CN106634431B - A kind of clinkery epoxy powder coating and preparation method thereof with super-drainage structure - Google Patents
A kind of clinkery epoxy powder coating and preparation method thereof with super-drainage structure Download PDFInfo
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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/03—Powdery paints
- C09D5/033—Powdery paints characterised by the additives
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- 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
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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- C09D7/61—Additives non-macromolecular inorganic
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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- C09D7/65—Additives macromolecular
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- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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Abstract
The present invention relates to a kind of clinkery epoxy powder coatings with super-drainage structure, the bisphenol A type epoxy resin of fluorine-containing hydrophobic material, 20-30 parts by weight including 10-20 parts by weight, the phenol aldehyde modified epoxy resin of 10-20 parts by weight, the phenols curing agent of 10-20 parts by weight, the promotor of 0.5-1 parts by weight, the parts by weight leveling auxiliary agent of 0.5-1, the defoaming agent of 0.5-1 parts by weight, the nanofiller of 10-30 parts by weight, the pigment of 1-10 parts by weight.The present invention also provides a kind of preparation methods of clinkery epoxy powder coating with super-drainage structure.The beneficial effects of the present invention are: powdery paints prepared by the present invention is mainly used in the corrosion-proof coating of steel pipe.Powdery paints is coated to the surface of steel pipe by the method for electrostatic spraying or fluidized bed dipping, the fluorine-containing surface that can precipitate into powdery paints at parts by weight of part when forming a film by being heating and curing in coating forms the fine and close surface layer with super-hydrophobic effect.The contact angle of the surface layer and water is greater than 150 °, has good hydrophobic effect.
Description
Technical field
The present invention is suitable for anticorrosive paint field, the fusion bonded epoxy with super-drainage structure especially suitable for steel pipe corrosion-proof
Powdery paints and preparation method thereof.
Background technique
The contact angle of super hydrophobic material water is greater than 150 °, often less than 5 ° of water contact angle lag, has waterproof, anti-pollution, anti-
Adhesion, anti-oxidant, anticorrosion and self-cleaning ability.Super hydrophobic material has in national defence, industrial and agricultural production and daily life at present
Be widely applied.
A kind of preparation method of super-hydrophobic powdery paints is disclosed in patent CN102925028A, is announced and is surpassed in the patent
Hydrophobic resin is the organosilicon chemistry modification by copolymerization epoxy resin that smooth surface and water contact angle are greater than 90 ° at normal temperatures and pressures,
Nano-ceramic particle is added in hydrophobic resin powder and forms mixture coating particles, is realized by electrostatic spraying and needs to protect
Surface combination；Nano-ceramic particle first uses coupling agent, dispersing agent pretreatment, and resin package ceramic particle is then made
Composite granule guarantees its sprawling on surface to be coated, and the rough surface of nanoscale is formed by nano-ceramic particle；It is logical
The type and additional amount for crossing adjustment nano-ceramic particle may be implemented not only antifriction, anti-aging and improvement superhydrophobic characteristic, but also improve
By protection materials and spray the bond strength between film layer.
A kind of croci coating of super-drainage structure is described in patent CN103589200A.The preparation method is:
First by micron ferric oxide powder, nanoscale iron powder, stearic acid and solid paraffin with (5-8): 10: (1-2): 2
Mass ratio stirred tank is added and stir the 30-60 minutes uniform mixtures of formation in 5-25 DEG C of atmospheric environment, then
Heat the mixture to 60-80 DEG C and continue stirring 30-50 minutes, then by mixture under atmospheric environment natural cooling 2-
8 hours, just obtain super-hydrophobic ferric oxide powder.
A kind of super-hydrophobic polyester resin powder coating is described in patent CN105694682A, powder described in the invention applies
Material contains polyester resin, phenolic resin, Hydroxylated acrylic resin, fluorine-containing hydrophobic material, pitch, magnesium carbonate, aluminium hydroxide, zinc powder
Equal materials are made, described in super hydrophobic material the preparation method comprises the following steps: by 12 heptyl ester of methacrylic acid, vinyl acetate, poly-
Dimethyl siloxane, azodiisobutyronitrile put into the first process equipment after mixing, are filled with dioxy into the first process equipment
Change carbon and carries out gas displacement；Then the first process equipment is placed in water-bath, continues to be filled with carbon dioxide to the first process equipment
In, carbon dioxide is discharged in holding after a certain period of time, obtains material A；Material A is put into the second process equipment containing toluene, is risen
High second process equipment temperature is kept the temperature, cooling, and taking-up obtains material B, is then successively cleaned, is dried with methanol, deionized water
To fluorine-containing hydrophobic material.
But at present with super-drainage structure steel pipe corrosion-proof with clinkery epoxy powder coating also not it has been found that.Super-hydrophobic knot
The epoxide powder coating of structure carries out steel pipe coating, can either play epoxide powder coating Anticorrosive Character can play again it is super-hydrophobic
The drag reduction of material, self-cleaning characteristic.
Summary of the invention
The technical problems to be solved by the present invention are: proposing a kind of clinkery epoxy powder coating with super-drainage structure
And preparation method thereof, there is splendid ultra-hydrophobicity and antiseptic property.
The present invention be solve the problems, such as it is set forth above used by technical solution be:
The present invention provides a kind of clinkery epoxy powder coatings with super-drainage structure, comprising: 10-20 parts by weight
The bisphenol A type epoxy resin of fluorine-containing hydrophobic material, 20-30 parts by weight, the phenol aldehyde modified epoxy resin of 10-20 parts by weight, 10-
The phenols curing agent of 20 parts by weight, the promotor of 0.5-1 parts by weight, the parts by weight leveling auxiliary agent of 0.5-1,0.5-1 parts by weight
Defoaming agent, the nanofiller of 10-30 parts by weight, the pigment of 1-10 parts by weight.
Preferably, the bisphenol-A-type epoxy resin is common solid epoxy resin, epoxy resin including one-step method and
The epoxy resin of two-step method preparation.
Preferably, the phenol aldehyde modified epoxy resin includes the 704 of NPCN-702, Ba Ling petrochemical industry that commercially available South Asia electronics produces
The products such as epoxy resin.
Preferably, the phenols curing agent is phenol aldehyde modified curing agent product, D.E.H.84 including Tao Shi,
D.E.H.85, D.E.H.80, D.E.H.81, D.E.H.82, D.E.H.87, KD404, KD405, the KD406 in South Korea national capital, Shaanxi
The phenols curing agent product of Shandong is celebrated in V-205, V-2088, V-2059 of Jin Chen, grand celebration.
Preferably, the promotor is imidazoles and ring amidine substance, wherein predominantly 2-methylimidazole.
Preferably, the leveling auxiliary agent is esters of acrylic acid product, selects the PV88 leveling auxiliary agent at the Ningbo South Sea.
Preferably, the antifoam additives are as follows: styrax class product.
Preferably, the nanofiller are as follows: nanoprecipitation barium sulfate, nanometer calcium carbonate, nano silica, nanometer silicon ash
One or more of fillers such as mountain flour, nano montmorillonite and mica powder.
Preferably, the pigment selects the nothings such as black titanium dioxide, mica iron oxide red, micaceous iron oxide, zinc oxide, aluminum phosphate
Machine anti-corrosion paint.
The fluorine-containing hydrophobic material, comprising:
The polyethylene wax of 100 parts by weight, the comonomer of 2 parts by weight, the fluorochemical monomer of 15-20 parts by weight, 0.1 parts by weight
Initiator.
Preferably, the fluorochemical monomer should be the fluorine material containing double bond structure, be dodecafluoroheptyl methacrylate,
Trifluoroethyl methacrylate, five fluorine propyl ester of methacrylic acid, methacrylic acid octafluoro pentyl ester, 17 fluorine nonyl ester of methacrylic acid
Or 17 fluorine last of the ten Heavenly stems ester of methacrylic acid.
Preferably, the comonomer is styrene, acrylate, methyl methacrylate or ethyl methacrylate.
Preferably, the initiator system are as follows: azo-initiator.
Preferably, the initiator is selected from azodiisobutyronitrile, cumyl peroxide, the bis- (uncles of 2,5- dimethyl -2,5-
Butyl peroxy) hexane, peroxidating bis- (2,4 dichloro benzene formyls), peroxidized t-butyl perbenzoate, di-t-butyl peroxide, uncle
Butylhydroperoxide, dibenzoyl peroxide, 1,1-bis(t-butylperoxy)cyclohexane, 1,1- bis(t-butylperoxy)-
One or more of 3,3,5- trimethyl-cyclohexane.
The present invention also provides a kind of preparation method of clinkery epoxy powder coating with super-drainage structure, including it is following
Step:
By the above-mentioned bisphenol A type epoxy resin centainly matched, phenol aldehyde modified epoxy resin, phenols curing agent, it is fluorine-containing dredge
Water material, leveling auxiliary agent, antifoam additives, nanofiller, pigment are uniform in high-speed mixer and mixing, by the raw material mixed through double spiral shells
Bar extruder squeezes out, and is milled through dedicated milling equipment ACM grading mill, and preparing can be by -180 mesh screen of 100 mesh
Powdery paints.
The present invention also provides a kind of preparation methods of fluorine-containing hydrophobic material described in above-mentioned technical proposal, including following step
It is rapid:
Polyethylene wax is added to heating and refluxing to dissolve in dimethylbenzene, by the comonomer, fluorochemical monomer and initiation of metering
Agent is added in solution, continues after being heated to reflux the regular hour, mixture after reaction is poured into 5-10 times of ethyl alcohol,
There is White Flocculus generation, washing is sufficiently stirred, after unreacted fluorochemical monomer is removed, after precipitating filtration drying, is contained
The hydrophobic material of fluorine.
The beneficial effects of the present invention are: powdery paints prepared by the present invention is mainly used in the anticorrosion painting of steel pipe
Dress.Powdery paints is coated to the surface of steel pipe by the method for electrostatic spraying or fluidized bed dipping, by being heated and cured into
The fluorine-containing surface that can precipitate into powdery paints at parts by weight of part when film in coating forms fine and close with super-hydrophobic effect
Surface layer.The contact angle of the surface layer and water is greater than 150 °, has good hydrophobic effect.
Specific embodiment
The present invention can be implemented according to following instance, but be not limited to following instance, and term as used in the present invention removes
It is non-to have other explanation, generally there is the normally understood meaning of those of ordinary skill in the art, it should be appreciated that these embodiments are to be
It illustrates the present invention, rather than limits the scope of the invention in any way, below in an example, be not described in detail
Various processes and method are conventional methods as known in the art.
Embodiment one:
Fluorine-containing hydrophobic material described in the present embodiment the preparation method comprises the following steps: the polyethylene wax of 100 parts by weight is added to three
In mouth bottle, suitable dimethylbenzene is added and is heated to reflux, is completely dissolved polyethylene wax, by the comonomer styrene of 2 parts by weight
It is added in there-necked flask, the fluorochemical monomer dodecafluoroheptyl methacrylate of 15 parts by weight is added, the initiation of 0.1 parts by weight is added
Reaction temperature is set to 130 DEG C by agent tert-butyl hydroperoxide.Reaction 6 hours.10 times are poured the mixture into after reaction
In ethyl alcohol, there is White Flocculus appearance, after washing is sufficiently stirred, obtains fluorine-containing hydrophobic material after precipitating filtration drying.
The proportion of clinkery epoxy powder coating raw material described in the present embodiment are as follows: bisphenol A type epoxy resin is South Asia ring
Oxygen resin 904, weight are 25 parts by weight；Phenol aldehyde modified epoxy resin used in it uses the ES-503 of Shaanxi gold occasion production,
Weight is 10 parts by weight；Phenols curing agent is the D.E.H.84 special curing agent of Tao Shi, and weight is 15 parts by weight；Fluorine-containing hydrophobic material
Expect 15 parts by weight；0.5 parts by weight of 2-methylimidazole；1 parts by weight of leveling auxiliary agent；Antifoam additives are styrax, 0.5 parts by weight；It receives
Rice filler is the compound of blanc fixe and nano silica, 30 parts by weight of weight, wherein nano barium sulfate and nanometer two
Proportion of silica is 1:1；Pigment is mica iron oxide red, and weight is 3 parts by weight.The powdery paints of preparation is through detecting, gelatinization
Time is 80 seconds (180 DEG C), and bottom horizontal flow sheet is 24.5mm (180 DEG C), and coating adhesion is 1 grade, and cathodic disbonding is 6mm (65
DEG C, 48h), the contact angle of coating surface and water is 160 °.
Embodiment two:
Fluorine-containing hydrophobic material described in the present embodiment the preparation method comprises the following steps: the polyethylene wax of 100 parts by weight is added to three
In mouth bottle, suitable dimethylbenzene is added and is heated to reflux, is completely dissolved polyethylene wax, by the comonomer styrene of 2 parts by weight
It is added in there-necked flask, the fluorochemical monomer trifluoroethyl methacrylate of 15 parts by weight is added, the initiator of 0.1 parts by weight is added
Reaction temperature is set to 130 DEG C by tert-butyl hydroperoxide.Reaction 6 hours.10 times of second is poured the mixture into after reaction
In alcohol, there is White Flocculus appearance, after washing is sufficiently stirred, obtains fluorine-containing hydrophobic material after precipitating filtration drying.
The proportion of clinkery epoxy powder coating raw material described in the present embodiment are as follows: bisphenol A type epoxy resin is South Asia ring
Oxygen resin 904, weight are 25 parts by weight；Phenol aldehyde modified epoxy resin used in it uses the ES-503 of Shaanxi gold occasion production,
Weight is 10 parts by weight；Phenols curing agent is the D.E.H.84 special curing agent of Tao Shi, and weight is 15 parts by weight；Fluorine-containing hydrophobic material
Expect 15 parts by weight；0.5 parts by weight of 2-methylimidazole；1 parts by weight of leveling auxiliary agent；Antifoam additives are styrax, 0.5 parts by weight；It receives
Rice filler is the compound of blanc fixe and nano silica, 30 parts by weight of weight, wherein nano barium sulfate and nanometer two
Proportion of silica is 1:1；Pigment is mica iron oxide red, and weight is 3 parts by weight.The powdery paints of preparation is through detecting, gelatinization
Time be 70 seconds (180 DEG C), bottom horizontal flow sheet be 23mm (180 DEG C), coating adhesion be 2 grades, cathodic disbonding be 8mm (65 DEG C,
48h), the contact angle of coating surface and water is 152 °.
Embodiment three:
Fluorine-containing hydrophobic material described in the present embodiment the preparation method comprises the following steps: the polyethylene wax of 100 parts by weight is added to three
In mouth bottle, suitable dimethylbenzene is added and is heated to reflux, is completely dissolved polyethylene wax, by the comonomer styrene of 2 parts by weight
It is added in there-necked flask, the fluorochemical monomer dodecafluoroheptyl methacrylate of 20 parts by weight is added, the initiation of 0.1 parts by weight is added
Reaction temperature is set to 130 DEG C by agent tert-butyl hydroperoxide.Reaction 6 hours.10 times are poured the mixture into after reaction
In ethyl alcohol, there is White Flocculus appearance, after washing is sufficiently stirred, obtains fluorine-containing hydrophobic material after precipitating filtration drying.
The proportion of clinkery epoxy powder coating raw material described in the present embodiment are as follows: bisphenol A type epoxy resin is South Asia ring
Oxygen resin 904, weight are 25 parts by weight；Phenol aldehyde modified epoxy resin used in it uses the ES-503 of Shaanxi gold occasion production,
Weight is 10 parts by weight；Phenols curing agent is the D.E.H.84 special curing agent of Tao Shi, and weight is 15 parts by weight；Fluorine-containing hydrophobic material
Expect 15 parts by weight；0.5 parts by weight of 2-methylimidazole；1 parts by weight of leveling auxiliary agent；Antifoam additives are styrax, 0.5 parts by weight；It receives
Rice filler is the compound of blanc fixe and nano silica, 30 parts by weight of weight, wherein nano barium sulfate and nanometer two
Proportion of silica is 1:1；Pigment is mica iron oxide red, and weight is 3 parts by weight.The powdery paints of preparation is through detecting, gelatinization
Time is 82 seconds (180 DEG C), and bottom horizontal flow sheet is 24.5mm (180 DEG C), and coating adhesion is 1 grade, and cathodic disbonding is 7mm (65
DEG C, 48h), the contact angle of coating surface and water is 155 °.
Claims (3)
1. a kind of clinkery epoxy powder coating with super-drainage structure, it is characterised in that: fluorine-containing thin including 10-20 parts by weight
The bisphenol A type epoxy resin of water material, 20-30 parts by weight, the phenol aldehyde modified epoxy resin of 10-20 parts by weight, 10-20 weight
The phenols curing agent of part, the promotor of 0.5-1 parts by weight, the parts by weight leveling auxiliary agent of 0.5-1, the defoaming agent of 0.5-1 parts by weight,
The nanofiller of 10-30 parts by weight, the pigment of 1-10 parts by weight, the fluorine hydrophobic material include 100 parts by weight polyethylene wax,
The comonomer of 2 parts by weight, the fluorochemical monomer of 15-20 parts by weight, 0.1 parts by weight initiator.
2. a kind of preparation method of the clinkery epoxy powder coating described in claim 1 with super-drainage structure, including it is following
Step: by the bisphenol A type epoxy resin above-mentioned centainly matched, phenol aldehyde modified epoxy resin, phenols curing agent, fluorine-containing hydrophobic
Material, leveling auxiliary agent, defoaming agent, nanofiller, pigment, promotor are uniform in high-speed mixer and mixing, and the raw material mixed is passed through
Double screw extruder squeezes out, and is milled through dedicated milling equipment ACM grading mill, -180 mesh of 100 mesh can be passed through by preparing
The powdery paints of net.
3. the preparation method of the clinkery epoxy powder coating according to claim 2 with super-drainage structure, feature exist
In the production technology of the fluorine-containing hydrophobic material, comprising the following steps: polyethylene wax is added in dimethylbenzene and is heated to reflux
The comonomer, fluorochemical monomer and initiator of metering are added in solution, continue after being heated to reflux the regular hour by dissolution, will
Mixture after reaction pours into 5-10 times of ethyl alcohol, there is White Flocculus generation, and washing is sufficiently stirred, will be unreacted
After fluorochemical monomer removes, after precipitating filtration drying, fluorine-containing hydrophobic material is obtained.
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| CN107760170A (en) * | 2017-11-13 | 2018-03-06 | 安徽迈高化工科技有限公司 | A kind of preparation method of self-cleaning powder paint |
| CN107955496B (en) * | 2017-12-01 | 2021-04-02 | 山东东宏管业股份有限公司 | Sintered epoxy powder coating and preparation method thereof |
| CN109337524A (en) * | 2018-11-16 | 2019-02-15 | 临沂大学 | A kind of drag reducing and anti-corrosion coating and preparation method thereof |
| CN115584188B (en) * | 2022-12-14 | 2023-04-11 | 佛山市涂亿装饰材料科技有限公司 | Preparation method of powder coating and marbleized powder spraying coating |
| CN116814134A (en) * | 2023-05-19 | 2023-09-29 | 泰州市创新电子有限公司 | A kind of superhydrophobic bionic nano coating for display support frame and preparation method thereof |
| CN118374209A (en) * | 2024-04-25 | 2024-07-23 | 广东傲博新材料有限公司 | A super hydrophobic corrosion-resistant powder coating and preparation method thereof |
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