CN113956510A - Temperature-sensitive color-changing hydrogel material based on temperature-sensitive color-changing microcapsule inclusion and preparation method thereof - Google Patents
Temperature-sensitive color-changing hydrogel material based on temperature-sensitive color-changing microcapsule inclusion and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a temperature-sensitive color-changing hydrogel material based on temperature-sensitive color-changing microcapsule inclusion and a preparation method thereof, wherein the preparation method comprises the following steps: (1) adding the temperature-sensitive color-changing microcapsules into the hydrogel monomer solution, and uniformly mixing; (2) adding a cross-linking agent, an initiator and a catalyst into the mixed solution of the temperature-sensitive color-changing microcapsules and the hydrogel monomers obtained in the step (1), and uniformly mixing to obtain precursor mother liquor; (3) and curing the precursor mother liquor to obtain the temperature-sensitive color-changing hydrogel material. The temperature-sensitive color-changing hydrogel material has good functional repeatability and color richness, and has high temperature response speed.
Description
Technical Field
The invention relates to a temperature-sensitive color-changing hydrogel, in particular to a temperature-sensitive color-changing hydrogel material based on inclusion of temperature-sensitive color-changing microcapsules and a preparation method thereof.
Background
Hydrogels have been derivatised with a wide variety of functional hydrogels due to their excellent functional integration. Different functional materials can be doped in the hydrogel system to endow the hydrogel system with corresponding response capability. Considering the good biocompatibility and mechanical property, the functional hydrogel is widely applied to the fields of medical treatment, intelligent wearing and the like.
Flexible displays and camouflage displays are also an important area of development for hydrogels after integration of functionality. There have been many studies on color-changing hydrogels. For example, reference is made to the literature (Wang, W., et al, Magnetic Photonic Hydrogel for an Alternating Magnetic Field-Responsive Color display, advanced Optical Materials,2018.6(4): p.1701093) which discloses a magneto-chromic Hydrogel comprising ferroferric oxide particles coated with a silica layer on the surface and a PNIPAAM Hydrogel matrix, wherein the ferroferric oxide particles are heated due to the thermomagnetic effect under the action of an Alternating Magnetic Field, and the generated heat can drive the temperature-sensitive aqueous gel matrix to dehydrate and shrink. Because the surface of the ferroferric oxide particles is coated with silicon dioxide, the particles uniformly arranged in the system can be considered as a photonic crystal. As the matrix deforms, the distance between the particles becomes shorter, resulting in a change in the reflection wavelength, which is macroscopically reflected as a change in the color of the material. The material has a wide color change range, but has the defect that the color display is unstable for the photonic crystal (the color distribution is difficult to control on the same color plane, and the colors are observed from different angles and are different). For example, there are references (Yang, Y., et al., Low-Cost, Rapid response, control, and Reversible Photochromic Hydrogel for Display and storage. ACS applied materials & interfaces,2018.10(16): p.13975-13984.) which disclose a Photochromic Hydrogel material prepared by crosslinking a molybdenum oxide group to a long chain of a foam Hydrogel. Under the irradiation of ultraviolet light, the color can be changed from deep blue to transparent. Has good reproducibility and color stability, but has the disadvantage of long recovery time, and requires several hours at room temperature after each color change to recover to a colorless state. The recovery efficiency of the color-changing material is low, the color is too single, and the natural dark blue color of the molybdenum oxide determines that the material can only display two states of dark blue and colorless.
The existing soft materials with flexible display or active color change mainly have two types: the color-changing soft material based on inorganic material doping and the organic composite color-changing soft material. The disadvantages of inorganic materials are mainly the insufficient stability and poor reproducibility of inorganic materials. The organic materials have the defects of slow response speed and complex preparation. The flexible color-changing soft material which can be recycled for many times, has rich and controllable colors and rapid color-changing response speed is yet to be developed.
Disclosure of Invention
The invention provides a temperature-sensitive color-changing hydrogel material based on inclusion of temperature-sensitive color-changing microcapsules and a preparation method thereof.
The technical scheme of the invention is as follows:
a preparation method of a temperature-sensitive color-changing hydrogel material based on inclusion of temperature-sensitive color-changing microcapsules comprises the following steps:
(1) adding the temperature-sensitive color-changing microcapsules into the hydrogel monomer solution, and uniformly mixing;
(2) adding a cross-linking agent, an initiator and a catalyst into the mixed solution of the temperature-sensitive color-changing microcapsules and the hydrogel monomers obtained in the step (1), and uniformly mixing to obtain precursor mother liquor;
(3) and curing the precursor mother liquor to obtain the temperature-sensitive color-changing hydrogel material.
