CN109666259B - Preparation method of modified graphene oxide, modified graphene and modified graphene epoxy resin dispersion liquid - Google Patents
Preparation method of modified graphene oxide, modified graphene and modified graphene epoxy resin dispersion liquid Download PDFInfo
- Publication number
- CN109666259B CN109666259B CN201710958014.8A CN201710958014A CN109666259B CN 109666259 B CN109666259 B CN 109666259B CN 201710958014 A CN201710958014 A CN 201710958014A CN 109666259 B CN109666259 B CN 109666259B
- Authority
- CN
- China
- Prior art keywords
- modified graphene
- epoxy resin
- graphene
- dispersion liquid
- graphene oxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/09—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids
- C08J3/091—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids characterised by the chemical constitution of the organic liquid
- C08J3/092—Hydrocarbons
-
- 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
- C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
-
- 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
- C08J2479/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2461/00 - C08J2477/00
- C08J2479/02—Polyamines
Abstract
The invention provides a preparation method of a modified graphene epoxy resin dispersion liquid, which is characterized in that a compound containing a benzene ring and graphene oxide are modified through a chemical reaction, benzene rigid chemical groups are grafted on the surface of graphene, the van der Waals force between large molecules of graphene is greatly reduced by utilizing the larger steric hindrance of the benzene rigid chemical groups, and in addition, the remaining compound containing the benzene ring and epoxy resin have stronger chemical compatibility, so that the graphene and the resin can be fused, and the graphene epoxy resin can be widely applied to the fields of coatings and the like. According to the invention, a chemical modification method is adopted, the graphene epoxy resin dispersion liquid is prepared in a relatively simple manner, the compounding degree of graphene in resin is high, the graphene is successfully uniformly dispersed in the epoxy resin, and the water absorption of the anticorrosive paint prepared from the graphene resin is greatly reduced.
Description
Technical Field
The invention belongs to the technical field of modified graphene, and relates to a preparation method of modified graphene oxide, modified graphene and modified graphene epoxy resin dispersion liquid, in particular to a preparation method of modified graphene oxide, modified graphene and chemically modified graphene epoxy resin dispersion liquid for an anticorrosive coating.
Background
Graphene (Graphene) is a new material with a monolayer sheet structure composed of carbon atoms. The material is a hexagonal honeycomb-shaped planar film consisting of carbon atoms in sp2 hybridized orbitals, and is a two-dimensional material with the thickness of only one carbon atom. As a two-dimensional crystal composed of carbon atoms and having only one atomic thickness, it is the thinnest material and the toughest material currently entering the field of application; meanwhile, the graphene has a huge theoretical specific surface area and stable physical and chemical properties, and can keep good structural stability under high working voltage and large-current rapid charge and discharge; the graphene also has excellent conductivity, so that the internal resistance can be reduced, and the circulation stability of the supercapacitor is improved; in addition, graphene is almost completely transparent, absorbing only 2.3% of light. And is very dense and impenetrable by even the smallest gas atoms (helium atoms). These characteristics make it well suited as a raw material for transparent electronic products such as transparent touch displays, light-emitting panels, and solar panels. Due to the excellent physicochemical properties of graphene, graphene is widely applied to energy storage materials, environmental engineering and sensitive sensing, is called as 'black gold' or 'king of new materials', has a wide potential application prospect, and has become a focus and a research hotspot in the world at present.
At present, all materials are lost by about 1 percent of weight per year due to corrosion, economic loss caused by corrosion accounts for about 4 percent of the total national economy, and the corrosion-resistant roads are far from the original roads. In the anticorrosive paint industry, the most important anticorrosive paints mainly comprise epoxy, polyurethane and zinc-rich primer paints. However, in China, industries such as ocean engineering, ship manufacturing and green ocean wind energy are rapidly developed, the economic benefit of ocean corrosion protection is huge under new international situation and national policy, and the rapid development of novel anticorrosive coatings is imperative under the background.
For anticorrosive coatings, water absorption is an important standard, directly influences various performances of the coatings, can cause poor water resistance of a film formed by the coatings, so that the film becomes soft, the hardness is reduced, the strength is poor, the higher the water absorption is, the greater the strength loss of the film is, and the corrosion resistance is reduced.
In recent years, coating products containing graphene-based materials have been reported, but in practical applications, graphene has many problems and restriction factors, such as easy agglomeration of graphene. Due to the fact that the graphene and the graphene derivative have large specific surface areas and strong van der Waals acting forces exist among the graphene and the graphene derivative, agglomeration and winding phenomena are obvious, the graphene and the graphene derivative cannot be stably dispersed, and the graphene derivative are easy to agglomerate together again after dispersion and are difficult to open. Although a great deal of research is carried out to improve the dispersion effect of graphene by adding different types of dispersants or modifying, the effect in practical application is poor, and other impurities are additionally introduced to cause negative effects on subsequent research.
Therefore, how to find a way to uniformly disperse graphene in the coating, successfully realize uniform dispersion of graphene in the epoxy resin, and better improve the performance of the coating has become one of the problems to be solved by leading-edge researchers in the field.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide a method for preparing a modified graphene oxide, a modified graphene and a modified graphene epoxy resin dispersion, and particularly a method for preparing a modified graphene oxide, a modified graphene and a modified graphene epoxy resin dispersion for an anticorrosive coating.
The invention provides a preparation method of a modified graphene epoxy resin dispersion liquid, which comprises the following steps:
A) reacting graphene oxide, a compound containing a benzene ring and a reinforcing agent to obtain a modified graphene oxide dispersion liquid;
the compound containing the benzene ring comprises one or more of aniline compounds, phenol compounds, benzoic acid compounds and phenyl ether compounds;
B) chemically reducing the modified graphene oxide dispersion liquid obtained in the step with a reducing agent to obtain a modified graphene dispersion liquid;
C) carrying out post-treatment on the modified graphene dispersion liquid obtained in the step to obtain modified graphene powder;
D) and mixing the modified graphene powder obtained in the step, epoxy resin and an organic solvent to obtain a modified graphene epoxy resin dispersion liquid.
