CN114516936A - Anti-freezing conductive gel and preparation method and application thereof - Google Patents

Anti-freezing conductive gel and preparation method and application thereof Download PDF

Info

Publication number
CN114516936A
CN114516936A CN202011311012.8A CN202011311012A CN114516936A CN 114516936 A CN114516936 A CN 114516936A CN 202011311012 A CN202011311012 A CN 202011311012A CN 114516936 A CN114516936 A CN 114516936A
Authority
CN
China
Prior art keywords
conductive gel
solution
gel
ionic liquid
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.)
Granted
Application number
CN202011311012.8A
Other languages
Chinese (zh)
Other versions
CN114516936B (en
Inventor
冯亮
支慧
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dalian Institute of Chemical Physics of CAS
Original Assignee
Dalian Institute of Chemical Physics of CAS
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Dalian Institute of Chemical Physics of CAS filed Critical Dalian Institute of Chemical Physics of CAS
Priority to CN202011311012.8A priority Critical patent/CN114516936B/en
Publication of CN114516936A publication Critical patent/CN114516936A/en
Application granted granted Critical
Publication of CN114516936B publication Critical patent/CN114516936B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

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
    • C08F251/00—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof
    • C08F251/02—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof on to cellulose 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
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
    • C08J3/09—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids
    • C08J3/091—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids characterised by the chemical constitution of the organic liquid
    • C08J3/095—Oxygen containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C08K3/041—Carbon nanotubes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/02—Ingredients treated with inorganic substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2351/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
    • C08J2351/02—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to polysaccharides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/001—Conductive additives
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids

Abstract

The application discloses antifreeze conductive gel and a preparation method thereof, and the antifreeze organic conductive gel at least comprises the following components: bacterial cellulose, acrylic esters, carbon nano tubes, ionic liquid, glycerol and deionized water; the ionic liquid is imidazole ionic liquid. The antifreeze conductive gel has good stability and mechanical property, can be suitable for operation at low temperature, and has good conductivity under the condition of low temperature.

