CN111253514A - High-strength zirconium hydroxide nano composite hydrogel, preparation thereof and application thereof as electric driver - Google Patents
High-strength zirconium hydroxide nano composite hydrogel, preparation thereof and application thereof as electric driver Download PDFInfo
- Publication number
- CN111253514A CN111253514A CN202010041351.2A CN202010041351A CN111253514A CN 111253514 A CN111253514 A CN 111253514A CN 202010041351 A CN202010041351 A CN 202010041351A CN 111253514 A CN111253514 A CN 111253514A
- Authority
- CN
- China
- Prior art keywords
- zirconium hydroxide
- hydrogel
- solution
- monomers
- acrylate
- 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.)
- Pending
Links
Images
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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/04—Acids; Metal salts or ammonium salts thereof
- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts 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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
-
- 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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F220/56—Acrylamide; Methacrylamide
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2244—Oxides; Hydroxides of metals of zirconium
-
- 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
Abstract
The invention discloses a high-strength zirconium hydroxide nano composite hydrogel, which is prepared by copolymerizing acrylic acid and acrylamide monomers by using zirconium hydroxide nano sol under the condition of adding a catalyst and an initiator by using an in-situ free radical polymerization method. The invention also discloses application of the composite hydrogel in preparing a hydrogel electric driver, wherein the hydrogel is assembled into an electric driving device in an electrolytic cell, and the hydrogel driver responds to an electric signal under stimulation of different conditions so as to drive. The hydrogel driver constructed by the composite hydrogel widens the application range of the electric driver, ensures that the mechanical strength of the electric driver meets the strength requirement of artificial muscles, can be used for constructing a bionic soft robot, and indicates that the electric driver has wide application prospects in the fields of bionic artificial muscles and microfluidic valves.
Description
Technical Field
The invention relates to hydrogel and preparation and application thereof, in particular to high-strength zirconium hydroxide nano composite hydrogel and preparation and application thereof as an electric driver, belonging to the field of composite drivers.
Background
The hydrogel driver is a soft driving device capable of generating volume phase change under external stimulation, and has wide application prospects in the aspects of microfluidic valves, drug delivery and artificial muscles. Among these hydrogel actuators, the electrical stimulation responsive hydrogel actuator has great advantages due to its low voltage and simple facility. The application of the hydrogel driver for electric stimulation response mainly focuses on small robots, cell scaffolds, micro mechanical devices and the like. For example: eddington et al prepared a hydrogel electrically controlled valve with a high swelling ratio that could effectively regulate the flow of water within the channel under the control of electrical stimulation. Recently, Morales et al designed a hydrogel walkable device with anions and cations that could move directionally in response to electrical signals in an electrolyte solution to simulate the motion behavior of a robot. [ D.Morales, E.Palleau, M.D.Dickey, O.D.Velev, Electro-activated hydrogel Walkers with product responsive leaves, Soft matter 10(9) (2014) 1337-.
High strength hydrogel actuators, which are generally required to withstand long, repeated deformations, are widely used in artificial muscles, smart valves and drug delivery systems. However, the poor mechanical properties and low young's modulus limit the application of conventional hydrogels in actuators. At present, the methods for solving the problem of poor mechanical strength of the hydrogel are as follows: introducing a novel cross-linking agent such as graphene oxide or block copolymer microspheres into a network structure to serve as cross-linking points, and preparing a hydrogel driving device with high mechanical strength and rapid electrical stimulation response capability; the other mode is as follows: the interaction between anionic and cationic monomers with opposite charges is used to construct a hydrogel actuator that responds dual to pH and ionic strength. However, the above-mentioned techniques have problems: existing electrically driven hydrogel actuators fail to meet the strength criteria of artificial muscles (-300 KPa). Therefore, the development of high strength hydrogel electrically driven devices remains a challenge.
