CN111333985A - Self-healing three-dimensional supermolecule polyvinyl alcohol hydrogel and preparation method thereof - Google Patents
Self-healing three-dimensional supermolecule polyvinyl alcohol 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-healing three-dimensional supramolecular polyvinyl alcohol hydrogel which comprises the following formula raw materials and components: polyvinyl alcohol, polyethylene glycol, 3-7 parts of a cross-linking agent and 2-5 parts of borated chitosan. According to the self-healing three-dimensional supermolecule polyvinyl alcohol hydrogel, 1,4,5, 8-naphthalene tetracarboxylic anhydride reacts with branched hydroxyl of polyvinyl alcohol and terminal hydroxyl of polyethylene glycol to form a supermolecule polyethylene glycol grafted polyvinyl alcohol of a three-dimensional network through cross-linking polymerization, boric acid groups react with the hydroxyl, and a chemical hydrogel of the supermolecule polyvinyl alcohol of the three-dimensional network is formed through the bonding effect of chemical bonds.
Description
Technical Field
The invention relates to the technical field of hydrogel materials, in particular to self-healing three-dimensional supramolecular polyvinyl alcohol hydrogel and a preparation method thereof.
Background
The hydrogel is a gel with a three-dimensional network structure with strong hydrophilicity, wherein a cross-linked network exists in the hydrogel, the hydrogel can be rapidly swelled in water, a large volume of water can be kept in a swelled state without dissolving, the water absorption capacity of the hydrogel is closely related to the cross-linking degree, the lower the cross-linking degree, the higher the water absorption capacity, the aggregation state of the hydrogel is a state between solid and liquid, the liquid state of the hydrogel is diffused or permeated from the hydrogel, the solid state can maintain a certain shape and volume, the hydrogel can be divided into chemical gel and gel physical gel according to network bonding, the chemical gel is a three-dimensional network polymer formed by chemical bond cross-linking, the chemical gel is a permanent true gel, the physical gel is formed by physical acting force such as electrostatic action, hydrogen bond, chain winding and the like, the physical gel is non-permanent and poor in stability, and can be transformed into a solution by heating the solid gel, such as polyvinyl alcohol, through ice, physical hydrogels can be formed below 60 ℃.
The hydrogel material has excellent high water absorption and high water retention performance, and is widely applied to various fields, such as dry cosmetic masks, antipyretic patches, analgesic patches, agricultural films, condensation preventing agents, petrochemical water shutoff agents, crude oil dehydrating agents, food preservatives and the like, but the polyvinyl alcohol hydrogel is formed by physical bond acting force, has poor stability and low toughness and compression strength, is easy to be changed from solid to liquid at high temperature, and cannot be changed into solid hydrogel when being recovered to normal temperature, and has no self-healing performance.
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides a self-healing three-dimensional supramolecular polyvinyl alcohol hydrogel and a preparation method thereof, and solves the problems that the common polyvinyl alcohol hydrogel is a physical hydrogel, has poor mechanical properties such as toughness, compressive strength and the like, and does not have self-healing performance.
(II) technical scheme
In order to achieve the purpose, the invention provides the following technical scheme: the self-healing type three-dimensional supermolecule polyvinyl alcohol hydrogel comprises the following formula raw materials in parts by weight: 63-77 parts of polyvinyl alcohol, 18-25 parts of polyethylene glycol, 3-7 parts of a cross-linking agent and 2-5 parts of borated chitosan.
Preferably, the crosslinking agent is 1,4,5, 8-naphthalene tetracarboxylic anhydride.
Preferably, the preparation method of the borated chitosan comprises the following steps:
(1) adding an acetic acid solution with the mass fraction of 2-4% into a reaction bottle, adding chitosan, stirring and dissolving, then adding 4-carboxyphenylboronic acid and a condensing agent dicyclohexylcarbodiimide, heating the solution to 50-80 ℃ by using an automatic stirrer, stirring at a constant speed for reaction for 25-35h, carrying out vacuum drying on the solution to remove the solvent, washing a solid product by using distilled water and ether, and fully drying to prepare the borated chitosan.
Preferably, the mass ratio of the chitosan stirring to the 4-carboxyphenylboronic acid to the dicyclohexylcarbodiimide is 1:1.2-1.5: 0.3-0.6.
