CN111410716A - High-strength modified acrylic acid-based degradable hydrogel and preparation method thereof - Google Patents
High-strength modified acrylic acid-based degradable hydrogel and preparation method thereof Download PDFInfo
- Publication number
- CN111410716A CN111410716A CN202010333422.6A CN202010333422A CN111410716A CN 111410716 A CN111410716 A CN 111410716A CN 202010333422 A CN202010333422 A CN 202010333422A CN 111410716 A CN111410716 A CN 111410716A
- Authority
- CN
- China
- Prior art keywords
- nano sio
- chitosan
- parts
- solvent
- modified
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F251/00—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
- C01B33/18—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
- C08B37/0024—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid beta-D-Glucans; (beta-1,3)-D-Glucans, e.g. paramylon, coriolan, sclerotan, pachyman, callose, scleroglucan, schizophyllan, laminaran, lentinan or curdlan; (beta-1,6)-D-Glucans, e.g. pustulan; (beta-1,4)-D-Glucans; (beta-1,3)(beta-1,4)-D-Glucans, e.g. lichenan; Derivatives thereof
- C08B37/0027—2-Acetamido-2-deoxy-beta-glucans; Derivatives thereof
- C08B37/003—Chitin, i.e. 2-acetamido-2-deoxy-(beta-1,4)-D-glucan or N-acetyl-beta-1,4-D-glucosamine; Chitosan, i.e. deacetylated product of chitin or (beta-1,4)-D-glucosamine; Derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
- C08J3/075—Macromolecular gels
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
- C08K7/26—Silicon- containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2351/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2351/02—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to polysaccharides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Nanotechnology (AREA)
- General Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Physics & Mathematics (AREA)
- Dispersion Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Composite Materials (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Biochemistry (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Cosmetics (AREA)
Abstract
The invention relates to the technical field of hydrogel materials, and discloses a high-strength modified acrylic-based degradable hydrogel which comprises the following formula raw materials and components: nano SiO2Modified alkenyl chitosan, acrylic acid, acrylamide, an initiator and a cross-linking agent. The high-strength modified acrylic acid-based degradable hydrogel is porous nano SiO2The hollow microspheres have larger specific surface area and stronger nano small-size effect, and the 3-aminopropyl triethoxysilane modified porous nano SiO2Hollow microsphere, chemical crosslinking reaction with chitosan, nano SiO2Enters the matrix of the acrylic-based hydrogel through a chemical bond combination method with chitosan, and improves the nano SiO2The compatibility in the acrylic-based hydrogel enhances the tensile strength and the compressive strength of the material, and when the chitosan is subjected to biodegradation, the molecular chain of the acrylic-based hydrogel is broken to destroy the matrix of the hydrogel material, so that the biodegradation effect is achieved.
Description
Technical Field
The invention relates to the technical field of hydrogel materials, in particular to high-strength modified acrylic acid-based degradable hydrogel and a preparation method thereof.
Background
The hydrogel has a physical or chemical crosslinking structure, can absorb a large amount of water without dissolving, has a three-dimensional space network structure and keeps a certain shape, is used as a high water absorption and water retention material, is a soft material similar to biological soft tissue, is widely applied to drought resistance in arid regions, cosmetic masks, biomedical functional materials and the like, is obtained by chemically crosslinking and polymerizing acrylic acid and derivatives thereof in the traditional hydrogel, is easy to break and lose due to poor mechanical properties, and limits the application field of the hydrogel, so that the development of high-strength hydrogel materials becomes a research hotspot, such as topological structure hydrogel, nano composite hydrogel, double-network structure hydrogel and the like, and has good mechanical properties.
Nano SiO2Excellent mechanical property, large surface area due to nano small-size effect, strong interaction with high molecular polymer matrix, and capability of enhancing mechanical property of high molecular material, and can be used as filler for preparing nano composite hydrogel, but nano SiO2The nano SiO is easy to agglomerate and agglomerate in acrylic-based hydrogel, can seriously affect the mechanical properties of the hydrogel material, and how to improve the nano SiO2Dispersibility in acrylic acid-based hydrogels is a difficult problem, and acrylic acid-based hydrogels are not natural polymer hydrogels, are difficult to biodegrade, and cause environmental pollution.
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides a high-strength modified acrylic acid-based degradable hydrogel and a preparation method thereof, which solve the problem of nano SiO2The problem of poor dispersibility in the acrylic-based hydrogel and the problem of poor mechanical properties and biodegradability of the acrylic group are solved.
(II) technical scheme
In order to achieve the purpose, the invention provides the following technical scheme: a high-strength modified acrylic acid-based degradable hydrogel comprises the following formula raw materials and components in parts by weight: 0.5-4 parts of nano SiO2Modified alkenyl chitosan, 44-67 parts of acrylic acid, 30-42 parts of acrylamide, 2-8 parts of initiator and 0.5-2 parts of cross-linking agent.
Preferably, the initiator is ammonium persulfate, and the crosslinking agent is NN-methylene bisacrylamide.
Preferably, the nano SiO2The preparation method of the modified alkenyl chitosan comprises the following steps:
(1) adding a mixed solvent of ethanol and distilled water into a reaction bottle, wherein the volume ratio of the two is 5-10:1, adding a formaldehyde aqueous solution and resorcinol, uniformly stirring, adding ammonia water, adjusting the pH value of the solution to 8-10, adding tetraethoxysilane, uniformly stirring at 30-40 ℃, reacting for 20-30h, centrifugally separating the solution to remove the solvent, washing a solid product by using distilled water and ethanol, fully drying, placing in a resistance furnace, heating at the rate of 3-8 ℃/min, heating to 530 ℃ and 580 ℃, carrying out heat preservation treatment for 3-5h, wherein the calcined product is porous nano SiO2Placing hollow microspheres in a mixed solvent of ethanol and distilled water, wherein the volume ratio of the hollow microspheres to the mixed solvent is 15-25:1, adding a silane coupling agent 3-aminopropyltriethoxysilane after uniform ultrasonic dispersion, stirring at a constant speed at 35-65 ℃ for reaction for 2-8h, centrifugally washing the solution to remove the solvent, and fully drying to prepare the 3-aminopropyltriethoxysilane grafted modified porous nano SiO2Hollow microspheres.
