CN110183752B - Preparation method of carboxyl nitrile rubber/carboxylated chitosan composite conductive film - Google Patents
Preparation method of carboxyl nitrile rubber/carboxylated chitosan composite conductive film Download PDFInfo
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- 229920001661 Chitosan Polymers 0.000 title claims abstract description 84
- 229920000459 Nitrile rubber Polymers 0.000 title claims abstract description 65
- 239000002131 composite material Substances 0.000 title claims abstract description 51
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000007864 aqueous solution Substances 0.000 claims abstract description 54
- 239000000243 solution Substances 0.000 claims abstract description 48
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000000839 emulsion Substances 0.000 claims abstract description 14
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 claims abstract description 14
- 235000019345 sodium thiosulphate Nutrition 0.000 claims abstract description 14
- 230000021523 carboxylation Effects 0.000 claims abstract description 13
- 238000006473 carboxylation reaction Methods 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 13
- 238000010438 heat treatment Methods 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 12
- 238000005266 casting Methods 0.000 claims description 31
- 239000011521 glass Substances 0.000 claims description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 30
- 239000007788 liquid Substances 0.000 claims description 20
- 239000012153 distilled water Substances 0.000 claims description 18
- 150000002825 nitriles Chemical class 0.000 claims description 18
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 claims description 12
- 229910000366 copper(II) sulfate Inorganic materials 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- 239000004816 latex Substances 0.000 claims description 10
- 229920000126 latex Polymers 0.000 claims description 10
- 239000011259 mixed solution Substances 0.000 claims description 10
- 229920000642 polymer Polymers 0.000 claims description 10
- 238000007790 scraping Methods 0.000 claims description 10
- 238000002791 soaking Methods 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
- XNINAOUGJUYOQX-UHFFFAOYSA-N 2-cyanobutanoic acid Chemical compound CCC(C#N)C(O)=O XNINAOUGJUYOQX-UHFFFAOYSA-N 0.000 claims description 2
- BHTJEPVNHUUIPV-UHFFFAOYSA-N pentanedial;hydrate Chemical compound O.O=CCCCC=O BHTJEPVNHUUIPV-UHFFFAOYSA-N 0.000 claims description 2
- 229910000365 copper sulfate Inorganic materials 0.000 abstract description 8
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 abstract description 8
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 abstract description 8
- 239000000463 material Substances 0.000 abstract description 8
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 abstract description 5
- 239000011159 matrix material Substances 0.000 abstract description 5
- 239000012528 membrane Substances 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 4
- 238000010521 absorption reaction Methods 0.000 abstract description 3
- 239000007888 film coating Substances 0.000 abstract description 2
- 238000009501 film coating Methods 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 abstract description 2
- 229920005597 polymer membrane Polymers 0.000 description 8
- 229920001971 elastomer Polymers 0.000 description 5
- 239000005060 rubber Substances 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 3
- 230000000536 complexating effect Effects 0.000 description 3
- 239000011231 conductive filler Substances 0.000 description 3
- 239000004020 conductor Substances 0.000 description 3
- 229910001431 copper ion Inorganic materials 0.000 description 3
- 125000004093 cyano group Chemical group *C#N 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 229910052976 metal sulfide Inorganic materials 0.000 description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- BWFPGXWASODCHM-UHFFFAOYSA-N copper monosulfide Chemical class [Cu]=S BWFPGXWASODCHM-UHFFFAOYSA-N 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 229920005570 flexible polymer Polymers 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 210000000056 organ Anatomy 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
Classifications
-
- 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
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- 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
- C08J2313/00—Characterised by the use of rubbers containing carboxyl groups
-
- 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
- C08J2405/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2401/00 or C08J2403/00
- C08J2405/08—Chitin; Chondroitin sulfate; Hyaluronic acid; Derivatives thereof
-
- 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
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
- C08K2003/3045—Sulfates
Abstract
The invention relates to the technical field of functional material preparation, in particular to a preparation method of a carboxyl nitrile rubber/carboxylation chitosan composite conductive film. The preparation method comprises the steps of mixing the carboxyl nitrile rubber emulsion, the carboxylated chitosan solution and the glutaraldehyde solution, immersing the mixture into a solution containing copper sulfate for curing after film coating, adding a sodium thiosulfate aqueous solution into the copper sulfate solution after forming, heating, and reacting by adopting a chemical bath method to generate copper sulfide, thereby finally obtaining the carboxyl nitrile rubber/carboxymethyl chitosan composite conductive film. The copper sulfate prepared by the method not only grows on the surface of the nitrile rubber, but also grows and polymerizes in the nitrile rubber, so that the formed copper sulfate can cover the surface of the carboxyl nitrile rubber/carboxymethyl chitosan matrix membrane and also penetrates into the membrane, the effective absorption of copper sulfide is really completed, and the composite material has excellent conductivity.
