Method for preparing stable polymer-colloid composite photonic crystal by using crosslinkable polymer

Abstract

The invention relates to a method for preparing a stable polymer-colloid composite photonic crystal by using a crosslinkable polymer, and belongs to the field of ordered polymer matrix composite materials. A compound containing double bonds reacts with a polymer with high molecular weight under a certain condition to obtain a polymer with modified double-bond groups. Monodisperse colloid particle dispersion liquid and the polymer modified with the double-bond groups are compounded, a compound is subjected to oscillation shearing, a composite film with bright structural color is obtained, crosslinking is achieved through polymerization of the double-bond groups, and therefore the polymer-colloid composite film with the stable structure is obtained. According to the invention, the polymer-colloid composite photonic crystal which has bright structural color and can be cross-linked is obtained by utilizing the dynamic reversible interaction of supramolecules. The polymer-colloid composite photonic crystal with a stable structure is obtained through crosslinking. The method is simple to operate and low in cost, has the potential of large-scale industrial production, and shows a good application prospect in the fields of display, sensing and anti-counterfeiting.

Description

Technical Field

[0001] The invention belongs to the field of ordered polymer composite materials, and more specifically, relates to a method for preparing stable polymer-colloid composite photonic crystals by using cross-linkable polymers. Background Art

[0002] The interaction between visible light and periodic micro-nanostructures can produce structural colors. Compared with pigment colors produced by selective absorption, structural colors have the advantages of low energy consumption, no pollution, not easy to fade and easy to adjust. They have received widespread attention in the fields of color coatings, visual sensing and anti-counterfeiting.

[0003] Due to the needs of production and life, people have developed various structural color materials with bright colors and functions. Invention patent application TW101144991 first obtains a colloidal microsphere array arranged in a periodic structure through the self-assembly of colloidal particles, and then infiltrates a liquid light-transmitting material, and obtains a photonic color-changing film with structural color after curing. However, this method, which relies on assembling the colloidal template first and then fixing it, has a cumbersome process and a small sample preparation area, which is not conducive to the large-scale production of structural color films. Chinese invention patent application CN202011123823.5 solves the problem of large-scale preparation of structural color films and provides a new idea for the large-scale preparation of responsive structural color films. It is of great significance to the development of structural color materials. At present, the application of this method is still relatively limited, and it can only be achieved by synthesizing colloidal particles with certain viscosity and specific core-shell structure. Chinese invention patent application CN202211347861.8 selects common colloidal particles and polymers, and uses the unique processing properties of supramolecular polymers to quickly and large-scale prepare structural color composite films by oscillating shear. However, due to the dynamic reversible interaction of supramolecular materials, the structural color of photonic crystals induced by shear is unstable, and temperature and humidity will destroy the long-range ordered structure of colloidal particles, so the chemical stability of polymer composite photonic crystals will be affected. Therefore, it is crucial to construct a supramolecular composite system with high stability. Summary of the invention

[0004] In view of the above defects or improvement needs of the prior art, the present invention provides a method for preparing a stable polymer-colloid composite photonic crystal using a cross-linkable polymer. The method modifies a small molecule compound on a polymer chain to obtain a polymer containing a double bond group, and after compounding with colloidal particles, uses an oscillating shearing technique to obtain a stable polymer-colloid composite film through cross-linking, thereby solving the problem of unstable chemical structure of the structural color composite film prepared by the prior method.

[0005] In order to achieve the above object, according to one aspect of the present invention, a method for preparing a stable polymer-colloid composite photonic crystal is provided, comprising the following steps:

[0006] (1) reacting a polymer with a compound containing a carbon-carbon double bond, wherein the polymer contains at least one of an amino group, a hydroxyl group, and a halogen atom, and the compound contains at least one of an anhydride reactive group, an epoxy reactive group, an acyl chloride reactive group, and a carboxylic acid reactive group, to obtain a polymer modified with a carbon-carbon double bond; dispersing the colloidal particles in a solvent to obtain a monodisperse colloidal particle dispersion;

[0007] (2) mixing the monodisperse colloidal particle dispersion obtained in step (1) with a polymer modified with a carbon-carbon double bond, adding an initiator, and obtaining a supramolecular polymer-colloid complex by solvent volatilization;

[0008] (3) subjecting the supramolecular polymer-colloid complex obtained in step (2) to oscillation shearing, so that the colloidal particles in the complex are arranged into an ordered structure, thereby obtaining a supramolecular polymer-colloid composite photonic crystal with bright structural color;

[0009] (4) cross-linking and curing the supramolecular polymer-colloid composite photonic crystal with bright structural color obtained in step (3) by light irradiation or heating to obtain a stable polymer-colloid composite photonic crystal with bright structural color.

