CN115367743A - Graphene stripping agent, preparation method of graphene, graphene modified rubber and preparation method of graphene modified rubber - Google Patents
Graphene stripping agent, preparation method of graphene, graphene modified rubber and preparation method of graphene modified rubber Download PDFInfo
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- CN115367743A CN115367743A CN202211077750.XA CN202211077750A CN115367743A CN 115367743 A CN115367743 A CN 115367743A CN 202211077750 A CN202211077750 A CN 202211077750A CN 115367743 A CN115367743 A CN 115367743A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/184—Preparation
- C01B32/19—Preparation by exfoliation
-
- 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
- C08K3/042—Graphene or derivatives, e.g. graphene oxides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
- C08L9/06—Copolymers with styrene
-
- 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
- C08K2201/017—Additives being an antistatic agent
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/04—Antistatic
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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
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- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Nanotechnology (AREA)
- Inorganic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a graphene stripping agent, a preparation method of graphene, graphene modified rubber and a preparation method of the graphene modified rubber, wherein the stripping agent is prepared by a first substance and a second substance through chemical reaction, and the first substance is an organic matter simultaneously having 3-10 aromatic rings and 3-10 carboxylic acid groups; the second substance is a long-chain alkyl amine or a long-chain alkyl alcohol having a carbon chain length of C16-C18. The graphene obtained by stripping the graphene stripping agent is high in yield, few in defects and regular in structure, and the obtained graphene can be stably combined with rubber, so that the interface combination effect of the graphene and a rubber macromolecule long-chain structure is improved, the performance of the rubber is improved, and the graphene stripping agent has wide application prospects and excellent economic benefits.
Description
Technical Field
The invention belongs to the technical field of preparation of high polymer materials, and particularly relates to a graphene stripping agent, a method for preparing graphene for rubber by stripping the graphene stripping agent, and application of the graphene prepared by the preparation method in graphene modified rubber.
Background
The rubber is a high-elasticity high-molecular polymer, has the characteristics of reversible deformation, lower glass transition temperature, excellent insulativity and the like, and is widely applied to various fields. When the surface of rubber is rubbed, charge accumulation is easy to cause, static electricity is formed, the release of the static electricity is easy to harm human health, dust is adsorbed, fire is caused, the aging of the surface of a rubber product is accelerated, great hidden danger is caused to traffic transportation, particularly flammable and explosive transportation, and the important work of the rubber industry is how to eliminate the harm of the static electricity. Because the performances of the rubber such as mechanics, wear resistance, antistatic property and the like can not meet the use requirements and have no practical application value, the rubber is generally reinforced by adding the filler, and the corresponding functions of the rubber are improved according to the specific application field of the rubber.
In general, the mechanical properties, abrasion resistance, heat conductivity and antistatic ability of the rubber are improved by introducing corresponding functional components. The traditional antistatic agent can fundamentally prevent static electricity, but the traditional antistatic agent can interact with other additives, so that other properties of the rubber product can be greatly reduced; and most antistatic agents belong to surfactants and have certain harmfulness to human bodies. Based on the consideration, research shows that the graphene with excellent performances in all aspects is selected as the rubber filler, so that the rubber can achieve the antistatic effect and has other good performances; in addition, the graphene is used as a reinforcing material of the rubber, so that the rubber has excellent antistatic property, the wear resistance and the heat conductivity of the rubber can be enhanced, and a novel rubber material with excellent performance is obtained. For example, chinese patent application publication No. CN108929469a discloses a graphene composite rubber material and a method for preparing the same, in which graphene is added to rubber and simultaneously other components are added, so that the rubber has excellent thermal conductivity and mechanical strength, but the hexamethylphosphoric triamide dispersant used in the method treats a reinforcing material, which does not promote uniform dispersion of the reinforcing material in the rubber, and the two are simply and mechanically blended, and there is no any force between the two, and there is a problem of nonuniform mixing; meanwhile, the reinforcing materials such as graphene and sepiolite powder need to be subjected to complex treatment such as grinding, spray drying and nitric acid acidification, and the subsequent mixing process with the rubber matrix is complex, so that the production cost is increased undoubtedly, and the economic benefit is insufficient. Also, for example, chinese patent application publication No. CN110256743A discloses an antistatic and wear-resistant graphene-based rubber for a tire, wherein graphene is modified by an ionic liquid, so that compatibility between graphene and rubber is improved, and the rubber has excellent antistatic and wear-resistant properties.
