Microphase separation photonic crystal gel and preparation method, structural color regulation method and application thereof

Abstract

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 and control method and application. Adding a polyglycol solution, a polymer precursor solution, a photoinitiator and a light absorber into the monodisperse colloid particle solution, and uniformly stirring to obtain a suspension; evaporating to remove a solvent in the monodisperse colloid particle solution; and finally, curing to obtain the microphase separation photonic crystal gel. The photonic crystal gel is composed of monodisperse colloid particles and polyglycol gel with a microphase separation characteristic, and the monodisperse colloid particles are self-assembled in the polyglycol gel to form a photonic crystal; in the preparation process, other conditions are kept unchanged, and the structural color of the microphase separation photonic crystal gel can be changed only by changing the particle size of monodisperse colloid particles or the molecular weight of polyglycol. The microphase separation photonic crystal gel is high in color change response sensitivity, simple in structural color regulation and control method, high in usability and lower in 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 purpose of the present invention is to solve the problems in the prior art and to provide a microphase separation photonic crystal gel and a preparation method thereof, a structural color regulation method and an application thereof.

[0008] In order to achieve the above object, the present invention adopts the following technical scheme:

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

[0010] Polyglycol gels have microphase separation properties. Figure 1 As shown, when the gel contacts water or other solutions, the cross-linked network stretched inside the gel produces local microphase separation, the scale of microphase separation is at the submicron level, similar to the scale of monodisperse colloidal particles, and the gel produces soft and hard segments. The polymer-rich hard segment produces local contraction, and the solvent-rich soft segment gradually elongates, which causes the lattice network of the photonic crystal to change from a balanced ordered state to a disordered state, breaking the requirement of periodic arrangement of the photonic crystal lattice, causing the photonic crystal to no longer conform to the Bragg law, that is, the structural color disappears. At the same time, during the stretching process, the hard segment will increase the strength in a way that dissipates energy, while the soft segment will prevent the gel from breaking prematurely, thereby showing high toughness. The traditional method requires the stimulation to accumulate to a threshold color before a significant change will occur. The threshold value of the color change response of the response method of the present invention will be significantly reduced, the response is more sensitive, and the color response can be triggered using only a trace amount of solution.

[0011] As the preferred technical solution:

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

[0013] In 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] In the microphase-separated photonic crystal gel as described above, the surface potential of the monodispersed colloidal particles is lower than -35 eV or higher than 35 eV.

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

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

[0017] In the microphase separation photonic crystal gel as described above, 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 separation photonic crystal gel as described in any one of the above items comprises the following steps:

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

[0020] (b) removing the solvent from the monodisperse colloidal particle solution by evaporation (at 60-100°C for 2-12 hours) to obtain a photonic crystal solution with structural color;

[0021] (c) solidification to obtain a microphase-separated photonic crystal gel; different processing methods can be selected to obtain microphase-separated photonic crystal gel products of different forms. For example, the photonic crystal solution can be cast, extruded and coated and then solidified to obtain a microphase-separated photonic crystal gel film, a microphase-separated photonic crystal gel fiber, or a microphase-separated photonic crystal gel coating. The digital light processing 3D printing technology can be used to repeat the "photonic crystal solution single-layer printing-solidification" operation to obtain a three-dimensional model.

[0022] As a preferred solution:

[0023] In the method as described above, in step (a), the concentration of the monodisperse colloidal particle solution is 5-15wt%, in the suspension, the volume percentage of the 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: irradiating under ultraviolet light for 5-30 minutes to obtain a microphase separation photonic crystal gel.

[0024] In the method as 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-methylacetone; and 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. In the process of preparing the microphase-separated photonic crystal gel by any of the methods described above, other conditions are kept unchanged, and only the particle size of monodisperse colloidal particles or the molecular weight of polyglycol is changed to 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 polyglycol is that the monodisperse colloidal particles are linked to the polyglycol in the form of hydrogen bonds, and the long-chain covalent bond of the polyglycol will promote the tight linking of the monodisperse colloidal particles compared to the hydrogen bond linking. The longer the polyglycol chain length, the more covalent bonds between the silicon spheres, and the smaller the distance between the silicon spheres, so that the structural color will tend to blue shift.

