higher than 33°C, the film shows a colorless state again. This inverse opal thermometer can indicate a temperature range of 30°C to 33°C. The sensitivity is 1°C.

Example 3:

Silica microspheres were synthesized by the optimized Stober method. First, mix 75ml of ethanol and 9ml of ammonia water into the reactor with mechanical agitation, and heat it to 33°C in a water bath; control the mechanical agitation to 350rpm. After the temperature stabilized, 6ml of tetraethyl orthosilicate was added to the system at a rate of 1 drop/s. After the dropwise addition was completed, 12h, the reaction was stopped. After the product was centrifuged, it was repeatedly washed four times with ethanol and its deionized water respectively. Dry and set aside.

The silica microspheres were ultrasonically dispersed in ethanol at a mass concentration of 1.7%. Put the glass substrate with surface hydrophilic treatment (the surface hydrophilic treatment is the same as that in Example 1) vertically into the silica-ethanol dispersion liquid storage tank. Set the temperature at 38°C and the humidity at 35%. After standing still for 68 hours, the silicon dioxide photonic crystal template was obtained after the ethanol evaporated completely.

Mix the polymerizable monomers C6M and A6OCB at a mass ratio of 8:2, add the photoinitiator Irgacure2959, and fully stir and dissolve in dichloromethane. After removal of the solvent by evaporation under reduced pressure, a compounded polymerizable monomer was obtained. Using the same method as in Example 1, a polymer film with one side embedded with silicon dioxide photonic crystals was obtained.

Cover the inverse opal film prepared in the previous step with a mask. Use a hydrofluoric acid solution with a mass concentration of 1.8% to evenly spread it on the mask for partial etching. After 1 min, wash with deionized water. A patterned inverse opal template was obtained.

Cholesteryl oleyl carbonate, cholesteryl nonanoate, and cholesteryl benzoate are mixed in a mass ratio of 40:50:10, heated to 85-95° C., and then added to the pattern of the patterned inverse opal template. Encapsulation with 1,6-hexanediol diacrylate: ethyl methacrylate mixed monomer with a mass ratio of 1:1 (photoinitiator Irgacure2959, accounting for 2% of the monomer mass), other conditions are the same as in Example 1, and the reaction product is obtained. Opal-structured temperature-sensing materials.

When the temperature is lower than 32°C, the film as a whole is in a colorless state. At 32°C, the film showed a red pattern; when heated from 32°C to 35°C, the color of the film changed to red, orange, green, and blue. When the temperature is higher than 35°C, the film shows a colorless state again. This inverse opal thermometer can indicate a temperature range of 32°C to 35°C. The sensitivity is 1°C.

Example 4:

Silica microspheres were synthesized by the optimized Stober method. First, mix 75ml of ethanol and 10ml of ammonia water into the reactor with mechanical agitation, and heat it to 34°C in a water bath; control the mechanical agitation to 370rpm. After the temperature stabilized, 6ml of tetraethyl orthosilicate was added to the system at a rate of 1 drop/s. After the dropwise addition was completed, 12h, the reaction was stopped. After the product was centrifuged, it was repeatedly washed four times with ethanol and its deionized water respectively. Dry and set aside.

The silica microspheres were ultrasonically dispersed in ethanol with a mass concentration of 2%. Put the glass substrate with surface hydrophilic treatment (the surface hydrophilic treatment is the same as that in Example 1) vertically into the silica-ethanol dispersion liquid storage tank. Set the temperature at 42°C and the humidity at 40%. After standing still for 68 hours, the silicon dioxide photonic crystal template was obtained after the ethanol evaporated completely.

Mix the polymerizable monomers C4M, C6M, and AC6CN at a mass ratio of 4:4:2, add the photoinitiator Irgacure 184, and fully stir and dissolve in dichloromethane. After removal of the solvent by evaporation under reduced pressure, a compounded polymerizable monomer was obtained. Using the same method as in Example 1, a polymer film with one side embedded with silicon dioxide photonic crystals was obtained.

