CN108017784A - Hydridization conductive hydrogel its preparation method and application - Google Patents
Hydridization conductive hydrogel its preparation method and application Download PDFInfo
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- CN108017784A CN108017784A CN201711315958.XA CN201711315958A CN108017784A CN 108017784 A CN108017784 A CN 108017784A CN 201711315958 A CN201711315958 A CN 201711315958A CN 108017784 A CN108017784 A CN 108017784A
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- DFRUMJYWIRWVJO-UHFFFAOYSA-N CC(C)C(CCCN=C=O)=O Chemical compound CC(C)C(CCCN=C=O)=O DFRUMJYWIRWVJO-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
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- 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 OR LIGHT-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
Abstract
The invention discloses a kind of hydridization conductive hydrogel and preparation method and application.Hydridization conductive hydrogel preparation method of the present invention comprises the step of：In protective atmosphere, ethyl methacrylate m-aminophenyl formyl urea and sodium styrene sulfonate monomer are subjected to polymerisation under the action of initiator in solvent；The kayexalate is dissolved in olefin(e) acid solution, aniline monomer is added and oxidant carries out polymerisation.Hydridization conductive hydrogel preparation method of the present invention by kayexalate main chain grafted methacrylic acid ethyl ester m-aminophenyl formyl urea be used as side chain, then aniline function between contained by the ethyl methacrylate m-aminophenyl formyl urea is polymerized among polyaniline molecule chain, so as to be formed in situ kayexalate/polyaniline hybridized conductive hydrogel, and assign the good mechanical property of the hybridized hydrogel, excellent chemical property.
Description
Technical field
The invention belongs to conductive hydrogel field, and in particular to a kind of hydridization conductive hydrogel and preparation method thereof and should
With.
Background technology
Polyalcohol hydrogel refer to water-soluble polymer in aqueous medium by covalent bond or Physical interaction crosslinking and
The three-dimensional network-like structure of formation, while hydrone is encapsulated in a kind of soft material formed in its network structure.One
As for, water content accounts for more than 60 the percent of material gross weight in hydrogel.Since hydrogel has good mechanical property
Flexibility not available for the materials such as energy, excellent biocompatibility, class loading are structural, conventional metals, ceramics, thus organizing
Engineering, medicine controlled releasing, flexible sensor, flexible robot, intelligent response material etc. have a wide range of applications.Although polymerization
Thing hydrogel has excellent flexibility, but it as a kind of electrical insulating property material, itself electrical conductivity is very low, and limiting it should
With being such as difficult to the needs that satisfaction prepares ultracapacitor.
Ultracapacitor is as a kind of new energy storage equipment because it is with high power density, excellent multiplying power
Performance and the energy density of continuous improvement, have attracted the extensive concern of more and more researchers both at home and abroad, have been expected under becoming
One of storage device of generation clean energy resource.Generation according to whether there is redox reaction in charge and discharge process can be divided into double
Electric layer capacitance and fake capacitance capacitor.Relatively for the double capacity capacitors of tradition, redox reaction draws in charge and discharge process
Enter to store capacitor and discharge more electric charges, hence in so that specific capacity greatly improves.In addition, general electric charge storage
On the surface of electrode of super capacitor active material, therefore the raising of electrode active material specific surface area can also be conducive to super electricity
The raising of container energy density.As electrode material for super capacitor, higher specific surface area is not only needed, but also to have at the same time
Standby good electric conductivity, so as to effective transmission of electric charge.In recent years, many researchers utilize carbon material, conducting polymer system
Standby electrode material for super capacitor, and obtain excellent chemical property.Dong etc. is first to utilize carbon nanotubes, electrically conductive polyaniline system
For the fiber electrode material with multilevel hierarchy, and applied in the preparation of ultracapacitor, the results showed that, preparation
Ultracapacitor has good chemical property and flexible.Wang etc. is mixed using the organic sulfonate that copper ion is coordinated
It is miscellaneous and be crosslinked polypyrrole and prepare the ultracapacitor based on polypyrrole.In addition, to improve the ratio of electrode material for super capacitor
The two-dimensional material such as surface area, graphene, molybdenum disulfide is also used for the preparation of electrode material.It is although poly- based on carbon material, conduction
The research of the ultracapacitor of compound has been achieved for significantly achievement, but the brittleness of carbon material, conducting polymer in itself is
Prepared ultracapacitor be difficult that there is the performance such as flexible, stretchable, significantly limit it in wearable device
Application.In addition, the prepared ultracapacitor that the brittleness of these traditional materials also can be is in multiple charge and discharge cycles process
Middle generation active material is from collection liquid surface obscission, so that its cycle performance declines.Therefore, how one kind is prepared
Both it is that the technology that this area always strives to solve is difficult just like the material with the performances such as good mechanics such as flexibility and electric conductivity
Topic.