One technical problem to be solved at present is: it is needed to develop a high-strength nano-composite hydrogel driver, a preparation method thereof and application of the driver of hydrogel under electric field stimulation, and the mechanical property of the electric field stimulation hydrogel can reach the strength range of human articular cartilage. Due to the small size effect of the nano material, the nano particles are easy to agglomerate, so that the dispersibility in a gel system is poor, and when the nano particles are used as an additive or a filler, the agglomerated nano particles provide a certain mechanical support, but the mechanical property of the material is weakened, and the application requirement of the material in the biomedical field such as the aspect of human tissue scaffolds cannot be met. In the literature about searching the range that the mechanical property of the prepared hydrogel driver is improved and the strength of the hydrogel driver is close to that of human articular cartilage, the technical scheme that the high-strength zirconium hydroxide nano-composite hydrogel is prepared by adopting an in-situ free radical polymerization method and the hydrogel is applied as an electric driver is not reported.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a high-strength zirconium hydroxide nano-composite hydrogel, and preparation and application thereof as an electric driver.
The invention relates to a high-strength zirconium hydroxide nano composite hydrogel, which is characterized in that: the composite hydrogel is composed of zirconium hydroxide nano sol, acrylic monomers, acrylamide monomers and the balance of water, and comprises the following components in percentage by weight: based on 10ml of composite hydrogel, the zirconium hydroxide nano sol accounts for 1-15 wt%, the sum of the concentrations of acrylic monomers and acrylamide monomers with the molar ratio of 1: 9-5: 5 is 1-3 mol/L, and the balance is water; the aperture size of the composite hydrogel is 0.05-0.4 μm, the elongation at break is 380-830%, the breaking strength is 0.5-2 MPa, and the driving angle is changed in the range of-70-80 degrees within 200 s.
The preferred embodiments of the high-strength zirconium hydroxide nanocomposite hydrogel are as follows: the composite hydrogel is composed of zirconium hydroxide nano sol, acrylic monomers, acrylamide monomers and the balance of water, and comprises the following components in percentage by weight: based on 10ml of composite hydrogel, the zirconium hydroxide nano sol accounts for 5-15 wt%, the sum of the concentrations of acrylic monomers and acrylamide monomers with the molar ratio of 1: 7-5: 5 is 1-2 mol/L, and the balance is water; the aperture size of the composite hydrogel is 0.07-0.3 mu m, the elongation at break is 380-430%, the breaking strength is 1.5-2 MPa, and the driving angle is changed in the range of-66-74 degrees within 200 s.
The most preferred embodiments of the high-strength zirconium hydroxide nanocomposite hydrogel described above are: the composite hydrogel is composed of zirconium hydroxide nano sol, acrylic monomers, acrylamide monomers and the balance of water, and comprises the following components in percentage by weight: based on 10ml of composite hydrogel, the zirconium hydroxide nano sol accounts for 10 wt%, the total concentration of acrylic monomers and acrylamide monomers with the molar ratio of 3:7 is 2mol/L, and the balance is water; the aperture size of the composite hydrogel is 0.07-0.2 mu m, the elongation at break is 380-400%, the breaking strength is 1.7-1.9 MPa, and the driving angle is changed within the range of-60-70 degrees within 200 s.
Wherein: the acrylic monomer is one of acrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, isobutyl acrylate, hexyl acrylate, isooctyl acrylate, lauryl acrylate, benzyl acrylate, cyclohexyl acrylate, perfluoroalkyl acrylate, hydroxyethyl phosphate acrylate, isobornyl acrylate and tetrahydrofuran methyl acrylate; the acrylamide monomer is one of N, N-dimethylacrylamide and acrylamide.
The high-strength zirconium hydroxide nano-composite hydrogel comprises the following components in parts by weight: the acrylic monomer is preferably acrylic acid; the acrylamide-based monomer is preferably N, N-dimethylacrylamide.
The preparation method of the high-strength zirconium hydroxide nano composite hydrogel comprises the following steps:
①, pouring 15 wt% of zirconium acetate into a container, placing the container in an oil bath pan at 50-70 ℃, adding 15 wt% of ammonia water, aging the container for 10-20 h at 50-70 ℃ after the pH value reaches 3-5, centrifuging the container, and washing the container with deionized water to remove redundant ammonium ions to obtain 1-15 wt% of zirconium hydroxide nano sol;
②, taking 1-9 g of the zirconium hydroxide nano sol prepared in the step ①, adding 1-9 g of deionized water for dilution, adding an acrylic monomer and an acrylamide monomer according to the monomer molar ratio of 1: 9-5: 5, keeping the molar concentration sum of the two monomers at 1-3 mol/L, and controlling the volume of the solution at 10 ml;
③ adding 0.5mL of 2 wt% potassium persulfate solution and 0.2-0.8 μ L of catalyst tetramethylethylenediamine into the solution prepared in the step ② in sequence to ensure that the volume of the reaction volume is constant to 10mL, stirring uniformly, injecting the solution into a glass container for sealing, and carrying out in-situ free radical polymerization reaction at 40-70 ℃ to generate the zirconium hydroxide nano-composite hydrogel.
