CN113337099B - Silver-plated graphene/synthetic rubber latex composition and preparation and application thereof - Google Patents
Silver-plated graphene/synthetic rubber latex composition and preparation and application thereof Download PDFInfo
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Abstract
The invention belongs to the field of rubber materials, and particularly relates to a silver-plated graphene/synthetic rubber latex composition and a preparation method thereof. The surface of the modified graphene is plated with silver to obtain the graphene with the surface covered with silver, and the graphene and the synthetic rubber latex form the silver-plated graphene/synthetic rubber latex composition. The latex composition has antibacterial property and excellent mechanical property, and in addition, the preparation method provided by the invention has the advantages of simple equipment, simplicity in operation, good controllability, contribution to industrial amplification and the like.
Description
Technical Field
The invention belongs to the technical field of rubber, and particularly relates to a silver-plated graphene/synthetic rubber latex composition and a preparation method and application thereof.
Background
Along with the progress of society, the living of materials is increasingly enriched, and the requirements of people on health are higher and higher. Common rubber protective products in daily life, such as medical gloves, condoms, protective gloves and the like, hope that the rubber protective products not only can play a role in protecting the safety of the rubber protective products, but also can block viruses, bacteria and other substances. However, rubber latex has micropores with a diameter of several hundred to several thousand nanometers, while bacteria generally have a diameter of 0.5 micrometer and a thickness of 0.5 micrometer, and some viruses are smaller, and have a maximum diameter of several hundred to several tens nanometers, and these bacteria and viruses will spread through the micropores, so how to further improve the protective performance of rubber latex products is one of the important directions of current research.
At present, natural rubber is a main matrix of latex products, and since natural latex contains various non-rubber components such as protein and phospholipid, which may be sensitized, and affect the size of voids and cracks in an adhesive film, it is of great importance to develop synthetic rubber instead of natural rubber, and to develop a high-barrier filler system suitable for synthetic rubber.
Since long ago, people know that silver has the function of keeping fresh, ancient imperial relatives and relatives use silverware to contain food, for example, milk contained in a silver cup cannot go bad in half a month, and milk contained in a common bowl goes bad in two or three days. Silver is now used in more medical applications. According to the current research, when silver materials enter a human body and approach to germs, the silver materials become silver ions with positive charges due to the coulomb attraction, so that sulfhydryl groups on enzyme proteins in bacteria are attracted, and the bacteria lose activity and die. The silver can also well identify flora in the sterilization process, can well maintain the living environment of beneficial flora, and can not damage the immune system of human body, so the silver has no toxicity and stimulation reaction to the human body.
Graphene is a novel carbon nanomaterial, and has a unique two-dimensional lamellar structure, so that graphene has become a hot point of research in various fields in recent years. In the field of rubber applications, graphene is widely used as a reinforcing and barrier material. According to related research reports, a small amount of graphene is added into a rubber latex matrix, so that the physical and mechanical properties, the heat and electricity conduction performance, the gas barrier performance and the like of the latex composite material are effectively improved. However, in the mixing process of the graphene and the rubber component, powder is easy to fly, the environment is polluted, and the health of operators is seriously harmed; and the filler has poor dispersibility during mixing and is easy to agglomerate.
Disclosure of Invention
In order to solve the technical problems, the invention provides a silver-plated graphene/synthetic rubber latex composition, which can improve the antibacterial effect of silver by using the large specific surface area of graphene as an excellent carrier of the silver.
One of the purposes of the invention is to provide a silver-plated graphene/synthetic rubber latex composition, which comprises silver-plated graphene and synthetic rubber latex, wherein the content of the silver-plated graphene is 0.1-10 parts, preferably 0.1-3 parts, based on 100 parts by weight of the solid content of the synthetic rubber latex.
Wherein the synthetic rubber latex is selected from at least one of polyurethane latex, styrene-butadiene rubber latex, carboxylic styrene-butadiene rubber latex, butyl rubber latex, brominated butyl rubber latex, chlorinated butyl rubber latex, chloroprene rubber latex, nitrile rubber latex, carboxylic nitrile rubber latex, fluorine rubber latex, silicon rubber latex and acrylate rubber latex;
the silver-plated graphene is a graphene substance with a surface modified with silver ions, and the graphene substance is at least one selected from graphene, graphene oxide, functionalized graphene and reduced graphene oxide;
the silver content of the silver-plated graphene is 1-80 wt%, preferably 1.5-60 wt%.