The content of the invention
It is an object of the invention to overcome the above-mentioned deficiency of the prior art, there is provided a kind of hydridization conductive hydrogel and its preparation
Method, to solve the undesirable technical problem of existing conductive carbon material, polymer-matrix electric conduction material mechanical performance.
In order to realize foregoing invention purpose, an aspect of of the present present invention, there is provided a kind of preparation side of hydridization conductive hydrogel
Method.The hydridization conductive hydrogel preparation method includes the following steps：
In protective atmosphere, by ethyl methacrylate m-aminophenyl formyl urea and sodium styrene sulfonate monomer in initiator
Under the action of polymerisation is carried out in solvent, rear purification process, obtains being grafted with ethyl methacrylate m-aminophenyl formyl
The kayexalate of urea；
The kayexalate is dissolved in olefin(e) acid solution, aniline monomer is added and oxidant carries out polymerisation,
Generate polyaniline/polystyrene sodium sulfonate group hydridization conductive hydrogel.
A kind of another aspect of the present invention, there is provided hydridization conductive hydrogel.The molecule knot of the hydridization conductive hydrogel
Structure general formula is as follows：
Wherein, m=1-100, n=100-100000, it is describedFor the repetitive unit of aniline.
Another aspect of the present invention, there is provided the application process of hydridization conductive hydrogel.The hydridization conductive hydrogel exists
Application in ultracapacitor, ultracapacitor
Compared with prior art, hydridization conductive hydrogel preparation method of the present invention passes through on kayexalate main chain
Grafted methacrylic acid ethyl ester m-aminophenyl formyl urea is as side chain, then by the ethyl methacrylate m-aminophenyl formyl
Aniline function is polymerized among polyaniline molecule chain between contained by urea, so as to be formed in situ kayexalate/polyphenyl
Amine hydridization conductive hydrogel, and assign the good mechanical property of the hybridized hydrogel, excellent chemical property.In addition, institute
State that preparation method process conditions are easily-controllable, the hybridized hydrogel performance of preparation is stablized, and yield is high.It is meanwhile raw materials used honest and clean
Valency is easy to get, the gentle capital equipment requirement of preparation condition is relatively low, is easy to large-scale production, reduces production cost.
Hydridization conductive hydrogel of the present invention has good mechanical property, excellent chemical property, and cost is low.Cause
This, extends its application range, and which raises the stability and flexible characteristic for being accordingly employed product.
Brief description of the drawings
Fig. 1 is the impedance diagram for the hydridization conductive hydrogel that the embodiment of the present invention 1 provides；
Fig. 2 is the cyclic voltammogram for the hydridization conductive hydrogel that the embodiment of the present invention 1 provides.
Embodiment
In order to which technical problems, technical solutions and advantageous effects to be solved by the present invention are more clearly understood, below in conjunction with
Embodiment, the present invention will be described in further detail.It should be appreciated that specific embodiment described herein is only explaining
The present invention, is not intended to limit the present invention.