(2) Adding 2-4% acetic acid solution into a reaction bottle, adding chitosan, stirring for dissolving, and adding modified porous nano SiO2Stirring the hollow microspheres and glutaraldehyde at a constant speed at 50-90 ℃ for crosslinking reaction for 6-12h, adding ammonia water into the solution to adjust the solution to be neutral, drying the solution in vacuum to remove the solvent, washing the solid product with distilled water, and fully drying to prepare the nano SiO2And (3) modifying chitosan.
(3) Introducing nitrogen into the reaction bottle to exhaust air, adding ethanol solvent and nano SiO2Modifying chitosan and relievingSlowly dripping acetic acid solution until the chitosan is dissolved, adding catalysts of ammonium ceric nitrate and maleic anhydride, stirring at a constant speed for reaction for 3-6h at 80-100 ℃, distilling the solution under reduced pressure to remove the solvent, washing the solid product by using distilled water and diethyl ether, and fully drying to prepare the nano SiO2Modifying the alkenyl chitosan.
Preferably, the mass ratio of the formaldehyde to the resorcinol to the ethyl orthosilicate is 0.12-0.18:0.05-0.08: 1.
Preferably, the 3-aminopropyl triethoxysilane and porous nano SiO2The mass ratio of the hollow microspheres is 15-22: 1.
Preferably, the chitosan and the porous nano SiO are2The mass ratio of the hollow microspheres to the glutaraldehyde is 5-10:1: 1.5-2.5.
Preferably, the nano SiO2The mass ratio of the modified chitosan to the ammonium ceric nitrate to the maleic anhydride is 1:0.08-0.12: 1-1.6.
Preferably, the preparation method of the high-strength modified acrylic-based degradable hydrogel comprises the following steps:
(1) adding a mixed solvent of distilled water and acetone and 0.5-4 parts of nano SiO into a reaction bottle2Modifying alkenyl chitosan, 44-67 parts of acrylic acid and 30-42 parts of acrylamide, adding 2-8 parts of initiator ammonium persulfate and 0.5-2 parts of cross-linking agent NN-methylene bisacrylamide after ultrasonic dispersion is uniform, stirring at a constant speed for reaction for 20-30h at 70-90 ℃, drying the solution in vacuum to remove the solvent, washing the solid product by using distilled water and ethanol, and then adding distilled water into a dialysis bag to carry out dialysis impurity removal process to prepare the high-strength modified acrylic acid-based degradable hydrogel.
(III) advantageous technical effects
Compared with the prior art, the invention has the following beneficial technical effects:
the high-strength modified acrylic acid-based degradable hydrogel is prepared by taking phenolic resin microspheres as sacrificial templates and pore-forming agents through an in-situ polymerization method and a high-temperature thermal cracking method2The hollow microspheres have larger specific surface area and show more nano small-size effectStrong and huge specific surface area is easy to react with 3-aminopropyltriethoxysilane to obtain the 3-aminopropyltriethoxysilane modified porous nano SiO with high grafting rate2The hollow microspheres are subjected to chemical crosslinking reaction with amino in chitosan by using glutaraldehyde as a crosslinking agent to obtain nano SiO2Modifying chitosan, and carrying out ring opening reaction on a large number of hydroxyl groups of the chitosan and maleic anhydride to obtain nano SiO2Modifying alkenyl chitosan, and carrying out free radical polymerization reaction on alkenyl in the chitosan, acrylic acid and acrylamide to obtain the acrylic acid-based hydrogel.
The high-strength modified acrylic acid-based degradable hydrogel is nano SiO2Enters the matrix of the acrylic-based hydrogel through a chemical bond combination method with chitosan, and improves the nano SiO2Compatible, porous hollow structured nano-SiO in acrylic based hydrogels2Nano SiO with higher elastic modulus and Young's modulus and uniform dispersion2The tensile strength and the compressive strength of the hydrogel material are greatly enhanced, the tensile strength can reach 3.47-4.17MPa, the compressive strength reaches 64.8-74.5MPa, and meanwhile, the chitosan and the acrylic-based hydrogel with excellent biodegradability are crosslinked through chemical bonds, so that when the chitosan is subjected to biodegradation, the molecular chains of the acrylic-based hydrogel are broken, the matrix of the hydrogel material is damaged, and the biodegradation effect is achieved.
Detailed Description
To achieve the above object, the present invention provides the following embodiments and examples: a high-strength modified acrylic acid-based degradable hydrogel comprises the following formula raw materials and components in parts by weight: 0.5-4 parts of nano SiO2Modified alkenyl chitosan, 44-67 parts of acrylic acid, 30-42 parts of acrylamide, 2-8 parts of initiator ammonium persulfate and 0.5-2 parts of cross-linking agent NN-methylene bisacrylamide.
