CN110563898A - preparation method of hydrogel based on spiropyran composite microspheres - Google Patents
preparation method of hydrogel based on spiropyran composite microspheres Download PDFInfo
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Abstract
the invention discloses a preparation method of hydrogel based on spiropyran composite microspheres, which comprises the steps of firstly adopting an activation technology to anchor spiropyran on the surface of mesoporous nano particles with primary amine groups on the surface in a covalent manner to prepare spiropyran composite microspheres, and then compounding the spiropyran composite microspheres with sodium alginate/polyacrylamide/metal ions to further synthesize the spiropyran composite microsphere hydrogel. The composite hydrogel has stronger coordination effect on metal ions under the irradiation of ultraviolet light, thereby forming a stable cross-linked network structure and greatly improving the mechanical strength of the hydrogel; under the irradiation of visible light, the spiropyran in the system automatically rearranges to shield active phenol oxygen anions, partial coordination bonds disappear, and the mechanical strength of the hydrogel system is obviously reduced. The spiropyran composite microsphere hydrogel obtained by the invention has photosensitive and controllable mechanical strength, and can be widely applied to the fields of flexible devices, wearable electronics and the like.
Description
Technical Field
The invention belongs to the field of functional materials, and particularly relates to a preparation method of a hydrogel based on spiropyran composite microspheres.
Background
The hydrogel is a polymer material with a three-dimensional network structure formed by physical or chemical crosslinking, the polymer network contains a large amount of water and can keep a certain shape, and the hydrogel is a special semisolid material. The hydrogel is used as a flexible material and widely applied to the fields of flexible devices, biomedicine, tissue engineering, bionic engineering and the like. However, the mechanical strength of the finished gel product is uncontrollable due to the irreversibility of the internal structure of the traditional hydrogel, so that the application of the traditional hydrogel as a structural material in the fields of flexible devices, wearable electronics and the like is limited. Therefore, it is an important direction for the development of the material to modify the internal structure of the hydrogel from the molecular level to control the mechanical strength of the gel.
Disclosure of Invention
the invention aims to provide a preparation method of hydrogel based on spiropyran composite microspheres, which aims to overcome the defects in the prior art.
In order to achieve the purpose, the invention adopts the following technical scheme:
the preparation method of the hydrogel based on the spiropyran composite microspheres comprises the following steps:
step 1, preparation of spiropyran composite microspheres
Step 101, preparing a nano composite microsphere with a primary amine group on the surface: dispersing 2-5 parts of mesoporous nano particles in 100-150 parts of solvent by mass, ultrasonically oscillating for 10min-15min at the temperature of 20-25 ℃, then dropwise adding 0.5-2 parts of silane coupling agent, heating to 90-110 ℃, reacting for 10h-20h, carrying out centrifugal separation on a reaction system, repeatedly washing the obtained precipitate with absolute ethyl alcohol, and drying to obtain the nano composite microspheres with the surface containing primary amine groups;
102, synthesizing spiropyran with carboxyl terminal: uniformly mixing 1-2 parts by mass of 2,3, 3-trimethyl-2, 3-indoline, 1-2 parts by mass of monobasic brominated organic acid and 50-100 parts by mass of solvent, carrying out reflux reaction for 15-20 h under the conditions of continuous stirring and nitrogen protection at 80-155 ℃, then removing the solvent through reduced pressure distillation to obtain a reaction product, grinding the reaction product by using ether, then putting the ground reaction product into dichloromethane for recrystallization to obtain brominated organic acid indole, uniformly mixing 1-2 parts by mass of brominated organic acid indole, 1-2 parts by mass of 5-nitrosalicylaldehyde, 2-3 parts by mass of triethylamine and 8-20 parts by mass of absolute ethyl alcohol, carrying out reflux reaction for 6-9 h under the conditions of continuous stirring and nitrogen protection at 80-100 ℃, and then carrying out filtration to obtain a precipitate, repeatedly washing the precipitate with absolute ethyl alcohol and drying to obtain spiropyran with carboxyl end;
