CN108017784B - Hybrid conductive hydrogel and preparation method and application thereof - Google Patents
Hybrid conductive hydrogel and preparation method and application thereof Download PDFInfo
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- CN108017784B CN108017784B CN201711315958.XA CN201711315958A CN108017784B CN 108017784 B CN108017784 B CN 108017784B CN 201711315958 A CN201711315958 A CN 201711315958A CN 108017784 B CN108017784 B CN 108017784B
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- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- FHFKRZADODCCPL-UHFFFAOYSA-N 3-amino-n-carbamoylbenzamide Chemical compound NC(=O)NC(=O)C1=CC=CC(N)=C1 FHFKRZADODCCPL-UHFFFAOYSA-N 0.000 claims abstract description 49
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims abstract description 49
- 239000000178 monomer Substances 0.000 claims abstract description 49
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 claims abstract description 44
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 29
- 229920001467 poly(styrenesulfonates) Polymers 0.000 claims abstract description 22
- 229940006186 sodium polystyrene sulfonate Drugs 0.000 claims abstract description 22
- MNCGMVDMOKPCSQ-UHFFFAOYSA-M sodium;2-phenylethenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C=CC1=CC=CC=C1 MNCGMVDMOKPCSQ-UHFFFAOYSA-M 0.000 claims abstract description 21
- 239000003999 initiator Substances 0.000 claims abstract description 15
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- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 10
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- LXEKPEMOWBOYRF-UHFFFAOYSA-N [2-[(1-azaniumyl-1-imino-2-methylpropan-2-yl)diazenyl]-2-methylpropanimidoyl]azanium;dichloride Chemical compound Cl.Cl.NC(=N)C(C)(C)N=NC(C)(C)C(N)=N LXEKPEMOWBOYRF-UHFFFAOYSA-N 0.000 description 12
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- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
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- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/02—Polyamines
- C08G73/026—Wholly aromatic polyamines
- C08G73/0266—Polyanilines or 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
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by heteroatoms or groups containing heteroatoms
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/48—Conductive polymers
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
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Abstract
The invention discloses a hybrid conductive hydrogel and a preparation method and application thereof. The preparation method of the hybrid conductive hydrogel comprises the following steps: in a protective atmosphere, carrying out polymerization reaction on ethyl methacrylate m-aminobenzoyl urea and a sodium styrene sulfonate monomer in a solvent under the action of an initiator; and dissolving the sodium polystyrene sulfonate in an olefine acid solution, and adding an aniline monomer and an oxidant to carry out polymerization reaction. According to the preparation method of the hybrid conductive hydrogel, the sodium polystyrene sulfonate main chain is grafted with ethyl methacrylate m-aminobenzoyl urea as a side chain, and then m-benzamide functional groups contained in the ethyl methacrylate m-aminobenzoyl urea are polymerized into polyaniline molecular chains, so that the sodium polystyrene sulfonate/polyaniline hybrid conductive hydrogel is formed in situ, and the hybrid hydrogel is endowed with good mechanical properties and excellent electrochemical properties.
Description
Technical Field
The invention belongs to the field of conductive hydrogel, and particularly relates to hybrid conductive hydrogel and a preparation method and application thereof.
Background
The polymer hydrogel is a soft matter material formed by a three-dimensional network structure formed by crosslinking water-soluble polymers in an aqueous medium through covalent bonds or physical interaction and simultaneously encapsulating water molecules in the network structure. Generally, hydrogels contain more than sixty percent water based on the total weight of the material. The hydrogel has good mechanical property, excellent biocompatibility and tissue-like structure, and flexibility which is not possessed by traditional materials such as metal, ceramic and the like, so the hydrogel has wide application in the aspects of tissue engineering, drug controlled release, flexible sensors, flexible robots, intelligent response materials and the like. Although polymer hydrogel has excellent flexibility, it is an electrically insulating material, and its own electrical conductivity is very low, which limits its applications, such as making supercapacitors difficult to meet.