Preferably, the automatic stirrer comprises a top seat, a bottom two-side fixedly connected with adjusting rod of the top seat, the bottom and the regulator swing joint of the adjusting rod, the regulator fixedly connected with supporting rod, the bottom and the base fixed connection of the supporting rod, the upper surface of the base is provided with a reaction bottle groove, the inside of the top seat is provided with a stirring and heating device, a heating rod and a stirring shaft are arranged in the stirring and heating device, the bottom and the protective layer of the stirring and heating device are fixedly connected, the outer surface of the protective layer is movably connected with a reaction bottle plug, the inside of the protective layer is provided with the heating rod, the inside of the heating rod is provided with the stirring shaft, the lower end of the stirring shaft is movably connected.
Preferably, the preparation method of the self-healing three-dimensional supramolecular polyvinyl alcohol hydrogel comprises the following steps:
(1) adding distilled water, 63-77 parts of polyvinyl alcohol, 18-25 parts of polyethylene glycol and 3-7 parts of cross-linking agent 1,4,5, 8-naphthalene tetracarboxylic anhydride into a reaction bottle, uniformly stirring for 20-40min, transferring the solution into a hydrothermal reaction kettle, placing the kettle in an oven, heating to 160 ℃ at 120 ℃, reacting for 15-20h, cooling the solution to room temperature, carrying out reduced pressure distillation to remove the solvent, placing the solid product in a dialysis bag, and removing impurities to prepare the polyethylene glycol grafted polyvinyl alcohol.
(2) Adding a distilled water solvent, polyethylene glycol grafted polyvinyl alcohol and 2-5 parts of borated chitosan into a reaction bottle, uniformly stirring, adding sodium hydroxide, heating the solution to 40-60 ℃ by using an automatic stirrer, uniformly stirring for reacting for 12-18h, cooling the solution to room temperature, filtering to remove the solvent, adding distilled water into a solid product, placing the solid product into a dialysis bag, and performing dialysis impurity removal to prepare the self-healing three-dimensional supramolecular polyvinyl alcohol hydrogel.
(III) advantageous technical effects
Compared with the prior art, the invention has the following beneficial technical effects:
the self-healing three-dimensional supermolecule polyvinyl alcohol hydrogel takes dicyclohexylcarbodiimide as a condensing agent to react carboxyl in 4-carboxyphenylboronic acid with hydroxyl in chitosan to generate borated chitosan, then takes 1,4,5, 8-naphthalene tetracarboxylic anhydride with a rigid naphthalene ring structure as a cross-linking agent to react with branched hydroxyl of polyvinyl alcohol and terminal hydroxyl of polyethylene glycol respectively through anhydride ring-opening reaction, and forms supermolecule polyethylene glycol grafted polyvinyl alcohol of a three-dimensional network through crosslinking polymerization of polyvinyl alcohol and polyethylene glycol, wherein the supermolecule polyethylene glycol grafted polyvinyl alcohol three-dimensional network has good reversibility and dynamic property, can be applied to shape memory materials and self-healing materials, takes borated chitosan as crosslinking neutrality, and reacts with hydroxyl in polyethylene glycol grafted polyvinyl alcohol through boric acid groups in borated chitosan, the supermolecule weight and the three-dimensional network structure are further increased, and the chemical hydrogel of the three-dimensional network supermolecule polyvinyl alcohol is formed through the bonding effect of chemical bonds.
According to the self-healing three-dimensional supermolecule polyvinyl alcohol hydrogel, the molecular chain of polyethylene glycol grafted polyvinyl alcohol is long, the molecular weight is large, the molecular chain contains a naphthalene ring rigid structure, so that the three-dimensional supermolecule polyvinyl alcohol chemical hydrogel shows excellent mechanical properties such as toughness, compressive strength and the like, meanwhile, borate groups belong to reversible dynamic covalent bonds, and when the hydrogel material deforms and cracks under the action of external force, the hydrogel material can recover the original appearance in a short time through reversible dynamic transformation of borate, and shows good self-healing performance.
Drawings
FIG. 1 is a schematic front view of an automatic blender;
FIG. 2 is a schematic view of adjustment of the adjustment lever;
FIG. 3 is an enlarged view of the mixing blade;
FIG. 4 is a schematic view of the adjustment of the mixing blades.