Preferably, the compound containing a benzene ring includes one or more of para-phenylenediamine, para-aminophenol, para-aminobenzoate, N-dimethylaniline and 2,4, 6-tris (dimethylaminomethyl) phenol;
the reinforcing agent comprises one or more of polyvinylpyrrolidone, polyethyleneimine and polyethylene glycol 600;
the graphene oxide comprises graphene oxide powder or a graphene oxide aqueous solution;
the reducing agent comprises one or more of sodium sulfite, glucose and hydrazine hydrate;
the organic solvent comprises one or more of N, N-dimethylacetamide, dimethylbenzene, N-dimethylformamide, N-methylpyrrolidone, 2-pyrrolidone, dimethyl sulfoxide, ethanol, ethylene glycol, isopropanol, N-butanol, acetone, butanone, propylene carbonate, propylene glycol methyl ether and butyl acetate.
Preferably, the mass ratio of the graphene oxide to the compound containing a benzene ring is 1: (1-20);
the mass ratio of the reinforcing agent to the compound containing the benzene ring is 1: (1-100);
the mass ratio of the reducing agent to the graphene oxide is (0.1-10) to 1;
the mass ratio of the modified graphene powder to the epoxy resin is (0.2-2): 100.
preferably, the reaction temperature is 50-100 ℃;
the reaction time is 2-8 h;
the temperature of the chemical reduction is 50-100 ℃;
the chemical reduction time is 6-48 h;
the post-treatment comprises centrifugation and/or drying.
Preferably, the centrifugal separation time is 20-60 min;
the rotation speed of the centrifugal separation is 2000-5000 r/min;
the drying time is 8-24 h;
the drying temperature is 40-70 ℃.
Preferably, the step D) is specifically:
D1) mixing the modified graphene powder obtained in the step with a first organic solvent to obtain modified graphene slurry;
D2) and mixing the diluent of the epoxy resin and the second organic solvent with the modified graphene slurry obtained in the step again to obtain the modified graphene epoxy resin dispersion liquid.
Preferably, the mass ratio of the modified graphene powder to the first organic solvent is 1: (5-100);
the mass fraction of the epoxy resin in the diluent is 50-80%;
the mixing time is 20-60 min; the mixing speed is 2000-5000 r/min;
the remixing time is 30-90 min; the rotation speed of the remixing is 2000-5000 r/min.
The invention provides modified graphene oxide, which is prepared from graphene oxide and a compound containing a benzene ring;
the compound containing the benzene ring comprises one or more of aniline compounds, phenol compounds, benzoic acid compounds and phenyl ether compounds.
Preferably, the composition also comprises a reinforcing agent;
the reinforcing agent comprises one or more of polyvinylpyrrolidone, polyethyleneimine and polyethylene glycol 600;
the compound containing a benzene ring comprises one or more of p-phenylenediamine, p-aminophenol, p-aminobenzoate, N-dimethylaniline and 2,4, 6-tris (dimethylaminomethyl) phenol;
the mass ratio of the graphene oxide to the compound containing the benzene ring is 1: (1-20);
the mass ratio of the reinforcing agent to the compound containing the benzene ring is 1: (1-100).
The invention also provides modified graphene, which is obtained by reducing the modified graphene oxide in any one of the technical schemes.
The invention provides a preparation method of a modified graphene epoxy resin dispersion liquid, which comprises the following steps of firstly reacting graphene oxide, a compound containing a benzene ring and a reinforcing agent to obtain a modified graphene oxide dispersion liquid; the compound containing the benzene ring comprises one or more of aniline compounds, phenol compounds, benzoic acid compounds and phenyl ether compounds; then carrying out chemical reduction on the modified graphene oxide dispersion liquid obtained in the step and a reducing agent to obtain a modified graphene dispersion liquid; carrying out post-treatment on the modified graphene dispersion liquid obtained in the step to obtain modified graphene powder; and finally, mixing the modified graphene powder obtained in the step, epoxy resin and an organic solvent to obtain a modified graphene epoxy resin dispersion liquid. Compared with the prior art, the method selects and adopts chemically modified graphene aiming at the disadvantages of physical modification, and most of the existing preparation methods of the chemically modified graphene composite epoxy resin material adopt a mode of acylating chlorination of carboxyl on the surface of the graphene and then reacting the chlorinated chlorination with an amine compound, and also adopt a mode of reacting the modified carboxyl on the surface of the graphene with benzoxazine. Therefore, the graphene needs to be subjected to multiple chemical reactions to obtain chemically modified graphene, and the problems of complex process and great harm to the environment exist. Meanwhile, an efficient preparation method of a chemically modified graphene composite epoxy resin material is still lacked, and the graphene sheet layer in the prior art is poor in binding property with resin, poor in stability and difficult to have practical application in the fields of anticorrosive coatings and the like.
The invention provides a preparation method of chemically modified graphene resin dispersion liquid for the field of graphene anticorrosive coatings, which is based on the high specific surface area of graphene and the strong pi-pi bond effect between sheets, ensures that the graphene is difficult to be uniformly dispersed in a polymer matrix, considers whether the graphene can be uniformly dispersed in the polymer matrix and generates strong interface effect with the polymer matrix as a key factor influencing composite materials, modifies benzene ring-containing compounds such as anilines, phenols, benzoic acids, phenyl ether compounds and the like and graphene oxide through chemical reaction, grafts benzene rigid chemical groups on the surface of the graphene, greatly reduces Van der Waals force between graphene macromolecules by utilizing larger steric hindrance, and has stronger chemical compatibility between the residual anilines, benzoic acids, phenyl ether substances and epoxy resin, the graphene can be fused with the resin, and the wide application of the graphene resin in the fields of coatings and the like is facilitated. According to the invention, a chemical modification method is adopted, the graphene epoxy resin dispersion liquid is prepared in a relatively simple manner, the compounding degree of graphene in resin is high, the graphene is successfully uniformly dispersed in the epoxy resin, and the water absorption of the anticorrosive paint prepared from the graphene resin is greatly reduced.
Experimental results show that the modified graphene epoxy resin dispersion liquid prepared by adopting the modified graphene has the advantages that the graphene is uniformly dispersed in the epoxy resin, the water absorption of the graphene epoxy resin is greatly reduced, and the water absorption after 48h of curing and soaking is only 0.5% at least.
Drawings
FIG. 1 is a schematic diagram of a process for preparing a modified graphene epoxy resin dispersion according to the present invention;
fig. 2 is a raman microscopic imaging spectrum of the modified graphene epoxy resin dispersion prepared in example 1 of the present invention;
fig. 3 is a scanning electron microscope image of the graphene epoxy resin dispersion prepared in example 1 of the present invention.
