CN105838195A - Waterborne epoxy anti-corrosion paint containing graphene oxide and preparing method of waterborne epoxy anti-corrosion paint - Google Patents
Waterborne epoxy anti-corrosion paint containing graphene oxide and preparing method of waterborne epoxy anti-corrosion paint Download PDFInfo
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- CN105838195A CN105838195A CN201610319677.0A CN201610319677A CN105838195A CN 105838195 A CN105838195 A CN 105838195A CN 201610319677 A CN201610319677 A CN 201610319677A CN 105838195 A CN105838195 A CN 105838195A
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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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
- C08G59/5046—Amines heterocyclic
- C08G59/5053—Amines heterocyclic containing only nitrogen as a heteroatom
- C08G59/5073—Amines heterocyclic containing only nitrogen as a heteroatom having two nitrogen atoms in the ring
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- 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
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- 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
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/32—Compounds containing nitrogen bound to oxygen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
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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
- 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
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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
- 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
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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
- 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
- C09D7/63—Additives non-macromolecular organic
Abstract
The invention discloses a waterborne epoxy anti-corrosion paint containing graphene oxide. The waterborne epoxy anti-corrosion paint is prepared from, by mass, 40-50% of waterborne epoxy resin, 7-10% of anti-corrosion pigment, 3-4% of a water repellent agent, 1-2% of graphene oxide, 4-5% of filler, 33-35% of deinoized water, 1-1.5% of a flash-rust inhibitor and 1-2% of a waterborne epoxy curing agent. The invention further discloses a preparing method of the waterborne epoxy anti-corrosion paint containing graphene oxide. By means of graphene oxide subjected to surface treatment, the abrasion resistance of the epoxy anti-corrosion paint is improved, the friction coefficient is decreased, and meanwhile the anti-corrosion performance of the waterborne epoxy anti-corrosion paint is improved. The anti-corrosion paint is easy to prepare and wide in raw material source, and production cost is greatly reduced.
Description
Technical field:
The invention belongs to chemical anticorrosion paint field, be specifically related to a kind of water corrosion-resistant epoxy paint containing graphene oxide and
Preparation method.
Background technology:
World today's environmental problem is increasingly severe, and discharging substantial amounts of harmful substance in the processing of coating and production process can cause
Environmental pollution is healthy with infringement workmen's.In order to control to pollute and the health of protection workmen, China formulates one and is
Row measure limits the use of high VOC coating.So environment friendly anti-corrosive paint becomes the emphasis of paint development.Numerous environment friendly coated
In material, water paint is the important directions of development.But currently water paint there is also some technical problems, so improving
The anti-corrosive properties of water paint have become the developing emphasis of environmental protection coating material.
The technical staff being engaged in coating research and development and preparation both knows about, containing epoxide group on epoxy molecule chain, it is possible to open loop shape
Become a kind of three-dimensional netted polymer.Epoxy resin has strong machinery, mechanics, a thermal property, high cohesiveness, excellent
The resin of Corrosion Protection, epoxy coating is a kind of environment-friendly type coating that can substitute high VOC coating.
Water-base epoxy coating is the optimal film forming matter of High Performance Corrosion Protective Coatings, is with emulsion dispersion state yet with water-base epoxy,
Different from solvent in the process of film forming, can be in formation hole, film surface, so that resistance to water reduces.Therefore it is necessary to improve aqueous
The water resistance of epoxy coating.
Graphene only has a carbon atom thickness, has surface area height, excellent in mechanical performance, good chemical stability, if will
Graphene joins and can solve the problems such as water-base epoxy coating coefficient of friction is high, wear rate is big in aqueous epoxy coating well,
The antiseptic power of water-base epoxy coating can also be strengthened.
Graphene oxide is that redox reaction prepares the material of a kind Graphene of gained, graphene oxide during Graphene
The lamellar structure of conjugation can form the diaphragm of densification in the coating, prevents the hydrone infiltration to coating, can stop Fe simultaneously
It is changed into Fe3+, prevent from generating iron rust.Compared with Graphene, graphene oxide has the existence of oxygen-containing functional group, and it causes oxygen
The hydrophobic performance of functionalized graphene is the best, so it must be carried out surface modification.By amino silicane coupling agent to graphite oxide
Alkene carries out surface modification.Amino unique in amino silicane coupling agent can react with oxygen-containing functional group in graphene oxide,
It is grafted in graphene oxide, thus improves hydrophobicity and itself and the affinity of epoxy resin of graphene oxide, reduce and reunite,
Improve its dispersity, improve hydrophobicity.
Based on the above, a kind of water corrosion-resistant epoxy paint containing graphene oxide of the present invention, by using through amino silicone
The graphene oxide that alkane coupling agent is modified, it has preferable affinity and stronger hydrophobicity with epoxy resin, effectively improves water
Property epoxy coating coefficient of friction is high, wear rate is big shortcoming, and make water corrosion-resistant epoxy paint have good temperature tolerance, resistance to
Corrosivity.
Summary of the invention:
The invention aims to solve the problem that prior art exists, it is provided that a kind of water-base epoxy containing graphene oxide
Coating.
The present invention is by selecting the graphene oxide through amino silicane coupling agent modified, and the surface utilizing graphene oxide special contains
Oxygen functional group, is grafted to graphene oxide molecular layer surface so that it is have more preferable parent with epoxy resin by amino silicane coupling agent
And power, graphene oxide itself can form the protective layer of densification, more can be with epoxy resin cross-linking reaction, it is thus achieved that well coating
Density, effective starvation and the entrance of hydrone.And the function of electrochemical anti-corrosive can be played, prevent iron rust from producing.And
And graphene oxide has the distinctive mechanical performance of Graphene, physical property, some defects of water-base epoxy coating can be improved,
While the coating of gained has good antiseptic property, there is good mechanical performance and physical property.
The present invention effectively improves the problem that epoxy coating coefficient of friction is high, easy to wear, meanwhile, more improves epoxy
Cold coating antiseptic property and temperature tolerance.
For reaching above-mentioned target, the technical solution used in the present invention is:
A kind of water corrosion-resistant epoxy paint containing graphene oxide, is 40～50% by aqueous epoxy resins by mass percentage,
Anti-corrosion paint is 7～10%, and water-repelling agent is 3～4%, and graphene oxide is 1～2%, and filler is 4～5%, and deionized water is 33～35%,
Anti-dodge rust agent be 1～1.5%, aqueous epoxy curing agent be 1～2% composition；The molecular structure of wherein said aqueous epoxy curing agent
It is characterized as:
Wherein, R is alkyl, and for 1-4 carbon atom, X is carboxyl or hydroxyl.
Water-repelling agent structural formula described above is:
Anti-corrosion paint described above is phosphate or molybdate, or trbasic zinc phosphate and the mixture of aluminum phosphate, its mixing quality ratio
For: trbasic zinc phosphate: aluminum phosphate=1.5:1.
Graphene oxide described above is the graphene oxide through aminosilane coupling agent modifying；Described amino silicane coupling agent
Molecular structure be:
Wherein, R is alkyl, for 1-10 carbon atom.
Anti-sudden strain of a muscle rust agent described above is the benzene ring compound containing nitro, and its structural formula is:
Wherein R is H or C1-C10。
Filler described above is that one or more in coarse whiting, wollastonite in powder, mica, talcum powder, kaolin, dolomite are appointed
The composition of meaning mass ratio.
The preparation method of a kind of water corrosion-resistant epoxy paint containing graphene oxide, comprises the steps:
1, by mass percentage by the aqueous epoxy resins in proportioning component, anti-corrosion paint, water-repelling agent, filler, anti-sudden strain of a muscle rust agent,
Water, graphene oxide mix, and stir, and obtain component A slip, and room temperature is placed, standby；
2, weighing the aqueous epoxy curing agent in proportioning component by mass percentage, as B component, Room-temperature seal preserves.
A kind of using method of the water corrosion-resistant epoxy paint containing anti-oxidation Graphene, step is:
During use, the B component that component A preparation method step (1) obtained and step (2) obtain mixes, stirring
Uniformly, then application, at 30 DEG C, solidify after 1h maintenance 1h at 120 DEG C again.
Compared with prior art, have the feature that and beneficial effect are mainly the present invention:
1, use the graphene oxide that aminosilane coupling agent modifying is crossed to improve the performance of water corrosion-resistant epoxy paint.
2, prepared aqueous epoxy coating has preferable wearability, anti-corrosive properties, heat resistance.
3, add the benzene ring compound containing nitro, be effectively prevented the problem that water paint dodges rust.
4, simple to operate, raw material is easy to get, greatly reduces the production cost of coating.
Detailed description of the invention:
Below in conjunction with specific embodiment, the present invention is expanded on further.Should be understood that these embodiments are merely to illustrate rather than limit
The scope of the present invention processed.In addition, it is to be understood that after having read the content that the present invention lectures, those skilled in the art can be to this
Invention makes various changes or modifications, and these equivalent form of values fall within the application depended on claims limited range equally.
Embodiment 1
One, the formula of composition
1, the mixture of anti-corrosion paint, filler is prepared the most respectively.
2, each constituent content of compositions formulated by mass percentage:
Two, preparation and application
1, preparation component A: according to mass percent by the aqueous epoxy resins in proportioning component, anti-corrosion paint, water-repelling agent,
Filler, anti-sudden strain of a muscle rust agent, water, graphene oxide mix, and stir, obtain component A slip, and room temperature is placed.
2, preparation B component: weigh the aqueous epoxy curing agent in proportioning component according to mass percent, as B component, room
Temperature seals and preserves.
When 3, using, component A and B component are mixed, stirs, then application, at 30 DEG C after solidification 1h again
Maintenance 1h at 120 DEG C.
Three, beneficial effect
The present embodiment resulting composition is coated on cold-rolled steel sheet, and through experiment and detection, the experiment of coating salt spray resistance occurs up to 510h
Corroding focus, adhesive force 2 grades on a small quantity, coating heatproof is up to 310 DEG C, and coefficient of friction is 0.5176.
Embodiment 2
One, the formula of composition
1, the mixture of anti-corrosion paint, filler is prepared the most respectively.
2, each constituent content of compositions formulated by mass percentage:
Two, preparation and application is with embodiment 1
Three, beneficial effect
The present embodiment resulting composition is coated on cold-rolled steel sheet, and through experiment and detection, the experiment of coating salt spray resistance occurs up to 620h
Corroding focus, adhesion 1 grade on a small quantity, coating heatproof is up to 400 DEG C, and coefficient of friction is 0.5166.
Embodiment 3
One, the formula of composition
1, the mixture of anti-corrosion paint, filler is prepared the most respectively.
2, each constituent content of compositions formulated by mass percentage:
Two, preparation and application is with embodiment 1
Three, beneficial effect
The present embodiment resulting composition is coated on cold-rolled steel sheet, and through experiment and detection, the experiment of coating salt spray resistance occurs up to 650h
Corroding focus, adhesion 1 grade on a small quantity, coating heatproof is up to 420 DEG C, and coefficient of friction is 0.5168.
Embodiment 4
One, the formula of composition
1, the mixture of anti-corrosion paint, filler is prepared the most respectively.
2, each constituent content of compositions formulated by mass percentage:
Two, preparation and application is with embodiment 1
Three, beneficial effect
The present embodiment resulting composition is coated on cold-rolled steel sheet, and through experiment and detection, the experiment of coating salt spray resistance occurs up to 670h
Corroding focus, adhesion 1 grade on a small quantity, coating heatproof is up to 450 DEG C, and coefficient of friction is 0.5208.
Embodiment 5
One, the formula of composition
1, the mixture of anti-corrosion paint, filler is prepared the most respectively.
2, each constituent content of compositions formulated by mass percentage:
Two, preparation and application is with embodiment 1
Three, beneficial effect
The present embodiment resulting composition is coated on cold-rolled steel sheet, and through experiment and detection, the experiment of coating salt spray resistance occurs up to 850h
Corroding focus, adhesion 1 grade on a small quantity, coating heatproof is up to 500 DEG C, and coefficient of friction is 0.5188.
Embodiment 6
One, the formula of composition
1, the mixture of anti-corrosion paint, filler is prepared the most respectively.
2, each constituent content of compositions formulated by mass percentage:
Two, preparation and application is with embodiment 1
Three, beneficial effect
The present embodiment resulting composition is coated on cold-rolled steel sheet, and through experiment and detection, the experiment of coating salt spray resistance goes out up to 1000h
Corroding focus, adhesion 1 grade the most on a small quantity, coating heatproof is up to 600 DEG C, and coefficient of friction is 0.5128.
Embodiment 7
One, the formula of composition
1, the mixture of anti-corrosion paint, filler is prepared the most respectively.
2, each constituent content of compositions formulated by mass percentage:
Two, preparation and application is with embodiment 1
Three, beneficial effect
The present embodiment resulting composition is coated on cold-rolled steel sheet, and through experiment and detection, the experiment of coating salt spray resistance occurs up to 900h
Corroding focus, adhesion 1 grade on a small quantity, coating heatproof is up to 600 DEG C, and coefficient of friction is 0.5118.
Embodiment 8
One, the formula of composition
1, the mixture of anti-corrosion paint, filler is prepared the most respectively.
2, each constituent content of compositions formulated by mass percentage:
Two, preparation and application is with embodiment 1
Three, beneficial effect
The present embodiment resulting composition is coated on cold-rolled steel sheet, and through experiment and detection, the experiment of coating salt spray resistance occurs up to 900h
Corroding focus, adhesion 1 grade on a small quantity, coating heatproof is up to 550 DEG C, and coefficient of friction is 0.5178.
The above is only the preferred embodiment of the present invention, it should be pointed out that: to those of ordinary skill in the art, do not taking off
On the premise of the principle of the invention, it is also possible to make some improvements and modifications, these improvements and modifications also should be regarded as the guarantor of the present invention
Protect scope.
Claims (7)
1. the water corrosion-resistant epoxy paint containing graphene oxide, it is characterised in that by mass percentage by water-base epoxy
Resin is 40～50%, and anti-corrosion paint is 7～10%, and water-repelling agent is 3～4%, and graphene oxide is 1～2%, and filler is 4～5%,
Deionized water is 33～35%, anti-dodge rust agent be 1～1.5%, aqueous epoxy curing agent be 1～2% composition；Wherein said aqueous ring
The molecular characterization of oxygen curing agent is:
Wherein, R is alkyl, and for 1-4 carbon atom, X is carboxyl or hydroxyl.
A kind of water corrosion-resistant epoxy paint containing graphene oxide the most according to claim 1, it is characterised in that institute
The water-repelling agent structural formula stated is:
A kind of water corrosion-resistant epoxy paint containing graphene oxide the most according to claim 1, it is characterised in that institute
The anti-corrosion paint stated is phosphate or molybdate, or trbasic zinc phosphate and the mixture of aluminum phosphate, and its mixing quality ratio is: trbasic zinc phosphate:
Aluminum phosphate=1.5:1.
A kind of water corrosion-resistant epoxy paint containing graphene oxide the most according to claim 1, it is characterised in that institute
The graphene oxide stated is the graphene oxide through aminosilane coupling agent modifying；The molecular structure of described amino silicane coupling agent
For:
Wherein, R is alkyl, for 1-10 carbon atom.
A kind of water corrosion-resistant epoxy paint containing graphene oxide the most according to claim 1, it is characterised in that institute
The anti-sudden strain of a muscle rust agent stated is the benzene ring compound containing nitro, and its structural formula is:
Wherein R is H or C1-C10。
A kind of water corrosion-resistant epoxy paint containing graphene oxide the most according to claim 1, it is characterised in that institute
The filler stated is any mass ratioes of one or more in coarse whiting, wollastonite in powder, mica, talcum powder, kaolin, dolomite
Composition.
7. a preparation method for the water corrosion-resistant epoxy paint containing graphene oxide according to claim 1, it is special
Levy and be to comprise the steps:
(1) by mass percentage by the aqueous epoxy resins in proportioning component, anti-corrosion paint, water-repelling agent, filler, anti-sudden strain of a muscle rust agent,
Water, graphene oxide mix, and stir, and obtain component A slip, and room temperature is placed, standby；
(2) weighing the aqueous epoxy curing agent in proportioning component by mass percentage, as B component, Room-temperature seal preserves；
(3) when using, the B component that component A step (1) obtained and step (2) obtain mixes, and stirring is all
Even, then application, at 30 DEG C, solidify after 1h maintenance 1h at 120 DEG C again.
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| CN106634461A (en) * | 2016-12-16 | 2017-05-10 | 深圳大学 | Oxidized graphene heat insulation glass double-ingredient paint and preparation method thereof |
| CN107216768A (en) * | 2017-05-31 | 2017-09-29 | 广州希森美克新材料科技有限公司 | A kind of ultrathin nanometer type anticorrosive paint and its Self-leveling dipping process |
| CN107815216A (en) * | 2017-10-27 | 2018-03-20 | 上海理工大学 | The Curing Agents for Waterborne Epoxy Coatings and preparation method and application that a kind of graphene is modified |
| CN107987680A (en) * | 2017-12-20 | 2018-05-04 | 海洋化工研究院有限公司 | Water-base epoxy graphene anticorrosive paint |
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| CN111704821A (en) * | 2020-06-19 | 2020-09-25 | 中国科学院金属研究所 | Graphene oxide grafting-based composite antirust pigment and application thereof in anticorrosive paint |
| CN111849216A (en) * | 2020-07-01 | 2020-10-30 | 中国船舶重工集团公司第七二五研究所 | Fatty amine hydrophobically modified graphene oxide suitable for water-based paint and preparation method thereof |
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| CN115141507A (en) * | 2022-06-23 | 2022-10-04 | 宁波市杭州湾大桥发展有限公司 | Riboflavin sodium phosphate modified two-dimensional lamellar composite material, and preparation method and application thereof |
| CN115216199A (en) * | 2022-07-15 | 2022-10-21 | 内蒙古电力(集团)有限责任公司内蒙古电力科学研究院分公司 | Economical and practical water-based epoxy graphene primer-topcoat coating capable of prolonging service life under severe working conditions and preparation method thereof |
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