CN108570273B - Solvent-free graphene oxide-glass flake anticorrosive paint and preparation method thereof - Google Patents

Solvent-free graphene oxide-glass flake anticorrosive paint and preparation method thereof Download PDF

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CN108570273B
CN108570273B CN201810352787.6A CN201810352787A CN108570273B CN 108570273 B CN108570273 B CN 108570273B CN 201810352787 A CN201810352787 A CN 201810352787A CN 108570273 B CN108570273 B CN 108570273B
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graphene oxide
glass flakes
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glass
stirring
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CN108570273A (en
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杨敏辉
崔国鹏
卞庆娅
刘政超
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Jiangsu Jinhua heavy anticorrosive coating Co.,Ltd.
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Shanghai Zhenhua Heavy Industry Changzhou Coatings Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08—Anti-corrosive paints
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/70—Additives characterised by shape, e.g. fibres, flakes or microspheres
    • 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
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2237—Oxides; Hydroxides of metals of titanium
    • C08K2003/2241—Titanium dioxide
    • 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
    • C08K3/32—Phosphorus-containing compounds
    • C08K2003/321—Phosphates
    • C08K2003/327—Aluminium phosphate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend

Abstract

The invention discloses a solvent-free graphene oxide-glass flake anticorrosive paint which comprises a component A and a component B, wherein the component A comprises graphene oxide modified glass flakes, epoxy resin, waterborne polyurethane resin, castor oil, an active diluent, aluminum tripolyphosphate, talcum powder, a defoaming agent and titanium dioxide; the component B is an epoxy curing agent H633, and when the epoxy curing agent is used, the component A and the component B are uniformly mixed according to the mass ratio of 1: 0.2-0.25. According to the invention, the graphene oxide is used for modifying the glass flakes, so that on one hand, graphene oxide sheet layers are uniformly spread on the surfaces of the glass flakes and filled in pores at the connecting parts between the glass flakes in a spread state, the shielding capability of the glass flakes is improved, and on the other hand, low-temperature curing is realized and the adhesive force of the glass flakes in a coating is enhanced. The solvent-free graphene oxide-glass flake anticorrosive coating disclosed by the invention has the advantages of strong adhesive force, impact resistance and better salt resistance.

Description

Solvent-free graphene oxide-glass flake anticorrosive paint and preparation method thereof
Technical Field
The invention belongs to the field of anticorrosive coatings, and particularly relates to a solvent-free graphene oxide-glass flake anticorrosive coating and a preparation method thereof.
Background
The corrosion coating is a coating which can protect a protected object for a long time in a corrosive environment. The anticorrosive paint is thick paste paint comprising anticorrosive resin as main filming matter, flaky glass flakes as aggregate and various additives. The glass flake anticorrosive paint is widely used in anticorrosive engineering of system equipment and buildings in metallurgy, chemical industry, petroleum, ocean and the like, and as the glass flakes in the paint have a fish scale effect, thousands of flakes are staggered to form a complex and tortuous permeation and diffusion path in a coating, so that the diffusion path of corrosive media becomes quite tortuous and is difficult to reach a base material, the diffusion path of the corrosive media in a coating film is greatly prolonged, and the corrosion of the corrosive media to the base material is effectively delayed.
The glass flake coating is widely regarded and applied due to excellent permeability, good corrosion resistance and long service life, but the use amount of the glass flakes greatly affects the shielding performance of a coating, and the multi-layer shielding effect cannot be formed when the use amount is small, so that the medium permeation resistance is affected; when the amount is large, the amount of the resin is relatively reduced, so that the adhesion and mechanical strength of the coating are reduced.
Chinese patent document (application No. 201610312743.1) discloses a solvent-free epoxy glass flake paint, which specifically discloses: the method is characterized in that calixarene molecules are grafted to the glass flakes by utilizing water-based isocyanate to modify the glass flakes, and the modified glass flakes form certain entanglement with epoxy resin molecular structures through the grafted calixarene molecules in the stirring process, so that the bonding force of the glass flakes and the epoxy resin is improved, the using amount of the glass flakes in the coating is increased, and better coating bonding force and mechanical strength are ensured. However, the document has the following technical drawbacks: when the later repair of the coating is carried out, the damaged coating needs to be polished firstly, but the glass flakes are hard and have higher polishing difficulty, and the difficulty of the later repair polishing is undoubtedly increased by introducing more glass flakes; the shielding efficiency of the glass flake is affected to some extent.