Detailed Description
For a further understanding of the invention, reference will now be made to the preferred embodiments of the invention by way of example, and it is to be understood that the description is intended to further illustrate features and advantages of the invention, and not to limit the scope of the claims.
All of the starting materials of the present invention, without particular limitation as to their source, may be purchased commercially or prepared according to conventional methods well known to those skilled in the art.
All the raw materials of the invention are not particularly limited in purity, and the invention preferably adopts the purity requirements of analytical purity or the purity requirements of the conventional graphene preparation field.
All the raw materials, the marks and the acronyms thereof belong to the conventional marks and acronyms in the field, each mark and acronym is clear and definite in the field of related application, and the raw materials can be purchased from the market or prepared by a conventional method by the technical staff in the field according to the marks, the acronyms and the corresponding application.
The invention provides a preparation method of a modified graphene epoxy resin dispersion liquid, which comprises the following steps:
A) reacting graphene oxide, a compound containing a benzene ring and a reinforcing agent to obtain a modified graphene oxide dispersion liquid;
the compound containing the benzene ring comprises one or more of aniline compounds, phenol compounds, benzoic acid compounds and phenyl ether compounds;
B) chemically reducing the modified graphene oxide dispersion liquid obtained in the step with a reducing agent to obtain a modified graphene dispersion liquid;
C) carrying out post-treatment on the modified graphene dispersion liquid obtained in the step to obtain modified graphene powder;
D) and mixing the modified graphene powder obtained in the step, epoxy resin and an organic solvent to obtain a modified graphene epoxy resin dispersion liquid.
Firstly, reacting graphene oxide, a compound containing a benzene ring and a reinforcing agent to obtain a modified graphene oxide dispersion liquid.
The definition of the graphene oxide is not particularly limited by the present invention, and it is sufficient in terms of the concept of graphene oxide well known to those skilled in the art, and those skilled in the art can select and adjust the graphene oxide according to the practical application, product requirements and quality requirements, and the graphene oxide of the present invention is preferably graphene oxide in a broad sense, preferably includes graphene oxide, partially reduced graphene oxide and the like, more preferably single-layer graphene oxide, multi-layer graphene oxide lamp, and in the present invention, the graphene oxide is particularly preferably one or more of high-quality graphene oxide (patent No. CN 106115669a) and graphene oxide (CN 106430175a) produced by the european platinum corporation.
The compound containing a benzene ring according to the present invention is not particularly limited, and may be a conventional compound containing a benzene ring, which is well known to those skilled in the art, and may be selected and adjusted by those skilled in the art according to practical application conditions, modification requirements, and quality control, and the compound containing a benzene ring according to the present invention preferably includes one or more of aniline compounds, phenol compounds, benzoic acid compounds, and phenyl ether compounds, more preferably one or more of aniline compounds, phenol compounds, benzoic acid compounds, or phenyl ether compounds, and may be, specifically, one or more of p-phenylenediamine, p-aminophenol, p-aminobenzoate, N-dimethylaniline and 2,4, 6-tris (dimethylaminomethyl) phenol, or p-phenylenediamine, p-aminophenol, p-aminobenzoate, N-dimethylaniline or 2,4, 6-tris (dimethylaminomethyl) phenol.
The addition amount of the compound containing a benzene ring is not particularly limited in the present invention, and may be a conventional graphene oxide modification addition amount well known to those skilled in the art, and those skilled in the art may select and adjust the addition amount according to actual production conditions, modification requirements and quality control, and the mass ratio of the graphene oxide to the compound containing a benzene ring in the present invention is preferably 1: (1-20), more preferably 1: (3-18), more preferably 1: (5-15), most preferably 1: (7-12).
The enhancer of the present invention is not particularly limited, and may be selected and adjusted by those skilled in the art according to the actual application, modification requirements and quality control, and may be any conventional enhancer known to those skilled in the art, and preferably includes one or more of polyvinylpyrrolidone, polyethyleneimine and polyethylene glycol 600, and more preferably polyvinylpyrrolidone, polyethyleneimine or polyethylene glycol 600.
The addition amount of the reinforcing agent is not particularly limited in the present invention, and may be a conventional graphene oxide modification addition amount well known to those skilled in the art, and those skilled in the art can select and adjust the addition amount according to actual production conditions, modification requirements and quality control, and the mass ratio of the reinforcing agent to the compound containing a benzene ring in the present invention is preferably 1: (1 to 100), more preferably 1: (10 to 90), more preferably 1: (20 to 80), more preferably 1: (40-60).
The reaction time is not particularly limited in the invention, and the reaction time is similar to that known by the skilled in the art, and can be selected and adjusted by the skilled in the art according to the actual production condition, modification requirement and quality control, and the reaction time is preferably 2-8 h, more preferably 3-7 h, and more preferably 4-6 h.
The reaction temperature is not particularly limited in the present invention, and may be selected and adjusted by those skilled in the art according to actual production conditions, modification requirements and quality control, and is preferably 50 to 100 ℃, more preferably 60 to 90 ℃, and more preferably 70 to 80 ℃.
The reaction mode of the present invention is not particularly limited, and may be a conventional reaction mode well known to those skilled in the art, and those skilled in the art can select and adjust the reaction mode according to actual production conditions, modification requirements and quality control, and the reaction mode of the present invention is preferably a reflux reaction, more preferably a reflux stirring reaction.
Carrying out chemical reduction on the modified graphene oxide dispersion liquid obtained in the step and a reducing agent to obtain a modified graphene dispersion liquid;
the reducing agent is not particularly limited in the present invention, and may be a conventional reducing agent well known to those skilled in the art, and may be selected and adjusted by those skilled in the art according to practical use, modification requirements, and quality control, and preferably includes one or more of sodium sulfite, glucose, and hydrazine hydrate, and more preferably sodium sulfite, glucose, or hydrazine hydrate.