1. A top seat; 2. adjusting a rod; 3. a regulator; 4. a support bar; 5. a base; 6. a groove; 7. a stirring and heating device; 8. a heating rod; 9. a stirring shaft; 10. a protective layer; 11. a reaction bottle stopper; 12. a bearing; 13. stirring fan blades.
Detailed Description
To achieve the above object, the present invention provides the following embodiments and examples: the self-healing type three-dimensional supermolecule polyvinyl alcohol hydrogel comprises the following formula raw materials in parts by weight: 63-77 parts of polyvinyl alcohol, 18-25 parts of polyethylene glycol, 2-5 parts of borated chitosan and 3-7 parts of a cross-linking agent, wherein the cross-linking agent is 1,4,5, 8-naphthalene tetracarboxylic anhydride.
The preparation method of the borated chitosan comprises the following steps:
(1) adding 2-4% by mass of acetic acid solution into a reaction bottle, adding chitosan, stirring and dissolving, then adding 4-carboxyphenylboronic acid and a condensing agent dicyclohexylcarbodiimide, wherein the mass ratio of the 4-carboxyphenylboronic acid to the condensing agent dicyclohexylcarbodiimide is 1:1.2-1.5:0.3-0.6, heating the solution to 50-80 ℃ by using an automatic stirrer, the automatic stirrer comprises a top seat and adjusting rods fixedly connected with two sides of the bottom of the top seat, the bottom of each adjusting rod is movably connected with the regulator, the regulator is fixedly connected with a supporting rod, the bottom of each supporting rod is fixedly connected with a base, a reaction bottle groove is arranged on the upper surface of the base, a stirring and heating device is arranged in the top seat, a heating rod and a stirring shaft are arranged in the stirring and heating device, the bottom of the stirring and heating device is fixedly connected with a protective layer, a reaction bottle plug is movably connected with the, and a stirring shaft is arranged in the heating rod, the lower end of the stirring shaft is movably connected with a bearing, the bearing is movably connected with a stirring fan blade, the stirring reaction is carried out at a constant speed for 25-35h, the solution is subjected to vacuum drying to remove the solvent, the solid product is washed by using distilled water and diethyl ether, and the solid product is fully dried to prepare the borated chitosan.
The preparation method of the self-healing three-dimensional supermolecule polyvinyl alcohol hydrogel comprises the following steps:
(1) adding distilled water, 63-77 parts of polyvinyl alcohol, 18-25 parts of polyethylene glycol and 3-7 parts of cross-linking agent 1,4,5, 8-naphthalene tetracarboxylic anhydride into a reaction bottle, uniformly stirring for 20-40min, transferring the solution into a hydrothermal reaction kettle, placing the kettle in an oven, heating to 160 ℃ at 120 ℃, reacting for 15-20h, cooling the solution to room temperature, carrying out reduced pressure distillation to remove the solvent, placing the solid product in a dialysis bag, and removing impurities to prepare the polyethylene glycol grafted polyvinyl alcohol.
(2) Adding a distilled water solvent, polyethylene glycol grafted polyvinyl alcohol and 2-5 parts of borated chitosan into a reaction bottle, uniformly stirring, adding sodium hydroxide, heating the solution to 40-60 ℃ by using an automatic stirrer, uniformly stirring for reacting for 12-18h, cooling the solution to room temperature, filtering to remove the solvent, adding distilled water into a solid product, placing the solid product into a dialysis bag, and performing dialysis impurity removal to prepare the self-healing three-dimensional supramolecular polyvinyl alcohol hydrogel.
Example 1
(1) Preparation of borated chitosan component 1: adding 2 mass percent acetic acid solution into a reaction bottle, adding chitosan, stirring and dissolving, then adding 4-carboxyphenylboronic acid and a condensing agent dicyclohexylcarbodiimide, wherein the mass ratio of the three is 1:1.2:0.3, heating the solution to 50 ℃ by using an automatic stirrer, the automatic stirrer comprises a top seat, adjusting rods are fixedly connected with two sides of the bottom of the top seat, the bottom of each adjusting rod is movably connected with the regulator, the regulator is fixedly connected with a supporting rod, the bottom of each supporting rod is fixedly connected with a base, a reaction bottle groove is arranged on the upper surface of the base, a stirring and heating device is arranged inside the top seat, a heating rod and a stirring shaft are arranged in the stirring and heating device, the bottom of the stirring and heating device is fixedly connected with a protective layer, a reaction bottle plug is movably connected with the outer surface of the protective layer, the heating rod is arranged inside the protective layer, and the, the lower end of the stirring shaft is movably connected with a bearing, the bearing is movably connected with a stirring fan blade, the stirring reaction is carried out at a constant speed for 25 hours, the solution is dried in vacuum to remove the solvent, the solid product is washed by distilled water and ether, and the solid product is fully dried to prepare the borated chitosan component 1.