Cover the inverse opal film prepared in the previous step with a mask. Use a hydrofluoric acid solution with a mass concentration of 1% to evenly spread on the mask for partial etching. After 1 min, wash with deionized water. A patterned inverse opal template was obtained.

Cholesteryl oleyl carbonate, cholesteryl nonanoate, and cholesteryl benzoate are mixed in a mass ratio of 36:44:10, heated to 90-100° C., and added to the pattern of the patterned inverse opal template. Encapsulate with a 1:1 mass ratio of 1,6-hexanediol diacrylate:methyl acrylate mixed monomer (photoinitiator Irgacure184, accounting for 2% of the monomer mass), and other conditions are the same as in Example 1 to obtain the inverse opal structure temperature Sensitive material.

When the temperature is lower than 34°C, the film as a whole is in a colorless state. At 34°C, the film showed a red pattern; when heated from 34°C to 37°C, the color of the film changed to red, orange, green, and blue. When the temperature is higher than 37°C, the film shows a colorless state again. This inverse opal thermometer can indicate a temperature range of 34°C to 37°C. The sensitivity is 1°C.

Example 5:

Silica microspheres were synthesized by the optimized Stober method. First, mix 75ml of ethanol and 11ml of ammonia water into the reactor with mechanical agitation, and heat it to 32°C in a water bath; control the mechanical agitation to 400rpm. After the temperature stabilized, 6ml of tetraethyl orthosilicate was added to the system at a rate of 1 drop/s. After the dropwise addition was completed, 12h, the reaction was stopped. After the product was centrifuged, it was repeatedly washed four times with ethanol and its deionized water respectively. Dry and set aside.

The silica microspheres were ultrasonically dispersed in ethanol at a mass concentration of 1.7%. Put the glass substrate with surface hydrophilic treatment (the surface hydrophilic treatment is the same as that in Example 1) vertically into the silica-ethanol dispersion liquid storage tank. Set the temperature at 45°C and the humidity at 25%. After standing still for 48 hours, the silicon dioxide photonic crystal template was obtained after the ethanol evaporated completely.

Mix the polymerizable monomers DHHA, C6M, and A6OCB at a mass ratio of 4:4:2, add the photoinitiator Irgacure1717, and fully stir and dissolve in dichloromethane. After removal of the solvent by evaporation under reduced pressure, a compounded polymerizable monomer was obtained. Using the same method as in Example 1, a polymer film with one side embedded with silicon dioxide photonic crystals was obtained.

Cover the inverse opal film prepared in the previous step with a mask. Use a hydrofluoric acid solution with a mass concentration of 3% to evenly spread on the mask for partial etching. After 1 min, wash with deionized water. A patterned inverse opal template was obtained.

Cholesteryl oleyl carbonate, cholesteryl nonanoate, and cholesteryl benzoate are mixed in a mass ratio of 32:48:10, heated to 90-100°C, and added to the pattern of the patterned inverse opal template. Encapsulate with a 1:1 mass ratio of 1,6-hexanediol diacrylate: methyl acrylate mixed monomer (photoinitiator Irgacure1717, accounting for 2% of the monomer mass), other conditions are the same as in Example 1, and the inverse opal structure temperature is obtained Sensitive material.

When the temperature is lower than 36°C, the film as a whole is in a colorless state. At 36°C, the film showed a red pattern; when heated from 36°C to 39°C, the color of the film changed to red, orange, green, and blue. When the temperature is higher than 39°C, the film shows a colorless state again. This inverse opal thermometer can indicate a temperature range of 36°C to 39°C. The sensitivity is 1°C.

Embodiment 6:

Silica microspheres were synthesized by the optimized Stober method. First, mix 75ml of ethanol and 8.5ml of ammonia water into the reactor with mechanical stirring, and heat it to 30°C in a water bath; control the mechanical stirring to 350rpm. After the temperature stabilized, 6ml of tetraethyl orthosilicate was added to the system at a rate of 1 drop/s. After the dropwise addition was completed, 12h, the reaction was stopped. After the product was centrifuged, it was repeatedly washed four times with ethanol and its deionized water respectively. Dry and set aside.