Disclosure of Invention
In order to solve the technical problems, the invention provides the graphene oxide-doped modified glass scale anticorrosive coating, which is characterized in that the graphene oxide coating of the glass scales is modified to enhance the bonding strength between the glass scales and the coating, in addition, the graphene oxide and the glass scales can generate a synergistic effect to enhance the shielding capability and the long-term anticorrosive capability of the coating, reduce the doping amount of the glass scales to a certain extent, and facilitate the later-stage repair and polishing.
The technical scheme adopted by the invention for solving the technical problems is as follows: a solvent-free graphene oxide-glass flake anticorrosive paint comprises a component A and a component B, wherein the component A comprises graphene oxide modified glass flakes, epoxy resin, aqueous polyurethane resin, castor oil, an active diluent, aluminum tripolyphosphate, talcum powder, an antifoaming agent and titanium dioxide; the component B is an epoxy curing agent H633, and when the epoxy curing agent is used, the component A and the component B are uniformly mixed according to the mass ratio of 1: 0.2-0.25.
Further, the graphene oxide modified glass flake comprises, by weight, 10-15 parts of graphene oxide modified glass flake, 30-40 parts of epoxy resin, 8-15 parts of waterborne polyurethane resin, 0.5-1 part of castor oil, 5-10 parts of reactive diluent, 12-25 parts of aluminum tripolyphosphate, 12-20 parts of titanium dioxide and 0.2-0.5 part of defoaming agent.
Further, the preparation method of the graphene oxide modified glass flake comprises the following steps:
(1) immersing the cleaned and dried glass flakes into a Piranha solution, and stirring for 30min at the temperature of 90 ℃; then washing the glass flakes to be neutral by using distilled water, and drying the glass flakes to obtain hydroxyl surface-modified glass flakes;
(2) placing the hydroxyl surface modified glass flakes prepared in the step (1) into a toluene solution of an aminosilane coupling agent, sealing and stirring for 30min, taking out and drying to prepare amino surface modified glass flakes;
(3) and (3) immersing the glass flake modified by the amino surface prepared in the step (2) into an N, N-dimethylamide dispersion liquid of graphene oxide, stirring and reacting for 12-24 h at the temperature of 60-80 ℃, and filtering, washing and vacuum drying in sequence after the reaction is finished to prepare the graphene oxide modified glass flake.
Furthermore, the method for cleaning and drying the glass flakes in the step (1) comprises the following steps: sequentially placing the glass flakes into acetone, ethanol and distilled water, ultrasonically cleaning for five minutes, taking out and drying; the preparation method of the Piranha solution comprises the following steps: 98 percent of concentrated sulfuric acid and 30 percent of hydrogen peroxide are uniformly mixed according to the volume ratio of 7: 3.
Furthermore, the general formula of the aminosilane coupling agent in the step (2) is NH2(CH2) nSiX3, wherein n is any integer of 1-3, and X is any one of methoxy or ethoxy; the volume content of the aminosilane coupling agent in the toluene solution of the aminosilane coupling agent is 2-8%.
Furthermore, the mass ratio of the graphene oxide in the N, N-dimethylamide dispersion liquid of the graphene oxide in the step (3) to the glass flakes after cleaning and drying in the step (1) is 0.01-0.05: 1.
Further, the preparation process of the component A comprises the following steps:
① 100-300 r/min, adding epoxy resin, reactive diluent, waterborne polyurethane resin and castor oil into a clean stirring kettle, and stirring to mix uniformly to obtain premix a;
②, adding aluminum tripolyphosphate, a defoaming agent, talcum powder and titanium dioxide into the premix a in sequence at the rotating speed of 200-400 rpm, dispersing for 30-60 min at the rotating speed of 800-1300 rpm, controlling the temperature not to exceed 40 ℃ in the stirring process, adding graphene oxide modified glass flakes into the mixture, and stirring until the mixture is uniformly dispersed.
