CN113604114A - Fluororesin powder coating composition with high corrosion resistance - Google Patents

Fluororesin powder coating composition with high corrosion resistance Download PDF

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Publication number
CN113604114A
CN113604114A CN202110953827.4A CN202110953827A CN113604114A CN 113604114 A CN113604114 A CN 113604114A CN 202110953827 A CN202110953827 A CN 202110953827A CN 113604114 A CN113604114 A CN 113604114A
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coating
powder
coating composition
etfe
fluororesin
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CN202110953827.4A
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宿梅香
郭希刚
冯奕轩
冯波
王帅
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Shandong Huafu Fluoro Chemical Co ltd
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Shandong Huafu Fluoro Chemical Co ltd
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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
    • C09D123/00—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers
    • C09D123/02—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
    • C09D123/04—Homopolymers or copolymers of ethene
    • C09D123/08—Copolymers of ethene
    • C09D123/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
    • C09D123/0892—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms containing monomers with other atoms than carbon, hydrogen or oxygen atoms
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/36—Successively applying liquids or other fluent materials, e.g. without intermediate treatment
    • B05D1/38—Successively applying liquids or other fluent materials, e.g. without intermediate treatment with intermediate treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/50—Multilayers
    • B05D7/56—Three layers or more
    • B05D7/58—No clear coat specified
    • B05D7/584—No clear coat specified at least some layers being let to dry, at least partially, before applying the next layer
    • 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
    • C09D5/03—Powdery paints
    • C09D5/033—Powdery paints characterised by the additives
    • 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
    • C09D5/03—Powdery paints
    • C09D5/033—Powdery paints characterised by the additives
    • C09D5/038—Anticorrosion agents
    • 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

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Paints Or Removers (AREA)

Abstract

The invention relates to a fluororesin powder coating composition with high corrosion resistance and a preparation method thereof, which can be used for substrate corrosion prevention and protection of a substrate by preventing corrosive acid and other chemicals from permeating the substrate. The existence of inherent pores and defects in the coating formed by the fluororesin can accelerate the failure of the coating, and limits the application and development of the coating protection technology. Therefore, in order to further enhance the protective performance of the fluororesin coating, the invention selects the multifunctional flaky filler to realize the effect of constructing a synergistic protective system of the fluororesin powder coating, and the optimal flow assistant is fumed silica which is used as a high-temperature-resistant powder coating and can be used for electrostatic spraying and a roll coating forming process with higher requirements on powder fluidity.