Disclosure of Invention
In view of the above, the present invention needs to provide a graphene stripping agent, which has a plurality of benzene ring structures and is connected with a non-polar long-chain alkyl chain, and a graphene slurry obtained by stripping with the graphene stripping agent has the advantages of few defects, regular structure and few layers, so that the yield of graphene is improved; the obtained graphene can be uniformly dispersed in a rubber matrix, so that the graphene and the rubber can be combined more stably, the interface combination effect of the graphene and a rubber macromolecule long-chain structure is improved, the performance of modified rubber is improved, and the graphene modified rubber has the advantage of low cost.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a graphene stripping agent which is prepared by a first substance and a second substance through chemical reaction, wherein the first substance is an organic substance which simultaneously has 3-10 aromatic rings and 3-10 carboxylic acid groups; the second substance is a long-chain alkyl amine or a long-chain alkyl alcohol having a carbon chain length of C16-C18.
Further, the first substance is selected from one of pyrene-1,3,6,8-tetracarboxylic acid, 3,6,8-tetrakis (4-carboxyphenyl) pyrene, 1,2,4,5-tetrakis (4 ' -carboxyphenyl) benzene, 1,3,6,8-tetrakis (3 ',5' -dicarboxyphenyl) pyrene, 2,4,6-tris (4-carboxyphenyl) -1,3,5-triazine, 4,4', 4' - (pyrazine-2,3,5,6-tetraalkyl) tetraphenoic acid; the second substance is one selected from hexadecylamine, hexadecyl alcohol, octadecyl amine and octadecyl alcohol.
In a further aspect, the molar ratio of carboxylic acid groups in the first material to the second material is 1: (1.1-1.5);
preferably, the molar ratio of carboxylic acid groups in the first material to the second material is 1:1.2.
the invention further provides a preparation method of graphene, which comprises the following steps:
fully mixing graphite powder with a stripping agent and a solvent, and mechanically stripping to obtain graphene slurry with the solid content of 1-5%; wherein the stripping agent is the graphene stripping agent.
Further, the solvent is selected from one of ionic liquid and organic solvent;
preferably, the organic solvent is selected from at least one of alkanes, amides, esters, benzene series or derivatives thereof and micromolecular solvents;
preferably, the ionic liquid is at least one of imidazoles, pyridines, quaternary ammonium salts and quaternary phosphonium salts.
In a further scheme, the mass ratio of the graphite powder to the stripping agent is 1 (0.2-2).
Further, the mechanical stripping comprises the following specific steps: performing ball milling stripping on the graphite powder in an ultrasonic environment;
preferably, the power of the ultrasonic wave is 2kW-10kW, the ball milling rotating speed is 2000-3000rpm, and the stripping time is 2-5h.
The invention further provides graphene modified rubber which comprises, by weight, 100 parts of rubber, 5-15 parts of graphene, 15-35 parts of carbon black, 5-8 parts of an active agent, 2-5 parts of an anti-aging agent, 1-3 parts of sulfur powder and 1-2 parts of an accelerator, wherein the graphene is prepared by the graphene preparation method.
Further, the rubber is selected from at least one of natural rubber, butadiene rubber and styrene butadiene rubber.
The invention further provides a preparation method of the graphene modified rubber, which comprises the following steps:
adding rubber latex particles into a polar organic solvent, mechanically stirring and mixing uniformly, adding graphene slurry, and mechanically stirring for 2-5 hours to obtain a uniform mixed solution;
carrying out tape casting and drying on the mixed solution to obtain rubber master batch;
mixing the rubber master batch with rubber latex, carbon black, an activator, an anti-aging agent, sulfur powder and an accelerator, uniformly mixing, and vulcanizing to obtain graphene modified rubber;
preferably, the polar organic solvent is at least one selected from tetrahydrofuran, N-dimethylformamide, methyl ethyl ketone, methyl isobutyl ketone, chloroform, and ethyl acetate.
The invention has the following beneficial effects:
the invention prepares a graphene stripping agent which has a plurality of benzene ring structures and is connected with a non-polar long-chain alkyl chain, and graphite powder is mechanically stripped under the action of the graphene stripping agent, so that few-layer graphene slurry with few defects and regular structure is obtained. The mechanical stripping of graphene is realized by adopting a solvent system, and the solvent and the stripping agent have a synergistic effect, so that on one hand, a weak acting force is formed between the solvent and a graphite flake layer, and the yield of mechanically stripped graphite is improved; on the other hand, the graphene is mixed with the rubber matrix. The preparation method has the advantages of mild and controllable conditions, high graphene yield, good compatibility with rubber matrix, suitability for industrial mass preparation and good economic benefit due to the adoption of a solvent system with a synergistic effect and a mechanical stripping mode.
The graphene modified rubber material prepared by the preparation method disclosed by the invention has the advantages of higher antistatic property and heat conductivity, excellent mechanical property and high wear resistance, the service life of the rubber material is prolonged, and the use range of rubber is expanded.
Drawings
Fig. 1 is a schematic structural diagram of a graphene peeling agent in example 1;
FIG. 2 is an X-ray diffraction pattern of graphene obtained by mechanical exfoliation in example 1;
fig. 3 is a DIN abrasion graph of graphene modified rubber in example 1 and comparative example.
Detailed Description
The following detailed description of embodiments of the invention is intended to be illustrative, and is not to be construed as limiting the invention.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
The invention provides a graphene stripping agent, which is prepared by carrying out chemical reaction on a first substance and a second substance, wherein the first substance is an organic substance which simultaneously has 3-10 aromatic rings and 3-10 carboxylic acid groups; the second substance is long-chain alkyl amine or long-chain alkyl alcohol with C16-C18 carbon chain length.
Specifically, the graphene peeling agent is prepared by a first substance and a second substance through a chemical reaction (such as an esterification reaction of acid alcohol or a condensation acylation reaction of carboxylic acid and amine), and the graphene peeling agent has a star-shaped structure. The graphene stripping agent is provided with a plurality of aromatic rings, so that pi-pi conjugation effect can be easily formed on the surface of graphene, the graphene stripping agent is gradually intercalated into graphite by virtue of mechanical stripping effect, and the van der Waals force between layers is destroyed, so that the graphene is stripped to obtain the graphene; the stripping agent contains a plurality of nonpolar long-chain alkyl chains, can prevent graphene sheets from stacking and stably dispersing, has a weak synergistic effect with benzene rings on glass graphene, can generate acting force with a rubber matrix to help the rubber matrix to be uniformly dispersed in a nonpolar rubber matrix, enables the graphene and the rubber to be combined more stably, improves the interface adhesion effect with a rubber macromolecule long-chain structure, and accordingly improves the performance of the rubber.
The first substance described herein is an organic substance having 3 to 10 aromatic rings and 3 to 10 carboxylic acid groups at the same time, and specific examples that may be mentioned include, but are not limited to, one of pyrene-1,3,6,8-tetracarboxylic acid, 3,6,8-tetrakis (4-carboxyphenyl) pyrene, 1,2,4,5-tetrakis (4 ' -carboxyphenyl) benzene, 1,3,6,8-tetrakis (3 ',5' -dicarboxyphenyl) pyrene, 2,4,6-tris (4-carboxyphenyl) -1,3,5-triazine, 4,4',4", 4' - (pyrazine-2,3,5,6-tetraalkyl) tetrabenzoic acid; the second substance is a long-chain alkylamine or a long-chain alkyl alcohol having a carbon chain length of C16 to C18, and specific examples include, but are not limited to, one of hexadecylamine, octadecylamine, and octadecylalcohol.
Further, considering the problem that carboxylic acid groups in a first substance need to be completely attached to a second substance, and the conversion rate of esterification reaction or condensation acylation reaction, the second substance is controlled to be slightly excessive in a specific preparation process, according to the embodiment of the invention, the molar ratio of carboxylic acid groups in the first substance to the second substance is 1: (1.1-1.5); preferably, the molar ratio of carboxylic acid groups in the first material to the second material is 1:1.2.
the second aspect of the present invention provides a method for preparing graphene, comprising the following steps:
fully mixing graphite powder with a stripping agent and a solvent, and mechanically stripping to obtain graphene slurry with solid content of 1-5%; wherein the stripping agent is the graphene stripping agent disclosed by the first aspect of the invention.
It is to be understood that the graphite powder used herein is not particularly limited, and specific examples that may be mentioned include, but are not limited to, one of expanded graphite, expandable graphite, natural flake graphite, and artificial graphite. The specific size can be selected according to actual needs, and in some exemplary embodiments of the present invention, the graphite powder is crystalline flake graphite with a particle size of 75 μm and a particle size of 200 meshes.
Further, the solvent is selected from one of ionic liquid and organic solvent. Both the ionic liquid and the organic solvent described herein may be those conventionally used in the art for preparing graphene by graphite exfoliation, such as those in which the ionic liquid is changed by at least one selected from imidazoles, pyridines, quaternary ammonium salts, and quaternary phosphonium salts, and specifically, at least one selected from 1-butyl-3-methylimidazolium hexafluorophosphate, 1-hydroxyethyl-3-methylimidazolium tetrafluoroborate, and 1-butyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide may be mentioned as examples. The organic solvent may be at least one selected from alkanes, amides, esters, benzenes or derivatives thereof, and small molecule solvents having surface energy close to that of graphene, and specifically, at least one selected from N-methylpyrrolidone, N-dimethylformamide, γ -butyrolactone, o-dichlorobenzene, and dimethyl sulfoxide may be mentioned as an example.
Further, in the stripping process, the specific ratio can be adjusted according to the amount of the graphite powder, and the like, and in some specific embodiments of the invention, the mass ratio of the graphite powder to the stripping agent is 1 (0.2-2).
Further, the specific steps of mechanical peeling described herein are: and carrying out ball milling stripping on the graphite powder under an ultrasonic environment. Through the synergistic action of the ultrasonic waves and the ball milling, the graphite powder is subjected to the strong shearing action of the ball milling while being subjected to the action of the ultrasonic waves, so that the stripping efficiency and effect are improved.
Further, the specific ultrasonic wave and ball milling parameters can be adjusted according to actual needs, in some exemplary embodiments of the invention, the power of the ultrasonic wave is 2kW to 10kW, the ball milling rotation speed is 2000rpm to 3000rpm, and the stripping time is 2h to 5h.
The third aspect of the invention provides graphene modified rubber which comprises, by weight, 100 parts of rubber, 5-15 parts of graphene, 15-35 parts of carbon black, 5-8 parts of an active agent, 2-5 parts of an anti-aging agent, 1-3 parts of sulfur powder and 1-2 parts of a promoter, wherein the graphene is prepared by the preparation method of the graphene according to the second aspect of the invention.
Wherein the rubber is selected from at least one of natural rubber, butadiene rubber and styrene butadiene rubber; the active agent, the anti-aging agent, the accelerator and the like adopted in the modified rubber can adopt conventional rubber components, for example, the active agent can be one selected from zinc oxide, magnesium oxide and stearic acid; the anti-aging agent is selected from one of thiol group benzene imidazole (MB), phenyl-2-naphthylamine (D), N-phenyl-N '-isopropyl-p-phenylenediamine, and N-N' -diphenyl-p-phenylenediamine; the accelerator may be one selected from 2-Mercaptobenzothiazole (MBT), dibenzothiazyl Disulfide (DM), and tetramethylthiuram disulfide (TMTD).
The fourth aspect of the invention provides a preparation method of graphene modified rubber, which comprises the following steps:
adding rubber latex particles into a polar organic solvent, mechanically stirring and mixing uniformly, adding graphene slurry, and mechanically stirring for 2-5 hours to obtain a uniform mixed solution;
carrying out tape casting and drying on the mixed solution to obtain rubber master batch;
and mixing the rubber master batch with rubber latex, carbon black, an activator, an anti-aging agent, sulfur powder and an accelerator, uniformly mixing, and vulcanizing to obtain the graphene modified rubber.
Wherein, the polar organic solvent can be selected from one of tetrahydrofuran, N-dimethylformamide, methyl ethyl ketone, methyl isobutyl ketone, chloroform and ethyl acetate.
It is understood that in the preparation of the graphene modified rubber, the casting, drying, mixing, vulcanizing and the like are all conventional means in the rubber preparation process, and specific process parameters thereof can be adjusted according to actual needs, so that no particular limitation is imposed. In addition, the ratio of the rubber master batch and the rubber latex can be adjusted according to the product performance, so that the detailed description is omitted.
According to the invention, the graphene is added into the rubber matrix, so that the mechanical strength, the wear resistance and the heat conductivity of the original rubber material are improved, the service life of the rubber material is prolonged, meanwhile, the insulating rubber is endowed with certain conductivity, the electric charge generated by friction is eliminated, and the antistatic effect is achieved. And the economic benefit is obvious, the preparation process is simple, and the industrial large-scale production is easy to realize.
The present invention is illustrated below by way of specific examples, which are intended to be illustrative only and not to limit the scope of the present invention in any way, and reagents and materials used therein are commercially available, unless otherwise specified, and conditions or steps thereof are not specifically described. Unless otherwise specified, parts, and the like described herein refer to parts by mass.
Example 1
Preparation of graphene slurry
Weighing 2 parts of graphite powder, 2 parts of a stripping agent (0.9 part of 1,3,6,8-tetra (3 ',5' -dicarboxyphenyl) pyrene and 1.1 part of hexadecanol, performing esterification reaction to obtain the stripping agent) and 96 parts of 1-butyl-3-methylimidazole hexafluorophosphate, fully mixing, and performing mechanical stripping of ball milling on the graphite powder under an ultrasonic environment to obtain graphene slurry with the solid content of 2% (the yield of graphene within 5 layers reaches 89%); wherein the ultrasonic power is 5kW, the ball milling rotating speed is 2000rpm, and the stripping time is 3h.
Preparation of graphene modified rubber
Adding 20 parts of natural rubber latex particles into 30 parts of tetrahydrofuran solution, and mechanically stirring and uniformly mixing; then adding 20 parts of 2% graphene slurry, stirring for 2-5h mechanically to obtain a uniform mixed solution with the solid content of graphene being 1%, and carrying out tape casting and drying on a tetrafluoroethylene plate to obtain rubber master batch;
mixing 10 parts of rubber master batch with 100 parts of natural rubber latex, 15 parts of carbon black, 5 parts of zinc oxide activator, 2 parts of antioxidant MB, 1 part of sulfur powder and 2 parts of accelerator MBT, uniformly mixing, and vulcanizing to obtain the graphene modified rubber.
In fig. 1, a schematic diagram of the structure of the release agent in example 1 is shown, and it can be seen that it has a polyphenyl ring structure and has a long non-polar alkyl chain attached thereto.
Fig. 2 shows an X-ray diffraction pattern of the graphene obtained by mechanical exfoliation in example 1, wherein a diffraction peak is present at 2 θ =26.52 °, and the diffraction peak corresponds to a crystal plane of the graphene material, which indicates that the graphene is successfully exfoliated by the exfoliating agent and the mechanical action.
Fig. 3 shows DIN abrasion diagrams for graphene-modified rubbers in example 1 and comparative examples 1-5. It can be seen that the DIN relative wear volume of the test sample in example 1 is the smallest and the wear resistance is the best, which proves that the stripping agent obtained by reacting 1,3,6,8-tetrakis (3 ',5' -dicarboxyphenyl) pyrene with hexadecanol in this example has a good effect on stripping graphene, and the graphene has a significant effect on enhancing rubber, and is beneficial to improving the wear resistance of the composite material.
Example 2
Preparation of graphene slurry
Weighing 2 parts of graphite powder, 2 parts of a stripping agent (0.9 part of pyrene-1,3,6,8-tetracarboxylic acid and 1.1 part of hexadecylamine, carrying out condensation and acylation reaction to obtain the stripping agent) and 67 parts of N, N-dimethylformamide according to parts by mass, fully mixing, and carrying out mechanical stripping of ball milling on the graphite powder under an ultrasonic environment to obtain graphene slurry with the solid content of 3% (the yield of graphene within 5 layers reaches 81.2%); wherein the ultrasonic power is 4kW, the ball milling rotating speed is 2500rpm, and the stripping time is 2.5h.
Preparation of graphene modified rubber
20 parts of butadiene rubber latex particles are added into 30 parts of N, N-dimethylformamide, and the mixture is mechanically stirred and uniformly mixed. Adding 20 parts of 3% graphene slurry, stirring for 2-5h by mechanical strength to obtain a uniform mixed solution with the solid content of graphene being 1.5%, and carrying out tape casting and drying on a tetrafluoroethylene plate to obtain rubber master batch;
mixing 10 parts of rubber master batch with 100 parts of butadiene rubber latex, 25 parts of carbon black, 6 parts of magnesium oxide activator, 1 part of antioxidant D, 2 parts of sulfur powder and 1 part of accelerator DM, uniformly mixing, and vulcanizing to obtain the graphene modified rubber.
Example 3
Preparation of graphene slurry
Weighing 2 parts of graphite powder, 1 part of a stripping agent (0.45 part of 3,6,8-tetra (4-carboxyphenyl) pyrene and 0.55 part of octadecanol, performing esterification reaction to obtain the stripping agent) and 197 parts of 1-hydroxyethyl-3-methylimidazole tetrafluoroborate, fully mixing, and performing mechanical stripping of ball milling on the graphite powder in an ultrasonic environment to obtain graphene slurry with the solid content of 1% (the yield of graphene within 5 layers reaches 90.3%); wherein the ultrasonic power is 8kW, the ball milling rotating speed is 2000rpm, and the stripping time is 2h.
Preparation of graphene modified rubber
20 parts of natural rubber latex particles are added into 30 parts of methyl ethyl ketone solution, and the mixture is mechanically stirred and uniformly mixed. Then adding 20 parts of 1% graphene slurry, stirring for 2-5h by mechanical force to obtain a uniform mixed solution with the solid content of graphene being 0.5%, and carrying out tape casting and drying on a tetrafluoroethylene plate to obtain rubber master batch;
mixing 10 parts of rubber master batch, 100 parts of natural rubber latex, 35 parts of carbon black, 8 parts of stearic acid activator, 3 parts of anti-aging agent N-phenyl-N' -isopropyl-p-phenylenediamine, 1 part of sulfur powder and 2 parts of accelerator TMTD, uniformly mixing, and vulcanizing to obtain the graphene modified rubber.
Example 4
Preparation of graphene slurry
Weighing 2 parts of graphite powder, 3 parts of a stripping agent (1.36 parts of 1,2,4,5-tetra (4' -carboxyphenyl) benzene and 1.64 parts of octadecylamine, carrying out condensation and acylation reaction to obtain the stripping agent) and 35 parts of gamma-butyrolactone, fully mixing, and carrying out ball-milling mechanical stripping on the graphite powder in an ultrasonic environment to obtain graphene slurry with the solid content of 5% (the yield of graphene in 5 layers reaches 93.6%); wherein the ultrasonic power is 10kW, the ball milling rotating speed is 2800rpm, and the stripping time is 3h.
Preparation of graphene modified rubber
20 parts of styrene butadiene rubber latex particles are added into 30 parts of methyl isobutyl ketone solution, and the mixture is mechanically stirred and uniformly mixed. Then adding 20 parts of 5% graphene slurry, stirring mechanically and strongly for 2-5h to obtain a uniform mixed solution with the solid content of graphene being 2.5%, and carrying out tape casting and drying on a tetrafluoroethylene plate to obtain rubber master batch;
mixing 10 parts of rubber master batch with 100 parts of styrene-butadiene rubber latex, 20 parts of carbon black, 7 parts of magnesium oxide active agent, 5 parts of antioxidant MB, 3 parts of sulfur powder and 2 parts of accelerator TMTD, uniformly mixing, and vulcanizing to obtain the graphene modified rubber.
Example 5
Preparation of graphene slurry
Weighing 2 parts of graphite powder, 4 parts of a stripping agent (1.8 parts of 1-anthracene carboxylic acid and 2.2 parts of octadecanol which are subjected to esterification reaction to obtain the stripping agent) and 94 parts of dimethyl sulfoxide according to parts by mass, fully mixing, and performing mechanical stripping of ball milling on the graphite powder under an ultrasonic environment to obtain graphene slurry with the solid content of 1% (the yield of graphene within 5 layers reaches 93.4%); wherein the ultrasonic power is 5kW, the ball milling rotating speed is 2800rpm, and the stripping time is 5h.
Preparation of graphene modified rubber
20 parts of styrene butadiene rubber latex particles are added into 30 parts of chloroform solution, and the mixture is stirred and mixed evenly by a machine. Adding 20 parts of 1% graphene slurry, stirring for 2-5h with strong mechanical force to obtain a uniform mixed solution with the solid content of graphene being 0.5%, and carrying out tape casting and drying on a tetrafluoroethylene plate to obtain rubber master batch;
mixing 10 parts of rubber master batch, 100 parts of rubber latex (containing 10 parts of natural rubber, 70 parts of butadiene styrene rubber and 20 parts of butadiene rubber), 23 parts of carbon black, 5 parts of stearic acid activator, 3 parts of antioxidant MB, 2 parts of sulfur powder and 2 parts of accelerator DM, uniformly mixing, and vulcanizing to obtain the graphene modified rubber.
Comparative example 1
Preparation of graphene slurry
The same embodiment as in example 1 was used except that: no release agent was added. The graphene slurry with the solid content of 2% is prepared, and the yield of graphene within 5 layers is 9.8%.
Preparation of graphene modified rubber
The graphene-modified rubber was prepared in the same manner as in example 1.
Comparative example 2
Preparation of graphene slurry
Graphene slurry having a solid content of 2% was prepared in the same manner as in example 1.
Preparation of graphene modified rubber
And drying the graphene slurry to obtain graphene powder, and directly mechanically mixing, mixing and vulcanizing the graphene powder with rubber latex, carbon black, an active agent, an anti-aging agent, sulfur powder and an accelerator to obtain the graphene modified rubber.
Comparative example 3
Preparation of graphene slurry
The same embodiment as in example 1 was used, except that: replacing 2 parts of stripping agent with 2 parts of 1,3,6,8-tetra (3 ',5' -dicarboxyphenyl) pyrene "to prepare graphene slurry with the solid content of 2%, wherein the yield of graphene within 5 layers is 13.2%.
Preparation of graphene modified rubber
The graphene-modified rubber was prepared in the same manner as in example 1.
Comparative example 4
The same embodiment as in example 1 was used except that: 2 parts of the stripper were replaced with "0.9 part 1,3,6,8-tetrakis (3 ',5' -dicarboxyphenyl) pyrene and 1.1 parts hexadecyltrimethylammonium bromide". The graphene slurry with the solid content of 2% is prepared, and the yield of graphene within 5 layers is 12.1%.
Preparation of graphene modified rubber
The graphene modified rubber was prepared in the same manner as in example 1.
Comparative example 5
The same embodiment as in example 1 was used except that: replacing 2 parts of stripping agent with 0.9 part of 1,3,6,8-tetra (3 ',5' -dicarboxyphenyl) pyrene and 1.1 part of stearoyl chloride to prepare graphene slurry with the solid content of 2%, wherein the yield of graphene within 5 layers is 11.5%.
Preparation of graphene modified rubber
The graphene modified rubber was prepared in the same manner as in example 1.
Test example
Relevant performance tests are carried out on the films (the film thickness is 1 mm) prepared from the graphene modified rubber and the examples, and the test results are shown in table 1.
TABLE 1 Performance test results
Note: the test methods in table 1 are as follows:
and (3) volume resistivity test: testing for 3 times at room temperature by using a SZT-2X digital four-probe resistivity instrument and taking an average value;
and (3) testing the heat conductivity coefficient: according to the method for measuring the normal-temperature heat conductivity coefficient of the DB23/T1905-2017 graphite film product;
and (3) testing tensile property: testing according to GB/T528-1998, and testing at room temperature for 3 times to obtain an average value;
DIN abrasion: the test was carried out according to GB/T9867-88, and the average value was taken 3 times at room temperature.
The quality of the stripped graphene is reduced, the number of layers is large, and the electric and heat conducting properties are reduced through the volume resistivity and the heat conducting property of the embodiment and the comparative example; and also the dispersibility thereof with the rubber latex is affected. According to the invention, the stripping agent is used for efficiently stripping high-quality few-layer graphene and helping the graphene to disperse in rubber, so that the prepared graphene modified rubber has high antistatic property and heat-conducting property, excellent mechanical property and high wear resistance, and has wide application prospects and economic benefits in the rubber industry.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent should be subject to the appended claims.
Claims (10)
1. The graphene stripping agent is characterized by being prepared by carrying out chemical reaction on a first substance and a second substance, wherein the first substance is an organic substance which simultaneously has 3-10 aromatic rings and 3-10 carboxylic acid groups; the second substance is long-chain alkyl amine or long-chain alkyl alcohol with C16-C18 carbon chain length.
2. The graphene stripping agent according to claim 1, wherein the first substance is selected from one of pyrene-1,3,6,8-tetracarboxylic acid, 3,6,8-tetra (4-carboxyphenyl) pyrene, 1,2,4,5-tetra (4 ' -carboxyphenyl) benzene, 1,3,6,8-tetra (3 ',5' -dicarboxyphenyl) pyrene, 2,4,6-tris (4-carboxyphenyl) -1,3,5-triazine, 4,4',4",4" ' - (pyrazine-2,3,5,6-tetraalkyl) tetrabenzoic acid; the second substance is one selected from hexadecylamine, hexadecyl alcohol, octadecyl amine and octadecyl alcohol.
3. The graphene stripping agent according to claim 1, wherein the molar ratio of carboxylic acid groups to the second substance in the first substance is 1: (1.1-1.5);
preferably, the molar ratio of carboxylic acid groups in the first material to the second material is 1:1.2.
4. a preparation method of graphene is characterized by comprising the following steps:
fully mixing graphite powder with a stripping agent and a solvent, and mechanically stripping to obtain graphene slurry with solid content of 1-5%; wherein the graphene peeling agent is adopted as the graphene peeling agent according to any one of claims 1 to 3.
5. The method for preparing graphene according to claim 4, wherein the solvent is selected from one of an ionic liquid and an organic solvent;
preferably, the organic solvent is selected from at least one of alkanes, amides, esters, benzene series or derivatives thereof and micromolecular solvents;
preferably, the ionic liquid is at least one of imidazoles, pyridines, quaternary ammonium salts and quaternary phosphonium salts.
6. The method for producing graphene according to claim 4, wherein the mass ratio of the graphite powder to the exfoliant is 1 (0.2-2).
7. The method for preparing graphene according to claim 4, wherein the mechanical exfoliation comprises the following specific steps: performing ball milling stripping on the graphite powder in an ultrasonic environment;
preferably, the power of the ultrasonic wave is 2kW-10kW, the ball milling rotating speed is 2000-3000rpm, and the stripping time is 2-5h.
8. The graphene modified rubber is characterized by comprising, by weight, 100 parts of rubber, 5-15 parts of graphene, 15-35 parts of carbon black, 5-8 parts of an active agent, 2-5 parts of an anti-aging agent, 1-3 parts of sulfur powder and 1-2 parts of an accelerator, wherein the graphene is prepared by the preparation method of the graphene according to any one of claims 4-7.
9. The graphene-modified rubber according to claim 8, wherein the rubber is at least one selected from the group consisting of natural rubber, butadiene rubber, and styrene butadiene rubber.
10. The method for preparing the graphene-modified rubber according to claim 8 or 9, comprising the steps of:
adding rubber latex particles into a polar organic solvent, mechanically stirring and mixing uniformly, adding graphene slurry, and mechanically stirring for 2-5 hours to obtain a uniform mixed solution;
carrying out tape casting and drying on the mixed solution to obtain rubber master batch;
mixing the rubber master batch with rubber latex, carbon black, an active agent, an anti-aging agent, sulfur powder and an accelerator, uniformly mixing, and vulcanizing to obtain graphene modified rubber;
preferably, the polar organic solvent is at least one selected from tetrahydrofuran, N-dimethylformamide, methyl ethyl ketone, methyl isobutyl ketone, chloroform, and ethyl acetate.
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| WO2022172021A1 (en) * | 2021-02-11 | 2022-08-18 | Cami Consultancy Ltd | Graphene production method |
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