The preparation method of the high-strength zirconium hydroxide nano-composite hydrogel can be implemented by amplifying or reducing the disclosed related dosage according to a proportion, and the preferable embodiment is that 4-6 g of the zirconium hydroxide nano-sol prepared in the step ① is taken, 4-5 g of deionized water is added for dilution, an acrylic monomer and an acrylamide monomer are added according to the monomer molar ratio of 1: 7-5: 5, the molar concentration sum of the two monomers is kept to be 1-2 mol/L, meanwhile, the volume of the solution is controlled to be 10mL, then 0.5mL of 2 wt% potassium persulfate solution and 0.5-0.8 muL of catalyst tetramethylethylenediamine are sequentially added into the just prepared solution, the volume of the reaction is kept to be 10mL, the solution is uniformly stirred, is injected into a glass container for sealing, and is subjected to in-situ free radical polymerization reaction at the temperature of 40-55 ℃ to generate the zirconium hydroxide nano-composite hydrogel.
The most preferable embodiment of the preparation method of the high-strength zirconium hydroxide nano-composite hydrogel is that 5g of zirconium hydroxide nano-sol prepared in the step ① is taken, 4-5 g of deionized water is added for dilution, an acrylic monomer and an acrylamide monomer are added according to the monomer molar ratio of 3:7, the molar concentration sum of the two monomers is kept to be 2mol/L, meanwhile, the volume of the solution is controlled to be 10mL, then 0.5mL of 2 wt% potassium persulfate solution and 0.8 muL of catalyst tetramethylethylenediamine are sequentially added into the just-prepared solution, the volume of the reaction is kept to be 10mL, the solution is uniformly stirred, the solution is injected into a glass container for sealing, and in-situ free radical polymerization reaction is carried out at the temperature of 40-45 ℃ to generate the zirconium hydroxide nano-composite hydrogel.
The invention relates to application of high-strength zirconium hydroxide nano composite hydrogel in preparation of a hydrogel electric driver.
Preparing 0.1 mol/L-1 mol/L NaSO4The solution is placed in an electrolytic cell, and two Pt electrode rods are inserted into the electrolytic cell and connected with an external power supply. The composite hydrogel prepared above was cut into a strip having a length of 30.0mm by 3.0mm in width by 1.0mm in thickness, which was kept at a distance of 50mm between electrodes, and placed in an electrolytic cell after being dyed with methylene blue, and the bending angle of the hydrogel was measured by energization at a controlled voltage of 6v to 15 v. The experiment proves that: the composite hydrogel has the elongation at break of 380-830 percent, the breaking strength of 0.5-2 MPa and the driving angle of-70-80 degrees within 200 s. The stress at break and Young's modulus of the hydrogel increase with the zirconium hydroxide content, and the elongation at break decreases with the zirconium hydroxide content. Assembling the hydrogel driver in an electrolytic cell, testing the driving angle of the hydrogel driver at different times under the electrified condition, and gradually increasing the driving angle of the hydrogel driver along with the increase of time.
The invention discloses a high-strength zirconium hydroxide nano composite hydrogel, a preparation method thereof and application of the hydrogel as an electric driver. The composite hydrogel is prepared by an in-situ free radical polymerization method, has extremely high mechanical strength of 2MPa and Young modulus of 1MPa, and can quickly respond to an electric signal in an electrolyte solution. The hydrogel driver constructed by the composite hydrogel widens the application range of the electric driver, ensures that the mechanical strength of the electric driver meets the strength requirement of artificial muscles, can be used for constructing a bionic soft robot, and indicates that the composite hydrogel has wide application prospects in the fields of bionic artificial muscles and microfluidic valves as the electric driver.
Drawings
FIG. 1 is a scanning electron micrograph of the nanocomposite hydrogels prepared at different zirconium hydroxide concentrations ((a)5 wt%, (b)10 wt%, (c)15 wt%).