Description

Fluororesin powder coating composition with high corrosion resistance
Technical Field
The invention relates to the field of coatings, in particular to a fluororesin powder coating composition with high corrosion resistance.
Background
The practical service life of fluororesins such as PFA, PVDF, FEP, ETFE and the like exceeds twenty years. The actual short sheet of corrosion resistance is such that the fluororesin has a coating film surface gloss inferior to that of a general coating material due to fluidity after melting or the like, the coating film has insufficient permeation resistance due to defects and pinholes, corrosive media permeate through the coating film to the interface between the coating film and the substrate to corrode the substrate, and the generated gas accumulates at the interface to form bubbles, thereby peeling off the coating film. The penetrated organic solvent with strong dissolving power (fluorocarbon, partial ketone and the like at high temperature) makes the coating swell, so that the strength of the coating is reduced, the coating deforms, and the protective property is lost. These defects make the service life of the fluororesin coating film much shorter than the durability, weather resistance, etc. of the fluororesin itself.
Various fillers such as mica powder, talc, barium sulfate, glass fiber, carbon fiber and the like can be added to improve the hardness and the like, but no technical application report for improving corrosion resistance, swelling resistance and permeability resistance when the fillers are added to fluororesin powder coating is reported. The present inventors have made experimental studies on the shape, size, amount of addition and the like of various plate-like fillers, and have found that a composition having high corrosion resistance, high swelling resistance and high fluidity can be obtained by appropriate addition.
US3087829 reports that flake mica powder added to a resin can provide a shiny aesthetic effect.
US4353950 reports that addition of mica flakes to fluororesin powder coatings, sprayed on cookware surfaces, improves non-stick properties.
WO9706208 reports the addition of flake mica powder to improve barrier properties in ETFE powder coatings.
These techniques are limited to the use of the physical barrier properties of the flake mica powder, and have the disadvantages of impaired fluidity, rough surface, impaired surface gloss, denseness and non-tackiness, and the decrease in fluidity makes it impossible to use the powder coating for the formation of a rolling lining.
Disclosure of Invention
The present invention provides a fluororesin powder coating composition having high corrosion resistance, in view of the problems of the prior art.
A high-corrosion-resistance fluororesin powder paint composition is prepared from fluororesin as matrix, micron-class filler and functional assistant.
Wherein the functional assistant is a heat stabilizer and/or a flow assistant.
Wherein the fluororesin is PFA, ETFE, ECTFE or FEP; the micron flaky filler is mica powder, kaolin powder, graphite powder, colloidal graphite powder, talcum powder, pyrophyllite powder, pearlescent mica, colored mica and basic zinc sulfate micron sheet.
Wherein the fluororesin is ETFE; the micron flaky filler is basic zinc sulfate micron sheet, and basic Zinc Sulfate (ZSH) micron sheet compensates for fluidity caused by the flaky filler and reduction of surface gloss after film forming.
Wherein the heat stabilizer is zinc oxide, cuprous iodide and ferric oxide; the flow assistant is fumed silica; the amount of fumed silica added to the powder coating composition is 0.1 to 0.5%.
Wherein, the ETFE, namely the ethylene tetrafluoroethylene copolymer, has the structural unit content of 60-40mol% based on tetrafluoroethylene and 40-60mol% based on ethylene in the copolymer structure, and can contain a small amount of modified monomer; the particle size of the ETFE powder is 40-120 μm.
Wherein, the basic Zinc Sulfate (ZSH) micron sheet is in a powder form; the thickness of the single piece is 1-2 μm, and the diameter is 10-130 μm; the content of the basic zinc sulfate micro-meter tablets is 3-25wt%, preferably 7.5-15wt%, and more preferably 10wt% based on the total weight of the ETFE resin powder and the basic zinc sulfate micro-meter tablets.
Wherein the coating mode of the composition is electrostatic spraying, fluidized bed dip coating or roll coating.
Wherein, the electrostatic spraying comprises the following steps:
(1) applying a layer of powder primer or liquid primer to a substrate;
(2) baking the powder primer at the temperature of 300-320 ℃ for melting and leveling to form a film, and directly drying the liquid primer;
(3) coating, namely coating at least one layer of coating composition on the primed substrate;
(4) heating the substrate coated with the primer and coating composition to 280-310 ℃ until the substrate is melted and leveled;
(5) and (5) repeating the steps (3) and (4) to obtain a coating with the thickness of 300-1000 microns.
Wherein the baking time is 10-20min, and the base material is a chemical container, a reactor or an anti-corrosion part.
The sheet structure of the micron sheet can effectively prolong the diffusion and migration paths of corrosive media such as water, oxygen and ions in the coating matrix, and is also due to the high-efficiency water and ion capture property and the swelling resistance of the micron sheet. When corrosive media such as water, oxygen and ions penetrate into the coating/filler interface, the micron sheet can realize the effect of water and ions (Cl) invading into the coating by means of crystal phase transformation-And Na+) Capture of water and ions (Cl) in the coating to allow free migration-And Na+) Is locked in its own sandwich structure, giving the coating active barrier properties. By adding the flaky filler, a synergistic protection system is formed, so that the service life of the coating is remarkably prolonged, and the anticorrosive coating composition with higher efficiency and long service life is obtained.