The silica microspheres were ultrasonically dispersed in ethanol at a mass concentration of 1.2%. Put the glass substrate with surface hydrophilic treatment (the surface hydrophilic treatment is the same as that in Example 1) vertically into the silica-ethanol dispersion liquid storage tank. Set the temperature at 38°C and the humidity at 30%. After standing still for 52 hours, the silicon dioxide photonic crystal template was obtained after the ethanol evaporated completely.

Mix the polymerizable monomers C4M, C6M, and A6OCB at a mass ratio of 45:35:20, add the photoinitiator Irgacure651, and fully stir and dissolve in dichloromethane. After removal of the solvent by evaporation under reduced pressure, a compounded polymerizable monomer was obtained. Using the same method as in Example 1, a polymer film with one side embedded with silicon dioxide photonic crystals was obtained.

Cover the inverse opal film prepared in the previous step with a mask. Use a hydrofluoric acid solution with a mass concentration of 1% to evenly spread on the mask for partial etching. After 1 min, wash with deionized water. A patterned inverse opal template was obtained.

Configure cholesteric liquid crystals, mix cholesteryl p-nonylphenyl carbonate, cholesteryl nonanoate, cholesteryl benzoate, and chlorinated cholesterol according to the mass ratio of 36.5:45.3:9.1:9.1, and heat to After 90-100°C, add to the pattern of the patterned inverse opal template. Encapsulate with a 1:1 mass ratio of 1,6-hexanediol diacrylate:methyl methacrylate mixed monomer (photoinitiator Irgacure651, accounting for 2% of the monomer mass), and other conditions are the same as in Example 1 to obtain inverse opal Structural temperature sensing materials.

When the temperature is lower than 33°C, the film is in a colorless state as a whole. At 33°C, the film showed a red pattern; when heated from 33°C to 37°C, the color of the film changed to red, orange, yellow, green, and blue. When the temperature is higher than 37°C, the film shows a colorless state again. This inverse opal thermometer can indicate a temperature range of 33°C to 37°C. The sensitivity is 1°C.

Claims (10)

1. a kind of counter opal structure temperature-sensitive material：Silica photon is assembled into using silicon dioxide microsphere vertical sedimentation Crystal is embedded in thin polymer film, and the thin polymer film selective etch of embedded silica photonic crystal is formed into counter opal area Domain, the counter opal area filling temperature sense material for being formed after the etching is encapsulated, forms counter opal structure temperature sense Material.

2. counter opal structure temperature-sensitive material according to claim 1, it is characterized in that：Described temperature sense material is courage Steroid phase liquid crystal；Selected from the one kind in following liquid crystal or their mixture：Cholesterol oil alkenyl carbonate, cholesteryl nonanoate, Cholesteryl benzoate, cholesteryl chloride, cholesteryl carbonic ester or cholesteryl are to nonyl benzol carbonate.

3. the preparation method of the counter opal structure temperature-sensitive material described in a kind of claim 1 or 2, specific steps and condition For：

(1) preparation of silicon dioxide microsphere

By the ammoniacal liquor of ethanol and mass concentration 25% according to volume ratio 45:1~3:1 mixing, takes 100 mass parts, in stirring and 20- Under 50 DEG C of steady temperature, 3-30 mass parts tetraethyl orthosilicates are added dropwise, were reacted by 6-48 hours, by product washing, dry, Obtain the silicon dioxide microsphere of uniform particle diameter；

(2) assembling of silica photonic crystal

The silicon dioxide microsphere that step (1) is obtained is configured to the alcohol dispersion liquid of mass concentration 0.1-5%, by surface hydrophilic Glass substrate be put into dispersion liquid, under the conditions of constant temperature and humidity, stand 24-96 hours, obtain silica in substrate surface Photonic crystal；Described constant temperature and humidity condition is：Temperature is 10-80 DEG C, and humidity is 5-80%；

(3) preparation of the thin polymer film of embedded silica photonic crystal

Separation pad is bonded at photonic crystal glass substrate both sides, another piece of glass substrate is added a cover and is formed cavity, by polymerisable monomer After the light trigger of addition mass ratio 1%-5%, it is packed into cavity, solidifies under ultraviolet light, cavity is placed on 60- Soaked 1-24 hours in 95 DEG C of hot water, the thin polymer film for being formed is taken out from cavity, obtain the embedded silica light of one side The thin polymer film of sub- crystal；