[0026] The present invention also provides an application of a microphase separation photonic crystal gel as described in any of the above items, which is used to make a patch and stick it on the surface of a skin wound or a pipeline gap, and indicates whether there is liquid seepage through color changes.

[0027] Beneficial effects:

[0028] The microphase separation photonic crystal gel prepared by the present invention effectively improves the sensitivity of color change response by utilizing microphase separation to induce the response change mode of colloidal particles from order to disorder. When it is applied to the monitoring of liquid seepage on the surface of skin wounds and pipeline gaps, no other additional equipment is required, the operation is simple, the monitoring is sensitive, and it is not only easier to use but also lower in cost. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] Figure 1 Schematic diagram of microphase separation response of microphase-separated photonic crystal gel;

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

[0031] Figure 3 These are pictures of microphase separation photonic crystal gel patches prepared in the examples. In the pictures, (a) is prepared in Example 3, (b) is prepared in Example 12, and (c) is prepared in Example 13. DETAILED DESCRIPTION

[0032] The above scheme is further described below in conjunction with non-limiting examples, so as to help relevant technical personnel in the field to more completely understand the present invention. It should be noted that the protection scope of the present invention should not be limited by this. For professional and technical personnel, several adjustments and improvements can also be made without departing from the principle of the present invention, and these adjustments and improvements should also be included in the protection scope of the present invention.

[0033] Example 1

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

[0035] (1) Raw material preparation:

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

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

[0038] Polymer precursor: 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 microphase-separated photonic crystal gel:

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

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

[0044] (c) After irradiation with UV light for 5 min, microphase-separated photonic crystal gel was obtained.

[0045] The microphase separation photonic crystal gel finally obtained is composed of monodisperse colloidal particles and PEG gel with microphase separation characteristics; wherein the monodisperse colloidal particles self-assemble in the PEG gel to form photonic crystals, the crystal structure of the photonic crystals is a non-dense packing structure, and the volume percentage of monodisperse colloidal particles in the microphase separation photonic crystal gel is 28.57%.

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

[0047] Example 2

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

[0049] (1) Raw material preparation:

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

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

[0052] Polymer precursor: 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 microphase-separated photonic crystal gel:

[0056] (a) adding polyglycol, polymer precursor, photoinitiator and light absorber to a monodisperse colloidal particle solution and stirring the mixture to obtain a suspension; in the suspension, the volume percentage of polyglycol is 7%, the volume percentage of polymer precursor is 18%, the volume percentage of photoinitiator is 0.065%, and the volume percentage of light absorber is 0.008%;

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

[0058] (c) After irradiation with UV light for 9 min, microphase-separated photonic crystal gel was obtained.

[0059] The microphase separation photonic crystal gel finally obtained is composed of monodisperse colloidal particles and PEG gel with microphase separation characteristics; wherein the monodisperse colloidal particles self-assemble in the PEG gel to form photonic crystals, the crystal structure of the photonic crystals is a non-dense packing structure, and the volume percentage of monodisperse colloidal particles in the microphase separation photonic crystal gel is 28.57%.

[0060] The microphase separation 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 the structural color changed as the wound healed.

[0061] Example 3

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

[0063] (1) Raw material preparation:

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

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

[0066] Polymer precursor: Hydroxyethyl methacrylate;

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

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

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

[0070] (a) adding polyglycol, polymer precursor, photoinitiator and light absorber to a monodisperse colloidal particle solution and stirring the mixture to obtain a suspension; in the suspension, the volume percentage of polyglycol is 9%, the volume percentage of polymer precursor is 16%, the volume percentage of photoinitiator is 0.08% and the volume percentage of light absorber is 0.012%;

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

[0072] (c) After irradiation with UV light for 12 min, microphase-separated photonic crystal gel was obtained.