Description

Anti-freezing conductive gel and preparation method and application thereof
Technical Field
The application relates to an anti-freezing conductive gel and a preparation method thereof, belonging to the field of preparation of organogels.
Background
In recent years, flexible electronic materials have great application prospects in the fields of flexible energy storage, flexible sensing, wearable devices and the like. The conductive hydrogel is widely applied to the field of flexible electronics by virtue of excellent conductivity and good mechanical properties.
However, under extreme conditions, such as low temperature, the conductive hydrogel inevitably loses conductivity due to freezing, and the mechanical properties are greatly weakened, which severely limits the application of the conductive hydrogel under extreme conditions. Therefore, it is important to prepare an anti-freezing conductive gel with excellent conductivity and mechanical properties under extreme conditions.
Disclosure of Invention
The invention provides an anti-freezing conductive gel and a preparation method and application thereof, and solves the problem that the existing conductive gel cannot maintain the conductivity and mechanical property under extreme conditions.
According to one aspect of the present application, there is provided a freeze resistant conductive gel comprising at least: bacterial cellulose, acrylate substances, carbon nano tubes, ionic liquid, a cross-linking agent, glycerol and deionized water;
the ionic liquid is imidazole ionic liquid.
Optionally, the mass ratio of the bacterial cellulose to the acrylate is 10: 0.1-1;
the mass ratio of the acrylate substances to the deionized water is 0.01-1: 1;
the mass ratio of the carbon nano tube to the deionized water is 1: 20-100;
the mass ratio of the ionic liquid to the deionized water is 1-20: 1;
the mass ratio of the glycerol to the deionized water is 0.1-10: 1.
Specifically, the lower limit of the mass ratio of the bacterial cellulose to the acrylate can be independently selected from 10:0.1, 10:0.2, 10:0.325, 10:0.4 and 10: 0.5; the upper limit of the mass ratio of the acrylate substance to the acrylate substance can be independently selected from 10:0.6, 10:0.7, 10:0.8, 10:0.9 and 10: 1.
Specifically, the lower limit of the mass ratio of the acrylate substance to the deionized water can be independently selected from 0.01:1, 0.05:1, 0.1:1, 0.2:1 and 0.4: 1; the upper limit of the mass ratio of the acrylate substance to the deionized water can be independently selected from 0.5:1, 0.6:1, 0.7:1, 0.9:1 and 1: 1.
Specifically, the lower limit of the mass ratio of the carbon nanotubes to the deionized water can be independently selected from 1:20, 1:25, 1:30, 1:40 and 1: 50; the upper limit of the mass ratio of the carbon nanotubes to the deionized water can be independently selected from 1:60, 1:70, 1:80, 1:90 and 1: 100.
Specifically, the lower limit of the mass ratio of the ionic liquid to the deionized water can be independently selected from 1:1, 2:1, 4:1, 5:1 and 6: 1; the upper limit of the mass ratio of the ionic liquid to the deionized water can be independently selected from 8:1, 10:1, 15:1, 18:1 and 20: 1.
Specifically, the lower limit of the mass ratio of the glycerol to the deionized water can be independently selected from 0.1:1, 0.5:1, 1:1, 4:1 and 5: 1; the upper limit of the mass ratio of the glycerol to the deionized water can be independently selected from 6:1, 7:1, 8:1, 9:1 and 10: 1.
Optionally, the acrylate is at least one selected from hydroxyethyl methacrylate, acrylate and vinyl acetate;
alternatively, the imidazole-based ionic liquid has a structural formula shown in formula I:
Figure BDA0002789826700000021
wherein R is1Any one selected from alkyl; r2Selected from an alkyl or alkenyl group; preferably, the alkyl group is a group having less than 5 carbon atoms; the alkenyl group is vinyl; further preferably, the alkyl group is selected from propyl or butyl;
x is selected from any one of halogen, preferably X is chlorine or bromine.
Optionally, the imidazole-based ionic liquid is selected from at least one of 1-butyl-3-methylimidazole bromide salt, 1-butyl-3-methylimidazole chloride salt, 1-propyl-3-methylimidazole bromide salt, 1-propyl-3-methylimidazole chloride salt, 1-vinyl-3-butylimidazole bromide salt and 1-propyl-3-methylimidazole chloride salt;
optionally, the carbon nanotubes are modified carbon nanotubes.
The carbon nanotubes used in the present application are not particularly limited, and those skilled in the art may select single-walled carbon nanotubes or multi-walled carbon nanotubes as desired; meanwhile, the modification mode of the carbon nanotube is not particularly limited, and as long as the dispersibility of the carbon nanotube can be improved, a person skilled in the art can select the modification mode of the carbon nanotube as required, and the specific implementation process of the present application adopts acidification modification.
Optionally, the components of the antifreeze organic conductive gel further comprise a cross-linking agent;
the cross-linking agent is at least one of polyethylene glycol diacrylate, N' -methylene bisacrylamide, phytic acid and diisocyanate;
the dosage of the cross-linking agent is 0.5-10% of the mass of the acrylate.
Preferably, the crosslinking agent is polyethylene glycol diacrylate, and the polymerization degree of the polyethylene glycol diacrylate is 200-1000.
Specifically, the lower limit of the degree of polymerization of the polyethylene glycol diacrylate may be independently selected from 200, 300, 400, 500, 600; the upper limit of the polymerization degree of the polyethylene glycol diacrylate can be independently selected from 700, 800, 900, 950 and 1000.
Specifically, the lower limit of the dosage of the cross-linking agent can be independently selected from 0.5%, 1%, 2%, 4% and 5% of the mass of the acrylate; the upper limit of the amount of the cross-linking agent can be independently selected from 6%, 7%, 8%, 9% and 10% of the mass of the acrylate.