The invention selects the multifunctional flaky filler to realize the effect of constructing the synergistic protection system of the fluororesin powder coating, and the multifunctional flaky filler can be used as a high-temperature-resistant powder coating, can be used for electrostatic spraying and can also be used for a roll coating forming process with higher requirements on powder fluidity.
The coating film can be applied to various substrates, such as molds, pipes, chemical containers, reactors, and the like. The base material is steel, carbon steel, aluminum, etc.
When the lining is formed in the container by a roll coating mode, the addition amount of about 5% by weight of the micron sheet can also play a role in corrosion resistance and permeation resistance, generally, the more the addition amount of the micron sheet is, the better the addition amount is, but when the addition amount exceeds 25% by weight, the incomplete melting of the coating can be caused, the compactness is reduced, and the mechanical performance is damaged.
The coating method comprises the following steps: the electrostatic spraying method comprises charging powder with an electrostatic generator, adsorbing the powder onto the surface of the substrate, and baking at a temperature of 270-340 deg.C.
The fluidized bed dipping method is characterized in that a base material is heated to the high temperature of 300-340 ℃ to be contacted with fluoropolymer composition powder suspended in a fluidized bed, and the resin powder is adhered to the surface of the base material to form a coating film while being molten.
The roll coating method is a method in which the calculated composition powder is put into a container and heated while rotating to be melted on the inner wall of the container to form a lining, or the container is formed after releasing the lining.
Wherein, the electrostatic spraying method is used, part of the micron sheets can be lost in the spraying process, but the coating film obtained under the general condition can also at least contain 4 to 6 weight percent of the micron sheets.
The coating film can be applied to various substrates, such as molds, pipes, chemical containers, reactors, and the like. When the lining is formed in the container by a roll coating mode, the addition amount of about 5% by weight of the micron sheet can also play a role in corrosion resistance and permeation resistance, generally, the more the addition amount of the micron sheet is, the better the addition amount is, but when the addition amount exceeds 25% by weight, the incomplete melting of the coating can be caused, the compactness is reduced, and the mechanical performance is damaged.
The thickness of the micron sheet is generally selected to be 0.01 to 2 μm, preferably 0.5 to 2.5 μm from the viewpoint of availability of raw materials, and the diameter is preferably 5 to 100. mu.m. If necessary, other corrosion-resistant fillers may be added, and various additives may be added to modify the properties of the powder coating composition. Because the micron flaky powder can cause slight reduction of the flowability of the composition powder, the flowability of the composition powder can be improved by adding fumed silica, the surface tension of the molten fluororesin is reduced, the leveling is easier, the interfacial tension of the ZSH micron sheets and the fluororesin is also reduced, the interface of the ZSH micron sheets and the fluororesin is completely infiltrated, and the swelling resistance and the corrosion resistance are improved.
The coating formed by the fluororesin powder is tested and confirmed to have improved corrosion resistance to a great extent by adding the micron-sized flaky powder, and the permeability of the coating to organic solvents is confirmed to be improved by a dipping method, from 2 days in the case of containing no micron-sized sheets to more than 3 weeks in the case of containing micron-sized sheets.
Although the above description has mainly illustrated that the composition of fluororesin powder compounded with ZSH flake powder has improved corrosion resistance and other chemical permeation properties, other polymer compounding may be employed. But the best combination is fluororesin powder and micron flake powder.
The average particle diameter of the fluororesin powder used is preferably 80 μm or less (dry measurement by laser particle size distribution), and a primer may be applied between the coating layer of the composition and the substrate to increase adhesion. The primer is generally composed of a fluororesin such as ETFE, ECTFE, PVDF resin mixed with an adhesive resin such as PPS resin, polyamideimide resin, etc., and a mixture thereof. The primer can be applied by various spraying methods depending on the form, for example, liquid can be sprayed, and powder can be applied by electrostatic spraying.
The primer is coated with a fluororesin/ZSH micron-sheet powder composition coating, which can be directly used as a top coating or coated with a layer of fluororesin powder coating without ZSH micron-sheet filler on the surface to obtain better surface smoothness and compactness, and the latter is preferred to better protect the substrate from penetration of corrosive media.