Step 103, preparation of spiropyran composite microspheres: dispersing 1-2 parts by mass of the nano composite microspheres containing primary amine groups on the surfaces obtained in the step 101 into 50-200 parts by mass of a solvent, adding 1-2 parts of dicyclohexylcarbodiimide, 0.5-1 part of N-hydroxysuccinimide and 0.5-1 part of the spiropyran with a carboxyl end obtained in the step 102 under the conditions of continuous stirring and nitrogen protection, carrying out amide activation reaction for 8-15 h at the temperature of-20-45 ℃, carrying out centrifugal separation on a reaction system, repeatedly washing the obtained precipitate with absolute ethyl alcohol, and drying to obtain the spiropyran composite microspheres;
Step 2, preparation of spiropyran composite microsphere hydrogel
step 201, preparation of a spiropyran composite microsphere hydrogel precursor: adding 2-3 parts of sodium alginate, 15-25 parts of acrylamide, 0.08-0.12 part of methylene bisacrylamide, 0.15-0.25 part of ammonium persulfate, 0.12-0.18 part of tetramethylethylenediamine and 2-5 parts of the spiropyran composite microspheres obtained in the step 103 into 120-200 parts of deionized water according to the parts by weight, stirring for 1-2 hours at the temperature of 20-30 ℃, then pouring into a glass mold and curing for 3-5 hours at the temperature of 40-50 ℃ to obtain a spiropyran composite microsphere hydrogel precursor;
Step 202, preparation of spiropyran composite microsphere hydrogel: immersing the precursor of the spiropyran composite microsphere hydrogel obtained in the step 201 in a metal chloride aqueous solution with the concentration of 0.2M-0.5M, standing for 3h-6h, wherein 100-800g of the spiropyran composite microsphere hydrogel precursor is added into every 200-800mL of the metal chloride aqueous solution to obtain the spiropyran composite microsphere hydrogel;
Light control of the mechanical strength of the spiropyran composite microsphere hydrogel: and (2) placing the spiropyran composite microsphere hydrogel obtained in the step (202) under ultraviolet light for irradiating for 15min-30min, and then placing the spiropyran composite microsphere hydrogel after being irradiated by the ultraviolet light under visible light for irradiating for 15min-30min, and then reducing the tensile strength.
the preparation method comprises the steps of firstly modifying mesoporous nano particles by adopting a silane coupling agent to obtain nano composite microspheres with primary amine groups on the surfaces, then preparing spiropyran with carboxyl terminals, activating carboxyl groups in the spiropyran to initiate amidation reaction between the carboxyl groups and the primary amine groups on the surfaces of the nano composite microspheres, thereby covalently anchoring the spiropyran on the surfaces of the nano composite microspheres to obtain spiropyran composite microspheres, doping the spiropyran composite microspheres into sodium alginate-polyacrylamide hydrogel to obtain spiropyran composite microsphere hydrogel precursors, and coordinating carboxyl groups (derived from sodium alginate) in the spiropyran composite microsphere hydrogel precursor structures with metal ions to obtain the spiropyran composite microsphere hydrogel.
the spiropyran composite microsphere hydrogel contains spiropyran composite microspheres, and because the spiropyran has photosensitivity, the spiropyran is converted into an open-loop state from a closed-loop state under the irradiation of ultraviolet light, phenoxy negative ions in a spiropyran structure are exposed and generate coordination reaction with metal ions compounded in a hydrogel system, so that sodium alginate-polyacrylamide, the metal ions and the spiropyran composite microspheres are combined to form a stable cross-linked network structure, and the mechanical strength of the composite hydrogel system is greatly enhanced; under the irradiation of visible light, the spiropyran is converted into a closed-loop state from an open-loop state, phenoxy negative ions disappear, coordinated metal ions automatically generate de-coordination, and the spiropyran composite microspheres are dissociated in a hydrogel system again, so that the mechanical strength of the composite hydrogel system is reduced. Therefore, after the spiropyran is introduced into the sodium alginate-polyacrylamide hydrogel system in the form of the spiropyran composite microsphere, metal ions are adopted as connecting substances of the spiropyran composite microsphere and the sodium alginate-polyacrylamide hydrogel system, and the open loop and the closed loop of the spiropyran are controlled by changing a light source by utilizing the photosensitive property of the spiropyran, namely the coordination and the de-coordination action of the metal ions and the spiropyran are controlled, so that the combination of the spiropyran composite microsphere and the sodium alginate-polyacrylamide hydrogel is controlled, and the photosensitive regulation and control of the mechanical strength of the composite hydrogel are realized.