The temperature-sensitive color-changing microcapsule is powder with the diameter of 2-5 mu m. The temperature-sensitive color-changing microcapsule comprises an organic shell, and a solvent and a color-changing agent which are coated by the organic shell. The organic shell mainly plays a role in protecting the solvent and the color-changing agent inside from leakage, and the solvent and the color-changing agent are chemical substances which can perform reversible reaction at a specific temperature. The temperature-sensitive color-changing microcapsule is insoluble in water because of the organic shell, and forms suspension when dispersed in hydrogel monomer solution. Since the color-changing reaction system of the color-changing agent is enclosed in the organic casing, the reaction can be repeated many times without attenuation.
The present invention mixes the existing temperature-sensitive color-changing microcapsule powder into the hydrogel matrix to prepare the hydrogel composite material capable of responding to temperature. The core functional part of the composite material is the color-changing powder, and the composite material has good functional repeatability and color richness. And has a fast temperature response speed, and the powder can complete the color change process in a very short time when reaching the critical temperature.
The hydrogel matrix and the temperature-sensitive color-changing microcapsule powder are purely and physically mixed, and because the densities of the two materials are close to each other, the temperature-sensitive color-changing microcapsule powder can be uniformly mixed in the hydrogel matrix through simple vibration in the preparation process, so that the whole gel displays uniform color.
The hydrogel monomer is at least one of acrylamide (AAm), acrylic acid (AAc) and sodium alginate.
Preferably, the density of the hydrogel monomer solution is not less than that of the temperature-sensitive color-changing microcapsules. When the density of the hydrogel monomer solution is not less than that of the temperature-sensitive color-changing microcapsules, the temperature-sensitive color-changing microcapsule powder can be uniformly dispersed in the hydrogel monomer solution to form a stable suspension state, and sedimentation is not easy to occur.
Preferably, in the temperature-sensitive color-changing hydrogel material, the mass fraction of the temperature-sensitive color-changing microcapsules is not more than 0.5%.
When the mass fraction of the temperature-sensitive color-changing microcapsules is not more than 0.5%, the temperature-sensitive color-changing microcapsules cannot influence the cross-linking of molecular chains in the hydrogel curing process, so that the mechanical property of a hydrogel matrix cannot be influenced; due to the constraint effect of hydrogel molecular chains, the temperature-sensitive color-changing microcapsules are limited in the molecular network of the hydrogel matrix after the hydrogel is cured, and obvious leakage and separation cannot occur in the using process.
The cross-linking agent is at least one of N, N-Methylene Bisacrylamide (MBAA) and polyethylene glycol diacrylate (PEGDA).
The initiator is at least one of Ammonium Persulfate (APS) and potassium persulfate (KPS).
The catalyst is Tetramethylethylenediamine (TEMED).
The corresponding curing method can be selected according to the type of the hydrogel monomer, when the hydrogel monomer is at least one of acrylamide (AAm), acrylic acid (AAc) and sodium alginate, ultraviolet light is adopted for curing in the step (3), and the curing conditions are as follows: the ultraviolet wavelength is 365nm, the power is 50-100W, and the curing time is 30-60 min.
The invention also provides a temperature-sensitive color-changing hydrogel material prepared by the preparation method.
Compared with the prior art, the invention has the beneficial effects that:
(1) in the preparation method, the color change of the temperature-sensitive color-changing hydrogel material is caused by the color change of the temperature-sensitive color-changing microcapsules, and due to the diversity of the color and the critical temperature of the temperature-sensitive color-changing powder, the temperature-sensitive color-changing hydrogel with various color-changing modes can be obtained by simply doping.
(2) The temperature-sensitive color-changing hydrogel material has the advantages of high response speed and color diversity.
(3) The mechanical property of the hydrogel matrix is not affected by the doping of the temperature-sensitive color-changing microcapsules.
(4) Due to the mature process of the temperature-sensitive allochroic powder, the temperature-sensitive allochroic powder with different critical allochroic temperatures and different colors can be easily obtained, and the temperature-sensitive allochroic hydrogel material is endowed with rich allochroic modes in consideration of the simplicity of the doping process.
Drawings
FIG. 1 is a schematic structural diagram of a temperature-sensitive color-changing microcapsule powder;
FIG. 2 is a schematic diagram illustrating the color change principle of a temperature-sensitive color-changing hydrogel material;
FIG. 3 is the color change behavior of the temperature-sensitive color-changing hydrogel prepared in example 1 along with the heating process;
FIG. 4 is a graph showing the mechanical properties of the temperature-sensitive color-changing hydrogels prepared in examples 1 and 2;
FIG. 5 is a functional stability performance of the temperature-sensitive color-changing hydrogel prepared in example 1 in temperature cycling;
FIG. 6 is a graph showing the stability of the color-changing function of the temperature-sensitive color-changing hydrogel prepared in example 1 after cyclic deformation loading.
Detailed Description
The structure of the temperature-sensitive color-changing powder used in the following examples is shown in fig. 1, each powder being composed of three components: an outermost organic shell, a solvent, and a color-changing agent. The shell mainly has the function of protecting the solvent and the color-changing agent in the shell from leakage, the solvent and the color-changing agent are chemical substances which can perform reversible reaction at a specific temperature, and the molecular formula of the color-changing agent is shown in the figure. The carboxyl groups and the reaction as shown in the figure occur when the temperature is changed, and the products before and after the reaction appear in two different colors of red and white. Since the entire system is enclosed in an organic shell, the reaction can be repeated many times without decay.
Example 1 (Single network base)
A thermo-sensitive color-changing hydrogel material based on thermochromic capsule inclusion is prepared by the following steps:
1. weighing 0.05g of temperature-sensitive Color-changing powder (Shenzhen organic Color Science & Technology Co.) (the Color-changing powder has the diameter of 2-5 mu m and the critical Color-changing temperature of 31 ℃, adding the powder into 10ml of prepared 2mol/L acrylamide (AAm) aqueous solution, and shaking for 1 minute, wherein the powder can be uniformly dispersed in the solution to be in a suspension state due to the fact that the density of the powder is equivalent to that of the AAm aqueous solution.
2. To the suspension were added 55.3 μm 0.1mol/L aqueous N, N-Methylenebisacrylamide (MBAA), 70 μm 0.1mol/L aqueous Ammonium Persulfate (APS) and 7.1 μm 10% by mass aqueous Tetramethylethylenediamine (TEMED) solution. Shaking for 1 minute to obtain the precursor mother solution doped with the temperature-sensitive color-changing powder.
3. Sealing the precursor mother liquor in a transparent mould with a fixed shape to ensure oxygen isolation, and carrying out ultraviolet curing in an ultraviolet environment. After irradiating the hydrogel for 45 minutes under 60W of 365nm ultraviolet light, a temperature-sensitive allochroic hydrogel having a predetermined shape and cured in a mold was obtained.
The prepared temperature-sensitive color-changing hydrogel can complete color change within 10s when heated at 80 ℃ and the color-changing hydrogel with the critical color-changing temperature of 31 ℃ and can recover to the original color within 20s after the heating is stopped.
Example 2 (Dual network base)
A thermo-sensitive color-changing hydrogel material based on thermochromic capsule inclusion is prepared by the following steps:
1. 0.05g of temperature-sensitive Color-changing powder (Shenzhen organic Color Science & Technology Co.) is weighed, 10ml of prepared acrylamide (AAm 2mol/L) -sodium alginate (sodium-alginate 0.1mol/L) aqueous solution is added to the powder, and the mixture is shaken for 1 minute, so that the powder forms suspension in the system due to the high consistency of the mixed solution of the sodium alginate and the AAm.
2. The suspension was drawn into syringe A, and into syringe B, 55.3 μm 0.1mol/L of an aqueous N, N-Methylenebisacrylamide (MBAA) solution, 70 μm 0.1mol/L of an aqueous Ammonium Persulfate (APS) solution, 7.1 μm 10% by mass of an aqueous Tetramethylethylenediamine (TEMED) solution, and 200 μm of an aqueous calcium sulfate solution (6% by mass) were drawn. Connecting the two injectors by a connector, and extruding back and forth to uniformly mix the components A and B of the injectors to obtain the precursor mother liquor doped with the temperature-sensitive color-changing powder.
3. Sealing the precursor mother liquor in a transparent mould with a fixed shape to ensure oxygen isolation, and carrying out ultraviolet curing in an ultraviolet environment. After irradiating the hydrogel for 45 minutes under 60W of 365nm ultraviolet light, a temperature-sensitive allochroic hydrogel having a predetermined shape and cured in a mold was obtained.
The hydrogel-temperature sensitive allochroic powder composite materials prepared by the manner of examples 1 and 2 have a temperature-responsive function, and can produce a color change upon heating, as shown in fig. 2.