Nano SiO2The preparation method of the modified alkenyl chitosan comprises the following steps:
(1) adding a mixed solvent of ethanol and distilled water into a reaction bottle, wherein the volume ratio of the ethanol to the distilled water is 5-10:1, and then adding formaldehydeAdding ammonia water into aqueous solution and resorcinol after uniformly stirring, adjusting the pH value of the solution to 8-10, then adding tetraethoxysilane, wherein the mass ratio of formaldehyde to resorcinol to tetraethoxysilane is 0.12-0.18:0.05-0.08:1, stirring at a constant speed at 30-40 ℃ for reaction for 20-30h, centrifugally separating the solution to remove the solvent, washing the solid product with distilled water and ethanol, fully drying, then placing in a resistance furnace, heating to 530 ℃ and 580 ℃ at a heating rate of 3-8 ℃/min, carrying out heat preservation treatment for 3-5h, and obtaining a calcined product which is porous nano SiO2Placing the hollow microspheres in a mixed solvent of ethanol and distilled water, wherein the volume ratio of the hollow microspheres to the mixed solvent is 15-25:1, adding 3-aminopropyltriethoxysilane serving as a silane coupling agent after uniform ultrasonic dispersion, and mixing with porous nano SiO2The mass ratio of the hollow microspheres is 15-22:1, the mixture is stirred at a constant speed at 35-65 ℃ for reaction for 2-8h, the solution is centrifugally washed to remove the solvent and is fully dried to prepare the 3-aminopropyltriethoxysilane grafted modified porous nano SiO2Hollow microspheres.
(2) Adding 2-4% acetic acid solution into a reaction bottle, adding chitosan, stirring for dissolving, and adding modified porous nano SiO2The mass ratio of the hollow microspheres to the glutaraldehyde is 5-10:1:1.5-2.5, the crosslinking reaction is carried out for 6-12h under the uniform stirring at 50-90 ℃, ammonia water is added into the solution to adjust the solution to be neutral, the solution is dried in vacuum to remove the solvent, distilled water is used for washing the solid product, and the solid product is fully dried to obtain the nano SiO2And (3) modifying chitosan.
(3) Introducing nitrogen into the reaction bottle to exhaust air, adding ethanol solvent and nano SiO2Modifying chitosan, slowly dripping acetic acid solution until the chitosan is dissolved, and then adding catalysts of ammonium ceric nitrate and maleic anhydride, wherein the nano SiO is2The mass ratio of the modified chitosan to the ammonium ceric nitrate to the maleic anhydride is 1:0.08-0.12:1-1.6, the mixture is stirred at a constant speed for reaction for 3-6h at the temperature of 80-100 ℃, the solution is decompressed and distilled to remove the solvent, the distilled water and the ether are used for washing the solid product, and the solid product is fully dried to prepare the nano SiO2Modifying the alkenyl chitosan.
The preparation method of the high-strength modified acrylic acid-based degradable hydrogel comprises the following steps:
(1) adding a mixed solvent of distilled water and acetone and 0.5-4 parts of nano SiO into a reaction bottle2Modifying alkenyl chitosan, 44-67 parts of acrylic acid and 30-42 parts of acrylamide, adding 2-8 parts of initiator ammonium persulfate and 0.5-2 parts of cross-linking agent NN-methylene bisacrylamide after ultrasonic dispersion is uniform, stirring at a constant speed for reaction for 20-30h at 70-90 ℃, drying the solution in vacuum to remove the solvent, washing the solid product by using distilled water and ethanol, and then adding distilled water into a dialysis bag to carry out dialysis impurity removal process to prepare the high-strength modified acrylic acid-based degradable hydrogel.
Example 1
(1) Preparation of modified porous nano SiO2Hollow microsphere component 1: adding a mixed solvent of ethanol and distilled water into a reaction bottle, wherein the volume ratio of the mixed solvent to the ethanol to the distilled water is 5:1, adding a formaldehyde aqueous solution and resorcinol, stirring uniformly, adding ammonia water, adjusting the pH of the solution to 8, adding tetraethoxysilane, wherein the mass ratio of the formaldehyde to the resorcinol to the tetraethoxysilane is 0.12:0.05:1, stirring at a constant speed at 30 ℃ for 20 hours, centrifugally separating the solution to remove the solvent, washing a solid product by using distilled water and ethanol, fully drying, placing in a resistance furnace, heating at the rate of 3 ℃/min to 530 ℃, carrying out heat preservation treatment for 3 hours, and calcining the product is porous nano SiO2Placing the hollow microspheres in a mixed solvent of ethanol and distilled water, wherein the volume ratio of the hollow microspheres to the mixed solvent is 15:1, adding a silane coupling agent 3-aminopropyl triethoxysilane after uniform ultrasonic dispersion, and mixing with porous nano SiO2The mass ratio of the hollow microspheres is 15:1, the mixture is stirred at a constant speed at 35 ℃ for reaction for 2 hours, the solution is centrifugally washed to remove the solvent and is fully dried to prepare the 3-aminopropyltriethoxysilane grafted modified porous nano SiO2Hollow microsphere component 1.
(2) Preparation of nano SiO2Modified chitosan component 1: adding 2 percent by mass of acetic acid solution into a reaction bottle, adding chitosan, stirring and dissolving, and then adding modified porous nano SiO2The mass ratio of the hollow microsphere component 1 to the glutaraldehyde is 5:1:1.5, the crosslinking reaction is carried out for 6 hours at 50 ℃ under uniform stirring, ammonia water is added into the solution to adjust the solution to be neutral, the solution is dried in vacuum to remove the solvent, and distilled water is used for washing and solidifyingFully drying the product to prepare the nano SiO2Modified chitosan component 1.
(3) Preparation of nano SiO2Modified alkenylated chitosan component 1: introducing nitrogen into the reaction bottle to exhaust air, adding ethanol solvent and nano SiO2Modifying chitosan component 1, slowly dripping acetic acid solution until chitosan is dissolved, adding catalyst ceric ammonium nitrate and maleic anhydride, wherein nano SiO2The mass ratio of the modified chitosan to the ammonium ceric nitrate to the maleic anhydride is 1:0.08:1, the mixture is stirred at a constant speed for reaction for 3 hours at the temperature of 80 ℃, the solution is decompressed and distilled to remove the solvent, the distilled water and the ether are used for washing the solid product, and the solid product is fully dried to prepare the nano SiO2Modified alkenylated chitosan component 1.