The addition amount of the reducing agent is not particularly limited, and can be selected and adjusted by the skilled in the art according to the actual production situation, modification requirements and quality control, and the mass ratio of the reducing agent to the graphene oxide is preferably (0.1-10): 1, more preferably (0.5-8): 1, more preferably (1-6): 1, more preferably (2-4): 1.
the time for the chemical reduction is not particularly limited, and the time similar to the chemical reduction known to those skilled in the art can be selected and adjusted by those skilled in the art according to the actual production condition, modification requirement and quality control, and the time for the chemical reduction is preferably 6-48 h, more preferably 16-38 h, and more preferably 20-30 h.
The temperature of the chemical reduction is not particularly limited, and can be selected and adjusted by a person skilled in the art according to the actual production situation, modification requirements and quality control, and is preferably 50-100 ℃, more preferably 60-90 ℃, and more preferably 70-80 ℃.
The modified graphene dispersion liquid obtained in the above step is subjected to post-treatment to obtain modified graphene powder.
The specific steps of the post-treatment are not particularly limited in the present invention, and may be conventional post-treatment steps well known to those skilled in the art, which may be selected and adjusted by those skilled in the art according to actual production conditions, activation requirements and quality control, and the post-treatment steps of the present invention preferably include separation and or drying, more preferably separation and drying, and may be specifically centrifugal separation and vacuum drying.
The specific drying conditions are not particularly limited, and a person skilled in the art can select and adjust the drying conditions according to actual production conditions, activation requirements and quality control, wherein the drying temperature is preferably 40-70 ℃, more preferably 45-65 ℃, more preferably 50-60 ℃, and particularly 55-60 ℃. The drying time is preferably 8-24 hours, more preferably 10-22 hours, more preferably 12-20 hours, and particularly 14-18 hours.
Finally, mixing the modified graphene powder obtained in the step, epoxy resin and an organic solvent to obtain the modified graphene epoxy resin dispersion liquid.
The epoxy resin is not particularly limited in the present invention, and may be selected and adjusted by those skilled in the art according to actual production conditions, product requirements and quality control, and the epoxy resin of the present invention preferably includes bisphenol a type epoxy resin, more preferably E-51 bisphenol a type epoxy resin and/or 601 bisphenol a type epoxy resin, and most preferably E-51 bisphenol a type epoxy resin or 601 bisphenol a type epoxy resin.
The present invention is not limited to other parameters of the epoxy resin, and the parameters of the conventional epoxy resin known to those skilled in the art can be selected and adjusted according to the actual application, the product requirements and the quality requirements.
The addition amount of the epoxy resin is not particularly limited, and can be selected and adjusted according to the actual application situation, the product requirement and the quality requirement by a person skilled in the art according to the conventional addition amount well known by the person skilled in the art, and the mass ratio of the modified graphene powder to the epoxy resin is (0.2-2): 100, more preferably (0.5 to 1.8): 100, more preferably (0.8 to 1.6): 100, more preferably (1.0 to 1.5): 100.
the selection of the organic solvent is not particularly limited in the present invention, and may be a conventional organic solvent well known to those skilled in the art, and those skilled in the art can select and adjust the organic solvent according to the actual application, product requirements and quality requirements, and the organic solvent of the present invention preferably includes one or more of N, N-dimethylacetamide, xylene, N-dimethylformamide, N-methylpyrrolidone, 2-pyrrolidone, dimethylsulfoxide, ethanol, ethylene glycol, isopropanol, N-butanol, acetone, butanone, propylene carbonate, propylene glycol methyl ether and butyl acetate, more preferably N, N-dimethylacetamide, xylene, N-dimethylformamide, N-methylpyrrolidone, 2-pyrrolidone, dimethylsulfoxide, ethanol, ethylene glycol, propylene glycol methyl ether and butyl acetate, Isopropanol, N-butanol, acetone, butanone, propylene carbonate, propylene glycol methyl ether or butyl acetate, and specifically may be N, N-dimethylacetamide, xylene, N-dimethylformamide, N-methylpyrrolidone or 2-pyrrolidone.
The addition amount of the organic solvent is not particularly limited in the present invention, and may be the addition amount of a conventional organic solvent well known to those skilled in the art, and those skilled in the art can select and adjust the organic solvent according to the actual application situation, the product requirement and the quality requirement.
In order to further improve the properties of the product, optimize and complete reaction routes, the step D) is particularly preferably as follows:
D1) mixing the modified graphene powder obtained in the step with a first organic solvent to obtain modified graphene slurry;
D2) and mixing the diluent of the epoxy resin and the second organic solvent with the modified graphene slurry obtained in the step again to obtain the modified graphene epoxy resin dispersion liquid.
The specific selection of the first organic solvent and the second organic solvent in the present invention is not particularly limited, and conventional organic solvents known to those skilled in the art may be used, and those skilled in the art may select and adjust the organic solvents according to the actual application situation, the product requirements, and the quality requirements.
The addition amount of the first organic solvent is not particularly limited, and may be the addition amount of a conventional organic solvent well known to those skilled in the art, and those skilled in the art may select and adjust the addition amount according to the actual application situation, the product requirement and the quality requirement, and the mass ratio of the modified graphene powder of the present invention to the first organic solvent is preferably 1: (5 to 100), more preferably 1: (10 to 80), more preferably 1: (15-60), specifically 1: 15.
The addition amount of the second organic solvent is not particularly limited in the present invention, and may be the addition amount of a conventional organic solvent well known to those skilled in the art, and those skilled in the art can select and adjust the addition amount according to the actual application situation, the product requirement and the quality requirement, and the mass fraction of the epoxy resin in the diluent of the present invention is preferably 50% to 80%, more preferably 55% to 75%, more preferably 60% to 70%, and particularly may be 75%.
The concrete mode of mixing is not particularly limited by the invention, and the mixing mode is a stirring mixing mode well known to those skilled in the art, and can be selected and adjusted by the skilled in the art according to the actual production situation, the product requirement and the quality control, and the invention optimizes the process route for further improving the uniformity and performance of the dispersion liquid and the subsequent coating product, and the mixing preferably comprises magnetic stirring and/or mechanical stirring, more preferably magnetic stirring or mechanical stirring, and particularly can be high-speed stirring mixing.
The mixing time is not particularly limited by the invention, and the stirring and mixing time known by the technicians in the field can be used, and the technicians in the field can select and adjust the mixing time according to the actual production condition, the product requirement and the quality control, the mixing time is preferably 20-60 min, more preferably 25-55 min, more preferably 30-50 min, and more preferably 35-45 min, so as to further improve the uniformity and the performance of the dispersion and optimize the process route.