[0010] Preferably, the colloidal particles have a size of 150-250 nm; the colloidal particles are at least one of silica colloidal particles, polystyrene colloidal particles, ferroferric oxide colloidal particles, metal organic framework colloidal particles, cellulose nanocrystals, zinc sulfide colloidal particles, and cadmium sulfide colloidal particles; and the colloidal particles have hydroxyl, amino or carboxyl functional groups on their surfaces.

[0011] Preferably, the polymer is at least one of polydimethylsiloxane polymers, acrylate polymers, polyethylene glycol derivative polymers, polyethyleneimine polymers and polyurethane polymers; and the molecular weight of the polymer is greater than 2000.

[0012] Preferably, the mass concentration of the monodisperse colloidal particle dispersion is 5%-20%; the volume ratio of the polymer to the colloidal particle dispersion is (42-150):100.

[0013] Preferably, the initiator is a thermal initiator or a photoinitiator.

[0014] Preferably, the thermal initiator is at least one of benzoyl peroxide, diisopropylbenzene peroxide, azobisisobutyronitrile, azodicarbonamide, and azobisisobutylamidine hydrochloride; the photoinitiator is at least one of 2-hydroxy-2-methyl-1-phenylpropanone, 1-hydroxycyclohexylphenyl ketone, 2-dimethylamino-2-benzyl-1-[4-(4-morpholinyl)phenyl]-1-butanone, 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]-1-propanone, and methyl benzoylformate.

[0015] Preferably, the oscillating shearing temperature is 25° C.-40° C.; the shearing strain is 50%-1000%; and the shearing times are 10 times-1000 times.

[0016] Preferably, in step (1), the solvent is at least one of water, tetrahydrofuran, N,N-dimethylformamide, n-hexane, cyclohexane, methanol, ethanol, isopropanol, dimethyl sulfoxide, N,N-dimethylacetamide, chloroform, dichloromethane, acetone and ethyl acetate.

[0017] According to another aspect of the present invention, a stable polymer-colloid composite photonic crystal prepared by any one of the methods is provided.

[0018] According to another aspect of the present invention, there is provided application of the stable polymer-colloid composite photonic crystal in display, sensing or anti-counterfeiting.

[0019] In general, the above technical solution conceived by the present invention has the following technical advantages compared with the prior art:

[0020] (1) The reaction synthesis of the present invention is simple and the reaction conditions are mild. A polymer modified with double bond groups on the polymer chain can be obtained through a one-step reaction. The product after the reaction does not require post-treatment and can be stored for a long time. The intermolecular force of the polymer after the reaction is small, the molecular chain has good flexibility, and it can form weak bond interactions with the colloidal particles. At the same time, it has unsaturated carbon-carbon double bonds on the polymer chain. On the one hand, the weak bond interaction can ensure that the polymer can flow during the oscillating shear process, and at the same time, there is sufficient force between the polymer and the colloidal particles to drive the colloidal particles to arrange in order; on the other hand, after the colloidal particles are arranged in order, the carbon-carbon double bonds can be polymerized to form strong covalent bonds through cross-linking, thereby fixing the ordered structure of the colloidal particles and allowing the structural color of the supramolecular polymer-colloidal composite photonic crystal to exist stably.

[0021] (2) The polymers and compounds in the present invention have a wide range of sources. Based on the physical properties of polymers, supramolecular polymer-colloid composite photonic crystals can be used with specific functionality, for example, the introduction of conductive polymers enables the structural color composite film to achieve the coordinated output of light and electrical signals under stress.