FIG. 2 is a bar graph (d) showing tensile (a), compressive stress-strain curves (b) and corresponding energy at break (c) and Young's modulus of nanocomposite hydrogels prepared at different zirconium hydroxide concentrations (5 wt%, 10 wt%, 15 wt%).
FIG. 3 is a graph of the change of the cycling driving angle of the zirconium hydroxide nanocomposite hydrogel with time.
Detailed Description
The present invention will be described in detail with reference to the following detailed drawings and examples. The following examples are only preferred embodiments of the present invention, and it should be noted that the following descriptions are only for explaining the present invention and not for limiting the present invention in any form, and any simple modifications, equivalent changes and modifications made to the embodiments according to the technical spirit of the present invention are within the scope of the technical solution of the present invention.
In the following examples, materials, reagents and the like used were obtained commercially unless otherwise specified.
Example 1:
① pouring 15 wt% zirconium acetate into a container, placing in an oil bath pan at 50 deg.C, adding 15 wt% ammonia water, aging at 70 deg.C for 10h after pH reaches 3, centrifuging, washing with deionized water to remove excessive ammonium ions, and dissolving with water to obtain 10 wt% zirconium hydroxide nanosol;
②, adding 3-4 g deionized water into 6g of the zirconium hydroxide nano sol prepared in the step ① for dilution, adding an acrylic acid monomer and an N, N-dimethylacrylamide monomer according to the monomer molar ratio of 3:7, keeping the molar concentration sum of the two monomers at 2mol/L, and controlling the volume of the solution at 10 ml;
③ adding 0.5mL of 2 wt% potassium persulfate solution and 0.8 μ L of tetramethylethylenediamine as catalyst into the solution prepared just in step ② in sequence to make the volume of the reaction constant to 10mL, stirring uniformly, injecting the solution into a glass container, sealing, and carrying out in-situ free radical polymerization at 40 ℃ to obtain the zirconium hydroxide nano-composite hydrogel.
The zirconium hydroxide nanocomposite hydrogel sample prepared in the examples was freeze-dried, and then adhered to an electron microscope stage, and the pore size of the composite hydrogel was 0.05 μm to 0.4 μm as measured and analyzed by a JSM-7401F type scanning electron microscope manufactured by JEOL corporation, japan.
The zirconium hydroxide nanocomposite hydrogel samples obtained in the examples were tested and analyzed by an AGS-J universal tester manufactured by Shimadzu corporation of Japan, and the composite hydrogel had an elongation at break of 380% to 830% and a strength at break of 0.5MPa to 2 MPa.
Preparing 0.1mol/L NaSO4The solution is placed in an electrolytic cell, and two Pt electrode rods are inserted into the electrolytic cell and connected with an external power supply. The distance between the electrodes was kept at 50mm, and the zirconium hydroxide nanocomposite hydrogel obtained in the example was cut into a strip having a length of 30.0mm by 3.0mm in width by 1.0mm in thickness, which was dyed with methylene blue and placed in an electrolytic cell, and the bending angle of the hydrogel was measured by energization at a controlled voltage of 6 v. The driving angle of the composite hydrogel is changed within the range of-70 degrees to 80 degrees within 200 s. And (4) conclusion: assembling the hydrogel driver in an electrolytic cell, testing the driving angle of the hydrogel driver at different times under the electrified condition, and gradually increasing the driving angle of the hydrogel driver along with the increase of time. The composite hydrogel disclosed by the invention has a wide application prospect in the fields of bionic artificial muscles and microfluidic valves as an electric driver.
Example 2:
① pouring 15 wt% zirconium acetate into a container, placing in an oil bath pan at 60 deg.C, adding 15 wt% ammonia water, aging at 60 deg.C for 15h after pH reaches 4, centrifuging, washing with deionized water to remove excessive ammonium ions, and dissolving with water to obtain 5 wt% zirconium hydroxide nanosol;
②, taking 8g of the zirconium hydroxide nano sol prepared in the step ①, adding 1-2 g of deionized water for dilution, adding an acrylic acid monomer and an N, N-dimethylacrylamide monomer according to the monomer molar ratio of 1:9, keeping the molar concentration sum of the two monomers at 3mol/L, and simultaneously controlling the volume of the solution to be 10 ml;
③ adding 0.5mL of 2 wt% potassium persulfate solution and 0.5 μ L of tetramethylethylenediamine as catalyst into the solution prepared in step ② in sequence to a constant volume of 10mL, stirring uniformly, injecting the solution into a glass container, sealing, and carrying out in-situ free radical polymerization at 60 ℃ to obtain the zirconium hydroxide nanocomposite hydrogel.
Example 3:
① pouring 15 wt% zirconium acetate into a container, placing in an oil bath pan at 70 deg.C, adding 15 wt% ammonia water, aging at 70 deg.C for 10h after pH reaches 5, centrifuging, washing with deionized water to remove excessive ammonium ions to obtain 15 wt% zirconium hydroxide nanosol;
②, taking 2g of the zirconium hydroxide nano sol prepared in the step ①, adding 7-8 g of deionized water for dilution, adding an acrylic acid monomer and an N, N-dimethylacrylamide monomer according to the monomer molar ratio of 5:5, keeping the molar concentration sum of the two monomers at 1mol/L, and simultaneously controlling the volume of the solution to be 10 ml;
③ adding 0.5mL of 2 wt% potassium persulfate solution and 0.3 μ L of tetramethylethylenediamine as catalyst into the solution prepared in step ② in sequence to a constant volume of 10mL, stirring uniformly, injecting the solution into a glass container, sealing, and carrying out in-situ free radical polymerization at 70 ℃ to obtain the zirconium hydroxide nanocomposite hydrogel.
The zirconium hydroxide nanocomposite hydrogel samples prepared in the above examples were freeze-dried, and then adhered to an electron microscope stage, and test analysis was performed using a JSM-7401F scanning electron microscope manufactured by JEOL corporation, and the microstructure of hydrogels with different zirconium hydroxide contents is shown in fig. 1. The pore diameter of the network structure is reduced along with the increase of the content of zirconium hydroxide, and the pore wall is thickened.
The zirconium hydroxide nanocomposite hydrogel samples obtained in the above examples were tested and analyzed by an AGS-J universal tester manufactured by Shimadzu corporation, and the results of the tensile stress-strain curves at different zirconium hydroxide contents are shown in FIG. 2. The stress at break and Young's modulus of the hydrogel increase with the zirconium hydroxide content, and the elongation at break decreases with the zirconium hydroxide content.
Preparing 0.1mol/L NaSO4The solution is placed in an electrolytic cell, and two Pt electrode rods are inserted into the electrolytic cell and connected with an external power supply. The distance between the electrodes was kept at 50mm, and the zirconium hydroxide nanocomposite hydrogel obtained in the example was cut into a strip having a length of 30.0mm by 3.0mm in width by 1.0mm in thickness, which was dyed with methylene blue and placed in an electrolytic cell, and the bending angle of the hydrogel was measured by energization at a controlled voltage of 6 v. The driving angle of the composite hydrogel prepared in the above example was varied within a range of-70 to 80 degrees within 200 seconds. And (4) conclusion: assembling the hydrogel driver in an electrolytic cell, testing the driving angle of the hydrogel driver at different times under the electrified condition, and gradually increasing the driving angle of the hydrogel driver along with the increase of time. The composite hydrogel disclosed by the invention has a wide application prospect in the fields of bionic artificial muscles and microfluidic valves as an electric driver.
Example 4:
① pouring 15 wt% zirconium acetate into a container, placing in an oil bath pan at 60 deg.C, adding 15 wt% ammonia water, aging at 60 deg.C for 15h after pH reaches 4, centrifuging, washing with deionized water to remove excessive ammonium ions, and dissolving with water to obtain 5 wt% zirconium hydroxide nanosol;
②, taking 4g of the zirconium hydroxide nano sol prepared in the step ①, adding 5-6 g of deionized water for dilution, adding a methyl acrylate monomer and an acrylamide monomer according to the monomer molar ratio of 2:5, keeping the molar concentration sum of the two monomers at 3mol/L, and simultaneously controlling the volume of the solution to be 10 ml;
③ adding 0.5mL of 2 wt% potassium persulfate solution and 0.7 μ L of tetramethylethylenediamine as catalyst into the solution prepared in step ② in sequence to a constant volume of 10mL, stirring uniformly, injecting the solution into a glass container, sealing, and carrying out in-situ free radical polymerization at 45 ℃ to obtain the zirconium hydroxide nanocomposite hydrogel.
