NL2032198B1 - Modified graphene oxide, waterborne anticorrosive paint and preparation method thereof - Google Patents

Modified graphene oxide, waterborne anticorrosive paint and preparation method thereof Download PDF

Info

Publication number
NL2032198B1
NL2032198B1 NL2032198A NL2032198A NL2032198B1 NL 2032198 B1 NL2032198 B1 NL 2032198B1 NL 2032198 A NL2032198 A NL 2032198A NL 2032198 A NL2032198 A NL 2032198A NL 2032198 B1 NL2032198 B1 NL 2032198B1
Authority
NL
Netherlands
Prior art keywords
parts
graphene oxide
agent
waterborne
modified graphene
Prior art date
Application number
NL2032198A
Other languages
Dutch (nl)
Inventor
Liu Shaojie
Tang Erjun
Hu Na
Sun Wenhui
Li Jing
Guo Xiaofeng
Yuan Miao
Chu Xiaomeng
Xing Xuteng
Pan Xiaodong
Original Assignee
Hebei Univ Of Science & Technology
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Hebei Univ Of Science & Technology filed Critical Hebei Univ Of Science & Technology
Application granted granted Critical
Publication of NL2032198B1 publication Critical patent/NL2032198B1/en

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/44—Carbon
    • C09C1/46—Graphite
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/182—Graphene
    • C01B32/198—Graphene oxide
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/006—Combinations of treatments provided for in groups C09C3/04 - C09C3/12
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/08—Treatment with low-molecular-weight non-polymer organic compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/10—Treatment with macromolecular organic 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
    • 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
    • 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
    • C09D5/082—Anti-corrosive paints characterised by the anti-corrosive pigment
    • C09D5/084—Inorganic 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
    • C09D7/20—Diluents or solvents
    • 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
    • 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
    • C08K9/00—Use of pretreated ingredients
    • C08K9/08—Ingredients agglomerated by treatment with a binding agent

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Inorganic Chemistry (AREA)
  • Nanotechnology (AREA)
  • Paints Or Removers (AREA)

Abstract

The present invention relates to the technical field of paint, and specifically relates to a deified graphene oxide, a waterborne anticorrosive paint and a preparation method thereof. The modified graphene oxide includes the following parts by mass of components: O.l—O.4 parts of graphene oxide, 0.1—0.2 parts of dopamine hydrochloride, 0.3—0.6 parts of tris(hydroxymethyl)methyl aminomethane (Tris) buffer agent, 0.05—0.2 parts of silane coupling agent, 0.1—0.25 parts of zinc nitrate, 0.1—0.3 parts of pH adjusting agent and 50—150 parts of deionized water. The present invention improves the agglomeration of graphene oxide to enhance the dispersity by grafting polydopamine on graphene oxide. The modified, graphene oxide is used, for the preparation. of a waterborne anticorrosive paint. When a crack appears on a coating, zinc ions are released from the modified graphene oxide to form a layer of oxidation film on the crack to achieve self—repairing, thus reducing the permeation of corrosive electrolyte. (+ Fig.)