(2) Preparation of polyethylene glycol grafted polyvinyl alcohol component 1: adding distilled water, 77 parts of polyvinyl alcohol, 18 parts of polyethylene glycol and 3 parts of cross-linking agent 1,4,5, 8-naphthalene tetracarboxylic anhydride into a reaction bottle, uniformly stirring for 20min, transferring the solution into a hydrothermal reaction kettle, placing the kettle in an oven, heating to 120 ℃, reacting for 15h, cooling the solution to room temperature, carrying out reduced pressure distillation to remove the solvent, placing the solid product in a dialysis bag, and removing impurities to prepare the polyethylene glycol grafted polyvinyl alcohol component 1.
(3) Preparing a self-healing three-dimensional supramolecular polyvinyl alcohol hydrogel material 1: adding a distilled water solvent, polyethylene glycol grafted polyvinyl alcohol and 2-borated chitosan component 1 into a reaction bottle, stirring uniformly, adding sodium hydroxide, heating the solution to 40 ℃ by using an automatic stirrer, stirring uniformly for reaction for 12 hours, cooling the solution to room temperature, filtering to remove the solvent, adding distilled water into a solid product, placing the solid product into a dialysis bag, and performing dialysis and impurity removal to prepare the self-healing three-dimensional supramolecular polyvinyl alcohol hydrogel material 1.
Example 2
(1) Preparation of borated chitosan component 2: adding 2 mass percent acetic acid solution into a reaction bottle, adding chitosan, stirring and dissolving, then adding 4-carboxyphenylboronic acid and a condensing agent dicyclohexylcarbodiimide, wherein the mass ratio of the three is 1:1.2:0.6, heating the solution to 80 ℃ by using an automatic stirrer, the automatic stirrer comprises a top seat, adjusting rods are fixedly connected with two sides of the bottom of the top seat, the bottom of each adjusting rod is movably connected with the regulator, the regulator is fixedly connected with a supporting rod, the bottom of each supporting rod is fixedly connected with a base, a reaction bottle groove is arranged on the upper surface of the base, a stirring and heating device is arranged inside the top seat, a heating rod and a stirring shaft are arranged in the stirring and heating device, the bottom of the stirring and heating device is fixedly connected with a protective layer, a reaction bottle plug is movably connected with the outer surface of the protective layer, the heating rod is arranged inside the protective layer, and the, the lower end of the stirring shaft is movably connected with a bearing, the bearing is movably connected with a stirring fan blade, the stirring reaction is carried out at a constant speed for 25 hours, the solution is dried in vacuum to remove the solvent, the solid product is washed by distilled water and ether, and the solid product is fully dried to prepare the borated chitosan component 2.
(2) Preparing polyethylene glycol grafted polyvinyl alcohol component 2: adding distilled water, 73 parts of polyvinyl alcohol, 20 parts of polyethylene glycol and 4 parts of cross-linking agent 1,4,5, 8-naphthalene tetracarboxylic anhydride into a reaction bottle, uniformly stirring for 20min, transferring the solution into a hydrothermal reaction kettle, placing the kettle in an oven, heating to 160 ℃, reacting for 20h, cooling the solution to room temperature, carrying out reduced pressure distillation to remove the solvent, placing the solid product in a dialysis bag, and removing impurities to prepare the polyethylene glycol grafted polyvinyl alcohol component 2.
(3) Preparing a self-healing three-dimensional supramolecular polyvinyl alcohol hydrogel material 2: adding a distilled water solvent, polyethylene glycol grafted polyvinyl alcohol and a 3-borated chitosan component 2 into a reaction bottle, stirring uniformly, adding sodium hydroxide, heating the solution to 60 ℃ by using an automatic stirrer, stirring uniformly for reaction for 12 hours, cooling the solution to room temperature, filtering to remove the solvent, adding distilled water into a solid product, placing the solid product into a dialysis bag, and performing dialysis and impurity removal to prepare the self-healing three-dimensional supramolecular polyvinyl alcohol hydrogel material 2.