The mixing speed is not particularly limited by the invention, and can be selected and adjusted by the technicians in the field according to the actual production condition, the product requirement and the quality control, the uniformity and the performance of the dispersion liquid and the subsequent coating product are further improved, the process route is optimized, and the mixing rotating speed is preferably 2000-5000 r/min, more preferably 2500-4500 r/min, and more preferably 3000-4000 r/min.
The specific mixing method of the remixing is not particularly limited by the present invention, and may be a stirring mixing method well known to those skilled in the art, and may be selected and adjusted by those skilled in the art according to the actual production situation, the product requirement and the quality control, and the remixing preferably includes magnetic stirring and/or mechanical stirring, more preferably magnetic stirring or mechanical stirring, and may be particularly high-speed stirring mixing to further improve the uniformity and performance of the dispersion and the subsequent coating product and optimize the process route.
The remixing time is not particularly limited by the invention, and the remixing time is selected and adjusted by the time known by the skilled in the art, and can be selected and adjusted according to the actual production condition, the product requirement and the quality control, and the remixing time is preferably 30-90 min, more preferably 40-80 min, and more preferably 50-70 min, in order to further improve the uniformity and the performance of the dispersion and optimize the process route.
The remixing speed is not particularly limited by the invention, and the remixing speed is selected and adjusted by the mixing speed known by the technicians in the field according to the actual production condition, the product requirement and the quality control, the remixing speed is preferably 2000-5000 r/min, more preferably 2500-4500 r/min, and more preferably 3000-4000 r/min, in order to further improve the uniformity and the performance of the dispersion liquid and the subsequent coating product and optimize the process route.
The invention provides modified graphene oxide, which is prepared from graphene oxide and a compound containing a benzene ring;
the compound containing the benzene ring comprises one or more of aniline compounds, phenol compounds, benzoic acid compounds and phenyl ether compounds.
In order to further improve the property of the product and optimize and complete the product route, the modified graphene oxide also comprises a reinforcing agent, namely the modified graphene oxide is preferably prepared from graphene oxide, a compound containing a benzene ring and the reinforcing agent.
The selection and composition of the raw materials in the modified graphene oxide and the corresponding preferred principle of the invention can correspond to the selection and composition of the raw materials corresponding to the preparation method of the modified graphene oxide epoxy resin dispersion liquid and the corresponding preferred principle, and are not described in detail herein.
The invention also provides modified graphene, which is obtained by reducing the modified graphene oxide in any one of the technical schemes.
The present invention is not particularly limited in the manner and procedure of the reduction, and the manner and procedure of the conventional graphene oxide reduction well known to those skilled in the art can be selected and adjusted by those skilled in the art according to actual production conditions, product requirements and quality requirements, and the reduction manner of the present invention is preferably chemical reduction.
The invention provides a preparation method of modified graphene oxide, modified graphene and modified graphene epoxy resin dispersion liquid. The invention provides a preparation method of a chemically modified graphene composite epoxy resin dispersion liquid used in the field of graphene anticorrosive coatings, which can effectively solve the problem that the performance of a composite material is not improved favorably, such as the agglomeration of graphene in resin. According to the method for chemically modifying the graphene oxide by adopting a one-time chemical reaction, substances such as aniline and the like and the graphene oxide are modified by the chemical reaction, benzene rigid chemical groups are grafted on the surface of the graphene oxide, the van der Waals force among graphene macromolecules is greatly reduced by utilizing the larger steric hindrance of the benzene rigid chemical groups, and the problems of graphene agglomeration, sedimentation and the like are avoided. In addition, the modified graphene epoxy resin dispersion liquid prepared by the invention has strong chemical compatibility between substances such as aniline and epoxy resin, can promote the modified graphene to be better fused with resin, and is beneficial to the wide application of graphene resin in the fields of coatings and the like.
The modified graphene oxide, the modified graphene and the modified graphene composite epoxy resin dispersion liquid are prepared relatively simply, the preparation process is simplified, the risk in the preparation process is reduced, low-harm environment-friendly materials are used, the pollution to the environment is reduced, and the industrial production is facilitated. The composite material dispersion liquid obtained by the method has high graphene and resin composite degree, and the graphene is successfully dispersed in the epoxy resin uniformly, so that the water absorption of the anticorrosive paint prepared from the graphene resin is greatly reduced, and the composite material dispersion liquid has good application prospects in the fields of anticorrosive paints and the like.
Experimental results show that the modified graphene epoxy resin dispersion liquid prepared by adopting the modified graphene has the advantages that the graphene is uniformly dispersed in the epoxy resin, the water absorption of the graphene epoxy resin is greatly reduced, and the water absorption after 48h of curing and soaking is only 0.5% at least.
For further illustration of the present invention, the following will describe in detail the preparation methods of a modified graphene oxide, a modified graphene and a modified graphene epoxy resin dispersion according to the present invention with reference to the following examples, but it should be understood that these examples are implemented on the premise of the technical solution of the present invention, and the detailed embodiments and specific procedures are given only for further illustration of the features and advantages of the present invention, but not for limitation of the claims of the present invention, and the scope of protection of the present invention is not limited to the following examples.
Example 1
Chemically modified graphene composite epoxy resin dispersion liquid:
firstly, adding a mixed solution of p-phenylenediamine and polyethyleneimine in a certain proportion into a graphene oxide aqueous solution, and refluxing and stirring at 80 ℃ for 4 hours to obtain a modified graphene oxide dispersion solution; (the mass ratio of the p-phenylenediamine to the polyethyleneimine is 80:1, and the mass ratio of the graphene oxide to the p-phenylenediamine is 1: 6);
and secondly, heating the modified graphene oxide dispersion liquid obtained in the step one, adding a certain amount of hydrazine hydrate, and reacting for a period of time to obtain the modified graphene dispersion liquid. Heating at 80 ℃, wherein the mass ratio of hydrazine hydrate to graphene oxide is 2:1, and the reaction time is 24 h;
thirdly, centrifuging the modified graphene dispersion liquid obtained in the second step for 10min at the speed of 5000r/min, and drying for 12h at the temperature of 60 ℃ in vacuum to obtain modified graphene powder;
fourthly, adding a certain amount of dimethylacetamide into the modified graphene powder obtained in the third step, and stirring at a high speed of 3000r/min for 40min to obtain modified graphene slurry, wherein the mass ratio of the modified graphene to the dimethylacetamide is 1: 15;
and fifthly, adding the modified graphene slurry obtained in the fourth step into the prepared epoxy resin xylene solution, and stirring at a high speed to obtain the modified graphene composite epoxy resin dispersion liquid. Wherein the mass fraction of the epoxy resin in the xylene solution is 75%, and the ratio of the modified graphene to the epoxy resin is 1.2%.
