CN111808300A - Preparation method of graphene-based waterborne epoxy resin emulsion - Google Patents
Preparation method of graphene-based waterborne epoxy resin emulsion Download PDFInfo
- Publication number
- CN111808300A CN111808300A CN202010680485.9A CN202010680485A CN111808300A CN 111808300 A CN111808300 A CN 111808300A CN 202010680485 A CN202010680485 A CN 202010680485A CN 111808300 A CN111808300 A CN 111808300A
- Authority
- CN
- China
- Prior art keywords
- parts
- graphene
- epoxy resin
- heating
- stirring
- 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.)
- Withdrawn
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- 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
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
-
- 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
- C08J2463/00—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
- C08J2471/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
- C08J2471/02—Polyalkylene oxides
-
- 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
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/06—Pretreated ingredients and ingredients covered by the main groups C08K3/00 - C08K7/00
-
- 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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/38—Boron-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/02—Ingredients treated with inorganic substances
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
Landscapes
- Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Paints Or Removers (AREA)
Abstract
The invention discloses a preparation method of a graphene-based waterborne epoxy resin emulsion, which comprises the following raw materials in parts by weight: 10-15 parts of modified graphene, 3-5 parts of an emulsifier, 35-50 parts of epoxy resin, 5-10 parts of polyethylene glycol, 120-150 parts of propylene glycol methyl ether, 20-30 parts of deionized water, 1-2 parts of boron trifluoride and 1-3 parts of a flatting agent; the modified graphene has a physical barrier effect, can reduce heat transfer and combustible gas volatilization when the emulsion is used for paint film combustion, can form a carbon layer to protect a substrate from being combusted, and endows the emulsion with excellent flame retardant property; the method solves the technical problems that the graphene has super van der Waals force and conjugate acting force, is easy to form a three-dimensional structure and has poor dispersibility in organic phase and aqueous phase solvents.
Description
Technical Field
The invention belongs to the technical field of epoxy resin emulsion preparation, and particularly relates to a preparation method of a graphene-based waterborne epoxy resin emulsion.
Background
Due to the excellent physical and mechanical properties of the epoxy resin, such as good adhesion, good chemical resistance, excellent solvent resistance, high hardness, good wear resistance and the like, the epoxy resin is widely applied to military use, civil use, industrial maintenance and the like, and particularly is widely applied in the field of coating industry. In order to effectively replace the common solvent-based epoxy resin coating, people continuously develop and research the water-based epoxy resin emulsion, and the common water-based epoxy resin emulsion is obtained by a method of adding an emulsifier, namely, the resin is dispersed in a water phase by external force in the presence of the emulsifier, but the method has the limitations, such as higher requirement on production equipment, high-speed dispersion equipment, larger particle size, and less ideal storage stability and application performance. At present, how to obtain a water-based epoxy resin system with high performance, good stability and rapid curing has become a great hot point of research.
Chinese patent CN101402739A discloses a method for producing aqueous epoxy resin emulsion, which comprises preparing aqueous epoxy resin emulsion by phase inversion method, dispersing the prepared epoxy resin emulsion with high-speed disperser, crushing and grinding with colloid mill, and emulsifying under high pressure with homogenizer. The dispersing speed of the high-speed dispersing machine is 100-140 r/min. Grinding with colloid mill at rotation speed of 2500-. Emulsifying under high pressure in a homogenizer at 30-100MPa for 0.5-1.5 h. The aqueous epoxy resin emulsion obtained by the invention has excellent performance: the effect of the centrifugal stability was 3000 rpm, and no separation occurred in 30 minutes.
Disclosure of Invention
In order to overcome the technical problems, the invention provides a preparation method of a graphene-based waterborne epoxy resin emulsion.
The technical problems to be solved by the invention are as follows:
(1) superstrong van der waals force and conjugate force exist between the graphene, so that a three-dimensional structure is easily formed, and the graphene is poor in dispersibility in an organic phase and a water phase solvent;
(2) in the prior art, the particle size of the emulsion cannot be controlled in the preparation process of the epoxy resin emulsion, the emulsion has poor stability due to uneven particle size distribution, the amine hydrogen and the epoxy group of the ethanolamine are converted into tertiary amine through ring opening, and the tertiary amine can promote the epoxy group to generate ring opening crosslinking, so that the epoxy group is gelatinized in the reaction process of a system.