The powder coating of the fluororesin/ZSH micron-scale composition may be dry-blended, for example, by uniformly mixing 90% by weight of ETFE powder and 10% by weight of the above-mentioned ZSH micron-scale powder. The ETFE can be selected from powder coatings of Shandonghua Fulu brand EC-01, EC-03 or EC-04, 532-6410 of Kemu company, and the like.
Depending on the application and purpose, additives such as other heat stabilizers and coloring pigments may be added.
The surface treatment of the substrate may be carried out by a general method such as sand blasting, polishing or the like to promote adhesion of the substrate to the coating.
If necessary, a primer may be applied between the coating film formed from the coating composition of the present invention and the substrate. Although the primer does not improve the permeation resistance of the coating as a whole, it improves the adhesion to the substrate, thereby extending the service life of the coating formed from the coating composition of the present invention.
The ETFE powder and the ZSH micrometer pieces can be uniformly mixed by dry mixing methods such as a V-shaped mixer, a double-cone mixer, a bucket mixer, a barrel mixer, a ribbon mixer, a horizontal cylinder mixer, a paddle mixer, a screw mixer and the like.
The invention has the beneficial effects
The invention can obviously improve the corrosion resistance and swelling resistance of the base material, and can be used for corrosion prevention of the base material and protection of the base material by preventing corrosive acid and other chemicals from permeating into the base material. The existence of inherent pores and defects in the coating formed by the fluororesin can accelerate the failure of the coating, and limits the application and development of the coating protection technology. Therefore, in order to further enhance the protective performance of the fluororesin coating, the multifunctional flaky filler is selected to realize the effect of constructing a synergistic protective system of the fluororesin powder coating.
Detailed Description
The following examples are intended to better illustrate the invention, but the scope of the invention is not limited thereto.
The compositions in the following examples were prepared: the selected ZSH micrometer piece has the thickness of about 1-2 μm and the diameter of 10-100 μm. EC-01 of Shandong Hua fluorine chemical industry, Inc. is selected as the ETFE powder coating. The ETFE powder coating EC-01 and ZSH micrometer piece powder with different weights are mixed uniformly by a V-shaped mixer to prepare the following three ETFE/ZSH micrometer piece powder coating compositions.
ETFE/ZSH micron flake powder coating composition 1: ETFE brand EC-01 of Shandong Hua fluorin, ZSH micron sheet weight percentage content 10%, fumed silica (Degussa R972) 0.2%.
ETFE/ZSH micron flake powder coating composition 2: ETFE brand EC-01 of Shandong Hua fluorin, weight percentage of ZSH micron sheet is 7.5%, and fumed silica (Degussa R972) is 0.2%.
ETFE/ZSH micron flake powder coating composition 3: ETFE brand EC-01 of Shandong Hua fluorin, ZSH micron sheet weight percentage content 5%, gas phase silicon dioxide (Degussa R972) 0.2%.
Substrate treatment and primer coating
The test plate substrate is made of carbon steel, and the carbon steel is treated by a traditional roughening method, such as 60-mesh aluminum oxide sand blasting treatment, so that the surface roughness Ra reaches 10-20 mu m. The ECP-01 primer is sprayed by a spraying device by using German Vargner EPG-Sprint with the voltage of 50kV by an electrostatic spraying method at room temperature, and is put into an oven to be baked for about 20 minutes at the temperature of 295-300 ℃ so that the thickness of the primer layer is about 20 mu m.
Testing of water vapor and dilute acid solution permeability
Using the atlas cell apparatus of ASTM C868, a low concentration HCl solution of 0.05mol/L was heated to maintain a boiling temperature to form a gas-liquid interface, and the ETFE powder coating or ETFE/ZSH micron sheet powder coating composition coated substrate was exposed to the gas-liquid interface formed by the two liquids until the interface of the coating and the substrate was blistered/peel-off. Blistering occurs when water vapor penetrates into the interface of the coating and the substrate and contacts the substrate. The coating film thickness selected for the test was about 400 and 500 microns. Tests have shown that the coating of ETFE powder coating with ZSH flakes added can be maintained for more than 3 weeks in both liquids.
Testing of organic solvent resistance to swelling
The ETFE powder coating composition was pressed into 1.5mm thick sheets at 300 ℃ and tested for weight change by immersion in acetone at 55 ℃ at a temperature and in N, N-dimethylformamide at 120 ℃ for 7 days.
Powder flowability test
The powder flowability was tested with the angle of repose. The angle of repose is also referred to as the angle of repose, and is the maximum angle that the free surface of the powder deposit layer forms with the horizontal plane at equilibrium. The smaller the angle of repose, the better the powder flowability. The device for measuring the repose angle comprises a bracket, a funnel and a round flat plate. And pouring the powder sample into a round funnel, enabling the sample to fall on a lower round flat plate through the funnel, gradually stacking the powder until the powder cannot be stacked, and testing the numerical value of the repose angle by using a protractor.
Example 1