(4) selective etch prepares pattern

Under mask covering, the polymeric film surface that embedded in photonic crystal is etched with hydrofluoric acid weak solution, patterned The thin polymer film of flexible counter opal structure；

(5) temperature sense material being inserted and encapsulates

By temperature sense material insert etching after counter opal structure space in, then film surface spraying with the addition of it is light-initiated The polymerizable encapsulation monomer of agent, after solidifying through ultraviolet lighting, temperature-sensitive material is encapsulated in counter opal structure, obtains anti- Opal structural temperature-sensitive material.

4. the preparation method of counter opal structure temperature-sensitive material according to claim 3, it is characterized in that：Step (3) Described in polymerisable monomer be selected from following monomer in one kind or their mixture：Methyl methacrylate, metering system Acetoacetic ester, n-BMA, Isobutyl methacrylate, hexyl methacrylate, hydroxy propyl methacrylate, methyl Glycidyl acrylate, vinylacetate, methyl acrylate, ethyl acrylate, Hexyl 2-propenoate, Isooctyl acrylate monomer, third Olefin(e) acid isodecyl ester, lauryl acrylate, hexanediyl ester, poly- diethanol diacrylate, trimethylolpropane tris third Olefin(e) acid ester, A6OCB, AC-6CN, 6CB, 5CB, C3M, C4M, C6M；The light trigger is selected from following light trigger Plant or their mixture：Irgacure 651、Irgacure 1717、Irgacure 1173、Irgacure 2959、 Irgacure 184、Irgacure 907、Irgacure 369、Irgacure 819、Irgacure 754、TPO、MBF。

5. the preparation method of counter opal structure temperature-sensitive material according to claim 3, it is characterized in that：Step (3) Middle ultraviolet light polymerization condition is that ultraviolet ray intensity is 5-50mw/cm2, and irradiation time is 5-200 minutes.

6. the preparation method of counter opal structure temperature-sensitive material according to claim 3, it is characterized in that：Step (5) Described in temperature sense material be following mass ratio liquid crystal compound：Cholesteryl is to nonyl benzol carbonate:Cholesterine Pelargonate:Cholesteryl benzoate:Cholesteryl chloride:Cholesteryl carbonic ester=(20-30):(30-50):(0-20):(0- 10):(0-25)。

7. the preparation method of counter opal structure temperature-sensitive material according to claim 3, it is characterized in that：Step (5) Described in temperature sense material be following mass ratio liquid crystal compound：Cholesterol oil alkenyl carbonate:Cholesteryl nonanoate: Cholesteryl benzoate=(30-45):(45-60):10.

8. the preparation method of counter opal structure temperature-sensitive material according to claim 3, it is characterized in that：Step (5) Described in polymerizable encapsulation monomer, be mass ratio 10:1~1:In 10 1,6 hexanediol diacrylate and following monomer A kind of mixture：Methyl methacrylate, EMA, n-BMA, Isobutyl methacrylate, Hexyl methacrylate, hydroxy propyl methacrylate, GMA, vinylacetate, methyl acrylate, third Olefin(e) acid ethyl ester, Hexyl 2-propenoate, Isooctyl acrylate monomer；Light trigger is selected from one kind in following light trigger or theirs is mixed Compound：Irgacure 651, Irgacure 1717, Irgacure 1173, Irgacure 2959, Irgacure 184, TPO, The addition of light trigger is the 1-4% of monomer gross mass.

9. the preparation method of counter opal structure temperature-sensitive material according to claim 3, it is characterized in that：Step (2) Described in constant temperature and humidity condition be：Temperature is 30-50 DEG C, and humidity is 30-50%.

10. the preparation method of counter opal structure temperature-sensitive material according to claim 3, it is characterized in that：Step (4) Described in hydrofluoric acid mass concentration be 0.05%-5%, etching period be 1-30 minutes.