CN110003777A - A kind of composite epoxy zinc-enriched paint and preparation method thereof - Google Patents
A kind of composite epoxy zinc-enriched paint and preparation method thereof Download PDFInfo
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- CN110003777A CN110003777A CN201910362852.8A CN201910362852A CN110003777A CN 110003777 A CN110003777 A CN 110003777A CN 201910362852 A CN201910362852 A CN 201910362852A CN 110003777 A CN110003777 A CN 110003777A
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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
- 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
- C09D5/10—Anti-corrosive paints containing metal dust
- C09D5/106—Anti-corrosive paints containing metal dust containing Zn
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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
- C09D7/70—Additives characterised by shape, e.g. fibres, flakes or microspheres
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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
- C08K3/08—Metals
- C08K2003/0893—Zinc
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Abstract
The invention belongs to anticorrosive paint technical fields, provide a kind of composite epoxy zinc-enriched paint, which is characterized in that including following components: 0.2~2wt% of polyacrylate coating modification graphene oxide；5~20wt% of epoxy resin；50 5~20wt% of curing agent of polyamide 6；30~60wt% of zinc powder；20~40wt% of mixed solvent；0.1~1wt% of agent mixture.The present invention utilizes esterification dehydration, acrylate polymer with hydroxyl group is modified with the graphene oxide prepared using Hummers method, obtain polyacrylate coating modification graphene oxide, then stirring and ultrasonic disperse are utilized, it is scattered in epoxy resin dicyandiamide solution, it will be proportionally added into zinc powder, realize and disperse through high speed grinding after auxiliary agent is added and is uniformly dispersed；When coating, curing agent is added with ratio as required；After coating, ambient temperature curable film forming.
Description
Technical field
The present invention relates to anticorrosive paint technical fields, and in particular to a kind of composite epoxy zinc-enriched paint and its preparation side
Method.
Background technique
Most important means of the coating antiseptic as metal protection, are applied extensively.With modern industry and scientific skill
The progress of art, many technical fields propose requirements at the higher level to coating material, except meet basic mechanical property such as hardness, attachment
Power, toughness and shock resistance, chemically-resistant is rotten, weather-proof, and good electrical insulation performance and chemical qualitativity etc. are outer, it is also necessary to which coating is answered certain
It can be had good conductive property with aspect.Epoxy zinc-enriched paint is one of anticorrosive paint, because of its excellent physics
Mechanical performance and antiseptic property and be used widely.The zinc powder that the coating is generally needed to be added mass fraction 70%~80% is made
For sacrificial anode, but if zinc content is excessively high, coating is easy porous, and adhesive force decline also can with the binding force of intermediate coat
It reduces.And if zinc content is too low, it cannot achieve electric action interconnected in coating between zinc powder.It can if be doped into
Conductive nano material is advantageously implemented in the case where zinc content reduces, still so that forming conductive channel between zinc powder
Keep good electric action.Graphene or graphene oxide are the materials with great development prospect to emerge in recent years, it
With performances such as unique conductive, thermally conductive, ventilative, mechanics, applies it to the fields such as coating and have become what people were attracted attention
Focus.But due to the nanometer planar structure of graphene, how to be effectively dispersed in polymer matrix, inhibit
Its nanocluster effect, to give full play to the particular advantages of graphene or graphene oxide, there are also to be further improved.
Summary of the invention
For the defects in the prior art, the present invention provides a kind of composite epoxy zinc-enriched paint, with excellent corrosion resistant
Lose antiseptic property.
In a first aspect, composite epoxy zinc-enriched paint provided by the invention, including following components:
Optionally, the epoxide number range of the epoxy resin is 0.10~0.55.
Optionally, the particle size of the zinc powder is 300 mesh~800 mesh.
Optionally, the mixed solvent includes including following components:
40~50vol% of butyl acetate；
30~50vol% of dimethylbenzene；
5~25vol% of propylene glycol methyl ether acetate.
Optionally, the agent mixture includes anti-settling auxiliary agent, levelling agent, the wetting agent for being in mass ratio 1:1:1:1
And defoaming agent.
Second aspect, the preparation method of composite epoxy zinc-enriched paint as mentioned provided by the invention, the composite epoxy
Zinc-rich paint includes component A and B component, is specifically comprised the following steps:
Epoxy resin: being dissolved in the in the mixed solvent of 60~80% volume fractions by step S1, is stirred 1~4h, is kept its molten
Solution is uniformly dispersed；
Step S2: agent mixture being added in the product of step S1, stirs 5~10min, and polyacrylate packet is added
Cover modified graphene oxide, 10~30min of ultrasonic disperse；
Step S3: being added zinc powder into the product of step S2 under the revolving speed of 500~800r/min, after addition,
0.5~4h is stirred under the revolving speed of 2000~3000r/min to get the component A of the composite epoxy zinc-enriched paint；
Step S4: the dissolution of 50 curing agent of polyamide 6 is dispersed in the in the mixed solvent of remaining 20~40% volume fractions, i.e.,
Obtain the B component of the composite epoxy zinc-enriched paint.
Optionally, the preparation process of the polyacrylate coating modification graphene oxide is as follows:
Step S11: methyl methacrylate, styrene, butyl acrylate, hydroxy-ethyl acrylate are mixed, azo is added
Bis-isobutyronitrile is uniformly dissolved；
Step S12: acetonitrile is poured into the reaction vessel with condensation reflux unit, is warming up to 60 DEG C~70 DEG C, will be walked
Rapid one obtained reaction mixture gradually instills in acetonitrile solvent, and time for adding is controlled in 4~8h, after being added dropwise, after of continuing rising
To 80 DEG C~85 DEG C, 4~8h of reaction is cooled to room temperature temperature after reaction, obtains polyacrylate polymers；
Step S13: the graphene oxide relative to polyacrylate polymers 5wt%~20wt% is added to step
In the reaction system of S12, ultrasonic 30min~60min；
Step S14: the dicyclohexylcarbodiimide with quality such as graphene oxides, room are added into the product of step S13
Under temperature, 24~72h is stirred；
Step S15: the reaction product of step S14 is removed into unreacted polyacrylate through centrifugation, then through N, N- bis-
Methylformamide washing, then be centrifugated, obtain the polyacrylate coating modification graphene oxide.
Optionally, the polyacrylate polymers include the raw material of following components:
Optionally, the graphene oxide includes following components:
Optionally, the graphene oxide is prepared using following steps:
Step S21: by reaction vessel and the concentrated sulfuric acid in 0 DEG C~4 DEG C cooling 0.5~1h；
Step S22: crystalline graphite powder, sodium nitrate, potassium permanganate are spread in closed reaction vessel layer by layer, then slowly
Drainage the concentrated sulfuric acid is added, then closed reaction vessel, and tightening in -1 DEG C~1 DEG C 8~10h of reaction, then by its lid moves to
5~8h is reacted in 90~140 DEG C of baking oven；
Step S23: the product of step S22 being cooled to room temperature and is poured into beaker, be added 1000~2000ml go from
Sub- water stirring is added hydrogen peroxide to bright orange or khaki in the case of stirring, adds concentrated hydrochloric acid stirring；
Step S24: being washed with deionized water centrifugal filtration to neutrality, 40 DEG C~60 DEG C vacuum dryings, obtains the oxygen
Graphite alkene.
Beneficial effects of the present invention:
1. composite epoxy zinc-enriched paint of the invention will have the acrylate of hydroxyl group using esterification dehydration
Polymer is modified with the graphene oxide prepared using Hummers method, obtains polyacrylate coating modification graphite oxide
Alkene is scattered in epoxy resin dicyandiamide solution then using stirring and ultrasonic disperse, will be uniformly dispersed auxiliary agent is added
Afterwards, it is proportionally added into zinc powder, realizes and disperses through high speed grinding；When coating, curing agent is added with ratio as required；It, can after coating
Room temperature curing film forming.
2. modified graphene oxide can be dispersed in resinous coat with lamella pattern due to the connection of chemical bond
In, the solidify coating barrier properties excellent using graphene oxide are acted in conjunction with the sacrificial anode of zinc powder, so that having excellent
Corrosion-resistant antiseptic property.
3. the present invention by the surface coating modification to graphene oxide, is conducive to its uniformly dividing in coating resin
It dissipates, it is made to give full play to its performance in system；Due to the surface coating modification of graphene oxide, make it in epoxy zinc-enriched paint
Middle realization is evenly dispersed, advantageously reduces zinc powder use, and improve coating antiseptic and mechanical property.
Specific embodiment
The embodiment of technical solution of the present invention will be described in detail below.Following embodiment is only used for clearer
Ground illustrates technical solution of the present invention, therefore is intended only as example, and not intended to limit the protection scope of the present invention.
It should be noted that unless otherwise indicated, technical term or scientific term used in this application should be this hair
The ordinary meaning that bright one of ordinary skill in the art are understood.
The concentrated sulfuric acid employed in the embodiment of the present invention is the concentrated sulfuric acid that conventional-volume concentration is 98%, used dense salt
Acid is the concentrated hydrochloric acid that conventional-volume concentration is 37%.
Embodiment 1
The preparation method that the present embodiment prepares composite epoxy zinc-enriched paint is shown in following steps:
One, graphene oxide is prepared
Raw material needed for preparing graphene oxide and component are prepared by table 1.
Table 1
| Raw material | Proportion | Quality |
| Crystalline graphite powder | 17wt% | 51g |
| Sodium nitrate | 1wt% | 3g |
| Potassium permanganate | 1wt% | 3g |
| The concentrated sulfuric acid | 12wt% | 36g |
| Hydrogen peroxide | 29wt% | 87g |
| Concentrated hydrochloric acid | 40wt% | 120g |
| It is total | 100wt% | 300g |
The step of preparing graphene oxide sees following S21~S24.
Step S21: by reaction vessel and the concentrated sulfuric acid in 0 DEG C of cooling 1h；
Step S22: crystalline graphite powder, sodium nitrate, potassium permanganate are spread in closed reaction vessel layer by layer, then slowly
Drainage the concentrated sulfuric acid is added, then closed reaction vessel, and tightening in -1 DEG C of reaction 10h, then by its lid moves to 140 DEG C
5h is reacted in baking oven；
Step S23: the product of step S22 being cooled to room temperature and is poured into beaker, and the deionized water that 1000ml is added is stirred
It mixes, hydrogen peroxide is added in the case of stirring to bright orange or khaki, adds concentrated hydrochloric acid stirring；
Step S24: being washed with deionized water centrifugal filtration to neutrality, 40 DEG C of vacuum dryings, obtains the graphite oxide
Alkene.
Two, polyacrylate coating modification graphene oxide is prepared
Raw material needed for preparing polyacrylate coating modification graphene oxide and component are prepared by table 2.
Table 2
| Raw material | Proportion | Quality |
| Methyl methacrylate | 10wt% | 20g |
| Styrene | 15wt% | 30g |
| Butyl acrylate | 10wt% | 20g |
| Hydroxy-ethyl acrylate | 1wt% | 2g |
| Azodiisobutyronitrile | 0.5wt% | 1g |
| Acetonitrile | 63.5wt% | 127g |
| Polyacrylate polymers (above total) | 100wt% | 200g |
| Graphene oxide | 5wt% (relative to polyacrylate polymers) | 10g |
| Dicyclohexylcarbodiimide | 5wt% (relative to polyacrylate polymers) | 10g |
The step of preparing polyacrylate coating modification graphene oxide sees following S11~S15.
S11: methyl methacrylate, styrene, butyl acrylate, hydroxy-ethyl acrylate are mixed, it is different that azo two is added
Butyronitrile is uniformly dissolved；
S12: acetonitrile is poured into the reaction vessel with condensation reflux unit, 60 DEG C is warming up to, step 1 is obtained
Reaction mixture gradually instills in acetonitrile solvent, and time for adding is controlled in 8h, after being added dropwise, is continuously heating to 80 DEG C, reaction
8h is cooled to room temperature after reaction, obtains polyacrylate polymers；
S13: the graphene oxide relative to polyacrylate polymers 5wt% is added to the reaction system of step S12
In, ultrasonic 60min；
S14: the dicyclohexylcarbodiimide with quality such as graphene oxides being added into the product of step S13, at room temperature,
Stir 72h；
S15: the reaction product of step S14 is removed into unreacted polyacrylate through centrifugation, then through N, N- dimethyl
Formamide washing, then be centrifugated, obtain the polyacrylate coating modification graphene oxide.
Three, composite epoxy zinc-enriched paint is prepared
Raw material needed for preparing composite epoxy zinc-enriched paint and component are prepared by table 3.
Table 3
The step of preparing composite epoxy zinc-enriched paint sees following S1~S4.
Epoxy resin: being dissolved in the in the mixed solvent of 80% volume fraction by S1, is stirred 4h, is made it dissolve and be uniformly dispersed；
S2: agent mixture being added in the product of step S1, stirs 10min, and polyacrylate coating modification is added
Graphene oxide, ultrasonic disperse 30min；
S3: being added zinc powder into the product of step S2 under the revolving speed of 500r/min, after addition, in 3000r/min
Revolving speed under stirring 0.5h to get the composite epoxy zinc-enriched paint component A；
S4: the in the mixed solvent of remaining 20% volume fraction is dispersed to get described multiple by the dissolution of 50 curing agent of polyamide 6
Close the B component of epoxy zinc-enriched paint.
Four, the use of composite epoxy zinc-enriched paint
In use, being coated on surface of bottom material, it can be achieved that room temperature is solid after component A and B component are mixed evenly by metering
It is melted into film.
Embodiment 2
The preparation method that the present embodiment prepares composite epoxy zinc-enriched paint is shown in following steps:
One, graphene oxide is prepared
Raw material needed for preparing graphene oxide and component are prepared by table 4.
Table 4
| Raw material | Proportion | Quality |
| Crystalline graphite powder | 20wt% | 60g |
| Sodium nitrate | 3wt% | 9g |
| Potassium permanganate | 5wt% | 15g |
| The concentrated sulfuric acid | 10wt% | 30g |
| Hydrogen peroxide | 32wt% | 96g |
| Concentrated hydrochloric acid | 30wt% | 90g |
| It is total | 100wt% | 300g |
The step of preparing graphene oxide sees following S21~S24.
Step S21: by reaction vessel and the concentrated sulfuric acid in 1 DEG C of cooling 0.8h；
Step S22: crystalline graphite powder, sodium nitrate, potassium permanganate are spread in closed reaction vessel layer by layer, then slowly
Drainage the concentrated sulfuric acid is added, then closed reaction vessel, and tightening in -0.5 DEG C of reaction 9.5h, then by its lid moves to 130 DEG C
Baking oven in react 6h；
Step S23: the product of step S22 being cooled to room temperature and is poured into beaker, and the deionized water that 1500ml is added is stirred
It mixes, hydrogen peroxide is added in the case of stirring to bright orange or khaki, adds concentrated hydrochloric acid stirring；
Step S24: being washed with deionized water centrifugal filtration to neutrality, 45 DEG C of vacuum dryings, obtains the graphite oxide
Alkene.
Two, polyacrylate coating modification graphene oxide is prepared
Raw material needed for preparing polyacrylate coating modification graphene oxide and component are prepared by table 5.
Table 5
| Raw material | Proportion | Quality |
| Methyl methacrylate | 25wt% | 50g |
| Styrene | 5wt% | 10g |
| Butyl acrylate | 5wt% | 10g |
| Hydroxy-ethyl acrylate | 2wt% | 4g |
| Azodiisobutyronitrile | 3wt% | 6g |
| Acetonitrile | 60wt% | 120g |
| Polyacrylate polymers (above total) | 100wt% | 200g |
| Graphene oxide | 20wt% (relative to polyacrylate polymers) | 40g |
| Dicyclohexylcarbodiimide | 20wt% (relative to polyacrylate polymers) | 40g |
The step of preparing polyacrylate coating modification graphene oxide sees following S11~S15.
S11: methyl methacrylate, styrene, butyl acrylate, hydroxy-ethyl acrylate are mixed, it is different that azo two is added
Butyronitrile is uniformly dissolved；
S12: acetonitrile is poured into the reaction vessel with condensation reflux unit, 64 DEG C is warming up to, step 1 is obtained
Reaction mixture gradually instills in acetonitrile solvent, and time for adding is controlled in 6h, after being added dropwise, is continuously heating to 81 DEG C, reaction
7h is cooled to room temperature after reaction, obtains polyacrylate polymers；
S13: the graphene oxide relative to polyacrylate polymers 20wt% is added to the reaction system of step S12
In, ultrasonic 30min；
S14: the dicyclohexylcarbodiimide with quality such as graphene oxides being added into the product of step S13, at room temperature,
Stir 60h；
S15: the reaction product of step S14 is removed into unreacted polyacrylate through centrifugation, then through N, N- dimethyl
Formamide washing, then be centrifugated, obtain the polyacrylate coating modification graphene oxide.
Three, composite epoxy zinc-enriched paint is prepared
Raw material needed for preparing composite epoxy zinc-enriched paint and component are prepared by table 6.
Table 6
The step of preparing composite epoxy zinc-enriched paint sees following S1~S4.
Epoxy resin: being dissolved in the in the mixed solvent of 60% volume fraction by S1, is stirred 1h, is made it dissolve and be uniformly dispersed；
S2: agent mixture being added in the product of step S1, stirs 5min, and polyacrylate coating modification oxygen is added
Graphite alkene, ultrasonic disperse 10min；
S3: being added zinc powder into the product of step S2 under the revolving speed of 800r/min, after addition, in 2000r/min
Revolving speed under stirring 4h to get the composite epoxy zinc-enriched paint component A；
S4: the in the mixed solvent of remaining 40% volume fraction is dispersed to get described multiple by the dissolution of 50 curing agent of polyamide 6
Close the B component of epoxy zinc-enriched paint.
Four, the use of composite epoxy zinc-enriched paint
In use, being coated on surface of bottom material, it can be achieved that room temperature is solid after component A and B component are mixed evenly by metering
It is melted into film.
Embodiment 3
The preparation method that the present embodiment prepares composite epoxy zinc-enriched paint is shown in following steps:
One, graphene oxide is prepared
Raw material needed for preparing graphene oxide and component are prepared by table 7.
Table 7
| Raw material | Proportion | Quality |
| Crystalline graphite powder | 16wt% | 48g |
| Sodium nitrate | 1.5wt% | 4.5g |
| Potassium permanganate | 2.5wt% | 7.5g |
| The concentrated sulfuric acid | 11wt% | 33g |
| Hydrogen peroxide | 40wt% | 120g |
| Concentrated hydrochloric acid | 29wt% | 87g |
| It is total | 100wt% | 300g |
The step of preparing graphene oxide sees following S21~S24.
Step S21: by reaction vessel and the concentrated sulfuric acid in 2 DEG C of cooling 0.6h；
Step S22: crystalline graphite powder, sodium nitrate, potassium permanganate are spread in closed reaction vessel layer by layer, then slowly
Drainage the concentrated sulfuric acid is added, then closed reaction vessel, and tightening in 0.5 DEG C of reaction 8.5h, then by its lid moves to 120 DEG C
Baking oven in react 7h；
Step S23: the product of step S22 being cooled to room temperature and is poured into beaker, and the deionized water that 1700ml is added is stirred
It mixes, hydrogen peroxide is added in the case of stirring to bright orange or khaki, adds concentrated hydrochloric acid stirring；
Step S24: being washed with deionized water centrifugal filtration to neutrality, 55 DEG C of vacuum dryings, obtains the graphite oxide
Alkene.
Two, polyacrylate coating modification graphene oxide is prepared
Raw material needed for preparing polyacrylate coating modification graphene oxide and component are prepared by table 8.
Table 8
The step of preparing polyacrylate coating modification graphene oxide sees following S11~S15.
S11: methyl methacrylate, styrene, butyl acrylate, hydroxy-ethyl acrylate are mixed, it is different that azo two is added
Butyronitrile is uniformly dissolved；
S12: acetonitrile is poured into the reaction vessel with condensation reflux unit, 68 DEG C is warming up to, step 1 is obtained
Reaction mixture gradually instills in acetonitrile solvent, and time for adding is controlled in 5h, after being added dropwise, is continuously heating to 83 DEG C, reaction
6h is cooled to room temperature after reaction, obtains polyacrylate polymers；
S13: the graphene oxide relative to polyacrylate polymers 10wt% is added to the reaction system of step S12
In, ultrasonic 50min；
S14: the dicyclohexylcarbodiimide with quality such as graphene oxides being added into the product of step S13, at room temperature,
Stirring is for 24 hours；
S15: the reaction product of step S14 is removed into unreacted polyacrylate through centrifugation, then through N, N- dimethyl
Formamide washing, then be centrifugated, obtain the polyacrylate coating modification graphene oxide.
Three, composite epoxy zinc-enriched paint is prepared
Raw material needed for preparing composite epoxy zinc-enriched paint and component are prepared by table 9.
Table 9
The step of preparing composite epoxy zinc-enriched paint sees following S1~S4.
Epoxy resin: being dissolved in the in the mixed solvent of 75% volume fraction by S1, is stirred 3h, is made it dissolve and be uniformly dispersed；
S2: agent mixture being added in the product of step S1, stirs 8min, and polyacrylate coating modification oxygen is added
Graphite alkene, ultrasonic disperse 15min；
S3: being added zinc powder into the product of step S2 under the revolving speed of 700r/min, after addition, in 2800r/min
Revolving speed under stirring 3h to get the composite epoxy zinc-enriched paint component A；
S4: the in the mixed solvent of remaining 25% volume fraction is dispersed to get described multiple by the dissolution of 50 curing agent of polyamide 6
Close the B component of epoxy zinc-enriched paint.
Four, the use of composite epoxy zinc-enriched paint
In use, being coated on surface of bottom material, it can be achieved that room temperature is solid after component A and B component are mixed evenly by metering
It is melted into film.
Embodiment 4
The preparation method that the present embodiment prepares composite epoxy zinc-enriched paint is shown in following steps:
One, graphene oxide is prepared
Raw material needed for preparing graphene oxide and component are prepared by table 10.
Table 10
| Raw material | Proportion | Quality |
| Crystalline graphite powder | 15wt% | 45g |
| Sodium nitrate | 2wt% | 6g |
| Potassium permanganate | 2wt% | 6g |
| The concentrated sulfuric acid | 25wt% | 75g |
| Hydrogen peroxide | 28wt% | 84g |
| Concentrated hydrochloric acid | 28wt% | 84g |
| It is total | 100wt% | 300g |
The step of preparing graphene oxide sees following S21~S24.
Step S21: by reaction vessel and the concentrated sulfuric acid in 4 DEG C of cooling 0.5h；
Step S22: crystalline graphite powder, sodium nitrate, potassium permanganate are spread in closed reaction vessel layer by layer, then slowly
Drainage the concentrated sulfuric acid is added, then closed reaction vessel, and tightening in 1 DEG C of reaction 8h, then by its lid moves to 90 DEG C of baking oven
Middle reaction 8h；
Step S23: the product of step S22 being cooled to room temperature and is poured into beaker, and the deionized water that 2000ml is added is stirred
It mixes, hydrogen peroxide is added in the case of stirring to bright orange or khaki, adds concentrated hydrochloric acid stirring；
Step S24: being washed with deionized water centrifugal filtration to neutrality, 60 DEG C of vacuum dryings, obtains the graphite oxide
Alkene.
Two, polyacrylate coating modification graphene oxide is prepared
Raw material needed for preparing polyacrylate coating modification graphene oxide and component are prepared by table 11.
Table 11
The step of preparing polyacrylate coating modification graphene oxide sees following S11~S15.
S11: methyl methacrylate, styrene, butyl acrylate, hydroxy-ethyl acrylate are mixed, it is different that azo two is added
Butyronitrile is uniformly dissolved；
S12: acetonitrile is poured into the reaction vessel with condensation reflux unit, 70 DEG C is warming up to, step 1 is obtained
Reaction mixture gradually instills in acetonitrile solvent, and time for adding is controlled in 4h, after being added dropwise, is continuously heating to 85 DEG C, reaction
4h is cooled to room temperature after reaction, obtains polyacrylate polymers；
S13: the graphene oxide relative to polyacrylate polymers 8wt% is added to the reaction system of step S12
In, ultrasonic 40min；
S14: the dicyclohexylcarbodiimide with quality such as graphene oxides being added into the product of step S13, at room temperature,
Stir 48h；
S15: the reaction product of step S14 is removed into unreacted polyacrylate through centrifugation, then through N, N- dimethyl
Formamide washing, then be centrifugated, obtain the polyacrylate coating modification graphene oxide.
Three, composite epoxy zinc-enriched paint is prepared
Raw material needed for preparing composite epoxy zinc-enriched paint and component are prepared by table 12.
Table 12
The step of preparing composite epoxy zinc-enriched paint sees following S1~S4.
Epoxy resin: being dissolved in the in the mixed solvent of 65% volume fraction by S1, is stirred 2h, is made it dissolve and be uniformly dispersed；
S2: agent mixture being added in the product of step S1, stirs 6min, and polyacrylate coating modification oxygen is added
Graphite alkene, ultrasonic disperse 25min；
S3: being added zinc powder into the product of step S2 under the revolving speed of 600r/min, after addition, in 2200r/min
Revolving speed under stirring 2h to get the composite epoxy zinc-enriched paint component A；
S4: the in the mixed solvent of remaining 35% volume fraction is dispersed to get described multiple by the dissolution of 50 curing agent of polyamide 6
Close the B component of epoxy zinc-enriched paint.
Four, the use of composite epoxy zinc-enriched paint
In use, being coated on surface of bottom material, it can be achieved that room temperature is solid after component A and B component are mixed evenly by metering
It is melted into film.
The mode of spraying is respectively adopted in composite epoxy zinc-enriched paint prepared by 1~embodiment of embodiment 4, is coated on ruler
On very little identical tinplate, the coat weight on each piece of tinplate is identical, and error is no more than ± 0.1g.Coating is finished
Tinplate at room temperature spontaneous curing form a film, test its performance after 7 days, test result is shown in Table 13.
Table 13
Unless specifically stated otherwise, the numerical value otherwise illustrated in these embodiments is not limit the scope of the invention.?
In all examples shown and described herein, unless otherwise prescribed, any occurrence should be construed as merely illustratively, and
Not by way of limitation, therefore, other examples of exemplary embodiment can have different values.
Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the present invention., rather than its limitations；To the greatest extent
Pipe present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that: its according to
So be possible to modify the technical solutions described in the foregoing embodiments, or to some or all of the technical features into
Row equivalent replacement；And these are modified or replaceed, various embodiments of the present invention technology that it does not separate the essence of the corresponding technical solution
The range of scheme should all cover within the scope of the claims and the description of the invention.
Claims (10)
1. a kind of composite epoxy zinc-enriched paint, which is characterized in that including following components:
2. composite epoxy zinc-enriched paint according to claim 1, which is characterized in that the epoxide number range of the epoxy resin
It is 0.10~0.55.
3. composite epoxy zinc-enriched paint according to claim 1, which is characterized in that the particle size of the zinc powder is 300
Mesh~800 mesh.
4. composite epoxy zinc-enriched paint according to claim 1, which is characterized in that the mixed solvent includes including following
Component:
40~50vol% of butyl acetate；
30~50vol% of dimethylbenzene；
5~25vol% of propylene glycol methyl ether acetate.
5. composite epoxy zinc-enriched paint according to claim 1, which is characterized in that the agent mixture includes pressing quality
Than anti-settling auxiliary agent, levelling agent, wetting agent and the defoaming agent for 1:1:1:1.
6. such as the preparation method of composite epoxy zinc-enriched paint according to any one of claims 1 to 5, which is characterized in that described
Composite epoxy zinc-enriched paint includes component A and B component, is specifically comprised the following steps:
Epoxy resin: being dissolved in the in the mixed solvent of 60~80% volume fractions by step S1, stirs 1~4h, is made it dissolve point
It dissipates uniform；
Step S2: agent mixture being added in the product of step S1, stirs 5~10min, and polyacrylate cladding is added and changes
Property graphene oxide, 10~30min of ultrasonic disperse；
Step S3: being added zinc powder into the product of step S2 under the revolving speed of 500~800r/min, after addition, 2000
0.5~4h is stirred under the revolving speed of~3000r/min to get the component A of the composite epoxy zinc-enriched paint；
Step S4: the in the mixed solvent of remaining 20~40% volume fractions is dispersed to get institute by the dissolution of 50 curing agent of polyamide 6
State the B component of composite epoxy zinc-enriched paint.
7. the preparation method of composite epoxy zinc-enriched paint according to claim 6, which is characterized in that the polyacrylate
The preparation process of coating modification graphene oxide is as follows:
Step S11: methyl methacrylate, styrene, butyl acrylate, hydroxy-ethyl acrylate are mixed, it is different that azo two is added
Butyronitrile is uniformly dissolved；
Step S12: acetonitrile is poured into the reaction vessel with condensation reflux unit, 60 DEG C~70 DEG C is warming up to, by step 1
Obtained reaction mixture gradually instills in acetonitrile solvent, and time for adding is controlled in 4~8h, after being added dropwise, is continuously heating to
80 DEG C~85 DEG C, 4~8h of reaction is cooled to room temperature after reaction, obtains polyacrylate polymers；
Step S13: the graphene oxide relative to polyacrylate polymers 5wt%~20wt% is added to step S12's
In reaction system, ultrasonic 30min~60min；
Step S14: the dicyclohexylcarbodiimide with quality such as graphene oxides being added into the product of step S13, at room temperature,
Stir 24~72h；
Step S15: the reaction product of step S14 is removed into unreacted polyacrylate through centrifugation, then through N, N- dimethyl
Formamide washing, then be centrifugated, obtain the polyacrylate coating modification graphene oxide.
8. the preparation method of composite epoxy zinc-enriched paint according to claim 7, which is characterized in that the polyacrylate
Polymer includes the raw material of following components:
9. the preparation method of composite epoxy zinc-enriched paint according to claim 7, which is characterized in that the graphene oxide
Including following components:
10. the preparation method of composite epoxy zinc-enriched paint according to claim 7, which is characterized in that the graphite oxide
Alkene is prepared using following steps:
Step S21: by reaction vessel and the concentrated sulfuric acid in 0 DEG C~4 DEG C cooling 0.5~1h；
Step S22: crystalline graphite powder, sodium nitrate, potassium permanganate are spread in closed reaction vessel layer by layer, then slowly drawn
Stream is added the concentrated sulfuric acid, closed reaction vessel, and tightening in -1 DEG C~1 DEG C 8~10h of reaction, then by its lid, then move to 90~
5~8h is reacted in 140 DEG C of baking oven；
Step S23: after reaction terminates, being cooled to room temperature and pour into beaker, and the deionization of 1000~2000ml is added
Water stirring is added hydrogen peroxide to bright orange or khaki in the case of stirring, adds concentrated hydrochloric acid stirring；
Step S24: being washed with deionized water centrifugal filtration to neutrality, 40 DEG C~60 DEG C vacuum dryings, obtains the oxidation stone
Black alkene.
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