(4) Preparation of high-strength modified acrylic-based degradable hydrogel material 1: adding a mixed solvent of distilled water and acetone and 0.5 part of nano SiO into a reaction bottle2Modifying 1 part of alkenyl chitosan component, 44 parts of acrylic acid and 30 parts of acrylamide, adding 2 parts of initiator ammonium persulfate and 0.5 part of cross-linking agent NN-methylene bisacrylamide after ultrasonic dispersion is uniform, stirring at a constant speed for reaction for 20 hours at 70 ℃, drying the solution in vacuum to remove the solvent, washing the solid product by using distilled water and ethanol, then adding distilled water into a dialysis bag to carry out dialysis impurity removal process, and preparing the high-strength modified acrylic acid based degradable hydrogel material 1.
Example 2
(1) Preparation of modified porous nano SiO2Hollow microsphere component 2: adding a mixed solvent of ethanol and distilled water into a reaction bottle, wherein the volume ratio of the mixed solvent to the ethanol to the distilled water is 5:1, adding a formaldehyde aqueous solution and resorcinol, stirring uniformly, adding ammonia water, adjusting the pH of the solution to 10, adding tetraethoxysilane, wherein the mass ratio of the formaldehyde to the resorcinol to the tetraethoxysilane is 0.12:0.05:1, stirring at a constant speed at 30 ℃ for reaction for 30 hours, centrifugally separating the solution to remove the solvent, washing a solid product by using distilled water and ethanol, fully drying, placing in a resistance furnace, heating at the rate of 3 ℃/min to 580 ℃, carrying out heat preservation treatment for 5 hours, and calcining the product is porous nano SiO2Hollow microspheres, and placing in a mixed solvent of ethanol and distilled water, the volume of the twoThe ratio is 15:1, 3-aminopropyl triethoxysilane as silane coupling agent and porous nanometer SiO are added after uniform ultrasonic dispersion2The mass ratio of the hollow microspheres is 15:1, the mixture is stirred at a constant speed at 65 ℃ for reaction for 8 hours, the solution is centrifugally washed to remove the solvent and is fully dried, and the 3-aminopropyltriethoxysilane grafted modified porous nano SiO is prepared2Hollow microsphere component 2.
(2) Preparation of nano SiO2Modified chitosan component 2: adding 2 percent by mass of acetic acid solution into a reaction bottle, adding chitosan, stirring and dissolving, and then adding modified porous nano SiO2The mass ratio of the hollow microsphere component 2 to the glutaraldehyde is 5:1:1.5, the cross-linking reaction is carried out for 6 hours under the uniform stirring at 50 ℃, the solution is added with ammonia water to adjust the solution to be neutral, the solution is dried in vacuum to remove the solvent, the solid product is washed by distilled water and is fully dried to prepare the nano SiO2Modified chitosan component 2.
(3) Preparation of nano SiO2Modified alkenylated chitosan component 2: introducing nitrogen into the reaction bottle to exhaust air, adding ethanol solvent and nano SiO2Modifying chitosan component 2, slowly adding acetic acid solution dropwise until chitosan is dissolved, adding catalyst ceric ammonium nitrate and maleic anhydride, wherein the catalyst is nano SiO2The mass ratio of the modified chitosan to the ammonium ceric nitrate to the maleic anhydride is 1:0.12:1, the mixture is stirred at a constant speed for reaction for 6 hours at the temperature of 80 ℃, the solution is decompressed and distilled to remove the solvent, the distilled water and the ether are used for washing the solid product, and the solid product is fully dried to prepare the nano SiO2Modified alkenylated chitosan component 2.
(4) Preparation of high-strength modified acrylic-based degradable hydrogel material 2: adding a mixed solvent of distilled water and acetone and 1 part of nano SiO into a reaction bottle2Modifying alkenyl chitosan component 2, acrylic acid 62 and acrylamide 33, adding initiator ammonium persulfate 3 and cross-linking agent NN-methylene bisacrylamide 1 after ultrasonic dispersion is uniform, stirring at uniform speed for reaction for 20h at 90 ℃, drying the solution in vacuum to remove the solvent, washing the solid product with distilled water and ethanol, then adding distilled water into a dialysis bag to carry out dialysis impurity removal process, and preparing the high-strength modified acrylic acidThe degradable hydrogel material 2.
Example 3
(1) Preparation of modified porous nano SiO2Hollow microsphere component 3: adding a mixed solvent of ethanol and distilled water into a reaction bottle, wherein the volume ratio of the mixed solvent to the ethanol to the distilled water is 8:1, adding a formaldehyde aqueous solution and resorcinol, stirring uniformly, adding ammonia water, adjusting the pH of the solution to 9, adding tetraethoxysilane, wherein the mass ratio of the formaldehyde to the resorcinol to the tetraethoxysilane is 0.15:0.06:1, stirring at a constant speed at 35 ℃ for reaction for 25 hours, centrifugally separating the solution to remove the solvent, washing a solid product by using distilled water and ethanol, fully drying, placing in a resistance furnace, heating at the rate of 5 ℃/min to 560 ℃, carrying out heat preservation treatment for 4 hours, and calcining the product is porous nano SiO2Placing the hollow microspheres in a mixed solvent of ethanol and distilled water, wherein the volume ratio of the hollow microspheres to the mixed solvent is 20:1, adding a silane coupling agent 3-aminopropyl triethoxysilane after uniform ultrasonic dispersion, and mixing with porous nano SiO2The mass ratio of the hollow microspheres is 18:1, the mixture is stirred at a constant speed at 50 ℃ for reaction for 5 hours, the solution is centrifugally washed to remove the solvent and is fully dried, and the 3-aminopropyltriethoxysilane grafted modified porous nano SiO is prepared2Hollow microsphere component 3.
(2) Preparation of nano SiO2Modified chitosan component 3: adding 3 percent by mass of acetic acid solution into a reaction bottle, adding chitosan, stirring and dissolving, and then adding modified porous nano SiO2The mass ratio of the hollow microsphere component 3 to the glutaraldehyde is 7:1:2, the cross-linking reaction is carried out for 8 hours under the uniform stirring at 70 ℃, ammonia water is added into the solution to adjust the solution to be neutral, the solution is dried in vacuum to remove the solvent, the solid product is washed by distilled water and is fully dried, and the nano SiO is prepared2Modified chitosan component 3.
(3) Preparation of nano SiO2Modified alkenylated chitosan component 3: introducing nitrogen into the reaction bottle to exhaust air, adding ethanol solvent and nano SiO2Modifying chitosan component 3, slowly adding acetic acid solution dropwise until chitosan is dissolved, adding catalyst ceric ammonium nitrate and maleic anhydride, wherein the catalyst is nano SiO2The mass ratio of the modified chitosan to the ammonium ceric nitrate to the maleic anhydride is 1:0.1:1.3,stirring at constant speed at 90 deg.C for 4.5h, distilling the solution under reduced pressure to remove solvent, washing the solid product with distilled water and diethyl ether, and drying to obtain nanometer SiO2Modified alkenylated chitosan component 3.
(4) Preparation of high-strength modified acrylic-based degradable hydrogel material 3: adding a mixed solvent of distilled water and acetone and 2 parts of nano SiO into a reaction bottle23 parts of modified alkenyl chitosan component, 56 parts of acrylic acid and 36 parts of acrylamide, adding 4.5 parts of initiator ammonium persulfate and 1.5 parts of cross-linking agent NN-methylene bisacrylamide after ultrasonic dispersion is uniform, stirring at a constant speed for reaction for 25 hours at 80 ℃, drying the solution in vacuum to remove the solvent, washing the solid product by using distilled water and ethanol, and then adding distilled water into a dialysis bag to carry out dialysis impurity removal process to prepare the high-strength modified acrylic acid-based degradable hydrogel material 3.
Example 4
(1) Preparation of modified porous nano SiO2Hollow microsphere component 4: adding a mixed solvent of ethanol and distilled water into a reaction bottle, wherein the volume ratio of the mixed solvent to the ethanol to the distilled water is 10:1, adding a formaldehyde aqueous solution and resorcinol, stirring uniformly, adding ammonia water, adjusting the pH of the solution to 8, adding tetraethoxysilane, wherein the mass ratio of the formaldehyde to the resorcinol to the tetraethoxysilane is 0.18:0.05:1, stirring at a constant speed at 40 ℃ for reaction for 30 hours, centrifugally separating the solution to remove the solvent, washing a solid product by using distilled water and ethanol, fully drying, placing in a resistance furnace, heating at the rate of 8 ℃/min to 580 ℃, carrying out heat preservation treatment for 5 hours, and calcining the product is porous nano SiO2Placing the hollow microspheres in a mixed solvent of ethanol and distilled water, wherein the volume ratio of the hollow microspheres to the mixed solvent is 15:1, adding a silane coupling agent 3-aminopropyl triethoxysilane after uniform ultrasonic dispersion, and mixing with porous nano SiO2The mass ratio of the hollow microspheres is 15:1, the mixture is stirred at a constant speed at 65 ℃ for reaction for 8 hours, the solution is centrifugally washed to remove the solvent and is fully dried, and the 3-aminopropyltriethoxysilane grafted modified porous nano SiO is prepared2A hollow microsphere component 4.
(2) Preparation of nano SiO2Modified chitosan component 4: adding 4 percent by mass of acetic acid solution into a reaction bottleAdding chitosan, stirring for dissolving, and adding modified porous nano SiO2The mass ratio of the hollow microsphere component 4 to the glutaraldehyde is 10:1:1.5, the crosslinking reaction is carried out for 12 hours at the temperature of 90 ℃ under uniform stirring, ammonia water is added into the solution to adjust the solution to be neutral, the solution is dried in vacuum to remove the solvent, the solid product is washed by distilled water and is fully dried to prepare the nano SiO2Modified chitosan component 4.
(3) Preparation of nano SiO2Modified alkenylated chitosan component 4: introducing nitrogen into the reaction bottle to exhaust air, adding ethanol solvent and nano SiO2Modifying chitosan component 4, slowly adding acetic acid solution dropwise until chitosan is dissolved, adding catalyst ceric ammonium nitrate and maleic anhydride, wherein the catalyst is nano SiO2The mass ratio of the modified chitosan to the ammonium ceric nitrate to the maleic anhydride is 1:0.08:1.6, the mixture is stirred at a constant speed for reaction for 6 hours at 100 ℃, the solution is distilled under reduced pressure to remove the solvent, the solid product is washed by distilled water and ether and is fully dried to prepare the nano SiO2Modified alkenylated chitosan component 4.
(4) Preparation of high-strength modified acrylic-based degradable hydrogel material 4: adding a mixed solvent of distilled water and acetone and 3 parts of nano SiO into a reaction bottle2Modifying 4 parts of alkenyl chitosan component, 49 parts of acrylic acid and 40 parts of acrylamide, adding 6.2 parts of initiator ammonium persulfate and 1.8 parts of cross-linking agent NN-methylene bisacrylamide after ultrasonic dispersion is uniform, stirring at a constant speed at 90 ℃ for reaction for 30 hours, carrying out vacuum drying on the solution to remove the solvent, washing the solid product by using distilled water and ethanol, then adding distilled water into a dialysis bag to carry out dialysis impurity removal process, and preparing the high-strength modified acrylic acid based degradable hydrogel material 4.
Example 5
(1) Preparation of modified porous nano SiO2Hollow microsphere component 5: adding a mixed solvent of ethanol and distilled water into a reaction bottle, wherein the volume ratio of the mixed solvent to the ethanol to the distilled water is 10:1, adding a formalin and resorcinol, stirring uniformly, adding ammonia water, adjusting the pH of the solution to 10, adding tetraethoxysilane, wherein the mass ratio of the formaldehyde to the resorcinol to the tetraethoxysilane is 0.18:0.08:1, stirring at a constant speed at 40 ℃ for reactionCentrifuging the solution for 30h to remove the solvent, washing the solid product with distilled water and ethanol, drying completely, placing in a resistance furnace, heating to 580 deg.C at a heating rate of 8 deg.C/min, maintaining the temperature for 5h to obtain a calcined product of porous nanometer SiO2Placing the hollow microspheres in a mixed solvent of ethanol and distilled water, wherein the volume ratio of the hollow microspheres to the mixed solvent is 25:1, adding a silane coupling agent 3-aminopropyl triethoxysilane after uniform ultrasonic dispersion, and mixing with porous nano SiO2The mass ratio of the hollow microspheres is 22:1, the mixture is stirred at a constant speed at 65 ℃ for reaction for 8 hours, the solution is centrifugally washed to remove the solvent and is fully dried, and the 3-aminopropyltriethoxysilane grafted modified porous nano SiO is prepared2A hollow microsphere component 5.
(2) Preparation of nano SiO2Modified chitosan component 5: adding 4 mass percent of acetic acid solution into a reaction bottle, adding chitosan, stirring and dissolving, and then adding modified porous nano SiO2The mass ratio of the hollow microsphere component 5 to the glutaraldehyde is 10:1:2.5, the crosslinking reaction is carried out for 12 hours at the temperature of 90 ℃ under uniform stirring, ammonia water is added into the solution to adjust the solution to be neutral, the solution is dried in vacuum to remove the solvent, the solid product is washed by distilled water and is fully dried to prepare the nano SiO2Modified chitosan component 5.
(3) Preparation of nano SiO2Modified alkenylated chitosan component 5: introducing nitrogen into the reaction bottle to exhaust air, adding ethanol solvent and nano SiO2Modifying chitosan component 5, slowly adding acetic acid solution dropwise until chitosan is dissolved, adding catalyst ceric ammonium nitrate and maleic anhydride, wherein the catalyst is nano SiO2The mass ratio of the modified chitosan to the ammonium ceric nitrate to the maleic anhydride is 1:0.12:1.6, the mixture is stirred at a constant speed for reaction for 6 hours at the temperature of 100 ℃, the solution is distilled under reduced pressure to remove the solvent, the solid product is washed by distilled water and ether and is fully dried to prepare the nano SiO2Modified alkenylated chitosan component 5.
(4) Preparation of high-strength modified acrylic-based degradable hydrogel material 5: adding a mixed solvent of distilled water and acetone and 4 parts of nano SiO into a reaction bottle25 parts of modified alkenyl chitosan, 44 parts of acrylic acid and 42 parts of acrylamide, and performing ultrasonic dispersionAnd after the mixture is homogenized, 8 parts of initiator ammonium persulfate and 2 parts of cross-linking agent NN-methylene bisacrylamide are added, the mixture is stirred at a constant speed for reaction for 30 hours at the temperature of 90 ℃, the solution is dried in vacuum to remove the solvent, distilled water and ethanol are used for washing a solid product, and then distilled water is added into a dialysis bag for dialysis impurity removal, so that the high-strength modified acrylic acid-based degradable hydrogel material 5 is prepared.
And respectively preparing the high-strength modified acrylic acid based degradable hydrogel materials 1-5 into cuboids with the length of 40mm, the width of 20mm and the height of 5mm, and testing the tensile strength and the compressive strength by a universal material testing machine.
In summary, the high-strength modified acrylic acid-based degradable hydrogel is prepared by taking phenolic resin microspheres as sacrificial templates and pore-forming agents through an in-situ polymerization method and a high-temperature thermal cracking method to obtain porous-structure nano SiO2The hollow microsphere has larger specific surface area, the expressed nano small-size effect is stronger, and the huge specific surface area is easy to react with 3-aminopropyltriethoxysilane to obtain the 3-aminopropyltriethoxysilane modified porous nano SiO with high grafting rate2The hollow microspheres are subjected to chemical crosslinking reaction with amino in chitosan by using glutaraldehyde as a crosslinking agent to obtain nano SiO2Modifying chitosan, and carrying out ring opening reaction on a large number of hydroxyl groups of the chitosan and maleic anhydride to obtain nano SiO2Modifying alkenyl chitosan, and carrying out free radical polymerization reaction on alkenyl in the chitosan, acrylic acid and acrylamide to obtain the acrylic acid-based hydrogel.
Nano SiO2Enters the matrix of the acrylic-based hydrogel through a chemical bond combination method with chitosan, and improves the nano SiO2Compatible, porous hollow structured nano-SiO in acrylic based hydrogels2Nano SiO with higher elastic modulus and Young's modulus and uniform dispersion2Greatly enhances the tensile strength and the compressive strength of the hydrogel material, and the tensile strength can reach 3.47 to 417MPa, the compressive strength reaches 64.8-74.5MPa, and the chitosan and the acrylic acid-based hydrogel with excellent biodegradability are crosslinked through chemical bonds, so that molecular chains of the acrylic acid-based hydrogel are broken when the chitosan is subjected to biodegradation, the matrix of the hydrogel material is damaged, and the biodegradation effect is achieved.
Claims (8)
1. The high-strength modified acrylic acid-based degradable hydrogel comprises the following formula raw materials and components in parts by weight, and is characterized in that: 0.5-4 parts of nano SiO2Modified alkenyl chitosan, 44-67 parts of acrylic acid, 30-42 parts of acrylamide, 2-8 parts of initiator and 0.5-2 parts of cross-linking agent.
2. The high-strength modified acrylic-based degradable hydrogel according to claim 1, wherein: the initiator is ammonium persulfate, and the cross-linking agent is NN-methylene bisacrylamide.