Example 3
(1) Preparation of borated chitosan component 3: adding 3 mass percent acetic acid solution into a reaction bottle, adding chitosan, stirring and dissolving, then adding 4-carboxyphenylboronic acid and a condensing agent dicyclohexylcarbodiimide, wherein the mass ratio of the three is 1:1.4:0.5, heating the solution to 65 ℃ by using an automatic stirrer, the automatic stirrer comprises a top seat, adjusting rods are fixedly connected with two sides of the bottom of the top seat, the bottom of each adjusting rod is movably connected with the regulator, the regulator is fixedly connected with a supporting rod, the bottom of each supporting rod is fixedly connected with a base, a reaction bottle groove is arranged on the upper surface of the base, a stirring and heating device is arranged inside the top seat, a heating rod and a stirring shaft are arranged in the stirring and heating device, the bottom of the stirring and heating device is fixedly connected with a protective layer, a reaction bottle plug is movably connected with the outer surface of the protective layer, the heating rod is arranged inside the protective layer, and the, the lower end of the stirring shaft is movably connected with a bearing, the bearing is movably connected with a stirring fan blade, the stirring reaction is carried out at a constant speed for 30 hours, the solution is dried in vacuum to remove the solvent, the solid product is washed by distilled water and ether, and the solid product is fully dried to prepare the borated chitosan component 3.
(2) Preparing polyethylene glycol grafted polyvinyl alcohol component 3: adding distilled water, 68 parts of polyvinyl alcohol, 22.5 parts of polyethylene glycol and 5.5 parts of crosslinking agent 1,4,5, 8-naphthalene tetracarboxylic anhydride into a reaction bottle, uniformly stirring for 30min, transferring the solution into a hydrothermal reaction kettle, placing the kettle in an oven, heating to 140 ℃, reacting for 18h, cooling the solution to room temperature, distilling under reduced pressure to remove the solvent, placing the solid product in a dialysis bag, and removing impurities to prepare the polyethylene glycol grafted polyvinyl alcohol component 3.
(3) Preparing a self-healing three-dimensional supramolecular polyvinyl alcohol hydrogel material 3: adding a distilled water solvent, polyethylene glycol grafted polyvinyl alcohol and 4-borated chitosan component 3 into a reaction bottle, stirring uniformly, adding sodium hydroxide, heating the solution to 50 ℃ by using an automatic stirrer, stirring uniformly for reaction for 15 hours, cooling the solution to room temperature, filtering to remove the solvent, adding distilled water into a solid product, placing the solid product into a dialysis bag, and performing dialysis and impurity removal to prepare the self-healing three-dimensional supramolecular polyvinyl alcohol hydrogel material 3.
Example 4
(1) Preparation of borated chitosan component 4: adding 4 mass percent of acetic acid solution into a reaction bottle, adding chitosan, stirring and dissolving, then adding 4-carboxyphenylboronic acid and a condensing agent dicyclohexylcarbodiimide, wherein the mass ratio of the three is 1:1.5:0.6, heating the solution to 80 ℃ by using an automatic stirrer, the automatic stirrer comprises a top seat, adjusting rods are fixedly connected with two sides of the bottom of the top seat, the bottom of each adjusting rod is movably connected with the regulator, the regulator is fixedly connected with a supporting rod, the bottom of each supporting rod is fixedly connected with a base, a reaction bottle groove is arranged on the upper surface of the base, a stirring and heating device is arranged inside the top seat, a heating rod and a stirring shaft are arranged in the stirring and heating device, the bottom of the stirring and heating device is fixedly connected with a protective layer, a reaction bottle plug is movably connected with the outer surface of the protective layer, the heating rod is arranged inside the protective layer, and, the lower end of the stirring shaft is movably connected with a bearing, the bearing is movably connected with a stirring fan blade, the stirring reaction is carried out at a constant speed for 35 hours, the solution is dried in vacuum to remove the solvent, the solid product is washed by distilled water and ether, and the solid product is fully dried to prepare the borated chitosan component 4.