Since the critical temperature of the temperature-sensitive allochroic powder is a constant value, the temperature-sensitive allochroic hydrogel is also endowed with the same critical allochroic temperature as the temperature-sensitive allochroic powder. As shown in fig. 3, the temperature-sensitive color-changing hydrogel also exhibits such a critical color-changing temperature after incorporating a temperature-sensitive color-changing powder that changes color at 31 ℃. At the time point when the temperature spans 31 ℃, the temperature-sensitive color-changing hydrogel generates rapid color-changing response.
As shown in fig. 4, the temperature-sensitive allochroic powder doped into the gel matrix at a mass fraction of 0.5% has no influence on the mechanical properties of the gel (mainly considering the mechanical properties of the two materials, namely the initial modulus and the tensile strength). In addition, the temperature-sensitive allochroic gel using the double-network hydrogel as the matrix in example 2 has good allochroic capacity and good mechanical properties.
The functional stability of the temperature-sensitive color-changing hydrogel prepared in example 1 was tested, the hydrogel was rapidly changed and faded in cold and hot water baths, and the reflectance spectrum of the material was measured after each complete color change, to obtain the color data of the material, repeated 100 times. Comparing the 100 cycles of color data, one can conclude that the functionality of the material is very stable, as shown in fig. 5. Very high color rendering accuracy can still be maintained after 100 cycles.
Fig. 6 is a measurement of primarily the mechanical force response stability of a material. Since hydrogel materials have excellent mechanical properties, it is also a property of concern whether the stability of the color-changing function can be maintained under denaturation. The temperature-sensitive color-changing hydrogel material prepared in example 1 was subjected to 300% uniaxial stretching cyclic loading, each cyclic loading was performed 50 times, the temperature-sensitive hydrogel material was subjected to color change in a cold and hot water bath after 50 times of loading, and color spectrum values before and after color change were respectively recorded, as shown in fig. 6, and the values measured at the four times were compared after 50 times, 100 times, 150 times, and 200 times. Experiments prove that after mechanical force loading circulation for up to 200 times, the color changing functionality of the temperature-sensitive color-changing hydrogel can still be maintained at a stable level, and the stable functionality of the temperature-sensitive color-changing hydrogel material is proved.
The above-mentioned embodiments are intended to illustrate the technical solutions and advantages of the present invention, and it should be understood that the above-mentioned embodiments are only specific embodiments of the present invention, and are not intended to limit the present invention, and any modifications, additions, equivalents, etc. made within the scope of the principles of the present invention should be included in the scope of the present invention.
Claims (8)
1. A preparation method of a temperature-sensitive color-changing hydrogel material based on inclusion of temperature-sensitive color-changing microcapsules is characterized by comprising the following steps:
(1) adding the temperature-sensitive color-changing microcapsules into the hydrogel monomer solution, and uniformly mixing;
(2) adding a cross-linking agent, an initiator and a catalyst into the mixed solution of the temperature-sensitive color-changing microcapsules and the hydrogel monomers obtained in the step (1), and uniformly mixing to obtain precursor mother liquor;
(3) and curing the precursor mother liquor to obtain the temperature-sensitive color-changing hydrogel material.
2. The preparation method of the temperature-sensitive color-changing hydrogel material according to claim 1, wherein the hydrogel monomer is at least one of acrylamide, acrylic acid and sodium alginate.
3. The preparation method of the temperature-sensitive color-changing hydrogel material according to claim 1 or 2, wherein the mass fraction of the temperature-sensitive color-changing microcapsules in the temperature-sensitive color-changing hydrogel material is not more than 0.5%.
4. The preparation method of the temperature-sensitive color-changing hydrogel material according to claim 1, wherein the cross-linking agent is at least one of N, N-methylene bisacrylamide and polyethylene glycol diacrylate.
5. The preparation method of the temperature-sensitive color-changing hydrogel material according to claim 1, wherein the initiator is at least one of ammonium persulfate and potassium persulfate.
6. The preparation method of the temperature-sensitive color-changing hydrogel material according to claim 1, wherein the catalyst is tetramethylethylenediamine.
7. The preparation method of the temperature-sensitive color-changing hydrogel material according to claim 2, wherein the ultraviolet light is adopted in the step (3) for curing, and the curing conditions are as follows: the ultraviolet wavelength is 365nm, the power is 50-100W, and the curing time is 30-60 min.
8. A temperature-sensitive color-changing hydrogel material, which is prepared according to the preparation method of any one of claims 1 to 7.
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