Referring to fig. 1, fig. 1 is a schematic process flow diagram of the modified graphene epoxy resin dispersion according to the present invention.
The modified graphene epoxy resin dispersion liquid prepared in example 1 of the present invention was subjected to raman spectroscopic imaging.
Referring to fig. 2, fig. 2 is a raman microscopic imaging spectrum of the modified graphene epoxy resin dispersion prepared in example 1 of the present invention. The left side of the composite material dispersion liquid is a Raman imaging image, the right side of the composite material dispersion liquid is a matching peak of at most two substances, and a red area and a blue area are both mixed peaks of graphene and epoxy resin (both have graphene characteristic peaks, namely a D peak and a G peak).
As can be seen from fig. 2, in the embodiment, the graphene composite epoxy resin material is successfully prepared, and the graphene and the epoxy resin are mutually blended, so that the graphene is well dispersed in the resin.
The modified graphene epoxy resin dispersion liquid prepared in example 1 of the present invention was observed with a scanning electron microscope.
Referring to fig. 3, fig. 3 is a scanning electron microscope image of the graphene epoxy resin dispersion prepared in example 1 of the present invention. As can be seen from fig. 3, the graphene composite epoxy resin has a dense structure.
After the modified graphene epoxy resin prepared in the embodiment of the invention is cured, a water absorption test is performed.
Referring to table 1, table 1 shows water absorption data of the modified graphene epoxy resin prepared according to the embodiment of the present invention after curing.
TABLE 1
As can be seen from table 1, the water absorption of the graphene epoxy resin obtained in example 1 after curing was 0.5% after soaking in deionized water for 48 hours.
Example 2
The chemically modified graphene composite epoxy resin is prepared by the following steps:
adding a mixed solution of p-aminophenol and polyethyleneimine in a certain proportion into a graphene oxide aqueous solution, and carrying out reflux stirring at 60 ℃ for 6 hours to obtain a modified graphene oxide dispersion solution; the mass ratio of the p-aminophenol to the polyethyleneimine is 20:1, and the mass ratio of the graphene oxide to the p-aminophenol is 1: 4.
And secondly, heating the modified graphene oxide dispersion liquid obtained in the step one, adding a certain amount of hydrazine hydrate, and reacting for a period of time to obtain the modified graphene dispersion liquid. Heating at 80 ℃, wherein the mass ratio of hydrazine hydrate to graphene oxide is 2:1, and the reaction time is 24 h;
thirdly, centrifuging the modified graphene dispersion liquid obtained in the second step for 10min at the speed of 5000r/min, and drying for 8h at the temperature of 60 ℃ in vacuum to obtain modified graphene powder;
fourthly, adding a certain amount of dimethylacetamide into the modified graphene powder obtained in the third step, and stirring at a high speed of 3000r/min for 40min to obtain modified graphene slurry, wherein the mass ratio of the modified graphene to the dimethylacetamide is 1: 35;
and fifthly, adding the modified graphene slurry obtained in the fourth step into the prepared epoxy resin xylene solution, and stirring at a high speed to obtain a modified graphene composite resin dispersion liquid, wherein the mass fraction of the epoxy resin in the xylene solution is 70%, and the ratio of the modified graphene to the epoxy resin is 0.4%.
The modified graphene epoxy resin prepared in the embodiment of the invention is subjected to a water absorption test.
As shown in table 1, the water absorption of the modified graphene epoxy resin obtained in this example 2 after curing is 1.8% after soaking in deionized water for 48 hours.
Example 3
The chemically modified graphene composite epoxy resin is prepared by the following steps:
adding a mixed solution of p-aminobenzoate and polyethyleneimine in a certain proportion into a graphene oxide aqueous solution, and carrying out reflux stirring at 60 ℃ for 6 hours to obtain a modified graphene oxide dispersion solution; the mass ratio of the p-aminobenzoate to the polyethyleneimine is 5:1, and the mass ratio of the graphene oxide to the p-aminobenzoate is 1:3.
And secondly, heating the modified graphene oxide dispersion liquid obtained in the step one, adding a certain amount of hydrazine hydrate, and reacting for a period of time to obtain the modified graphene dispersion liquid. Heating at 80 ℃, wherein the mass ratio of hydrazine hydrate to graphene oxide is 2:1, and the reaction time is 24 h;
thirdly, centrifuging the modified graphene dispersion liquid obtained in the second step for 10min at the speed of 5000r/min, and drying for 12h at the temperature of 60 ℃ in vacuum to obtain modified graphene powder;
fourthly, adding a certain amount of propylene oxide into the modified graphene powder obtained in the third step, and stirring at a high speed of 3000r/min for 40min to obtain modified graphene slurry, wherein the mass ratio of the modified graphene to the propylene oxide is 1: 15;
and fifthly, adding the modified graphene slurry obtained in the fourth step into a prepared epoxy resin xylene solution, and stirring at a high speed to obtain a modified graphene composite resin dispersion liquid, wherein the mass fraction of the epoxy resin in the xylene solution is 60%, and the ratio of the modified graphene to the epoxy resin is 0.5%.
The modified graphene epoxy resin prepared in the embodiment of the invention is subjected to a water absorption test.
As can be seen from table 1, the water absorption of the modified graphene epoxy resin obtained in this example 3 after curing is 1.3% after soaking in deionized water for 48 hours.
Example 4
The chemically modified graphene composite epoxy resin is prepared by the following steps:
adding a mixed solution of N-N dimethylaniline and polyethyleneimine in a certain proportion into a graphene oxide aqueous solution, and carrying out reflux stirring at 60 ℃ for 6 hours to obtain a modified graphene oxide dispersion solution; the mass ratio of the N-dimethylaniline to the polyethyleneimine is 10:1, and the mass ratio of the graphene oxide to the N-dimethylaniline is 1: 3.5.