The invention also aims to provide a preparation method of the silver-plated graphene/synthetic rubber latex composition, which comprises the steps of mixing and stirring the graphene solution and the silver salt solution, adding the synthetic rubber latex, stirring and mixing to obtain the silver-plated graphene/synthetic rubber latex composition. The method specifically comprises the following steps:
the method comprises the following steps: dispersing graphene in a solvent to obtain a graphene precursor dispersion liquid, dissolving a surface modifier in the solvent to obtain a surface modifier solution, and then mixing the graphene precursor dispersion liquid and the surface modifier solution to obtain a modified graphene solution;
step two: mixing and stirring the modified graphene solution obtained in the step one and a silver salt solution to obtain a silver-plated graphene solution;
step three: and mixing the silver-plated graphene solution and the synthetic rubber latex to obtain the silver-plated graphene/synthetic rubber latex composition.
Wherein the graphene is a graphene substance and is selected from at least one of graphene, graphene oxide, functionalized graphene and reduced graphene oxide;
the solvent of the graphene precursor dispersion liquid is a solvent A, and is selected from at least one of deionized water, absolute methanol, absolute ethanol, tetrahydrofuran, nitrogen methyl pyrrolidone, diethyl ether, propylene oxide and dichloromethane, and preferably is selected from deionized water;
the surface modifier is selected from at least one of gamma-hydrophobic propyl trimethoxy silane, gamma-hydrophobic propyl triethoxy silane, dopamine, polyaniline and tannic acid, preferably at least one of dopamine and tannic acid;
the solvent of the surface modifier solution is solvent B, and is selected from buffer solution, preferably Tris-HCl buffer solution; the buffer solution is used as a solvent of the surface modifier, so that the surface modifier can be fully soaked in the matrix and deposited on the surface of the matrix, and the graphene and the derivatives thereof can be more fully silvered on the surface of the matrix, and are compact, continuous and uniform;
the silver salt is inorganic soluble silver salt and is selected from at least one of silver nitrate, silver chloride, silver acetate, silver fluoride and silver perchlorate;
the synthetic rubber latex is selected from at least one of polyurethane latex, styrene-butadiene rubber latex, carboxylic styrene-butadiene rubber latex, butyl rubber latex, brominated butyl rubber latex, chlorinated butyl rubber latex, chloroprene rubber latex, nitrile rubber latex, carboxylic nitrile rubber latex, fluorine rubber latex, silicon rubber latex and acrylate rubber latex.
In the preparation process, the solid content of the synthetic rubber latex is 50-80%; the graphene accounts for 0.01-10 parts by weight, preferably 0.05-5 parts by weight of the solid content in the synthetic rubber latex; the dosage of the silver salt is 0.01-20 parts by weight, preferably 0.03-10 parts by weight based on 1 part by weight of graphene; the surface modifier accounts for 0.1-5 parts by weight of 1 part by weight of graphene; the concentration of the graphene dispersion liquid is 0.5-60 g/L, preferably 1-40 g/L; the concentration of the surface modifier solution is 0.01-10 g/L, preferably 1-6 g/L; the concentration of the silver salt solution is 0.1-10 g/L, preferably 1-10 g/L.
In the preparation method, a weakly alkaline compound and/or an anti-coagulation compound are also added into the silver salt solution in the second step; wherein, the dosage of the alkalescent compound is 20-100% of the silver salt by mass percent, and the dosage of the anti-coagulation compound is 25-250% of the silver salt by mass percent; the alkalescent compound is at least one of ammonia water and ammonium chloride, and the added alkalescent compound can react with silver salt to generate silver, thereby being beneficial to the next reaction; the anti-coagulation compound is at least one selected from polyvinylpyrrolidone, methyl acetate, sodium chloride, and oxalate, and is added for preventing Ag + The modified graphene can generate a complex reaction with the modified graphene when being modified, and Ag is reduced + The effective utilization rate of (2);
a reducing agent solution is also added in the second step, and the concentration of the reducing agent solution is 0.1-20 g/L, preferably 1-10 g/L; the dosage of the reducing agent is 5-200% of the mass of the silver salt; the reducing agent is at least one of glucose and ascorbic acid;
the mixing temperature in the third step is 10-60 ℃.
The invention also aims to provide a silver-plated graphene-containing adhesive film product prepared from the silver-plated graphene/synthetic rubber latex composition or the silver-plated graphene/synthetic rubber latex composition prepared by the preparation method. The preparation method of the adhesive film product comprises the step of drying the silver-plated graphene/synthetic rubber latex composition into a film, and specifically comprises the following steps: fully soaking a mould in a coagulant solution, then airing, fully soaking in the silver-plated graphene/synthetic rubber latex composition, taking out, drying, demoulding, and drying the demoulded glue film to obtain the glue film product; wherein the coagulant solution is at least one selected from calcium nitrate solution and calcium chloride-anhydrous ethanol solution.