The invention has the technical effects that: 1) firstly, the surface of the glass flake is aminated, so that the glass flake is more favorable for polymerization with oxygen-containing functional groups on the surface of graphene oxide, the adhesive force of the graphene oxide on the surface of the glass flake and among the glass flakes is reinforced through chemical bonds, and the complete spreading of the graphene oxide on the glass flakes is effectively ensured; 2) the reaction activity of amino on the surface of the glass flake and graphene oxide is high, so that the adhesion rate of the graphene oxide on the surface of the glass flake can be effectively improved; 3) the graphene oxide lamellar structure is uniformly spread on the surface of the glass scale and is filled in the pores at the connecting part between the glass scale and the glass scale in a spread state, so that the shielding capacity of the glass scale is effectively improved, and the longer and more effective corrosion resistance is favorably realized; 4) the surface group of the graphene oxide is easy to form a hydrogen bond on the coating, and the bonding force between the glass flake and the coating is enhanced through the action of the hydrogen bond; 5) the castor oil and the waterborne polyurethane are added to be combined with the oxygen-containing functional group on the surface of the graphene oxide through hydrogen bonds to form a relatively durable and stable adhesive force which is not influenced by factors such as temperature, hydrolysis and the like, so that the anticorrosive coating is promoted to have relatively good low-temperature resistance and hydrolysis resistance; 5) the method is beneficial to reducing the using amount of the glass flakes so as to be convenient for later-stage repairing and polishing, and the reduction of the using amount of the glass flakes can also effectively reduce the construction thickness and improve the construction efficiency.
Detailed Description
The invention is described in more detail below with reference to the following examples:
the raw materials used in the examples of the present invention are shown in table 1:
TABLE 1
Name of raw materials Manufacturer of the product
Epoxy resin All-grass of Jiangsu Sanmu
Aqueous polyurethane resin Guangdong Yue beautification industries, Ltd
Reactive diluent Wuxi commercial product Hua chemical Co Ltd
Castor oil Basf-Fr
Aluminium triphosphate Nocheng fine powder industry Co Ltd
Talcum powder Jiangxi Shengtai chemical Co., Ltd
Defoaming agent Shandong Youso chemical technology Co Ltd
Titanium white powder Chuzhou Gerui mining Limited liability Co Ltd
Glass flakes Five-sun anticorrosive material plant in Wen' an county of Hebei province
Graphene oxide Hexigen element of Heizhou
Epoxy curing agent H633 Heizhou Hanke chemical technology Co Ltd
Example 1:
a preparation method of a solvent-free graphene oxide-glass flake anticorrosive paint comprises the following steps of: 15 parts of graphene oxide modified glass flakes, 30 parts of epoxy resin, 8 parts of waterborne polyurethane resin, 0.5 part of castor oil, 5 parts of reactive diluent, 25 parts of aluminum tripolyphosphate, 20 parts of titanium dioxide and 0.2 part of defoaming agent.
The preparation method of the graphene oxide modified glass flake in the component A comprises the following steps:
(1) mixing 98% concentrated sulfuric acid and 30% hydrogen peroxide uniformly according to the volume ratio of 7:3 to prepare a Piranha solution; then, the glass flakes are sequentially placed in acetone, ethanol and distilled water for ultrasonic cleaning for five minutes, and taken out and dried; then immersing the cleaned and dried glass flakes into Piranha solution, and stirring for 30min at the temperature of 90 ℃; washing the glass flakes with distilled water to be neutral and drying the washed glass flakes to obtain hydroxyl surface-modified glass flakes;
(2) immersing the hydroxyl surface modified glass flake prepared in the step (1) into NH2CH2Si(OCH3)3Is hermetically stirred for 30min and then taken out for drying to prepare the glass flake with the amino surface modified, wherein NH is2CH2Si(OCH3)3NH in toluene solution2CH2Si(OCH3)3The volume content of (A) is 2%;
(3) and (3) immersing the glass flake modified by the amino surface prepared in the step (2) into an N, N-dimethylamide dispersion liquid of graphene oxide, stirring and reacting for 12 hours at the temperature of 75-80 ℃, and after the reaction is finished, sequentially filtering, washing and vacuum drying to prepare the graphene oxide modified glass flake.