[0022] (3) The method of obtaining a structural color composite film is simple and easy to scale up. By directly compounding a high molecular weight polymer containing double bonds with colloidal particles, due to the dynamic reversible interaction of supramolecular particles, the oscillating shearing technology can be used to achieve rapid and large-scale preparation of supramolecular polymer-colloid composite photonic crystals with structural colors. The method of the present invention can obtain supramolecular polymer-colloid composite photonic crystal films with different structural colors by flexibly adjusting the size and content of colloidal particles.

[0023] (4) The present invention constructs a supramolecular polymer-colloid composite photonic crystal film with a stable colloidal particle structure by modifying double bonds on the polymer chain. Compared with the composite film without modified double bonds, the supramolecular polymer-colloid composite photonic crystal film of the present invention has greatly improved mechanical properties, swelling cycle properties, and folding cycle properties after cross-linking, and is suitable for a wider range of application scenarios. BRIEF DESCRIPTION OF THE DRAWINGS

[0024] Figure 1 The diagram is a schematic diagram of the preparation and structure of the polymer-colloid composite photonic crystal described in the present invention.

[0025] Figure 2 This is the stretching cyclic stability and swelling cyclic stability of the polymer-colloid composite photonic crystal in Example 1.

[0026] Figure 3 The folding cycle of the polymer-colloid composite photonic crystal in Example 1 is stable.

[0027] Figure 4 Optical photographs and corresponding reflection spectra of the polymer-colloid composite photonic crystals in Examples 2-4.

[0028] Figure 5 These are electron microscope photos and optical photos of the polymer-colloid composite photonic crystals in Examples 5-7.

[0029] Figure 6 1 is the stress-strain curve of the polymer-colloid composite photonic crystal in Examples 8-10.

[0030] Figure 7 : Optical photograph of the polymer-colloid composite photonic crystal in Example 11 and the corresponding reflection spectrum. DETAILED DESCRIPTION

[0031] In order to make the purpose, technical solutions and advantages of the present invention more clearly understood, the present invention is further described in detail below in conjunction with the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not intended to limit the present invention. In addition, the technical features involved in the various embodiments of the present invention described below can be combined with each other as long as they do not conflict with each other.

[0032] Example 1

[0033] Figure 1 The figure is a schematic diagram of the preparation and structure of the polymer-colloid composite photonic crystal of the present invention. The present invention uses a cross-linkable polymer to prepare a stable polymer-colloid composite photonic crystal, comprising the following steps: first, polyethyleneimine with a molecular weight of 10K and glycidyl methacrylate are dispersed in ethanol respectively to prepare a dispersion with a mass fraction of 20%. The polyethyleneimine dispersion and the glycidyl methacrylate dispersion are added to a reaction container at a mass ratio of 15:1, and reacted at 15°C for 5.5 hours to obtain a polyethyleneimine-glycidyl methacrylate dispersion.

[0034] (1) Dispersing silicon dioxide with a size of 170 nm in ethanol, mixing the polyethyleneimine-methacrylate glycidyl dispersion obtained in step (1) with the silicon dioxide dispersion to form a precursor dispersion, wherein the volume fraction of silicon dioxide colloidal particles is 50%, and the initiator 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]-1-propanone is added in an amount of 0.15% of the mass of polyethyleneimine-methacrylate glycidyl. Then placing the precursor solution on a heating table at 40° C., volatilizing the ethanol under the action of magnetic stirring, and obtaining a supramolecular polymer-colloid composite slurry, wherein the solvent content is controlled to be 20%.

[0035] (2) placing the supramolecular polymer-colloid composite slurry obtained in step (1) between two PET films, pressing the composite into a film using a flat-plate hot press at 25° C. and a pressure of 5 MPa, and reciprocatingly shearing the film along a fixed rod at 25° C. for 30 times, so that the colloidal particles in the composite are arranged in an orderly manner, thereby producing a cross-linkable supramolecular polymer-colloid composite photonic crystal.

[0036] (3) The supramolecular polymer-colloid composite photonic crystal in step (2) is photocured under ultraviolet light for 10 minutes, thereby fixing the arrangement structure of the colloidal particles and generating a polymer-colloid composite photonic crystal with a stable structure.

[0037] like Figure 2 , Figure 3 As shown, its mechanical cycle performance, folding cycle performance and swelling cycle performance all have good stability.

[0038] Embodiment 2-4

[0039] A method for preparing a stable polymer-colloid composite photonic crystal using a cross-linkable polymer comprises the following steps:

[0040] (1) First, polyethyleneimine with a molecular weight of 10K and glycidyl methacrylate are dispersed in ethanol to prepare a dispersion with a mass fraction of 20%. The polyethyleneimine dispersion and the glycidyl methacrylate dispersion are added to a reaction container at a mass ratio of 15:1, and reacted at 15°C for 5.5 hours to obtain a polyethyleneimine-glycidyl methacrylate dispersion.

[0041] (2) Dispersing silica particles with a size of 186 nm in ethanol, mixing the polyethyleneimine-methacrylate glycidyl dispersion obtained in step (1) with the silica dispersion to form a precursor dispersion, wherein the volume fraction of silica colloidal particles is 40%, 50%, and 60%, and the content of the added initiator 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]-1-propanone is 0.15% of the mass of polyethyleneimine-methacrylate glycidyl. Then, placing the precursor solution on a heating table at 40° C., volatilizing the ethanol under the action of magnetic stirring, and obtaining a supramolecular polymer-colloid composite slurry, wherein the solvent content is controlled to be 20%.

[0042] (3) placing the supramolecular polymer-colloid composite slurry obtained in step (2) between two PET films, pressing the composite into a film using a flat-plate hot press at 25° C. and a pressure of 5 MPa, and reciprocatingly shearing the film along a fixed rod at 25° C. for 50 times, so that the colloidal particles in the composite are arranged in an orderly manner, thereby obtaining a cross-linkable supramolecular polymer-colloid composite photonic crystal.

[0043] (4) The supramolecular polymer-colloid composite photonic crystal in step (3) is photocured under ultraviolet light for 10 minutes to fix the arrangement structure of the colloidal particles and obtain a polymer-colloid composite film with a stable structure.

[0044] like Figure 4 Shown are optical photographs and corresponding reflection spectra of polymer-colloid composite photonic crystals prepared when the volume fraction of silica colloidal particles is 40%, 50%, and 60%.

[0045] Embodiment 5-7

[0046] A method for preparing a stable polymer-colloid composite photonic crystal using a cross-linkable polymer comprises the following steps:

[0047] (1) First, polyethyleneimine with a molecular weight of 10K and glycidyl methacrylate are dispersed in ethanol to prepare a dispersion with a mass fraction of 20%. The polyethyleneimine dispersion and the glycidyl methacrylate dispersion are added to a reaction container at a mass ratio of 15:1, and reacted at 15°C for 5.5 hours to obtain a polyethyleneimine-glycidyl methacrylate dispersion.

[0048] (2) Silica particles with sizes of 140 nm, 171 nm, and 200 nm are dispersed in ethanol respectively, and the polyethyleneimine-methacrylate glycidyl ester dispersion obtained in step (1) is mixed with the silica dispersion to form a precursor dispersion, wherein the volume ratio of polyethyleneimine-methacrylate glycidyl ester to silica colloidal particles is 1:1, and the initiator 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]-1-propanone is added in an amount of 0.15% of the mass of polyethyleneimine-methacrylate glycidyl ester. Then, the precursor solution is placed on a heating table at 40° C., and the ethanol is volatilized under the action of magnetic stirring to obtain a supramolecular polymer-colloid composite slurry, wherein the solvent content is controlled to be 20%.

[0049] (3) placing the supramolecular polymer-colloid composite slurry obtained in step (2) between two PET films, pressing the composite into a film using a flat-plate hot press at 25° C. and a pressure of 5 MPa, and reciprocatingly shearing the film along a fixed rod at 25° C. for 50 times, so that the colloidal particles in the composite are arranged in an orderly manner, thereby obtaining a cross-linkable supramolecular polymer-colloid composite photonic crystal.

[0050] (4) The supramolecular polymer-colloid composite photonic crystal in step (3) is photocured under ultraviolet light for 10 minutes to fix the arrangement structure of the colloidal particles and obtain a polymer-colloid composite film with a stable structure.

[0051] like Figure 5 Shown are optical photographs and corresponding electron microscope photographs of polymer-colloid composite photonic crystals prepared when the size of silica colloidal particles is 140nm, 171nm, and 200nm.

[0052] Embodiment 8-10

[0053] A method for preparing a stable polymer-colloid composite photonic crystal using a cross-linkable polymer comprises the following steps:

[0054] (1) First, polyethyleneimine with a molecular weight of 10K and glycidyl methacrylate were dispersed in ethanol to prepare a dispersion with a mass fraction of 20%. The polyethyleneimine dispersion and the glycidyl methacrylate dispersion were added to a reaction container at a mass ratio of 10:1, 15:1, and 20:1, and reacted at 15° C. for 5.5 hours to obtain a polyethyleneimine-glycidyl methacrylate dispersion.

[0055] (2) Dispersing silica particles with a size of 180 nm in ethanol, mixing the polyethyleneimine-methacrylate glycidyl dispersion obtained in step (1) with the silica dispersion to form a precursor dispersion, wherein the volume ratio of polyethyleneimine-methacrylate glycidyl and silica colloidal particles is 1:1, and the initiator 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]-1-propanone is added in an amount of 0.15% of the mass of polyethyleneimine-methacrylate glycidyl. Then, placing the precursor solution on a heating table at 40° C., volatilizing the ethanol under the action of magnetic stirring, and obtaining a supramolecular polymer-colloid composite slurry, wherein the solvent content is controlled to be 20%.

[0056] (3) placing the supramolecular polymer-colloid composite slurry obtained in step (2) between two PET films, pressing the composite into a film using a flat-plate hot press at 25° C. and a pressure of 5 MPa, and reciprocatingly shearing the film along a fixed rod at 25° C. for 50 times, so that the colloidal particles in the composite are arranged in an orderly manner, thereby obtaining a cross-linkable supramolecular polymer-colloid composite photonic crystal.

[0057] (4) The polymer-colloid composite film in step (3) is photocured under ultraviolet light for 10 minutes to fix the arrangement structure of the colloidal particles and obtain a supramolecular polymer-colloid composite photonic crystal with a stable structure.

[0058] like Figure 6 Shown are stress-strain curves of polymer-colloid composite photonic crystals prepared when the mass ratio of the polyethyleneimine dispersion to the glycidyl methacrylate dispersion is 10:1, 15:1, and 20:1.

[0059] Embodiment 11

[0060] A method for preparing a stable polymer-colloid composite photonic crystal using a cross-linkable polymer comprises the following steps:

[0061] (1) First, polyethyleneimine with a molecular weight of 10K and methacrylic anhydride are dispersed in ethanol to prepare a dispersion with a mass fraction of 20%. The polyethyleneimine dispersion and the glycidyl methacrylate dispersion are added to a reaction container at a mass ratio of 15:1, and reacted at 50°C for 3 hours to obtain a polyethyleneimine-methacrylic anhydride dispersion.

[0062] (2) Dispersing silica particles with a size of 176 nm in ethanol, mixing the polyethyleneimine-methacrylic anhydride dispersion obtained in step (1) with the silica dispersion to form a precursor dispersion, wherein the volume ratio of polyethyleneimine-methacrylic anhydride to silica colloidal particles is 1:1, and the initiator 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]-1-propanone is added in an amount of 0.15% of the mass of polyethyleneimine-methacrylic anhydride. Then, placing the precursor solution on a heating table at 40° C., volatilizing the ethanol under the action of magnetic stirring, and obtaining a supramolecular polymer-colloid composite slurry, wherein the solvent content is controlled to be 20%.

[0063] (3) placing the supramolecular polymer-colloid composite slurry obtained in step (2) between two PET films, pressing the composite into a film using a flat-plate hot press at 25° C. and a pressure of 5 MPa, and reciprocatingly shearing the film along a fixed rod at 25° C. for 50 times, so that the colloidal particles in the composite are arranged in an orderly manner, thereby obtaining a cross-linkable supramolecular polymer-colloid composite photonic crystal.

[0064] (4) The polymer-colloid composite film in step (3) is photocured under ultraviolet light for 10 minutes to fix the arrangement structure of the colloidal particles and obtain a supramolecular polymer-colloid composite photonic crystal with a stable structure.

[0065] like Figure 7 Shown are optical photographs and corresponding reflection spectra of polymer-colloid composite photonic crystals prepared from a composite of polyethylene imine and methacrylic anhydride and silica.

[0066] Example 12

[0067] A method for preparing a stable polymer-colloid composite photonic crystal using a cross-linkable polymer comprises the following steps:

[0068] (1) First, polyethylene glycol-polypropylene glycol-polyethylene glycol block copolymer with a molecular weight of 10K and methacrylic anhydride are dispersed in ethanol to prepare a dispersion with a mass fraction of 20%. The dispersion of polyethylene imine and the dispersion of glycidyl methacrylate are added to a reaction container at a mass ratio of 15:1, and reacted at 50° C. for 3 hours to obtain a polyethylene glycol-polypropylene glycol-polyethylene glycol-methacrylic anhydride dispersion.

[0069] (2) Dispersing silica particles with a size of 186 nm in ethanol, mixing the polyethylene glycol-polypropylene glycol-polyethylene glycol-methacrylic anhydride dispersion obtained in step (1) with the silica dispersion to form a precursor dispersion, wherein the volume ratio of polyethyleneimine-methacrylic anhydride to silica colloidal particles is 1:1, and the initiator 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]-1-propanone is added in an amount of 0.15% of the mass of polyethyleneimine-methacrylic anhydride. Then, placing the precursor solution on a heating table at 40° C., volatilizing the ethanol under the action of magnetic stirring, and obtaining a supramolecular polymer-colloid composite slurry, wherein the solvent content is controlled to be 20%.

[0070] (3) placing the supramolecular polymer-colloid composite slurry obtained in step (2) between two PET films, pressing the composite into a film using a flat-plate hot press at 25° C. and a pressure of 5 MPa, and reciprocatingly shearing the film along a fixed rod at 25° C. for 50 times, so that the colloidal particles in the composite are arranged in an orderly manner, thereby obtaining a cross-linkable supramolecular polymer-colloid composite photonic crystal.

[0071] (4) The supramolecular polymer-colloid composite photonic crystal in step (3) is photocured under ultraviolet light for 10 minutes to fix the arrangement structure of the colloidal particles and obtain a supramolecular polymer-colloid composite photonic crystal with a stable structure.

[0072] Embodiment 13

[0073] A method for preparing a stable polymer-colloid composite photonic crystal using a cross-linkable polymer comprises the following steps:

[0074] (1) First, polyethyleneimine with a molecular weight of 10K and glycidyl methacrylate are dispersed in ethanol to prepare a dispersion with a mass fraction of 20%. The polyethyleneimine dispersion and the glycidyl methacrylate dispersion are added to a reaction container at a mass ratio of 15:1, and reacted at 15°C for 5.5 hours to obtain a polyethyleneimine-glycidyl methacrylate dispersion.

[0075] (2) Dispersing poly(styrene-co-acrylic acid) with a size of 210 nm in ethanol, mixing the polyethyleneimine-methacrylate glycidyl dispersion obtained in step (1) with the poly(styrene-co-acrylic acid) dispersion to form a precursor dispersion, wherein the volume ratio of polyethyleneimine-methacrylate glycidyl and silica colloidal particles is 1:1, and the content of the initiator 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]-1-propanone added is 0.15% of the mass of polyethyleneimine-methacrylate glycidyl. Then, placing the precursor solution on a heating table at 40° C., volatilizing the ethanol under the action of magnetic stirring, and obtaining a supramolecular polymer-colloid composite slurry, wherein the solvent content is controlled to be 20%.

[0076] (3) placing the supramolecular polymer-colloid composite slurry obtained in step (2) between two PET films, pressing the composite into a film using a flat-plate hot press at 25° C. and a pressure of 5 MPa, and reciprocatingly shearing the film along a fixed rod at 25° C. for 30 times, so that the colloidal particles in the composite are arranged in an orderly manner, thereby obtaining a cross-linkable supramolecular polymer-colloid composite photonic crystal.

[0077] (4) The supramolecular polymer-colloid composite photonic crystal in step (3) is photocured under ultraviolet light for 10 minutes to fix the arrangement structure of the colloidal particles and obtain a supramolecular polymer-colloid composite photonic crystal with a stable structure.

[0078] It will be easily understood by those skilled in the art that the above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should be included in the protection scope of the present invention.

Claims

1. A method for preparing a stable polymer-colloid composite photonic crystal, characterized in that: The following steps are involved: (1) reacting a polymer with a compound containing a carbon-carbon double bond, wherein the polymer contains at least one of an amino group, a hydroxyl group, and a halogen atom, and the compound contains at least one of an anhydride reactive group, an epoxy reactive group, an acyl chloride reactive group, and a carboxylic acid reactive group, to obtain a polymer modified with a carbon-carbon double bond; dispersing the colloidal particles in a solvent to obtain a monodisperse colloidal particle dispersion; (2) mixing the monodisperse colloidal particle dispersion obtained in step (1) with a polymer modified with a carbon-carbon double bond, adding an initiator, and obtaining a supramolecular polymer-colloid complex by solvent volatilization; (3) subjecting the supramolecular polymer-colloid complex obtained in step (2) to oscillation shearing, so that the colloidal particles in the complex are arranged into an ordered structure, thereby obtaining a supramolecular polymer-colloid composite photonic crystal with bright structural color; (4) cross-linking and curing the supramolecular polymer-colloid composite photonic crystal with bright structural color obtained in step (3) by light irradiation or heating to obtain a stable polymer-colloid composite photonic crystal with bright structural color.

2. The method for preparing a stable polymer-colloid composite photonic crystal according to claim 1, characterized in that: The colloidal particles have a size of 150-250 nm; the colloidal particles are at least one of silicon dioxide colloidal particles, polystyrene colloidal particles, ferroferric oxide colloidal particles, metal organic framework colloidal particles, cellulose nanocrystals, zinc sulfide colloidal particles, and cadmium sulfide colloidal particles; and the colloidal particles have hydroxyl, amino or carboxyl functional groups on their surfaces.

3. The method for preparing a stable polymer-colloid composite photonic crystal according to claim 1, characterized in that: The polymer is at least one of polydimethylsiloxane polymers, acrylate polymers, polyethylene glycol derivative polymers, polyethyleneimine polymers and polyurethane polymers; and the molecular weight of the polymer is greater than 2000.

4. The method for preparing a stable polymer-colloid composite photonic crystal according to claim 1, characterized in that: The mass concentration of the monodisperse colloidal particle dispersion is 5%-20%; the volume ratio of the polymer to the colloidal particle dispersion is (42-150):

100.

5. The method for preparing a stable polymer-colloid composite photonic crystal according to claim 1, characterized in that: The initiator is a thermal initiator or a photoinitiator.

6. The method for preparing a stable polymer-colloid composite photonic crystal according to claim 5, characterized in that: The thermal initiator is at least one of benzoyl peroxide, diisopropylbenzene peroxide, azobisisobutyronitrile, azodicarbonamide, and azobisisobutylamidine hydrochloride; the photoinitiator is at least one of 2-hydroxy-2-methyl-1-phenylpropanone, 1-hydroxycyclohexylphenyl ketone, 2-dimethylamino-2-benzyl-1-[4-(4-morpholinyl)phenyl]-1-butanone, 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]-1-propanone, and methyl benzoylformate.

7. The method for preparing a stable polymer-colloid composite photonic crystal according to claim 1, characterized in that: The oscillating shearing temperature is 25° C.-40° C.; the shearing strain is 50%-1000%; and the shearing times are 10 times-1000 times.

8. The method for preparing a stable polymer-colloid composite photonic crystal according to claim 1, characterized in that: In step (1), the solvent is at least one of water, tetrahydrofuran, N,N-dimethylformamide, n-hexane, cyclohexane, methanol, ethanol, isopropanol, dimethyl sulfoxide, N,N-dimethylacetamide, chloroform, dichloromethane, acetone and ethyl acetate.

9. A stable polymer-colloid composite photonic crystal prepared by the method of any one of claims 1 to 8.

10. Application of the stable polymer-colloid composite photonic crystal as claimed in claim 9 in display, sensing or anti-counterfeiting.

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