The invention also provides a rubber composition containing the silver-plated graphene/synthetic rubber latex composition and/or the adhesive film thereof, or the silver-plated graphene/synthetic rubber latex composition or the adhesive film thereof obtained by the preparation method. The rubber composition may also contain other conventional adjuvants, such as casein solution, potassium hydroxide solution, accelerator, sulfur, zinc oxide, and antioxidant.
According to the invention, the graphene substance is modified by adopting the modifier, the surface of the graphene can be effectively modified by adopting the modifiers such as dopamine and tannic acid, the modification time is short, and the combination of the modifier and the surface of the graphene is firmer. The invention adopts the buffer solution as the solvent to dissolve the surface modifier, can ensure that the surface modifier is fully soaked in the matrix, reacts with the matrix and is deposited on the surface of the matrix, thereby ensuring that the graphene substance can more fully silver-plated on the surface of the matrix, and is compact, continuous and uniform.
In order to improve the dispersion of graphene in the rubber formulation, a coupling agent is usually added to the rubber formulation to improve the uniform dispersion of graphene in the rubber. However, if the coupling agent is used for modification, because the grafting of the coupling agent requires more hydroxyl groups on the surface of the substrate, the surface of the substrate is generally required to be roughened to have more hydroxyl groups (such as graphene oxide) so as to enable the coupling agent and silver to have stronger covalent bond effects, and the modification of the coupling agent requires a large amount of ethanol as a solvent, so that a large amount of organic volatile solvent (VOC) is generated, which does not meet the requirement of green production, and the effect is inferior to the effect after the modification of dopamine, because the catechol group contained in dopamine molecules has the effect of adsorbing metal ions, can reduce metal atoms to deposit on the surface of the substrate, and shows good metal binding capacity.
The silver-plated graphene/synthetic rubber latex composition is prepared by combining the modified graphene, silver and synthetic rubber latex, can give full play to the synergistic benefits of the graphene and the silver, not only gives full play to the enhancement effect of the graphene, but also gives full play to the antibacterial property of the silver, and can be widely applied to the aspects of enhancement, barrier, antibacterial property and the like of latex products.
Compared with the prior art, the invention has the following advantages:
1. the silver-plated graphene/synthetic rubber latex composition provided by the invention adopts the synthetic rubber latex, so that allergy of a user can be prevented, cavities and cracks in a glue film are reduced, and the safety performance is enhanced;
2. the modified graphene is plated with silver on the surface, and then synthetic rubber latex is added to finally obtain a silver-plated graphene/synthetic rubber latex composition which has antibacterial property, excellent mechanical property and high barrier property;
3. the preparation method provided by the invention has the advantages of simple equipment, simple operation, good controllability, contribution to industrial amplification and the like.
Drawings
Fig. 1 is a Scanning Electron Microscope (SEM) image of a silver-coated graphene/synthetic rubber latex composition adhesive film prepared in example 1 of the present invention.
Detailed Description
While the present invention will be described in detail with reference to the following examples, it should be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the present invention.
Test methods used in the examples
Tensile properties were determined according to GB/T528: three test pieces were cut out from each glove, and a median value was taken therefrom, and the test pieces should be cut out from the palm or back of each palm in the glove dipping direction.
The sources of the raw materials used in the examples are as follows:
graphene, graphene oxide, functionalized graphene, industrial grade, commercially available;
potassium hydroxide (KOH), analytically pure, tianjin, changxing chemical reagents manufacturing ltd;
ammonia (NH) 3 ·H 2 O), analyzing and purifying, and refining a plant in a Laiyang economic and technical development area;
common sulfur powder (S), accelerator ZDC, casein, anti-aging agent, zinc oxide, industrial grade, market selling;
ammonium chloride, PVP (polyvinylpyrrolidone), dopamine, tris-HCl buffer solution and silver nitrate which are all commercial products;
polyurethane latex, analytically pure, shanghai Hao republic of chemical Co., ltd;
silicone rubber latex, styrene-butadiene latex, carboxylated nitrile latex, neoprene latex, industrial grade, commercially available.
Natural latex, commercially available from Dow chemical Co., ltd.
Example 1
(1) Silver plating on graphene
Weighing 1.5g of graphene oxide, dissolving in 100mL of deionized water, and performing ultrasonic treatment to obtain a graphene dispersion liquid; a dopamine solution was prepared by dissolving 0.3g of dopamine in 100mL of Tris-HCl buffer solution (10 mM, pH = 8.5); adding the prepared graphene solution into the dopamine solution, and uniformly mixing and stirring; weighing 0.5g of silver nitrate, dissolving the silver nitrate in 100g of water, dropwise adding ammonia water until the solution is just clear, adding 0.25g of PVP, uniformly mixing and stirring, adding the mixed solution, mixing and stirring, adding 100mL of glucose solution with the concentration of 10g/L, and stirring for 1 hour;
(2) Preparation of silver-plated graphene/synthetic rubber latex composition
Taking 180g of polyurethane latex, adding the solution obtained in the step (1) into the latex, and ultrasonically stirring for 20min to obtain the silver-plated graphene/synthetic rubber latex composition;
(3) Glue film product for preparing silver-plated graphene/synthetic rubber latex composition
Dipping a mould into a 10% calcium chloride-absolute ethyl alcohol solution, dipping the mould into the latex composition obtained in the step (2), placing the latex composition into an oven, and drying the latex composition for 30min at 50 ℃; demoulding, leaching in water at 60 ℃ for 10min, airing, placing the adhesive film in an oven at 70 ℃ for 30min, and taking out to obtain the required adhesive film product.
Example 2
(1) Silver plating on graphene
Weighing 0.1g of graphene, dissolving in 60mL of deionized water, and performing ultrasonic treatment to obtain a graphene dispersion liquid; a dopamine solution was prepared by dissolving 0.4g of dopamine in 100mL of Tris-HCl buffer solution (10 mM, pH = 8.5); adding the prepared graphene solution into the dopamine solution, and mixing and stirring uniformly; weighing 1g of silver nitrate, dissolving the silver nitrate in 100g of water, dropwise adding ammonia water until the solution is just clear, adding 0.25g of PVP, uniformly mixing and stirring, adding the mixed solution, mixing and stirring, adding 50mL of glucose solution with the concentration of 1g/L, and stirring for 1 hour;
(2) Preparation of silver-plated graphene/synthetic rubber latex composition
Taking 180g of silicone rubber latex, adding the solution obtained in the step (1) into the latex, and ultrasonically stirring for 20min to obtain the silver-plated graphene/synthetic rubber latex composition;
(3) Glue film product for preparing silver-plated graphene/synthetic rubber latex composition
Firstly, dipping a mould in 10% of calcium nitrate coagulant, and then airing after extracting; then dipping the mould into the latex composition obtained in the step (2), and then placing the mould into an oven to be dried for 20min at 50 ℃; demoulding, leaching in 70 deg.C water for 10min, air drying, placing the above-mentioned glue film in 70 deg.C oven for 30min, then taking out to obtain the required glue film product.
Example 3
(1) Silver plating on graphene
Weighing 0.8g of graphene, dissolving in 70mL of deionized water, and performing ultrasonic treatment to obtain a graphene oxide dispersion liquid; a tannic acid solution was prepared by dissolving 0.5g of tannic acid in 100mL of Tris-HCl buffer solution (10 mM, pH = 8.5); adding the prepared graphene solution into the tannic acid solution, and mixing and stirring uniformly; dissolving 1g of silver fluoride in 100mL of aqueous solution, dropwise adding 0.5g/L of ammonium chloride solution until the solution is just clear, adding 0.25g of PVP, uniformly mixing and stirring, adding the mixed solution, mixing and stirring, adding 50mL of glucose solution with the concentration of 1g/L, and stirring for 1 hour;
(2) Preparation of silver-plated graphene/synthetic rubber latex composition
Taking 180g of styrene-butadiene latex, adding the solution obtained in the step (1) into the latex, and ultrasonically stirring for 20min to obtain the silver-plated graphene/synthetic rubber latex composition;
(3) Glue film product for preparing silver-plated graphene/synthetic rubber latex composition
Firstly, dipping a mould in 10% of calcium nitrate coagulant, extracting and then drying; then dipping the mould into the latex composition in the step (2), and then placing the mould into an oven to be dried for 20min at 50 ℃; demoulding, leaching in 70 deg.C water for 10min, air drying, placing the above-mentioned glue film in 70 deg.C oven for 30min, then taking out to obtain the required glue film product.
Example 4
(1) Silver plating on graphene
Weighing 3.0g of graphene, dissolving in 80mL of deionized water, and performing ultrasonic treatment to obtain a graphene dispersion liquid; a tannic acid solution was prepared by dissolving 0.6g of tannic acid in 100mL of Tris-HCl buffer solution (10 mM, pH = 8.5); adding the prepared graphene solution into the tannic acid solution, and mixing and stirring uniformly; preparing 100mL of 1g/L silver nitrate solution, dropwise adding ammonia water until the solution is just clear, adding 0.25g of sodium chloride, uniformly mixing and stirring, adding the mixed solution, mixing and stirring, adding 50mL of 1g/L glucose solution, and stirring for 0.5 hour;
(2) Preparation of silver-plated graphene/synthetic rubber latex composition
Taking 180g of neoprene latex, adding the solution obtained in the step (1) into the latex, and ultrasonically stirring for 20min to obtain the silver-plated graphene/synthetic rubber latex composition;
(3) Glue film product for preparing silver-plated graphene/synthetic rubber latex composition
Firstly, dipping a mould into 10 percent of calcium nitrate, and then airing the mould after the mould is extracted; then dipping the mould into the latex composition obtained in the step (2), and then placing the mould into an oven to be dried for 20min at 60 ℃; demoulding, leaching in water at 60 deg.C for 10min, air drying, placing the above-mentioned glue film in oven at 60 deg.C for 30min, then taking out to obtain the required glue film product.
Example 5
(1) Silver plating on graphene
Weighing 2.0g of functionalized graphene, dissolving in 70mL of deionized water, and performing ultrasonic treatment to obtain a graphene dispersion liquid; a tannic acid solution was prepared by dissolving 0.4g of tannic acid in 100mL of Tris-HCl buffer solution (10 mM, pH = 8.0); adding the prepared graphene solution into the tannic acid solution, and mixing and stirring uniformly; preparing 100mL of 5g/L silver nitrate solution, dropwise adding ammonia water until the solution is just clear, adding 0.25g of PVP, uniformly mixing and stirring, adding the mixed solution, mixing and stirring, adding 50mL of ascorbic acid solution with the concentration of 5g/L, and stirring for 1 hour;
(2) Preparation of silver-plated graphene/synthetic rubber latex composition
Taking 180g of carboxylated nitrile latex, adding the solution obtained in the step (1) into the latex, and ultrasonically stirring for 20min to obtain the silver-plated graphene/synthetic rubber latex composition;
(3) Glue film product for preparing silver-plated graphene/synthetic rubber latex composition
Soaking a mould in 20% calcium chloride-absolute ethyl alcohol solution, extracting and drying; then dipping the mould into the latex composition obtained in the step (2), and then placing the mould into an oven to be dried for 20min at 60 ℃; demoulding, leaching in water at 60 ℃ for 10min, airing, placing the adhesive film in an oven at 60 ℃ for 30min, and taking out to obtain the required adhesive film product.
Example 6
(1) Silver plating on graphene
Taking 0.5g of graphene oxide, dissolving in 100mL of deionized water, and performing ultrasonic treatment to obtain a graphene dispersion liquid; a dopamine solution was prepared by dissolving 0.4g of dopamine in 100mL of Tris-HCl buffer solution (10 mM, pH = 8.0); adding the prepared graphene solution into the dopamine solution, and uniformly mixing and stirring; preparing 100mL of 5g/L silver nitrate solution, dropwise adding ammonia water until the solution is just clear, adding 0.25g of PVP, uniformly mixing and stirring, adding the mixed solution, mixing and stirring, adding 50mL of glucose solution with the concentration of 5g/L, and stirring for 30 minutes.
(2) Preparation of silver-plated graphene/synthetic rubber latex composition
Taking 100g of neoprene latex, adding the solution obtained in the step (1) into the latex, and ultrasonically stirring for 20min to obtain the silver-plated graphene/synthetic rubber latex composition;
(3) Glue film product for preparing silver-plated graphene/synthetic rubber latex composition
Firstly, dipping a mould into a 10% calcium chloride-absolute ethyl alcohol solution, and then airing after extracting; then dipping the mould into the latex composition obtained in the step (2), and then placing the mould into an oven to be dried for 30min at 60 ℃; demoulding, leaching in water at 60 ℃ for 10min, airing, placing the adhesive film in an oven at 70 ℃ for 30min, and taking out to obtain the required adhesive film product.
Example 7
(1) Silver plating on graphene
Taking 0.5g of graphene oxide, dissolving in 100mL of deionized water, and performing ultrasonic treatment to obtain a graphene dispersion liquid; a tannic acid solution was prepared by dissolving 0.4g of tannic acid in 100mL of Tris-HCl buffer solution (10 mM, pH = 8.0); adding the prepared graphene solution into the tannic acid solution, and mixing and stirring uniformly; preparing 100mL of 5g/L silver nitrate solution, dropwise adding ammonia water until the solution is just clear, adding 0.25g of PVP, uniformly mixing and stirring, adding the mixed solution, mixing and stirring, adding 50mL of glucose solution with the concentration of 5g/L, and stirring for 30 minutes;
(2) Preparation of silver-plated graphene/synthetic rubber latex composition
Taking 100g of neoprene latex, adding the solution obtained in the step (1) into the latex, and ultrasonically stirring for 20min to obtain the silver-plated graphene/synthetic rubber latex composition;
(3) Glue film product for preparing silver-plated graphene/synthetic rubber latex composition
Firstly, dipping a mould into a 10% calcium chloride-absolute ethyl alcohol solution, and then airing the mould after the mould is extracted; then dipping the mould into the latex composition obtained in the step (2), and then placing the mould into an oven to be dried for 30min at 60 ℃; demoulding, leaching in water at 60 ℃ for 10min, airing, placing the adhesive film in an oven at 70 ℃ for 30min, and taking out to obtain the required adhesive film product.
Comparative example 1
Preparing a neoprene latex film without adding any filler: taking 100g of latex, ultrasonically stirring for 20min, dipping a mould into a 10% calcium chloride-absolute ethyl alcohol solution, and airing; defoaming; soaking, placing in oven, and oven drying at 70 deg.C for 20min; demoulding, leaching in water at 60 deg.C for 10min, air drying, placing the above-mentioned glue film in oven at 70 deg.C for 30min, then taking out to obtain the required glue film.
Comparative example 2
Adding graphene oxide into neoprene latex to prepare a graphene/latex composite material: taking 100g of neoprene latex, firstly dipping a mould into a 10% calcium chloride-absolute ethyl alcohol solution, and airing; weighing 0.5g of graphene oxide, dissolving the graphene oxide in 100mL of deionized water, fully stirring and ultrasonically treating for 20min, adding the graphene oxide solution into latex, ultrasonically stirring for 20min, and defoaming; soaking, placing in oven, and oven drying at 70 deg.C for 20min; demoulding, leaching in water at 60 deg.C for 10min, air drying, placing the above-mentioned glue film in oven at 70 deg.C for 30min, then taking out to obtain the required glue film.
Comparative example 3
(1) Silver plating on graphene
Taking 0.5g of graphene oxide, dissolving in 100mL of deionized water, and performing ultrasonic treatment to obtain a graphene dispersion liquid; a dopamine solution was prepared by dissolving 0.4g of dopamine in 100mL of Tris-HCl buffer solution (10 mM, pH = 8.0); adding the prepared graphene solution into the dopamine solution, and uniformly mixing and stirring; preparing 100mL of 5g/L silver nitrate solution, dropwise adding ammonia water until the solution is just clear, adding 0.25g of PVP, mixing and stirring uniformly, adding the mixed solution, mixing and stirring, adding 50mL of glucose solution with the concentration of 5g/L, and stirring for 30min.
(2) Preparation of silver-plated graphene/natural rubber latex composition
Taking 100g of natural latex, adding the solution obtained in the step (1) into the latex, and ultrasonically stirring for 20min to obtain the silver-plated graphene/natural rubber latex composition;
(3) Preparation of silver-plated graphene/natural rubber latex composition adhesive film product
Firstly, dipping a mould into a 10% calcium chloride-absolute ethyl alcohol solution, and then airing the mould after the mould is extracted; then dipping the mould into the latex composition obtained in the step (2), and then placing the mould into an oven to be dried for 30min at 60 ℃; demoulding, leaching in water at 60 ℃ for 10min, airing, placing the adhesive film in an oven at 70 ℃ for 30min, and taking out to obtain the required adhesive film product.
Performance test of rubber composition:
the mechanical property test is carried out according to GB/T528-2009.
Rubber film products obtained in comparative example 1, comparative example 2, comparative example 3, example 6 and example 7 were used as rubber components, and other auxiliaries were added to prepare rubber compositions and to test the properties thereof.
The experimental formulation was as follows: based on 100 parts by weight of the adhesive film product, 0.5 part of casein, 0.1 part of KOH, 1.0 part of accelerator, 0.3 part of sulfur, 0.5 part of zinc oxide, 0.2 part of anti-aging agent 246, 0.5 part of anti-aging agent MB and 0.5 part of graphene oxide GO.
Preparation of rubber composition: sequentially putting casein solution, potassium hydroxide solution, accelerator, sulfur, zinc oxide, anti-aging agent and GO into latex according to a formula, and uniformly mixing; firstly, dipping a mould into a 10% calcium chloride-absolute ethyl alcohol solution, and then airing the mould after the mould is extracted; then, the mould is dipped in the rubber composition solution, and then is placed in an oven and is dried for 30min at the temperature of 60 ℃; demoulding, leaching in water at 60 deg.C for 10min, air drying, placing the above-mentioned glue film in oven at 70 deg.C for 30min, then taking out to obtain the required glue film.
The test results for the rubber compositions of comparative example 1, comparative example 2, comparative example 3, example 6, and example 7 are as follows:
the difference between the natural latex and the synthetic latex is found by comparison, namely firstly, the sensitization is eliminated, and secondly, the barrier property of the synthetic latex is better, and the tensile strength is stronger; the mechanical property and the barrier property of the synthetic latex are enhanced to a certain extent due to the large aspect ratio of GO and the uniform dispersion of GO in the matrix, so that the mechanical property of the rubber composition can be better improved. In addition, the invention can react with silver salt by adding alkalescent compound, for example, ammonia water can react with silver salt to generate[Ag(NH 3 ) 2 ] + The next reaction is facilitated; the buffer solution has the function of fully soaking the surface modifier in the matrix and enabling the surface modifier to react, for example, dopamine can form polydopamine in the buffer solution and continuously react with the matrix to enable the polydopamine to be deposited on the surface of the matrix, a layer of metal simple substance is deposited on the surface of various matrix materials by means of the weak oxidation-reduction property of phenolic hydroxyl groups in polydopamine molecules and the complexing capacity of N-containing groups to metal ions, and a uniform and dense silver layer deposited on the surface is prepared.
The above embodiments have described the specific implementation procedures of the present invention in detail, but the present invention is not limited to the embodiments, and those skilled in the art can make various equivalent modifications, such as functionalized modification of graphene oxide or graphene with different modifying agents, reduction of graphene oxide with different reducing agents or different reduction methods, etc., which are all within the scope of the claims of the present application.
Claims (15)
1. A silver-plated graphene/synthetic rubber latex composition comprises silver-plated graphene and synthetic rubber latex, wherein the content of the silver-plated graphene is 0.1 to 3 parts by weight based on 100 parts by weight of the solid content of the synthetic rubber latex;
the preparation method of the silver-plated graphene/synthetic rubber latex composition comprises the following steps:
the method comprises the following steps: dispersing graphene in a solvent to obtain a graphene precursor dispersion liquid, dissolving a surface modifier in the solvent to obtain a surface modifier solution, and then mixing the graphene precursor dispersion liquid and the surface modifier solution to obtain a modified graphene solution;
step two: mixing and stirring the modified graphene solution obtained in the step one and a silver salt solution to obtain a silver-plated graphene solution;
step three: mixing the silver-plated graphene solution and the synthetic rubber latex to obtain a silver-plated graphene/synthetic rubber latex composition;
wherein, alkalescent compound and anti-coagulation compound are also added into the silver salt solution, and reducing agent solution is also added in the second step; the weak alkaline compound is at least one of ammonia water and ammonium chloride; the anti-coagulation compound is at least one of polyvinylpyrrolidone, sodium chloride and oxalate; the reducing agent is at least one of glucose and ascorbic acid; the silver salt is 0.03 to 1.25 parts by weight of graphene.
2. The composition of claim 1,
the synthetic rubber latex is selected from at least one of polyurethane latex, styrene-butadiene rubber latex, carboxylic styrene-butadiene rubber latex, butyl rubber latex, brominated butyl rubber latex, chlorinated butyl rubber latex, chloroprene rubber latex, nitrile rubber latex, carboxylic nitrile rubber latex, fluorine rubber latex, silicon rubber latex and acrylate rubber latex; and/or the presence of a gas in the atmosphere,
the silver-plated graphene is a graphene substance with a surface modified with silver ions, and the graphene substance is at least one selected from graphene, graphene oxide, functionalized graphene and reduced graphene oxide; and/or the presence of a gas in the gas,
the silver content of the silver-plated graphene is 1-80wt%.
3. The composition of claim 2,
the silver content of the silver-plated graphene is 1.5-60wt%.
4. The method of preparing a silver-plated graphene/synthetic rubber latex composition according to claim 1, comprising the steps of:
the method comprises the following steps: dispersing graphene in a solvent to obtain a graphene precursor dispersion liquid, dissolving a surface modifier in the solvent to obtain a surface modifier solution, and then mixing the graphene precursor dispersion liquid and the surface modifier solution to obtain a modified graphene solution;
step two: mixing and stirring the modified graphene solution obtained in the step one and a silver salt solution to obtain a silver-plated graphene solution;
step three: mixing the silver-plated graphene solution and the synthetic rubber latex to obtain a silver-plated graphene/synthetic rubber latex composition;
wherein, alkalescent compound and anti-coagulation compound are also added into the silver salt solution, and reducing agent solution is also added in the second step; the weak alkaline compound is at least one of ammonia water and ammonium chloride; the anti-coagulation compound is at least one of polyvinylpyrrolidone, sodium chloride and oxalate; the reducing agent is at least one of glucose and ascorbic acid; the silver salt is 0.03 to 1.25 parts by weight of graphene.
5. The production method according to claim 4,
the graphene is a graphene substance and is selected from at least one of graphene, graphene oxide, functionalized graphene and reduced graphene oxide; and/or the presence of a gas in the gas,
the solvent of the graphene precursor dispersion liquid is a solvent A, and is selected from at least one of deionized water, absolute methanol, absolute ethanol, tetrahydrofuran, N-methylpyrrolidone, diethyl ether, propylene oxide and dichloromethane; and/or the presence of a gas in the gas,
the surface modifier is at least one selected from gamma-mercaptopropyl trimethoxysilane, gamma-mercaptopropyl triethoxysilane, dopamine, polyaniline and tannic acid; and/or the presence of a gas in the gas,
the solvent of the surface modifier solution is a solvent B selected from a buffer solution; and/or the presence of a gas in the gas,
the silver salt is inorganic soluble silver salt and is selected from at least one of silver nitrate, silver fluoride and silver perchlorate; and/or the presence of a gas in the gas,
the synthetic rubber latex is selected from at least one of polyurethane latex, styrene-butadiene rubber latex, carboxylic styrene-butadiene rubber latex, butyl rubber latex, brominated butyl rubber latex, chlorinated butyl rubber latex, chloroprene rubber latex, nitrile rubber latex, carboxylic nitrile rubber latex, fluorine rubber latex, silicon rubber latex and acrylate rubber latex.
6. The production method according to claim 5,
the solvent of the graphene precursor dispersion liquid is deionized water; and/or the presence of a gas in the gas,
the surface modifier is selected from at least one of dopamine and tannic acid; and/or the presence of a gas in the atmosphere,
the solvent of the surface modifier solution is solvent B selected from Tris-HCl buffer solution.
7. The production method according to claim 4,
the solid content of the synthetic rubber latex is 50 to 80 percent; and/or the presence of a gas in the gas,
the surface modifier is used in an amount of 0.1 to 5 parts by weight based on 1 part by weight of graphene; and/or the presence of a gas in the gas,
the concentration of the graphene dispersion liquid is 0.5-60g/L; and/or the presence of a gas in the gas,
the concentration of the surface modifier solution is 0.01-10g/L; and/or the presence of a gas in the atmosphere,
the concentration of the silver salt solution is 0.1-10g/L.
8. The production method according to claim 4,
the solid content of the synthetic rubber latex is 50 to 80 percent; and/or the presence of a gas in the gas,
the surface modifier is used in an amount of 0.1 to 5 parts by weight based on 1 part by weight of graphene; and/or the presence of a gas in the gas,
the concentration of the graphene dispersion liquid is 1-40 g/L; and/or the presence of a gas in the gas,
the concentration of the surface modifier solution is 1 to 6g/L; and/or the presence of a gas in the gas,
the concentration of the silver salt solution is 1 to 10g/L.
9. The production method according to claim 4,
the mixing temperature in the third step is 10 to 60 ℃.
10. The method according to claim 9, wherein:
the dosage of the alkalescent compound is 20 to 100 percent of the mass of the silver salt; and/or the presence of a gas in the gas,
the dosage of the anti-condensation compound is 25 to 250 percent of the mass of the silver salt; and/or the presence of a gas in the gas,
the concentration of the reducing agent solution is 0.1-20g/L; and/or the presence of a gas in the gas,
the dosage of the reducing agent is 5 to 200 percent of the mass of the silver salt.
11. The method of manufacturing according to claim 10, wherein:
the concentration of the reducing agent solution is 1-10g/L.
12. An adhesive film product containing silver-plated graphene, which is prepared from the silver-plated graphene/synthetic rubber latex composition according to claim 1~3 or the silver-plated graphene/synthetic rubber latex composition prepared by the preparation method according to any one of claims 4 to 11.
13. The method for preparing silver-plated graphene-containing glue film product according to claim 12, comprising drying the silver-plated graphene/synthetic rubber latex composition into a film.
14. The method of claim 13, comprising the steps of: fully soaking a mould in a coagulant solution, then airing, fully soaking in the silver-plated graphene/synthetic rubber latex composition, taking out, drying, demoulding, and drying the demoulded glue film to obtain the glue film product; wherein the coagulant solution is at least one selected from calcium nitrate solution and calcium chloride-absolute ethyl alcohol solution.
15. A rubber composition containing the silver-coated graphene/synthetic rubber latex composition according to any one of claims 1~3 and/or the adhesive film product according to claim 12, or containing the silver-coated graphene/synthetic rubber latex composition obtained by the preparation method according to any one of claims 4 to 11 or the adhesive film product obtained by the preparation method according to any one of claims 13 to 14.
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