The purpose of the invention can be realized by the following technical scheme:
a preparation method of a graphene-based waterborne epoxy resin emulsion comprises the following steps:
firstly, weighing the following raw materials in parts by weight: 10-15 parts of modified graphene, 3-5 parts of an emulsifier, 35-50 parts of epoxy resin, 5-10 parts of polyethylene glycol, 120-150 parts of propylene glycol methyl ether, 20-30 parts of deionized water, 1-2 parts of boron trifluoride and 1-3 parts of a flatting agent;
secondly, adding epoxy resin into a beaker filled with propylene glycol monomethyl ether, heating in water bath at 60-65 ℃ and stirring at constant speed until a transparent solution is formed, then adding an emulsifier and polyethylene glycol, and continuing stirring for 30 min;
and thirdly, adding boron trifluoride and modified graphene, cooling to 30-35 ℃, uniformly stirring for 10min, heating to 85 ℃, reacting for 2h at the temperature, cooling to 60 ℃, dropwise adding deionized water, controlling the dropwise adding time to be 1h, uniformly stirring, reacting for 30min, adding a leveling agent, and uniformly mixing to obtain the graphene-based waterborne epoxy resin emulsion.
Further, the leveling agent is one or two of BD-3307 and GSK-550.
Further, the modified graphene is prepared from the following raw materials in parts by weight: 10-15 parts of graphene, 5-8 parts of sodium nitrate, 100-150 parts of 98% concentrated sulfuric acid by mass fraction, 1-2 parts of potassium chlorate, 20-30 parts of 10% aqueous hydrogen peroxide by mass fraction, 180-200 parts of maleic anhydride, 15-20 parts of 1-hydroxybenzotriazole, 100-150 parts of dimethylformamide and 3-10 parts of dicyclohexylcarbon.
Further, the modified graphene is prepared by the following method:
(1) grinding graphene, adding the ground graphene into a beaker, adding sodium nitrate and 98% concentrated sulfuric acid, stirring in an ice bath for 15min, then adding potassium chlorate, heating in a water bath at 45 ℃, reacting for 2-3h at the temperature, adding deionized water, heating to 75 ℃, reacting for 30min, adding 10% aqueous hydrogen peroxide, and continuing to react for 5-8min to obtain a graphene oxide solution;
(2) adding maleic anhydride into deionized water, heating to melt, transferring into a graphene oxide solution, stirring at a rotating speed of 120r/min for 3 hours, adding distilled water, heating to 65-70 ℃, stirring and reacting at the temperature for 10 hours, condensing, refluxing and drying to obtain treated graphene oxide;
(3) adding the treated graphene oxide and 1-hydroxybenzotriazole into dimethylformamide for uniform dispersion, then adding dicyclohexyl carbon, introducing nitrogen, heating in an oil bath at 80-85 ℃, reacting for 40-45h at the temperature, filtering, washing with absolute ethyl alcohol for three times, and drying at 50-60 ℃ for 8-10h to obtain the modified graphene.
The method comprises the following steps that (1) superstrong van der Waals force and conjugate acting force exist among graphene, a three-dimensional structure is easy to form, and the dispersibility of the graphene in an organic phase and an aqueous phase solvent is poor, graphene oxide is prepared from the graphene under the action of potassium chlorate, 10% hydrogen peroxide water solution and the like, the graphene oxide can be dispersed in water and can also be dispersed in the organic solvent, and rich oxygen-containing functional groups are added on the surface of the graphene oxide, so that the graphene oxide is not easy to agglomerate; and (3) mixing maleic anhydride and the prepared graphene oxide for reaction in the step (2) to obtain the treated graphene oxide, wherein hydroxyl on the surface of the graphene oxide is modified into carboxyl by the maleic anhydride, adding 1-hydroxybenzotriazole in the step (3), using dimethylformamide as a solvent, and reacting the hydroxyl on the 1-hydroxybenzotriazole with the carboxyl on the surface of the treated graphene oxide to form an ester bond to obtain the modified graphene.
Further, the emulsifier is prepared by the following method:
step S1, adding epoxy resin and propylene glycol monomethyl ether into a three-neck flask, heating in a water bath at 45-50 ℃, magnetically stirring at a rotating speed of 140-;
step S2, adding polyethylene glycol diglycidyl ether into the mixed solution A prepared in the step S1, uniformly mixing, then dropwise adding ethanolamine, controlling the dropwise adding speed to be 0.5-1mL/min, continuously stirring for 30imn after the dropwise adding is finished, then heating to 75-80 ℃, reacting for 3-3.5h at the temperature, cooling to 55-60 ℃ after the reaction is finished, adding glacial acetic acid, and reducing pressure and distilling to prepare the emulsifier.