3. The high-strength modified acrylic-based degradable hydrogel according to claim 1, wherein: the nano SiO2The preparation method of the modified alkenyl chitosan comprises the following steps:
(1) adding a formaldehyde aqueous solution and resorcinol into a mixed solvent of ethanol and distilled water with a volume ratio of 5-10:1, adding ammonia water to adjust the pH value of the solution to 8-10, adding tetraethoxysilane, reacting at 30-40 ℃ for 20-30h, removing the solvent, washing, drying, placing in a resistance furnace, heating at a rate of 3-8 ℃/min to 530 ℃ and 580 ℃, carrying out heat preservation treatment for 3-5h, wherein the calcined product is porous nano SiO2Placing the hollow microspheres in a mixed solvent of ethanol and distilled water with a volume ratio of 15-25:1, ultrasonically dispersing uniformly, adding a silane coupling agent 3-aminopropyltriethoxysilane, reacting at 35-65 ℃ for 2-8h, removing the solvent, and drying to obtain the 3-aminopropyltriethoxysilane grafted modified porous nano SiO2Hollow microspheres;
(2) adding chitosan into acetic acid solution with mass fraction of 2-4%, stirring for dissolving, and adding modified porous sodiumSiO rice2Carrying out cross-linking reaction on the hollow microspheres and glutaraldehyde for 6-12h at 50-90 ℃, adding ammonia water into the solution to adjust the solution to be neutral, removing the solvent, washing and drying to prepare the nano SiO2Modifying chitosan;
(3) adding nano SiO into ethanol solvent2Modifying chitosan, slowly dropwise adding acetic acid solution until the chitosan is dissolved, then adding catalysts of ammonium ceric nitrate and maleic anhydride, reacting for 3-6h at 80-100 ℃ in a nitrogen atmosphere, removing the solvent, washing and drying to prepare the nano SiO2Modifying the alkenyl chitosan.
4. The high-strength modified acrylic-based degradable hydrogel according to claim 3, wherein: the mass ratio of the formaldehyde to the resorcinol to the ethyl orthosilicate is 0.12-0.18:0.05-0.08: 1.
5. The high-strength modified acrylic-based degradable hydrogel according to claim 3, wherein: the 3-aminopropyl triethoxysilane and porous nano SiO2The mass ratio of the hollow microspheres is 15-22: 1.
6. The high-strength modified acrylic-based degradable hydrogel according to claim 3, wherein: the chitosan and the porous nano SiO2The mass ratio of the hollow microspheres to the glutaraldehyde is 5-10:1: 1.5-2.5.
7. The high-strength modified acrylic-based degradable hydrogel according to claim 3, wherein: the nano SiO2The mass ratio of the modified chitosan to the ammonium ceric nitrate to the maleic anhydride is 1:0.08-0.12: 1-1.6.
8. The high-strength modified acrylic-based degradable hydrogel according to claim 1, wherein: the preparation method of the high-strength modified acrylic acid-based degradable hydrogel comprises the following steps:
(1) to distilled water and acetoneAdding 0.5-4 parts of nano SiO into the mixed solvent2Modifying alkenyl chitosan, 44-67 parts of acrylic acid and 30-42 parts of acrylamide, adding 2-8 parts of initiator ammonium persulfate and 0.5-2 parts of cross-linking agent NN-methylene bisacrylamide after ultrasonic dispersion is uniform, reacting for 20-30h at 70-90 ℃, removing the solvent, washing the solid product, then adding distilled water into a dialysis bag, and carrying out dialysis impurity removal process to prepare the high-strength modified acrylic acid-based degradable hydrogel.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010333422.6A CN111410716A (en) | 2020-04-24 | 2020-04-24 | High-strength modified acrylic acid-based degradable hydrogel and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010333422.6A CN111410716A (en) | 2020-04-24 | 2020-04-24 | High-strength modified acrylic acid-based degradable hydrogel and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111410716A true CN111410716A (en) | 2020-07-14 |
Family
ID=71489989
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010333422.6A Withdrawn CN111410716A (en) | 2020-04-24 | 2020-04-24 | High-strength modified acrylic acid-based degradable hydrogel and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111410716A (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111793169A (en) * | 2020-08-11 | 2020-10-20 | 李方 | High-salt-tolerance super absorbent resin and preparation process thereof |
| CN112029117A (en) * | 2020-08-17 | 2020-12-04 | 嵊州市鉴亭新材料科技有限公司 | Acrylic copolymer magnetic porous hydrogel adsorbent and preparation method thereof |
| CN112825854A (en) * | 2021-01-08 | 2021-05-25 | 杭州师范大学钱江学院 | Novel high-adhesion environment-friendly pesticide auxiliary agent and application and preparation method thereof |
| CN112851975A (en) * | 2021-01-12 | 2021-05-28 | 河北工程大学 | Based on Fe3O4Preparation method of polyacrylamide hydrogel with nanosheet cross-linked structure |
| CN114057940A (en) * | 2021-12-02 | 2022-02-18 | 中山大学 | Biodegradable carbomer polymer microsphere with core-shell structure as well as preparation method and application thereof |
| CN114181411A (en) * | 2021-12-10 | 2022-03-15 | 成都德斐生物科技有限公司 | Hydrogel material with high cold/heat insulation effect |
| CN115849884A (en) * | 2022-11-17 | 2023-03-28 | 新化县顺达电子陶瓷有限公司 | High-strength alumina ceramic material and preparation method thereof |
| CN116768435A (en) * | 2023-05-29 | 2023-09-19 | 浙江湖州赛诚生态科技有限公司 | Environment-friendly silt stabilizing curing agent and preparation method thereof |
| CN117126652A (en) * | 2023-07-14 | 2023-11-28 | 西安川秦石油科技有限公司 | Degradable temporary plugging agent for fracturing of oil and gas well and preparation method |
-
2020
- 2020-04-24 CN CN202010333422.6A patent/CN111410716A/en not_active Withdrawn
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111793169B (en) * | 2020-08-11 | 2021-09-17 | 乐清市川嘉电气科技有限公司 | High-salt-tolerance super absorbent resin and preparation process thereof |
| CN111793169A (en) * | 2020-08-11 | 2020-10-20 | 李方 | High-salt-tolerance super absorbent resin and preparation process thereof |
| CN112029117A (en) * | 2020-08-17 | 2020-12-04 | 嵊州市鉴亭新材料科技有限公司 | Acrylic copolymer magnetic porous hydrogel adsorbent and preparation method thereof |
| CN112825854B (en) * | 2021-01-08 | 2022-05-17 | 杭州师范大学钱江学院 | Novel high-adhesion environment-friendly pesticide auxiliary agent and application and preparation method thereof |
| CN112825854A (en) * | 2021-01-08 | 2021-05-25 | 杭州师范大学钱江学院 | Novel high-adhesion environment-friendly pesticide auxiliary agent and application and preparation method thereof |
| CN112851975A (en) * | 2021-01-12 | 2021-05-28 | 河北工程大学 | Based on Fe3O4Preparation method of polyacrylamide hydrogel with nanosheet cross-linked structure |
| CN112851975B (en) * | 2021-01-12 | 2022-04-01 | 河北工程大学 | Based on Fe3O4Preparation method of polyacrylamide hydrogel with nanosheet cross-linked structure |
| CN114057940A (en) * | 2021-12-02 | 2022-02-18 | 中山大学 | Biodegradable carbomer polymer microsphere with core-shell structure as well as preparation method and application thereof |
| CN114057940B (en) * | 2021-12-02 | 2023-11-03 | 中山大学 | Biodegradable carbomer core-shell structure polymer microsphere and preparation method and application thereof |
| CN114181411A (en) * | 2021-12-10 | 2022-03-15 | 成都德斐生物科技有限公司 | Hydrogel material with high cold/heat insulation effect |
| CN114181411B (en) * | 2021-12-10 | 2023-12-08 | 马素德 | Hydrogel material with high cold/heat insulation effect |
| CN115849884A (en) * | 2022-11-17 | 2023-03-28 | 新化县顺达电子陶瓷有限公司 | High-strength alumina ceramic material and preparation method thereof |
| CN115849884B (en) * | 2022-11-17 | 2023-08-25 | 新化县顺达电子陶瓷有限公司 | High-strength alumina ceramic material and preparation method thereof |
| CN116768435A (en) * | 2023-05-29 | 2023-09-19 | 浙江湖州赛诚生态科技有限公司 | Environment-friendly silt stabilizing curing agent and preparation method thereof |
| CN116768435B (en) * | 2023-05-29 | 2024-05-07 | 浙江赛诚生态科技有限公司 | Environment-friendly silt stabilizing curing agent and preparation method thereof |
| CN117126652A (en) * | 2023-07-14 | 2023-11-28 | 西安川秦石油科技有限公司 | Degradable temporary plugging agent for fracturing of oil and gas well and preparation method |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111410716A (en) | High-strength modified acrylic acid-based degradable hydrogel and preparation method thereof | |
| CN108929412B (en) | Preparation method of temperature-responsive adhesive injectable hydrogel | |
| CN111333917A (en) | Hydrophobic cellulose-chitosan high-barrier composite film and preparation method thereof | |
| CN102229711B (en) | Preparation and application of silicane functionalized high-water-solubility silicon dioxide nano particles | |
| CN111171520B (en) | Modified carbon nano tube reinforced shape memory epoxy resin composite material and preparation method thereof | |
| CN111499815A (en) | SiO (silicon dioxide)2-GO (graphene oxide) -crosslinked polypropylene-based high-strength hydrogel and preparation method thereof | |
| CN110358009B (en) | Stretchable hydrogel based on modified silica nanoparticle cross-linking agent and preparation method and application thereof | |
| CN114790342B (en) | Silane modified carbon black composite filler and preparation method thereof | |
| CN111333990A (en) | Self-repairing double-network cross-linked degradable acrylic hydrogel and preparation method thereof | |
| CN109971047B (en) | Natural rubber-white carbon black composite material and preparation method and application thereof | |
| CN113605094B (en) | Antibacterial degradable composite fiber and preparation method thereof | |
| CN104629494A (en) | Polycarboxyl silicon dioxide nanoparticles and preparation method thereof | |
| CN108329686B (en) | Preparation method of high-performance nylon nano composite material | |
| CN114702632A (en) | Filtrate reducer for water-based drilling fluid and preparation method thereof | |
| CN112724325B (en) | Preparation method and application of nano-silicon cross-linking agent and quick-response hydrogel | |
| CN113292762A (en) | Dialdehyde nano-cellulose three-dimensional flexible material and preparation method and application thereof | |
| CN100577705C (en) | Preparation method of nano particle-polyurethane complex particle for macromolecule material | |
| CN111875915A (en) | High-strength SiO2-polyacrylic acid-polyvinyl alcohol interpenetrating network hydrogel and preparation method thereof | |
| CN112175197A (en) | Preparation method of magnetically-modified natural polysaccharide | |
| CN114656605B (en) | Nano SiO 2 Preparation method of LPF composite material | |
| CN109851965B (en) | Nano composite high water absorption material and preparation method thereof | |
| CN113861624A (en) | Preparation method of epoxy resin composite material | |
| CN112521705A (en) | Method for preparing modified aramid pulp/PMMA (polymethyl methacrylate) composite material by supercritical carbon dioxide polymerization | |
| CN109851815B (en) | Preparation method of nano composite hydrogel based on hydrogen bond crosslinking of polymer nano microspheres | |
| CN113004545A (en) | Preparation method of polyaspartic acid semi-interpenetrating nano-composite hydrogel |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WW01 | Invention patent application withdrawn after publication | ||
| WW01 | Invention patent application withdrawn after publication |
Application publication date: 20200714 |