And secondly, heating the modified graphene oxide dispersion liquid obtained in the step one, adding a certain amount of hydrazine hydrate, and reacting for a period of time to obtain the modified graphene dispersion liquid. Heating at 80 ℃, wherein the mass ratio of hydrazine hydrate to graphene oxide is 2:1, and the reaction time is 24 h;
thirdly, centrifuging the modified graphene dispersion liquid obtained in the second step for 10min at the speed of 5000r/min, and drying for 12h at the temperature of 60 ℃ in vacuum to obtain modified graphene powder;
fourthly, adding a certain amount of propylene oxide into the modified graphene powder obtained in the third step, and stirring at a high speed of 3000r/min for 40min to obtain modified graphene slurry, wherein the mass ratio of the modified graphene to the propylene oxide is 1: 15;
and fifthly, adding the modified graphene slurry obtained in the fourth step into the prepared epoxy resin xylene solution, and stirring at a high speed to obtain a modified graphene composite resin dispersion liquid, wherein the mass fraction of the epoxy resin in the xylene solution is 60%, and the ratio of the modified graphene to the epoxy resin is 2%.
The modified graphene epoxy resin prepared in the embodiment of the invention is subjected to a water absorption test.
As shown in table 1, the water absorption of the modified graphene epoxy resin obtained in this example 4 after curing is 1.6% after soaking in deionized water for 48 hours.
The above detailed description of the method for preparing a modified graphene oxide, a modified graphene, and a modified graphene epoxy resin dispersion for an anticorrosive coating according to the present invention is provided, and the principles and embodiments of the present invention are described herein using specific examples, which are provided only to help understand the method of the present invention and its core ideas, including the best mode, and also to enable any person skilled in the art to practice the present invention, including making and using any device or system, and implementing any method in combination. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention. The scope of the invention is defined by the claims and may include other embodiments that occur to those skilled in the art. Such other embodiments are intended to be within the scope of the claims if they have structural elements that do not differ from the literal language of the claims, or if they include equivalent structural elements with insubstantial differences from the literal languages of the claims.
Claims (9)
1. A preparation method of a modified graphene epoxy resin organic dispersion liquid is characterized by comprising the following steps:
A) reacting graphene oxide, a compound containing a benzene ring and a reinforcing agent to obtain a modified graphene oxide dispersion liquid;
the compound containing a benzene ring comprises one or more of p-phenylenediamine, p-aminophenol, p-aminobenzoate, N-dimethylaniline and 2,4, 6-tris (dimethylaminomethyl) phenol;
the reinforcing agent comprises one or more of polyvinylpyrrolidone, polyethyleneimine and polyethylene glycol 600;
the mass ratio of the graphene oxide to the compound containing the benzene ring is 1: (1-20);
the mass ratio of the reinforcing agent to the compound containing the benzene ring is 1: (1-100);
B) chemically reducing the modified graphene oxide dispersion liquid obtained in the step with a reducing agent to obtain a modified graphene dispersion liquid;
C) carrying out post-treatment on the modified graphene dispersion liquid obtained in the step to obtain modified graphene powder;
D) mixing the modified graphene powder obtained in the step, epoxy resin and an organic solvent to obtain a modified graphene epoxy resin dispersion liquid;
the organic solvent comprises one or more of N, N-dimethylacetamide, dimethylbenzene, N-dimethylformamide, N-methylpyrrolidone, 2-pyrrolidone, dimethyl sulfoxide, ethanol, ethylene glycol, isopropanol, N-butanol, acetone, butanone, propylene carbonate, propylene glycol methyl ether and butyl acetate.
2. The preparation method according to claim 1, wherein the graphene oxide comprises a graphene oxide powder or an aqueous graphene oxide solution;
the reducing agent comprises one or more of sodium sulfite, glucose and hydrazine hydrate.
3. The preparation method according to claim 1, wherein the mass ratio of the reducing agent to the graphene oxide is (0.1-10): 1;
the mass ratio of the modified graphene powder to the epoxy resin is (0.2-2): 100.
4. The preparation method according to claim 1, wherein the reaction temperature is 50-100 ℃;
the reaction time is 2-8 h;
the temperature of the chemical reduction is 50-100 ℃;
the chemical reduction time is 6-48 h;
the post-treatment comprises centrifugation and/or drying.
5. The preparation method according to claim 4, wherein the time for centrifugal separation is 20-60 min;
the rotation speed of the centrifugal separation is 2000-5000 r/min;
the drying time is 8-24 h;
the drying temperature is 40-70 ℃.
6. The method according to claim 1, wherein step D) is in particular:
D1) mixing the modified graphene powder obtained in the step with a first organic solvent to obtain modified graphene slurry;
D2) and mixing the diluent of the epoxy resin and the second organic solvent with the modified graphene slurry obtained in the step again to obtain the modified graphene epoxy resin dispersion liquid.
7. The preparation method according to claim 6, wherein the mass ratio of the modified graphene powder to the first organic solvent is 1: (5-100);
the mass fraction of the epoxy resin in the diluent is 50-80%;
the mixing time is 20-60 min; the mixing speed is 2000-5000 r/min;
the remixing time is 30-90 min; the rotation speed of the remixing is 2000-5000 r/min.
8. The modified graphene oxide is characterized by being prepared from graphene oxide, a compound containing a benzene ring and a reinforcing agent;
the compound containing a benzene ring comprises one or more of p-phenylenediamine, p-aminophenol, p-aminobenzoate, N-dimethylaniline and 2,4, 6-tris (dimethylaminomethyl) phenol;
the reinforcing agent comprises one or more of polyvinylpyrrolidone, polyethyleneimine and polyethylene glycol 600;
the mass ratio of the graphene oxide to the compound containing the benzene ring is 1: (1-20);
the mass ratio of the reinforcing agent to the compound containing the benzene ring is 1: (1-100).