The quality of each component noted in the disclosure of the embodiment of the present invention not only may refer to the specific of each component and contain
Amount, can also represent the proportionate relationship of quality between each component, therefore, as long as according to specification each component of the embodiment of the present invention
Content is scaled up or reduced within specification of embodiment of the present invention scope of disclosure.Specifically, the embodiment of the present invention
Quality described in specification can be mass unit known to the chemical fields such as μ g, mg, g, kg.It is described
On the one hand, an embodiment of the present invention provides a kind of while have the hydridization of excellent mechanical performances and chemical property concurrently and lead
Electric hydrogel.The hydridization conduction water-setting general formula of molecular structure is as follows：
Wherein, m=1-100, n=100-100000, it is describedFor the repetitive unit of aniline.Therefore, in the hydridization
In conductive hydrogel, including the repetitive unit of the repetitive unit of sodium styrene sulfonate and aniline, and the sodium styrene sulfonate
The repetitive unit of repetitive unit and aniline is by covalently cross-linked, so as to have good mechanical property and electric conductivity at the same time.
In one embodiment, the quantity of the repetitive unit of aniline is identical with n and m implications, is such as 100-5000.
On the other hand, on the basis of the hydridization conduction water-setting shown in general formula of molecular structure above, the present invention is implemented
Example additionally provides a kind of preparation method of hydridization conductive hydrogel described above.The hydridization conductive hydrogel preparation method includes
Following steps：
S01：In protective atmosphere, ethyl methacrylate m-aminophenyl formyl urea is being drawn with sodium styrene sulfonate monomer
Polymerisation is carried out in solvent under the action of hair agent, rear purification process, obtains being grafted with ethyl methacrylate m-aminophenyl
The kayexalate of formyl urea；
S02：The kayexalate is dissolved in olefin(e) acid solution, aniline monomer is added and oxidant polymerize instead
Should, generate polyaniline/polystyrene sodium sulfonate group hydridization conductive hydrogel.
Specifically, the ethyl methacrylate m-aminophenyl formyl urea in the step S01 and sodium styrene sulfonate monomer
In the polymerization process, sodium styrene sulfonate monomer passes through free radical with ethyl methacrylate m-aminophenyl formyl urea
Copolyreaction generates poly- (sodium styrene sulfonate-ethyl methacrylate m-aminophenyl formyl urea) copolymer, which is denoted as
PSSNa/CA.Aniline function between being carried due to ethyl methacrylate m-aminophenyl formyl urea, also so that generation gathers
The side chain of compound PSSNa/CA carries the aniline function between aniline progress redox copolymerization.
In polymerization reaction system in the step S01, control the ethyl methacrylate m-aminophenyl formyl urea with
The mass ratio of the sodium styrene sulfonate monomer is preferably (0.00001~0.01)：1, amino between the ethyl methacrylate
Benzoyl urea and total mass concentration of the sodium styrene sulfonate monomer in the solvent are 4~30%, the initiator with
The ratio of the quality (or mole etc. other unit) of the sodium styrene sulfonate monomer is preferably (0.001-0.010)：1.Having
In body embodiment, the initiator includes at least one of azo-bis-isobutyrate hydrochloride, ammonium persulfate.Reaction dissolvent can be with
It is at least one of water, dimethylformamide, dimethyl sulfoxide (DMSO).
Pass through the control to the polymerization reaction system so that a certain amount of methyl-prop is grafted on kayexalate
Olefin(e) acid ethyl ester m-aminophenyl formyl urea side chain, while the efficiency of polymerisation is provided, so as to improve the yield of product.
On the basis of the polymerization reaction system, the polymeric reaction temperature in the step S01 is 20~70 DEG C, described
Under conditions of reaction temperature, the polymerisation should be sufficient.In protective atmosphere can with but not just for nitrogen atmosphere,
It can also be the atmosphere of other inert gases, can also be vacuum environment certainly.
After the polymerisation for treating the step S01, the processing purified to product PSSNa/CA is further included, one is real
Apply in example, removed the water-solubility impurity in PSSNa/CA solution using the method for dialysis, freeze-drying, obtains polymer
PSSNa/CA powder.
In addition, the ethyl methacrylate m-aminophenyl formyl urea in the step S01 can be prepared as follows：
M-aminophenyl methylamine, isocyanatoethyl are subjected to condensation reaction and generate the ethyl methacrylate
M-aminophenyl formyl urea.The condensation chemical equation is as follows：
In the condensation reaction, the temperature of the condensation reaction is preferably 0~40 DEG C, and the time of reaction is preferably 1~8
Hour；The mole of the m-aminophenyl methylamine is preferably the 1.0~3.0 of the isocyanatoethyl mole
Times.The solvent of condensation reaction system includes at least one of dichloromethane, chloroform, dimethylformamide.By to described poly-
The control and optimization of reaction condition are closed, improves the yield of product, improves polymerisation efficiency.
After the polymerisation, further include and ethyl methacrylate m-aminophenyl formyl urea product is carried out at purifying
Reason.The method of the purification process is but not only as follows：
Have to generation in the reaction solution of the ethyl methacrylate m-aminophenyl formyl urea add precipitating reagent precipitated,
Washing.Wherein, the precipitating reagent includes at least one of n-hexane, ether, petroleum ether.The precipitating reagent is used to be foot
Amount, such as the volume of the precipitating reagent has stated the reaction solution cumulative volume of ethyl methacrylate m-aminophenyl formyl urea for generation
7~11 times.The ethyl methacrylate m-aminophenyl formyl urea product after precipitation is washed fully to remove impurity elimination
Matter, the reactant such as reaction dissolvent and for reaction.Specifically, repeatedly washed using the precipitating reagent, such as at least 3 times, it is rear dry
Such as vacuum drying treatment.
In polymerisation in the step S02, redox polymerization life occurs under the action of initiator for aniline monomer
Into polyaniline, simultaneously, by the polyphenyl second for being grafted with ethyl methacrylate m-aminophenyl formyl urea prepared in step S01
Aniline monomer functional group take part in the polymerization of the aniline monomer between contained by alkene sodium sulfonate, so as to be formed in situ polystyrene sulphur
Sour sodium/polyaniline hybridized conductive hydrogel.Wherein, the polymerization chemistry formula in the step S02 is as follows：
In polymerization reaction system in the step S02, the quality for controlling the aniline monomer is preferably anti-in step S01
Answer kayexalate described in product i.e. the 20~100% of PSSNa/CA mass.The polymeric reaction temperature of the aniline is preferred
For 0~30 DEG C, when the reaction time is preferably 1~6 small.The dosage of the oxidant should be enough, such as aniline monomer
Molar ratio with oxidant is 1:1.Wherein, the oxidant is at least one of ammonium persulfate, hydrogen peroxide.
Pass through the control to the polymerization reaction system so that aniline carries out sufficient polymerisation, so as to provide polymerization
The efficiency of reaction, so as to improve the yield of product.
Therefore, the hydridization conductive hydrogel preparation method on kayexalate main chain by being grafted metering system
Acetoacetic ester m-aminophenyl formyl urea side chain, then by aniline official between contained by the ethyl methacrylate m-aminophenyl formyl urea
It can roll into a ball and be polymerized among polyaniline molecule chain, be formed in situ kayexalate/polyaniline hybridized conductive hydrogel.This
Sample, more water-soluble poly sodium styrene sulfonate contained by the hydridization conductive hydrogel pass through covalently cross-linked with hydrophobicity polyaniline
And the hydridization conductive hydrogel formed, while there is good mechanical property and electric conductivity.In addition, the preparation method technique
Condition is easily-controllable, and the hybridized hydrogel performance of preparation is stablized, and yield is high.It is raw materials used it is cheap and easy to get, preparation condition is gentle
Capital equipment requirement is relatively low, is easy to large-scale production, reduces production cost.
Since the hydridization conductive hydrogel of the present invention has good mechanical property, excellent chemical property, and
Cost is low.Therefore, it can effectively be used for the application in sensor, flexible electrode, ultracapacitor.Such as in specific embodiment
In, the hydridization conductive hydrogel prepares flexible electrode as flexible electrode material, further, can be by the flexible electrode
Prepare flexible super capacitor.So as to assign flexible electrode and excellent flexible specific of flexible super capacitor, while energy is close
Degree is high.