Description

MODIFIED GRAPHENE OXIDE, WATERBORNE ANTICORROSIVE PAINT AND
PREPARATION METHOD THEREOF
TECHNICAL FIELD
The present invention relates to the technical field of paint, and in particular to a modified graphene oxide, a water- borne anticorrosive paint and a preparation method thereof.
BACKGROUND ART
With the rapid development of society, science and technolo- gy, there is an increasing demand for the paint with protective and decorative functions. Moreover, with the increasingly strengthened environmental awareness, a green and environmental- protection waterborne paint with an ultralow VOC content has be- come a development direction in the paint industry. The waterborne epoxy paint has been more and more concerned due to its advantages such as, low toxicity, low volatile organic compounds, excellent adhesive force and chemical resistance. However, there are still disadvantages to the waterborne epoxy paints, such as poor dura- bility, prone to cracking, damage and failure of a painting due to the external force and aging action, and insufficient anticorro- sion effect.
Graphene, as a kind of typical 2D material, has higher elec- trical conductivity, good heat stability, impermeability and ex- cellent barrier property, good physical shielding property and chemical stability in coatings and thus, can be used for the prep- aration of a composite waterborne epoxy coating. However, due to a high diameter-thickness ratio, high Van der Waals' force (VDW) be- tween sheet layers and n-mn bond interaction between aromatic rings, graphene is prone to agglomeration and thus, is hardly dis- persed into water or organic solvents uniformly, which will affect the exertion of the action of graphene in coatings. Currently, graphene is modified mainly by in-situ polymerization, but the preparation process is complex and not easy to achieve industrial- ization. Moreover, after graphene is modified by a modifying agent, the dispersity and binding force to a substrate interface can be improved, but the corrosion resistance of the coating will decrease obviously, and corrosion of the coating will be acceler- ated in case of crack; and there is no self-repairing function.
SUMMARY
In view of this, the present invention provides a modified graphene oxide, a waterborne anticorrosive paint and a preparation method thereof. The graphene oxide is modified by polydopamine and silane coupling agent to improve the agglomeration of graphene ox- ide, enhance the dispersity of graphene oxide and compatibility thereof in a waterborne epoxy resin and improve the corrosion re- sistance of the waterborne anticorrosive paint.
To achieve the above objectives of the present invention, the following technical solutions are adopted in the examples of the present invention.
A first aspect of the present application provides a modified graphene oxide, including the following parts by mass of compo- nents: 0.1-0.4 parts of graphene oxide, 0.1-0.2 parts of dopamine hydrochloride, 0.3-0.6 parts of tris (hydroxymethyl)methyl amino- methane (Tris) buffer agent, 0.05-0.2 parts of silane coupling agent, 0.1-0.25 parts of zinc nitrate, 0.1-0.3 parts of pH adjust- ing agent and 50-150 parts of deionized water; the silane coupling agent is 3-aminopropyl triethoxysilane (KH550).
Relative to the prior art, the modified graphene oxide pro- vided by the present application has the following advantages.
The present application improves the agglomeration of gra- phene oxide and enhances the dispersity of graphene oxide, thus improving the compatibility thereof in a waterborne epoxy resin and improving the corrosion resistance of the waterborne anticor- rosive paint by grafting polydopamine on graphene oxide.
The epoxy group, carboxy group and hydroxy group on the sur- face of graphene oxide provide grafting sites for the modification of graphene oxide; dopamine performs intramolecular cyclization in a Tris buffer agent to form polydopamine containing a biphenol structure; two hydroxyl groups in polydopamine are subjected to a covalent reaction with silicon oxygen bonds in the silane coupling agent, thus forming a protecting net in a form of covalent bonds on the surface of graphene oxide. Zinc ions in zinc nitrate pro- vide positive charges and interact with dissociative hydrophilic groups providing negative charges on the interface of graphene ox- ide via hydrogen bonds and n-n to be adhered on the surface of graphene oxide, thus finally forming a neutral polydopamine- modified graphene oxide zinc ion-loaded nanocomposite filler.
The polydopamine-modified graphene oxide zinc ion-loaded nanocomposite filler is added to a waterborne epoxy resin to form a coating. When a crack appears on the coating, zinc ions are re- leased from the nanocomposite filler to form a layer of oxidation film on the crack, which reduces the permeation of corrosive elec- trolyte, completes the self-repairing of the crack, and improves the shortages of easy aging and cracking of the waterborne epoxy resin.
Optionally, the pH adjusting agent is sodium bicarbonate or sodium dihydrogen phosphate.
Optionally, a mass ratio of the dopamine hydrochloride to the graphene oxide is 1:0.9-1.1.
Optionally, a mass ratio of the dopamine hydrochloride to the silane coupling agent is 1:0.4-0.6.
A preferred ratio of each reactant can not only improve the use ratio of raw materials to decrease the occurrence of side re- action and guarantee the formation of a specific protecting net obtained by performing a covalent reaction on polydopamine and the silane coupling agent on the surface of graphene oxide at the same time, but also can avoid the waste of raw materials to further de- crease the production cost.
A second aspect of the present application further provides a method for preparing the above modified graphene oxide, at least including the following steps of:
Sl, dispersing the graphene oxide and the tris (hydroxymethyl)methyl aminomethane (Tris) buffer agent into deionized water, and then adding the dopamine hydrochloride, the silane coupling agent and the pH adjusting agent for reaction for 23-25 h at 55°C-65°C to obtain a first reaction solution; 32, adding zinc nitrate to the first reaction solution for reaction for 1.5-2.5 h at 55°C-65°C to obtain the modified graphene oxide.
In this present application, polydopamine is first grafted on graphene oxide via a silane coupling agent, and then zinc nitrate is added such that zinc ions form modified graphene oxide loaded with zinc ions. The preparation method is simple and process is easy to be controlled. Therefore, the present application is bene- ficial to industrialization promotion and application.
Optionally, in the steps S1 and S2, the reaction has a stir- ring rate of 400-600 rpm.
Optionally, in the S1, the reaction has a pH value of 8.3- 8.7.
Optionally, in the S2, the reaction has a pH value of 7.8- 8.2.
A third aspect of the present application further provides a waterborne anticorrosive paint, including the above modified gra- phene oxide.
After graphene oxide is modified by polydopamine and zinc ni- trate, the agglomeration of graphene oxide is improved obviously to enhance the dispersity of graphene oxide. Therefore, the modi- fied graphene oxide is used for the preparation of a waterborne paint, which greatly improves the corrosion resistance of the wa- terborne anticorrosive paint.
Optionally, the waterborne anticorrosive paint includes the following parts by weight of components: 20-25 parts of waterborne epoxy emulsion, 0.1-0.3 parts of modified graphene oxide, 3-5 parts of curing agent, 0.3-0.6 parts of dispersant, 0.2-0.25 parts of quick-drying agent, 0.3-0.8 parts of antifoaming agent, 0.1-0.3 parts of film-forming auxiliary, 0.3-0.6 parts of thickening agent, and 5-8 parts of deionized water.
The modified graphene oxide provided by the present applica- tion endows the self-repairing function to the waterborne anticor- rosive paint. When a crack appears on a coating, zinc ions are re- leased from the modified graphene oxide to form a layer of oxida- tion film on the crack to achieve self-repairing, thus reducing the permeation of corrosive electrolyte, improving the shortages of easy aging and cracking of the waterborne epoxy resin, and com-
pleting the repairing of the crack.
With water as a solvent, the waterborne anticorrosive paint provided by the present application almost achieves the zero emis- sion of VOCs. The waterborne anticorrosive paint has good corro- 5 sion resistance, simple process, and convenient operation, safe and reliable, green and environmental protection.
Optionally, the waterborne epoxy emulsion is a non-ionic aqueous dispersion of a bisphenol A-type epoxy resin.
Preferably, the bisphenol A epoxy resin contains more hydroxy groups and thus, has stronger polarity, chemical activity and stronger adhesive force and thus, is easy to interact with an ob- ject to be painted.
Optionally, the waterborne epoxy emulsion has an epoxy equiv- alent of 450 g/mol-600 g/mol or 200 g/mol-1100 g/mol.
Preferably, the epoxy resin has a larger crosslinking density after being cured, thus improving the adhesive force of the coat- ing. Moreover, a preferred epoxide equivalent may not only ensure the complete curing reaction, but also avoid too high viscosity of the paint system, affecting the curing reaction rate.
Optionally, the curing agent is at least one of a fatty amine curing agent or modified polyamide curing agent; and the fatty amine curing agent has an amine value of 230-250; the modified polyamide curing agent has an amine value of 140-160.
A preferred amine value may ensure the complete curing reac- tion of epoxy resin, and the paint system is free of dissociative amine.
Optionally, the dispersant is a copolymer aqueous solution containing a pigment-affinity group.
Optionally, the thickening agent is at least one of a modi- fied urea aqueous solution or a polyether polyurethane thickening agent.
Optionally, the film-forming auxiliary is an aliphatic alco- hol ester compound having a boiling point of 170°C-180°C.
Optionally, the quick-drying agent is propylene glycol methyl ether.
Opticnally, the antifoaming agent is at least one of a poly- ethylene glycol-hydrophobic solid-antifoaming polysiloxane mixture or a polyether siloxane copolymer.
The present invention enables the modified graphene oxide to be uniformly dispersed into the epoxy resin by compounding the dispersant, thickening agent, quick-drying agent, antifoaming agent and other auxiliaries. Moreover, the present invention ac- celerates the sufficient curing reaction between the epoxy resin and the curing agent such that the coating has an excellent corro- sion resistance.
A fourth aspect of the present application further provides a method for preparing the above waterborne anticorrosive paint, at least including the following steps of: mixing the waterborne epoxy emulsion, the modified graphene oxide, the dispersant, the quick-drying agent, the antifoaming agent, the film-forming auxiliary, the thickening agent and the deionized water to obtain a first mixture; and mixing the first mixture with the curing agent to obtain the waterborne anticorrosive paint.
The preparation method of the waterborne anticorrosive paint provided by the present application is simple and beneficial to industrialization promotion.
Optionally, the above method for preparing the waterborne an- ticorrosive paint at least includes the following steps of: dispersing the modified graphene oxide into 10 wt®-15 wt% de- ionized water, performing ultrasonic treatment for 8-12 min, then adding the waterborne epoxy emulsion and stirring uniformly to ob- tain a waterborne epoxy emulsion mixture; mixing the dispersant, the film-forming auxiliary and the an- tifoaming agent, then adding to the waterborne epoxy emulsion mix- ture to be stirred uniformly, and adding the quick-drying agent, the thickening agent and the remaining deionized water, and stir- ring uniformly to obtain a first mixture; and mixing the first mixture with the curing agent, and stirring uniformly to obtain the waterborne anticorrosive paint.
BRIEF DESCRIPTION OF THE DRAWINGS
To describe the technical solutions in the examples of the present invention more clearly, the accompanying drawings to be used in the examples will be introduced briefly. Apparently, the accompanying drawings in the following description are merely some examples of the present invention. Moreover, a person skilled in the art can further obtain other accompanying drawings according to these accompanying drawings without any inventive labor.
FIG. 1 is an infrared spectrum provided by Test Example 1 of the present invention;
FIG. 2 is a polarization curve provided by Test Example 2 of the present invention;
FIG. 3 is a diagram showing salt water resistance of a scratch coating provided by Test Example 3 of the present inven- tion.
FIG. 4 is a concentration changing curve of Fe** in a NaCl so- lution provided by Test Example 3 of the present invention.
DETAILED DESCRIPTION OF THE EMBODIMENTS
To make the objectives, technical solutions and advantages of the present invention more clear and apparent, the present inven- tion will be further described in detail with reference to the ex- amples below. It should be understood that detailed examples de- scribed herein are merely used for explaining the present inven- tion, but not construed as limiting the present invention.
Example 1
The example of the present invention provides a modified gra- phene oxide, including the following parts by mass of components: 0.2 parts of graphene oxide, 0.2 parts of dopamine hydrochloride, 0.3 parts of tris (hydroxymethyl)methyl aminomethane (Tris) buffer agent, 0.1 parts of silane coupling agent, 0.2 parts of zinc ni- trate, 0.1 parts of pH adjusting agent and 120 parts of deionized water; the silane coupling agent is 3-aminopropyl triethoxysilane (KH550) .
A method for preparing the above modified graphene oxide in- cludes the following steps:
S31, the graphene oxide and the tris (hydroxymethyl)methyl ami- nomethane (Tris) buffer agent were dispersed into deionized water, and then dopamine hydrochloride was added for ultrasonic disper- sion for 10 min, then the silane coupling agent and the pH adjust-
ing agent were added for reaction for 24 h at a pH value of 8.5, a rotational speed of 500 rpm and 60°C to obtain a first reaction solution;
S2, zinc nitrate was added to the first reaction solution for reaction for 2 h at a pH value of 8, a rotational speed of 500 rpm and 60°C to obtain the modified graphene oxide.
Example 2
The example of the present invention provides a modified gra- phene oxide, including the following parts by mass of components: 0.1 parts of graphene oxide, 0.21 parts of dopamine hydrochloride, 0.6 parts of tristhydroxymethyl)methyl aminomethane (Tris) buffer agent, 0.2 parts of silane coupling agent, 0.1 parts of zinc ni- trate, 0.3 parts of pH adjusting agent and 150 parts of deionized water; the silane coupling agent is 3-aminopropyl triethoxysilane (KH550).
A method for preparing the above modified graphene oxide in- cludes the following steps:
Sl, the graphene oxide and the tris (hydroxymethyl)methyl ami- nomethane (Tris) buffer agent were dispersed into deionized water, and then dopamine hydrochloride was added for ultrasonic disper- sion for 10 min, then the silane coupling agent and the pH adjust- ing agent were added for reaction for 23 h at a pH value of 8.3, a rotational speed of 600 rpm and 65°C to obtain a first reaction solution; 52, zinc nitrate was added to the first reaction solution for reaction for 1.5 h at a pH value of 7.8, a rotational speed of 600 rpm and 65°C to obtain the modified graphene oxide.
Example 3
The example of the present invention provides a modified gra- phene oxide, including the following parts by mass of components: 0.4 parts of graphene oxide, 0.15 parts of dopamine hydrochloride, 0.5 parts of tris (hydroxymethyl)methyl aminomethane (Tris) buffer agent, 0.15 parts of silane coupling agent, 0.25 parts of zinc ni- trate, 0.1 parts of pH adjusting agent and 50 parts of deionized water; the silane coupling agent is 3-aminopropyl triethoxysilane (KH550) .
A method for preparing the above modified graphene oxide in- cludes the following steps:
Sl, the graphene oxide and the tris (hydroxymethyl)methyl ami- nomethane (Tris) buffer agent were dispersed into deionized water, and then dopamine hydrochloride was added for ultrasonic disper- sion for 10 min, then the silane coupling agent and the pH adjust- ing agent were added for reaction for 25 h at a pH value of 8.7, a rotational speed of 4600 rpm and 55°C to obtain a first reaction solution;
S2, zinc nitrate was added to the first reaction solution for reaction for 2.5 h at a pH value of 7.8, a rotational speed of 400 rpm and 55°C to obtain the modified graphene oxide.
Example 4
The example of the present invention provides a modified gra- phene oxide, including the following parts by mass of components: 0.3 parts of graphene oxide, 0.1 parts of dopamine hydrochloride, 0.3 parts of tris (hydroxymethyl)methyl aminomethane (Tris) buffer agent, 0.05 parts of silane coupling agent, 0.15 parts of zinc ni- trate, 0.2 parts of pH adjusting agent and 100 parts of deionized water; the silane coupling agent is 3-aminopropyl triethoxysilane (KH550).
A method for preparing the above modified graphene oxide in- cludes the following steps:
S1, the graphene oxide and the tris(hydroxymethyl)methyl ami- nomethane (Tris) buffer agent were dispersed into deionized water, and then dopamine hydrochloride was added for ultrasonic disper- sion for 10 min, then the silane coupling agent and the pH adjust- ing agent were added for reaction for 24 h at a pH value of 8.5, a rotational speed of 550 rpm and 60°C to obtain a first reaction solution;
S2, zinc nitrate was added to the first reaction solution for reaction for 2 h at a pH value of 8, a rotational speed of 550 rpm and 60°C to obtain the modified graphene oxide.
Example 5
The example of the present invention provides a waterborne anticorrosive paint, including the following parts by weight of components: 20 parts of waterborne epoxy emulsion, 0.3 parts of modified graphene oxide, 3 parts of curing agent, 0.5 parts of dispersant, 0.2 parts of quick-drying agent, 0.4 parts of anti- foaming agent, 0.2 parts of film-forming auxiliary, 0.4 parts of thickening agent, and 8 parts of deionized water.
The above modified graphene oxide was the modified graphene oxide prepared in Example 1; the above waterborne epoxy emulsion had an epoxy equivalent of 550 g/mol-600 g/mol; the above antifoaming agent was a polyether siloxane copoly- mer; the above thickening agent was a modified urea aqueous solu- tion; the above curing agent was a fatty amine curing agent having an amine value of 240.
The method for preparing the above waterborne anticorrosive paint includes the following steps: the modified graphene oxide was dispersed into 10 wt$% deion- ized water and subjected to ultrasonic treatment for 10 min, then the waterborne epoxy emulsion was added and stirred uniformly to obtain a waterborne epoxy emulsion mixture; the dispersant, the film-forming auxiliary and the antifoam- ing agent were mixed and then added to the waterborne epoxy emul- sion mixture to be stirred uniformly, and the quick-drying agent, the thickening agent and the deionized water were added and stirred uniformly to obtain a first mixture; the first mixture was mixed with the curing agent, and stirred uniformly to obtain the waterborne anticorrosive paint.
Example 6
The example of the present invention provides a waterborne anticorrosive paint, including the following parts by weight of components: 25 parts of waterborne epoxy emulsion, 0.1 parts of modified graphene oxide, 5 parts of curing agent, 0.3 parts of dispersant, 0.25 parts of quick-drying agent, 0.8 parts of anti- foaming agent, 0.1 parts of film-forming auxiliary, 0.5 parts of thickening agent, and 5 parts of deionized water.
The above modified graphene oxide was the modified graphene oxide prepared in Example 1; the above waterborne epoxy emulsion had an epoxy equivalent of 450 g/mol-550 g/mol; the above antifoaming agent was a polyethylene glycol- hydrophobic solid-antifoaming polysiloxane mixture; the above thickening agent was a polyether polyurethane thickening agent; the above curing agent was a modified polyamide curing agent having an amine value of 150.
The method for preparing the above waterborne anticorrosive paint was the same as that in Example 5 and thus, not described any more.
Example 7
The example of the present invention provides a waterborne anticorrosive paint, including the following parts by weight of components: 22 parts of waterborne epoxy emulsion, 0.2 parts of modified graphene oxide, 4 parts of curing agent, 0.6 parts of dispersant, 0.23 parts of quick-drying agent, 0.3 parts of anti- foaming agent, 0.2 parts of film-forming auxiliary, 0.6 parts of thickening agent, and 7 parts of deionized water.
The above modified graphene oxide was the modified graphene oxide prepared in Example 1; the above waterborne epoxy emulsion had an epoxy equivalent of 900 g/mol-1100 g/mol; the above antifoaming agent was a polyethylene glycol- hydrophobic solid-antifoaming polysiloxane mixture; the above thickening agent was a modified urea aqueous solu- tion; the above curing agent was a modified polyamide curing agent having an amine value of 150.
The method for preparing the above waterborne anticorrosive paint was the same as that in Example 5 and thus, not described any more.
Example 8
The example of the present invention provides a waterborne anticorrosive paint, including the following parts by weight of components: 23 parts of waterborne epoxy emulsion, 0.15 parts of modified graphene oxide, 4 parts of curing agent, 0.4 parts of dispersant, 0.24 parts of quick-drying agent, 0.6 parts of anti- foaming agent, 0.2 parts of film-forming auxiliary, 0.3 parts of thickening agent, and 6 parts of deionized water.
The above modified graphene oxide was the modified graphene oxide prepared in Example 1; the above waterborne epoxy emulsion had an epoxy equivalent of 900 g/mol-1100 g/mol; the above antifoaming agent was a polyethylene glycol- hydrophobic solid-antifoaming polysiloxane mixture; the above thickening agent was a polyether polyurethane thickening agent; the above curing agent was a fatty amine curing agent having an amine value of 250.
The method for preparing the above waterborne anticorrosive paint was the same as that in Example 5 and thus, not described any more.
To describe the technical solutions of the present invention better, comparative examples and examples of the present invention will be subjected to further comparison below.
Comparative Example 1
This Comparative Example provides a modified graphene oxide, including the following parts by mass of components: 0.2 parts of graphene oxide, 0.2 parts of dopamine hydrochloride, 0.3 parts of tris (hydroxymethyl)methyl aminomethane (Tris) buffer agent, 0.1 parts of silane coupling agent KH550, 0.1 parts of pH adjusting agent and 120 parts of deionized water.
A method for preparing the above modified graphene oxide in- cludes the following steps: the graphene oxide and the tris (hydroxymethyl)methyl amino- methane (Tris) buffer agent were dispersed into deionized water, and then dopamine hydrochloride was added for ultrasonic disper- sion for 10 min, then the silane coupling agent and the pH adjust- ing agent were added for reaction for 24 h at a pH value of 8.5, a rotational speed of 500 rpm and 60°C to obtain the modified gra- phene oxide.
The Comparative Example provides a waterborne anticorrosive paint, including the following parts by weight of components: 20 parts of waterborne epoxy emulsion, 0.3 parts of modified graphene oxide prepared in Comparative Example 1, 3 parts of curing agent, 0.5 parts of dispersant, 0.2 parts of quick-drying agent, 0.4 parts of antifoaming agent, 0.2 parts of film-forming auxiliary, 0.4 parts of thickening agent, 0.2 parts of zinc nitrate and 8 parts of deionized water.
The above waterborne epoxy resin, curing agent, antifoaming agent and the thickening agent were chosen the same as those in
Example 5 and thus, not described any mere.
The method for preparing the above waterborne anticorrosive paint includes the following steps: the modified graphene oxide was dispersed into 10 wt% deion- ized water and subjected to ultrasonic treatment for 10 min, then the waterborne epoxy emulsion was added and stirred uniformly to obtain a waterborne epoxy emulsion mixture; the dispersant, the film-forming auxiliary, the antifoaming agent and the zinc nitrate were mixed and then added to the water- borne epoxy emulsion mixture to be stirred uniformly, and the quick-drying agent, the thickening agent and the deionized water were added and stirred uniformly to obtain a first mixture; the first mixture was mixed with the curing agent, and stirred uniformly to obtain the waterborne anticorrosive paint.
Comparative Example 2
This Comparative Example provides a modified graphene oxide, including the following parts by mass of components: 0.2 parts of graphene oxide, 0.2 parts of dopamine hydrochloride, 0.3 parts of tris (hydroxymethyl)methyl aminomethane (Tris) buffer agent, 0.1 parts of silane coupling agent, 0.2 parts of zinc nitrate, 0.1 parts of pH adjusting agent and 120 parts of deionized water.
The above silane coupling agent was y-(2,;3-epoxypropoxy) propyltrimethoxy silane (KH560).
The method for preparing the above modified graphene oxide was the same as that in Example 1 and thus, not described any more.
The Comparative Example further provides a waterborne anti- corrosive paint, including the following parts by weight of compo-
nents: 20 parts of waterborne epoxy emulsion, 0.3 parts of modi- fied graphene oxide prepared in Comparative Example 2, 3 parts of curing agent, 0.5 parts of dispersant, 0.2 parts of quick-drying agent, 0.4 parts of antifoaming agent, 0.2 parts of film-forming auxiliary, 0.4 parts of thickening agent, and 8 parts of deionized water.
The above waterborne epoxy resin, curing agent, antifoaming agent and the thickening agent were chosen the same as those in
Example 5 and thus, not described any more.
The method for preparing the above waterborne anticorrosive paint was the same as that in Example 5 and thus, not described any more.
Comparative Example 3
The Comparative Example provides a waterborne anticorrosive paint, including the following parts by weight of components: 20 parts of waterborne epoxy emulsion, 0.3 parts of modified graphene oxide, 3 parts of curing agent, 0.5 parts of dispersant, 0.2 parts of quick-drying agent, 0.4 parts of antifoaming agent, 0.2 parts of film-forming auxiliary, 0.4 parts of thickening agent, 0.2 parts of zinc nitrate and 8 parts of deionized water.
The above waterborne epoxy resin, curing agent, antifoaming agent and the thickening agent were chosen the same as those in
Example 5 and thus, not described any more.
The method for preparing the above waterborne anticorrosive paint was the same as that in Comparative Example 1 and thus, not described any more.
Test Example 1
The modified graphene oxides and graphene oxides prepared in
Example 1 of the prevent invention and Comparative Example 1 were subjected to infrared spectroscopic analysis. Results are shown in
FIG. 1.
It can be seen from FIG. 1 that graphene oxide has broad and strong -OH stretching vibration peaks nearby 3456 cm’, -C=0 stretching vibration peaks on carboxyl at 1723 cm, C-0H bending vibration absorption peaks at 1624 cm‘, and C-0-C vibration ab- sorption peaks at 1040 cm™, thus providing reactive sites for the modification of graphene oxide.
It can be seen from FIG. 1 that the modified graphene oxide prepared in Comparative Example 1 shows new peaks, respectively symmetric stretching vibration peak of methylene at 2984 cmt and asymmetric stretching vibration peak of methylene at 2908 cm’; Si-
O-C and Si-0-Si have stronger stretching vibration peaks at 1113 cmt and 1058 cm; there are less smaller stretching vibration ab- sorption peaks formed by free -OH at 3684 cm. The hydroxy group shows no extensive stretching vibration peaks, indicating that the hydroxy group on the surface of graphene oxide participates in the reaction. There are -C=N and -C=C bonds at 1416 cm’ and 1575 cm* to prove the formation of aromatic amine; there are out-of-plane bending vibration peaks of -N-H at 924 cm to indicate that amino in amino silane (KH550) interacts with -OH on the surface of gra- phene oxide to graft polydopamine on the surface of graphene ox- ide.
It can be seen from FIG. 1 that the modified graphene oxide prepared in Example 1 hardly has new peaks relative to the infra- red spectrum of Comparative Example 1, thus indicating that zinc ions are loaded on graphene oxide via chemical absorption of the -
NH; group.
Test Example 2
The waterborne anticorrosive paints prepared in Examples 5-8 and Comparative Examples 1-3 were sprayed on a pretreated Q235 iron plate with a spray gun, and the thickness of film was con- trolled within 100 pm-120 pm, then the Q235 with the film was put to a drying oven for drying for 1 h at 80°C, and cured for 3 d at an ambient temperature (25°C) simultaneously.
The waterborne anticorrosive coatings prepared in Examples 5- 8 and Comparative Examples 1-3 were placed into a NaCl solution having a concentration of 3.5 wt% to respectively test the polari- zation curves. The coatings were subjected to corrosion resistance evaluation. Polarization resistances and corrosion rates were ob- tained by a method for fitting cathode and anode slopes based on
Tafal. The polarization curves are shown in FIG. 2; polarization resistances and corrosion rates are shown in Table 1.
Table 1 Polarization resistance and corrosion rate
Polarization re- ‚ Corrosion fate
Ecorr{V) fcorr(Afem™) sistance Rp (kQ . CR(mm/year) cm”)
Example 5 -0.374 1.15E-08 16346.41 0.007
Example 6 -0.481 2.29E-07 628.22 0.134
Example 7 -0.502 2.39E-07 956.74
Example 8 -0.449 7.94E-08 5332 0.042
Comparative 0.595 2.80E-06 420.75 0.252
Example 1
Comparative 0.771 4.90E-06 43.08 3.062
Example 2
Comparative -0.665 5.25E-06 40.19 3.281
Example 3
It can be seen from FIG. 2 and Table 1 that the waterborne anticorrosive coatings prepared in Examples 5-8 of the present in- vention have excellent corrosion resistance, and the corrosion rate is up to 0.007 mm/year. The modified graphene oxide not load- ed zinc ions and separate zinc nitrate were added in Comparative
Example 1, but the corrosion rate was 0.252 mm/year. The above re- sult indicates that the capacity of the corrosion resistance of zinc ions in the coating is necessarily related to the structural state thereof existing in the paint; zinc ions are loaded on gra- phene oxide via hydrogen bonds and large n bonds, which is more beneficial to improving the corrosion resistance of the coating.
The corrosion rate of Comparative Example 2 was 3.062 mm/year.
Therefore, the result indicates that the selection of the silane coupling agent is also one of the key points to the preparation of modified graphene oxide; the silane coupling agent KH550 contains hydrophilic groups -NH; on the tail end. The hydrophilic groups not only graft polydopamine on the surface of graphene oxide, but also render zinc ions loaded thereon via the chemical adsorption of the group -NH,, thereby greatly improving the dispersity of graphene oxide and the corrosion resistance of the composite waterborne epoxy paint. The corrosion rate of Comparative Example 3 was 3.281 mm/year. Therefore, the result indicates even though zinc nitrate is added to the waterborne anticorrosive paint, the bonding force between the coating and the iron plate is weak due to easy agglom- eration of the non-modified graphene oxide; and the anticorrosion effect is unsatisfactory.
Test Example 3
To test the self-repairing and anticorrosion effects of the waterborne anticorrosive paint, scratches were made on Q235 test pieces sprayed with the coatings of Examples 5-8 and Comparative
Examples 1-3, then the test pieces were soaked into 150 mL Nacl solution having a concentration of 3.5 wt% for 15 d, and the vol- ume of the solution was always kept 150 mL. Results of the salt water resistance of the scratch coatings in the 3.5 wt? NaCl solu- tion are shown in FIG. 3. Fe’ concentrations in the NaCl solution were respectively tested. The results are shown in FIG. 4.
It can be seen from FIG. 3 that the waterborne anticorrosive paint prepared in this present application has excellent salt wa- ter resistance and anticorrosion effect. Therefore, the results indicate that the modified graphene forms a layer of protective film on the crack of the coating of the waterborne anticorrosive paint to reduce the corrosion rate.
It can be seen from FIG. 4 that after the waterborne anticor- rosive coatings prepared in Examples 5-8 and Comparative Examples 1-3 are soaked into the NaCl solution for 15 d, the concentrations of Fe’ in the NaCl solution are respectively 1.45 mg/L*, 2.08 mg/L, 2.21 mg/L, 1.73 mg/L, 6.12 mg/L, 6.94 mg/L" and 7.71 mg/L}. Therefore, the above results indicate that for the zinc ions loaded by modified graphene oxide, when the composite water- borne epoxy coating encounters cracks, the zinc ions absorbed in the nanccomposite filler of the coating will be released to form a layer of oxidation film with oxygen in the air or -OH in the cor- rosive electrolyte in the crack, which may reduce the further cor- rosion of the coatings, and has self-repairing functions and may achieve the long-term corrosion resistance.
Test Example 4
Coatings of the waterborne anticorrosive paints prepared in
Examples 5-8 and Comparative Examples 1-3 were subjected to adhe- sive force testing. The test results are shown in Table 2 below.
The preparation process of the coatings was the same as that in
Test Example 2 and thus, not described any more.
Table 2 Test results of adhesive force
Example 6 2.17
Comparative Example 2 2.06
It can be seen from Table 2 that the waterborne anticorrosive paints prepared by the polydopamine-modified graphene oxide have excellent adhesive force. This is because there are catechol and amine in the structure of polydopamine at the same time; the structure may be adsorbed on a substrate to form a film. Moreover, the adhesive force will be not affected by different epoxide equivalents of epoxy resin and curing agents with different amine values.
What are described above are merely preferred embodiments of the present invention, and are not construed as limiting the pre- sent invention. Any modification, equivalent replacement or im- provement, or the like made within the spirit and principle of the present invention shall fall within the protection scope of the present invention.

Claims (10)

CONCLUSIESCONCLUSIONS 1. Gemodificeerd grafeenoxide, omvattende de volgende massadelen aan componenten: 0,1 tot 0,4 delen grafeenoxide, 0,1 tot 0,2 delen dopaminehydrochloride, 0,3 tot 0,6 delen tris (hydroxymethyl) me- thylaminomethaan (Tris) buffermiddel, 0,05 tot 0,2 delen si- laankoppelingsmiddel, 0,1 tot 0,25 delen zinknitraat, 0,1 tot 0,3 delen pH-aanpassend middel en 50 tot 150 delen gedeioniseerd wa- ter; waarbij het silaankoppelingsmiddel is 3- aminopropyltriethoxysilaan.1. Modified graphene oxide comprising the following parts by mass of components: 0.1 to 0.4 parts graphene oxide, 0.1 to 0.2 parts dopamine hydrochloride, 0.3 to 0.6 parts tris (hydroxymethyl) methylaminomethane (Tris) buffering agent, 0.05 to 0.2 parts silane coupling agent, 0.1 to 0.25 parts zinc nitrate, 0.1 to 0.3 parts pH adjusting agent, and 50 to 150 parts deionized water; wherein the silane coupling agent is 3-aminopropyltriethoxysilane. 2. Gemodificeerd grafeenoxide volgens conclusie 1, waarbij het pH- regelende middel natriumbicarbonaat of natriumdiwaterstoffosfaat is; en/of een massaverhouding van het dopaminehydrochloride tot het grafeenoxide is 1: (0,9 tot 1,1); en/of een massaverhouding van het dopaminehydrochloride tot het si- laankoppelingsmiddel is 1: (0,4 tot 0,6).The modified graphene oxide of claim 1, wherein the pH adjusting agent is sodium bicarbonate or sodium dihydrogen phosphate; and/or a mass ratio of the dopamine hydrochloride to the graphene oxide is 1: (0.9 to 1.1); and/or a mass ratio of the dopamine hydrochloride to the silane coupling agent is 1:(0.4 to 0.6). 3. Werkwijze voor het bereiden van het gemodificeerde grafeenoxide volgens een van de conclusies 1 tot 2: die ten minste de volgende stappen omvat: Sl, het dispergeren van het grafeenoxide en het tris (hydroxyme- thyl) methylaminomethaan (Tris) buffermiddel in gedeioniseerd wa- ter en vervolgens het toevoegen van het dopaminehydrochloride, het silaankoppelingsmiddel en het pH-aanpassende middel voor reactie gedurende 23 tot 25 uur bij 55 °C tot 65 °C om een eerste reactie- oplossing te verkrijgen; S2, het toevoegen van zinknitraat aan de eerste reactieoplossing voor reactie gedurende 1,5 tot 2,5 uur bij 55 °C tot 65 °C om het gemodificeerde grafeenoxide te verkrijgen.A process for preparing the modified graphene oxide according to any one of claims 1 to 2: comprising at least the following steps: S1, dispersing the graphene oxide and the tris (hydroxymethyl) methylaminomethane (Tris) buffering agent in deionized water - ter and then adding the dopamine hydrochloride, the silane coupling agent and the pH adjusting agent for reaction at 55°C to 65°C for 23 to 25 hours to obtain a first reaction solution; S2, adding zinc nitrate to the first reaction solution for reaction at 55°C to 65°C for 1.5 to 2.5 hours to obtain the modified graphene oxide. 4. Werkwijze voor het bereiden van het gemodificeerde grafeenoxide volgens conclusie 3, waarbij in de stappen S1 en S2 de reactie een roersnelheid heeft van 400 tot 600 rpm; en/of in de stap S1 heeft de reactie een pH-waarde van 8,3 tot 8,7;The method for preparing the modified graphene oxide according to claim 3, wherein in steps S1 and S2, the reaction has a stirring speed of 400 to 600 rpm; and/or in step S1 the reaction has a pH value of 8.3 to 8.7; en/of in de stap S2 heeft de reactie een pH-waarde van 7,8 tot 8,2.and/or in step S2, the reaction has a pH value of 7.8 to 8.2. 5. Watergedragen corrosiewerende verf, die het gemodificeerde grafeenoxide volgens een van de conclusies 1 tot 2 omvat.A waterborne anticorrosive paint comprising the modified graphene oxide according to any one of claims 1 to 2. 6. Watergedragen roestwerende verf volgens conclusie 5, omvattende de volgende gewichtsdelen aan componenten: 20 tot 25 delen wa- tergedragen epoxy-emulsie, 0,1 tot 0,3 delen gemodificeerd grafeenoxide, 3 tot 5 delen uithardingsmiddel, 0,3 tot 0,6 delen dispergeermiddel, 0,2 tot 0,25 delen sneldrogend middel, 0,3 tot 0,8 delen antischuimmiddel, 0,1 tot 0,3 delen filmvormende hulp- stof, 0,3 tot 0,6 delen verdikkingsmiddel en 5 tot 8 delen gedeioniseerd water.A waterborne anticorrosion paint according to claim 5, comprising the following parts by weight of components: 20 to 25 parts waterborne epoxy emulsion, 0.1 to 0.3 parts modified graphene oxide, 3 to 5 parts curing agent, 0.3 to 0, 6 parts dispersant, 0.2 to 0.25 parts fast drying agent, 0.3 to 0.8 parts defoamer, 0.1 to 0.3 parts film-forming agent, 0.3 to 0.6 parts thickener and 5 to 8 parts deionized water. 7. Watergedragen corrosiewerende verf volgens conclusie 6, waarbij de watergedragen epoxy-emulsie een niet-ionische waterige dis- persie van een bisfenol A-type epoxyhars is; en/of de watergedragen epoxy-emulsie heeft een epoxy-equivalent van 450 g/mol tot 600 g/mol of 900 g/mol tot 1100 g/mol.The waterborne anticorrosive paint according to claim 6, wherein the waterborne epoxy emulsion is a nonionic aqueous dispersion of a bisphenol A type epoxy resin; and/or the waterborne epoxy emulsion has an epoxy equivalent of 450 g/mol to 600 g/mol or 900 g/mol to 1100 g/mol. 8. Watergedragen corrosiewerende verf volgens conclusie 6, waarbij het uithardingsmiddel ten minste één van een vetamine uitharding- smiddel of een gemodificeerd polyamide-uithardingsmiddel is; en het vetamine uithardingsmiddel heeft een aminewaarde van 230 tot 250; het gemodificeerde polyamide uithardingsmiddel heeft een aminewaarde van 140 tot 160.The waterborne anticorrosive paint according to claim 6, wherein the curing agent is at least one of a fatty amine curing agent or a modified polyamide curing agent; and the fatty amine curing agent has an amine value of 230 to 250; the modified polyamide curing agent has an amine value of 140 to 160. 9. Watergedragen corrosiewerende verf volgens conclusie 6, waarbij het dispergeermiddel een waterige copolymeeroplossing is die een pigment-affiniteitsgroep omvat; en/of het verdikkingsmiddel is ten minste één van een gemodificeerde wa- terige ureumoplossing of een polyetherpolyurethaan verdikkingsmid- del; en/of het filmvormende hulpmiddel is een alifatische alcoholester verbinding met een kookpunt van 170°C tot 180°C; en/of het sneldrogende middel is propyleenglycolmethylether; en/of het antischuimmiddel is ten minste één van een polyethyleenglycol- hydrofobe vaste-antischuimpolysiloxzaan mengsel of een polyeth- ersiloxaancopolymeer.The waterborne anticorrosive paint according to claim 6, wherein the dispersant is an aqueous copolymer solution comprising a pigment affinity group; and/or the thickener is at least one of a modified aqueous urea solution or a polyether polyurethane thickener; and/or the film-forming aid is an aliphatic alcohol ester compound having a boiling point of 170°C to 180°C; and/or the fast-drying agent is propylene glycol methyl ether; and/or the antifoam agent is at least one of a polyethylene glycol hydrophobic solid antifoam polysiloxane blend or a polyether siloxane copolymer. 10. Werkwijze voor het bereiden van de watergedragen corrosiew- erende verf volgens een van de conclusies 5 tot 9, die ten minste de volgende stappen omvat: het mengen van de watergedragen epoxy emulsie, het gemodificeerde grafeenoxide, het dispergeermiddel, het sneldrogende middel, het antischuimmiddel, het filmvormende hulpmiddel, het verdikkingsmid- del en het gedeïoniseerde water om een eerste mengsel te verkrijgen; en het eerste mengsel mengen met het uithardingsmiddel om de wa- tergedragen corrosiewerende verf te verkrijgen.A process for preparing the waterborne anticorrosive paint according to any one of claims 5 to 9, comprising at least the following steps: mixing the waterborne epoxy emulsion, the modified graphene oxide, the dispersant, the quick-drying agent, the anti-foaming agent, the film-forming aid, the thickening agent and the deionized water to obtain a first mixture; and mixing the first mixture with the curing agent to obtain the waterborne anticorrosive paint.
NL2032198A 2021-09-18 2022-06-17 Modified graphene oxide, waterborne anticorrosive paint and preparation method thereof NL2032198B1 (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202111101474.1A CN113755036B (en) 2021-09-18 2021-09-18 Modified graphene oxide, water-based anticorrosive paint and preparation method thereof

Publications (1)

Publication Number Publication Date
NL2032198B1 true NL2032198B1 (en) 2023-03-27

Family

ID=78796443

Family Applications (1)

Application Number Title Priority Date Filing Date
NL2032198A NL2032198B1 (en) 2021-09-18 2022-06-17 Modified graphene oxide, waterborne anticorrosive paint and preparation method thereof

Country Status (2)

Country Link
CN (1) CN113755036B (en)
NL (1) NL2032198B1 (en)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114456711B (en) * 2021-12-15 2023-03-10 浙江亚厦装饰股份有限公司 Chromium-free Dacromet coating liquid and preparation method and application thereof
CN114517046B (en) * 2022-03-01 2023-02-10 天津职业技术师范大学(中国职业培训指导教师进修中心) Water-based epoxy coating based on divalent zinc ion modified graphene oxide and preparation method thereof
CN114857409A (en) * 2022-05-07 2022-08-05 山东非金属材料研究所 Protective coating system for outer wall of high-risk pipeline
CN115029025A (en) * 2022-05-18 2022-09-09 安徽大学 Dual-modified graphene oxide modified waterborne epoxy resin anticorrosive paint
CN115305042B (en) * 2022-08-24 2024-04-09 杭州福斯特功能膜材料有限公司 Black adhesive and aluminum plastic film
CN115353777B (en) * 2022-09-06 2023-10-13 安徽新大陆特种涂料有限责任公司 Preparation method of high-permeability conversion rust-free anti-corrosion primer
CN115557675B (en) * 2022-11-04 2023-11-21 湖北瑞信养生用品科技有限公司 Modified graphite composite ceramic trough for glass production and preparation method thereof

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113292902A (en) * 2021-05-20 2021-08-24 常州大学 Modified graphene oxide anticorrosive paint and preparation method thereof

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102993810A (en) * 2012-11-28 2013-03-27 天长市开林化工有限公司 General water-based quick-drying anti-rust paint and preparation method thereof
CN109082203B (en) * 2018-07-25 2020-06-19 东北石油大学 Scale-inhibiting and corrosion-preventing functional coating and preparation method and use method thereof
CN109385179A (en) * 2018-09-25 2019-02-26 临沂大学 A kind of coating and preparation method thereof containing modified graphene oxide
CN109627904A (en) * 2018-11-07 2019-04-16 西北工业大学 A kind of selfreparing graphene zinc-rich anti-corrosive paint and preparation method thereof
CN110230058B (en) * 2019-05-31 2020-08-14 上海交通大学 Method for constructing medical titanium alloy surface for promoting growth and differentiation of bone marrow mesenchymal stem cells
CN110698616B (en) * 2019-11-01 2022-01-25 河北科技大学 Graphene/acrylic acid composite emulsion, anticorrosive water-based paint and preparation method thereof
CN111607319A (en) * 2020-07-07 2020-09-01 四川大学 Self-repairing waterborne polyurethane/rGO @ PDA composite material and preparation method and application thereof
CN112457698A (en) * 2020-10-29 2021-03-09 广东海洋大学 Graphene-modified zinc powder, preparation method and application of graphene-modified zinc powder in zinc-rich anticorrosive coating
CN112358638A (en) * 2020-11-09 2021-02-12 张小兰 High-strength degradable environment-friendly plastic and preparation method thereof
CN113214738B (en) * 2021-05-13 2022-04-12 青岛理工大学 Polydopamine-modified graphene oxide-modified silane emulsion and preparation method and application thereof

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113292902A (en) * 2021-05-20 2021-08-24 常州大学 Modified graphene oxide anticorrosive paint and preparation method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
HABIBIYAN AYLIN ET AL: "Rational assembly of mussel-inspired polydopamine (PDA)-Zn (II) complex nanospheres on graphene oxide framework tailored for robust self-healing anti-corrosion coatings application", CHEMICAL ENGENEERING JOURNAL, ELSEVIER, AMSTERDAM, NL, vol. 391, 30 November 2019 (2019-11-30), XP086162578, ISSN: 1385-8947, [retrieved on 20191130], DOI: 10.1016/J.CEJ.2019.123630 *

Also Published As

Publication number Publication date
CN113755036B (en) 2022-06-14
CN113755036A (en) 2021-12-07

Similar Documents

Publication Publication Date Title
NL2032198B1 (en) Modified graphene oxide, waterborne anticorrosive paint and preparation method thereof
CN107987680B (en) Water-based epoxy graphene anticorrosive paint
CN107868567B (en) Epoxy zinc powder primer, paint matching composition and application
EP3004419B1 (en) Ambient curable corrosion resistant sol-gel coating and composition and process for making the same
CN104017458A (en) Solvent-free epoxy antirust coating capable of coating with rust and preparation method thereof
CN103122186A (en) Environment-friendly treating fluid for preventing steel rails from corrosion and steel rail corrosion prevention material
CN104530911A (en) Preparation method for high-performance water-based environmentally-friendly anticorrosive paint used for metal base material
CN106336773B (en) It can load-carrying solvent-free epoxy resin floor coatings
CN105219218A (en) A kind of aqueous phenolic aldehyde epoxy anticorrosive paint and preparation method thereof
CN104845499A (en) Preparation method for waterborne epoxy paste paint
CN110698908B (en) Colored water-based paint composition and preparation method thereof
CN114479660A (en) Chromium-free zinc-aluminum-nickel coating composite product and application thereof
CN110845902B (en) Transparent coating composition and preparation method thereof
CN112625532A (en) Efficient anticorrosive water-based acrylic coating and preparation method thereof
CN116769335A (en) Water-based chromium-free zinc-aluminum coating and preparation method thereof
CN111117311A (en) Water-based zinc-aluminum coating containing borate and/or aluminate
CN106010106B (en) A kind of high-rating generator dizzy three proofings coatings of suppression and preparation method thereof
CN111500152B (en) Epoxy anti-corrosion primer, preparation method thereof and product with primer layer
CN114181588A (en) Water-based epoxy zinc-rich primer and preparation method thereof
CN110183932B (en) Water-based epoxy anticorrosive paint containing composite active salt and preparation method thereof
CN113861791B (en) Single-component curing acidic water-based rust conversion coating and preparation and application thereof
KR20090061193A (en) Coating composition for rust proof of metal
CN106433404A (en) Waterborne automobile wheel hub paint
CN105925090A (en) Water-based finishing paint for hub and preparation method thereof
CN115521697A (en) Organic-inorganic hybrid UV thermal dual-curing epoxy cathode electrophoretic coating and preparation method thereof