[0073] The microphase separation photonic crystal gel finally obtained is composed of monodisperse colloidal particles and PEG gel with microphase separation characteristics; wherein the monodisperse colloidal particles self-assemble in the PEG gel to form photonic crystals, the crystal structure of the photonic crystals is a non-dense packing structure, and the volume percentage of monodisperse colloidal particles in the microphase separation photonic crystal gel is 28.57%.

[0074] The microphase separation 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 (e.g. Figure 2 as shown).

[0075] Comparative Example 1

[0076] A method for preparing a photonic crystal gel is basically the same as that of Example 3, except that the polyglycol is replaced with the same volume of deionized water in this comparative example.

[0077] The photonic crystal gel finally obtained is composed of monodisperse colloidal particles and hydrogel; wherein the monodisperse colloidal particles are self-assembled in the hydrogel to form a photonic crystal, and the crystal structure of the photonic crystal is a non-densely 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 predictive effect on the wound healing process and had extremely poor mechanical properties. The reason for this phenomenon in Comparative Example 1 is that the hydrogel material does not produce a two-phase after absorbing water and cannot undergo microphase separation, so it is unresponsive to the water environment. Moreover, since the molecular weight of water is extremely low compared to that of polyglycol, it has no mechanical enhancement properties for the patch.

[0079] Example 4

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

[0081] (1) Raw material preparation:

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

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

[0084] Polymer precursor: 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 microphase-separated photonic crystal gel:

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

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

[0090] (c) After irradiation with UV light for 15 min, microphase-separated photonic crystal gel was obtained.

[0091] The microphase separation photonic crystal gel finally obtained is composed of monodisperse colloidal particles and PEG gel with microphase separation characteristics; wherein the monodisperse colloidal particles self-assemble in the PEG gel to form photonic crystals, the crystal structure of the photonic crystals is a non-dense packing structure, and the volume percentage of monodisperse colloidal particles in the microphase separation photonic crystal gel is 16.12%.

[0092] The microphase separation 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 the structural color changed as the wound healed.

[0093] Example 5

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

[0095] (1) Raw material preparation:

[0096] Monodisperse colloidal particle solution: concentration is 7wt%, solvent is ethanol, wherein the monodisperse colloidal particles are silica microspheres with carboxylated surface modification, with a surface potential of -32eV, an average particle size of 200nm, and a polydispersity index of 0.02;

[0097] Polyglycol: 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-methylacetone in a mass ratio of 1:1;

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

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

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

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

[0104] (c) After irradiation with UV light for 18 min, microphase-separated photonic crystal gel was obtained.

[0105] The microphase separation photonic crystal gel finally obtained is composed of monodisperse colloidal particles and PEG gel with microphase separation characteristics; wherein, the monodisperse colloidal particles self-assemble in the PEG gel to form photonic crystals, the crystal structure of the photonic crystals is a non-dense packing structure, and the volume percentage of monodisperse colloidal particles in the microphase separation photonic crystal gel is 21.21%.

[0106] The microphase separation photonic crystal gel (with structural color) prepared in this embodiment was made into a patch and attached to the surface of the pipeline gap. It was found that the structural color changed with the expansion degree of the pipeline gap.

[0107] Example 6

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

[0109] (1) Raw material preparation:

[0110] Monodisperse colloidal particle solution: concentration is 13wt%, solvent is methanol, wherein the monodisperse colloidal particles are silica microspheres with carboxylated surface modification, with a surface potential of -32eV, an average particle size of 300nm, and a polydispersity index of 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 30 nm) and silver nanoparticles (average particle size 50 nm) in a mass ratio of 1:1;

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

[0116] (a) adding polyglycol, polymer precursor, photoinitiator and light absorber to a monodisperse colloidal particle solution and stirring 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) evaporating the solvent in the monodisperse colloidal particle solution at 85°C to obtain a photonic crystal solution with structural color;

[0118] (c) After irradiation with UV light for 20 min, microphase-separated photonic crystal gel was obtained.

[0119] The final microphase separation photonic crystal gel is composed of monodisperse colloidal particles and PPG gel with microphase separation characteristics; wherein, the monodisperse colloidal particles self-assemble in the PPG gel to form photonic crystals, the crystal structure of the photonic crystals is a non-dense packing structure, and the volume percentage of monodisperse colloidal particles in the microphase separation photonic crystal gel is 34.21%.

[0120] The microphase separation photonic crystal gel (with structural color) prepared in this embodiment was made into a patch and attached to the surface of the pipeline gap. It was found that the structural color changed with the expansion degree of the pipeline gap.

[0121] Example 7

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

[0123] (1) Raw material preparation:

[0124] Monodisperse colloidal particle solution: concentration of 15wt%, solvent is acetone, wherein the monodisperse colloidal particles are silica microspheres with carboxylated surface modification, with a surface potential of -32eV, an average particle size of 600nm, and a polydispersity index of 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) Preparation of microphase-separated photonic crystal gel:

[0130] (a) adding polyglycol, polymer precursor, photoinitiator and light absorber to a monodisperse colloidal particle solution and stirring 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) evaporating the solvent in the monodisperse colloidal particle solution at 90°C to obtain a photonic crystal solution with structural color;

[0132] (c) After irradiation with UV light for 25 min, microphase-separated photonic crystal gel was obtained.

[0133] The final microphase separation photonic crystal gel is composed of monodisperse colloidal particles and PPG gel with microphase separation characteristics; wherein the monodisperse colloidal particles self-assemble in the PPG gel to form photonic crystals, the crystal structure of the photonic crystals is a non-dense packing structure, and the volume percentage of monodisperse colloidal particles in the microphase separation photonic crystal gel is 37.50%.

[0134] The microphase separation photonic crystal gel (with structural color) prepared in this embodiment was made into a patch and attached to the surface of the pipeline gap. It was found that the structural color changed with the expansion degree of the pipeline gap.

[0135] Example 8

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

[0137] (1) Raw material preparation:

[0138] Monodisperse colloidal particle solution: concentration is 15wt%, solvent is ethanol, wherein the monodisperse colloidal particles are silica microspheres with carboxylated surface modification, with a surface potential of -32eV, an average particle size of 1000nm, and a polydispersity index of 0.02;

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

[0140] Polymer precursor: a mixture of hydroxyethyl acrylate and hydroxyethyl methacrylate in 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) adding polyglycol, polymer precursor, photoinitiator and light absorber to a monodisperse colloidal particle solution and stirring the mixture to obtain a suspension; in the suspension, the volume percentage of polyglycol is 20%, the volume percentage of polymer precursor is 5%, the volume percentage of photoinitiator is 0.15% and the volume percentage of light absorber is 0.025%;

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

[0146] (c) After irradiation with UV light for 30 min, microphase-separated photonic crystal gel was obtained.

[0147] The final microphase separation photonic crystal gel is composed of monodisperse colloidal particles and PPG gel with microphase separation characteristics; wherein the monodisperse colloidal particles self-assemble in the PPG gel to form photonic crystals, the crystal structure of the photonic crystals is a non-dense packing structure, and the volume percentage of monodisperse colloidal particles in the microphase separation photonic crystal gel is 37.50%.

[0148] The microphase separation photonic crystal gel (with structural color) prepared in this embodiment was made into a patch and attached to the surface of the pipeline gap. It was found that the structural color changed with the expansion degree of the pipeline gap.

[0149] Example 9

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

[0151] The microphase separation photonic crystal gel finally prepared is composed of monodisperse colloidal particles and PEG gel with microphase separation characteristics; wherein 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-densely packed structure.

[0152] The microphase separation photonic crystal gel (with bright and vivid structural colors) prepared in this example 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.

[0153] Example 10

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

[0155] The microphase separation photonic crystal gel finally prepared is composed of monodisperse colloidal particles and PEG gel with microphase separation characteristics; wherein 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-densely packed structure.

[0156] The microphase separation photonic crystal gel (with more vivid and bright structural colors) prepared in this embodiment was made into a patch and attached to the surface of a skin wound. It was observed that the patch responded quickly to liquid exudation and completed the structural color change within a few minutes.

[0157] Embodiment 11

[0158] A method for preparing a microphase-separated photonic crystal gel is basically the same as that in 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 microphase separation photonic crystal gel finally prepared is composed of monodisperse colloidal particles and PEG gel with microphase separation characteristics; wherein 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-densely packed structure.

[0160] The microphase separation photonic crystal gel (with more vivid and bright structural colors) prepared in this embodiment was made into a patch and attached to the surface of a skin wound. It was observed that the patch responded quickly to liquid exudation and completed the structural color change within a few minutes.

[0161] Example 12

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

[0163] The microphase separation photonic crystal gel finally prepared is composed of monodisperse colloidal particles and PEG gel with microphase separation characteristics; wherein 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-densely packed structure.

[0164] The microphase separation photonic crystal gel prepared in this example (having a bright and vivid structural color, which is blue-shifted 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 with the progress of wound healing.

[0165] Embodiment 13

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

[0167] The microphase separation photonic crystal gel finally prepared is composed of monodisperse colloidal particles and PEG gel with microphase separation characteristics; wherein 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-densely packed structure.

[0168] The microphase separation photonic crystal gel prepared in this example (having a bright and vivid structural color, which is red-shifted 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 with the progress of wound healing.

[0169] Depend on Figure 3 It can be seen from the microphase separation photonic crystal gel patches prepared in Example 3, Example 12 and Example 13 that, in the process of preparing the microphase separation photonic crystal gel, the structural color of the microphase separation photonic crystal gel can be changed by only changing the particle size of the monodisperse colloidal particles or the molecular weight of the polyglycol while keeping other conditions unchanged.

Claims

1. A microphase separation photonic crystal gel, characterized in that: The invention comprises monodisperse colloidal particles and polyglycol gel with microphase separation characteristics. The monodisperse colloidal particles are self-assembled in the polyglycol gel to form photonic crystals. The reaction raw materials of the polyglycol gel include polyglycol.

2. The microphase separation photonic crystal gel according to claim 1, characterized in that: The crystal structure of the photonic crystal is a non-densely packed structure, and the monodispersed colloidal particles are silicon dioxide microspheres whose surfaces are modified by sulfonation or carboxylation.

3. The microphase separation photonic crystal gel according to claim 2, characterized in that: The surface potential of 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. The microphase separation photonic crystal gel according to claim 1, characterized in that: The volume percentage of monodisperse colloidal particles in microphase-separated photonic crystal gels ranges from 15 to 74%.

5. The microphase separation photonic crystal gel according to claim 1, characterized in that: The polyglycol is PEG and / or PPG, 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 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 separation photonic crystal gel as claimed in any one of claims 1 to 5, characterized in that: The following steps are involved: (a) adding a polyglycol solution, a polymer precursor solution, a photoinitiator, and a light absorber to a monodisperse colloidal particle solution and stirring the mixture to obtain a suspension; (b) evaporating and removing the solvent in the monodisperse colloidal particle solution to obtain a photonic crystal solution with structural color; (c) Curing to obtain microphase-separated 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 5-15wt%, in the suspension, the volume percentage of the 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: irradiating under ultraviolet light for 5-30 minutes to obtain a microphase separation photonic crystal gel.

8. The method according to claim 7, characterized in that 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-methylacetone; and 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 microphase separation photonic crystal gel by the method described in any one of claims 6 to 8, keeping other conditions unchanged and only changing the particle size of monodisperse colloidal particles or the molecular weight of polyglycol can change the structural color of the microphase separation photonic crystal gel.

10. The use of a microphase separation photonic crystal gel according to any one of claims 1 to 5, characterized in that: It is used to make patches and stick them on the surface of skin wounds or pipe gaps, and the color changes will show whether there is liquid leakage.

Images