Description
Technical Field
The invention relates to the technical field of functional material preparation, in particular to a preparation method of a carboxyl nitrile rubber/carboxylation chitosan composite conductive film.
Background
The flexible conductive composite material has excellent stretchability, conductivity and strain sensitivity, so that the flexible conductive composite material has wide application prospects in the aspects of sensors, foldable electronic screens, artificial skins and organs and the like. Flexible electronics is a new electronic technology combining organic or inorganic material electronic devices with flexible substrates, and has wide application prospects in various fields of information, energy, medical treatment, national defense and the like due to good flexibility, ductility, high-efficiency and low-cost preparation processes. In recent years, flexible electronic technology has been rapidly developed, and many colleges with known names have established research institutions for flexible electronic technology in turn and have conducted a great deal of research on materials and preparation processes of flexible electronic devices.
The nitrile rubber is non-crystalline rubber prepared by copolymerizing butadiene and acrylonitrile, has polar cyano groups in molecules, has good oil resistance, wear resistance, air tightness, antistatic property and the like, and is special synthetic rubber with the largest consumption at present. The composite conductive rubber material is obtained by filling conductive filler in a rubber matrix, has the properties of good flexibility, electric conduction, heat conduction, easy processing and the like, and has wide application in the aspects of electromagnetic shielding, electric conduction, wave absorption and sensing. The conductivity of the composite conductive rubber material is influenced by a plurality of factors such as the dosage of the conductive filler, the conductive filling network structure, the type and viscosity of the polymer, the dispersion condition of the filling filler in the polymer matrix, the processing technology and the like. Generally, the conductivity of the conductive rubber composite material is improved, and a large amount of conductive filler needs to be filled, so that the mechanical property of the composite material is reduced, the processability of the composite material is poor, and the cost is increased.
The metal sulfide has special performance in the aspects of optics, photoelectrochemistry, catalysis, environmental protection and the like. They have good chemical and thermal stability and are good photoelectric materials. The method for producing the flexible polymer composite conductive material by utilizing the characteristics of the metal sulfide is mostly a polymer surface chemical reaction method which is mainly used for generating adsorption on the surface of a polymer by chemical treatment, namely by dipping reaction liquid, and then covering the surface of a high polymer material with the metal sulfide by chemical reaction. The method has the advantages of simple process, low cost, and less damage to the strength, flexibility, smoothness and the like of the high polymer material. However, the cyano group in the nitrile rubber has limited complexing ability to copper ions, and the copper sulfide/nitrile rubber composite conductive material prepared by the method often has the problems of insecure combination of copper sulfide and a matrix, uneven surface dispersion and the like, so that the composite conductive material has poor stability and low conductivity. Therefore, the development of the conductive flexible material with high flexibility, high conductivity and durability is particularly important by selecting a proper method to modify the nitrile rubber.
Disclosure of Invention
In order to solve the technical problems, the invention provides a preparation method of a carboxyl nitrile rubber/carboxylation chitosan composite conductive film, and the obtained material has good conductivity, mechanical strength and flexibility.
The technical scheme of the invention is realized as follows:
a preparation method of a carboxyl nitrile rubber/carboxylation chitosan composite conductive film comprises the following steps:
(1) uniformly mixing the carboxylated nitrile-butadiene rubber emulsion with the carboxylated chitosan solution, adding a glutaraldehyde aqueous solution, stirring at 40-60 ℃ for 0.5-2 hours to obtain a mixed solution, and standing and defoaming to obtain a polymer casting solution;
(2) and (2) casting the polymer casting solution obtained in the step (1) on a glass plate, scraping the glass plate into a liquid film with the thickness of 400-1200 microns by using a scraper, immersing the glass plate with the liquid film into a blue vitriol aqueous solution, soaking for 1-4 hours at the temperature of 10-40 ℃, adding a sodium thiosulfate aqueous solution, heating to the temperature of 75-95 ℃, reacting for 0.5-4 hours, taking out the blended film, rinsing with water, and drying to obtain the carboxylated nitrile butadiene rubber/carboxylated chitosan composite conductive film.
The mass ratio of the carboxyl nitrile rubber emulsion, the carboxylated chitosan solution and the glutaraldehyde aqueous solution in the step (1) is (60-80): (20-40): (1-5).
The carboxylated chitosan solution is an aqueous solution with the mass concentration of 3-6% prepared by dissolving carboxylated chitosan in distilled water; the mass concentration of the glutaraldehyde water solution is 0.5-2%.
The carboxyl butyronitrile latex has the model number of FM 301, the solid content of 41 +/-1 percent and the content of bound nitrile of more than or equal to 30 percent.
In the step (2), the mass concentration of the blue copperas aqueous solution is 2-8%, and the mass concentration of the sodium thiosulfate aqueous solution is 2-8%.
The invention has the beneficial effects that:
(1) the preparation method comprises the steps of mixing the carboxyl nitrile rubber emulsion, the carboxylated chitosan solution and the glutaraldehyde solution, immersing the mixture into a solution containing copper sulfate for curing after film coating, adding a sodium thiosulfate aqueous solution into the copper sulfate solution after forming, heating, and reacting by adopting a chemical bath method to generate copper sulfide, thereby finally obtaining the carboxyl nitrile rubber/carboxymethyl chitosan composite conductive film. The copper sulfate prepared by the method not only grows on the surface of the nitrile rubber, but also grows and polymerizes in the nitrile rubber, so that the formed copper sulfate can cover the surface of the carboxyl nitrile rubber/carboxymethyl chitosan matrix membrane and also penetrates into the membrane, the effective absorption of copper sulfide is really completed, and the composite material has excellent conductivity.
(2) The cyano in the carboxylated nitrile rubber has a complexing effect on copper ions, and due to the introduction of the strong chelating adsorption effect of the carboxylated chitosan, a large number of amino N atoms are arranged on a macromolecular chain of the carboxylated nitrile rubber, so that the carboxylated nitrile rubber has strong electron accepting performance, the carboxylated chitosan can generate a strong complexing effect on the copper ions, the loading capacity of copper sulfides on the carboxylated nitrile rubber/carboxymethyl chitosan is improved, and the conductivity durability of the flexible film are effectively improved.
(3) The preparation method has the advantages of easily controlled conditions, simple operation, low raw material cost and low energy consumption, and is suitable for large-scale industrial production. Compared with other products, the adhesion between the conductive layer and the substrate of the copper sulfide flexible composite material prepared by the invention is remarkably improved, the conductive layer is more compact, and the copper sulfide flexible composite material has outstanding wear resistance and solvent resistance; the product has good electromagnetic shielding property and flexibility, and the surface resistance of the product is sensitive to the change of environment such as pressure, elasticity and the like, so the product can be widely applied to the fields of sensors, static prevention, electromagnetic shielding and the like.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without inventive effort based on the embodiments of the present invention, are within the scope of the present invention.
Example 1
The preparation method of the carboxylated nitrile rubber/carboxylated chitosan composite conductive film of the embodiment comprises the following steps:
(1) preparing carboxylated chitosan into an aqueous solution with the mass percentage concentration of 6% by using distilled water;
(2) preparing glutaraldehyde into an aqueous solution with the mass percentage concentration of 2% by using distilled water;
(3) uniformly mixing 8 g of carboxylated nitrile rubber emulsion with 2 g of carboxylated chitosan solution obtained in the step (1), adding 0.1 g of glutaraldehyde aqueous solution obtained in the step (2), and stirring at 60 ℃ for 0.5 hour to obtain a mixed solution; standing and defoaming to prepare a polymer membrane casting solution;
(4) and (3) casting the casting solution obtained in the step (3) onto a glass plate, scraping the casting solution into a liquid film with the thickness of 400 microns by using a scraper, immersing the glass plate with the liquid film into 50 g of a 5% aqueous solution of blue vitriol, soaking at 10 ℃ for 4 hours, adding 50 g of a 5% aqueous solution of sodium thiosulfate, heating to 95 ℃ for reaction for 0.5 hour, taking out the blended film, rinsing with water, and drying to obtain the carboxylated nitrile rubber/carboxylated chitosan composite conductive film. The conductivity of the carboxyl nitrile rubber/carboxylation chitosan composite conductive film is 1.3S/cm.
The type of the carboxylated nitrile latex used in the embodiment is FM 301, the solid content is 41 +/-1 percent, and the content of the combined nitrile is more than or equal to 30 percent; the carboxylated chitosan is water-soluble chitosan from Aladdin company.
Example 2
The preparation method of the carboxylated nitrile rubber/carboxylated chitosan composite conductive film of the embodiment comprises the following steps:
(1) preparing carboxylated chitosan into an aqueous solution with the mass percentage concentration of 3% by using distilled water;
(2) preparing glutaraldehyde into 0.5% water solution by mass percentage concentration with distilled water;
(3) uniformly mixing 6 g of carboxylated nitrile rubber emulsion with 4 g of carboxylated chitosan solution obtained in the step (1), adding 0.5 g of glutaraldehyde aqueous solution obtained in the step (2), and stirring at 40 ℃ for 2 hours to obtain a mixed solution; standing and defoaming to prepare a polymer membrane casting solution;
(4) and (3) casting the casting solution obtained in the step (3) onto a glass plate, scraping the glass plate into a liquid film with the thickness of 600 microns by using a scraper, immersing the glass plate with the liquid film into 50 g of 2% aqueous solution of blue vitriol, soaking for 1 hour at 40 ℃, adding 50 g of 2% aqueous solution of sodium thiosulfate, heating to 75 ℃ for reaction for 4 hours, taking out the blended film, rinsing with water, and drying to obtain the carboxyl nitrile rubber/carboxylated chitosan composite conductive film. The conductivity of the carboxyl nitrile rubber/carboxylation chitosan composite conductive film is 0.9S/cm.
The type of the carboxylated nitrile latex used in the embodiment is FM 301, the solid content is 41 +/-1 percent, and the content of the combined nitrile is more than or equal to 30 percent; the carboxylated chitosan is water-soluble chitosan from Aladdin company.
Example 3
The preparation method of the carboxylated nitrile rubber/carboxylated chitosan composite conductive film of the embodiment comprises the following steps:
(1) preparing carboxylated chitosan into an aqueous solution with the mass percentage concentration of 4% by using distilled water;
(2) preparing glutaraldehyde into 1% aqueous solution by mass percentage concentration with distilled water;
(3) uniformly mixing 7 g of carboxylated nitrile rubber emulsion with 3 g of carboxylated chitosan solution obtained in the step (1), adding 0.2 g of glutaraldehyde aqueous solution obtained in the step (2), and stirring at 50 ℃ for 1.5 hours to obtain a mixed solution; standing and defoaming to prepare a polymer membrane casting solution;
(4) and (3) casting the casting solution obtained in the step (3) onto a glass plate, scraping the glass plate into a liquid film with the thickness of 1200 microns by using a scraper, immersing the glass plate with the liquid film into 50 g of 7% aqueous solution of blue vitriol, soaking at 30 ℃ for 2 hours, adding 50 g of 7% aqueous solution of sodium thiosulfate, heating to 85 ℃ for reaction for 2 hours, taking out the blended film, rinsing with water, and drying to obtain the carboxyl nitrile rubber/carboxylated chitosan composite conductive film. The conductivity of the carboxyl nitrile rubber/carboxylation chitosan composite conductive film is 5.5S/cm.
The type of the carboxylated nitrile latex used in the embodiment is FM 301, the solid content is 41 +/-1 percent, and the content of the combined nitrile is more than or equal to 30 percent; the carboxylated chitosan is water-soluble chitosan from Aladdin company.
Example 4
The preparation method of the carboxylated nitrile rubber/carboxylated chitosan composite conductive film of the embodiment comprises the following steps:
(1) preparing carboxylated chitosan into an aqueous solution with the mass percentage concentration of 5% by using distilled water;
(2) preparing glutaraldehyde into 1.5% aqueous solution by mass percentage concentration with distilled water;
(3) uniformly mixing 6.5 g of carboxylated nitrile rubber emulsion with 3.5 g of carboxylated chitosan solution obtained in the step (1), adding 0.3 g of glutaraldehyde aqueous solution obtained in the step (2), and stirring at 55 ℃ for 1.5 hours to obtain a mixed solution; standing and defoaming to prepare a polymer membrane casting solution;
(4) and (3) casting the casting solution obtained in the step (3) onto a glass plate, scraping the glass plate into a liquid film with the thickness of 900 microns by using a scraper, immersing the glass plate with the liquid film into 50 g of 8% aqueous solution of blue vitriol, soaking at 35 ℃ for 2 hours, adding 50 g of 8% aqueous solution of sodium thiosulfate, heating to 90 ℃ for reaction for 1 hour, taking out the blended film, rinsing with water, and drying to obtain the carboxyl nitrile rubber/carboxylated chitosan composite conductive film. The conductivity of the carboxyl nitrile rubber/carboxylation chitosan composite conductive film is 4.5S/cm.
The type of the carboxylated nitrile latex used in the embodiment is FM 301, the solid content is 41 +/-1 percent, and the content of the combined nitrile is more than or equal to 30 percent; the carboxylated chitosan is water-soluble chitosan from Aladdin company.
Example 5
The preparation method of the carboxylated nitrile rubber/carboxylated chitosan composite conductive film of the embodiment comprises the following steps:
(1) preparing carboxylated chitosan into an aqueous solution with the mass percentage concentration of 5.5% by using distilled water;
(2) preparing glutaraldehyde into 1.2% aqueous solution by mass percentage concentration with distilled water;
(3) uniformly mixing 7.5 g of carboxylated nitrile rubber emulsion with 2.5 g of carboxylated chitosan solution obtained in the step (1), adding 0.3 g of glutaraldehyde aqueous solution obtained in the step (2), and stirring at 45 ℃ for 1.5 hours to obtain a mixed solution; standing and defoaming to prepare a polymer membrane casting solution;
(4) and (3) casting the casting solution obtained in the step (3) onto a glass plate, scraping the glass plate into a liquid film with the thickness of 500 microns by using a scraper, immersing the glass plate with the liquid film into 50 g of 3% aqueous solution of blue vitriol, soaking for 3 hours at 25 ℃, adding 50 g of 3% aqueous solution of sodium thiosulfate, heating to 80 ℃, reacting for 1.5 hours, taking out the blended film, rinsing with water, and drying to obtain the carboxyl nitrile rubber/carboxylated chitosan composite conductive film. The conductivity of the carboxyl nitrile rubber/carboxylation chitosan composite conductive film is 1.2S/cm.
The type of the carboxylated nitrile latex used in the embodiment is FM 301, the solid content is 41 +/-1 percent, and the content of the combined nitrile is more than or equal to 30 percent; the carboxylated chitosan is water-soluble chitosan from Aladdin company.
Example 6
The preparation method of the carboxylated nitrile rubber/carboxylated chitosan composite conductive film of the embodiment comprises the following steps:
(1) preparing carboxylated chitosan into an aqueous solution with the mass percentage concentration of 4.5% by using distilled water;
(2) preparing glutaraldehyde into 1.6% water solution by mass percentage concentration with distilled water;
(3) uniformly mixing 6.8 g of carboxylated nitrile rubber emulsion with 3.2 g of carboxylated chitosan solution obtained in the step (1), adding 0.4 g of glutaraldehyde aqueous solution obtained in the step (2), and stirring at 56 ℃ for 1.8 hours to obtain a mixed solution; standing and defoaming to prepare a polymer membrane casting solution;
(4) and (3) casting the polymer casting solution obtained in the step (3) on a glass plate, scraping the glass plate into a liquid film with the thickness of 1100 microns by using a scraper, immersing the glass plate with the liquid film into 50 g of 4% aqueous solution of blue vitriol, soaking the glass plate for 2 hours at 28 ℃, adding 50 g of 4% aqueous solution of sodium thiosulfate, heating the glass plate to 82 ℃ for reaction for 1.5 hours, taking out the blended film, rinsing the blended film by using water, and drying the blended film to obtain the carboxylated nitrile butadiene rubber/carboxylated chitosan composite conductive film. The conductivity of the carboxyl nitrile rubber/carboxylation chitosan composite conductive film is 2.1S/cm.
The type of the carboxylated nitrile latex used in the embodiment is FM 301, the solid content is 41 +/-1 percent, and the content of the combined nitrile is more than or equal to 30 percent; the carboxylated chitosan is water-soluble chitosan from Aladdin company.
Example 7
The preparation method of the carboxylated nitrile rubber/carboxylated chitosan composite conductive film of the embodiment comprises the following steps:
(1) preparing carboxylated chitosan into an aqueous solution with the mass percentage concentration of 3.6% by using distilled water;
(2) preparing glutaraldehyde into 0.9 mass percent aqueous solution by using distilled water;
(3) uniformly mixing 7.5 g of carboxylated nitrile rubber emulsion with 3.5 g of carboxylated chitosan solution obtained in the step (1), adding 0.5 g of glutaraldehyde aqueous solution obtained in the step (2), and stirring at 52 ℃ for 0.9 hour to obtain a mixed solution; standing and defoaming to prepare a polymer membrane casting solution;
(4) and (3) casting the polymer casting solution obtained in the step (3) on a glass plate, scraping the glass plate into a liquid film with the thickness of 900 microns by using a scraper, immersing the glass plate with the liquid film into 50 g of 6% aqueous solution of blue vitriol, soaking for 2.5 hours at 25 ℃, adding 50 g of 6% aqueous solution of sodium thiosulfate, heating to 88 ℃ for reaction for 1.5 hours, taking out the blended film, rinsing with water, and drying to obtain the carboxyl nitrile rubber/carboxylated chitosan composite conductive film. The conductivity of the carboxyl nitrile rubber/carboxylation chitosan composite conductive film is 3.3S/cm.
The type of the carboxylated nitrile latex used in the embodiment is FM 301, the solid content is 41 +/-1 percent, and the content of the combined nitrile is more than or equal to 30 percent; the carboxylated chitosan is water-soluble chitosan from Aladdin company.
Example 8
The preparation method of the carboxylated nitrile rubber/carboxylated chitosan composite conductive film of the embodiment comprises the following steps:
(1) preparing carboxylated chitosan into an aqueous solution with the mass percentage concentration of 5.5% by using distilled water;
(2) preparing glutaraldehyde into 1.8 mass percent aqueous solution by using distilled water;
(3) uniformly mixing 7.8 g of carboxylated nitrile rubber emulsion with 3.2 g of carboxylated chitosan solution obtained in the step (1), adding 0.3 g of glutaraldehyde aqueous solution obtained in the step (2), and stirring at 47 ℃ for 1.2 hours to obtain a mixed solution; standing and defoaming to prepare a polymer membrane casting solution;
(4) and (3) casting the casting solution obtained in the step (3) onto a glass plate, scraping the glass plate into a liquid film with the thickness of 950 microns by using a scraper, immersing the glass plate with the liquid film into 50 g of 6% aqueous solution of blue vitriol, soaking for 2.5 hours at 23 ℃, adding 50 g of 6% aqueous solution of sodium thiosulfate, heating to 85 ℃, reacting for 2 hours, taking out the blended film, rinsing with water, and drying to obtain the carboxyl nitrile rubber/carboxylated chitosan composite conductive film. The conductivity of the carboxyl nitrile rubber/carboxylation chitosan composite conductive film is 3.1S/cm.
The type of the carboxylated nitrile latex used in the embodiment is FM 301, the solid content is 41 +/-1 percent, and the content of the combined nitrile is more than or equal to 30 percent; the carboxylated chitosan is water-soluble chitosan from Aladdin company.
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, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (3)
1. A preparation method of a carboxyl nitrile rubber/carboxylation chitosan composite conductive film is characterized by comprising the following steps:
(1) uniformly mixing the carboxylated nitrile-butadiene rubber emulsion with the carboxylated chitosan solution, adding a glutaraldehyde aqueous solution, stirring at 40-60 ℃ for 0.5-2 hours to obtain a mixed solution, and standing and defoaming to obtain a polymer casting solution;
(2) casting the polymer casting solution obtained in the step (1) on a glass plate, scraping the glass plate into a liquid film with the thickness of 400-1200 microns by using a scraper, immersing the glass plate with the liquid film into a blue vitriol aqueous solution, soaking for 1-4 hours at the temperature of 10-40 ℃, adding a sodium thiosulfate aqueous solution, heating to the temperature of 75-95 ℃ for reaction for 0.5-4 hours, taking out the blended film, rinsing with water, and drying to obtain the carboxyl nitrile rubber/carboxylated chitosan composite conductive film;
the mass ratio of the carboxyl nitrile rubber emulsion, the carboxylated chitosan solution and the glutaraldehyde aqueous solution in the step (1) is (60-80): (20-40): (1-5);
the carboxylated chitosan solution is an aqueous solution with the mass concentration of 3-6% prepared by dissolving carboxylated chitosan in distilled water; the mass concentration of the glutaraldehyde water solution is 0.5-2%.
2. The method for preparing a carboxylated nitrile rubber/carboxylated chitosan composite conductive film according to claim 1, wherein the method comprises the following steps: the carboxyl butyronitrile latex has the model number of FM 301, the solid content of 41 +/-1 percent and the content of bound nitrile of more than or equal to 30 percent.
3. The method for preparing a carboxylated nitrile rubber/carboxylated chitosan composite conductive film according to claim 1, wherein the method comprises the following steps: in the step (2), the mass concentration of the blue copperas aqueous solution is 2-8%, and the mass concentration of the sodium thiosulfate aqueous solution is 2-8%.
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