(2) Preparation of polyethylene glycol grafted polyvinyl alcohol component 4: adding distilled water, 63 parts of polyvinyl alcohol, 25 parts of polyethylene glycol and 7 parts of cross-linking agent 1,4,5, 8-naphthalene tetracarboxylic anhydride into a reaction bottle, uniformly stirring for 40min, transferring the solution into a hydrothermal reaction kettle, placing the kettle in an oven, heating to 160 ℃, reacting for 20h, cooling the solution to room temperature, carrying out reduced pressure distillation to remove the solvent, placing the solid product in a dialysis bag, and removing impurities to prepare the polyethylene glycol grafted polyvinyl alcohol component 4.
(3) Preparing a self-healing three-dimensional supramolecular polyvinyl alcohol hydrogel material 4: adding a distilled water solvent, polyethylene glycol grafted polyvinyl alcohol and 5-borated chitosan component 4 into a reaction bottle, stirring uniformly, adding sodium hydroxide, heating the solution to 60 ℃ by using an automatic stirrer, stirring uniformly for reacting for 18 hours, cooling the solution to room temperature, filtering to remove the solvent, adding distilled water into a solid product, placing the solid product into a dialysis bag, and performing dialysis and impurity removal to prepare the self-healing three-dimensional supramolecular polyvinyl alcohol hydrogel material 4.
Comparative example 1
(1) Preparation of borated chitosan comparative material 1: adding 2 mass percent acetic acid solution into a reaction bottle, adding chitosan, stirring and dissolving, then adding 4-carboxyphenylboronic acid and a condensing agent dicyclohexylcarbodiimide, wherein the mass ratio of the three is 1:1.2:0.6, heating the solution to 80 ℃ by using an automatic stirrer, the automatic stirrer comprises a top seat, adjusting rods are fixedly connected with two sides of the bottom of the top seat, the bottom of each adjusting rod is movably connected with the regulator, the regulator is fixedly connected with a supporting rod, the bottom of each supporting rod is fixedly connected with a base, a reaction bottle groove is arranged on the upper surface of the base, a stirring and heating device is arranged inside the top seat, a heating rod and a stirring shaft are arranged in the stirring and heating device, the bottom of the stirring and heating device is fixedly connected with a protective layer, a reaction bottle plug is movably connected with the outer surface of the protective layer, the heating rod is arranged inside the protective layer, and the, the lower end of the stirring shaft is movably connected with a bearing, the bearing is movably connected with a stirring fan blade, the stirring reaction is carried out at a constant speed for 25 hours, the solution is dried in vacuum to remove the solvent, the solid product is washed by distilled water and ether, and the solid product is fully dried to prepare the borated chitosan contrast component 1.
(2) Preparation of polyethylene glycol grafted polyvinyl alcohol comparative component 1: adding distilled water, 81 parts of polyvinyl alcohol, 16 parts of polyethylene glycol and 2 parts of cross-linking agent 1,4,5, 8-naphthalene tetracarboxylic anhydride into a reaction bottle, uniformly stirring for 40min, transferring the solution into a hydrothermal reaction kettle, placing the kettle in an oven, heating to 160 ℃, reacting for 15h, cooling the solution to room temperature, carrying out reduced pressure distillation to remove the solvent, placing the solid product in a dialysis bag, and removing impurities to prepare the polyethylene glycol grafted polyvinyl alcohol comparative component 1.
(3) Preparing a self-healing three-dimensional supermolecule polyvinyl alcohol hydrogel contrast component 1: adding a distilled water solvent, polyethylene glycol grafted polyvinyl alcohol and 1 borated chitosan contrast component 1 into a reaction bottle, stirring uniformly, adding sodium hydroxide, heating the solution to 40 ℃ by using an automatic stirrer, stirring uniformly for reaction for 12 hours, cooling the solution to room temperature, filtering to remove the solvent, adding distilled water into a solid product, placing the solid product into a dialysis bag, and performing dialysis impurity removal to prepare the self-healing three-dimensional supramolecular polyvinyl alcohol hydrogel contrast material 1.
Comparative example 2
(1) Preparation of borated chitosan comparative component 2: adding 4 mass percent of acetic acid solution into a reaction bottle, adding chitosan, stirring and dissolving, then adding 4-carboxyphenylboronic acid and a condensing agent dicyclohexylcarbodiimide, wherein the mass ratio of the three is 1:1.5:0.3, heating the solution to 80 ℃ by using an automatic stirrer, the automatic stirrer comprises a top seat, adjusting rods are fixedly connected with two sides of the bottom of the top seat, the bottom of each adjusting rod is movably connected with the regulator, the regulator is fixedly connected with a supporting rod, the bottom of each supporting rod is fixedly connected with a base, a reaction bottle groove is arranged on the upper surface of the base, a stirring and heating device is arranged inside the top seat, a heating rod and a stirring shaft are arranged in the stirring and heating device, the bottom of the stirring and heating device is fixedly connected with a protective layer, a reaction bottle plug is movably connected with the outer surface of the protective layer, the heating rod is arranged inside the protective layer, and, the lower end of the stirring shaft is movably connected with a bearing, the bearing is movably connected with a stirring fan blade, the stirring reaction is carried out at a constant speed for 25 hours, the solution is dried in vacuum to remove the solvent, the solid product is washed by distilled water and ether, and the solid product is fully dried to prepare the borated chitosan contrast component 2.
(2) Preparation of polyethylene glycol grafted polyvinyl alcohol comparative component 2: adding distilled water, 60 parts of polyvinyl alcohol, 26 parts of polyethylene glycol and 8 parts of crosslinking agent 1,4,5, 8-naphthalene tetracarboxylic anhydride into a reaction bottle, uniformly stirring for 40min, transferring the solution into a hydrothermal reaction kettle, placing the kettle in an oven, heating to 160 ℃, reacting for 15h, cooling the solution to room temperature, carrying out reduced pressure distillation to remove the solvent, placing the solid product in a dialysis bag, and removing impurities to prepare the polyethylene glycol grafted polyvinyl alcohol comparative component 2.
(3) Preparing a self-healing three-dimensional supermolecule polyvinyl alcohol hydrogel contrast material 2: adding a distilled water solvent, polyethylene glycol grafted polyvinyl alcohol and 6-borated chitosan contrast component 2 into a reaction bottle, uniformly stirring, adding sodium hydroxide, heating the solution to 50 ℃ by using an automatic stirrer, uniformly stirring for reaction for 15 hours, cooling the solution to room temperature, filtering to remove the solvent, adding distilled water into a solid product, placing the solid product into a dialysis bag, and performing dialysis impurity removal to obtain the self-healing three-dimensional supramolecular polyvinyl alcohol hydrogel contrast material 2.
The compression strength of the self-healing three-dimensional supramolecular polyvinyl alcohol hydrogel material in the examples and the comparative examples was tested by using a DRK113B compression tester, and the test standard is GB/T26691-2011.
To sum up, the self-healing three-dimensional supramolecular polyvinyl alcohol hydrogel takes dicyclohexylcarbodiimide as a condensing agent, carboxyl in 4-carboxyphenylboronic acid reacts with hydroxyl in chitosan to generate borated chitosan, then 1,4,5, 8-naphthalene tetracarboxylic anhydride with a rigid naphthalene ring structure is taken as a cross-linking agent, the anhydride ring-opening reaction is respectively reacted with branched hydroxyl of polyvinyl alcohol and terminal hydroxyl of polyethylene glycol, the polyvinyl alcohol and the polyethylene glycol are cross-linked and polymerized to form supramolecular polyethylene glycol grafted polyvinyl alcohol with a three-dimensional network, the supramolecular polyethylene glycol grafted polyvinyl alcohol three-dimensional network has good reversibility and dynamic property, can be applied to shape memory materials and self-healing materials, the borated chitosan is taken as cross-linking neutrality, and boric acid groups in the borated chitosan react with the hydroxyl in the polyethylene glycol grafted polyvinyl alcohol, the supermolecule weight and the three-dimensional network structure are further increased, and the chemical hydrogel of the three-dimensional network supermolecule polyvinyl alcohol is formed through the bonding effect of chemical bonds.
The molecular chain of the polyglycol grafted polyvinyl alcohol is very long, the molecular weight is very large, the molecular chain contains a naphthalene ring rigid structure, so that the three-dimensional supermolecule polyvinyl alcohol chemical hydrogel shows excellent mechanical properties such as toughness, compressive strength and the like, meanwhile, the borate group belongs to a reversible dynamic covalent bond, and when the hydrogel material deforms and cracks under the action of external force, the hydrogel material can recover the original appearance in a short time through reversible dynamic transformation of borate, and shows good self-healing performance.