The super capacitor as a novel energy storage device attracts more and more researchers' extensive attention in China and abroad due to the extremely high power density, excellent rate capability and continuously improved energy density, and is expected to become one of the storage devices of the next generation of clean energy. There are two types of capacitors, an electric double layer capacitor and a pseudo capacitor, depending on whether or not there is an oxidation-reduction reaction occurring during charge and discharge. Compared with the traditional double-capacitor, the introduction of the oxidation-reduction reaction in the charging and discharging process can enable the capacitor to store and release more charges, so that the specific capacity is greatly improved. In addition, electric charges are generally stored on the surface of the electrode active material of the supercapacitor, so that the increase of the specific surface area of the electrode active material is also beneficial to the increase of the energy density of the supercapacitor. As an electrode material of a super capacitor, the electrode material not only needs to have a high specific surface area, but also needs to have good conductivity so as to effectively transport charges. In recent years, many researchers use carbon materials and conductive polymers to prepare electrode materials of super capacitors, and achieve excellent electrochemical performance. Dong and the like firstly use carbon nanotubes and conductive polyaniline to prepare a fiber electrode material with a multi-stage structure, and apply the fiber electrode material to the preparation of a super capacitor, and the result shows that the prepared super capacitor has good electrochemical performance and flexibility. Wang et al prepared polypyrrole-based supercapacitors by doping and crosslinking polypyrrole with an organic sulfonate coordinated with copper ions. In addition, in order to increase the specific surface area of the electrode material of the supercapacitor, two-dimensional materials such as graphene and molybdenum disulfide are also used for preparing the electrode material. Although the research on the supercapacitor based on the carbon material and the conductive polymer has achieved remarkable results, the brittleness of the carbon material and the conductive polymer is that the prepared supercapacitor is difficult to have the properties of flexibility, stretchability and the like, and the application of the supercapacitor in wearable equipment is greatly limited. In addition, the brittleness of the traditional materials can also cause the phenomenon that the active materials fall off from the surface of the current collector in the process of multiple charge-discharge cycles of the prepared super capacitor, so that the cycle performance of the super capacitor is reduced. Therefore, how to prepare a material with good mechanical properties such as flexibility and electrical conductivity is a technical problem which is always attempted to be solved in the field.
Disclosure of Invention
The invention aims to overcome the defects in the prior art, and provides a hybrid conductive hydrogel and a preparation method thereof, so as to solve the technical problem that the mechanical properties of the conventional conductive carbon material and polymer-based conductive material are not ideal.
In order to achieve the above objects, in one aspect of the present invention, a method for preparing a hybrid conductive hydrogel is provided. The preparation method of the hybrid conductive hydrogel comprises the following steps:
in a protective atmosphere, carrying out polymerization reaction on ethyl methacrylate m-aminobenzoyl urea and a sodium styrene sulfonate monomer in a solvent under the action of an initiator, and carrying out post-purification treatment to obtain sodium polystyrene sulfonate grafted with ethyl methacrylate m-aminobenzoyl urea;
and dissolving the sodium polystyrene sulfonate in an olefine acid solution, adding an aniline monomer and an oxidant to carry out polymerization reaction, and generating the polyaniline/sodium polystyrene sulfonate-based hybrid conductive hydrogel.
In another aspect of the invention, a hybrid conductive hydrogel is provided. The general molecular structure formula of the hybrid conductive hydrogel is as follows:
wherein m is 1-100, n is 100-
Is a repeating unit of aniline.
In yet another aspect of the invention, methods of using the hybrid conductive hydrogels are provided. Application of hybrid conductive hydrogel in super capacitor and super capacitor
Compared with the prior art, the preparation method of the hybrid conductive hydrogel comprises the steps of grafting ethyl methacrylate m-aminobenzoyl urea on a main chain of sodium polystyrene sulfonate to serve as a side chain, and then polymerizing m-aniline functional groups contained in the ethyl methacrylate m-aminobenzoyl urea into a polyaniline molecular chain, so that the sodium polystyrene sulfonate/polyaniline hybrid conductive hydrogel is formed in situ, and the hybrid hydrogel is endowed with good mechanical properties and excellent electrochemical properties. In addition, the preparation method has easily controlled process conditions, and the prepared hybrid hydrogel has stable performance and high yield. Meanwhile, the raw materials are cheap and easy to obtain, the preparation conditions are mild, the equipment requirements are low, the large-scale production is easy, and the production cost is reduced.
The hybrid conductive hydrogel has good mechanical property, excellent electrochemical property and low cost. Thus, the range of applications thereof is expanded, which improves the stability and flexibility characteristics of the respective applied products.
Drawings
FIG. 1 is an impedance diagram of a hybrid conductive hydrogel provided in example 1 of the present invention;
FIG. 2 is a cyclic voltammogram of the hybrid conductive hydrogel provided in example 1 of the present invention.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects to be solved by the present invention more clearly apparent, the present invention is further described in detail below with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The mass of each component mentioned in the description of the embodiment of the present invention may not only refer to the specific content of each component, but also represent the proportional relationship of the mass between each component, and therefore, it is within the scope of the disclosure of the description of the embodiment of the present invention to scale up or down the content of each component according to the description of the embodiment of the present invention. Specifically, the mass described in the description of the embodiments of the present invention may be a mass unit known in the chemical industry field, such as μ g, mg, g, and kg. The above-mentioned
On one hand, the embodiment of the invention provides hybrid conductive hydrogel with good mechanical property and electrochemical property. The structural general formula of the hybrid conductive hydrogel is as follows:
wherein m is 1-100, n is 100-
Is a repeating unit of aniline. Therefore, the hybrid conductive hydrogel comprises the repeating unit of the sodium styrene sulfonate and the repeating unit of the aniline, and the repeating unit of the sodium styrene sulfonate and the repeating unit of the aniline are crosslinked through covalent bonds, so that the hybrid conductive hydrogel has good mechanical properties and conductive performance. In one embodiment, the number of repeating units of aniline is the same as n and m, e.g., 100-.
On the other hand, on the basis of the hybrid conductive hydrogel shown in the general molecular structural formula, the embodiment of the invention also provides a preparation method of the hybrid conductive hydrogel. The preparation method of the hybrid conductive hydrogel comprises the following steps:
s01: in a protective atmosphere, carrying out polymerization reaction on ethyl methacrylate m-aminobenzoyl urea and a sodium styrene sulfonate monomer in a solvent under the action of an initiator, and carrying out post-purification treatment to obtain sodium polystyrene sulfonate grafted with ethyl methacrylate m-aminobenzoyl urea;
s02: and dissolving the sodium polystyrene sulfonate in an olefine acid solution, adding an aniline monomer and an oxidant to carry out polymerization reaction, and generating the polyaniline/sodium polystyrene sulfonate-based hybrid conductive hydrogel.
Specifically, in the polymerization reaction process of the ethyl methacrylate m-aminobenzoyl urea and the sodium styrene sulfonate monomer in the step S01, the sodium styrene sulfonate monomer and the ethyl methacrylate m-aminobenzoyl urea generate a poly (sodium styrene sulfonate-ethyl methacrylate m-aminobenzoyl urea) copolymer through a radical copolymerization reaction, and the copolymer is marked as PSSNa/CA. Since ethyl methacrylate m-aminobenzoyl urea carries m-aniline functions, the side chains of the resulting polymer PSSNa/CA also carry m-aniline functions which undergo redox copolymerization with aniline.
In the polymerization reaction system in the step S01, the mass ratio of the ethyl methacrylate m-aminobenzoyl urea to the sodium styrene sulfonate monomer is preferably controlled to be (0.00001-0.01): 1, the total mass concentration of the ethyl methacrylate m-aminobenzoyl urea and the sodium styrene sulfonate monomer in the solvent is 4-30%, and the ratio of the mass (or other units such as mol) of the initiator to the mass (or other units such as mol) of the sodium styrene sulfonate monomer is preferably (0.001-0.010): 1. in a particular embodiment, the initiator comprises at least one of azobisisobutyramidine hydrochloride, ammonium persulfate. The reaction solvent may be at least one of water, dimethylformamide, and dimethylsulfoxide.
By controlling the polymerization reaction system, a certain amount of ethyl methacrylate m-aminobenzoyl urea side chain is grafted on the sodium polystyrene sulfonate, and the efficiency of polymerization reaction is improved, so that the yield of the product is improved.
The polymerization temperature in the step S01 is 20 to 70 ℃ based on the polymerization system, and the polymerization reaction should be sufficient under the reaction temperature condition. The protective atmosphere may be, but not limited to, a nitrogen atmosphere, an atmosphere of other inert gases, and a vacuum atmosphere.
After the polymerization reaction in step S01 is finished, the method further includes a step of purifying the product PSSNa/CA, in an embodiment, water-soluble impurities in the PSSNa/CA solution are removed by a dialysis method, and the polymer PSSNa/CA powder is obtained by freeze-drying.
In addition, the ethyl methacrylate m-aminobenzoyl urea in the step S01 can be prepared according to the following method:
and carrying out condensation reaction on m-aminobenzylamine and isocyano ethyl methacrylate to generate the ethyl methacrylate m-aminobenzoyl urea. The condensation chemical reaction formula is as follows:
in the condensation reaction, the temperature of the condensation reaction is preferably 0-40 ℃, and the reaction time is preferably 1-8 hours; the molar weight of the m-aminobenzylamine is preferably 1.0 to 3.0 times that of the isocyanoethyl methacrylate. The solvent of the condensation reaction system comprises at least one of dichloromethane, chloroform and dimethylformamide. By controlling and optimizing the polymerization reaction conditions, the yield of the product is improved, and the polymerization reaction efficiency is improved.
After the polymerization reaction, the method also comprises the step of purifying the ethyl methacrylate m-aminobenzene formyl urea product. The purification treatment method is, but not limited to, the following:
adding a precipitator into the reaction liquid in which the ethyl methacrylate m-aminobenzoyl urea is generated for precipitation and washing. Wherein the precipitant comprises at least one of n-hexane, diethyl ether and petroleum ether. The volume of the precipitant is 7-11 times of the total volume of the reaction liquid in which the ethyl methacrylate m-aminobenzoyl urea is generated. The ethyl methacrylate meta-aminobenzoyl urea product after precipitation is washed to remove impurities such as reaction solvent and reactant for reaction sufficiently. Specifically, the precipitant is used for washing a plurality of times, such as at least 3 times, and then dried, such as vacuum drying treatment.
In the polymerization reaction in the step S02, aniline monomer is subjected to redox polymerization under the action of an initiator to generate polyaniline, and at the same time, the m-aniline monomer functional group contained in the sodium polystyrene sulfonate grafted with ethyl methacrylate m-aminobenzoyl urea prepared in the step S01 participates in the polymerization of the aniline monomer, so that the sodium polystyrene sulfonate/polyaniline hybrid conductive hydrogel is formed in situ. Wherein the polymerization reaction chemical formula in the step S02 is as follows:
in the polymerization reaction system in the step S02, the mass of the aniline monomer is preferably controlled to be 20 to 100% of the mass of the sodium polystyrene sulfonate (PSSNa/CA) which is a reaction product in the step S01. The polymerization temperature of the aniline is preferably 0-30 ℃, and the reaction time is preferably 1-6 hours. The amount of the oxidizing agent should be sufficient, such as a molar ratio of the aniline monomer to the oxidizing agent of 1: 1. Wherein the oxidant is at least one of ammonium persulfate and hydrogen peroxide.
By controlling the polymerization reaction system, aniline is subjected to full polymerization reaction, so that the efficiency of polymerization reaction is improved, and the yield of products is improved.
Therefore, the preparation method of the hybrid conductive hydrogel comprises the steps of grafting a side chain of ethyl methacrylate m-aminobenzoyl urea on a main chain of sodium polystyrene sulfonate, and then polymerizing m-benzamide functional groups contained in the ethyl methacrylate m-aminobenzoyl urea into a polyaniline molecular chain to form the sodium polystyrene sulfonate/polyaniline hybrid conductive hydrogel in situ. Therefore, the hybrid conductive hydrogel formed by crosslinking the multi-water-soluble sodium polystyrene sulfonate contained in the hybrid conductive hydrogel with the hydrophobic polyaniline through covalent bonds has good mechanical properties and conductivity. In addition, the preparation method has easily controlled process conditions, and the prepared hybrid hydrogel has stable performance and high yield. The raw materials are cheap and easy to obtain, the preparation conditions are mild, the cost and equipment requirements are low, the large-scale production is easy, and the production cost is reduced.
The hybrid conductive hydrogel has good mechanical property, excellent electrochemical property and low cost. Therefore, it can be effectively used for applications in sensors, flexible electrodes, supercapacitors. As in the specific embodiment, the hybrid conductive hydrogel is used as a flexible electrode material to prepare a flexible electrode, and further, the flexible electrode can be used to prepare a flexible supercapacitor. Thereby endowing the flexible electrode and the flexible super capacitor with excellent flexibility characteristics and high energy density.
The hybrid conductive hydrogel and the preparation method thereof according to the embodiment of the invention will now be described in further detail with reference to specific examples.
Example 1
This example provides a hybrid electrically conductive hydrogel and a method for making the same. The hybrid conductive hydrogel is prepared according to the following steps:
(1) dissolving 2.0g of m-aminophenylmethylamine in 20mL of dichloromethane to obtain a dichloromethane solution of m-aminophenylamine, adding 2.5g of isocyano ethyl methacrylate, stirring at 25 ℃ for reacting for 2h, adding the solution into 140mL of diethyl ether after the reaction is finished to precipitate the solution, carrying out vacuum filtration on the obtained precipitate product to obtain a white solid powder product, washing the product with a precipitator for three times, and carrying out vacuum drying to obtain a monomer ethyl methacrylate m-aminobenzoyl urea (CA);
(2) dissolving 0.01g of ethyl methacrylate m-aminobenzoyl urea monomer and 2.0g of sodium styrene sulfonate monomer in 10mL of distilled water, adding 5mg of water-soluble initiator azodiisobutyl amidine hydrochloride (V-50), replacing air in a reaction system by a method of circularly vacuumizing and introducing nitrogen for three times, heating to 40 ℃ and polymerizing for 12 hours to obtain a polymer PSSNa/CA solution; dialyzing the solution with dialysis bag with molecular weight cutoff of 3000 for three days, and freeze drying to obtain polymer PSSNa/CA powder;
(3) 0.1g of PSSNa/CA was dissolved in 1mL of a 1mol/L diluted hydrochloric acid solution, and 20mg of an aniline monomer was added to prepare a PSSNa/CA-aniline solution (solution A). The oxidant ammonium persulfate, 50mg, was dissolved in distilled 0.5mL of water as solution B. And adding the solution B into the solution A at 0 ℃, uniformly mixing, and reacting for 3h to obtain the hybrid conductive hydrogel.
The hybrid conductive hydrogel provided in this example 1 was subjected to impedance and cyclic voltammetry performance measurements, wherein the impedance performance test results are shown in fig. 1, and the cyclic voltammetry performance test results are shown in fig. 2. As can be seen from FIG. 1, the electrochemical impedance of the hydrogel is 3 ohms, the internal resistance is small, and the hydrogel has excellent conductivity; as can be seen from fig. 2, the hydrogel has good capacitance.
Example 2
This example provides a hybrid electrically conductive hydrogel and a method for making the same. The hybrid conductive hydrogel is prepared according to the following steps:
(1) dissolving 2.0g of m-aminophenylmethylamine in 25mL of dichloromethane to obtain a dichloromethane solution of m-aminophenylamine, adding 2.8g of isocyano ethyl methacrylate, stirring at 20 ℃ for reacting for 3h, adding the solution into 140mL of diethyl ether after the reaction is finished to precipitate the solution, carrying out vacuum filtration on the obtained precipitate product to obtain a white solid powder product, washing the product with a precipitator for three times, and carrying out vacuum drying to obtain a monomer ethyl methacrylate m-aminobenzoyl urea (CA);
(2) dissolving 0.01g of ethyl methacrylate m-aminobenzoyl urea monomer and 3.0g of sodium styrene sulfonate monomer in 15mL of distilled water, adding 5mg of water-soluble initiator azodiisobutyl amidine hydrochloride (V-50), replacing air in a reaction system by a method of circularly vacuumizing and introducing nitrogen for three times, heating to 40 ℃ and polymerizing for 12 hours to obtain a polymer PSSNa/CA solution; dialyzing the solution with dialysis bag with molecular weight cutoff of 3000 for three days, and freeze drying to obtain polymer PSSNa/CA powder;
(3) 0.1g of PSSNa/CA was dissolved in 0.9mL of a 0.5mol/L dilute hydrochloric acid solution, and 30mg of an aniline monomer was added to prepare a PSSNa/CA-aniline solution (solution A). 60mg of oxidant ammonium persulfate was dissolved in distilled 0.5mL of water as solution B. And adding the solution B into the solution A at 0 ℃, uniformly mixing, and reacting for 3h to obtain the hybrid conductive hydrogel.
The impedance and cyclic voltammetry performance of the hybrid conductive hydrogel provided in this example 2 were measured, and the test result shows that the electrochemical impedance of the hybrid conductive hydrogel in this example is 5 ohms and has good capacitance.
Example 3
This example provides a hybrid electrically conductive hydrogel and a method for making the same. The hybrid conductive hydrogel is prepared according to the following steps:
(1) dissolving 2.0g of m-aminophenylmethylamine in 30mL of dichloromethane to obtain a dichloromethane solution of m-aminophenylamine, adding 2.8g of isocyano ethyl methacrylate, stirring at 20 ℃ for reacting for 3h, adding the solution into 180mL of diethyl ether after the reaction is finished to precipitate the solution, carrying out vacuum filtration on the obtained precipitate product to obtain a white solid powder product, washing the product with a precipitator for three times, and carrying out vacuum drying to obtain a monomer ethyl methacrylate m-aminobenzoyl urea (CA);
(2) dissolving 0.01g of ethyl methacrylate m-aminobenzoyl urea monomer and 3.0g of sodium styrene sulfonate monomer in 15mL of distilled water, adding 5mg of water-soluble initiator azodiisobutyl amidine hydrochloride (V-50), replacing air in a reaction system by a method of circularly vacuumizing and introducing nitrogen for three times, heating to 45 ℃ and polymerizing for 12 hours to obtain a polymer PSSNa/CA solution; dialyzing the solution with dialysis bag with molecular weight cutoff of 3000 for three days, and freeze drying to obtain polymer PSSNa/CA powder;
(3) 0.1g of PSSNa/CA was dissolved in 0.9mL of a 0.5mol/L dilute hydrochloric acid solution, and 30mg of an aniline monomer was added to prepare a PSSNa/CA-aniline solution (solution A). 60mg of oxidant ammonium persulfate was dissolved in distilled 0.5mL of water as solution B. And adding the solution B into the solution A at 4 ℃, uniformly mixing, and reacting for 3 hours to obtain the hybrid conductive hydrogel.
The impedance and cyclic voltammetry performance of the hybrid conductive hydrogel provided in this example 3 were measured, and the test result shows that the electrochemical impedance of the hybrid conductive hydrogel in this example is 7 ohms and has good capacitance.
Example 4
This example provides a hybrid electrically conductive hydrogel and a method for making the same. The hybrid conductive hydrogel is prepared according to the following steps:
(1) dissolving 2.0g of m-aminophenylmethylamine in 40mL of dichloromethane to obtain a dichloromethane solution of m-aminophenylamine, adding 2.8g of isocyano ethyl methacrylate, stirring at 20 ℃ for reacting for 5 hours, adding the solution into 180mL of diethyl ether after the reaction is finished to precipitate the solution, carrying out vacuum filtration on the obtained precipitate product to obtain a white solid powder product, washing the product with a precipitator for three times, and carrying out vacuum drying to obtain a monomer ethyl methacrylate m-aminobenzoyl urea (CA);
(2) dissolving 0.01g of ethyl methacrylate m-aminobenzoyl urea monomer and 2.0g of sodium styrene sulfonate monomer in 15mL of distilled water, adding 5mg of water-soluble initiator azodiisobutyl amidine hydrochloride (V-50), replacing air in a reaction system by a method of circularly vacuumizing and introducing nitrogen for three times, heating to 50 ℃ and polymerizing for 12 hours to obtain a polymer PSSNa/CA solution; dialyzing the solution with dialysis bag with molecular weight cutoff of 3000 for three days, and freeze drying to obtain polymer PSSNa/CA powder;
(3) 0.1g of PSSNa/CA was dissolved in 1.2mL of a 0.8mol/L dilute hydrochloric acid solution, and 30mg of an aniline monomer was added to prepare a PSSNa/CA-aniline solution (solution A). 60mg of oxidant ammonium persulfate was dissolved in distilled 0.5mL of water as solution B. And adding the solution B into the solution A at 4 ℃, uniformly mixing, and reacting for 5 hours to obtain the hybrid conductive hydrogel.
The impedance and cyclic voltammetry performance of the hybrid conductive hydrogel provided in this example 4 were measured, and the test result shows that the electrochemical impedance of the hybrid conductive hydrogel in this example is 6.5 ohms and has good capacitance.
Example 5
This example provides a hybrid electrically conductive hydrogel and a method for making the same. The hybrid conductive hydrogel is prepared according to the following steps:
(1) dissolving 3.0g of m-aminophenylmethylamine in 35mL of dichloromethane to obtain a dichloromethane solution of m-aminophenylamine, adding 5.0g of isocyano ethyl methacrylate, stirring at 25 ℃ for reaction for 5 hours, adding the solution into 300mL of diethyl ether after the reaction is finished to precipitate the solution, carrying out vacuum filtration on the obtained precipitate product to obtain a white solid powder product, washing the product with a precipitator for three times, and carrying out vacuum drying to obtain a monomer ethyl methacrylate m-aminobenzoyl urea (CA);
(2) dissolving 0.01g of ethyl methacrylate m-aminobenzoyl urea monomer and 5.0g of sodium styrene sulfonate monomer in 30mL of distilled water, adding 5mg of water-soluble initiator azodiisobutyl amidine hydrochloride (V-50), replacing air in a reaction system by a method of circularly vacuumizing and introducing nitrogen for three times, heating to 45 ℃ and polymerizing for 12 hours to obtain a polymer PSSNa/CA solution; dialyzing the solution with dialysis bag with molecular weight cutoff of 3000 for three days, and freeze drying to obtain polymer PSSNa/CA powder;
(3) 0.1g of PSSNa/CA was dissolved in 0.9mL of a 1mol/L diluted hydrochloric acid solution, and 30mg of an aniline monomer was added to prepare a PSSNa/CA-aniline solution (solution A). 60mg of oxidant ammonium persulfate was dissolved in distilled 0.5mL of water as solution B. And adding the solution B into the solution A at the temperature of 5 ℃, uniformly mixing, and reacting for 4 hours to obtain the hybrid conductive hydrogel.
The impedance and cyclic voltammetry performance of the hybrid conductive hydrogel provided in this example 5 were measured, and the test result shows that the electrochemical impedance of the hybrid conductive hydrogel in this example is 10 ohms and has good capacitance.
Example 6
This example provides a hybrid electrically conductive hydrogel and a method for making the same. The hybrid conductive hydrogel is prepared according to the following steps:
(1) dissolving 3.0g of m-aminophenylmethylamine in 40mL of dichloromethane to obtain a dichloromethane solution of m-aminophenylamine, adding 5.0g of isocyano ethyl methacrylate, stirring at 25 ℃ for reacting for 4h, adding the solution into 350mL of diethyl ether after the reaction is finished to precipitate the solution, carrying out vacuum filtration on the obtained precipitate product to obtain a white solid powder product, washing the product with a precipitator for three times, and carrying out vacuum drying to obtain a monomer ethyl methacrylate m-aminobenzoyl urea (CA);
(2) dissolving 0.02g of ethyl methacrylate m-aminobenzoyl urea monomer and 5.0g of sodium styrene sulfonate monomer in 30mL of distilled water, adding 5mg of water-soluble initiator azodiisobutyl amidine hydrochloride (V-50), replacing air in a reaction system by a method of circularly vacuumizing and introducing nitrogen for three times, heating to 35 ℃ and polymerizing for 12 hours to obtain a polymer PSSNa/CA solution; dialyzing the solution with dialysis bag with molecular weight cutoff of 3000 for three days, and freeze drying to obtain polymer PSSNa/CA powder;
(3) 0.1g of PSSNa/CA was dissolved in 0.9mL of a 1mol/L diluted hydrochloric acid solution, and 50mg of aniline monomer was added to prepare a PSSNa/CA-aniline solution (solution A). 80mg of oxidant ammonium persulfate was dissolved in distilled 0.5mL of water as solution B. And adding the solution B into the solution A at the temperature of 5 ℃, uniformly mixing, and reacting for 5 hours to obtain the hybrid conductive hydrogel.
The impedance and cyclic voltammetry performance of the hybrid conductive hydrogel provided in this example 5 were measured, and the test result shows that the electrochemical impedance of the hybrid conductive hydrogel in this example is 8 ohms and has good capacitance.
The test results of the above embodiments show that the hybrid conductive hydrogel provided by the embodiments of the present invention has good conductivity, good capacitance, and good mechanical properties.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (8)
1. A preparation method of hybrid conductive hydrogel comprises the following steps:
in a protective atmosphere, carrying out polymerization reaction on ethyl methacrylate m-aminobenzoyl urea and a sodium styrene sulfonate monomer in a solvent under the action of an initiator, and carrying out post-purification treatment to obtain sodium polystyrene sulfonate grafted with ethyl methacrylate m-aminobenzoyl urea; wherein the mass ratio of the ethyl methacrylate m-aminobenzoyl urea to the sodium styrene sulfonate monomer is (0.00001-0.01): 1; and the total mass concentration of the ethyl methacrylate m-aminobenzoyl urea and the sodium styrene sulfonate monomer in the solvent is 4-30%;
dissolving the sodium polystyrene sulfonate grafted with the ethyl methacrylate m-aminobenzoyl urea in a dilute hydrochloric acid solution, adding an aniline monomer and an oxidant to carry out polymerization reaction to generate the polyaniline/sodium polystyrene sulfonate-based hybrid conductive hydrogel, wherein the mass of the aniline monomer is 20-100% of that of the sodium polystyrene sulfonate.
2. The method of claim 1, wherein: the mass ratio of the initiator to the sodium styrene sulfonate monomer is (0.0001-0.01): 1;
the initiator comprises at least one of azodiisobutyramidine hydrochloride and ammonium persulfate;
the polymerization reaction temperature of the sodium styrene sulfonate monomer is 20-70 DEGoC。
3. The method of claim 1, wherein:
the polymerization reaction temperature of the aniline monomer is 0-30 ℃, and the reaction time is 1-6 hours.
4. The production method according to any one of claims 1 and 3, characterized in that: the molar ratio of the aniline monomer to the oxidant is 1: 1; and/or
The oxidant is at least one of ammonium persulfate, hydrogen peroxide and ferric trichloride.
5. The method of claim 1, wherein: the preparation method of the ethyl methacrylate m-aminobenzoyl urea comprises the following steps:
and carrying out condensation reaction on m-aminobenzylamine and isocyano ethyl methacrylate to generate the ethyl methacrylate m-aminobenzoyl urea.
6. The method of claim 5, wherein: the condensation reaction temperature is 0-40 ℃, and the reaction time is 1-8 hours;
the molar weight of the m-aminobenzylamine is 1.0-3.0 times of that of the isocyano ethyl methacrylate.
7. The production method according to claim 5 or 6, characterized in that: the method also comprises the step of carrying out precipitation treatment on the generated ethyl methacrylate m-aminobenzoyl urea:
adding a precipitator into the reaction liquid in which the ethyl methacrylate m-aminobenzoyl urea is generated for precipitation and washing.
8. The hybrid conductive hydrogel prepared by the preparation method of claim 1 is applied to sensors, flexible electrodes and supercapacitors.
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