Example 5:
① pouring 15 wt% zirconium acetate into a container, placing in an oil bath pan at 65 ℃, adding 15 wt% ammonia water, aging at 65 ℃ for 17h after the pH value reaches 3.5, centrifuging, washing with deionized water to remove redundant ammonium ions, and dissolving with water to obtain 12 wt% zirconium hydroxide nanosol;
②, taking 7g of the zirconium hydroxide nano sol prepared in the step ①, adding 2-3 g of deionized water for dilution, adding an isobutyl acrylate monomer and an N, N-dimethylacrylamide monomer according to the monomer molar ratio of 4:8, keeping the molar concentration sum of the two monomers at 2mol/L, and simultaneously controlling the volume of the solution to be 10 ml;
③ adding 0.5mL of 2 wt% potassium persulfate solution and 0.4 μ L of tetramethylethylenediamine as catalyst into the solution prepared in step ② in sequence to a constant volume of 10mL, stirring uniformly, injecting the solution into a glass container, sealing, and carrying out in-situ free radical polymerization at 65 ℃ to obtain the zirconium hydroxide nanocomposite hydrogel.
Claims (9)
1. A high-strength zirconium hydroxide nano-composite hydrogel is characterized in that: the composite hydrogel is composed of zirconium hydroxide nano sol, acrylic monomers, acrylamide monomers and the balance of water, and comprises the following components in percentage by weight: based on 10ml of composite hydrogel, the zirconium hydroxide nano sol accounts for 1-15 wt%, the sum of the concentrations of acrylic monomers and acrylamide monomers with the molar ratio of 1: 9-5: 5 is 1-3 mol/L, and the balance is water; the aperture size of the composite hydrogel is 0.05-0.4 μm, the elongation at break is 380-830%, the breaking strength is 0.5-2 MPa, and the driving angle is changed in the range of-70-80 degrees within 200 s.
2. The high strength zirconium hydroxide nanocomposite hydrogel according to claim 1, characterized in that: the composite hydrogel is composed of zirconium hydroxide nano sol, acrylic monomers, acrylamide monomers and the balance of water, and comprises the following components in percentage by weight: based on 10ml of composite hydrogel, the zirconium hydroxide nano sol accounts for 5-15 wt%, the sum of the concentrations of acrylic monomers and acrylamide monomers with the molar ratio of 1: 7-5: 5 is 1-2 mol/L, and the balance is water; the aperture size of the composite hydrogel is 0.07-0.3 mu m, the elongation at break is 380-430%, the breaking strength is 1.5-2 MPa, and the driving angle is changed in the range of-66-74 degrees within 200 s.
3. The high strength zirconium hydroxide nanocomposite hydrogel according to claim 2, wherein: the composite hydrogel is composed of zirconium hydroxide nano sol, acrylic monomers, acrylamide monomers and the balance of water, and comprises the following components in percentage by weight: based on 10ml of composite hydrogel, the zirconium hydroxide nano sol accounts for 10 wt%, the total concentration of acrylic monomers and acrylamide monomers with the molar ratio of 3:7 is 2mol/L, and the balance is water; the aperture size of the composite hydrogel is 0.07-0.2 mu m, the elongation at break is 380-400%, the breaking strength is 1.7-1.9 MPa, and the driving angle is changed within the range of-60-70 degrees within 200 s.
4. The high strength zirconium hydroxide nanocomposite hydrogel according to claim 1, 2 or 3, characterized in that: the acrylic monomer is one of acrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, isobutyl acrylate, hexyl acrylate, isooctyl acrylate, lauryl acrylate, benzyl acrylate, cyclohexyl acrylate, perfluoroalkyl acrylate, hydroxyethyl phosphate acrylate, isobornyl acrylate and tetrahydrofuran methyl acrylate; the acrylamide monomer is one of N, N-dimethylacrylamide and acrylamide.
5. The high strength zirconium hydroxide nanocomposite hydrogel according to claim 4, wherein: the acrylic monomer is acrylic acid; the acrylamide monomer is N, N-dimethylacrylamide.
6. The method for preparing the high-strength zirconium hydroxide nanocomposite hydrogel according to claim 1, comprising the steps of:
①, pouring 15 wt% of zirconium acetate into a container, placing the container in an oil bath pan at 50-70 ℃, adding 15 wt% of ammonia water, aging the container for 10-20 h at 50-70 ℃ after the pH value reaches 3-5, centrifuging the container, and washing the container with deionized water to remove redundant ammonium ions to obtain 1-15 wt% of zirconium hydroxide nano sol;
②, taking 1-9 g of the zirconium hydroxide nano sol prepared in the step ①, adding 1-9 g of deionized water for dilution, adding an acrylic monomer and an acrylamide monomer according to the monomer molar ratio of 1: 9-5: 5, keeping the molar concentration sum of the two monomers at 1-3 mol/L, and controlling the volume of the solution at 10 ml;
③ adding 0.5mL of 2 wt% potassium persulfate solution and 0.2-0.8 μ L of catalyst tetramethylethylenediamine into the solution prepared in the step ② in sequence to ensure that the volume of the reaction volume is constant to 10mL, stirring uniformly, injecting the solution into a glass container for sealing, and carrying out in-situ free radical polymerization reaction at 40-70 ℃ to generate the zirconium hydroxide nano-composite hydrogel.
7. The preparation method of the high-strength zirconium hydroxide nanocomposite hydrogel according to claim 6, wherein 4-5 g of deionized water is added to dilute 4-6 g of the zirconium hydroxide nanocomposite sol prepared in step ①, an acrylic monomer and an acrylamide monomer are added according to a monomer molar ratio of 1: 7-5: 5, the molar concentration sum of the two monomers is kept at 1-2 mol/L, the volume of the solution is controlled to be 10mL, 0.5mL of 2 wt% potassium persulfate solution and 0.5-0.8 μ L of catalyst tetramethylethylenediamine are sequentially added to the just-prepared solution, the volume of the reaction is kept at 10mL, the solution is uniformly stirred, the solution is injected into a glass container and sealed, and the in-situ radical polymerization reaction is carried out at 40-55 ℃ to obtain the zirconium hydroxide nanocomposite hydrogel.
8. The preparation method of the high-strength zirconium hydroxide nanocomposite hydrogel according to claim 7, wherein 5g of the zirconium hydroxide nanocomposite hydrogel prepared in step ① is diluted by adding 4-5 g of deionized water, an acrylic monomer and an acrylamide monomer are added according to a monomer molar ratio of 3:7, the molar concentration sum of the two monomers is kept at 2mol/L, the volume of the solution is controlled at 10mL, 0.5mL of a 2 wt% potassium persulfate solution and 0.8 μ L of a catalyst tetramethylethylenediamine are sequentially added into the just-prepared solution, the volume of the reaction is kept at 10mL, the solution is uniformly stirred, the solution is injected into a glass container for sealing, and in-situ radical polymerization is performed at 40-45 ℃ to obtain the zirconium hydroxide nanocomposite hydrogel.
9. Use of the high strength zirconium hydroxide nanocomposite hydrogel of claim 1, 2 or 3 in the manufacture of a hydrogel electrical actuator.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010041351.2A CN111253514A (en) | 2020-01-15 | 2020-01-15 | High-strength zirconium hydroxide nano composite hydrogel, preparation thereof and application thereof as electric driver |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010041351.2A CN111253514A (en) | 2020-01-15 | 2020-01-15 | High-strength zirconium hydroxide nano composite hydrogel, preparation thereof and application thereof as electric driver |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111253514A true CN111253514A (en) | 2020-06-09 |
Family
ID=70923585
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010041351.2A Pending CN111253514A (en) | 2020-01-15 | 2020-01-15 | High-strength zirconium hydroxide nano composite hydrogel, preparation thereof and application thereof as electric driver |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111253514A (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106863335A (en) * | 2017-03-06 | 2017-06-20 | 青岛大学 | Double finger grabbers of a kind of ionic copolymer inorganic compounding electric drive and preparation method thereof |
| CN107141407A (en) * | 2017-05-25 | 2017-09-08 | 华南理工大学 | It is a kind of can spontaneous driving polyampholyte hydrogel driver and preparation method thereof and type of drive |
| CN107236085A (en) * | 2017-06-26 | 2017-10-10 | 北京理工大学 | A kind of method that large area quickly prepares stretching discoloration photon crystal water gel duplicature |
| CN108659236A (en) * | 2018-05-22 | 2018-10-16 | 吉林大学 | A kind of preparation method of the light-operated intelligent aqueous gel driver of high intensity |
| CN109021166A (en) * | 2018-07-03 | 2018-12-18 | 北京理工大学 | A kind of method that simple and fast prepares high adhesive attraction power hydrogel duplicature |
-
2020
- 2020-01-15 CN CN202010041351.2A patent/CN111253514A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106863335A (en) * | 2017-03-06 | 2017-06-20 | 青岛大学 | Double finger grabbers of a kind of ionic copolymer inorganic compounding electric drive and preparation method thereof |
| CN107141407A (en) * | 2017-05-25 | 2017-09-08 | 华南理工大学 | It is a kind of can spontaneous driving polyampholyte hydrogel driver and preparation method thereof and type of drive |
| CN107236085A (en) * | 2017-06-26 | 2017-10-10 | 北京理工大学 | A kind of method that large area quickly prepares stretching discoloration photon crystal water gel duplicature |
| CN108659236A (en) * | 2018-05-22 | 2018-10-16 | 吉林大学 | A kind of preparation method of the light-operated intelligent aqueous gel driver of high intensity |
| CN109021166A (en) * | 2018-07-03 | 2018-12-18 | 北京理工大学 | A kind of method that simple and fast prepares high adhesive attraction power hydrogel duplicature |
Non-Patent Citations (2)
| Title |
|---|
| JIANG, HAOYANG等: "Tough and electro-responsive hydrogel actuators with bidirectional bending behavior", 《NANOSCALE》 * |
| 王牧群: "氢氧化锆纳米粒子交联的高强度水凝胶的研究", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108707252B (en) | Nano composite ionic liquid gel material, preparation thereof and strain sensor based on material | |
| CN107840970B (en) | Double-layer hydrogel for promoting interface combination by adopting non-covalent effect and preparation method thereof | |
| CN106008799A (en) | Preparation method of hydrogel electrode with high mechanical property and self-healing property | |
| CN110698697B (en) | Preparation method of polyethyleneimine-polyvinyl alcohol hydrogel with self-healing performance | |
| CN107840926B (en) | A kind of preparation method of the high-intensitive poly(N-isopropylacrylamide) hydrogel of quick response | |
| CN104448158B (en) | A kind of preparation method of lithium battery aqueous binder | |
| CN110372885B (en) | Chitosan/zwitterion and acrylic acid copolymer double-network self-healing hydrogel and preparation method thereof | |
| CN108192020B (en) | Preparation method of intelligent zwitterionic polymer material | |
| CN102167837B (en) | Method for preparing ionic polymer-metal smart electric driving composite material | |
| CN103196965A (en) | Method for preparing carbon nanotube composite conductive hydrogel coating modified electrode | |
| CN110551297A (en) | preparation method and application of gradient hydrogel soft driver | |
| CN105175970B (en) | The preparation and application of high-strength tear-resistant magnetic hydrogel | |
| CN108300451A (en) | A kind of nano material complex intensifying gelled fracturing fluid and preparation method thereof | |
| CN103304730A (en) | CO2/N2 type switch-type stiffening water-soluble polymer and synthetic method thereof | |
| CN112322268B (en) | Stretchable slow-expansion acrylic resin and preparation process and application thereof | |
| JP2008163055A (en) | High-strength gel and method for producing the gel | |
| CN109942745A (en) | A kind of preparation method of double cross-linked hydrogels | |
| CN103575781A (en) | Electrochemical sensor and its preparation method | |
| CN109705366A (en) | It is a kind of with intensive shear is thinning and the preparation method of shear-thickening behavior gel | |
| CN111253514A (en) | High-strength zirconium hydroxide nano composite hydrogel, preparation thereof and application thereof as electric driver | |
| EP1162676A4 (en) | Gelating agent for alkaline cell and alkaline cell | |
| CN105330885A (en) | Piezoelectric gel and preparation method and application thereof | |
| CN110642335B (en) | Method for recovering and adsorbing tungstate radicals in scheelite beneficiation wastewater | |
| CN109289560B (en) | Preparation method of electromagnetic field regulation and control self-healing separation membrane | |
| EP1483572A2 (en) | Device for measuring and regulating the ph-value of a medium |
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 | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20200609 |
|
| WD01 | Invention patent application deemed withdrawn after publication |