In the method, the mass ratio of the graphene oxide in the N, N-dimethylamide dispersion liquid of the graphene oxide to the glass flakes washed and dried in the step (1) is 0.01: 1.
The preparation method of the component A comprises the following steps:
① 300 rpm, adding epoxy resin, waterborne polyurethane resin, castor oil and reactive diluent into a clean stirring kettle, and uniformly stirring to obtain premix a;
②, adding aluminum tripolyphosphate, a defoaming agent, talcum powder and titanium dioxide into the premix a in sequence at the rotating speed of 400 r/min, dispersing for 30min at the rotating speed of 1300 r/min, controlling the temperature to be 35-40 ℃ in the stirring process, adding the graphene oxide modified glass flakes, and stirring until the glass flakes are uniformly dispersed.
When in use, the component A and the component B are uniformly mixed according to the mass ratio of 1: 0.2.
Example 2
A preparation method of a solvent-free graphene oxide-glass flake anticorrosive paint comprises the following steps of: the graphene oxide modified glass flake comprises, by weight, 18 parts of graphene oxide modified glass flakes, 40 parts of epoxy resin, 15 parts of waterborne polyurethane resin, 1 part of castor oil, 10 parts of reactive diluent, 12 parts of aluminum tripolyphosphate, 12 parts of titanium dioxide and 0.5 part of an antifoaming agent.
The preparation method of the graphene oxide modified glass flake in the component A comprises the following steps:
(1) mixing 98% concentrated sulfuric acid and 30% hydrogen peroxide uniformly according to the volume ratio of 7:3 to prepare a Piranha solution; then, the glass flakes are sequentially placed in acetone, ethanol and distilled water for ultrasonic cleaning for five minutes, and taken out and dried; then immersing the cleaned and dried glass flakes into Piranha solution, and stirring for 30min at the temperature of 90 ℃; washing the glass flakes with distilled water to be neutral and drying the washed glass flakes to obtain hydroxyl surface-modified glass flakes;
(2) soaking the prepared hydroxyl surface modified glass flake into NH2CH2CH2Si(OCH2CH3)3Sealing and stirring the mixture in a toluene solution for 30min, taking out the mixture and drying the mixture to prepare glass flakes with amino surface modified, wherein NH is contained in the glass flakes2CH2CH2Si(OCH2CH3)3NH in toluene solution2CH2CH2Si(OCH2CH3)3The volume content of (A) is 8%;
(3) and (3) immersing the glass flake modified by the amino surface prepared in the step (2) into an N, N-dimethylamide dispersion liquid of graphene oxide, stirring and reacting for 24 hours at the temperature of 65-70 ℃, and after the reaction is finished, sequentially filtering, washing and vacuum drying to prepare the graphene oxide modified glass flake.
In the method, the mass ratio of the graphene oxide in the N, N-dimethylamide dispersion liquid of the graphene oxide to the glass flakes washed and dried in the step (1) is 0.05: 1.
The preparation method of the component A comprises the following steps:
① 200 rpm, adding epoxy resin, waterborne polyurethane resin, castor oil and reactive diluent into a clean stirring kettle, and uniformly stirring to prepare premix a;
②, adding aluminum tripolyphosphate, a defoaming agent, talcum powder and titanium dioxide into the premix a in sequence at the rotating speed of 300 r/min, dispersing for 60min at the rotating speed of 1000 r/min, controlling the temperature to be 25-30 ℃ in the stirring process, adding the graphene oxide modified glass flakes, and stirring until the glass flakes are uniformly dispersed.
When in use, the component A and the component B are uniformly mixed according to the mass ratio of 1: 0.25.
Example 3
A preparation method of a solvent-free graphene oxide-glass flake anticorrosive paint comprises the following steps of: 25 parts of graphene oxide modified glass flakes, 35 parts of epoxy resin, 13 parts of waterborne polyurethane resin, 0.8 part of castor oil, 8 parts of active diluent, 20 parts of aluminum tripolyphosphate, 15 parts of titanium dioxide and 0.4 part of defoaming agent.
The preparation method of the graphene oxide modified glass flake in the component A comprises the following steps:
(1) mixing 98% concentrated sulfuric acid and 30% hydrogen peroxide uniformly according to the volume ratio of 7:3 to prepare a Piranha solution; then, the glass flakes are sequentially placed in acetone, ethanol and distilled water for ultrasonic cleaning for five minutes, and taken out and dried; then immersing the cleaned and dried glass flakes into Piranha solution, and stirring for 30min at the temperature of 90 ℃; washing the glass flakes with distilled water to be neutral and drying the washed glass flakes to obtain hydroxyl surface-modified glass flakes;
(2) soaking the prepared hydroxyl surface modified glass flake into NH2CH2CH2CH2Si(OCH2CH3)3Is hermetically stirred for 30min and then taken out for drying to prepare the glass flake with the amino surface modified, wherein NH is2CH2CH2CH2Si(OCH2CH3)3NH in toluene solution2CH2CH2CH2Si(OCH2CH3)3The volume content of (A) is 8%;
(3) and (3) immersing the glass flake modified by the amino surface prepared in the step (2) into an N, N-dimethylamide dispersion liquid of graphene oxide, stirring and reacting for 18 hours at the temperature of 60-65 ℃, and after the reaction is finished, sequentially filtering, washing and vacuum drying to prepare the graphene oxide modified glass flake.
In the method, the mass ratio of the graphene oxide in the N, N-dimethylamide dispersion liquid of the graphene oxide to the glass flakes washed and dried in the step (1) is 0.035: 1.
The preparation method of the component A comprises the following steps:
① 100 r/min, adding epoxy resin, waterborne polyurethane resin, castor oil and reactive diluent into a clean stirring kettle, and uniformly stirring to obtain premix a;
②, adding aluminum tripolyphosphate, a defoaming agent, talcum powder and titanium dioxide into the premix a in sequence at the rotating speed of 200 r/min, dispersing for 40min at the rotating speed of 800 r/min, controlling the temperature to be 20-25 ℃ in the stirring process, adding the graphene oxide modified glass flakes, and stirring until the glass flakes are uniformly dispersed.
When in use, the component A and the component B are uniformly mixed according to the mass ratio of 1: 0.23.
Example 4
A preparation method of a solvent-free graphene oxide-glass flake anticorrosive paint comprises the following steps of: the graphene oxide modified glass flake comprises, by weight, 30 parts of graphene oxide modified glass flake, 30 parts of epoxy resin, 10 parts of waterborne polyurethane resin, 0.6 part of castor oil, 10 parts of active diluent, 25 parts of aluminum tripolyphosphate, 20 parts of titanium dioxide and 0.5 part of defoaming agent.
The preparation method of the graphene oxide modified glass flake in the component A comprises the following steps:
(1) mixing 98% concentrated sulfuric acid and 30% hydrogen peroxide uniformly according to the volume ratio of 7:3 to prepare a Piranha solution; then, the glass flakes are sequentially placed in acetone, ethanol and distilled water for ultrasonic cleaning for five minutes, and taken out and dried; then immersing the cleaned and dried glass flakes into Piranha solution, and stirring for 30min at the temperature of 90 ℃; washing the glass flakes with distilled water to be neutral and drying the washed glass flakes to obtain hydroxyl surface-modified glass flakes;
(2) soaking the prepared hydroxyl surface modified glass flake into NH2CH2CH2CH2Si(OCH2CH3)3Is hermetically stirred for 30min and then taken out for drying to prepare the glass flake with the amino surface modified, wherein NH is2CH2CH2CH2Si(OCH2CH3)3NH in toluene solution2CH2CH2CH2Si(OCH2CH3)3The volume content of (A) is 6%;
(3) immersing the amino surface modified glass flakes prepared in the step (2) into an N, N-dimethylamide dispersion liquid of graphene oxide, and stirring and reacting for 18 hours at the temperature of 60-65 ℃; and after the reaction is finished, sequentially filtering, washing and vacuum drying to obtain the graphene oxide modified glass flakes.
In the method, the mass ratio of the graphene oxide in the N, N-dimethylamide dispersion liquid of the graphene oxide to the glass flakes washed and dried in the step (1) is 0.035: 1.
The preparation method of the component A comprises the following steps:
① 100 r/min, adding epoxy resin, waterborne polyurethane resin, castor oil and reactive diluent into a clean stirring kettle, and uniformly stirring to obtain premix a;
②, adding aluminum tripolyphosphate, a defoaming agent, talcum powder and titanium dioxide into the premix a in sequence at the rotating speed of 200 r/min, dispersing for 40min at the rotating speed of 800 r/min, controlling the temperature to be 20-25 ℃ in the stirring process, adding the graphene oxide modified glass flakes, and stirring until the glass flakes are uniformly dispersed.
When in use, the component A and the component B are uniformly mixed according to the mass ratio of 1: 0.23.
Comparative example 1
A preparation method of a solvent-free glass flake anticorrosive paint comprises the following steps of preparing a component A by mass: the weight parts of the glass flake are 30 parts, the weight part of the epoxy resin is 30 parts, the weight part of the reactive diluent is 10 parts, the weight part of the aluminum tripolyphosphate is 25 parts, the weight part of the titanium dioxide is 20 parts, and the weight part of the defoaming agent is 0.5 part.
The preparation method of the component A comprises the following steps:
① 100 r/min, adding epoxy resin and reactive diluent into a clean stirring kettle, and uniformly stirring to obtain premix a;
② adding aluminum tripolyphosphate, defoamer, talcum powder and titanium dioxide powder into the premix a in sequence at the rotating speed of 200 r/min, dispersing for 40min at the rotating speed of 800 r/min, controlling the temperature to be 20-25 ℃ in the stirring process, adding glass flakes, and stirring until the glass flakes are uniformly dispersed.
When in use, the component A and the component B are uniformly mixed according to the mass ratio of 1: 0.23.
Comparative example 2
A preparation method of a solvent-free graphene oxide-glass flake anticorrosive paint comprises the following steps of: the graphene oxide modified glass flake comprises, by weight, 30 parts of graphene oxide modified glass flake, 30 parts of epoxy resin, 10 parts of active diluent, 25 parts of aluminum tripolyphosphate, 20 parts of titanium dioxide and 0.5 part of defoaming agent.
The preparation method of the graphene oxide modified glass flake in the component A comprises the following steps:
(1) mixing 98% concentrated sulfuric acid and 30% hydrogen peroxide uniformly according to the volume ratio of 7:3 to prepare a Piranha solution; then, the glass flakes are sequentially placed in acetone, ethanol and distilled water for ultrasonic cleaning for five minutes, and taken out and dried; then immersing the cleaned and dried glass flakes into Piranha solution, and stirring for 30min at the temperature of 90 ℃; washing the glass flakes with distilled water to be neutral and drying the washed glass flakes to obtain hydroxyl surface-modified glass flakes;
(2) soaking the prepared hydroxyl surface modified glass flake into NH2CH2CH2CH2Si(OCH2CH3)3Is hermetically stirred for 30min and then taken out for drying to prepare the glass flake with the amino surface modified, wherein NH is2CH2CH2CH2Si(OCH2CH3)3NH in toluene solution2CH2CH2CH2Si(OCH2CH3)3The volume content of (A) is 6%;
(3) immersing the amino surface modified glass flakes prepared in the step (2) into an N, N-dimethylamide dispersion liquid of graphene oxide, and stirring and reacting for 18 hours at the temperature of 60-65 ℃; and after the reaction is finished, sequentially filtering, washing and vacuum drying to obtain the graphene oxide modified glass flakes.
In the method, the mass ratio of the graphene oxide in the N, N-dimethylamide dispersion liquid of the graphene oxide to the glass flakes washed and dried in the step (1) is 0.035: 1.
The preparation method of the component A comprises the following steps:
① 100 r/min, adding epoxy resin and reactive diluent into a clean stirring kettle, and uniformly stirring to obtain premix a;
②, adding aluminum tripolyphosphate, a defoaming agent, talcum powder and titanium dioxide into the premix a in sequence at the rotating speed of 200 r/min, dispersing for 40min at the rotating speed of 800 r/min, controlling the temperature to be 20-25 ℃ in the stirring process, adding the graphene oxide modified glass flakes, and stirring until the glass flakes are uniformly dispersed.