The test panel after base material treatment and primer coating is taken out of the oven, a layer of ETFE/ZSH micron sheet powder coating composition 1 is sprayed by a Wagner spray gun when the test panel is hot, the test panel is put into the oven again and baked for 20min at the temperature of 295 plus 300 ℃, the ETFE is melted, leveled and formed into a film by baking at the temperature above the melting point of the ETFE, the thickness of the film coated once is about 100 mu m, and the baking temperature and time are controlled to ensure that the coating is smooth, glossy and free of bubbles. And repeating the spraying and baking for 3 times to obtain the coating layer of the coating laminate. The peel bubble time was greater than 30 days as measured by the atlas test. The test results are shown in Table 1.
Example 2
The test panel after base material treatment and primer coating is taken out of the oven, a layer of ETFE/ZSH micron sheet powder coating composition 2 is sprayed by a Wagner spray gun when the test panel is hot, the test panel is put into the oven again and baked for 20min at the temperature of 295 plus 300 ℃, the ETFE is melted, leveled and formed into a film by baking at the temperature above the melting point of the ETFE, the thickness of the film coated once is about 100 mu m, and the baking temperature and time are controlled to ensure that the coating is smooth, glossy and free of bubbles. And repeating the spraying and baking for 4 times to obtain the coating layer of the coating laminate. The test results are shown in Table 1.
Example 3
The test panel after base material treatment and primer coating is taken out of the oven, a layer of ETFE/ZSH micron sheet powder coating composition 3 is sprayed by a Wagner spray gun when the test panel is hot, the test panel is put into the oven again and baked for 20min at the temperature of 295 plus 300 ℃, the ETFE is melted, leveled and formed into a film by baking at the temperature above the melting point of the ETFE, the thickness of the film coated once is about 100 mu m, and the baking temperature and time are controlled to ensure that the coating is smooth, glossy and free of bubbles. And repeating the spraying and baking for 3 times to obtain the coating layer of the coating laminate. The test results are shown in Table 1.
Comparative example 1
Comparison 1: the ETFE brand EC-01 and ZSH micron sheet content of ETFE and Shandong Hua fluorin are adopted, and the fumed silica is not contained.
The test panel after base material treatment and primer coating is taken out of the oven, a layer of ETFE/ZSH micron sheet powder coating composition is sprayed by a Wagner spray gun when the test panel is hot (comparison 1), the test panel is put into the oven again and baked for 20min at the temperature of 295 plus 300 ℃, the ETFE is melted and leveled into a film by baking at the temperature above the melting point of the ETFE, the film thickness is about 100 mu m after one construction, and the baking temperature and time are controlled to ensure that the coating is smooth, glossy and free of bubbles. And repeating the spraying and baking for 3 times to obtain the coating layer of the coating laminate. The test results are shown in Table 1.
Comparative example 2
Comparison 2: ETFE brand EC-01 with ETFE, santong huafu, no ZSH nanoplatelets, fumed silica (degussa R972) 0.2%.
The test panel after the base material treatment and the primer coating is taken out of the oven, a layer of ETFE powder coating composition (comparison 2) is sprayed by a Wagner spray gun when the test panel is hot, the test panel is put into the oven again and baked for 20min at the temperature of 295-300 ℃, the ETFE is melted, leveled and formed into a film by baking at the temperature above the melting point of the ETFE, the film thickness of the test panel is about 100 mu m after the construction, and the baking temperature and time are controlled to ensure that the coating is smooth, glossy and has no bubbles. And repeating the spraying and baking for 3 times to obtain the coating layer of the coating laminate. The test results are shown in Table 1.
Comparative example 3
The ETFE powder coating adopted is EC-01 of Shandong Hua fluorin.
The test plate after base material treatment and primer coating is taken out of the oven, a layer of ETFE EC-01 is sprayed by a Wagner spray gun when the test plate is hot, the test plate is put into the oven again and baked for 20min at the temperature of 295-300 ℃, the ETFE is melted and leveled into a film by baking at the temperature above the melting point of the ETFE, the thickness of the film coated once is about 100 mu m, and the baking temperature and time are controlled to ensure that the coating is smooth, glossy and free of bubbles. The spray-baking was repeated 3 times to obtain a laminate coating layer coated with a total film thickness of 518. mu.m. The test results are shown in Table 1.
TABLE 1
Figure DEST_PATH_IMAGE002
As can be seen from Table 1, the coating without the added ZSH micrometer powder layer after being exposed to water vapor for 3 days has blistered and peeled from the substrate, indicating that water vapor and corrosive ions have penetrated between the substrate and the coating and have been destroyed. And more than 5wt% of ZSH micron sheet powder is added, so that the corrosion-resistant medium rate can be obviously improved, and the corrosion resistance is improved to more than 21 days. In a solvent permeation resistance test, under the condition of soaking for the same time, the weight of the coating added with the ZSH micron flake powder is obviously less than that of the ETFE powder coating without the ZSH micron flake powder, which indicates that the coating also plays a role in blocking. The addition of 0.2wt% fumed silica can significantly reduce the angle of repose, improve the flowability of the powder composition, reduce the ZSH micrometer sheet-fused EFET interfacial tension, improve the bonding degree and reduce the swelling weight gain.

