CN105838195B - A kind of water corrosion-resistant epoxy paint and preparation method thereof containing graphene oxide - Google Patents

A kind of water corrosion-resistant epoxy paint and preparation method thereof containing graphene oxide Download PDF

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Publication number
CN105838195B
CN105838195B CN201610319677.0A CN201610319677A CN105838195B CN 105838195 B CN105838195 B CN 105838195B CN 201610319677 A CN201610319677 A CN 201610319677A CN 105838195 B CN105838195 B CN 105838195B
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graphene oxide
corrosion
paint
agent
water
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CN105838195A (en
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高延敏
左银泽
陈亮
周建军
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Gansu Jingbang Environmental Protection Technology Co., Ltd.
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Jiangsu University of Science and Technology
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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING 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
    • C09D163/00Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00Polycondensates 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
    • C08G59/18Macromolecules 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
    • C08G59/40Macromolecules 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
    • C08G59/50Amines
    • C08G59/5046Amines heterocyclic
    • C08G59/5053Amines heterocyclic containing only nitrogen as a heteroatom
    • C08G59/5073Amines heterocyclic containing only nitrogen as a heteroatom having two nitrogen atoms in the ring
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/02Elements
    • C08K3/04Carbon
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/16Nitrogen-containing compounds
    • C08K5/32Compounds containing nitrogen bound to oxygen
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00Use of pretreated ingredients
    • C08K9/04Ingredients treated with organic substances
    • C08K9/06Ingredients treated with organic substances with silicon-containing compounds
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING 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
    • C09D5/00Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08Anti-corrosive paints
    • C09D5/082Anti-corrosive paints characterised by the anti-corrosive pigment
    • C09D5/084Inorganic compounds
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING 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
    • C09D7/00Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40Additives
    • C09D7/60Additives non-macromolecular
    • C09D7/61Additives non-macromolecular inorganic
    • C09D7/62Additives non-macromolecular inorganic modified by treatment with other compounds
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING 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
    • C09D7/00Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40Additives
    • C09D7/60Additives non-macromolecular
    • C09D7/63Additives non-macromolecular organic

Abstract

The invention discloses a kind of water corrosion-resistant epoxy paints containing graphene oxide, by mass percentage by following material composition: aqueous epoxy resins are 40~50%, anti-corrosion paint is 7~10%, hydrophobing agent is 3~4%, graphene oxide is 1~2%, and filler is 4~5%, and deionized water is 33~35%, anti- flash rusting agent is 1~1.5%, and aqueous epoxy curing agent is 1~2%.The invention also discloses a kind of preparation methods of corrosion-resistant epoxy paint containing graphene oxide, the wearability of corrosion-resistant epoxy paint is improved by surface treated graphene oxide, reduces coefficient of friction, while improving the corrosion resistance of water corrosion-resistant epoxy paint.Anticorrosive paint preparation of the invention is simple, raw material sources are extensive, greatly reduces production cost.

Description

A kind of water corrosion-resistant epoxy paint and preparation method thereof containing graphene oxide
Technical field:
The invention belongs to chemical anticorrosion paint fields, and in particular to a kind of water-base epoxy anti-corrosion painting containing graphene oxide Material and preparation method thereof.
Background technique:
World today's environmental problem is increasingly severe, releases a large amount of harmful substance in the processing and production process of coating It will cause environmental pollution and damage the health of construction personnel.In order to control pollution and protect the health of construction personnel, China Formulate the use that a series of measures limits high VOC coating.So environment friendly anti-corrosive paint becomes the emphasis of paint development.Numerous In environment-friendly type coating, water paint is the important directions of development.However current water paint is there is also some technical problems, So the anti-corrosive properties for improving water paint have become the developing emphasis of environmental protection coating material.
The technical staff for being engaged in coating research and development and preparation both knows about, and contains epoxy group on epoxy molecule chain, can Open loop forms a kind of three-dimensional netted polymer.Epoxy resin has strong machinery, mechanics, thermal property, and high cohesiveness is excellent The resin of different Corrosion Protection, epoxy coating are a kind of environment-friendly type coatings that can substitute high VOC coating.
Water-base epoxy coating is the best film forming matter of High Performance Corrosion Protective Coatings, however since water-base epoxy is with lotion point Bulk state, it is different from solvent in the process of film forming, hole can be formed in film surface, so that water resistance be made to reduce.Therefore it is necessary to improve To the water resistance of water-base epoxy coating.
Graphene only has a carbon atom thickness, has surface area height, excellent in mechanical performance, good chemical stability, If graphene, which is added in waterborne epoxy coatings, can well solve water-base epoxy coating coefficient of friction is high, wear rate is big etc. Problem can also enhance the anti-corrosion ability of water-base epoxy coating.
Graphene oxide is that redox reaction prepares a kind of substance of class graphene obtained in graphene process, oxidation The lamellar structure of graphene conjugation can form fine and close protective film in the coating, prevent infiltration of the hydrone to coating, while can To prevent Fe from being changed into Fe3+, prevent from generating iron rust.Compared with graphene, graphene oxide has the presence of oxygen-containing functional group, Cause the hydrophobic performance of graphene oxide not good enough, so must be surface modified to it.Pass through amino silicane coupling agent pair Graphene oxide is surface modified.Unique amino can be with oxygen-containing functional group in graphene oxide in amino silicane coupling agent It reacts, is grafted in graphene oxide, so that the hydrophobicity of graphene oxide and the affinity of itself and epoxy resin are improved, It reduces and reunites, improve its dispersity, improve hydrophobicity.
Based on the above, a kind of water corrosion-resistant epoxy paint containing graphene oxide of the invention, by using warp The graphene oxide of amino silicane coupling agent modification, has preferable affinity and stronger hydrophobicity with epoxy resin, effectively The disadvantage that waterborne epoxy coatings coefficient of friction is high, wear rate is big is improved, and it is good to have water corrosion-resistant epoxy paint Temperature tolerance, corrosion resistance.
Summary of the invention:
The purpose of the present invention is to solve problems of the existing technology, provide a kind of water containing graphene oxide Property epoxy coating.
The present invention is special using graphene oxide by selecting the graphene oxide through amino silicane coupling agent modified Amino silicane coupling agent is grafted to graphene oxide molecule layer surface, has it with epoxy resin by surface oxygen functional group Better affinity, graphene oxide itself can form fine and close protective layer, can more obtain very with epoxy resin cross-linking reaction Good coating density, the entrance of effective starvation and hydrone.And the function of electrochemical anti-corrosive can be played, prevent iron rust Production.And graphene oxide has the distinctive mechanical performance of graphene, physical property, can improve the one of water-base epoxy coating A little defects while resulting coating has good antiseptic property, have good mechanical performance and physical property.
The present invention effectively improves epoxy coating coefficient of friction height, problem easy to wear more improves at the same time Epoxy coating antiseptic property and temperature tolerance.
To reach above-mentioned target, the technical solution adopted by the present invention is that:
A kind of water corrosion-resistant epoxy paint containing graphene oxide, by mass percentage by aqueous epoxy resins be 40~ 50%, anti-corrosion paint is 7~10%, and hydrophobing agent is 3~4%, and graphene oxide is 1~2%, and filler is 4~5%, deionization Water is 33~35%, and anti-flash rusting agent is 1~1.5%, and aqueous epoxy curing agent is 1~2% composition;The wherein water-base epoxy The molecular characterization of curing agent are as follows:
Wherein, R is alkyl, is 1-4 carbon atom, and X is carboxyl or hydroxyl.
Hydrophobing agent structural formula described above are as follows:
Anti-corrosion paint described above is the mixture of phosphate or molybdate or trbasic zinc phosphate and aluminum phosphate, mixes matter Measure ratio are as follows: trbasic zinc phosphate: aluminum phosphate=1.5:1.
Graphene oxide described above is the graphene oxide through aminosilane coupling agent modifying;The amino silane The molecular structure of coupling agent are as follows:
Wherein, R is alkyl, is 1-10 carbon atom.
Anti- flash rusting agent described above is the benzene ring compound containing nitro, structural formula are as follows:
Wherein R is H or C1-C10
Filler described above is one of coarse whiting, wollastonite in powder, mica, talcum powder, kaolin, dolomite or a variety of The composition of any mass ratio.
A kind of preparation method of the water corrosion-resistant epoxy paint containing graphene oxide, includes the following steps:
1, the aqueous epoxy resins in component, anti-corrosion paint, hydrophobing agent, filler, anti-flash rusting will be matched by mass percentage Agent, water, graphene oxide are mixed, and are stirred evenly, and are obtained component A slurry, are placed at room temperature for, spare;
2, the aqueous epoxy curing agent in proportion component is weighed by mass percentage, and as B component, Room-temperature seal is saved.
A kind of application method of the water corrosion-resistant epoxy paint containing anti-oxidation graphene, step is:
In use, the component A that preparation method step (1) obtains and the B component that step (2) obtains are mixed, stir Uniformly, then coating conserves 1h after solidifying 1h at 30 DEG C at 120 DEG C again.
Compared with prior art, the present invention possessed feature and beneficial effect are mainly:
1, improve the performance of water corrosion-resistant epoxy paint using the graphene oxide that aminosilane coupling agent modifying is crossed.
2, prepared waterborne epoxy coatings has preferable wearability, anti-corrosive properties, heat resistance.
3, the problem of benzene ring compound containing nitro is added, effectively prevents water paint flash rusting.
4, easy to operate, raw material is easy to get, greatly reduces the production cost of coating.
Specific embodiment:
Present invention will be further explained below with reference to specific examples.It should be understood that these embodiments are merely to illustrate and do not have to In limiting the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, those skilled in the art can be with The present invention is made various changes or modifications, such equivalent forms equally fall within model defined by the depended on claims of the application It encloses.
Embodiment 1
One, the formula of composition
1, the mixture of anti-corrosion paint, filler is prepared respectively in mass ratio.
2, compositions formulated each component content by mass percentage:
Two, preparation and application
1, prepare component A: according to mass percent will match component in aqueous epoxy resins, anti-corrosion paint, hydrophobing agent, Filler, anti-flash rusting agent, water, graphene oxide are mixed, and are stirred evenly, are obtained component A slurry, be placed at room temperature for.
2, it prepares B component: the aqueous epoxy curing agent in proportion component is weighed according to mass percent, as B component, room Temperature is sealed.
3, it in use, component A and B component are mixed, stirs evenly, then coating, at 30 DEG C after solidification 1h again 1h is conserved at 120 DEG C.
Three, beneficial effect
The present embodiment resulting composition is coated on cold-rolled steel sheet, is tested and is detected, and the experiment of coating salt spray resistance is reachable There is a small amount of corrosion lesion in 510h, and 2 grades of adhesive force, coating heatproof is up to 310 DEG C, coefficient of friction 0.5176.
Embodiment 2
One, the formula of composition
1, the mixture of anti-corrosion paint, filler is prepared respectively in mass ratio.
2, compositions formulated each component content by mass percentage:
Two, preparation and application is the same as embodiment 1
Three, beneficial effect
The present embodiment resulting composition is coated on cold-rolled steel sheet, is tested and is detected, and the experiment of coating salt spray resistance is reachable There is a small amount of corrosion lesion in 620h, adhesion 1 grade, and coating heatproof is up to 400 DEG C, coefficient of friction 0.5166.
Embodiment 3
One, the formula of composition
1, the mixture of anti-corrosion paint, filler is prepared respectively in mass ratio.
2, compositions formulated each component content by mass percentage:
Two, preparation and application is the same as embodiment 1
Three, beneficial effect
The present embodiment resulting composition is coated on cold-rolled steel sheet, is tested and is detected, and the experiment of coating salt spray resistance is reachable There is a small amount of corrosion lesion in 650h, adhesion 1 grade, and coating heatproof is up to 420 DEG C, coefficient of friction 0.5168.
Embodiment 4
One, the formula of composition
1, the mixture of anti-corrosion paint, filler is prepared respectively in mass ratio.
2, compositions formulated each component content by mass percentage:
Two, preparation and application is the same as embodiment 1
Three, beneficial effect
The present embodiment resulting composition is coated on cold-rolled steel sheet, is tested and is detected, and the experiment of coating salt spray resistance is reachable There is a small amount of corrosion lesion in 670h, adhesion 1 grade, and coating heatproof is up to 450 DEG C, coefficient of friction 0.5208.
Embodiment 5
One, the formula of composition
1, the mixture of anti-corrosion paint, filler is prepared respectively in mass ratio.
2, compositions formulated each component content by mass percentage:
Two, preparation and application is the same as embodiment 1
Three, beneficial effect
The present embodiment resulting composition is coated on cold-rolled steel sheet, is tested and is detected, and the experiment of coating salt spray resistance is reachable There is a small amount of corrosion lesion in 850h, adhesion 1 grade, and coating heatproof is up to 500 DEG C, coefficient of friction 0.5188.
Embodiment 6
One, the formula of composition
1, the mixture of anti-corrosion paint, filler is prepared respectively in mass ratio.
2, compositions formulated each component content by mass percentage:
Two, preparation and application is the same as embodiment 1
Three, beneficial effect
The present embodiment resulting composition is coated on cold-rolled steel sheet, is tested and is detected, and the experiment of coating salt spray resistance is reachable There is a small amount of corrosion lesion in 1000h, adhesion 1 grade, and coating heatproof is up to 600 DEG C, coefficient of friction 0.5128.
Embodiment 7
One, the formula of composition
1, the mixture of anti-corrosion paint, filler is prepared respectively in mass ratio.
2, compositions formulated each component content by mass percentage:
Two, preparation and application is the same as embodiment 1
Three, beneficial effect
The present embodiment resulting composition is coated on cold-rolled steel sheet, is tested and is detected, and the experiment of coating salt spray resistance is reachable There is a small amount of corrosion lesion in 900h, adhesion 1 grade, and coating heatproof is up to 600 DEG C, coefficient of friction 0.5118.
Embodiment 8
One, the formula of composition
1, the mixture of anti-corrosion paint, filler is prepared respectively in mass ratio.
2, compositions formulated each component content by mass percentage:
Two, preparation and application is the same as embodiment 1
Three, beneficial effect
The present embodiment resulting composition is coated on cold-rolled steel sheet, is tested and is detected, and the experiment of coating salt spray resistance is reachable There is a small amount of corrosion lesion in 900h, adhesion 1 grade, and coating heatproof is up to 550 DEG C, coefficient of friction 0.5178.
The above is only a preferred embodiment of the present invention, it should be pointed out that: those skilled in the art are come It says, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications also should be regarded as Protection scope of the present invention.

Claims (2)

1. a kind of water corrosion-resistant epoxy paint containing graphene oxide, which is characterized in that by mass percentage by water-base epoxy Resin is 40 ~ 50%, and anti-corrosion paint is 7 ~ 10%, and hydrophobing agent is 3 ~ 4%, and graphene oxide is 1 ~ 2%, and filler is 4 ~ 5%, deionization Water is 33 ~ 35%, and anti-flash rusting agent is 1 ~ 1.5%, and aqueous epoxy curing agent is 1 ~ 2% composition;The wherein aqueous epoxy curing agent Molecular characterization are as follows:
Wherein, R is alkyl, is 1-4 carbon atom, and X is carboxyl or hydroxyl;
The hydrophobing agent structural formula are as follows:
n=1~5;
Mixture of the anti-corrosion paint for trbasic zinc phosphate and aluminum phosphate, mixing mass ratio are as follows: trbasic zinc phosphate: aluminum phosphate=1.5: 1;
The graphene oxide is the graphene oxide through aminosilane coupling agent modifying;The amino silicane coupling agent Molecular structure are as follows:
Wherein, R is alkyl, is 1-10 carbon atom;
The anti-flash rusting agent is the benzene ring compound containing nitro, structural formula are as follows:
Wherein R is H or C1-C10
The filler is one of coarse whiting, wollastonite in powder, mica, talcum powder, kaolin, dolomite or a variety of any quality The composition of ratio.
2. a kind of preparation method of the water corrosion-resistant epoxy paint according to claim 1 containing graphene oxide, special Sign is to include the following steps:
(1) by mass percentage will match component in aqueous epoxy resins, anti-corrosion paint, hydrophobing agent, filler, anti-flash rusting agent, Water, graphene oxide are mixed, and are stirred evenly, and are obtained component A slurry, are placed at room temperature for, spare;
(2) aqueous epoxy curing agent in proportion component is weighed by mass percentage, and as B component, Room-temperature seal is saved;
(3) it in use, the component A that step (1) obtains and the B component that step (2) obtains are mixed, stirs evenly, then Coating conserves 1h after solidifying 1h at 30 DEG C at 120 DEG C again.
CN201610319677.0A 2016-05-13 2016-05-13 A kind of water corrosion-resistant epoxy paint and preparation method thereof containing graphene oxide Active CN105838195B (en)

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