When in use, the component A and the component B are uniformly mixed according to the mass ratio of 1: 0.23.
The results of the product testing of the above examples are shown in table 2:
TABLE 2
Figure BDA0001633819010000111
As can be seen from Table 2, the solvent-free anticorrosive coating for the graphene oxide-glass flakes, the aqueous polyurethane resin and castor oil provided by the invention has better performances than common glass flake anticorrosive coatings, strong adhesion, impact resistance and better salt resistance.

Claims (5)

1. A solvent-free graphene oxide-glass flake anticorrosive paint is characterized in that: the coating comprises a component A and a component B, wherein the component A comprises graphene oxide modified glass flakes, epoxy resin, waterborne polyurethane resin, castor oil, an active diluent, aluminum tripolyphosphate, talcum powder, a defoaming agent and titanium dioxide; the component B is an epoxy curing agent H633, and when the epoxy curing agent is used, the component A and the component B are uniformly mixed according to the mass ratio of 1: 0.2-0.25;
the graphene oxide modified glass flake is prepared by the following steps:
(1) immersing the cleaned and dried glass flakes into a Piranha solution, and stirring for 30min at the temperature of 90 ℃; then washing the glass flakes to be neutral by using distilled water, and drying the glass flakes to obtain hydroxyl surface-modified glass flakes;
(2) immersing the hydroxyl surface modified glass flakes prepared in the step (1) into a toluene solution of an aminosilane coupling agent, sealing and stirring for 30min, taking out and drying to prepare amino surface modified glass flakes;
(3) immersing the amino surface modified glass flakes prepared in the step (2) into an N, N-dimethylamide dispersion liquid of graphene oxide, stirring and reacting for 12-24 h at the temperature of 60-80 ℃, and after the reaction is finished, sequentially filtering, washing and vacuum drying to prepare graphene oxide modified glass flakes;
the component A comprises 15-30 parts by weight of graphene oxide modified glass flakes, 30-40 parts by weight of epoxy resin, 8-15 parts by weight of water-based polyurethane resin, 0.5-1 part by weight of castor oil, 5-10 parts by weight of active diluent, 12-25 parts by weight of aluminum tripolyphosphate, 12-20 parts by weight of titanium dioxide and 0.2-0.5 part by weight of defoaming agent.
2. The solvent-free graphene oxide-glass flake anticorrosive paint according to claim 1, wherein the method for cleaning and drying the glass flakes in the step (1) comprises the following steps: sequentially placing the glass flakes into acetone, ethanol and distilled water, ultrasonically cleaning for five minutes, taking out and drying; the preparation method of the Piranha solution comprises the following steps: 98 percent of concentrated sulfuric acid and 30 percent of hydrogen peroxide are uniformly mixed according to the volume ratio of 7: 3.
3. According to claim 1The solvent-free graphene oxide-glass flake anticorrosive paint is characterized in that the general formula of the aminosilane coupling agent in the step (2) is NH2(CH2)nSiX3Wherein n is any integer of 1-3, and X is any one of methoxyl or ethoxyl; the volume content of the aminosilane coupling agent in the toluene solution of the aminosilane coupling agent is 2-8%.
4. The solvent-free graphene oxide-glass flake anticorrosive paint according to claim 1, wherein the mass ratio of the graphene oxide in the N, N-dimethylamide dispersion liquid of the graphene oxide in the step (3) to the glass flakes after cleaning and drying in the step (1) is 0.01-0.05: 1.
5. The solvent-free graphene oxide-glass flake anticorrosive paint according to claim 1, wherein the component A is prepared by the following steps:
① 100-300 r/min, adding epoxy resin, reactive diluent, waterborne polyurethane resin and castor oil into a clean stirring kettle, and stirring to mix uniformly to obtain premix a;
②, sequentially adding aluminum tripolyphosphate, a defoaming agent, talcum powder and titanium dioxide into the premix a at the rotating speed of 200-400 rpm, dispersing for 30-60 min at the rotating speed of 800-1300 rpm, controlling the temperature not to exceed 40 ℃ in the stirring process, adding the graphene oxide modified glass flakes, and stirring until the glass flakes are uniformly dispersed.
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