In the prior art, the particle size of the emulsion cannot be controlled in the preparation process of the epoxy resin emulsion, the stability of the emulsion is poor due to uneven particle size distribution, propylene glycol methyl ether is used as a solvent in step S1, n-butyl alcohol is used as a cosolvent to dissolve the epoxy resin, polyethylene glycol diglycidyl ether is added in step S2, contains a large number of ether bonds and can form hydrogen bonds with water, so that the hydrophilic performance of the prepared emulsifier can be improved, and the ether bonds have flexibility, so that the flexibility of the epoxy resin can be improved, ethanolamine and glacial acetic acid are added, the glacial acetic acid can neutralize the system, the amine hydrogen and the epoxy group of ethanolamine are subjected to ring opening to become tertiary amine, the tertiary amine can promote the epoxy group to undergo ring opening crosslinking, so that the glacial acetic acid is added to undergo neutralization reaction with the tertiary amine, prevent from gelling.
Further, in step S2, the weight ratio of the mixed solution A, the polyethylene glycol diglycidyl ether, the ethanolamine and the glacial acetic acid is controlled to be 100: 2: 3: 2-3.
The invention has the beneficial effects that:
(1) according to the water-based epoxy resin emulsion based on graphene, modified graphene, an emulsifier and the like are used as raw materials in the preparation process, in the preparation process of the modified graphene, graphene is used for preparing graphene oxide under the action of potassium chlorate, 10% hydrogen peroxide water solution and the like in the step (1), the graphene oxide can be dispersed in water and can also be dispersed in an organic solvent, and rich oxygen-containing functional groups are added on the surface of the graphene oxide, so that the graphene oxide is not easy to agglomerate; then, in the step (2), maleic anhydride and the prepared graphene oxide are mixed and react to prepare the treated graphene oxide, hydroxyl on the surface of the graphene oxide is modified into carboxyl by maleic anhydride, then, 1-hydroxybenzotriazole is added in the step (3), dimethylformamide is used as a solvent, and the hydroxyl on the 1-hydroxybenzotriazole and the carboxyl on the surface of the treated graphene oxide react to form an ester bond to prepare the modified graphene, wherein the modified graphene has a physical barrier effect, so that when the emulsion is used for paint film combustion, heat transfer and combustible gas volatilization can be reduced, a carbon layer can be formed, a matrix is protected from being combusted, and the emulsion is endowed with excellent flame retardant property; the technical problems that super van der Waals force and conjugate acting force exist between graphene, a three-dimensional structure is easily formed, and the graphene is poor in dispersibility in an organic phase and a water phase solvent are solved;
(2) in the prior art, the particle size of the emulsion cannot be controlled in the preparation process of the epoxy resin emulsion, the stability of the emulsion is poor due to uneven particle size distribution, so that propylene glycol methyl ether is used as a solvent in the step S1 of the emulsifier in the preparation process, n-butyl alcohol is used as a cosolvent to dissolve the epoxy resin, polyethylene glycol diglycidyl ether is added in the step S2, the polyethylene glycol diglycidyl ether contains a large number of ether bonds and can form hydrogen bonds with water, the hydrophilic performance of the prepared emulsifier can be improved, the ether bonds have flexibility, the flexibility of the epoxy resin can be improved, ethanolamine and glacial acetic acid are added, the glacial acetic acid can neutralize the system, the amine hydrogen and the epoxy group of the ethanolamine are converted into tertiary amine through ring opening, the tertiary amine can promote the epoxy group to generate ring opening crosslinking, the gelation is caused in the reaction process of the system, and the glacial acetic acid can be added to generate neutralization reaction with the tertiary, preventing gelatinization; the technical problems that in the prior art, the particle size of the emulsion cannot be controlled in the preparation process of the epoxy resin emulsion, the emulsion is poor in stability due to uneven particle size distribution, the ring opening of the amine hydrogen and the epoxy group of the ethanolamine is changed into the tertiary amine, and the tertiary amine can promote the epoxy group to generate the ring opening crosslinking, so that the epoxy group is gelatinized in the reaction process of the system are solved.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
A preparation method of a graphene-based waterborne epoxy resin emulsion comprises the following steps:
firstly, weighing the following raw materials in parts by weight: 10 parts of modified graphene, 3 parts of an emulsifier, 35 parts of epoxy resin, 5 parts of polyethylene glycol, 120 parts of propylene glycol methyl ether, 20 parts of deionized water, 1 part of boron trifluoride and 1 part of GSK-550;
secondly, adding epoxy resin into a beaker filled with propylene glycol monomethyl ether, heating in a water bath at 60 ℃ and stirring at a constant speed until a transparent solution is formed, then adding an emulsifier and polyethylene glycol, and continuing stirring for 30 min;
and thirdly, adding boron trifluoride and modified graphene, cooling to 30 ℃, uniformly stirring for 10min, heating to 85 ℃, reacting for 2h at the temperature, cooling to 60 ℃, dropwise adding deionized water, controlling the dropwise adding time to be 1h, uniformly stirring, reacting for 30min, adding GSK-550, and uniformly mixing to obtain the graphene-based waterborne epoxy resin emulsion.