According to a further aspect of the application, a method for preparing the above freeze resistant conductive gel comprises at least:
crosslinking a solution I containing acrylate substances, carbon nano tubes and bacterial cellulose to obtain a pre-gel;
replacing the pre-gel in glycerol with a solvent to obtain the antifreeze conductive gel;
wherein the solution I comprises imidazole ionic liquid and water.
Optionally, the conditions of the crosslinking reaction include:
adding a cross-linking agent and an initiator into the solution I to perform cross-linking reaction to obtain the antifreeze conductive gel;
the temperature of the crosslinking reaction is 50-120 ℃, and the reaction time is 0.5-12 h.
Specifically, the lower limit of the crosslinking temperature can be independently selected from 50 ℃, 55 ℃, 60 ℃, 65 ℃ and 70 ℃; the upper limit of the crosslinking reaction temperature may be independently selected from 90 deg.C, 95 deg.C, 100 deg.C, 110 deg.C, and 120 deg.C.
Specifically, the lower limit of the crosslinking reaction time may be independently selected from 0.5h, 2h, 4h, 5h, 6 h; the upper limit of the crosslinking reaction time can be independently selected from 8h, 9h, 10h, 11h, 12 h.
Optionally, the initiator is at least one of ammonium persulfate, potassium persulfate and azobisisobutyronitrile;
the amount of the initiator is 1-15% of the mass of the acrylate.
Specifically, the lower limit of the amount of the initiator can be independently selected from 1%, 1.5%, 2%, 4% and 5% of the mass of the acrylate; the upper limit of the amount of the initiator can be independently selected from 8%, 10%, 12%, 14% and 15% of the mass of the acrylate.
Alternatively, the conditions for solvent displacement include:
the time of the solvent replacement treatment is 5-120 min.
Specifically, the lower limit of the solvent replacement treatment time may be independently selected from 5min, 10min, 30min, 40min, 50 min; the upper limit of the solvent replacement treatment time may be independently selected from 60min, 70min, 80min, 90min, and 100 min.
Alternatively, the obtaining of solution I comprises:
adding an acrylate substance and a carbon nano tube into a homogeneous solution containing ionic liquid, and mixing to obtain a mixed solution A;
and adding the mixed solution A into a dispersion liquid containing bacterial cellulose, and mixing to obtain a solution I.
Optionally, in the dispersion liquid containing bacterial cellulose, the content of bacterial cellulose is 0.1 wt% to 2.0 wt%.
Optionally, the mixing temperature of the obtained mixed solution A is 60-100 ℃;
the mixing temperature of the obtained solution I is 80-120 ℃.
Specifically, the lower limit of the mixing temperature of the mixed solution A can be independently selected from 60 ℃, 65 ℃, 70 ℃, 75 ℃ and 80 ℃; the upper limit of the mixing temperature can be independently selected from 80 deg.C, 85 deg.C, 90 deg.C, 95 deg.C, and 100 deg.C.
Specifically, the lower limit of the mixing temperature for obtaining the solution I can be independently selected from 80 ℃, 85 ℃, 90 ℃, 95 ℃ and 100 ℃; the upper limit of the mixing temperature can be independently selected from 100 deg.C, 105 deg.C, 110 deg.C, 115 deg.C, and 120 deg.C.
In one embodiment, a method for preparing a freeze resistant conductive gel comprises the steps of:
s001, modifying the carbon nano tube to obtain a modified carbon nano tube;
s002, adding hydroxyethyl methacrylate and the modified carbon nano tube into the homogeneous solution containing the ionic liquid, and mixing to obtain a mixed solution A;
the homogeneous solution containing the ionic liquid is a homogeneous solution of the ionic liquid and deionized water;
s003, adding the mixed solution A into a dispersion liquid containing bacterial cellulose, and mixing to obtain a mixed solution B;
s004, performing a crosslinking reaction on the mixed solution B to obtain the antifreeze conductive gel;
and S005, performing post-treatment on the pre-gel to obtain the anti-freezing conductive gel.
Optionally, step S001 includes at least:
carrying out acidification modification on the carbon nano tube to obtain a modified carbon nano tube;
preferably, in the acidification modification, the adopted modifier is a mixed solution of concentrated sulfuric acid and concentrated nitric acid;
the temperature of acidification modification is 120-180 ℃, and the modification time is 1-10 h.
Concentrated sulfuric acid and concentrated nitric acid adopted in the application are commercially available reagents, the concentration of the concentrated sulfuric acid is 70 wt% -98 wt%, and the concentration of the concentrated nitric acid is 65 wt% -70 wt%.
Specifically, the lower limit of the acidification modification temperature can be independently selected from 120 ℃, 125 ℃, 130 ℃, 135 ℃ and 140 ℃; the upper limit of the acidification modification temperature can be independently selected from 145 ℃, 150 ℃, 160 ℃, 170 ℃ and 180 ℃.
Optionally, in the mixed solution, the volume ratio of concentrated sulfuric acid to concentrated nitric acid is 1-10: 1;
the mass-volume ratio of the carbon nano tube to the mixed solution is 0.5-1.5 mg/mL.
Specifically, the lower limit of the volume ratio of the concentrated sulfuric acid to the concentrated nitric acid may be independently selected from 1:1, 2:1, 3:1, 4:1, 5: 1; the upper limit of the volume ratio of the concentrated sulfuric acid and the concentrated nitric acid can be independently selected from 6:1, 7:1, 8:1, 9:1 and 10: 1.
Alternatively, step S004 includes:
and under the atmosphere of protective gas, adding a cross-linking agent and an initiator into the mixed solution B to perform cross-linking reaction to obtain the anti-freezing conductive gel.
The protective gas used is an inert gas, preferably nitrogen.
According to a further aspect of the present application, there is provided the use of the above freeze resistant conductive gel or the freeze resistant conductive gel prepared by the above method in a flexible electronic device.
The beneficial effects that this application can produce include:
1) according to the anti-freezing conductive gel, the bacterial cellulose is introduced, and the stability is provided for the gel by utilizing the strong hydrogen bonding effect among a large number of hydroxyl groups in the bacterial cellulose;
2) according to the antifreeze conductive gel provided by the application, by introducing the modified carbon nano tube, not only can the gel conductivity be improved, but also the modified carbon nano tube can be used as a functional cross-linking agent, so that the whole gel network is more compact and stable;
3) the antifreeze conductive gel provided by the application utilizes an ionic liquid/glycerin/water three-solvent system, not only is the stability of the conductive gel enhanced, but also the gel is endowed with antifreeze property, so that the gel has operability at low temperature.
Drawings
FIG. 1 is a graph of tensile stress-strain curves of freeze resistant conductive gels prepared in examples 1-4 of the present application;
FIG. 2 is a graph of compressive stress-strain curves for freeze resistant conductive gels prepared in examples 1-4 of the present application;
FIG. 3 is a graph showing the change in resistance at low temperature and 30% strain of the antifreeze conductive gel prepared in example 4 of the present application.
Detailed Description
The present application will be described in detail with reference to examples, but the present application is not limited to these examples.
Unless otherwise stated, the experimental methods used in the examples of the present application are all conventional methods; the raw materials in the examples of the present application were all purchased commercially, unless otherwise specified.
The bacterial cellulose dispersion liquid adopted in the embodiment of the application is produced by Guilin Qihong scientific and technology limited company, and the content of the bacterial cellulose is 0.65%; hydroxyethyl methacrylate, wherein the manufacturer is Shanghai aladine, > 97%, and the manufacturer is a multi-walled carbon nanotube, the manufacturer is Shanghai aladine, > 95%, the inner diameter is 3-5nm, the outer diameter is 8-15 nm, and the length is-50 μm; the polyethylene glycol diacrylate is prepared by Shanghai alatin with average molecular weight of 600; the 1-butyl-3-methylimidazolium chloride salt is obtained from the institute of chemico-physical, Lanzhou, national academy of sciences, and has a purity of 99%; glycerol, manufactured by Shanghai test.
The ionic liquid is a liquid organic salt composed of organic cations and inorganic or organic anions, has good chemical stability and thermal stability and low vapor pressure (almost zero), and is widely applied to the fields of separation analysis, biosensing, biocatalysis and the like. Most ionic liquids are stable to water and air, with a wide temperature window. Meanwhile, the ionic liquid has good solubility to a plurality of inorganic micromolecules and organic macromolecules, so that various materials can be prepared in the ionic liquid.
The bacterial cellulose is a superfine fiber net structure high molecular polymer synthesized by microbial fermentation. The structure of bacterial cellulose is approximately the same as that of plant cellulose, and the main difference is that the bacterial cellulose does not contain hemicellulose and lignin. The bacterial cellulose has high water-retaining property, air permeability, biocompatibility and degradability, and is an ideal raw material for preparing hydrogel.
The multi-wall carbon nano tube is a seamless hollow tube body formed by curling a graphite sheet consisting of a layer of carbon atoms at a certain angle, and has excellent conductivity, thermal stability, high temperature resistance and easy processability. The multi-walled carbon nano tube is used as a reinforcing body of the composite hydrogel, so that the hydrogel is endowed with conductivity, and the mechanical property of the hydrogel is greatly improved.
Example 1
Taking 150mg of multi-walled carbon nano-tube, and dispersing the multi-walled carbon nano-tube in 200mL of mixed solution of concentrated sulfuric acid (the mass fraction is 70%) and concentrated nitric acid (the mass fraction is 65%), wherein the volume ratio of the concentrated sulfuric acid to the concentrated nitric acid is 3: 1. And (3) reacting the dispersion solution at 120 ℃ for 3h, cooling, washing with deionized water and ethanol for three times respectively, and vacuum-drying at room temperature for 24h to obtain the modified multi-walled carbon nanotube. 0.4g of hydroxyethyl methacrylate and 0.04g of modified multi-walled carbon nanotubes were added to a homogeneous solution consisting of 1g of deionized water and 2g of 1-butyl-3-methylimidazolium chloride, stirred at 80 ℃ for 3 hours, and mixed to obtain a mixed solution A. The mixed solution A was added to 2g of the bacterial cellulose dispersion, and stirred at 100 ℃ for 5 hours to obtain a mixed solution B. Under nitrogen atmosphere, 0.016g of polyethylene glycol diacrylate (n is 600) and 0.02g of ammonium persulfate are sequentially added into the solution, and the mixture is stirred at 100 ℃ for 5 hours to obtain the pre-gel. The obtained pre-gel was immersed in 1g of glycerin for 30min, and subjected to solution substitution treatment to obtain PBH1 gel.
Example 2
Taking 150mg of multi-walled carbon nano-tubes, and dispersing the multi-walled carbon nano-tubes into 200mL of mixed solution of concentrated sulfuric acid (the mass fraction is 70%) and concentrated nitric acid (the mass fraction is 65%), wherein the volume ratio of the concentrated sulfuric acid to the concentrated nitric acid is 3: 1. And (3) reacting the dispersion solution at 120 ℃ for 3h, cooling, washing with deionized water and ethanol for three times respectively, and vacuum-drying at room temperature for 24h to obtain the modified multi-walled carbon nanotube. 0.4g of hydroxyethyl methacrylate and 0.04g of modified multi-walled carbon nanotubes were added to a homogeneous solution consisting of 1g of deionized water and 4g of 1-butyl-3-methylimidazolium chloride, stirred at 80 ℃ for 3 hours, and mixed to obtain a mixed solution A. The mixed solution A was added to 2g of the bacterial cellulose dispersion, and stirred at 100 ℃ for 5 hours to obtain a mixed solution B. Under nitrogen atmosphere, 0.016g of polyethylene glycol diacrylate (n is 600) and 0.02g of ammonium persulfate are sequentially added into the solution, and the mixture is stirred at 100 ℃ for 5 hours to obtain the pre-gel. The obtained pre-gel was soaked in 2g of glycerol for 30min, and subjected to solution displacement treatment to obtain PBH2 gel.
Example 3
Taking 150mg of multi-walled carbon nano-tube, and dispersing the multi-walled carbon nano-tube in 200mL of mixed solution of concentrated sulfuric acid (the mass fraction is 70%) and concentrated nitric acid (the mass fraction is 65%), wherein the volume ratio of the concentrated sulfuric acid to the concentrated nitric acid is 3: 1. And (3) reacting the dispersion solution at 120 ℃ for 3h, cooling, washing with deionized water and ethanol for three times respectively, and vacuum-drying at room temperature for 24h to obtain the modified multi-walled carbon nanotube. 0.4g of hydroxyethyl methacrylate and 0.04g of modified multi-walled carbon nanotubes were added to a homogeneous solution consisting of 1g of deionized water and 6g of 1-butyl-3-methylimidazolium chloride, stirred at 80 ℃ for 3 hours, and mixed to obtain a mixed solution A. The mixed solution A was added to 2g of the bacterial cellulose dispersion, and stirred at 100 ℃ for 5 hours to obtain a mixed solution B. Under nitrogen atmosphere, 0.016g of polyethylene glycol diacrylate (n is 600) and 0.02g of ammonium persulfate are sequentially added into the solution, and the mixture is stirred at 100 ℃ for 5 hours to obtain the pre-gel. The obtained pre-gel is placed in 3g of glycerol to be soaked for 30min, and solution replacement treatment is carried out to obtain PBH3 gel.
Example 4
Taking 150mg of multi-walled carbon nano-tube, and dispersing the multi-walled carbon nano-tube in 200mL of mixed solution of concentrated sulfuric acid (the mass fraction is 70%) and concentrated nitric acid (the mass fraction is 65%), wherein the volume ratio of the concentrated sulfuric acid to the concentrated nitric acid is 3: 1. And (3) reacting the dispersion solution at 120 ℃ for 3h, cooling, washing with deionized water and ethanol for three times respectively, and vacuum-drying at room temperature for 24h to obtain the modified multi-walled carbon nanotube. 0.4g of hydroxyethyl methacrylate and 0.04g of modified multi-walled carbon nanotubes were added to a homogeneous solution consisting of 1g of deionized water and 8g of 1-butyl-3-methylimidazolium chloride, stirred at 80 ℃ for 3 hours, and mixed to obtain a mixed solution A. The mixed solution A was added to 2g of the bacterial cellulose dispersion, and stirred at 100 ℃ for 5 hours to obtain a mixed solution B. Under nitrogen atmosphere, 0.016g of polyethylene glycol diacrylate (n is 600) and 0.02g of ammonium persulfate are sequentially added into the solution, and the mixture is stirred at 100 ℃ for 5 hours to obtain the pre-gel. The obtained pre-gel was placed in 4g of glycerin and soaked for 30min, and solution displacement treatment was performed to obtain PBH4 gel.
Example 5
Taking 150mg of single-walled carbon nanotubes, and dispersing the single-walled carbon nanotubes in 200mL of mixed solution of concentrated sulfuric acid (the mass fraction is 70%) and concentrated nitric acid (the mass fraction is 65%), wherein the volume ratio of the concentrated sulfuric acid to the concentrated nitric acid is 5: 1. And (3) reacting the dispersion solution at 160 ℃ for 3h, cooling, washing with deionized water and ethanol for three times respectively, and vacuum-drying at room temperature for 24h to obtain the modified single-walled carbon nanotube. 1g of vinyl acetate and 0.01g of modified single-walled carbon nanotubes are added into a homogeneous solution consisting of 1g of deionized water and 20g of 1-vinyl-3-butylimidazolium bromide, stirred for 5 hours at 60 ℃ and mixed to obtain a mixed solution A. The mixed solution A was added to 10g of the bacterial cellulose dispersion, and stirred at 120 ℃ for 4 hours to obtain a mixed solution B. Under nitrogen atmosphere, 0.01g of polyethylene glycol diacrylate (n 900) and 0.01g of azobisisobutyronitrile were sequentially added to the solution, and the mixture was stirred at 120 ℃ for 1 hour to obtain a pregel. The obtained pre-gel was placed in 4g of glycerin and soaked for 60min, and solution displacement treatment was performed to obtain PBH5 gel.
Example 6
Taking 150mg of single-walled carbon nanotubes, and dispersing the single-walled carbon nanotubes in 200mL of mixed solution of concentrated sulfuric acid (the mass fraction is 70%) and concentrated nitric acid (the mass fraction is 65%), wherein the volume ratio of the concentrated sulfuric acid to the concentrated nitric acid is 3: 1. And (3) reacting the dispersion solution at 160 ℃ for 3h, cooling, washing with deionized water and ethanol for three times respectively, and vacuum-drying at room temperature for 24h to obtain the modified single-walled carbon nanotube. 1g of vinyl acetate and 0.01g of modified single-walled carbon nanotubes are added into a homogeneous solution consisting of 1g of deionized water and 20g of 1-vinyl-3-butylimidazolium bromide, stirred for 5 hours at 60 ℃ and mixed to obtain a mixed solution A. The mixed solution A was added to 10g of the bacterial cellulose dispersion, and stirred at 120 ℃ for 4 hours to obtain a mixed solution B. Under nitrogen atmosphere, 0.01g of polyethylene glycol diacrylate (n 900) and 0.01g of azobisisobutyronitrile were sequentially added to the solution, and the mixture was stirred at 120 ℃ for 1 hour to obtain a pregel. The obtained pre-gel was placed in 4g of glycerin and soaked for 60min, and solution displacement treatment was performed to obtain PBH6 gel.
Example 7
Taking 150mg of single-walled carbon nanotubes, and dispersing the single-walled carbon nanotubes in 200mL of mixed solution of concentrated sulfuric acid (the mass fraction is 70%) and concentrated nitric acid (the mass fraction is 65%), wherein the volume ratio of the concentrated sulfuric acid to the concentrated nitric acid is 4: 1. And (3) reacting the dispersion solution at 160 ℃ for 3h, cooling, washing with deionized water and ethanol for three times respectively, and vacuum-drying at room temperature for 24h to obtain the modified single-walled carbon nanotube. 0.5g of vinyl acetate and 0.01g of modified single-walled carbon nanotubes are added into a homogeneous solution consisting of 1g of deionized water and 20g of 1-vinyl-3-butylimidazolium bromide, stirred for 5 hours at 60 ℃ and mixed to obtain a mixed solution A. The mixed solution A was added to 10g of the bacterial cellulose dispersion, and stirred at 120 ℃ for 4 hours to obtain a mixed solution B. Under nitrogen atmosphere, 0.01g of polyethylene glycol diacrylate (n: 900) and 0.01g of azobisisobutyronitrile were sequentially added to the solution, and the mixture was stirred at 120 ℃ for 1 hour to obtain a pregel. The obtained pre-gel was placed in 4g of glycerin and soaked for 60min, and solution displacement treatment was performed to obtain PBH7 gel.
Example 8
The gel specimens prepared in examples 1 to 4 were subjected to tensile property testing in an Instron universal tester at a set tensile rate of 20 mm/min. And after the test is finished, corresponding tensile load-displacement data is derived, and is converted into a tensile stress-strain curve by using a formula. The formula for converting displacement data to tensile strain data in a tensile test is:
Figure BDA0002789826700000102
wherein epsilontRepresents tensile strain,. ltRepresents the displacement of the stretching of the spline, and d represents the length of the spline at the initial state of stretching. The formula for converting tensile load into tensile stress data is
Figure BDA0002789826700000103
Wherein sigmatRepresents tensile stress, FlRepresents the tensile load and S represents the cross-sectional area (i.e., width x thickness) of the spline. Specific test results are shown in fig. 1, and as the amount of glycerol and ionic liquid is increased, the tensile property of the conductive gel is increased, wherein the tensile property of PBH4 is optimal. This is because a large number of hydrogen bonds are present in glycerol and the hydrogen bonding effect is gradually increased as the amount of glycerol used is increased. When the gel is stretched, the gel network can take on more energy dissipation and thus increased stability and hence tensile properties.
Example 9
The gel sample blocks prepared in examples 1 to 4 were subjected to a compression performance test in an Instron universal tester at a compression speed of 2 mm/min. And after the test is finished, corresponding compression load-displacement data is derived, and is converted into a compression stress-strain curve by using a formula. The formula for converting displacement data to compressive strain data in a compression test is:
Figure BDA0002789826700000101
wherein epsiloncRepresents compressive strain,. lcRepresenting the displacement of the sample block compression, and h represents the original thickness of the sample block. The formula for converting the compressive load to compressive stress data is:
Figure BDA0002789826700000111
wherein sigmacRepresenting compressive stress, FcRepresenting the compression load, S represents the base area of the cylinder block
Figure BDA0002789826700000112
The specific test results are shown in fig. 2, and the conductive gel compression performance is increased along with the increase of the using amount of the glycerol and the ionic liquid, wherein the compression performance of the PBH4 is optimal. This is because a large number of hydrogen bonds are present in glycerol, and as the amount of glycerol increases, the hydrogen bonding effect increases, and as the gel is subjected to pressure, the gel network can take on more energy dissipation, and thus the stability increases, and the compression performance increases.
Example 10
The gel strips from example 4 were each stretched to a strain of 30% at-40 ℃ and the relative resistance change Δ R/R of the antifreeze gel was recorded0Wherein R is0Representing the original resistance of the gel before testing, and Δ R represents the difference between the resistance after stretching for a certain strain and the original resistance. The specific test results are shown in fig. 3, and the gel has good resistance response at 30% strain at-40 ℃, which indicates that the antifreeze conductive gel prepared by the application can conduct electricity under low temperature condition and has operability at low temperature.
Example 11
The resistivity of the carbon nanotube-based conductive hydrogel prepared in the embodiment 1-4 is tested, and the test method comprises the following steps: the prepared carbon nanotube-based conductive hydrogel is tested by a four-probe resistivity tester, the resistivity of the MWCNT1-H carbon nanotube-based conductive hydrogel is 123388 +/-972.9 omega cm, the resistivity of the MWCNT2-H carbon nanotube-based conductive hydrogel is 114154 +/-4177.5 omega cm, the resistivity of the MWCNT3-H carbon nanotube-based conductive hydrogel is 93666 +/-429.9 omega cm, the resistivity of the MWCNT4-H carbon nanotube-based conductive hydrogel is 75610 +/-1626.3 omega cm, the resistivity is reciprocal of the conductivity, the larger the resistivity is, the smaller the conductivity is, and the conductivity is increased along with the increase of the dosage of the modified carbon nanotube.
Although the present application has been described with reference to a few embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the application as defined by the appended claims.