In conjunction with instantiation, hydridization conductive hydrogel of the embodiment of the present invention and preparation method thereof is carried out further detailed
Explanation.
Embodiment 1
The present embodiment provides a kind of hydridization conductive hydrogel and preparation method thereof.The hydridization conductive hydrogel according to including
It is prepared by the steps：
(1) 2.0g m-aminophenyl methylamines are dissolved in 20mL dichloromethane, obtain the dichloromethane solution of m-aminophenyl amine,
2.5g isocyanatoethyls are added, is stirred at 25 DEG C and carries out reaction 2h, will be added after reaction in the solution
Enter into 140mL ether to make its precipitation, obtained precipitated product depressurized and is filtered, obtains white solid powder powdery product,
The product is washed three times with precipitating reagent, vacuum drying obtains monomer methacrylic acid ethyl ester m-aminophenyl formyl urea (CA)；
(2) it is 0.01g ethyl methacrylate m-aminophenyl formyl urea monomers and 2.0g sodium styrene sulfonate monomers is molten
In 10mL distilled water, 5mg water soluble starters azo-bis-isobutyrate hydrochloride (V-50) is added, logical nitrogen is vacuumized with circulation
Method three times replaces the air in reaction system, and heat up 40 DEG C of polymerization 12h, obtains polymer P SSNa/CA solution；Should
The bag filter that solution molecular cut off is 3000 is dialysed three days, and freeze-drying, obtains polymer P SSNa/CA powder；
(3) 0.1g PSSNa/CA are dissolved in the dilute hydrochloric acid solution that 1mL concentration is 1mol/L, add 20mg aniline monomers,
It is prepared into PSSNa/CA- aniline solutions (A liquid).50mg oxidant ammonium persulfates are dissolved in distillation 0.5mL water as B liquid.B liquid
It is added in A liquid, is uniformly mixed at 0 DEG C, hydridization conductive hydrogel is obtained after reacting 3h.
The hydridization conductive hydrogel that the present embodiment 1 is provided carries out impedance and cyclic voltammetric performance measurement, wherein, resistance
Energy test result is as shown in Figure 1, cyclic voltammetric the performance test results are as shown in Figure 2.As shown in Figure 1, hydrogel electrochemical impedance
For 3 ohm, internal resistance is small, has excellent electric conductivity；As shown in Figure 2, the hydrogel has good capacitance.
Embodiment 2
The present embodiment provides a kind of hydridization conductive hydrogel and preparation method thereof.The hydridization conductive hydrogel according to including
It is prepared by the steps：
(1) 2.0g m-aminophenyl methylamines are dissolved in 25mL dichloromethane, obtain the dichloromethane solution of m-aminophenyl amine,
2.8g isocyanatoethyls are added, is stirred at 20 DEG C and carries out reaction 3h, will be added after reaction in the solution
Enter into 140mL ether to make its precipitation, obtained precipitated product depressurized and is filtered, obtains white solid powder powdery product,
The product is washed three times with precipitating reagent, vacuum drying obtains monomer methacrylic acid ethyl ester m-aminophenyl formyl urea (CA)；
(2) it is 0.01g ethyl methacrylate m-aminophenyl formyl urea monomers and 3.0g sodium styrene sulfonate monomers is molten
In 15mL distilled water, 5mg water soluble starters azo-bis-isobutyrate hydrochloride (V-50) is added, logical nitrogen is vacuumized with circulation
Method three times replaces the air in reaction system, and heat up 40 DEG C of polymerization 12h, obtains polymer P SSNa/CA solution；Should
The bag filter that solution molecular cut off is 3000 is dialysed three days, and freeze-drying, obtains polymer P SSNa/CA powder；
(3) 0.1g PSSNa/CA are dissolved in the dilute hydrochloric acid solution that 0.9mL concentration is 0.5mol/L, add 30mg aniline
Monomer, is prepared into PSSNa/CA- aniline solutions (A liquid).60mg oxidant ammonium persulfates are dissolved in distillation 0.5mL water as B
Liquid.B liquid is added at 0 DEG C in A liquid, is uniformly mixed, and hydridization conductive hydrogel is obtained after reacting 3h.
The hydridization conductive hydrogel that the present embodiment 2 provides is subjected to impedance and cyclic voltammetric performance measurement, test result obtain
Know, the present embodiment hydridization conductive hydrogel electrochemical impedance is 5 ohm, and has good capacitance.
Embodiment 3
The present embodiment provides a kind of hydridization conductive hydrogel and preparation method thereof.The hydridization conductive hydrogel according to including
It is prepared by the steps：
(1) 2.0g m-aminophenyl methylamines are dissolved in 30mL dichloromethane, obtain the dichloromethane solution of m-aminophenyl amine,
2.8g isocyanatoethyls are added, is stirred at 20 DEG C and carries out reaction 3h, will be added after reaction in the solution
Enter into 180mL ether to make its precipitation, obtained precipitated product depressurized and is filtered, obtains white solid powder powdery product,
The product is washed three times with precipitating reagent, vacuum drying obtains monomer methacrylic acid ethyl ester m-aminophenyl formyl urea (CA)；
(2) it is 0.01g ethyl methacrylate m-aminophenyl formyl urea monomers and 3.0g sodium styrene sulfonate monomers is molten
In 15mL distilled water, 5mg water soluble starters azo-bis-isobutyrate hydrochloride (V-50) is added, logical nitrogen is vacuumized with circulation
Method three times replaces the air in reaction system, and heat up 45 DEG C of polymerization 12h, obtains polymer P SSNa/CA solution；Should
The bag filter that solution molecular cut off is 3000 is dialysed three days, and freeze-drying, obtains polymer P SSNa/CA powder；
(3) 0.1g PSSNa/CA are dissolved in the dilute hydrochloric acid solution that 0.9mL concentration is 0.5mol/L, add 30mg aniline
Monomer, is prepared into PSSNa/CA- aniline solutions (A liquid).60mg oxidant ammonium persulfates are dissolved in distillation 0.5mL water as B
Liquid.B liquid is added at 4 DEG C in A liquid, is uniformly mixed, and hydridization conductive hydrogel is obtained after reacting 3h.
The hydridization conductive hydrogel that the present embodiment 3 provides is subjected to impedance and cyclic voltammetric performance measurement, test result obtain
Know, the present embodiment hydridization conductive hydrogel electrochemical impedance is 7 ohm, and has good capacitance.
Embodiment 4
The present embodiment provides a kind of hydridization conductive hydrogel and preparation method thereof.The hydridization conductive hydrogel according to including
It is prepared by the steps：
(1) 2.0g m-aminophenyl methylamines are dissolved in 40mL dichloromethane, obtain the dichloromethane solution of m-aminophenyl amine,
2.8g isocyanatoethyls are added, is stirred at 20 DEG C and carries out reaction 5h, will be added after reaction in the solution
Enter into 180mL ether to make its precipitation, obtained precipitated product depressurized and is filtered, obtains white solid powder powdery product,
The product is washed three times with precipitating reagent, vacuum drying obtains monomer methacrylic acid ethyl ester m-aminophenyl formyl urea (CA)；
(2) it is 0.01g ethyl methacrylate m-aminophenyl formyl urea monomers and 2.0g sodium styrene sulfonate monomers is molten
In 15mL distilled water, 5mg water soluble starters azo-bis-isobutyrate hydrochloride (V-50) is added, logical nitrogen is vacuumized with circulation
Method three times replaces the air in reaction system, and heat up 50 DEG C of polymerization 12h, obtains polymer P SSNa/CA solution；Should
The bag filter that solution molecular cut off is 3000 is dialysed three days, and freeze-drying, obtains polymer P SSNa/CA powder；
(3) 0.1g PSSNa/CA are dissolved in the dilute hydrochloric acid solution that 1.2mL concentration is 0.8mol/L, add 30mg aniline
Monomer, is prepared into PSSNa/CA- aniline solutions (A liquid).60mg oxidant ammonium persulfates are dissolved in distillation 0.5mL water as B
Liquid.B liquid is added at 4 DEG C in A liquid, is uniformly mixed, and hydridization conductive hydrogel is obtained after reacting 5h.
The hydridization conductive hydrogel that the present embodiment 4 provides is subjected to impedance and cyclic voltammetric performance measurement, test result obtain
Know, the present embodiment hydridization conductive hydrogel electrochemical impedance is 6.5 ohm, and has good capacitance.
Embodiment 5
The present embodiment provides a kind of hydridization conductive hydrogel and preparation method thereof.The hydridization conductive hydrogel according to including
It is prepared by the steps：
(1) 3.0g m-aminophenyl methylamines are dissolved in 35mL dichloromethane, obtain the dichloromethane solution of m-aminophenyl amine,
5.0g isocyanatoethyls are added, is stirred at 25 DEG C and carries out reaction 5h, will be added after reaction in the solution
Enter into 300mL ether to make its precipitation, obtained precipitated product depressurized and is filtered, obtains white solid powder powdery product,
The product is washed three times with precipitating reagent, vacuum drying obtains monomer methacrylic acid ethyl ester m-aminophenyl formyl urea (CA)；
(2) it is 0.01g ethyl methacrylate m-aminophenyl formyl urea monomers and 5.0g sodium styrene sulfonate monomers is molten
In 30mL distilled water, 5mg water soluble starters azo-bis-isobutyrate hydrochloride (V-50) is added, logical nitrogen is vacuumized with circulation
Method three times replaces the air in reaction system, and heat up 45 DEG C of polymerization 12h, obtains polymer P SSNa/CA solution；Should
The bag filter that solution molecular cut off is 3000 is dialysed three days, and freeze-drying, obtains polymer P SSNa/CA powder；
(3) 0.1g PSSNa/CA are dissolved in the dilute hydrochloric acid solution that 0.9mL concentration is 1mol/L, add 30mg aniline lists
Body, is prepared into PSSNa/CA- aniline solutions (A liquid).60mg oxidant ammonium persulfates are dissolved in distillation 0.5mL water as B liquid.
B liquid is added in A liquid at 5 DEG C, is uniformly mixed, and hydridization conductive hydrogel is obtained after reacting 4h.
The hydridization conductive hydrogel that the present embodiment 5 provides is subjected to impedance and cyclic voltammetric performance measurement, test result obtain
Know, the present embodiment hydridization conductive hydrogel electrochemical impedance is 10 ohm, and has good capacitance.
Embodiment 6
The present embodiment provides a kind of hydridization conductive hydrogel and preparation method thereof.The hydridization conductive hydrogel according to including
It is prepared by the steps：
(1) 3.0g m-aminophenyl methylamines are dissolved in 40mL dichloromethane, obtain the dichloromethane solution of m-aminophenyl amine,
5.0g isocyanatoethyls are added, is stirred at 25 DEG C and carries out reaction 4h, will be added after reaction in the solution
Enter into 350mL ether to make its precipitation, obtained precipitated product depressurized and is filtered, obtains white solid powder powdery product,
The product is washed three times with precipitating reagent, vacuum drying obtains monomer methacrylic acid ethyl ester m-aminophenyl formyl urea (CA)；
(2) it is 0.02g ethyl methacrylate m-aminophenyl formyl urea monomers and 5.0g sodium styrene sulfonate monomers is molten
In 30mL distilled water, 5mg water soluble starters azo-bis-isobutyrate hydrochloride (V-50) is added, logical nitrogen is vacuumized with circulation
Method three times replaces the air in reaction system, and heat up 35 DEG C of polymerization 12h, obtains polymer P SSNa/CA solution；Should
The bag filter that solution molecular cut off is 3000 is dialysed three days, and freeze-drying, obtains polymer P SSNa/CA powder；
(3) 0.1g PSSNa/CA are dissolved in the dilute hydrochloric acid solution that 0.9mL concentration is 1mol/L, add 50mg aniline lists
Body, is prepared into PSSNa/CA- aniline solutions (A liquid).80mg oxidant ammonium persulfates are dissolved in distillation 0.5mL water as B liquid.
B liquid is added in A liquid at 5 DEG C, is uniformly mixed, and hydridization conductive hydrogel is obtained after reacting 5h.
The hydridization conductive hydrogel that the present embodiment 5 provides is subjected to impedance and cyclic voltammetric performance measurement, test result obtain
Know, the present embodiment hydridization conductive hydrogel electrochemical impedance is 8 ohm, and has good capacitance.
From the various embodiments described above test result, the good conduction of hydridization conductive hydrogel provided in an embodiment of the present invention
Performance, and there is good capacitance, also with good mechanical property.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all essences in the present invention
All any modification, equivalent and improvement made within refreshing and principle etc., should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of preparation method of hydridization conductive hydrogel, includes the following steps：
In protective atmosphere, by ethyl methacrylate m-aminophenyl formyl urea and sodium styrene sulfonate monomer initiator work
Polymerisation is carried out in solvent under, rear purification process, obtains being grafted with ethyl methacrylate m-aminophenyl formyl urea
Kayexalate；
The kayexalate is dissolved in olefin(e) acid solution, aniline monomer is added and oxidant carries out polymerisation, generation
Polyaniline/polystyrene sodium sulfonate group hydridization conductive hydrogel.
2. preparation method according to claim 1, it is characterised in that：The ethyl methacrylate m-aminophenyl formyl urea
Mass ratio with the sodium styrene sulfonate monomer is (0.00001~0.01)：1；And/or
The ethyl methacrylate m-aminophenyl formyl urea and total matter of the sodium styrene sulfonate monomer in the solvent
It is 4~30% to measure concentration.
3. according to any preparation methods of claim 1-2, it is characterised in that：The initiator and the styrene sulfonic acid
The ratio (0.0001-0.01) of the quality of sodium monomer：1；
The initiator includes at least one of azo-bis-isobutyrate hydrochloride, ammonium persulfate；
The polymeric reaction temperature of the sodium styrene sulfonate monomer is 20~70 DEG C.
4. preparation method according to claim 1, it is characterised in that：The quality of the aniline monomer is the polystyrene
The 20~100% of sodium sulfonate quality；And/or
The polymeric reaction temperature of the aniline monomer is 0~30 DEG C, when the reaction time is 1~6 small.
5. according to any preparation method of claim 1,2,4, it is characterised in that：The aniline monomer and oxidant rub
You are than being 1:1；And/or
The oxidant is at least one of ammonium persulfate, hydrogen peroxide, ferric trichloride.
6. preparation method according to claim 1, it is characterised in that：The ethyl methacrylate m-aminophenyl formyl urea
Preparation method it is as follows：
By ammonia between m-aminophenyl methylamine, the isocyanatoethyl progress condensation reaction generation ethyl methacrylate
Base benzoyl urea.
7. preparation method according to claim 6, it is characterised in that：The temperature of the condensation reaction is 0~40 DEG C, reaction
Time for 1~8 it is small when；
The mole of the m-aminophenyl methylamine is 1.0~3.0 times of the isocyanatoethyl mole.
8. the preparation method according to claim 6 or 7, it is characterised in that：Further include the methacrylic acid of generation
Ethyl ester m-aminophenyl formyl urea carries out the step of precipitation process：
There is addition precipitating reagent in the reaction solution of the ethyl methacrylate m-aminophenyl formyl urea to be precipitated, washed to generation
Wash.
9. a kind of hydridization conductive hydrogel, the general formula of molecular structure of the hydridization conductive hydrogel is as follows：
Wherein, m=1-100, n=100-100000, it is describedFor the repetitive unit of aniline.
10. hydridization conductive hydrogel prepared by preparation method according to claim 9 is in sensor, flexible electrode, super
Application in capacitor.
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