The modified graphene is prepared from the following raw materials in parts by weight: 10 parts of graphene, 5 parts of sodium nitrate, 100 parts of 98% concentrated sulfuric acid, 1 part of potassium chlorate, 20 parts of 10% aqueous hydrogen peroxide, 180 parts of maleic anhydride, 15 parts of 1-hydroxybenzotriazole, 100 parts of dimethylformamide and 3 parts of dicyclohexylcarbon.
Further, the modified graphene is prepared by the following method:
(1) grinding graphene, adding the ground graphene into a beaker, adding sodium nitrate and 98% concentrated sulfuric acid, stirring in an ice bath for 15min, then adding potassium chlorate, heating in a water bath at 45 ℃, reacting for 2h at the temperature, adding deionized water, heating to 75 ℃, reacting for 30min, adding 10% aqueous hydrogen peroxide, and continuing to react for 5min to obtain a graphene oxide solution;
(2) adding maleic anhydride into deionized water, heating to melt, transferring to a graphene oxide solution, stirring at a rotating speed of 120r/min for 3 hours, adding distilled water, heating to 65 ℃, stirring at the temperature and reacting for 10 hours, condensing, refluxing and drying to obtain treated graphene oxide;
(3) adding the treated graphene oxide and 1-hydroxybenzotriazole into dimethylformamide to be uniformly dispersed, then adding dicyclohexyl carbon, introducing nitrogen, heating in an oil bath at 80 ℃, reacting for 40h at the temperature, filtering, washing with absolute ethyl alcohol for three times, and drying at 50 ℃ for 8h to obtain the modified graphene.
The emulsifier is prepared by the following method:
step S1, adding epoxy resin and propylene glycol monomethyl ether into a three-neck flask, heating in a water bath at 45 ℃, magnetically stirring at a rotating speed of 140r/min for 10min, then adding n-butanol, heating to 65 ℃, stirring for 30min to prepare a mixed solution A, and controlling the weight ratio of the epoxy resin, the propylene glycol monomethyl ether and the n-butanol to be 1: 85: 5;
step S2, adding polyethylene glycol diglycidyl ether into the mixed solution A prepared in the step S1, uniformly mixing, then dropwise adding ethanolamine, controlling the dropwise adding speed to be 0.5mL/min, continuously stirring for 30imn after the dropwise adding is finished, then heating to 75 ℃, reacting for 3 hours at the temperature, cooling to 55 ℃ after the reaction is finished, adding glacial acetic acid, reducing the pressure, distilling to prepare an emulsifier, and controlling the weight ratio of the mixed solution A, the polyethylene glycol diglycidyl ether, the ethanolamine and the glacial acetic acid to be 100: 2: 3: 2.
Example 2
A preparation method of a graphene-based waterborne epoxy resin emulsion comprises the following steps:
firstly, weighing the following raw materials in parts by weight: 12 parts of modified graphene, 4 parts of an emulsifier, 40 parts of epoxy resin, 8 parts of polyethylene glycol, 130 parts of propylene glycol methyl ether, 22 parts of deionized water, 1 part of boron trifluoride and 2 parts of GSK-550;
secondly, adding epoxy resin into a beaker filled with propylene glycol monomethyl ether, heating in a water bath at 60 ℃ and stirring at a constant speed until a transparent solution is formed, then adding an emulsifier and polyethylene glycol, and continuing stirring for 30 min;
and thirdly, adding boron trifluoride and modified graphene, cooling to 30 ℃, uniformly stirring for 10min, heating to 85 ℃, reacting for 2h at the temperature, cooling to 60 ℃, dropwise adding deionized water, controlling the dropwise adding time to be 1h, uniformly stirring, reacting for 30min, adding GSK-550, and uniformly mixing to obtain the graphene-based waterborne epoxy resin emulsion.
The rest is the same as example 1.
Example 3
A preparation method of a graphene-based waterborne epoxy resin emulsion comprises the following steps:
firstly, weighing the following raw materials in parts by weight: 14 parts of modified graphene, 4 parts of an emulsifier, 45 parts of epoxy resin, 8 parts of polyethylene glycol, 140 parts of propylene glycol methyl ether, 28 parts of deionized water, 2 parts of boron trifluoride and 2 parts of GSK-550;
secondly, adding epoxy resin into a beaker filled with propylene glycol monomethyl ether, heating in a water bath at 60 ℃ and stirring at a constant speed until a transparent solution is formed, then adding an emulsifier and polyethylene glycol, and continuing stirring for 30 min;
and thirdly, adding boron trifluoride and modified graphene, cooling to 30 ℃, uniformly stirring for 10min, heating to 85 ℃, reacting for 2h at the temperature, cooling to 60 ℃, dropwise adding deionized water, controlling the dropwise adding time to be 1h, uniformly stirring, reacting for 30min, adding GSK-550, and uniformly mixing to obtain the graphene-based waterborne epoxy resin emulsion.
The rest is the same as example 1.
Example 4
A preparation method of a graphene-based waterborne epoxy resin emulsion comprises the following steps:
firstly, weighing the following raw materials in parts by weight: 15 parts of modified graphene, 5 parts of an emulsifier, 50 parts of epoxy resin, 10 parts of polyethylene glycol, 150 parts of propylene glycol methyl ether, 30 parts of deionized water, 2 parts of boron trifluoride and 3 parts of GSK-550;
secondly, adding epoxy resin into a beaker filled with propylene glycol monomethyl ether, heating in a water bath at 60 ℃ and stirring at a constant speed until a transparent solution is formed, then adding an emulsifier and polyethylene glycol, and continuing stirring for 30 min;
and thirdly, adding boron trifluoride and modified graphene, cooling to 30 ℃, uniformly stirring for 10min, heating to 85 ℃, reacting for 2h at the temperature, cooling to 60 ℃, dropwise adding deionized water, controlling the dropwise adding time to be 1h, uniformly stirring, reacting for 30min, adding GSK-550, and uniformly mixing to obtain the graphene-based waterborne epoxy resin emulsion.
The rest is the same as example 1.
Comparative example 1
Compared with example 1, the preparation method of the comparative example is as follows:
a preparation method of a graphene-based waterborne epoxy resin emulsion comprises the following steps:
firstly, weighing the following raw materials in parts by weight: 10 parts of graphene, 3 parts of an emulsifier, 35 parts of epoxy resin, 5 parts of polyethylene glycol, 120 parts of propylene glycol methyl ether, 20 parts of deionized water, 1 part of boron trifluoride and 1 part of GSK-550;
secondly, adding epoxy resin into a beaker filled with propylene glycol monomethyl ether, heating in a water bath at 60 ℃ and stirring at a constant speed until a transparent solution is formed, then adding an emulsifier and polyethylene glycol, and continuing stirring for 30 min;
and thirdly, adding boron trifluoride and graphene, cooling to 30 ℃, uniformly stirring for 10min, then heating to 85 ℃, reacting for 2h at the temperature, then cooling to 60 ℃, dropwise adding deionized water, controlling the dropwise adding time to be 1h, uniformly stirring, reacting for 30min, then adding GSK-550, and uniformly mixing to obtain the graphene-based waterborne epoxy resin emulsion.
The rest is the same as example 1.
Comparative example 2
This comparative example was prepared as follows, using K-5014 in place of the emulsifier, compared to example 1:
a preparation method of a graphene-based waterborne epoxy resin emulsion comprises the following steps:
firstly, weighing the following raw materials in parts by weight: 10 parts of modified graphene, 3 parts of K-5014, 35 parts of epoxy resin, 5 parts of polyethylene glycol, 120 parts of propylene glycol methyl ether, 20 parts of deionized water, 1 part of boron trifluoride and 1 part of GSK-550;
secondly, adding epoxy resin into a beaker filled with propylene glycol monomethyl ether, heating in water bath at 60 ℃ and stirring at constant speed until a transparent solution is formed, then adding K-5014 and polyethylene glycol, and continuing stirring for 30 min;
and thirdly, adding boron trifluoride and modified graphene, cooling to 30 ℃, uniformly stirring for 10min, heating to 85 ℃, reacting for 2h at the temperature, cooling to 60 ℃, dropwise adding deionized water, controlling the dropwise adding time to be 1h, uniformly stirring, reacting for 30min, adding GSK-550, and uniformly mixing to obtain the graphene-based waterborne epoxy resin emulsion.
The rest is the same as example 1.
Comparative example 3
This comparative example is a water-borne epoxy resin emulsion in the market.
The average particle diameter, the centrifugal stability and the storage stability of examples 1 to 4 and comparative examples 1 to 3 were measured, and the results are shown in the following table;
as can be seen from the above table, the average particle diameters in examples 1 to 4 were 440-450(nm), and they were not delaminated and not broken in the centrifugal stability test and in the storage stability test for 6 months; comparative examples 1-3, which had an average particle diameter of 650-750(nm), showed delamination in the centrifugal stability test and delamination in the storage stability test for 6 months; therefore, in the prior art, the particle size of the emulsion cannot be controlled in the preparation process of the epoxy resin emulsion, the stability of the emulsion is poor due to uneven particle size distribution, so that propylene glycol methyl ether is used as a solvent and n-butyl alcohol is used as a cosolvent in the preparation process of the emulsifier to dissolve the epoxy resin, polyethylene glycol diglycidyl ether is added in the step S2, the polyethylene glycol diglycidyl ether contains a large number of ether bonds and can form hydrogen bonds with water, the hydrophilic performance of the prepared emulsifier can be improved, and the ether bonds have flexibility, so that the flexibility of the epoxy resin can be improved, ethanolamine and glacial acetic acid are added, the glacial acetic acid can neutralize the system, the amine hydrogen and the epoxy group of the ethanolamine are subjected to ring opening to become tertiary amine, the tertiary amine can promote the epoxy group to be subjected to ring opening crosslinking, the gelation is caused in the reaction process of the system, and the glacial acetic acid can be added to perform neutralization reaction with the, prevent from gelling.
In the description herein, references to the description of "one embodiment," "an example," "a specific example" or the like are intended to mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The foregoing is illustrative and explanatory only and is not intended to be exhaustive or to limit the invention to the precise embodiments described, and various modifications, additions, and substitutions may be made by those skilled in the art without departing from the scope of the invention or exceeding the scope of the claims.
Claims (6)
1. A preparation method of a graphene-based waterborne epoxy resin emulsion is characterized by comprising the following steps:
firstly, weighing the following raw materials in parts by weight: 10-15 parts of modified graphene, 3-5 parts of an emulsifier, 35-50 parts of epoxy resin, 5-10 parts of polyethylene glycol, 120-150 parts of propylene glycol methyl ether, 20-30 parts of deionized water, 1-2 parts of boron trifluoride and 1-3 parts of a flatting agent;
secondly, adding epoxy resin into a beaker filled with propylene glycol monomethyl ether, heating in water bath at 60-65 ℃ and stirring at constant speed until a transparent solution is formed, then adding an emulsifier and polyethylene glycol, and continuing stirring for 30 min;
and thirdly, adding boron trifluoride and modified graphene, cooling to 30-35 ℃, uniformly stirring for 10min, heating to 85 ℃, reacting for 2h at the temperature, cooling to 60 ℃, dropwise adding deionized water, controlling the dropwise adding time to be 1h, uniformly stirring, reacting for 30min, adding a leveling agent, and uniformly mixing to obtain the graphene-based waterborne epoxy resin emulsion.
2. The method for preparing the graphene-based aqueous epoxy resin emulsion according to claim 1, wherein the leveling agent is one or both of BD-3307 and GSK-550.
3. The preparation method of the graphene-based aqueous epoxy resin emulsion according to claim 1, wherein the modified graphene is prepared from the following raw materials in parts by weight: 10-15 parts of graphene, 5-8 parts of sodium nitrate, 100-containing 150 parts of 98% concentrated sulfuric acid, 1-2 parts of potassium chlorate, 20-30 parts of 10% aqueous hydrogen peroxide, 180-containing 200 parts of maleic anhydride, 15-20 parts of 1-hydroxybenzotriazole, 100-containing 150 parts of dimethylformamide and 3-10 parts of dicyclohexylcarbon.
4. The preparation method of the graphene-based aqueous epoxy resin emulsion according to claim 3, wherein the modified graphene is prepared by the following method:
(1) grinding graphene, adding the ground graphene into a beaker, adding sodium nitrate and 98% concentrated sulfuric acid, stirring in an ice bath for 15min, then adding potassium chlorate, heating in a water bath at 45 ℃, reacting for 2-3h at the temperature, adding deionized water, heating to 75 ℃, reacting for 30min, adding 10% aqueous hydrogen peroxide, and continuing to react for 5-8min to obtain a graphene oxide solution;
(2) adding maleic anhydride into deionized water, heating to melt, transferring into a graphene oxide solution, stirring at a rotating speed of 120r/min for 3 hours, adding distilled water, heating to 65-70 ℃, stirring and reacting at the temperature for 10 hours, condensing, refluxing and drying to obtain treated graphene oxide;
(3) adding the treated graphene oxide and 1-hydroxybenzotriazole into dimethylformamide for uniform dispersion, then adding dicyclohexyl carbon, introducing nitrogen, heating in an oil bath at 80-85 ℃, reacting for 40-45h at the temperature, filtering, washing with absolute ethyl alcohol for three times, and drying at 50-60 ℃ for 8-10h to obtain the modified graphene.
5. The preparation method of the graphene-based aqueous epoxy resin emulsion according to claim 1, wherein the emulsifier is prepared by the following method:
step S1, adding epoxy resin and propylene glycol monomethyl ether into a three-neck flask, heating in a water bath at 45-50 ℃, magnetically stirring at a rotating speed of 140-;
step S2, adding polyethylene glycol diglycidyl ether into the mixed solution A prepared in the step S1, uniformly mixing, then dropwise adding ethanolamine, controlling the dropwise adding speed to be 0.5-1mL/min, continuously stirring for 30imn after the dropwise adding is finished, then heating to 75-80 ℃, reacting for 3-3.5h at the temperature, cooling to 55-60 ℃ after the reaction is finished, adding glacial acetic acid, and reducing pressure and distilling to prepare the emulsifier.
6. The method for preparing the graphene-based waterborne epoxy resin emulsion according to claim 5, wherein the weight ratio of the mixed solution A, the polyethylene glycol diglycidyl ether, the ethanolamine and the glacial acetic acid is controlled to be 100: 2: 3: 2-3 in the step S2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010680485.9A CN111808300A (en) | 2020-07-15 | 2020-07-15 | Preparation method of graphene-based waterborne epoxy resin emulsion |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010680485.9A CN111808300A (en) | 2020-07-15 | 2020-07-15 | Preparation method of graphene-based waterborne epoxy resin emulsion |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111808300A true CN111808300A (en) | 2020-10-23 |
Family
ID=72866286
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010680485.9A Withdrawn CN111808300A (en) | 2020-07-15 | 2020-07-15 | Preparation method of graphene-based waterborne epoxy resin emulsion |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111808300A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112724601A (en) * | 2020-12-25 | 2021-04-30 | 北京化工大学 | Carbon fiber reinforced composite material with high interface strength and strong interface conductivity and preparation method thereof |
| CN112920660A (en) * | 2021-01-26 | 2021-06-08 | 刘小平 | Nano-material modified heat-insulation interior wall coating and preparation method thereof |
| CN113527985A (en) * | 2021-06-17 | 2021-10-22 | 广东绿树环保涂料科技有限公司 | Heavy-duty anticorrosive coating environment-friendly water-based industrial coating and preparation method thereof |
| CN113683938A (en) * | 2021-08-23 | 2021-11-23 | 亚士创能科技(上海)股份有限公司 | Epoxy graphene intermediate and preparation method and application thereof |
| CN115386214A (en) * | 2022-10-09 | 2022-11-25 | 万华化学（宁波）有限公司 | Weather-proof halogen-free flame-retardant polycarbonate alloy material and preparation method thereof |
| CN116535930A (en) * | 2023-03-07 | 2023-08-04 | 中海油常州涂料化工研究院有限公司 | High-crosslinking-density water-based epoxy anticorrosive paint and preparation method thereof |
-
2020
- 2020-07-15 CN CN202010680485.9A patent/CN111808300A/en not_active Withdrawn
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112724601A (en) * | 2020-12-25 | 2021-04-30 | 北京化工大学 | Carbon fiber reinforced composite material with high interface strength and strong interface conductivity and preparation method thereof |
| CN112724601B (en) * | 2020-12-25 | 2022-06-21 | 北京化工大学 | Carbon fiber reinforced composite material with high interface strength and strong interface conductivity and preparation method thereof |
| CN112920660A (en) * | 2021-01-26 | 2021-06-08 | 刘小平 | Nano-material modified heat-insulation interior wall coating and preparation method thereof |
| CN113527985A (en) * | 2021-06-17 | 2021-10-22 | 广东绿树环保涂料科技有限公司 | Heavy-duty anticorrosive coating environment-friendly water-based industrial coating and preparation method thereof |
| CN113683938A (en) * | 2021-08-23 | 2021-11-23 | 亚士创能科技(上海)股份有限公司 | Epoxy graphene intermediate and preparation method and application thereof |
| CN115386214A (en) * | 2022-10-09 | 2022-11-25 | 万华化学（宁波）有限公司 | Weather-proof halogen-free flame-retardant polycarbonate alloy material and preparation method thereof |
| CN115386214B (en) * | 2022-10-09 | 2023-10-17 | 万华化学（宁波）有限公司 | Weather-resistant halogen-free flame-retardant polycarbonate alloy material and preparation method thereof |
| CN116535930A (en) * | 2023-03-07 | 2023-08-04 | 中海油常州涂料化工研究院有限公司 | High-crosslinking-density water-based epoxy anticorrosive paint and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111808300A (en) | Preparation method of graphene-based waterborne epoxy resin emulsion | |
| CN101250374B (en) | Nano hollow silica dioxide micro-sphere/polyurethane composite aqueous paint and preparation method thereof | |
| CN113292902B (en) | Modified graphene oxide anticorrosive paint and preparation method thereof | |
| CN111117426A (en) | High-corrosion-resistance flash-rust-resistant waterborne epoxy primer and preparation method thereof | |
| CN108929616B (en) | Metal substrate graphene modified long-acting anticorrosive paint and preparation method thereof | |
| CN108587441A (en) | A kind of watersoluble plumbago alkene acroleic acid polyurethane coating and preparation method thereof | |
| CN108329793B (en) | Graphene modified anti-rust pigment anti-corrosion primer and preparation method thereof | |
| CN101880508A (en) | Preparation method of high abrasion water-borne wood coating | |
| CN115044279B (en) | Two-dimensional polydopamine reinforced waterborne epoxy composite anticorrosive paint and preparation method and application thereof | |
| CN113371696A (en) | Surface-modified oversized graphene for efficient corrosion prevention and preparation and application thereof | |
| CN111849296A (en) | Low-carbon environment-friendly anticorrosive paint and preparation method thereof | |
| WO2012035865A1 (en) | Method for producing latent curing agent | |
| CN112029408A (en) | Environment-friendly waterproof coating and preparation method thereof | |
| CN112280246A (en) | Graphene modified epoxy resin material and preparation method thereof | |
| CN109439195B (en) | Wear-resistant coating for new energy automobile and preparation method thereof | |
| CN114574062B (en) | Preparation method of emulsion for water-based paint | |
| CN108822702A (en) | A kind of super thick-slurry type quick drying paint and preparation method thereof for vehicle arrangement | |
| CN104177656A (en) | Light-resistant light calcium carbonate filler and preparation method thereof | |
| CN109096821A (en) | A kind of ageing-resistant additive of building inorganic coating graphene and preparation method | |
| CN110746648A (en) | Preparation method of modified white carbon black for nylon 6 | |
| CN112266671A (en) | High-hardness high-gloss environment-friendly coating for metal surface and preparation process thereof | |
| CN109021640B (en) | Preparation method of automobile coating | |
| CN113480912A (en) | High-performance curing agent, preparation method thereof and application of curing agent in epoxy anticorrosive paint | |
| CN113105790B (en) | Graphene/polystyrene reinforced waterborne epoxy resin composite coating and preparation method thereof | |
| CN113416452B (en) | Heat-conducting and heat-dissipating water-soluble fluoride coating and preparation method thereof |
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 | ||
| WW01 | Invention patent application withdrawn after publication |
Application publication date: 20201023 |
|
| WW01 | Invention patent application withdrawn after publication |