Further, in step 101, the average particle diameter of the mesoporous nanoparticles is 30nm to 50nm, and the mesoporous nanoparticles are SiO2、TiO2Or ZnO.
Further, in step 101, the solvent is toluene, N-dimethylformamide or tetrahydrofuran.
Further, in step 101, the silane coupling agent is gamma-aminopropyltriethoxysilane, gamma-aminopropyltrimethoxysilane or N-beta (aminoethyl) -gamma-aminopropyltrimethoxysilane.
Further, in step 102, the monobromo organic acid is bromoacetic acid, 3-bromopropionic acid or 4-bromobutyric acid.
further, in step 102, the solvent is toluene, N-dimethylformamide or o-xylene.
Further, in step 103, the solvent is dichloromethane, N-dimethylacetamide or acetonitrile.
further, the size of the glass mold in step 201 is 10cm × 10cm (length × width), and the glass mold is separated by using a silica gel strip with a thickness of 2mm to 3 mm.
Further, the metal chloride in the aqueous metal chloride solution in step 202 is lithium chloride, calcium chloride or ferric chloride.
Compared with the prior art, the invention has the following beneficial technical effects:
1. According to the spiropyran composite microsphere hydrogel disclosed by the invention, spiropyran composite microspheres are introduced into a sodium alginate-polyacrylamide hydrogel system, metal ions are used as connecting substances of the spiropyran composite microspheres and a sodium alginate-polyacrylamide hydrogel network structure, and the combination of the spiropyran composite microspheres and the sodium alginate-polyacrylamide hydrogel network can be controlled by changing a light source by utilizing the photosensitive property of spiropyran, so that the photosensitive regulation and control of the mechanical strength of the composite hydrogel are realized, and the spiropyran composite microsphere hydrogel is simple in regulation and control method, accurate, controllable, environment-friendly and nontoxic, and is suitable for the fields of flexible devices, wearable electronics and the like.
2. The invention adopts the mesoporous nano particles as the base material modified by the photosensitive compound spiropyran, provides guarantee for the free transformation of the spiropyran on the surface conformation by utilizing the small size, the large specific surface area and the mesoporous performance of the mesoporous nano particles, and is beneficial to better and subsequently and sensitively regulating and controlling the mechanical strength of the composite hydrogel system.
3. the method firstly activates carboxyl in the spiropyran, and then initiates the amidation reaction between the carboxyl and primary amine groups on the surface of the nano composite microsphere, so that the spiropyran is covalently anchored on the surface of the nano composite microsphere, and the method has the advantages of mild reaction conditions, less side reactions and high grafting rate.
4. The conversion between the open loop and the closed loop of the spiropyran in the spiropyran composite microsphere hydrogel is photo-reversible, so that the spiropyran composite microsphere hydrogel is photo-reversible in the photosensitive regulation of the mechanical strength and has excellent light fatigue resistance.
Drawings
FIG. 1 is a schematic diagram of the preparation of the spiropyran composite microspheres of the present invention.
FIG. 2 is a schematic diagram of the light control of the spiropyran composite microsphere hydrogel of the present invention.
Detailed Description
The invention is described in detail below with reference to examples, which are intended to be illustrative only and not to be construed as limiting the scope of the invention, and many insubstantial modifications and variations of the invention can be made by an engineer skilled in the art based on the teachings of the invention.
as shown in FIG. 1, the preparation principle of the spiropyran composite microsphere of the invention is as follows: firstly, modifying mesoporous nano particles by using a silane coupling agent to obtain nano composite microspheres with primary amine groups on the surfaces, then preparing brominated organic acid indole by carrying out reflux reaction on 2,3, 3-trimethyl-2, 3-indoline and monobasic brominated organic acid, then preparing spiropyran with carboxyl terminals by reacting the brominated organic acid indole with 5-nitro salicylaldehyde, and initiating the amidation reaction of the carboxyl and the primary amine groups on the surfaces of the nano composite microspheres by activating the carboxyl in the spiropyran so as to covalently anchor the spiropyran on the surfaces of the nano composite microspheres to obtain the spiropyran composite microspheres.
As shown in FIG. 2, the light control principle of the spiropyran composite microsphere hydrogel of the present invention is as follows: under the irradiation of ultraviolet light, the spiropyran in the spiropyran composite microsphere hydrogel is converted into an open-loop state from a closed-loop state, and phenoxy anions in a spiropyran structure are exposed and generate coordination reaction with metal ions compounded in a hydrogel system, so that sodium alginate-polyacrylamide, the metal ions and the spiropyran composite microsphere are combined to form a stable cross-linked network structure, and the mechanical strength of the composite hydrogel system is greatly enhanced; under the irradiation of visible light, the spiropyran is converted into a closed-loop state from an open-loop state, phenoxy negative ions disappear, coordinated metal ions automatically generate de-coordination, the spiropyran composite microspheres are dissociated in a hydrogel system again, and the mechanical strength of the composite hydrogel system is reduced.
example 1
The embodiment comprises the following steps:
step 1, preparation of spiropyran composite microspheres
Step 101, a sodium containing primary amine group on the surfacePreparing the rice composite microspheres: 2 parts of mesoporous SiO with the average grain diameter of 30nm by weight2Dispersing nano particles in 100 parts of toluene, performing ultrasonic oscillation for 10min at the temperature of 20 ℃, then dropwise adding 0.5 part of gamma-aminopropyltriethoxysilane, heating to 90 ℃ for reaction for 20h, performing centrifugal separation on a reaction system, repeatedly washing the obtained precipitate by absolute ethyl alcohol, and drying to obtain the nano composite microspheres with primary amine groups on the surfaces;
102, synthesizing spiropyran with carboxyl terminal: uniformly mixing 1 part of 2,3, 3-trimethyl-2, 3-indoline, 1 part of 3-bromopropionic acid and 50 parts of toluene in parts by mass, carrying out reflux reaction for 20 hours under the conditions of continuous stirring and nitrogen protection at 80 ℃, then carrying out reduced pressure distillation to remove a solvent to obtain a reaction product, grinding the reaction product by using ether, then putting the ground reaction product into dichloromethane for recrystallization to obtain brominated organic acid indole, uniformly mixing 1 part of brominated organic acid indole, 1 part of 5-nitro salicylaldehyde, 2 parts of triethylamine and 8 parts of absolute ethyl alcohol in parts by mass, carrying out reflux reaction for 9 hours under the conditions of continuous stirring and nitrogen protection at 80 ℃, then carrying out filtration to obtain a precipitate, repeatedly washing the precipitate by using absolute ethyl alcohol, and then drying to obtain spiropyran with a carboxyl terminal;
Step 103, preparation of spiropyran composite microspheres: dispersing 1 part of the nano composite microspheres containing primary amine groups on the surfaces, which are obtained in the step 101, in 50 parts of dichloromethane by mass, adding 1 part of dicyclohexylcarbodiimide, 0.5 part of N-hydroxysuccinimide and 0.5 part of the spiropyran with carboxyl ends, which is obtained in the step 102, under the conditions of continuous stirring and nitrogen protection, reacting for 15 hours at-20 ℃, carrying out centrifugal separation on a reaction system, repeatedly washing the obtained precipitate with absolute ethyl alcohol, and drying to obtain the spiropyran composite microspheres;
Step 2, preparation of spiropyran composite microsphere hydrogel
Step 201, preparation of a spiropyran composite microsphere hydrogel precursor: adding 2 parts of sodium alginate, 15 parts of acrylamide, 0.08 part of methylene bisacrylamide, 0.15 part of ammonium persulfate, 0.12 part of tetramethylethylenediamine and 2 parts of the spiropyran composite microspheres obtained in the step 103 into 120 parts of deionized water by mass, stirring for 1h at 20 ℃, then pouring into a glass mold, placing in an oven, and curing for 5h at 40 ℃ to obtain a spiropyran composite microsphere hydrogel precursor; the size of the glass mold is 10cm multiplied by 10cm (length multiplied by width);
step 202, preparation of spiropyran composite microsphere hydrogel: immersing the spiropyran composite microsphere hydrogel precursor obtained in the step 201 in a lithium chloride aqueous solution with the concentration of 0.5M, and standing for 3 hours, wherein 100g of the spiropyran composite microsphere hydrogel precursor is added into every 200mL of the lithium chloride aqueous solution to obtain spiropyran composite microsphere hydrogel;
Light control of the mechanical strength of the spiropyran composite microsphere hydrogel: and (3) placing the spiropyran composite microsphere hydrogel obtained in the step (202) under ultraviolet light for irradiating for 15min, and then placing the spiropyran composite microsphere hydrogel after being irradiated by the ultraviolet light under visible light for irradiating for 15 min.
the tensile strength of the spiropyran composite microsphere hydrogel after being irradiated by ultraviolet light and the tensile strength of the spiropyran composite microsphere hydrogel after being irradiated by visible light are respectively tested by a universal test stretcher, and the result shows that the tensile strength of the spiropyran composite microsphere hydrogel prepared in the embodiment after being irradiated by the ultraviolet light is 402kPa, the tensile strength of the spiropyran composite microsphere hydrogel after being irradiated by the visible light is 280kPa, and after 5 times of circulation, the difference value between the tensile strength of the spiropyran composite microsphere hydrogel after being irradiated by the ultraviolet light and the tensile strength of the spiropyran composite microsphere hydrogel after being irradiated by the visible light is 122kPa, which shows that the spiropyran composite microsphere hydrogel prepared in the embodiment can regulate and control the mechanical strength performance through light sensitivity and has.
Example 2
The embodiment comprises the following steps:
Step 1, preparation of spiropyran composite microspheres
step 101, preparing a nano composite microsphere with a primary amine group on the surface: 3 parts of mesoporous TiO with the average particle size of 35nm by weight2Dispersing nanoparticles in 120 parts of N, N-dimethylformamide, ultrasonically oscillating for 12min at 25 ℃, then dropwise adding 1.2 parts of gamma-aminopropyltrimethoxysilane, heating to 100 ℃, reacting for 15h, centrifugally separating a reaction system, and obtaining precipitateRepeatedly washing the precipitate with absolute ethyl alcohol, and drying to obtain the nano composite microspheres with the primary amine groups on the surface;
102, synthesizing spiropyran with carboxyl terminal: uniformly mixing 1.5 parts by mass of 2,3, 3-trimethyl-2, 3-indoline, 1.5 parts by mass of bromoacetic acid and 80 parts by mass of N, N-dimethylformamide, carrying out reflux reaction for 18 hours under the conditions of continuous stirring and nitrogen protection at 140 ℃, then carrying out reduced pressure distillation to remove a solvent to obtain a reaction product, grinding the reaction product by using diethyl ether, then putting the ground reaction product into dichloromethane for recrystallization to obtain brominated organic acid indole, uniformly mixing 1.5 parts by mass of brominated organic acid indole, 1.5 parts by mass of 5-nitrosalicylaldehyde, 2.5 parts by mass of triethylamine and 15 parts by mass of absolute ethyl alcohol, carrying out reflux reaction for 8 hours under the conditions of continuous stirring and nitrogen protection at 90 ℃, then carrying out filtration to obtain a precipitate, repeatedly washing the precipitate by using absolute ethyl alcohol and then drying to obtain spiropyran with a carboxyl terminal;
step 103, preparation of spiropyran composite microspheres: dispersing 1.5 parts by mass of the nano composite microspheres containing primary amine groups on the surfaces obtained in the step 101 into 120 parts of N, N-dimethylacetamide, adding 1.5 parts of dicyclohexylcarbodiimide, 0.7 part of N-hydroxysuccinimide and 0.7 part of the spiropyran with carboxyl ends obtained in the step 102 under the conditions of continuous stirring and nitrogen protection, reacting for 12 hours at 20 ℃, carrying out centrifugal separation on a reaction system, repeatedly washing the obtained precipitate with absolute ethyl alcohol, and drying to obtain the spiropyran composite microspheres;
Step 2, preparation of spiropyran composite microsphere hydrogel
Step 201, preparation of a spiropyran composite microsphere hydrogel precursor: adding 2.5 parts of sodium alginate, 20 parts of acrylamide, 0.09 part of methylene bisacrylamide, 0.20 part of ammonium persulfate, 0.15 part of tetramethylethylenediamine and 4 parts of the spiropyran composite microspheres obtained in the step 103 into 180 parts of deionized water according to the mass parts, stirring for 1.5 hours at the temperature of 30 ℃, then pouring into a glass mold, placing in an oven, and curing for 4 hours at the temperature of 45 ℃ to obtain a spiropyran composite microsphere hydrogel precursor; the size of the glass mold is 10cm multiplied by 10cm (length multiplied by width);