9. A modified graphene obtained by reducing the modified graphene oxide according to claim 8.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710958014.8A CN109666259B (en) | 2017-10-16 | 2017-10-16 | Preparation method of modified graphene oxide, modified graphene and modified graphene epoxy resin dispersion liquid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710958014.8A CN109666259B (en) | 2017-10-16 | 2017-10-16 | Preparation method of modified graphene oxide, modified graphene and modified graphene epoxy resin dispersion liquid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109666259A CN109666259A (en) | 2019-04-23 |
| CN109666259B true CN109666259B (en) | 2022-05-27 |
Family
ID=66139240
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710958014.8A Active CN109666259B (en) | 2017-10-16 | 2017-10-16 | Preparation method of modified graphene oxide, modified graphene and modified graphene epoxy resin dispersion liquid |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109666259B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111454641B (en) * | 2020-05-29 | 2022-06-17 | 南京长江涂料有限公司 | Aqueous single-component conductive coating for insulator and preparation method thereof |
| CN113150599A (en) * | 2021-03-26 | 2021-07-23 | 杭州安誉科技有限公司 | High-thermal-conductivity PCR reaction tube and preparation process thereof |
| CN113292739A (en) * | 2021-06-18 | 2021-08-24 | 广东航迈新材料科技有限公司 | Production method of high-graphene-concentration latex |
| CN114032674A (en) * | 2021-12-17 | 2022-02-11 | 南通强生石墨烯科技有限公司 | Graphene chemical-resistant fiber and preparation method thereof |
| CN115206689B (en) * | 2022-07-07 | 2024-02-09 | 浙江理工大学 | Graphene modified material and preparation method thereof |
| CN115746704B (en) * | 2022-10-17 | 2023-06-27 | 保利长大工程有限公司 | Steel bridge deck composite structure with excellent corrosion resistance |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104211053A (en) * | 2014-09-04 | 2014-12-17 | 济宁利特纳米技术有限责任公司 | Preparation method of modified graphene aqueous dispersion |
| CN104231547A (en) * | 2014-09-04 | 2014-12-24 | 济宁利特纳米技术有限责任公司 | Method for preparing aqueous graphene/epoxy resin nanocomposite material |
| CN105385310A (en) * | 2016-01-04 | 2016-03-09 | 沈阳顺风实业集团有限公司 | Steel structure fireproof anticorrosion function integrated coating and preparing method thereof |
| CN106744834A (en) * | 2016-11-28 | 2017-05-31 | 江南大学 | A kind of preparation method of aqueous-dispersible conductive Graphene |
-
2017
- 2017-10-16 CN CN201710958014.8A patent/CN109666259B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104211053A (en) * | 2014-09-04 | 2014-12-17 | 济宁利特纳米技术有限责任公司 | Preparation method of modified graphene aqueous dispersion |
| CN104231547A (en) * | 2014-09-04 | 2014-12-24 | 济宁利特纳米技术有限责任公司 | Method for preparing aqueous graphene/epoxy resin nanocomposite material |
| CN105385310A (en) * | 2016-01-04 | 2016-03-09 | 沈阳顺风实业集团有限公司 | Steel structure fireproof anticorrosion function integrated coating and preparing method thereof |
| CN106744834A (en) * | 2016-11-28 | 2017-05-31 | 江南大学 | A kind of preparation method of aqueous-dispersible conductive Graphene |
Non-Patent Citations (2)
| Title |
|---|
| B. Ramezanzadeh et al.Enhancement of barrier and corrosion protection performance of an epoxy coating through wet transfer of amino functionalized graphene oxide.《Corrosion Science》.2016,(第103期),第283-304页. * |
| Enhancement of barrier and corrosion protection performance of an epoxy coating through wet transfer of amino functionalized graphene oxide;B. Ramezanzadeh et al;《Corrosion Science》;20161231(第103期);第283-304页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109666259A (en) | 2019-04-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109666259B (en) | Preparation method of modified graphene oxide, modified graphene and modified graphene epoxy resin dispersion liquid | |
| US20080281014A1 (en) | Nanosubstance-Containing Composition, Process for Producing the Same, and Composite Made With the Same | |
| CN109054584B (en) | Nano-scale cellulose functional doped modified coating and preparation method thereof | |
| Wei et al. | Durable superhydrophobic coatings for prevention of rain attenuation of 5G/weather radomes | |
| WO2020071658A1 (en) | Copper sulfide nanoparticles having core-shell structure included in coating composition for blocking near-infrared light, and preparation method therefor | |
| WO2006016729A1 (en) | Composition for functional coatings, film formed therefrom and method for forming the composition and the film | |
| KR102482030B1 (en) | Ink composition for carbon material dispersion and method for preparing the same | |
| Liu et al. | A synergetic strategy of well dispersing hydrophilic Ti3C2Tx MXene into hydrophobic polybenzoxazine composites for improved comprehensive performances | |
| CN102504252B (en) | Amino phenoxy phthalonitrile pre-polymer, condensate and preparation method and application thereof | |
| CN106634102A (en) | Graphite phase carbon nitride/graphene oxide heterojunction-epoxy acrylate composite material as well as preparation method and application thereof | |
| CN108929616B (en) | Metal substrate graphene modified long-acting anticorrosive paint and preparation method thereof | |
| CN109054610A (en) | A kind of aluminum alloy doors and windows anticorrosive paint and preparation method thereof | |
| Hano et al. | Monodisperse surface-charge-controlled black nanoparticles for near-infrared shielding | |
| JP5599967B2 (en) | Pigment dispersion | |
| CN108388040B (en) | Resin optical filter and preparation method thereof | |
| CN110256814B (en) | Preparation method of piperazine structure-containing DOPO derivative modified flame-retardant epoxy resin | |
| Zheng et al. | Graphene dispersed by pyrene‐terminated polyethylene glycol for reinforced epoxy composites | |
| CN103254686A (en) | High-covering property glass lens ink and preparation method thereof | |
| CN111849275B (en) | Preparation method and application of water-based two-component electric heating coating | |
| Zhan et al. | Thermally stable and dielectric nanocomposite based on poly (arylene ether nitrile) and BaTiO 3 functionalized by modified mussel-inspired route | |
| CN102093717A (en) | Sulfonated polyethersulfone/TiO2 nano composite material and preparation method thereof | |
| CN116218360A (en) | Shading sheet coating and preparation method thereof, and shading sheet | |
| JP2002347155A (en) | Particle-dispersion-system resin sheet and liquid crystal display | |
| JP2009181917A (en) | Colored conductive film, and colored conductive paint | |
| CN111057270B (en) | Modified carbon black and preparation method thereof, resin composition and copper-clad plate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |