Microphase-separated photonic crystal gel, its preparation method, structural color regulation method and application

Abstract

The present invention belongs to the technical field of intelligent response biomedical materials, and relates to a microphase-separated photonic crystal gel, its preparation method, structural color regulation method and application. A suspension is obtained by adding a polyglycol solution, a polymer precursor solution, a photoinitiator, and a light absorber to a monodisperse colloidal particle solution and stirring evenly; then the solvent in the monodisperse colloidal particle solution is evaporated; finally, curing is carried out to obtain a microphase-separated photonic crystal gel; the photonic crystal gel is composed of monodisperse colloidal particles and a polyglycol-based gel with microphase separation characteristics, and the monodisperse colloidal particles self-assemble into photonic crystals in the polyglycol-based gel; during the preparation process, while keeping other conditions unchanged, only changing the particle size of the monodisperse colloidal particles or the molecular weight of the polyglycol can change the structural color of the microphase-separated photonic crystal gel. The microphase-separated photonic crystal gel of the present invention has a high color change response sensitivity, and the structural color regulation method is simple, not only with high usability but also lower cost.

Description

Technical Field

[0001] The invention belongs to the technical field of intelligent response biomedical materials, and relates to microphase separation photonic crystal gel and a preparation method thereof, a structural color regulation method and an application thereof. Background Art

[0002] Colloidal photonic crystals are an ordered material composed of two or more materials with different dielectric constants, which have a spatial periodic structure. With their unique structural properties, photonic crystals can control the light path through the photonic band gap in a multi-scale environment and show specific, vivid and bright colors, namely structural colors. This property enables the color of photonic crystals to be intelligently controlled by stimuli from the external environment. Based on this principle, researchers have developed a series of photonic crystal materials that respond to mechanical and temperature changes.

[0003] When a conventional photonic crystal is subjected to external mechanical, temperature or other forms of stimulation, its lattice spacing will expand or contract uniformly, thereby changing from a balanced ordered state to a tense ordered state. This change will cause a continuous color response. For example, there are related descriptions in the patent application with publication number CN117777512A and the patent application with publication number CN117843886. However, the degree of this color response depends on the degree of change in the lattice spacing, so the response sensitivity is relatively low. This limitation limits the application of conventional photonic crystals in certain fields, especially in situations where high-sensitivity color response is required.

[0004] In addition, existing technologies mainly control the structural color of photonic crystal materials by changing the particle size of monodisperse colloidal particles. This method does have certain limitations in terms of control range and flexibility.

[0005] Timely and accurate monitoring of liquid exudation from skin wounds or pipeline gaps is crucial for evaluating wound recovery, preventing wound infection, and detecting pipeline leaks. However, existing technologies, such as direct observation, dressing absorption, weighing, and listening / acoustic vibration for pipeline gaps, infrared thermal imaging, ground penetrating radar, and regional metering, all have their own drawbacks, such as insufficient accuracy, low sensitivity, high cost, complex operation, and poor environmental adaptability.

[0006] Therefore, developing a photonic crystal material with higher response sensitivity and more diverse structural color regulation methods, and applying it to monitor liquid seepage on the surface of skin wounds or pipeline gaps will have great practical significance and potential value. Summary of the invention

[0007] The object of the present invention is to solve the problems in the prior art and provide a microphase-separated photonic crystal gel, a preparation method thereof, a structural color regulation method and an application thereof.

[0008] To achieve the above object, the present invention adopts the following technical solutions:

[0009] A microphase-separated photonic crystal gel includes monodisperse colloidal particles and a polyglycol gel with microphase separation characteristics. The monodisperse colloidal particles self-assemble in the polyglycol gel to form a photonic crystal. The reaction raw materials of the polyglycol gel include polyglycol.

[0010] The polyglycol gel has microphase separation characteristics. As Figure 1 shown, when the gel contacts water or other solutions, a local microphase separation occurs in the stretched cross-linked network inside the gel. The scale of the microphase separation is at the sub-micron level, similar to the scale of the monodisperse colloidal particles, and hard and soft segments are generated in the gel. The polymer-rich hard segments undergo local contraction, and the solvent-rich soft segments gradually elongate. This causes the lattice network of the photonic crystal to change from a balanced ordered state to a disordered state, breaking the requirement of the periodic arrangement of the photonic crystal lattice, resulting in the photonic crystal no longer conforming to Bragg's law, that is, the structural color disappears. At the same time, during the stretching process, the hard segments increase the strength by dissipating energy, while the soft segments prevent the gel from breaking prematurely, thus showing high toughness. In the traditional method, a threshold of stimulation needs to be accumulated before an obvious color change occurs. The threshold of the color change response in the response method of the present invention will be significantly reduced, and the response is more sensitive. Only a trace amount of solution can trigger a color response.

[0011] As a preferred technical solution:

[0012] For the microphase-separated photonic crystal gel as described above, the crystal structure of the photonic crystal is a non-close-packed structure, and the monodisperse colloidal particles are silica microspheres modified by sulfonation or carboxylation on the surface. The silica microspheres modified by sulfonation or carboxylation on the surface have extremely high surface charges and can form a non-close-packed structure by electrostatic stabilization.

[0013] For the microphase-separated photonic crystal gel as described above, the surface potential of the monodisperse colloidal particles is lower than -30 eV or higher than 30 eV, the particle size is 50 - 1000 nm, and the polydispersity index is less than or equal to 0.05.

[0014] For the microphase-separated photonic crystal gel as described above, the surface potential of the monodisperse colloidal particles is lower than -35 eV or higher than 35 eV.

[0015] For the microphase-separated photonic crystal gel as described above, the surface potential of the monodisperse colloidal particles is lower than -40 eV or higher than 40 eV, and the particle size is 80 - 500 nm.

[0016] A microphase-separated photonic crystal gel as described above, wherein the volume percentage of monodisperse colloidal particles in the microphase-separated photonic crystal gel is 15% to 74%.

[0017] A microphase-separated photonic crystal gel as described above, wherein the polyglycol is PEG and / or PPG, the PEG is one or more of PEG with a molecular weight of 100 g / mol, PEG with a molecular weight of 200 g / mol, PEG with a molecular weight of 400 g / mol, PEG with a molecular weight of 600 g / mol, and PEG with a molecular weight of 800 g / mol, and the PPG is one or more of PPG with a molecular weight of 400 g / mol, PPG with a molecular weight of 600 g / mol, and PPG with a molecular weight of 800 g / mol.

[0018] A method for preparing a microphase-separated photonic crystal gel as described in any one of the above, comprising the following steps:

[0019] (a) Adding a polyglycol solution, a polymer precursor solution, a photoinitiator, and a light absorber to the monodisperse colloidal particle solution and stirring evenly to obtain a suspension;

[0020] (b) Evaporating (for 2 to 12 h at 60 to 100 °C) to remove the solvent in the monodisperse colloidal particle solution to obtain a photonic crystal solution with structural color;

[0021] (c) Curing to obtain a microphase-separated photonic crystal gel; different processing methods can be selected to obtain microphase-separated photonic crystal gel products with different morphologies. For example, after pouring, extruding, and coating the photonic crystal solution and then curing, a microphase-separated photonic crystal gel film, a microphase-separated photonic crystal gel fiber, and a microphase-separated photonic crystal gel coating can be obtained. By repeating the "single-layer printing - curing of the photonic crystal solution" operation using digital light processing 3D printing technology, a three-dimensional model can be obtained.

[0022] As a preferred solution:

[0023] In the method as described above, in step (a), the concentration of the monodisperse colloidal particle solution is 5 to 15 wt%, in the suspension, the volume percentage of the polyglycol is 5 to 20%, the volume percentage of the polymer precursor is 5 to 20%, the volume percentage of the photoinitiator is 0.05 to 0.15%, and the volume percentage of the light absorber is 0.005 to 0.025%; the specific process of step (c) is: irradiating under ultraviolet light for 5 to 30 min to obtain a microphase-separated photonic crystal gel.

[0024] In the method described above, in step (a), the polymer precursor is one or more of hydroxyethyl acrylate, hydroxyethyl methacrylate, benzyl methacrylate, polyethylene glycol monomethacrylate, and polymethyl methacrylate; the photoinitiator is one or more of diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide and 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone; the light absorber is one or more of carbon black, polydopamine nanoparticles, and silver nanoparticles.

[0025] A method for regulating the structural color of a microphase-separated photonic crystal gel. During the preparation of the microphase-separated photonic crystal gel by using the method described in any one of the above, while keeping other conditions unchanged, only changing the particle size of the monodisperse colloidal particles or the molecular weight of the polyglycol can change the structural color of the microphase-separated photonic crystal gel. The principle of changing the structural color of the microphase-separated photonic crystal gel by changing the molecular weight of the polyglycol is as follows: The monodisperse colloidal particles are linked to the polyglycol by hydrogen bonds, and the covalent bond link of the long chain of the polyglycol will promote the close link of the monodisperse colloidal particles compared with the hydrogen bond link. The longer the polyglycol chain length, the more covalent bond combinations between the silica spheres, and the smaller the spacing between the silica spheres, making the structural color tend to blue shift.

[0026] The present invention also provides an application of a microphase-separated photonic crystal gel described in any one of the above, which is used to make a patch and attach it to the surface of a skin wound or a pipeline gap, and shows whether there is liquid leakage through color change.

[0027] Beneficial effects:

[0028] The microphase-separated photonic crystal gel prepared by the present invention effectively improves the sensitivity of the color change response by using the microphase separation to trigger the response change mode of the colloidal particles from order to disorder. When it is applied to the liquid leakage monitoring of skin wounds and pipeline gap surfaces, no other additional equipment is required, the operation is simple, the monitoring is sensitive, and it not only has higher usability but also lower cost. Description of the drawings

[0029] Figure 1 It is a schematic diagram of the microphase separation response of the microphase-separated photonic crystal gel;

[0030] Figure 2 It is a graph showing the change of the structural color of the microphase-separated photonic crystal gel patch prepared in Example 3 with the phase separation time;

[0031] Figure 3 It is a diagram of the microphase-separated photonic crystal gel patch prepared in the example part. In the figure, (a) is prepared in Example 3, (b) is prepared in Example 12, and (c) is prepared in Example 13. Detailed implementation manners

[0032] The above solution is further illustrated below in conjunction with non-limiting examples, so as to help those skilled in the relevant art understand the present invention more completely. It should be noted that the protection scope of the present invention should not be limited thereby. For those skilled in the art, several adjustments and improvements can be made without departing from the principle of the present invention, and these adjustments and improvements should also be covered by the protection scope of the present invention.

[0033] Example 1

[0034] A preparation method of a microphase-separated photonic crystal gel is as follows:

[0035] (1) Raw material preparation:

[0036] Monodisperse colloidal particle solution: with a concentration of 10 wt%, the solvent is acetone. Among them, the monodisperse colloidal particles are silica microspheres modified by sulfonation on the surface, with a surface potential of -36 eV, an average particle size of 50 nm, and a polydispersity index of 0.03;

[0037] Polyethylene glycol: PEG with a molecular weight of 100 g / mol;

[0038] Polymer precursor: 2-Hydroxyethyl acrylate;

[0039] Photoinitiator: Diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide;

[0040] Light absorber: Carbon black with an average particle size of 30 nm;

[0041] (2) Preparation of the microphase-separated photonic crystal gel:

[0042] (a) Add polyethylene glycol, polymer precursor, photoinitiator, and light absorber to the monodisperse colloidal particle solution and stir evenly to obtain a suspension; in the suspension, the volume percentage of polyethylene glycol is 5%, the volume percentage of the polymer precursor is 20%, the volume percentage of the photoinitiator is 0.05%, and the volume percentage of the light absorber is 0.005%;

[0043] (b) Evaporate the solvent in the monodisperse colloidal particle solution at 60 °C to obtain a photonic crystal solution with structural color;

[0044] (c) Irradiate with ultraviolet light for 5 min to obtain a microphase-separated photonic crystal gel.

[0045] The finally prepared microphase-separated photonic crystal gel is composed of monodisperse colloidal particles and a PEG gel with microphase separation characteristics; among them, the monodisperse colloidal particles self-assemble into a photonic crystal in the PEG gel, the crystal structure of the photonic crystal is a non-close-packed structure, and the volume percentage of the monodisperse colloidal particles in the microphase-separated photonic crystal gel is 28.57%.

[0046] The microphase-separated photonic crystal gel (with structural color) prepared in this example was made into a patch and applied to the surface of the skin wound. It was observed that the structural color changed as the wound healed, indicating that the microphase-separated photonic crystal gel prepared in this example has a clear responsiveness to liquid exudation.

[0047] Example 2

[0048] A preparation method of a microphase-separated photonic crystal gel is as follows:

[0049] (1) Raw material preparation:

[0050] Monodisperse colloidal particle solution: with a concentration of 10 wt%, and the solvent is ethanol. Among them, the monodisperse colloidal particles are silica microspheres modified by sulfonation on the surface, with a surface potential of -36 eV, an average particle size of 120 nm, and a polydispersity index of 0.03;

[0051] Polyethylene glycol: PEG with a molecular weight of 200 g / mol;

[0052] Polymer precursor: 2-Hydroxyethyl acrylate;

[0053] Photoinitiator: Diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide;

[0054] Light absorber: Carbon black with an average particle size of 30 nm;

[0055] (2) Preparation of the microphase-separated photonic crystal gel:

[0056] (a) Add polyethylene glycol, polymer precursor, photoinitiator, and light absorber to the monodisperse colloidal particle solution and stir evenly to obtain a suspension; in the suspension, the volume percentage of polyethylene glycol is 7%, the volume percentage of the polymer precursor is 18%, the volume percentage of the photoinitiator is 0.065%, and the volume percentage of the light absorber is 0.008%;

[0057] (b) Evaporate the solvent in the monodisperse colloidal particle solution at 65 °C to obtain a photonic crystal solution with structural color;

[0058] (c) Irradiate with ultraviolet light for 9 min to obtain a microphase-separated photonic crystal gel.

[0059] The finally prepared microphase-separated photonic crystal gel is composed of monodisperse colloidal particles and a PEG gel with microphase separation characteristics; among them, the monodisperse colloidal particles self-assemble to form a photonic crystal in the PEG gel. The crystal structure of this photonic crystal is a non-close-packed structure, and the volume percentage of the monodisperse colloidal particles in the microphase-separated photonic crystal gel is 28.57%.

[0060] The microphase-separated photonic crystal gel (with structural color) prepared in this example was made into a patch and applied to the surface of the skin wound. It was observed that the structural color changed as the wound healed.

[0061] Example 3

[0062] A preparation method of a microphase-separated photonic crystal gel is as follows:

[0063] (1) Raw material preparation:

[0064] Monodisperse colloidal particle solution: with a concentration of 10 wt%, the solvent is methanol. Among them, the monodisperse colloidal particles are silica microspheres modified by sulfonation on the surface, with a surface potential of -36 eV, an average particle size of 140 nm, and a polydispersity index of 0.04;

[0065] Polyethylene glycol: PEG with a molecular weight of 400 g / mol;

[0066] Polymer precursor: 2-hydroxyethyl methacrylate;

[0067] Photoinitiator: 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone;

[0068] Light absorber: Polydopamine nanoparticles with an average particle size of 50 nm;

[0069] (2) Preparation of the microphase-separated photonic crystal gel:

[0070] (a) Add polyethylene glycol, polymer precursor, photoinitiator, and light absorber to the monodisperse colloidal particle solution and stir evenly to obtain a suspension; in the suspension, the volume percentage of polyethylene glycol is 9%, the volume percentage of the polymer precursor is 16%, the volume percentage of the photoinitiator is 0.08%, and the volume percentage of the light absorber is 0.012%;

[0071] (b) Evaporate the solvent in the monodisperse colloidal particle solution at 70 °C to obtain a photonic crystal solution with structural color;

[0072] (c) Irradiate with ultraviolet light for 12 min to obtain a microphase-separated photonic crystal gel.

[0073] The finally prepared microphase-separated photonic crystal gel is composed of monodisperse colloidal particles and a PEG gel with microphase separation characteristics; among them, the monodisperse colloidal particles self-assemble into a photonic crystal in the PEG gel. The crystal structure of this photonic crystal is a non-close-packed structure, and the volume percentage of the monodisperse colloidal particles in the microphase-separated photonic crystal gel is 28.57%.

[0074] The microphase-separated photonic crystal gel (with structural color) prepared in this example was made into a patch and applied to the surface of a skin wound. It was observed that as the wound healed, the structural color changed (as Figure 2 shown).

[0075] Comparative Example 1

[0076] A preparation method of a photonic crystal gel is basically the same as that of Example 3, except that: in this comparative example, the polyglycol was changed to deionized water of the same volume.

[0077] The finally prepared photonic crystal gel is composed of monodisperse colloidal particles and a hydrogel; among them, the monodisperse colloidal particles self-assemble to form a photonic crystal in the hydrogel, and the crystal structure of the photonic crystal is a non-close-packed structure.

[0078] The photonic crystal gel prepared in Comparative Example 1 was made into a patch and applied to the surface of a skin wound. It was found that the hydrogel patch only responded to the stretching of the wound, but had no predictability for the wound healing process, and its mechanical properties were extremely poor; the reason for such a phenomenon in Comparative Example 1 was that the hydrogel material would not produce a biphasic phase after absorbing water and could not undergo microphase separation, so it had no responsiveness to the water environment, and because the molecular weight of water was extremely low compared to polyglycol, the patch had no mechanical enhancement characteristics.

[0079] Example 4

[0080] A preparation method of a microphase-separated photonic crystal gel is as follows:

[0081] (1) Raw material preparation:

[0082] Monodisperse colloidal particle solution: with a concentration of 5 wt%, the solvent is acetone, where the monodisperse colloidal particles are sulfonated surface-modified silica microspheres with a surface potential of -36 eV, an average particle size of 160 nm, and a polydispersity index of 0.02;

[0083] Polyglycol: PEG with a molecular weight of 600 g / mol;

[0084] Polymer precursor: 2-Hydroxyethyl methacrylate;

[0085] Photoinitiator: Diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide;

[0086] Light absorber: Polydopamine nanoparticles with an average particle size of 50 nm;

[0087] (2) Preparation of the microphase-separated photonic crystal gel:

[0088] (a) Add polyethylene glycol, polymer precursor, photoinitiator, and light absorber to the monodisperse colloidal particle solution and stir evenly to obtain a suspension; in the suspension, the volume percentage of polyethylene glycol is 12%, the volume percentage of the polymer precursor is 14%, the volume percentage of the photoinitiator is 0.09%, and the volume percentage of the light absorber is 0.015%;

[0089] (b) Evaporate the solvent in the monodisperse colloidal particle solution at 75 °C to obtain a photonic crystal solution with structural color;

[0090] (c) Irradiate with ultraviolet light for 15 min to obtain a microphase-separated photonic crystal gel.

[0091] The finally prepared microphase-separated photonic crystal gel is composed of monodisperse colloidal particles and a PEG gel with microphase separation characteristics; among them, the monodisperse colloidal particles self-assemble into a photonic crystal in the PEG gel, the crystal structure of the photonic crystal is a non-close-packed structure, and the volume percentage of the monodisperse colloidal particles in the microphase-separated photonic crystal gel is 16.12%.

[0092] The microphase-separated photonic crystal gel (with structural color) prepared in this example was made into a patch and applied to the surface of the skin wound. It was observed that the structural color changed as the wound healed.

[0093] Example 5

[0094] A preparation method of a microphase-separated photonic crystal gel is as follows:

[0095] (1) Raw material preparation:

[0096] Monodisperse colloidal particle solution: with a concentration of 7 wt%, the solvent is ethanol, among which the monodisperse colloidal particles are silica microspheres modified by carboxylation on the surface, the surface potential is -32 eV, the average particle size is 200 nm, and the polydispersity index is 0.02;

[0097] Polyethylene glycol: PEG with a molecular weight of 800 g / mol;

[0098] Polymer precursor: benzyl methacrylate;

[0099] Photoinitiator: a mixture of diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide and 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylacetophenone with a mass ratio of 1:1;

[0100] Light absorber: silver nanoparticles with an average particle size of 50 nm;

[0101] (2) Preparation of the microphase-separated photonic crystal gel:

[0102] (a) Add polyglycol, polymer precursor, photoinitiator, and light absorber to the monodisperse colloidal particle solution and stir evenly to obtain a suspension; in the suspension, the volume percentage of polyglycol is 14%, the volume percentage of the polymer precursor is 12%, the volume percentage of the photoinitiator is 0.1%, and the volume percentage of the light absorber is 0.018%;

[0103] (b) Evaporate the solvent in the monodisperse colloidal particle solution at 80 °C to obtain a photonic crystal solution with structural color;

[0104] (c) Irradiate with ultraviolet light for 18 min to obtain a microphase-separated photonic crystal gel.

[0105] The finally prepared microphase-separated photonic crystal gel is composed of monodisperse colloidal particles and a PEG gel with microphase separation characteristics; among them, the monodisperse colloidal particles self-assemble to form a photonic crystal in the PEG gel. The crystal structure of the photonic crystal is a non-close-packed structure, and the volume percentage of the monodisperse colloidal particles in the microphase-separated photonic crystal gel is 21.21%.

[0106] Make the microphase-separated photonic crystal gel (with structural color) prepared in this example into a patch and attach it to the surface of the pipeline gap. It is observed that the structural color changes with the expansion degree of the pipeline gap.

[0107] Example 6

[0108] A preparation method of a microphase-separated photonic crystal gel is as follows:

[0109] (1) Raw material preparation:

[0110] Monodisperse colloidal particle solution: The concentration is 13 wt%, the solvent is methanol. Among them, the monodisperse colloidal particles are silica microspheres modified by carboxylation on the surface, the surface potential is -32 eV, the average particle size is 300 nm, and the polydispersity index is 0.02;

[0111] Polyglycol: PPG with a molecular weight of 400 g / mol;

[0112] Polymer precursor: Polyethylene glycol monomethacrylate with a molecular weight of 375 g / mol;

[0113] Photoinitiator: Diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide;

[0114] Light absorber: A mixture of carbon black (average particle size of 30 nm) and silver nanoparticles (average particle size of 50 nm) with a mass ratio of 1:1;

[0115] (2) Preparation of microphase-separated photonic crystal gel:

[0116] (a) Add polyglycol, polymer precursor, photoinitiator, and light absorber to the monodisperse colloidal particle solution and stir evenly to obtain a suspension; in the suspension, the volume percentage of polyglycol is 16%, the volume percentage of polymer precursor is 9%, the volume percentage of photoinitiator is 0.115%, and the volume percentage of light absorber is 0.02%.

[0117] (b) Evaporate the solvent in the monodisperse colloidal particle solution at 85 °C to obtain a photonic crystal solution with structural color.

[0118] (c) Irradiate with ultraviolet light for 20 min to obtain a microphase-separated photonic crystal gel.

[0119] The finally prepared microphase-separated photonic crystal gel is composed of monodisperse colloidal particles and PPG gel with microphase-separation characteristics; among them, the monodisperse colloidal particles self-assemble into a photonic crystal in the PPG gel, the crystal structure of the photonic crystal is a non-close-packed structure, and the volume percentage of the monodisperse colloidal particles in the microphase-separated photonic crystal gel is 34.21%.

[0120] Make the microphase-separated photonic crystal gel (with structural color) prepared in this example into a patch and attach it to the surface of the pipeline gap. It is observed that the structural color changes with the expansion degree of the pipeline gap.

[0121] Example 7

[0122] A preparation method of a microphase-separated photonic crystal gel is as follows:

[0123] (1) Raw material preparation:

[0124] Monodisperse colloidal particle solution: The concentration is 15 wt%, the solvent is acetone, among which the monodisperse colloidal particles are silica microspheres modified by carboxylation on the surface, the surface potential is -32 eV, the average particle size is 600 nm, and the polydispersity index is 0.02.

[0125] Polyglycol: PPG with a molecular weight of 600 g / mol.

[0126] Polymer precursor: Polymethyl methacrylate with a molecular weight of 575 g / mol.

[0127] Photoinitiator: 2-Hydroxy-4'-(2-hydroxyethoxy)-2-methylacetone.

[0128] Light absorber: Polydopamine nanoparticles with an average particle size of 50 nm.

[0129] (2) Prepare the microphase-separated photonic crystal gel:

[0130] (a) Add polyglycol, polymer precursor, photoinitiator, and light absorber to the monodisperse colloidal particle solution and stir evenly to obtain a suspension; in the suspension, the volume percentage of polyglycol is 18%, the volume percentage of polymer precursor is 7%, the volume percentage of photoinitiator is 0.13%, and the volume percentage of light absorber is 0.023%;

[0131] (b) Evaporate the solvent in the monodisperse colloidal particle solution at 90 °C to obtain a photonic crystal solution with structural color;

[0132] (c) Irradiate with ultraviolet light for 25 min to obtain a microphase-separated photonic crystal gel.

[0133] The finally prepared microphase-separated photonic crystal gel is composed of monodisperse colloidal particles and PPG gel with microphase separation characteristics; among them, the monodisperse colloidal particles self-assemble to form a photonic crystal in the PPG gel, the crystal structure of the photonic crystal is a non-close-packed structure, and the volume percentage of the monodisperse colloidal particles in the microphase-separated photonic crystal gel is 37.50%.

[0134] The microphase-separated photonic crystal gel (with structural color) prepared in this example was made into a patch and pasted on the surface of the pipeline gap. It was observed that the structural color changed with the change of the pipeline gap expansion degree.

[0135] Example 8

[0136] A preparation method of a microphase-separated photonic crystal gel is as follows:

[0137] (1) Raw material preparation:

[0138] Monodisperse colloidal particle solution: with a concentration of 15 wt%, the solvent is ethanol, among which the monodisperse colloidal particles are silica microspheres modified by carboxylation on the surface, the surface potential is -32 eV, the average particle size is 1000 nm, and the polydispersity index is 0.02;

[0139] Polyglycol: PPG with a molecular weight of 800 g / mol;

[0140] Polymer precursor: a mixture of hydroxyethyl acrylate and hydroxyethyl methacrylate with a mass ratio of 1:1;

[0141] Photoinitiator: diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide;

[0142] Light absorber: silver nanoparticles with an average particle size of 50 nm;

[0143] (2) Preparation of microphase-separated photonic crystal gel:

[0144] (a) Add polyethylene glycol, polymer precursor, photoinitiator, and light absorber to the monodisperse colloidal particle solution and stir evenly to obtain a suspension; in the suspension, the volume percentage of polyethylene glycol is 20%, the volume percentage of the polymer precursor is 5%, the volume percentage of the photoinitiator is 0.15%, and the volume percentage of the light absorber is 0.025%.

[0145] (b) Evaporate the solvent in the monodisperse colloidal particle solution at 100 °C to obtain a photonic crystal solution with structural color.

[0146] (c) Irradiate with ultraviolet light for 30 min to obtain a microphase-separated photonic crystal gel.

[0147] The finally prepared microphase-separated photonic crystal gel is composed of monodisperse colloidal particles and a PPG gel with microphase-separation characteristics; among them, the monodisperse colloidal particles self-assemble into a photonic crystal in the PPG gel, the crystal structure of the photonic crystal is a non-close-packed structure, and the volume percentage of the monodisperse colloidal particles in the microphase-separated photonic crystal gel is 37.50%.

[0148] Make the microphase-separated photonic crystal gel (with structural color) prepared in this example into a patch and attach it to the surface of the pipeline gap. It is observed that the structural color changes with the expansion degree of the pipeline gap.

[0149] Example 9

[0150] A preparation method of a microphase-separated photonic crystal gel is basically the same as that of Example 1, except that: the surface potential of the monodisperse colloidal particles in this example is 36 eV.

[0151] The finally prepared microphase-separated photonic crystal gel is composed of monodisperse colloidal particles and a PEG gel with microphase-separation characteristics; among them, the monodisperse colloidal particles self-assemble into a photonic crystal in the PEG gel, and the crystal structure of the photonic crystal is a non-close-packed structure.

[0152] Make the microphase-separated photonic crystal gel (with bright and vivid structural color) prepared in this example into a patch and attach it to the surface of the skin wound. It is observed that the structural color changes with the wound healing process.

[0153] Example 10

[0154] A preparation method of a microphase-separated photonic crystal gel is basically the same as that of Example 1, except that: the surface potential of the monodisperse colloidal particles in this example is -42 eV, and the average particle size is 160 nm.

[0155] The finally obtained microphase-separated photonic crystal gel is composed of monodisperse colloidal particles and a PEG gel with microphase-separation characteristics; among them, the monodisperse colloidal particles self-assemble in the PEG gel to form a photonic crystal, and the crystal structure of this photonic crystal is a non-close-packed structure.

[0156] The microphase-separated photonic crystal gel prepared in this example (with a more vivid and bright structural color) was made into a patch and applied to the surface of a skin wound. It was observed that the patch had a rapid response to liquid exudation and completed the structural color change within a few minutes.

[0157] Example 11

[0158] A preparation method of a microphase-separated photonic crystal gel is basically the same as that of Example 1, except that: in this example, the surface potential of the monodisperse colloidal particles is 46 eV and the average particle size is 160 nm.

[0159] The finally obtained microphase-separated photonic crystal gel is composed of monodisperse colloidal particles and a PEG gel with microphase-separation characteristics; among them, the monodisperse colloidal particles self-assemble in the PEG gel to form a photonic crystal, and the crystal structure of this photonic crystal is a non-close-packed structure.

[0160] The microphase-separated photonic crystal gel prepared in this example (with a more vivid and bright structural color) was made into a patch and applied to the surface of a skin wound. It was observed that the patch had a rapid response to liquid exudation and completed the structural color change within a few minutes.

[0161] Example 12

[0162] A preparation method of a microphase-separated photonic crystal gel is basically the same as that of Example 3, except that: in this example, the polyglycol is PEG with a molecular weight of 800 g / mol.

[0163] The finally obtained microphase-separated photonic crystal gel is composed of monodisperse colloidal particles and a PEG gel with microphase-separation characteristics; among them, the monodisperse colloidal particles self-assemble in the PEG gel to form a photonic crystal, and the crystal structure of this photonic crystal is a non-close-packed structure.

[0164] The microphase-separated photonic crystal gel prepared in this example (with a vivid and bright structural color, showing a blue shift compared to Example 3) was made into a patch and applied to the surface of a skin wound. It was observed that the structural color changed as the wound healed.

[0165] Example 13

[0166] A preparation method of a microphase-separated photonic crystal gel is basically the same as that of Example 3, except that: in this example, the particle size of the monodisperse colloidal particles is 160 nm.

[0167] The finally obtained microphase-separated photonic crystal gel is composed of monodisperse colloidal particles and a PEG gel with microphase separation characteristics; among them, the monodisperse colloidal particles self-assemble in the PEG gel to form a photonic crystal, and the crystal structure of the photonic crystal is a non-close-packed structure.

[0168] The microphase-separated photonic crystal gel prepared in this example (with bright and vivid structural colors, showing a red shift compared to Example 3) is made into a patch and applied to the surface of the skin wound. It is observed that the structural color changes as the wound heals.

[0169] From Figure 3 As can be seen from the microphase-separated photonic crystal gel patches prepared in Example 3, Example 12, and Example 13 shown, during the preparation of the microphase-separated photonic crystal gel, when other conditions are kept unchanged, the structural color of the microphase-separated photonic crystal gel can be changed by only changing the particle size of the monodisperse colloidal particles or the molecular weight of the polyglycol.

Claims

1. A microphase-separated photonic crystal gel, characterized in that, It includes monodisperse colloidal particles and polyglycol gels with microphase separation characteristics. The monodisperse colloidal particles self-assemble into photonic crystals in the polyglycol gels. The reaction raw materials of the polyglycol gels include polyglycol and polymer precursors. The polyglycol is PEG and / or PPG, and the polymer precursor is one or more of hydroxyethyl acrylate, hydroxyethyl methacrylate, benzyl methacrylate, and polyethylene glycol monomethacrylate; The preparation method of the microphase separation photonic crystal gel includes the following steps: (a)Add polyglycol, polymer precursor, photoinitiator, and light absorber to the monodisperse colloidal particle solution and stir evenly to obtain a suspension; (b)Evaporate the solvent in the monodisperse colloidal particle solution to obtain a photonic crystal solution with structural color; (c)Cure to obtain the microphase separation photonic crystal gel.

2. The microphase-separated photonic crystal gel according to claim 1, wherein The crystal structure of the photonic crystal is a non-close-packed structure, and the monodisperse colloidal particles are silica microspheres with sulfonated or carboxylated surface modification.

3. The microphase-separated photonic crystal gel according to claim 2, wherein The surface potential of the monodisperse colloidal particles is lower than -30 eV or higher than 30 eV, the particle size is 50~1000 nm, and the polydispersity index is less than or equal to 0.

05.

4. A microphase-separated photonic crystal gel according to claim 1, wherein The volume percentage of the monodisperse colloidal particles in the microphase separation photonic crystal gel is 15~74%.

5. A microphase-separated photonic crystal gel according to claim 1, characterized in that, The PEG is one or more of PEG with a molecular weight of 100 g / mol, PEG with a molecular weight of 200 g / mol, PEG with a molecular weight of 400 g / mol, PEG with a molecular weight of 600 g / mol, and PEG with a molecular weight of 800 g / mol. The PPG is one or more of PPG with a molecular weight of 400 g / mol, PPG with a molecular weight of 600 g / mol, and PPG with a molecular weight of 800 g / mol.

6. A method for preparing a microphase-separated photonic crystal gel according to any one of claims 1 to 5, characterized in that, It includes the following steps: (a)Add polyglycol, polymer precursor, photoinitiator, and light absorber to the monodisperse colloidal particle solution and stir evenly to obtain a suspension; (b)Evaporate the solvent in the monodisperse colloidal particle solution to obtain a photonic crystal solution with structural color; (c)Cure to obtain the microphase separation photonic crystal gel.

7. The method according to claim 6, characterized in that In step (a), the concentration of the monodisperse colloidal particle solution is 5~15 wt%. In the suspension, the volume percentage of polyglycol is 5~20%, the volume percentage of the polymer precursor is 5~20%, the volume percentage of the photoinitiator is 0.05~0.15%, and the volume percentage of the light absorber is 0.005~0.025%. The specific process of step (c) is: irradiate under ultraviolet light for 5~30 min to obtain the microphase separation photonic crystal gel.

8. The method according to claim 7, characterized in that In step (a), the photoinitiator is one or more of diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide and 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylacetophenone; the light absorber is one or more of carbon black, polydopamine nanoparticles, and silver nanoparticles.

9. A method for regulating the structural color of a microphase-separated photonic crystal gel, characterized in that, In the process of preparing the microphase separation photonic crystal gel by using the method described in any one of claims 6~8, while keeping other conditions unchanged, only changing the particle size of the monodisperse colloidal particles or the molecular weight of the polyglycol can change the structural color of the microphase separation photonic crystal gel.

10. The application of a microphase-separated photonic crystal gel according to any one of claims 1 to 5, characterized in that, It is used to be made into a patch and applied to the surface of a skin wound or a pipe gap, and shows whether there is liquid leakage through color change.

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