Claims (10)

1. The antifreeze conductive gel is characterized by comprising the following components: bacterial cellulose, acrylate substances, carbon nano tubes, ionic liquid, a cross-linking agent, glycerol and deionized water;
the ionic liquid is imidazole ionic liquid.
2. The freeze resistant conductive gel of claim 1,
the mass ratio of the bacterial cellulose to the acrylate substances is 10: 0.1-1;
the mass ratio of the acrylate substances to the deionized water is 0.01-1: 1;
the mass ratio of the carbon nano tube to the deionized water is 1: 20-100;
the mass ratio of the ionic liquid to the deionized water is 1-20: 1;
the mass ratio of the glycerol to the deionized water is 0.1-10: 1.
3. The antifreeze conductive gel of claim 1, wherein said acrylate is selected from at least one of hydroxyethyl methacrylate, acrylate, vinyl acetate;
the imidazole ionic liquid is selected from at least one of 1-butyl-3-methylimidazole bromine salt, 1-butyl-3-methylimidazole chlorine salt, 1-propyl-3-methylimidazole bromine salt, 1-propyl-3-methylimidazole chlorine salt, 1-vinyl-3-butylimidazole bromine salt and 1-propyl-3-methylimidazole chlorine salt;
the carbon nano tube is a modified carbon nano tube.
4. The antifreeze conductive gel of claim 1, wherein the constituents of said antifreeze organic conductive gel further comprise a crosslinking agent;
the cross-linking agent is at least one of polyethylene glycol diacrylate, N' -methylene bisacrylamide, phytic acid and diisocyanate;
the dosage of the cross-linking agent is 0.5-10% of the mass of the acrylate substances.
5. Process for the preparation of a freeze resistant conductive gel according to any one of claims 1 to 4, characterized in that it comprises at least:
crosslinking a solution I containing acrylate substances, carbon nano tubes and bacterial cellulose to obtain a pre-gel;
replacing the pre-gel in glycerol to obtain the anti-freezing conductive gel;
the solution I comprises imidazole ionic liquid and water.
6. The method of claim 5, wherein the conditions of the crosslinking reaction include:
adding a cross-linking agent and an initiator into the solution I to perform cross-linking reaction to obtain the anti-freezing conductive gel;
the temperature of the crosslinking reaction is 50-120 ℃, and the reaction time is 0.5-12 h.
7. Method for producing antifreeze conductive gel according to claim 6,
the initiator is at least one of ammonium persulfate, potassium persulfate and azobisisobutyronitrile;
the dosage of the initiator is 1-15% of the mass of the acrylate substances.
8. The method of preparing a freeze resistant conductive gel of claim 5 wherein the solvent displacement conditions include:
the time of the solvent replacement treatment is 5-120 min.
9. The method of claim 5, wherein solution I is obtained by:
adding an acrylate substance and a carbon nano tube into a homogeneous solution containing ionic liquid, and mixing to obtain a mixed solution A;
adding the mixed solution A into a dispersion liquid containing bacterial cellulose, and mixing to obtain a solution I;
preferably, the mixing temperature for obtaining the mixed solution A is 60-100 ℃;
preferably, the mixing temperature for obtaining the solution I is 80-120 ℃.
10. Use of the antifreeze conductive gel of any one of claims 1 to 4 or the antifreeze conductive gel prepared by the method of any one of claims 5 to 9 in flexible electronic devices.
CN202011311012.8A 2020-11-20 2020-11-20 Anti-freezing conductive gel and preparation method and application thereof Active CN114516936B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202011311012.8A CN114516936B (en) 2020-11-20 2020-11-20 Anti-freezing conductive gel and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202011311012.8A CN114516936B (en) 2020-11-20 2020-11-20 Anti-freezing conductive gel and preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN114516936A true CN114516936A (en) 2022-05-20
CN114516936B CN114516936B (en) 2024-01-16