Claims (10)

1. A fluororesin powder coating composition having high corrosion resistance, characterized by comprising a fluororesin as a matrix, a micron-sized flaky filler and a functional assistant.
2. The coating composition of claim 1, wherein the functional additive is a thermal stabilizer and/or a flow aid.
3. The coating composition of claim 1, wherein the fluororesin is PFA, ETFE, ECTFE, FEP; the micron flaky filler is mica powder, kaolin powder, graphite powder, colloidal graphite powder, talcum powder, pyrophyllite powder, pearlescent mica, colored mica and basic zinc sulfate micron sheet.
4. The coating composition of claim 3, wherein the fluororesin is ETFE; the micron flaky filler is basic zinc sulfate micron tablets.
5. The coating composition of claim 2, wherein said heat stabilizer is zinc oxide, cuprous iodide, iron oxide; the flow assistant is fumed silica.
6. The coating composition according to claim 4, wherein the ETFE, an ethylene tetrafluoroethylene copolymer, has a tetrafluoroethylene-based structural unit content of 60 to 40mol% and an ethylene-based structural unit content of 40 to 60mol% in the copolymer structure, and may contain a small amount of a modifying monomer; the particle size of the ETFE powder is 40-120 μm.
7. The coating composition of claim 4, wherein the zinc hydroxide sulfate micro-tablets are in powder form; the thickness of the single piece is 1-2 μm, and the diameter is 10-130 μm; the content of the basic zinc sulfate micron sheet is 3-25wt% based on the total weight of the ETFE resin powder and the basic zinc sulfate micron sheet.
8. The coating composition of claim 1, wherein said composition is applied by electrostatic spraying, fluidized bed dip coating, or roll coating.
9. The coating composition of claim 8, wherein said electrostatic spraying comprises the steps of:
(1) applying a layer of powder primer or liquid primer to a substrate;
(2) baking the powder primer at the temperature of 300-320 ℃ for melting and leveling to form a film, and directly drying the liquid primer;
(3) coating, namely coating at least one layer of coating composition on the primed substrate;
(4) heating the substrate coated with the primer and coating composition to 280-310 ℃ until the substrate is melted and leveled;
(5) and (5) repeating the steps (3) and (4) to obtain a coating with the thickness of 300-1000 microns.
10. The coating composition of claim 9, wherein the baking time is 10-20min, and the substrate is a chemical container, a reactor or an anti-corrosion component.
CN202110953827.4A 2021-08-19 2021-08-19 Fluororesin powder coating composition with high corrosion resistance Withdrawn CN113604114A (en)

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Cited By (6)

* Cited by examiner, † Cited by third party
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CN114381172A (en) * 2021-12-31 2022-04-22 山东东岳未来氢能材料股份有限公司 Stripping-resistant ethylene-tetrafluoroethylene copolymer powder coating and preparation method thereof
CN114410196A (en) * 2021-12-20 2022-04-29 江南载福粉末涂料（张家港）有限公司 Boiling-resistant powder coating and preparation method and application thereof
CN114574050A (en) * 2022-01-28 2022-06-03 大连理工大学 Composite anticorrosive coating for condensation type flue gas waste heat recovery heat exchange equipment and preparation method thereof
CN115353781A (en) * 2022-09-19 2022-11-18 浙江省化工研究院有限公司 Anticorrosive powder coating and preparation method and application of anticorrosive coating
CN116410626A (en) * 2021-12-29 2023-07-11 山东东岳未来氢能材料股份有限公司 Antistatic agent for ETFE powder coating and antistatic ETFE powder coating
CN116925602A (en) * 2023-03-01 2023-10-24 格林斯达(北京)环保科技股份有限公司 Modified ETFE powder coating resistant to chemical medium permeation and electrostatic spraying process thereof

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114410196A (en) * 2021-12-20 2022-04-29 江南载福粉末涂料（张家港）有限公司 Boiling-resistant powder coating and preparation method and application thereof
CN116410626A (en) * 2021-12-29 2023-07-11 山东东岳未来氢能材料股份有限公司 Antistatic agent for ETFE powder coating and antistatic ETFE powder coating
CN116410626B (en) * 2021-12-29 2024-06-11 山东东岳未来氢能材料股份有限公司 Antistatic agent for ETFE powder coating and antistatic ETFE powder coating
CN114381172A (en) * 2021-12-31 2022-04-22 山东东岳未来氢能材料股份有限公司 Stripping-resistant ethylene-tetrafluoroethylene copolymer powder coating and preparation method thereof
CN114574050A (en) * 2022-01-28 2022-06-03 大连理工大学 Composite anticorrosive coating for condensation type flue gas waste heat recovery heat exchange equipment and preparation method thereof
CN115353781A (en) * 2022-09-19 2022-11-18 浙江省化工研究院有限公司 Anticorrosive powder coating and preparation method and application of anticorrosive coating
CN116925602A (en) * 2023-03-01 2023-10-24 格林斯达(北京)环保科技股份有限公司 Modified ETFE powder coating resistant to chemical medium permeation and electrostatic spraying process thereof
CN116925602B (en) * 2023-03-01 2024-03-26 格林斯达(北京)环保科技股份有限公司 Modified ETFE powder coating resistant to chemical medium permeation and electrostatic spraying process thereof

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