CN108570273A - A kind of solvent-free graphene oxide-glass flake anticorrosion paint and preparation method thereof - Google Patents
A kind of solvent-free graphene oxide-glass flake anticorrosion paint and preparation method thereof Download PDFInfo
- Publication number
- CN108570273A CN108570273A CN201810352787.6A CN201810352787A CN108570273A CN 108570273 A CN108570273 A CN 108570273A CN 201810352787 A CN201810352787 A CN 201810352787A CN 108570273 A CN108570273 A CN 108570273A
- Authority
- CN
- China
- Prior art keywords
- glass flake
- graphene oxide
- parts
- component
- weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/70—Additives characterised by shape, e.g. fibres, flakes or microspheres
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
- C08K2003/327—Aluminium phosphate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Paints Or Removers (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
Abstract
The invention discloses a kind of solvent-free graphene oxide glass flake anticorrosion paints, including component A and B component, the component A includes glass flake, epoxy resin, waterborne polyurethane resin, castor oil, reactive diluent, aluminium triphosphate, talcum powder, antifoaming agent and the titanium dioxide for aoxidizing graphene oxide and being modified；The B component is epoxy hardener H633, by component A and B component with 1 when use:0.2~0.25 mass ratio uniformly mixes.The present invention passes through graphene oxide modified glass flakes, on the one hand realize that graphene oxide layer is uniformly sprawled on glass flake surface and to sprawl the hole for the junction that state is filled between glass flake and scale, the screening ability of glass flake is improved, on the other hand realize low-temperature setting and reinforces the cohesive force of glass flake in the coating.There is the solvent-free graphene oxide glass flake anticorrosion paint of the present invention strong adhesive force, impact resistance to have better salt tolerance.
Description
Technical field
The invention belongs to anticorrosive paint fields, and in particular to a kind of solvent-free graphene oxide-glass flake anticorrosion paint
And preparation method thereof.
Background technology
Rotten coating refers to can have the coating of extended protection effect to protected object in corrosive environment.Glass flake is anti-
Rotten coating is using corrosion-resisting resin as main film forming substance, and laminar glass flake is aggregate, adds various additives
The high build paint of composition.Glass flake anticorrosion paint is widely used in the system equipments such as metallurgy, chemical industry, oil, ocean and building
In the antiseptic project of object, since there is the glass flake in coating fish scale effect, thousands of scale to be staggered, formed
Complicated tortuous diffusion approach in coating so that the diffused line of corrosive medium becomes quite tortuous, is hard to reach base
Material substantially prolongs diffusion path of the Korrosionsmedium in film, to effectively delay corrosive medium to base material
Corrosion.
Glass-flake coating is due to superior permeability, good corrosion resistance, service life it is long and obtained extensive attention and
Using still, the dosage of glass flake is very big on the influence of the shielding properties of coating, and dosage cannot form multilayer screen when few
Effect influences media-resistant penetrating power；When dosage is big, resin opposite can be reduced, and make the bonding force and mechanical strength drop of coating
It is low.
Chinese patent literature (application No. is 201610312743.1) discloses a kind of non-solvent epoxy glass flake paint,
It specifically discloses：Calixarenes molecule is grafted on glass flake using water-based isocyanate, glass flake is modified,
The calixarenes that modified glass flake is got in whipping process by grafting forms certain with epoxy molecule structure
It tangles, to improve the cohesive force of glass flake and epoxy resin, and then increases dosage of the glass flake in coating, together
When ensure preferable coated adhesive power and mechanical strength.But there is also following technological deficiencies for the document：When the coating later stage repairs
It needs first to polish to damaged coating, but glass flake is harder, polishing difficulty is larger, introduces more glass flakes undoubtedly
The difficulty of later stage repairing polishing can seriously be increased；The shield effectiveness of glass flake can be influenced to a certain extent.
Invention content
In order to solve the above technical problem, the present invention provides a kind of glass squama anti-corrosions being modified doped with graphene oxide
Coating reinforces the adhesion strength of glass flake and coating, in addition, oxygen by the graphene oxide coating modification to glass flake
Both graphite alkene and glass flake can generate synergistic function, reinforce screening ability, reinforce the permanent anti-corrosion energy of coating
Power also reduces glass flake volume to a certain extent, and polishing is repaired convenient for the later stage.
The technical solution adopted by the present invention to solve the technical problems is：A kind of solvent-free graphene oxide-glass flake
Anticorrosive paint, including component A and B component, component A include the glass flake, epoxy resin, aqueous that graphene oxide is modified
Polyurethane resin, castor oil, reactive diluent, aluminium triphosphate, talcum powder, antifoaming agent and titanium dioxide；The B component is
Epoxy hardener H633, by component A and B component with 1 when use:0.2~0.25 mass ratio uniformly mixes.
Further, the parts by weight for the glass flake that graphene oxide is modified are 10~15 parts, the parts by weight of epoxy resin
For 30~40 parts, waterborne polyurethane resin parts by weight be 8~15 parts, castor oil parts by weight are 0.5~1 part, reactive diluent
Parts by weight are 5~10 parts, the parts by weight of aluminium triphosphate are 12~25 parts, titanium dioxide parts by weight are 12~20 parts, antifoaming agent
Parts by weight are 0.2~0.5 part.
Further, the preparation method for the glass flake that graphene oxide is modified includes the following steps：
(1) glass flake after cleaning, drying is immersed into Piranha solution, 30min is stirred at a temperature of 90 DEG C；So
Afterwards with being dried after distilled water flushing to neutrality, the glass flake of hydroxyl surface modification is obtained；
(2) glass flake of hydroxyl surface modification obtained in step (1) is molten as the toluene of amino silicane coupling agent
In liquid, drying is taken out after sealing stirring 30min, the glass flake of amino surface modification is made；
(3) glass flake for modifying amino surface made from step (2) immerses the N of graphene oxide, N- diformamides
In dispersion liquid, at a temperature of 60~80 DEG C, it is stirred to react 12~for 24 hours, after reaction, it is filtered, washs successively, very
Sky is dry, and the glass flake that graphene oxide is modified is made.
Further, the cleaning, drying method of the glass flake in step (1) is：By glass flake successively as third
It is cleaned by ultrasonic five minutes in ketone, ethyl alcohol and distilled water, takes out drying；The configuration method of the Piranha solution is：It will
98% concentrated sulfuric acid and 30% hydrogen peroxide are with 7:3 volume ratio is uniformly mixed.
Further, the general formula of the amino silicane coupling agent described in step (2) is NH2 (CH2) nSiX3, wherein n
For 1~3 arbitrary integer, X is any one in methoxy or ethoxy；The toluene solution of the amino silicane coupling agent
The volume content of middle amino silicane coupling agent is 2%~8%.
Further, graphene oxide in the N of the graphene oxide described in step (3), N- diformamide dispersion liquid
Quality proportioning with the glass flake after the cleaning, drying described in step (1) is 0.01~0.05:1.
Further, the preparation process of the component A includes the following steps：
1. under the rotating speed of 100~300 turns/min, epoxy resin, reactive diluent, water are added in clean stirred tank
Property polyurethane resin and castor oil, be stirred until homogeneous mixing, premix a be made；
2. under the rotating speed of 200~400 turns/min, aluminium triphosphate, antifoaming agent, talcum are sequentially added into premix a
Then powder and titanium dioxide disperse 30~60min in 800~1300 turns/min rotating speeds, the control of whipping process temperature is no more than 40
℃；Then the glass flake that graphene oxide is modified is added thereto, and is stirred until homogeneous dispersion.
What the present invention obtained has the technical effect that：1) it first by glass flake surface amination, is more advantageous to and graphite oxide
The oxygen-containing functional group on alkene surface polymerize, and attachment of the graphene oxide between glass flake surface and scale is reinforced by chemical bond
Power, while graphene oxide sprawling completely on glass flake is effectively ensured；2) amino on glass flake surface and oxidation stone
The reactivity of black alkene is higher, can effectively improve graphene oxide glass flake surface adhesive rate；3) oxidation stone is realized
Black alkene lamellar structure uniformly spreads over glass flake surface and to sprawl the junction that state is filled between glass flake and scale
Hole, and then effectively improve the screening ability of glass flake, be advantageously implemented more permanent more effective anti-corrosion ability；4) oxygen
Graphite alkene surface group is easy to coating and forms hydrogen bond, reinforces glass flake by hydrogen bond action and applies the cohesive force of interlayer；5)
The addition of castor oil and aqueous polyurethane and the oxygen-containing functional group of surface of graphene oxide are formed by Hydrogenbond not by temperature
The cohesive force for the relatively lasting stability that the factors such as degree, hydrolysis influence, promotes anticorrosive paint to have preferable lower temperature resistance and hydrolysis
Property；5) dosage for advantageously reducing glass flake is polished in order to the repairing in later stage, and the reduction of glass flake dosage also may be used
With effective reduction construction thickness, construction efficiency is improved.
Specific implementation mode
The present invention is described in further detail with reference to embodiment：
Raw materials are as shown in table 1 in the embodiment of the present invention：
Table 1
| Material name | Manufacturer |
| Epoxy resin | Three wood of Jiangsu |
| Waterborne polyurethane resin | Guangdong Yue Mei Chemical Co., Ltd.s |
| Reactive diluent | Wuxi City Pin Hua Chemical Co., Ltd.s |
| Castor oil | BASF |
| Aluminium triphosphate | Nuo Cheng fine powders Industrial Co., Ltd |
| Talcum powder | Jiangxi Sheng Tai Chemical Co., Ltd.s |
| Antifoaming agent | Shandong You Suo Chemical Industry Science Co., Ltd |
| Titanium dioxide | Chuzhou Grea Minerals Co., Ltd. |
| Glass flake | Five Yang Fangfucailiaochang of Wenan County of Hebei province |
| Graphene oxide | The hexa-atomic element in Changzhou |
| Epoxy hardener H633 | Changzhou Han Ke Chemical Industry Science Co., Ltd |
Embodiment 1：
A kind of preparation of solvent-free graphene oxide-glass flake anticorrosion paint, component A are prepared former by following mass parts
Material：The parts by weight for the glass flake that graphene oxide is modified are 15 parts, the parts by weight of epoxy resin are 30 parts, aqueous polyurethane
Weight resin part is 8, castor oil parts by weight are 0.5, the parts by weight of reactive diluent are 5 parts, the parts by weight of aluminium triphosphate are
25 parts, titanium dioxide parts by weight be 20 parts, the parts by weight of antifoaming agent are 0.2 part.
The preparation method for the glass flake that graphene oxide is modified in component A includes the following steps：
(1) by 98% concentrated sulfuric acid and 30% hydrogen peroxide with 7:3 volume ratio is uniformly mixed, and it is molten to configure Piranha
Liquid；Then, glass flake is cleaned by ultrasonic five minutes as in acetone, ethyl alcohol and distilled water successively, takes out drying；It again will be clear
The glass flake washed after drying immerses Piranha solution, and 30min is stirred at a temperature of 90 DEG C；Again with distilled water flushing into
Property after dry, obtain hydroxyl surface modification glass flake；
(2) glass flake by hydroxyl surface modification obtained in step (1) immerses NH2CH2Si(OCH3)3Toluene it is molten
In liquid, drying is taken out after sealing stirring 30min, the glass flake of amino surface modification, wherein NH is made2CH2Si(OCH3)3's
NH in toluene solution2CH2Si(OCH3)3Volume content be 2%；
(3) glass flake for modifying amino surface made from step (2) immerses the N of graphene oxide, N- diformamides
In dispersion liquid, at a temperature of 75~80 DEG C, it is stirred to react 12h, after reaction, is filtered, washs successively, vacuum is done
It is dry, the glass flake that graphene oxide is modified is made.
In the above method, the N of graphene oxide, in N- diformamide dispersion liquids graphene oxide with it is clear in step (1)
The quality proportioning for washing the glass flake after drying is 0.01:1.
The preparation method of component A includes the following steps：
1. under the rotating speed of 300 turns/min, epoxy resin, waterborne polyurethane resin, castor-oil plant are added in clean stirred tank
Oil, stirs evenly at reactive diluent, and premix a is made；
2. under the rotating speed of 400 turns/min, sequentially added into premix a aluminium triphosphate, antifoaming agent, talcum powder with
And titanium dioxide, 30min is then disperseed under 1300 turns/min rotating speeds, the control of whipping process temperature is 35~40 DEG C；Then to it
The middle glass flake that graphene oxide is added and is modified, and it is stirred until homogeneous dispersion.
In use, the quality proportioning of component A and B component is 1:0.2 is uniformly mixed.
Embodiment 2
A kind of preparation of solvent-free graphene oxide-glass flake anticorrosion paint, component A are prepared former by following mass parts
Material：The parts by weight for the glass flake that graphene oxide is modified are 18 parts, the parts by weight of epoxy resin are 40 parts, aqueous polyurethane
Weight resin part is 15 parts, castor oil parts by weight are 1 part, the parts by weight of reactive diluent are 10 parts, the weight of aluminium triphosphate
Part is 12 parts, titanium dioxide parts by weight are 12 parts, the parts by weight of antifoaming agent are 0.5 part.
The preparation method for the glass flake that graphene oxide is modified in component A includes the following steps：
(1) by 98% concentrated sulfuric acid and 30% hydrogen peroxide with 7:3 volume ratio is uniformly mixed, and it is molten to configure Piranha
Liquid；Then, glass flake is cleaned by ultrasonic five minutes as in acetone, ethyl alcohol and distilled water successively, takes out drying；It again will be clear
The glass flake washed after drying immerses Piranha solution, and 30min is stirred at a temperature of 90 DEG C；Again with distilled water flushing into
Property after dry, obtain hydroxyl surface modification glass flake；
(2) glass flake for modifying hydroxyl surface obtained immerses NH2CH2CH2Si(OCH2CH3)3Toluene solution
In, drying is taken out after sealing stirring 30min, the glass flake of amino surface modification, wherein NH is made2CH2CH2Si
(OCH2CH3)3Toluene solution in NH2CH2CH2Si(OCH2CH3)3Volume content be 8%；
(3) glass flake for modifying amino surface made from step (2) immerses the N of graphene oxide, N- diformamides
It in dispersion liquid, at a temperature of 65~70 DEG C, is stirred to react for 24 hours, after reaction, is filtered, washs successively, vacuum is done
It is dry, the glass flake that graphene oxide is modified is made.
In the above method, the N of graphene oxide, in N- diformamide dispersion liquids graphene oxide with it is clear in step (1)
The quality proportioning for washing the glass flake after drying is 0.05:1.
The preparation method of component A includes the following steps：
1. under the rotating speed of 200 turns/min, epoxy resin, waterborne polyurethane resin, castor-oil plant are added in clean stirred tank
Oil, stirs evenly at reactive diluent, and premix a is made；
2. under the rotating speed of 300 turns/min, sequentially added into premix a aluminium triphosphate, antifoaming agent, talcum powder with
And titanium dioxide, then disperse 60min in 1000 turns/min rotating speeds, the control of whipping process temperature is 25~30 DEG C；Then thereto
The glass flake that graphene oxide is modified is added, and is stirred until homogeneous dispersion.
In use, the quality proportioning of component A and B component is 1:0.25 is uniformly mixed.
Embodiment 3
A kind of preparation of solvent-free graphene oxide-glass flake anticorrosion paint, component A are prepared former by following mass parts
Material：The parts by weight for the glass flake that graphene oxide is modified are 25 parts, the parts by weight of epoxy resin are 35 parts, aqueous polyurethane
Weight resin part is 13 parts, castor oil parts by weight are 0.8 part, the parts by weight of reactive diluent are 8 parts, the weight of aluminium triphosphate
Amount part is 20 parts, titanium dioxide parts by weight are 15 parts, the parts by weight of antifoaming agent are 0.4 part.
The preparation method for the glass flake that graphene oxide is modified in component A includes the following steps：
(1) by 98% concentrated sulfuric acid and 30% hydrogen peroxide with 7:3 volume ratio is uniformly mixed, and it is molten to configure Piranha
Liquid；Then, glass flake is cleaned by ultrasonic five minutes as in acetone, ethyl alcohol and distilled water successively, takes out drying；It again will be clear
The glass flake washed after drying immerses Piranha solution, and 30min is stirred at a temperature of 90 DEG C；Again with distilled water flushing into
Property after dry, obtain hydroxyl surface modification glass flake；
(2) glass flake for modifying hydroxyl surface obtained immerses NH2CH2CH2CH2Si(OCH2CH3)3Toluene it is molten
In liquid, drying is taken out after sealing stirring 30min, the glass flake of amino surface modification, wherein NH is made2CH2CH2CH2Si
(OCH2CH3)3Toluene solution in NH2CH2CH2CH2Si(OCH2CH3)3Volume content be 8%；
(3) glass flake for modifying amino surface made from step (2) immerses the N of graphene oxide, N- diformamides
In dispersion liquid, at a temperature of 60~65 DEG C, it is stirred to react 18h, after reaction, is filtered, washs successively, vacuum is done
It is dry, the glass flake that graphene oxide is modified is made.
In the above method, the N of graphene oxide, in N- diformamide dispersion liquids graphene oxide with it is clear in step (1)
The quality proportioning for washing the glass flake after drying is 0.035:1.
The preparation method of component A includes the following steps：
1. under the rotating speed of 100 turns/min, epoxy resin, waterborne polyurethane resin, castor-oil plant are added in clean stirred tank
Oil, stirs evenly at reactive diluent, and premix a is made；
2. under the rotating speed of 200 turns/min, sequentially added into premix a aluminium triphosphate, antifoaming agent, talcum powder with
And titanium dioxide, then disperse 40min in 800 turns/min rotating speeds, the control of whipping process temperature is 20~25 DEG C；Then thereto
The glass flake that graphene oxide is modified is added, and is stirred until homogeneous dispersion.
In use, the quality proportioning of component A and B component is 1:0.23 is uniformly mixed.
Embodiment 4
A kind of preparation of solvent-free graphene oxide-glass flake anticorrosion paint, component A are prepared former by following mass parts
Material：The parts by weight for the glass flake that graphene oxide is modified are 30 parts, the parts by weight of epoxy resin are 30 parts, aqueous polyurethane
Weight resin part is 10 parts, castor oil parts by weight are 0.6 part, the parts by weight of reactive diluent are 10 parts, the weight of aluminium triphosphate
Amount part is 25 parts, titanium dioxide parts by weight are 20 parts, the parts by weight of antifoaming agent are 0.5 part.
The preparation method for the glass flake that graphene oxide is modified in component A includes the following steps：
(1) by 98% concentrated sulfuric acid and 30% hydrogen peroxide with 7:3 volume ratio is uniformly mixed, and it is molten to configure Piranha
Liquid；Then, glass flake is cleaned by ultrasonic five minutes as in acetone, ethyl alcohol and distilled water successively, takes out drying；It again will be clear
The glass flake washed after drying immerses Piranha solution, and 30min is stirred at a temperature of 90 DEG C；Again with distilled water flushing into
Property after dry, obtain hydroxyl surface modification glass flake；
(2) glass flake for modifying hydroxyl surface obtained immerses NH2CH2CH2CH2Si(OCH2CH3)3Toluene it is molten
In liquid, drying is taken out after sealing stirring 30min, the glass flake of amino surface modification, wherein NH is made2CH2CH2CH2Si
(OCH2CH3)3Toluene solution in NH2CH2CH2CH2Si(OCH2CH3)3Volume content be 6%；
(3) glass flake for modifying amino surface made from step (2) immerses the N of graphene oxide, N- diformamides
In dispersion liquid, at a temperature of 60~65 DEG C, it is stirred to react 18h；, after reaction, it is filtered, washs successively, vacuum is done
It is dry, the glass flake that graphene oxide is modified is made.
In the above method, the N of graphene oxide, in N- diformamide dispersion liquids graphene oxide with it is clear in step (1)
The quality proportioning for washing the glass flake after drying is 0.035:1.
The preparation method of component A includes the following steps：
1. under the rotating speed of 100 turns/min, epoxy resin, waterborne polyurethane resin, castor-oil plant are added in clean stirred tank
Oil, stirs evenly at reactive diluent, and premix a is made；
2. under the rotating speed of 200 turns/min, sequentially added into premix a aluminium triphosphate, antifoaming agent, talcum powder with
And titanium dioxide, then disperse 40min in 800 turns/min rotating speeds, the control of whipping process temperature is 20~25 DEG C；Then thereto
The glass flake that graphene oxide is modified is added, and is stirred until homogeneous dispersion.
In use, the quality proportioning of component A and B component is 1:0.23 is uniformly mixed.
Comparative example 1
A kind of preparation of solvent-free glass flake anticorrosion paint, component A prepare raw material by following mass parts：Glass flake
Parts by weight be 30 parts, the parts by weight of epoxy resin are 30 parts, the parts by weight of reactive diluent are 10 parts, aluminium triphosphate
Parts by weight are 25 parts, titanium dioxide parts by weight are 20 parts, the parts by weight of antifoaming agent are 0.5 part.
The preparation method of component A includes the following steps：
1. under the rotating speed of 100 turns/min, epoxy resin, reactive diluent, stirring are added in clean stirred tank
It is even, premix a is made；
2. under the rotating speed of 200 turns/min, sequentially added into premix a aluminium triphosphate, antifoaming agent, talcum powder with
And titanium dioxide, then disperse 40min in 800 turns/min rotating speeds, the control of whipping process temperature is 20~25 DEG C；Then thereto
Glass flake is added, and is stirred until homogeneous dispersion.
In use, the quality proportioning of component A and B component is 1:0.23 is uniformly mixed.
Comparative example 2
A kind of preparation of solvent-free graphene oxide-glass flake anticorrosion paint, component A are prepared former by following mass parts
Material：The parts by weight for the glass flake that graphene oxide is modified are 30 parts, the parts by weight of epoxy resin are 30 parts, reactive diluent
Parts by weight be 10 parts, the parts by weight of aluminium triphosphate are 25 parts, titanium dioxide parts by weight are 20 parts, the parts by weight of antifoaming agent are
0.5 part.
The preparation method for the glass flake that graphene oxide is modified in component A includes the following steps：
(1) by 98% concentrated sulfuric acid and 30% hydrogen peroxide with 7:3 volume ratio is uniformly mixed, and it is molten to configure Piranha
Liquid；Then, glass flake is cleaned by ultrasonic five minutes as in acetone, ethyl alcohol and distilled water successively, takes out drying；It again will be clear
The glass flake washed after drying immerses Piranha solution, and 30min is stirred at a temperature of 90 DEG C；Again with distilled water flushing into
Property after dry, obtain hydroxyl surface modification glass flake；
(2) glass flake for modifying hydroxyl surface obtained immerses NH2CH2CH2CH2Si(OCH2CH3)3Toluene it is molten
In liquid, drying is taken out after sealing stirring 30min, the glass flake of amino surface modification, wherein NH is made2CH2CH2CH2Si
(OCH2CH3)3Toluene solution in NH2CH2CH2CH2Si(OCH2CH3)3Volume content be 6%；
(3) glass flake for modifying amino surface made from step (2) immerses the N of graphene oxide, N- diformamides
In dispersion liquid, at a temperature of 60~65 DEG C, it is stirred to react 18h；, after reaction, it is filtered, washs successively, vacuum is done
It is dry, the glass flake that graphene oxide is modified is made.
In the above method, the N of graphene oxide, in N- diformamide dispersion liquids graphene oxide with it is clear in step (1)
The quality proportioning for washing the glass flake after drying is 0.035:1.
The preparation method of component A includes the following steps：
1. under the rotating speed of 100 turns/min, epoxy resin, reactive diluent, stirring are added in clean stirred tank
It is even, premix a is made；
2. under the rotating speed of 200 turns/min, sequentially added into premix a aluminium triphosphate, antifoaming agent, talcum powder with
And titanium dioxide, then disperse 40min in 800 turns/min rotating speeds, the control of whipping process temperature is 20~25 DEG C；Then thereto
The glass flake that graphene oxide is modified is added, and is stirred until homogeneous dispersion.
In use, the quality proportioning of component A and B component is 1:0.23 is uniformly mixed.
The product testing of the various embodiments described above the results are shown in Table 2：
Table 2
As can be seen that graphene oxide-glass flake provided by the invention and waterborne polyurethane resin and castor-oil plant in table 2
The solvent free corrosion prevention coating property that oil is used in conjunction has superior performance, strong adhesive force resistance to compared with simple glass flake anticorrosive paint
Impact has better salt tolerance.
Claims (7)
1. a kind of solvent-free graphene oxide-glass flake anticorrosion paint, it is characterised in that：The coating includes component A and B groups
Point, the component A include graphene oxide be modified glass flake, epoxy resin, waterborne polyurethane resin, castor oil, activity
Diluent, aluminium triphosphate, talcum powder, antifoaming agent and titanium dioxide；The B component is epoxy hardener H633, by A when use
Component is with B component with 1:0.2~0.25 mass ratio uniformly mixes.
2. solvent-free graphene oxide-glass flake anticorrosion paint according to claim 1, which is characterized in that the A groups
The parts by weight for the glass flake that graphene oxide in point is modified are 15~30 parts, the parts by weight of epoxy resin are 30~40 parts,
Waterborne polyurethane resin parts by weight are 8~15 parts, castor oil parts by weight are 0.5~1 part, the parts by weight of reactive diluent be 5~
10 parts, the parts by weight of aluminium triphosphate be 12~25 parts, titanium dioxide parts by weight are 12~20 parts, the parts by weight of antifoaming agent are 0.2
~0.5 part.
3. solvent-free graphene oxide-glass flake anticorrosion paint according to any one of claim 1 to 2, feature
It is, the glass flake that the graphene oxide is modified is through the following steps that be made：
(1) glass flake after cleaning, drying is immersed into Piranha solution, 30min is stirred at a temperature of 90 DEG C；Then with steaming
Distilled water is dried after rinsing to neutrality, obtains the glass flake of hydroxyl surface modification；
(2) glass flake by hydroxyl surface modification obtained in step (1) immerses in the toluene solution of amino silicane coupling agent,
Drying is taken out after sealing stirring 30min, the glass flake of amino surface modification is made；
(3) glass flake for modifying amino surface made from step (2) immerses the N of graphene oxide, the dispersion of N- diformamides
In liquid, at a temperature of 60~80 DEG C, be stirred to react 12~for 24 hours, after reaction, be filtered, wash successively, vacuum it is dry
It is dry, the glass flake that graphene oxide is modified is made.
4. solvent-free graphene oxide-glass flake anticorrosion paint according to claim 3, which is characterized in that step (1)
Described in the cleaning, drying method of glass flake be：Glass flake is clear as ultrasound in acetone, ethyl alcohol and distilled water successively
It washes five minutes, takes out drying；The configuration method of the Piranha solution is：By 98% concentrated sulfuric acid and 30% hydrogen peroxide
With 7:3 volume ratio is uniformly mixed.
5. solvent-free graphene oxide-glass flake anticorrosion paint according to claim 3, which is characterized in that step (2)
Described in amino silicane coupling agent general formula be NH2(CH2)nSiX3, wherein n be 1~3 arbitrary integer, X be methoxyl group or
Any one in ethyoxyl；The volume content of amino silicane coupling agent is in the toluene solution of the amino silicane coupling agent
2%~8%.
6. solvent-free graphene oxide-glass flake anticorrosion paint according to claim 3, which is characterized in that step (3)
Described in graphene oxide N, in N- diformamide dispersion liquids graphene oxide with after the cleaning, drying described in step (1)
Glass flake quality proportioning be 0.01~0.05:1.
7. solvent-free graphene oxide-glass flake anticorrosion paint according to claim 1, which is characterized in that the A
Component is through the following steps that be made：
1. under the rotating speed of 100~300 turns/min, epoxy resin, reactive diluent, aqueous poly- ammonia are added in clean stirred tank
Ester resin and castor oil are stirred until homogeneous mixing, and premix a is made；
2. under the rotating speed of 200~400 turns/min, sequentially added into premix a aluminium triphosphate, antifoaming agent, talcum powder with
And titanium dioxide, then disperse 30~60min in 800~1300 turns/min rotating speeds, the control of whipping process temperature is no more than 40 DEG C；So
The glass flake that graphene oxide is modified is added thereto afterwards, and is stirred until homogeneous dispersion.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810352787.6A CN108570273B (en) | 2018-04-19 | 2018-04-19 | Solvent-free graphene oxide-glass flake anticorrosive paint and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810352787.6A CN108570273B (en) | 2018-04-19 | 2018-04-19 | Solvent-free graphene oxide-glass flake anticorrosive paint and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108570273A true CN108570273A (en) | 2018-09-25 |
| CN108570273B CN108570273B (en) | 2020-04-28 |
Family
ID=63575025
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810352787.6A Active CN108570273B (en) | 2018-04-19 | 2018-04-19 | Solvent-free graphene oxide-glass flake anticorrosive paint and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108570273B (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109486409A (en) * | 2018-11-29 | 2019-03-19 | 福建省东海海洋研究院 | The preparation method of the graphene-based coating of marine monitoring device |
| CN111732882A (en) * | 2020-07-04 | 2020-10-02 | 上海暄洋化工材料科技有限公司 | Composite sheet layer material modified water-based heavy-duty anticorrosive coating and preparation process thereof |
| CN112538313A (en) * | 2020-12-14 | 2021-03-23 | 武汉材料保护研究所有限公司 | Long-acting anticorrosion graphene modified solvent-free epoxy coating and preparation method thereof |
| CN115449248A (en) * | 2022-10-14 | 2022-12-09 | 山东京博装备制造安装有限公司 | Graphene heavy-duty anticorrosive paint for outer wall of earthing storage tank |
| CN116514533A (en) * | 2023-05-31 | 2023-08-01 | 宜兴兴贝耐火材料制品有限公司 | Special corrosion-resistant wear-resistant plastic for SNCR (selective non-catalytic reduction) of CFB (CFB) target area and preparation method of special corrosion-resistant wear-resistant plastic |
| CN118460069A (en) * | 2024-07-11 | 2024-08-09 | 中国电建集团华东勘测设计研究院有限公司 | Coating for deep sea equipment under pressure alternating working condition, and preparation method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104356868A (en) * | 2014-11-18 | 2015-02-18 | 江苏科技大学 | Coating composition directly painted on rust layer |
| CN105838195A (en) * | 2016-05-13 | 2016-08-10 | 江苏科技大学 | Waterborne epoxy anti-corrosion paint containing graphene oxide and preparing method of waterborne epoxy anti-corrosion paint |
| CN106243922A (en) * | 2016-08-23 | 2016-12-21 | 西北永新涂料有限公司 | A kind of low-viscosity solvent-free graphite-epoxy alkene glass-flake coating and preparation method thereof |
| CN107266999A (en) * | 2017-05-17 | 2017-10-20 | 青岛瑞利特新材料科技有限公司 | A kind of watersoluble plumbago alkene anticorrosive paint and preparation method thereof |
| CN107603358A (en) * | 2017-09-18 | 2018-01-19 | 浙江汉邦化工有限公司 | A kind of preparation method of the fluorine carbon anticorrosive paint of composite graphite alkene |
-
2018
- 2018-04-19 CN CN201810352787.6A patent/CN108570273B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104356868A (en) * | 2014-11-18 | 2015-02-18 | 江苏科技大学 | Coating composition directly painted on rust layer |
| CN105838195A (en) * | 2016-05-13 | 2016-08-10 | 江苏科技大学 | Waterborne epoxy anti-corrosion paint containing graphene oxide and preparing method of waterborne epoxy anti-corrosion paint |
| CN106243922A (en) * | 2016-08-23 | 2016-12-21 | 西北永新涂料有限公司 | A kind of low-viscosity solvent-free graphite-epoxy alkene glass-flake coating and preparation method thereof |
| CN107266999A (en) * | 2017-05-17 | 2017-10-20 | 青岛瑞利特新材料科技有限公司 | A kind of watersoluble plumbago alkene anticorrosive paint and preparation method thereof |
| CN107603358A (en) * | 2017-09-18 | 2018-01-19 | 浙江汉邦化工有限公司 | A kind of preparation method of the fluorine carbon anticorrosive paint of composite graphite alkene |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109486409A (en) * | 2018-11-29 | 2019-03-19 | 福建省东海海洋研究院 | The preparation method of the graphene-based coating of marine monitoring device |
| CN111732882A (en) * | 2020-07-04 | 2020-10-02 | 上海暄洋化工材料科技有限公司 | Composite sheet layer material modified water-based heavy-duty anticorrosive coating and preparation process thereof |
| CN112538313A (en) * | 2020-12-14 | 2021-03-23 | 武汉材料保护研究所有限公司 | Long-acting anticorrosion graphene modified solvent-free epoxy coating and preparation method thereof |
| CN112538313B (en) * | 2020-12-14 | 2022-04-29 | 武汉材料保护研究所有限公司 | Long-acting anticorrosion graphene modified solvent-free epoxy coating and preparation method thereof |
| CN115449248A (en) * | 2022-10-14 | 2022-12-09 | 山东京博装备制造安装有限公司 | Graphene heavy-duty anticorrosive paint for outer wall of earthing storage tank |
| CN116514533A (en) * | 2023-05-31 | 2023-08-01 | 宜兴兴贝耐火材料制品有限公司 | Special corrosion-resistant wear-resistant plastic for SNCR (selective non-catalytic reduction) of CFB (CFB) target area and preparation method of special corrosion-resistant wear-resistant plastic |
| CN118460069A (en) * | 2024-07-11 | 2024-08-09 | 中国电建集团华东勘测设计研究院有限公司 | Coating for deep sea equipment under pressure alternating working condition, and preparation method and application thereof |
| CN118460069B (en) * | 2024-07-11 | 2024-10-15 | 中国电建集团华东勘测设计研究院有限公司 | Coating for deep sea equipment under pressure alternating working condition, and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108570273B (en) | 2020-04-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108570273A (en) | A kind of solvent-free graphene oxide-glass flake anticorrosion paint and preparation method thereof | |
| CN104508056B (en) | adjustable material | |
| CN103360931A (en) | Waterborne strippable coating for temporarily protecting metal | |
| CN109517516B (en) | Certified bentonite modified waterborne polyurethane coating and preparation method thereof | |
| CN1106433C (en) | Nm-class Ti polymer paint | |
| CN111961412B (en) | Polysilazane modified epoxy single-component anticorrosive coating slurry, coating and preparation method | |
| EP2895570A2 (en) | Siloxane organic hybrid materials providing flexibility to epoxy-based coating compositons | |
| CN108559358A (en) | A kind of solvent-free graphene-glass flake anticorrosion paint and preparation method thereof | |
| CN104774526A (en) | Room temperature-curing two-component aqueous epoxy zinc-rich primer | |
| CN107312435A (en) | A kind of super water-fast self-repair type Aqueous acrylic urethane coating and preparation method thereof | |
| CN112724428A (en) | Preparation method and application of weather-resistant wear-resistant hydrophobic auxiliary agent | |
| CN108441097A (en) | A kind of nanometer of low surface energy anti-fouling paint and preparation method | |
| CN100451079C (en) | Bicomponent epoxy zinc enriched base paint and its manufacturing method | |
| CN114958179A (en) | High-adhesion stain-resistant water-based paint and preparation method and application thereof | |
| KR102103537B1 (en) | Funtional coating material | |
| CN110305563A (en) | A kind of preparation method of antibacterial anticorrosion waterborne epoxy coatings | |
| CN108559376B (en) | High-hardness low-contact-angle emulsion coating and application thereof | |
| CN110982387B (en) | Water-based epoxy coating with good adhesive force and corrosion resistance on surface of metal substrate and preparation method thereof | |
| CN111303727B (en) | Solvent-free super-thick-paste organic-inorganic hybrid nano modified heavy-duty anticorrosive paint and preparation method thereof | |
| CN112210274A (en) | Moisture-curable epoxy resin coating and preparation method thereof | |
| CN103992721B (en) | A kind of polyaniline-modified many carboxyls epoxy resin base material for Treatment of Metal Surface | |
| CN109439144A (en) | A kind of ocean engineering anticorrosion coating and preparation method thereof | |
| CN115304973A (en) | Microcosmic corrosion type nylon glass fiber treating agent and preparation method and application thereof | |
| CN114410151A (en) | Super-infiltrated metal net film and preparation method and application thereof | |
| CN113667117A (en) | Preparation method of water-soluble polyaniline, water-soluble polyaniline-containing high-temperature conductive primer for glass fiber reinforced plastics and preparation method of water-soluble polyaniline-containing water-soluble high-temperature conductive primer |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CP01 | Change in the name or title of a patent holder | ||
| CP01 | Change in the name or title of a patent holder |
Address after: 213164 No.205, Fenglin South Road, Wujin national high tech Industrial Development Zone, Changzhou City, Jiangsu Province Patentee after: Jiangsu Jinhua heavy anticorrosive coating Co.,Ltd. Address before: 213164 No.205, Fenglin South Road, Wujin national high tech Industrial Development Zone, Changzhou City, Jiangsu Province Patentee before: SHANGHAI ZHENHUA HEAVY INDUSTRY CHANGZHOU COATINGS Co.,Ltd. |