Family

ID=81594770

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202011311012.8A Active CN114516936B (en) 2020-11-20 2020-11-20 Anti-freezing conductive gel and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN114516936B (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114920957A (en) * 2022-05-25 2022-08-19 中国科学院新疆理化技术研究所 Anti-freezing white hydrogel for chemical colorimetric sensor substrate and preparation method thereof

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050037082A1 (en) * 2003-08-13 2005-02-17 Wan-Kei Wan Poly(vinyl alcohol)-bacterial cellulose nanocomposite
CN101906233A (en) * 2010-07-26 2010-12-08 武汉大学 Cellulose gel/acrylic acid series polymer composition
CN105440296A (en) * 2015-01-14 2016-03-30 湖南工业大学 High-strength cellulose-based nanocomposite temperature and pH dual stimuli-responsive gel and preparation method thereof
US20170000903A1 (en) * 2013-11-28 2017-01-05 University Of Saskatchewan Crystalline cellulose gel-based cryptands, surface active agents, emulsions and vesicles
CN109734842A (en) * 2018-12-04 2019-05-10 华南理工大学 A kind of electrically conducting transparent flexibility bacteria cellulose composite material and preparation method thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050037082A1 (en) * 2003-08-13 2005-02-17 Wan-Kei Wan Poly(vinyl alcohol)-bacterial cellulose nanocomposite
CN101906233A (en) * 2010-07-26 2010-12-08 武汉大学 Cellulose gel/acrylic acid series polymer composition
US20170000903A1 (en) * 2013-11-28 2017-01-05 University Of Saskatchewan Crystalline cellulose gel-based cryptands, surface active agents, emulsions and vesicles
CN105440296A (en) * 2015-01-14 2016-03-30 湖南工业大学 High-strength cellulose-based nanocomposite temperature and pH dual stimuli-responsive gel and preparation method thereof
CN109734842A (en) * 2018-12-04 2019-05-10 华南理工大学 A kind of electrically conducting transparent flexibility bacteria cellulose composite material and preparation method thereof

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114920957A (en) * 2022-05-25 2022-08-19 中国科学院新疆理化技术研究所 Anti-freezing white hydrogel for chemical colorimetric sensor substrate and preparation method thereof

Also Published As

Publication number Publication date
CN114516936B (en) 2024-01-16

Similar Documents

Publication Publication Date Title
CN110760152B (en) Anti-freezing hydrogel and preparation method and application thereof
Lin et al. One-step radiation synthesis of agarose/polyacrylamide double-network hydrogel with extremely excellent mechanical properties
CN110938894B (en) Anti-freezing self-repairing conductive nano composite hydrogel fiber and preparation method thereof
CN110591118B (en) Multifunctional light-driven low-temperature-resistant double-network hydrogel and preparation method and application thereof
Lee et al. Fabrication and evaluation of bacterial cellulose-polyaniline composites by interfacial polymerization
Pei et al. Self-healing and toughness cellulose nanocrystals nanocomposite hydrogels for strain-sensitive wearable flexible sensor
CN109485877B (en) High-temperature and low-temperature resistant high-toughness organic hydrogel and preparation method thereof
CN113012947B (en) Preparation method and application of water-based solid electrolyte
CN114516936B (en) Anti-freezing conductive gel and preparation method and application thereof
CN110595347A (en) Low-Young modulus hydrogel flexible strain sensor
CN110164704A (en) A kind of enhanced flexible super capacitor of light and preparation method thereof
Li et al. Phytic acid-assist for self-healing nanocomposite hydrogels with surface functionalization of cellulose nanocrystals via SI-AGET ATRP
CN112552533B (en) Preparation method of high-strength anisotropic crystal hydrogel
Wang et al. Fabrication of an ion-enhanced low-temperature tolerant graphene/PAA/KCl hydrogel and its application for skin sensors
Feng et al. Facile and rapid synthesis of flexible PEG porous polymers as substrates for functional materials by thiol-ene click chemistry
CN112300336B (en) Self-repairing conductive hydrogel material and preparation method thereof
CN115010862B (en) Preparation method of cellulose-based ion conductive elastomer
CN112210114A (en) Preparation method of ultrahigh-strength multifunctional polyvinyl alcohol-based oil gel elastomer
CN112724325A (en) Preparation method and application of nano-silicon cross-linking agent and quick-response hydrogel
CN113332936A (en) High-toughness conductive anti-freezing carbon nanotube organic hydrogel
CN109679295B (en) Method for enhancing composite performance of carbon fiber and resin matrix
CN110060878B (en) Polyaniline/graphene oxide nanofiber composite material and preparation method and application thereof
KR101162039B1 (en) PVA/PAAc/oxyfluorinated carbon nanotubes composite nanofibers coated with polyaniline and its manufacturing method
Huang et al. Preparation and Properties of Cellulose Nanofiber-Reinforced Ionic Conductive Hydrogels Sensor
CN111218012A (en) Preparation method of photo-thermal induced self-repairing conductive hydrogel

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant