CN111333990A - Self-repairing double-network cross-linked degradable acrylic hydrogel and preparation method thereof - Google Patents
Self-repairing double-network cross-linked degradable acrylic hydrogel and preparation method thereof Download PDFInfo
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Abstract
The invention relates to the technical field of hydrogel materials, and discloses a self-repairing double-network cross-linked degradable acrylic hydrogel which comprises the following formula raw materials and components: aldehydized polyethylene glycol, alkenyl chitosan, alkenyl sodium alginate, acrylic acid, methacrylic acid and potassium persulfate. Alkenyl chitosan, alkenyl sodium alginate, acrylic acid and methacrylic acid are polymerized through free radicals to serve as a first double chemical crosslinking network, aldehyde polyethylene glycol serves as a gel factor to perform crosslinking condensation reaction with amino in the chitosan, and generated reversible dynamic Schiff base imino bonds serve as a second double chemical crosslinking network to obtain the double-network crosslinked acrylic acid hydrogel which has ultrahigh crosslinking degree, tensile strength and breaking strength.
Description
Technical Field
The invention relates to the technical field of hydrogel materials, in particular to a self-repairing double-network cross-linked degradable acrylic hydrogel and a preparation method thereof.
Background
Hydrogels are a class of very hydrophilic three-dimensional network-structured gels that swell rapidly in water and hold a large volume of water in this swollen state without dissolving, the amount of water absorbed is closely related to the degree of crosslinking, the higher the degree of crosslinking, the lower the amount of water absorbed, the gel is neither a completely solid nor a completely liquid in its aggregated state, the behavior of a solid is such that it can maintain a certain shape and volume under certain conditions, and the behavior of a liquid is such that a solute can diffuse or permeate from the hydrogel.
The hydrogel can be divided into natural polymer hydrogel, such as cellulose, chitosan, poly-L-glutamic acid and the like, the synthetic polymer hydrogel comprises hydrophilic polymers including alcohol, acrylic acid and derivatives thereof and the like, the artificially synthesized hydrogel usually has the defects of low gel strength, poor toughness and the like, a hydrogel material matrix is easy to deform and break under the stretching and compression of external force, and has no self-healing and self-repairing performance, and the artificially synthesized synthetic polymer hydrogel has no biodegradation performance and is easy to cause environmental pollution.
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides a self-repairing double-network cross-linked degradable acrylic hydrogel and a preparation method thereof, which solve the problems that the acrylic hydrogel has poor mechanical properties such as strength and toughness and does not have self-healing property, and simultaneously solve the problem that the acrylic synthetic polymer hydrogel does not have a biodegradation function.
(II) technical scheme
In order to achieve the purpose, the invention provides the following technical scheme: a self-repairing double-network cross-linked degradable acrylic hydrogel comprises the following raw materials and components: the mass ratio of the aldehyde polyethylene glycol to the alkenyl chitosan to the alkenyl sodium alginate to the acrylic acid to the methacrylic acid to the potassium persulfate is 6-12:10-18:2-6:20-60:100: 0.4-0.8.
Preferably, the preparation method of the self-repairing double-network cross-linked degradable acrylic hydrogel comprises the following steps:
(1) introducing nitrogen into a reaction bottle, adding an anhydrous tetrahydrofuran solvent, polyethylene glycol 2000 and 4-formylbenzoic acid, uniformly stirring, adding a catalyst 4-dimethylaminopyridine and a condensing agent diisopropylcarbodiimide, reacting at room temperature for 12-24h, filtering the solution to remove insoluble solid impurities, and recrystallizing the filtrate to obtain the aldehyde polyethylene glycol.
(2) Adding distilled water solvent and chitosan into a reaction bottle, placing the reaction bottle in a constant-temperature ultrasonic processor, carrying out ultrasonic treatment for 1 to 3 hours at the ultrasonic frequency of 25 to 40KHz at the temperature of between 50 and 80 ℃, adding N, N' -methylene bisacrylamide and an accelerant triethylamine, carrying out uniform stirring reaction for 72 to 96 hours at the temperature of between 50 and 70 ℃, carrying out reduced pressure distillation on the solution to remove the solvent, washing a solid product by using diethyl ether and distilled water, and fully drying to prepare the alkenyl chitosan.
(3) Adding distilled water solvent and sodium alginate into a reaction bottle, stirring and dissolving, slowly dropwise adding dimethyl sulfoxide solution of glycidyl methacrylate, adding catalyst 4-dimethylaminopyridine, stirring at a constant speed at room temperature for reaction for 48-72h, cooling the solution in ice-water bath, and adding ethanol solvent until a large amount of precipitate is separated out to prepare the alkenyl sodium alginate.
(4) Adding a distilled water solvent, acrylic acid and methacrylic acid into a reaction bottle, adding a buffer solution to adjust the pH value of the solution to 6-7, adding alkenyl chitosan and alkenyl sodium alginate, slowly dropwise adding an initiator potassium persulfate after uniform ultrasonic dispersion, stirring at a constant speed at room temperature for reaction for 10-20min, adding aldehyde polyethylene glycol as a cross-linking agent, reacting for 1-3h, filtering the solution to remove the solvent, washing and dialyzing to remove impurities by using distilled water and ethanol, and preparing the self-repairing type double-network cross-linked degradable acrylic acid hydrogel.
Preferably, the mass ratio of the polyethylene glycol 2000, the 4-formylbenzoic acid, the 4-dimethylaminopyridine and the diisopropylcarbodiimide in the step (1) is 3-4:1:0.04-0.05: 1-1.3.
Preferably, the mass ratio of the chitosan, the N, N' -methylene bisacrylamide and the triethylamine in the step (2) is 1: 3-4.
Preferably, the constant temperature ultrasonic processor in step (2) includes water bath, the inside below fixedly connected with base of water bath, the base is provided with the governing valve, governing valve swing joint has the carriage release lever, carriage release lever fixedly connected with fixture block, fixture block and draw-in groove swing joint, draw-in groove fixedly connected with objective table, objective table top are provided with the reaction flask, the outside fixedly connected with heat preservation of water bath, the inside both sides of heat preservation are provided with constant temperature heating ware, the inside top of heat preservation is provided with the supersound ware, supersound ware below fixedly connected with ultrasonic probe.
Preferably, the mass ratio of the sodium alginate to the glycidyl methacrylate to the 4-dimethylaminopyridine in the step (3) is 1:0.6-0.8: 0.4-0.5.
(III) advantageous technical effects
Compared with the prior art, the invention has the following beneficial technical effects:
the self-repairing double-network cross-linked degradable acrylic acid hydrogel is characterized in that carboxyl of 4-formylbenzoic acid reacts with hydroxyl of polyethylene glycol under the action of a catalyst and an accelerator to obtain aldehydized polyethylene glycol, part of amino of chitosan reacts with one olefinic bond of N, N' -methylene bisacrylamide under an alkaline condition to obtain alkenyl chitosan, sodium alginate reacts with an epoxy group of glycidyl methacrylate under the action of the catalyst to obtain alkenyl sodium alginate, alkenyl groups of the alkenyl chitosan and the alkenyl sodium alginate are polymerized with acrylic acid and methacrylic acid through free radicals to obtain a chitosan-sodium alginate-polyacrylic acid copolymer, the alkenyl cross-linking polymerization serves as a first heavy chemical cross-linking network, the aldehydized polyethylene glycol is added, and two aldehyde groups at the chain end serve as a gel factor to perform cross-linking condensation reaction with amino in the chitosan, and taking the generated Schiff base imino bond as a second chemical crosslinking network to obtain the double-network crosslinking acrylic acid hydrogel.
The self-repairing double-network cross-linked degradable acrylic acid hydrogel has ultrahigh cross-linking degree, takes Schiff base imino bond as reversible dynamic covalent bond, under the synergistic effect, the mechanical properties of the tensile strength and the breaking strength of the hydrogel material are obviously enhanced, under the action of external force, the Schiff base imino bond can be dynamically recombined in a short time after being broken, so that the hydrogel has good self-repairing and self-healing capabilities, and introduces the biomass molecule chitosan and sodium alginate into polyacrylic acid molecular chains in a chemical covalent grafting way, when the chitosan and the sodium alginate are biodegraded, the molecular chain of the chitosan-sodium alginate-polyacrylic acid copolymer can be damaged, so that the acrylic acid hydrogel has a good biodegradation function, and the pollution of the polyacrylic acid hydrogel which is difficult to decompose to the environment is avoided.
Drawings
FIG. 1 is a schematic front view of a thermostatic ultrasonic processor;
FIG. 2 is an enlarged schematic view of the base;
FIG. 3 is a schematic view of the travel bar adjustment;
FIG. 4 is an infrared spectrum of an aldehyde-based polyethylene glycol;
FIG. 5 is a 13C NMR spectrum of alkenylated chitosan.
1. A constant temperature ultrasonic processor; 2. a water bath; 3. a base; 4. adjusting a valve; 5. a travel bar; 6. a clamping block; 7. a card slot; 8. an object stage; 9. a reaction bottle; 10. a heat insulation layer 11 and a constant temperature heater; 12. an ultrasonic device; 13 ultrasound probe.
Detailed Description
To achieve the above object, the present invention provides the following embodiments and examples: a self-repairing double-network cross-linked degradable acrylic hydrogel comprises the following raw materials and components: the mass ratio of the aldehyde polyethylene glycol to the alkenyl chitosan to the alkenyl sodium alginate to the acrylic acid to the methacrylic acid to the potassium persulfate is 6-12:10-18:2-6:20-60:100: 0.4-0.8.
The preparation method of the self-repairing double-network cross-linked degradable acrylic hydrogel comprises the following steps:
(1) introducing nitrogen into a reaction bottle, adding an anhydrous tetrahydrofuran solvent, polyethylene glycol 2000 and 4-formylbenzoic acid, uniformly stirring, adding a catalyst 4-dimethylaminopyridine and a condensing agent diisopropylcarbodiimide in a mass ratio of 3-4:1:0.04-0.05:1-1.3, reacting at room temperature for 12-24h, filtering the solution to remove insoluble solid impurities, and recrystallizing the filtrate to obtain the formylated polyethylene glycol.
(2) Adding distilled hydrosolvent and chitosan into a reaction bottle, placing the reaction bottle in a constant temperature ultrasonic processor, wherein the constant temperature ultrasonic processor comprises a water bath, a base fixedly connected with the lower part of the inner part of the water bath, an adjusting valve arranged on the base, a moving rod movably connected with the adjusting valve, a fixture block fixedly connected with the moving rod and movably connected with a fixture groove, a carrier fixedly connected with the fixture groove, a reaction bottle arranged above the carrier, a heat-insulating layer fixedly connected with the outer part of the water bath, constant temperature heaters arranged on two sides of the inner part of the heat-insulating layer, an ultrasonic device arranged above the inner part of the heat-insulating layer, an ultrasonic probe fixedly connected with the lower part of the ultrasonic device, wherein the ultrasonic frequency is 25-40KHz, performing ultrasonic treatment for 1-3h at 50-80 ℃, adding N, N' -methylene bisacrylamide and a promoter triethylamine, the mass ratio of the three components is 1, the solution was distilled under reduced pressure to remove the solvent, and the solid product was washed with diethyl ether and distilled water and sufficiently dried to prepare an alkenylated chitosan.
(3) Adding distilled water solvent and sodium alginate into a reaction bottle, stirring and dissolving, slowly dropwise adding dimethyl sulfoxide solution of glycidyl methacrylate, adding catalyst 4-dimethylaminopyridine, controlling the mass ratio of the sodium alginate to the glycidyl methacrylate to the 4-dimethylaminopyridine to be 1:0.6-0.8:0.4-0.5, stirring at a constant speed at room temperature for reaction for 48-72 hours, cooling the solution in ice water bath, and adding ethanol solvent until a large amount of precipitate is separated out to prepare the alkenyl sodium alginate.
(4) Adding a distilled water solvent, acrylic acid and methacrylic acid into a reaction bottle, adding a buffer solution to adjust the pH value of the solution to 6-7, adding alkenyl chitosan and alkenyl sodium alginate, slowly dropwise adding an initiator potassium persulfate after uniform ultrasonic dispersion, stirring at a constant speed at room temperature for reaction for 10-20min, adding aldehyde polyethylene glycol as a cross-linking agent, reacting for 1-3h, filtering the solution to remove the solvent, washing and dialyzing to remove impurities by using distilled water and ethanol, and preparing the self-repairing type double-network cross-linked degradable acrylic acid hydrogel.
Example 1
(1) Introducing nitrogen into a reaction bottle, adding an anhydrous tetrahydrofuran solvent, polyethylene glycol 2000 and 4-formylbenzoic acid, uniformly stirring, adding a catalyst 4-dimethylaminopyridine and a condensing agent diisopropylcarbodiimide in a mass ratio of 3:1:0.04:1, reacting at room temperature for 12 hours, filtering the solution to remove insoluble solid impurities, and recrystallizing the filtrate to obtain the formylated polyethylene glycol.
(2) Adding distilled hydrosolvent and chitosan into a reaction bottle, placing the reaction bottle in a constant temperature ultrasonic processor, wherein the constant temperature ultrasonic processor comprises a water bath, a base is fixedly connected below the inner part of the water bath, an adjusting valve is arranged on the base, a moving rod is movably connected with the adjusting valve, a fixture block is fixedly connected with the moving rod and is movably connected with a clamp groove, the clamp groove is fixedly connected with an objective table, a reaction bottle is arranged above the objective table, a heat-insulating layer is fixedly connected with the outer part of the water bath, constant temperature heaters are arranged on two sides of the inner part of the heat-insulating layer, an ultrasonic device is arranged above the inner part of the heat-insulating layer, an ultrasonic probe is fixedly connected below the ultrasonic device, the ultrasonic frequency is 25KHz, ultrasonic treatment is carried out for 1-3h at 50 ℃, N' -methylene bisacrylamide and triethylamine serving as an accelerant are added, the mass, the solid product was washed with diethyl ether and distilled water, and sufficiently dried to prepare alkenylated chitosan.
(3) Adding distilled water solvent and sodium alginate into a reaction bottle, stirring and dissolving, slowly dropwise adding dimethyl sulfoxide solution of glycidyl methacrylate, adding catalyst 4-dimethylaminopyridine, controlling the mass ratio of the sodium alginate to the glycidyl methacrylate to the 4-dimethylaminopyridine to be 1:0.6:0.4, stirring at a constant speed for reaction for 48 hours at room temperature, placing the solution in ice water bath for cooling, and adding ethanol solvent until a large amount of precipitate is separated out to prepare the alkenyl sodium alginate.
(4) Adding a distilled water solvent, acrylic acid and methacrylic acid into a reaction bottle, adding a buffer solution to adjust the pH value of the solution to 6, adding alkenyl chitosan and alkenyl sodium alginate, uniformly dispersing by ultrasonic waves, slowly dropwise adding an initiator potassium persulfate, reacting at room temperature under uniform stirring for 10min, adding aldehyde polyethylene glycol as a cross-linking agent, wherein the mass ratio of aldehyde polyethylene glycol, alkenyl chitosan, alkenyl sodium alginate, acrylic acid, methacrylic acid and potassium persulfate is 6:10:2:20:100:0.4, reacting for 1h, filtering the solution to remove the solvent, washing and dialyzing by using distilled water and ethanol to remove impurities, and preparing the self-repairing type double-network cross-linking degradable acrylic hydrogel material 1.
Example 2
(1) Introducing nitrogen into a reaction bottle, adding an anhydrous tetrahydrofuran solvent, polyethylene glycol 2000 and 4-formylbenzoic acid, uniformly stirring, adding a catalyst 4-dimethylaminopyridine and a condensing agent diisopropylcarbodiimide in a mass ratio of 3:1:0.042:1.1, reacting at room temperature for 24 hours, filtering the solution to remove insoluble solid impurities, and recrystallizing the filtrate to prepare the aldehyde polyethylene glycol.
(2) Adding distilled hydrosolvent and chitosan into a reaction bottle, placing the reaction bottle in a constant-temperature ultrasonic processor, wherein the constant-temperature ultrasonic processor comprises a water bath, a base is fixedly connected below the inner part of the water bath, an adjusting valve is arranged on the base, a moving rod is movably connected with the adjusting valve, a fixture block is fixedly connected with the moving rod and is movably connected with a clamp groove, an objective table is fixedly connected with the clamp groove, a reaction bottle is arranged above the objective table, a heat-insulating layer is fixedly connected with the outer part of the water bath, constant-temperature heaters are arranged on two sides of the inner part of the heat-insulating layer, an ultrasonic device is arranged above the inner part of the heat-insulating layer, an ultrasonic probe is fixedly connected below the ultrasonic device, the ultrasonic frequency is 40KHz, ultrasonic treatment is carried out for 3h at 50 ℃, then N, N' -methylene bisacrylamide and triethylamine serving as an accelerant are added, the solid product was washed with diethyl ether and distilled water, and sufficiently dried to prepare alkenylated chitosan.
(3) Adding distilled water solvent and sodium alginate into a reaction bottle, stirring and dissolving, slowly dropwise adding dimethyl sulfoxide solution of glycidyl methacrylate, adding catalyst 4-dimethylaminopyridine, controlling the mass ratio of the sodium alginate to the glycidyl methacrylate to the 4-dimethylaminopyridine to be 1:0.65:0.43, stirring at a constant speed for reaction for 60 hours at room temperature, placing the solution in ice water bath for cooling, and adding ethanol solvent until a large amount of precipitate is separated out to prepare the alkenyl sodium alginate.
(4) Adding a distilled water solvent, acrylic acid and methacrylic acid into a reaction bottle, adding a buffer solution to adjust the pH value of the solution to 6, adding alkenyl chitosan and alkenyl sodium alginate, uniformly dispersing by ultrasonic waves, slowly dropwise adding an initiator potassium persulfate, reacting at room temperature under uniform stirring for 20min, adding aldehyde polyethylene glycol as a cross-linking agent, wherein the mass ratio of the aldehyde polyethylene glycol to the alkenyl chitosan to the alkenyl sodium alginate to the acrylic acid to the methacrylic acid to the potassium persulfate is 8:12:3:30:100:0.5, reacting for 3h, filtering the solution to remove the solvent, washing and dialyzing by using distilled water and ethanol to remove impurities, and preparing the self-repairing type double-network cross-linking degradable acrylic hydrogel material 2.
Example 3
(1) Introducing nitrogen into a reaction bottle, adding an anhydrous tetrahydrofuran solvent, polyethylene glycol 2000 and 4-formylbenzoic acid, uniformly stirring, adding a catalyst 4-dimethylaminopyridine and a condensing agent diisopropylcarbodiimide in a mass ratio of 3.5:1:0.045:1.2, reacting at room temperature for 18h, filtering the solution to remove insoluble solid impurities, and recrystallizing the filtrate to prepare the aldehyde polyethylene glycol.
(2) Adding distilled hydrosolvent and chitosan into a reaction bottle, placing the reaction bottle in a constant-temperature ultrasonic processor, wherein the constant-temperature ultrasonic processor comprises a water bath, a base is fixedly connected below the inner part of the water bath, an adjusting valve is arranged on the base, a moving rod is movably connected with the adjusting valve, a clamping block is fixedly connected with the moving rod, the clamping block is movably connected with a clamping groove, an objective table is fixedly connected with the clamping groove, a reaction bottle is arranged above the objective table, a heat-insulating layer is fixedly connected with the outer part of the water bath, constant-temperature heaters are arranged on two sides of the inner part of the heat-insulating layer, an ultrasonic device is arranged above the inner part of the heat-insulating layer, an ultrasonic probe is fixedly connected below the ultrasonic device, the ultrasonic frequency is 30KHz, ultrasonic treatment is carried out for 2h at 65 ℃, then N, N' -methylene bisacrylamide and triethylamine serving as an accelerant, the solid product was washed with diethyl ether and distilled water, and sufficiently dried to prepare alkenylated chitosan.
(3) Adding distilled water solvent and sodium alginate into a reaction bottle, stirring and dissolving, slowly dropwise adding dimethyl sulfoxide solution of glycidyl methacrylate, adding catalyst 4-dimethylaminopyridine, controlling the mass ratio of the sodium alginate to the glycidyl methacrylate to the 4-dimethylaminopyridine to be 1:0.7:0.45, stirring at a constant speed for reaction for 60 hours at room temperature, placing the solution in ice water bath for cooling, and adding ethanol solvent until a large amount of precipitate is separated out to prepare the alkenyl sodium alginate.
(4) Adding a distilled water solvent, acrylic acid and methacrylic acid into a reaction bottle, adding a buffer solution to adjust the pH value of the solution to 6, adding alkenyl chitosan and alkenyl sodium alginate, uniformly dispersing by ultrasonic wave, slowly dropwise adding an initiator potassium persulfate, reacting for 15min at a constant speed by stirring, adding aldehyde polyethylene glycol as a cross-linking agent, wherein the mass ratio of the aldehyde polyethylene glycol to the alkenyl chitosan to the alkenyl sodium alginate to the acrylic acid to the methacrylic acid to the potassium persulfate is 9:15:4:40:100:0.6, reacting for 2h, filtering the solution to remove the solvent, washing and dialyzing to remove impurities by using distilled water and ethanol, and preparing the self-repairing type double-network cross-linking degradable acrylic acid hydrogel material 3.
Example 4
(1) Introducing nitrogen into a reaction bottle, adding an anhydrous tetrahydrofuran solvent, polyethylene glycol 2000 and 4-formylbenzoic acid, uniformly stirring, adding a catalyst 4-dimethylaminopyridine and a condensing agent diisopropylcarbodiimide in a mass ratio of 3.8:1:0.047:1.25, reacting at room temperature for 24 hours, filtering the solution to remove insoluble solid impurities, and recrystallizing the filtrate to prepare the aldehyde polyethylene glycol.
(2) Adding distilled hydrosolvent and chitosan into a reaction bottle, placing the reaction bottle in a constant-temperature ultrasonic processor, wherein the constant-temperature ultrasonic processor comprises a water bath, a base is fixedly connected below the inner part of the water bath, an adjusting valve is arranged on the base, a moving rod is movably connected with the adjusting valve, a clamping block is fixedly connected with a clamping groove, the clamping groove is movably connected with an objective table, a reaction bottle is arranged above the objective table, a heat-insulating layer is fixedly connected with the outer part of the water bath, constant-temperature heaters are arranged on two sides of the inner part of the heat-insulating layer, an ultrasonic device is arranged above the inner part of the heat-insulating layer, an ultrasonic probe is fixedly connected below the ultrasonic device, the ultrasonic frequency is 25KHz, ultrasonic treatment is carried out for 3h at 80 ℃, then N, N' -methylene bisacrylamide and triethylamine serving as an accelerant are added, the mass ratio of the three components is, the solid product was washed with diethyl ether and distilled water, and sufficiently dried to prepare alkenylated chitosan.
(3) Adding distilled water solvent and sodium alginate into a reaction bottle, stirring and dissolving, slowly dropwise adding dimethyl sulfoxide solution of glycidyl methacrylate, adding catalyst 4-dimethylaminopyridine, controlling the mass ratio of the sodium alginate to the glycidyl methacrylate to the 4-dimethylaminopyridine to be 1:0.75:0.48, stirring at a constant speed for reaction for 72 hours at room temperature, placing the solution in ice water bath for cooling, and adding ethanol solvent until a large amount of precipitate is separated out to prepare the alkenyl sodium alginate.
(4) Adding a distilled water solvent, acrylic acid and methacrylic acid into a reaction bottle, adding a buffer solution to adjust the pH value of the solution to 6, adding alkenyl chitosan and alkenyl sodium alginate, uniformly dispersing by ultrasonic waves, slowly dropwise adding an initiator potassium persulfate, reacting at room temperature under uniform stirring for 20min, adding aldehyde polyethylene glycol as a cross-linking agent, wherein the mass ratio of the aldehyde polyethylene glycol to the alkenyl chitosan to the alkenyl sodium alginate to the acrylic acid to the methacrylic acid to the potassium persulfate is 10:17:5:45:100:0.7, reacting for 3h, filtering the solution to remove the solvent, washing and dialyzing by using distilled water and ethanol to remove impurities, and preparing the self-repairing type double-network cross-linking degradable acrylic acid hydrogel material 4.
Example 5
(1) Introducing nitrogen into a reaction bottle, adding an anhydrous tetrahydrofuran solvent, polyethylene glycol 2000 and 4-formylbenzoic acid, uniformly stirring, adding a catalyst 4-dimethylaminopyridine and a condensing agent diisopropylcarbodiimide in a mass ratio of 4:1:0.05:1.3, reacting at room temperature for 24 hours, filtering the solution to remove insoluble solid impurities, and recrystallizing the filtrate to prepare the aldehyde polyethylene glycol.
(2) Adding distilled hydrosolvent and chitosan into a reaction bottle, placing the reaction bottle in a constant-temperature ultrasonic processor, wherein the constant-temperature ultrasonic processor comprises a water bath, a base is fixedly connected below the inner part of the water bath, an adjusting valve is arranged on the base, a moving rod is movably connected with the adjusting valve, a fixture block is fixedly connected with the moving rod and is movably connected with a clamp groove, an objective table is fixedly connected with the clamp groove, a reaction bottle is arranged above the objective table, a heat-insulating layer is fixedly connected with the outer part of the water bath, constant-temperature heaters are arranged on two sides of the inner part of the heat-insulating layer, an ultrasonic device is arranged above the inner part of the heat-insulating layer, an ultrasonic probe is fixedly connected below the ultrasonic device, the ultrasonic frequency is 40KHz, ultrasonic treatment is carried out for 3h at 80 ℃, then N, N' -methylene bisacrylamide and triethylamine serving as an accelerant are, the solid product was washed with diethyl ether and distilled water, and sufficiently dried to prepare alkenylated chitosan.
(3) Adding distilled water solvent and sodium alginate into a reaction bottle, stirring and dissolving, slowly dropwise adding dimethyl sulfoxide solution of glycidyl methacrylate, adding catalyst 4-dimethylaminopyridine, controlling the mass ratio of the sodium alginate to the glycidyl methacrylate to the 4-dimethylaminopyridine to be 1:0.8:0.5, stirring at a constant speed for reaction for 72 hours at room temperature, placing the solution in ice water bath for cooling, and adding ethanol solvent until a large amount of precipitate is separated out to prepare the alkenyl sodium alginate.
(4) Adding a distilled water solvent, acrylic acid and methacrylic acid into a reaction bottle, adding a buffer solution to adjust the pH of the solution to 7, adding alkenyl chitosan and alkenyl sodium alginate, uniformly dispersing by ultrasonic waves, slowly dropwise adding an initiator potassium persulfate, reacting at room temperature under uniform stirring for 20min, adding aldehyde polyethylene glycol serving as a cross-linking agent, wherein the mass ratio of the aldehyde polyethylene glycol to the alkenyl chitosan to the alkenyl sodium alginate to the acrylic acid to the methacrylic acid to the potassium persulfate is 12:18:6:60:100:0.8, reacting for 3h, filtering the solution to remove the solvent, washing and dialyzing by using distilled water and ethanol to remove impurities, and thus obtaining the self-repairing type double-network cross-linking degradable acrylic hydrogel material 5.
The tensile strength and the breaking strength of the self-repairing double-network cross-linked degradable acrylic hydrogel materials 1 to 5 in the examples are tested by using an WEW-1000D hydraulic universal tester, and the test standard is GB/T33428-2016.
To sum up, in the self-repairing type double-network cross-linked degradable acrylic acid hydrogel, carboxyl of 4-formyl benzoic acid reacts with hydroxyl of polyethylene glycol under the action of a catalyst and an accelerator to obtain aldehyde polyethylene glycol, part of amino of chitosan reacts with one olefinic bond of N, N' -methylene bisacrylamide under an alkaline condition to obtain alkenyl chitosan, sodium alginate reacts with an epoxy group of glycidyl methacrylate under the action of the catalyst to obtain alkenyl sodium alginate, alkenyl groups of the alkenyl chitosan and the alkenyl sodium alginate are polymerized with acrylic acid and methacrylic acid through free radicals to obtain a chitosan-sodium alginate-polyacrylic acid copolymer, the alkenyl cross-linked polymerization is used as a first heavy chemical cross-linked network, then the aldehyde polyethylene glycol is added, and (3) performing crosslinking condensation reaction on two aldehyde groups at the chain end as a gel factor and amino groups in the chitosan to generate Schiff base imino bonds as a second chemical crosslinking network to obtain the double-network crosslinking acrylic acid hydrogel.
The self-repairing double-network cross-linked degradable acrylic acid hydrogel has ultrahigh cross-linking degree, takes Schiff base imino bond as reversible dynamic covalent bond, under the synergistic effect, the mechanical properties of the tensile strength and the breaking strength of the hydrogel material are obviously enhanced, under the action of external force, the Schiff base imino bond can be dynamically recombined in a short time after being broken, so that the hydrogel has good self-repairing and self-healing capabilities, and introduces the biomass molecule chitosan and sodium alginate into polyacrylic acid molecular chains in a chemical covalent grafting way, when the chitosan and the sodium alginate are biodegraded, the molecular chain of the chitosan-sodium alginate-polyacrylic acid copolymer can be damaged, so that the acrylic acid hydrogel has a good biodegradation function, and the pollution of the polyacrylic acid hydrogel which is difficult to decompose to the environment is avoided.
Claims (6)
1. A self-repairing double-network cross-linked degradable acrylic hydrogel comprises the following raw materials and components, and is characterized in that: the mass ratio of the aldehyde polyethylene glycol to the alkenyl chitosan to the alkenyl sodium alginate to the acrylic acid to the methacrylic acid to the potassium persulfate is 6-12:10-18:2-6:20-60:100: 0.4-0.8.
2. The self-repairing double-network cross-linked degradable acrylic hydrogel according to claim 1, wherein the self-repairing double-network cross-linked degradable acrylic hydrogel is characterized in that: the preparation method of the self-repairing double-network cross-linked degradable acrylic hydrogel comprises the following steps:
(1) adding polyethylene glycol 2000, 4-formylbenzoic acid, a catalyst 4-dimethylaminopyridine and a condensing agent diisopropylcarbodiimide into an anhydrous tetrahydrofuran solvent, reacting for 12-24h at room temperature in a nitrogen atmosphere, filtering, and recrystallizing filtrate to prepare aldehyde polyethylene glycol;
(2) adding chitosan into a distilled water solvent, placing the mixture into a constant-temperature ultrasonic processor, performing ultrasonic treatment for 1 to 3 hours at the ultrasonic frequency of 25 to 40KHz at the temperature of between 50 and 80 ℃, adding N, N' -methylene bisacrylamide and an accelerant triethylamine, reacting for 72 to 96 hours at the temperature of between 50 and 70 ℃, performing reduced pressure distillation, washing and drying to prepare the alkenyl chitosan;
(3) adding sodium alginate, dimethyl sulfoxide solution of glycidyl methacrylate and catalyst 4-dimethylaminopyridine into a distilled water solvent, reacting at room temperature for 48-72h, cooling, precipitating, filtering and washing to prepare the alkenyl sodium alginate;
(4) adding acrylic acid and methacrylic acid into a distilled water solvent, adding a buffer solution to adjust the pH value of the solution to 6-7, adding alkenyl chitosan and alkenyl sodium alginate, slowly dropwise adding an initiator potassium persulfate after uniform ultrasonic dispersion, reacting at room temperature for 10-20min, adding aldehyde polyethylene glycol as a cross-linking agent, reacting for 1-3h, filtering, washing and dialyzing to remove impurities, and preparing the self-repairing type double-network cross-linked degradable acrylic hydrogel.
3. The self-repairing double-network cross-linked degradable acrylic hydrogel according to claim 2, wherein the self-repairing double-network cross-linked degradable acrylic hydrogel is characterized in that: the mass ratio of the polyethylene glycol 2000, the 4-formylbenzoic acid, the 4-dimethylaminopyridine and the diisopropylcarbodiimide in the step (1) is 3-4:1:0.04-0.05: 1-1.3.
4. The self-repairing double-network cross-linked degradable acrylic hydrogel according to claim 2, wherein the self-repairing double-network cross-linked degradable acrylic hydrogel is characterized in that: the mass ratio of the chitosan, the N, N' -methylene bisacrylamide and the triethylamine in the step (2) is 1: 3-4.
5. The self-repairing double-network cross-linked degradable acrylic hydrogel according to claim 2, wherein the self-repairing double-network cross-linked degradable acrylic hydrogel is characterized in that: the constant temperature ultrasonic processor in step (2) includes water bath, the inside below fixedly connected with base of water bath, and the base is provided with the governing valve, governing valve swing joint has the carriage release lever, carriage release lever fixedly connected with fixture block, fixture block and draw-in groove swing joint, draw-in groove fixedly connected with objective table, objective table top are provided with the reaction flask, the outside fixedly connected with heat preservation of water bath, the inside both sides of heat preservation are provided with constant temperature heating ware, the inside top of heat preservation is provided with the supersound ware, supersound ware below fixedly connected with ultrasonic probe.
6. The self-repairing double-network cross-linked degradable acrylic hydrogel according to claim 2, wherein the self-repairing double-network cross-linked degradable acrylic hydrogel is characterized in that: the mass ratio of the sodium alginate to the glycidyl methacrylate to the 4-dimethylaminopyridine in the step (3) is 1:0.6-0.8: 0.4-0.5.
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| CN111710850A (en) * | 2020-07-17 | 2020-09-25 | 樊梦林 | NiCo with shell-core structure2S4Porous microsphere-graphene negative electrode material and preparation method thereof |
| CN114957728A (en) * | 2022-06-29 | 2022-08-30 | 陕西科技大学 | Double-network collagen-based supramolecular hydrogel and preparation method thereof |
| CN115569107A (en) * | 2022-06-29 | 2023-01-06 | 湖南工业大学 | Double-network pH-sensitive drug-release hydrogel and preparation method and application thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111710850A (en) * | 2020-07-17 | 2020-09-25 | 樊梦林 | NiCo with shell-core structure2S4Porous microsphere-graphene negative electrode material and preparation method thereof |
| CN111710850B (en) * | 2020-07-17 | 2021-06-29 | 吉林中溢炭素科技有限公司 | NiCo with shell-core structure2S4Porous microsphere-graphene negative electrode material and preparation method thereof |
| CN114957728A (en) * | 2022-06-29 | 2022-08-30 | 陕西科技大学 | Double-network collagen-based supramolecular hydrogel and preparation method thereof |
| CN115569107A (en) * | 2022-06-29 | 2023-01-06 | 湖南工业大学 | Double-network pH-sensitive drug-release hydrogel and preparation method and application thereof |
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