Claims (6)
1. The self-healing three-dimensional supermolecule polyvinyl alcohol hydrogel comprises the following formula raw materials and components in parts by weight, and is characterized in that: 63-77 parts of polyvinyl alcohol, 18-25 parts of polyethylene glycol, 3-7 parts of a cross-linking agent and 2-5 parts of borated chitosan.
2. A self-healing three-dimensional supramolecular polyvinyl alcohol hydrogel according to claim 1, characterized in that: the cross-linking agent is 1,4,5, 8-naphthalene tetracarboxylic anhydride.
3. A self-healing three-dimensional supramolecular polyvinyl alcohol hydrogel according to claim 1, characterized in that: the preparation method of the borated chitosan comprises the following steps:
(1) adding chitosan, 4-carboxyphenylboronic acid and a condensing agent dicyclohexylcarbodiimide into an acetic acid solution with the mass fraction of 2-4%, heating the solution to 50-80 ℃ by using an automatic stirrer, stirring at a constant speed for reaction for 25-35h, removing the solvent from the solution, washing a solid product, and drying to prepare the borated chitosan.
4. A self-healing three-dimensional supramolecular polyvinyl alcohol hydrogel according to claim 2, characterized in that: the mass ratio of the 4-carboxyl phenylboronic acid to the dicyclohexyl carbodiimide is 1:1.2-1.5: 0.3-0.6.
5. A self-healing three-dimensional supramolecular polyvinyl alcohol hydrogel according to claim 3, characterized in that: the automatic stirrer comprises a top seat, a bottom two-side fixedly connected with adjusting rod of the top seat, the bottom of the adjusting rod is movably connected with the regulator, the regulator is fixedly connected with a supporting rod, the bottom of the supporting rod is fixedly connected with a base, the upper surface of the base is provided with a reaction bottle groove, the inside of the top seat is provided with a stirring and heating device, a heating rod and a stirring shaft are arranged in the stirring and heating device, the bottom of the stirring and heating device is fixedly connected with a protective layer, the outer surface of the protective layer is movably connected with a reaction bottle plug, the inside of the protective layer is provided with the heating rod, the inside of the heating rod is provided with the stirring shaft, the lower end of the.
6. A self-healing three-dimensional supramolecular polyvinyl alcohol hydrogel according to claim 1, characterized in that: the preparation method of the self-healing three-dimensional supramolecular polyvinyl alcohol hydrogel comprises the following steps:
(1) adding 63-77 parts of polyvinyl alcohol and 18-25 parts of polyethylene glycol and 3-7 parts of cross-linking agent 1,4,5, 8-naphthalene tetracarboxylic anhydride into distilled water, stirring at constant speed for 20-40min, transferring the solution into a hydrothermal reaction kettle, heating to 160 ℃ for reaction for 15-20h, removing the solvent from the solution, and placing the solid product in a dialysis bag to remove impurities to prepare the polyethylene glycol grafted polyvinyl alcohol.
(2) Adding polyethylene glycol grafted polyvinyl alcohol and 2-5 parts of borated chitosan into distilled water, stirring uniformly, adding sodium hydroxide, heating the solution to 40-60 ℃ by using an automatic stirrer, stirring at a constant speed for reaction for 12-18h, filtering the solution to remove the solvent, adding distilled water into a solid product, placing the solid product into a dialysis bag, and performing dialysis impurity removal to prepare the self-healing three-dimensional supramolecular polyvinyl alcohol hydrogel.
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| CN112337441A (en) * | 2020-09-23 | 2021-02-09 | 江苏理工学院 | Phenylboronic acid-chitosan modified monolithic column and preparation method and application thereof |
| CN114509383A (en) * | 2022-01-12 | 2022-05-17 | 江苏集萃未来城市应用技术研究所有限公司 | Detection device and experimental method for impact resistance self-healing performance of organic silicon gel |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112337441A (en) * | 2020-09-23 | 2021-02-09 | 江苏理工学院 | Phenylboronic acid-chitosan modified monolithic column and preparation method and application thereof |
| CN114509383A (en) * | 2022-01-12 | 2022-05-17 | 江苏集萃未来城市应用技术研究所有限公司 | Detection device and experimental method for impact resistance self-healing performance of organic silicon gel |
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