Step 202, preparation of spiropyran composite microsphere hydrogel: immersing the spiropyran composite microsphere hydrogel precursor obtained in the step 201 in a calcium chloride aqueous solution with the concentration of 0.4M, and standing for 4 hours, wherein 800g of the spiropyran composite microsphere hydrogel precursor is added into every 800mL of the calcium chloride aqueous solution to obtain spiropyran composite microsphere hydrogel;
Light control of the mechanical strength of the spiropyran composite microsphere hydrogel: and (3) placing the spiropyran composite microsphere hydrogel obtained in the step (202) under ultraviolet light for irradiating for 20min, and then placing the spiropyran composite microsphere hydrogel after being irradiated by the ultraviolet light under visible light for irradiating for 20 min.
The tensile strength of the spiropyran composite microsphere hydrogel after being irradiated by ultraviolet light and the tensile strength of the spiropyran composite microsphere hydrogel after being irradiated by visible light are respectively tested by a universal test stretcher, and the result shows that the tensile strength of the spiropyran composite microsphere hydrogel prepared in the embodiment after being irradiated by ultraviolet light is 849kPa, the tensile strength of the spiropyran composite microsphere hydrogel after being irradiated by visible light is 610kPa, and after 5 times of circulation, the difference value between the tensile strength of the spiropyran composite microsphere hydrogel after being irradiated by ultraviolet light and the tensile strength of the spiropyran composite microsphere hydrogel after being irradiated by visible light is 239kPa, so that the spiropyran composite microsphere hydrogel prepared in the embodiment can regulate the mechanical strength performance through light sensitivity, and has excellent light fatigue resistance.
Example 3
The embodiment comprises the following steps:
step 1, preparation of spiropyran composite microspheres
Step 101, preparing a nano composite microsphere with a primary amine group on the surface: dispersing 5 parts of mesoporous ZnO nanoparticles with the average particle size of 50nm in 150 parts of tetrahydrofuran by mass, ultrasonically oscillating for 15min at 22 ℃, then dropwise adding 2 parts of N-beta (aminoethyl) -gamma-aminopropyltrimethoxysilane, heating to 110 ℃, reacting for 10h, carrying out centrifugal separation on a reaction system, repeatedly washing the obtained precipitate with absolute ethyl alcohol, and drying to obtain the nano composite microspheres with the surface containing primary amine groups;
102, synthesizing spiropyran with carboxyl terminal: uniformly mixing 2 parts of 2,3, 3-trimethyl-2, 3-indoline, 2 parts of 4-bromobutyric acid and 100 parts of o-xylene by mass, carrying out reflux reaction for 15 hours at 155 ℃ under the conditions of continuous stirring and nitrogen protection, then carrying out reduced pressure distillation to remove a solvent to obtain a reaction product, grinding the reaction product by using ether, then placing the ground reaction product into dichloromethane for recrystallization to obtain brominated organic acid indole, uniformly mixing 2 parts of brominated organic acid indole, 2 parts of 5-nitrosalicylaldehyde, 3 parts of triethylamine and 20 parts of absolute ethyl alcohol by mass, carrying out reflux reaction for 6 hours at 100 ℃ under the conditions of continuous stirring and nitrogen protection, then carrying out filtration to obtain a precipitate, repeatedly washing the precipitate by using absolute ethyl alcohol, and then drying to obtain spiropyran with a carboxyl terminal;
step 103, preparation of spiropyran composite microspheres: dispersing 2 parts by mass of the nano composite microspheres containing primary amine groups on the surfaces obtained in the step 101 into 200 parts by mass of acetonitrile, adding 2 parts by mass of dicyclohexylcarbodiimide, 1 part by mass of N-hydroxysuccinimide and 1 part by mass of the spiropyran with carboxyl ends obtained in the step 102 under the conditions of continuous stirring and nitrogen protection, reacting for 8 hours at 45 ℃, carrying out centrifugal separation on a reaction system, repeatedly washing the obtained precipitate with absolute ethyl alcohol, and drying to obtain the spiropyran composite microspheres;
step 2, preparation of spiropyran composite microsphere hydrogel
Step 201, preparation of a spiropyran composite microsphere hydrogel precursor: adding 3 parts of sodium alginate, 25 parts of acrylamide, 0.12 part of methylene bisacrylamide, 0.25 part of ammonium persulfate, 0.18 part of tetramethylethylenediamine and 5 parts of the spiropyran composite microspheres obtained in the step 103 into 200 parts of deionized water by mass, stirring for 2 hours at 25 ℃, then pouring into a glass mold, placing in an oven, and curing for 3 hours at 50 ℃ to obtain a spiropyran composite microsphere hydrogel precursor; the size of the glass mold is 10cm multiplied by 10cm (length multiplied by width);
step 202, preparation of spiropyran composite microsphere hydrogel: immersing the spiropyran composite microsphere hydrogel precursor obtained in the step 201 in a ferric chloride aqueous solution with the concentration of 0.2M, and standing for 6 hours, wherein 600g of the spiropyran composite microsphere hydrogel precursor is added into every 500mL of the ferric chloride aqueous solution to obtain spiropyran composite microsphere hydrogel;
light control of the mechanical strength of the spiropyran composite microsphere hydrogel: and (3) placing the spiropyran composite microsphere hydrogel obtained in the step (202) under ultraviolet light for irradiating for 30min, and then placing the spiropyran composite microsphere hydrogel after being irradiated by the ultraviolet light under visible light for irradiating for 30 min.
The tensile strength of the spiropyran composite microsphere hydrogel after being irradiated by ultraviolet light and the tensile strength of the spiropyran composite microsphere hydrogel after being irradiated by visible light are respectively tested by a universal test stretcher, and the result shows that the tensile strength of the spiropyran composite microsphere hydrogel prepared in the embodiment after being irradiated by ultraviolet light is 1152kPa, the tensile strength of the spiropyran composite microsphere hydrogel after being irradiated by visible light is 651kPa, and after 5 times of circulation, the difference value between the tensile strength of the spiropyran composite microsphere hydrogel after being irradiated by ultraviolet light and the tensile strength of the spiropyran composite microsphere hydrogel after being irradiated by visible light is 501kPa, which indicates that the spiropyran composite microsphere hydrogel prepared in the embodiment can regulate the mechanical strength performance through light sensitivity and has excellent light fatigue resistance.
Claims (9)
1. The preparation method of the hydrogel based on the spiropyran composite microspheres is characterized by comprising the following steps:
step 1, preparation of spiropyran composite microspheres
Step 101, preparing a nano composite microsphere with a primary amine group on the surface: dispersing 2-5 parts of mesoporous nano particles in 100-150 parts of solvent by mass, ultrasonically oscillating for 10min-15min at the temperature of 20-25 ℃, then dropwise adding 0.5-2 parts of silane coupling agent, heating to 90-110 ℃, reacting for 10h-20h, carrying out centrifugal separation on a reaction system, repeatedly washing the obtained precipitate with absolute ethyl alcohol, and drying to obtain the nano composite microspheres with the surface containing primary amine groups;
102, synthesizing spiropyran with carboxyl terminal: uniformly mixing 1-2 parts by mass of 2,3, 3-trimethyl-2, 3-indoline, 1-2 parts by mass of monobasic brominated organic acid and 50-100 parts by mass of solvent, carrying out reflux reaction for 15-20 h under the conditions of continuous stirring and nitrogen protection at 80-155 ℃, then removing the solvent through reduced pressure distillation to obtain a reaction product, grinding the reaction product by using ether, then putting the ground reaction product into dichloromethane for recrystallization to obtain brominated organic acid indole, uniformly mixing 1-2 parts by mass of brominated organic acid indole, 1-2 parts by mass of 5-nitrosalicylaldehyde, 2-3 parts by mass of triethylamine and 8-20 parts by mass of absolute ethyl alcohol, carrying out reflux reaction for 6-9 h under the conditions of continuous stirring and nitrogen protection at 80-100 ℃, and then carrying out filtration to obtain a precipitate, repeatedly washing the precipitate with absolute ethyl alcohol and drying to obtain spiropyran with carboxyl end;
Step 103, preparation of spiropyran composite microspheres: dispersing 1-2 parts by mass of the nano composite microspheres containing primary amine groups on the surfaces obtained in the step 101 into 50-200 parts by mass of a solvent, adding 1-2 parts of dicyclohexylcarbodiimide, 0.5-1 part of N-hydroxysuccinimide and 0.5-1 part of the spiropyran with a carboxyl end obtained in the step 102 under the conditions of continuous stirring and nitrogen protection, carrying out amide activation reaction for 8-15 h at the temperature of-20-45 ℃, carrying out centrifugal separation on a reaction system, repeatedly washing the obtained precipitate with absolute ethyl alcohol, and drying to obtain the spiropyran composite microspheres;
step 2, preparation of spiropyran composite microsphere hydrogel
Step 201, preparation of a spiropyran composite microsphere hydrogel precursor: adding 2-3 parts of sodium alginate, 15-25 parts of acrylamide, 0.08-0.12 part of methylene bisacrylamide, 0.15-0.25 part of ammonium persulfate, 0.12-0.18 part of tetramethylethylenediamine and 2-5 parts of the spiropyran composite microspheres obtained in the step 103 into 120-200 parts of deionized water according to parts by weight, stirring for 1-2 hours at the temperature of 20-30 ℃, and then curing for 3-5 hours at the temperature of 40-50 ℃ to obtain a spiropyran composite microsphere hydrogel precursor;
Step 202, preparation of spiropyran composite microsphere hydrogel: immersing the precursor of the spiropyran composite microsphere hydrogel obtained in the step 201 in a metal chloride aqueous solution with the concentration of 0.2M-0.5M, standing for 3h-6h, wherein 100-800g of the spiropyran composite microsphere hydrogel precursor is added into every 200-800mL of the metal chloride aqueous solution, and obtaining the spiropyran composite microsphere hydrogel.
2. The method for preparing hydrogel based on spiropyran composite microspheres according to claim 1, wherein said mesoporous nano-particles in step 101The average particle diameter of the rice particles is 30nm-50nm, and the mesoporous nano particles are SiO2、TiO2Or ZnO.
3. The method for preparing a hydrogel based on spiropyran composite microspheres according to claim 1, wherein said solvent in step 101 is toluene, N-dimethylformamide or tetrahydrofuran.
4. The method for preparing a hydrogel based on spiropyran composite microspheres according to claim 1, wherein said silane coupling agent in step 101 is γ -aminopropyltriethoxysilane, γ -aminopropyltrimethoxysilane or N- β (aminoethyl) - γ -aminopropyltrimethoxysilane.
5. The method for preparing the hydrogel based on the spiropyran composite microspheres according to claim 1, wherein in the step 102, the monobromo organic acid is bromoacetic acid, 3-bromopropionic acid or 4-bromobutyric acid.
6. The method for preparing a hydrogel based on spiropyran composite microspheres according to claim 1, wherein said solvent in step 102 is toluene, N-dimethylformamide or o-xylene.
7. the method for preparing a hydrogel based on spiropyran composite microspheres according to claim 1, wherein said solvent in step 103 is dichloromethane, N-dimethylacetamide, or acetonitrile.
8. the method for preparing a hydrogel based on spiropyran composite microspheres according to claim 1, wherein the stirring in step 201 is poured into a glass mold for curing, and the length x width of the glass mold is 10cm x 10 cm.
9. The method for preparing a hydrogel based on spiropyran composite microspheres according to claim 1, wherein said metal chloride in said aqueous solution of metal chloride in step 202 is lithium chloride, calcium chloride or ferric chloride.
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