CN112341905A - High-solid-content rust-conversion acid-resistant anticorrosive paint and preparation method thereof - Google Patents
High-solid-content rust-conversion acid-resistant anticorrosive paint and preparation method thereof Download PDFInfo
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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
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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
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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
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
- C08K2003/3045—Sulfates
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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
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
- C08K2003/327—Aluminium phosphate
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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
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
- C08K2003/328—Phosphates of heavy metals
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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
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—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
Abstract
The invention relates to application in the field of anticorrosive paint, in particular to high-solid rust-conversion acid-resistant anticorrosive paint and a preparation method thereof. The anticorrosive paint is prepared from A, B two components according to the mass ratio of 10: 1-15: the paint comprises a component A, wherein the component A comprises, by weight, 0-30 parts of epoxy resin, 0-20 parts of modified special acid-resistant resin, 30-50 parts of pigment/filler, 0.5-2 parts of auxiliary agent and 0.78-20 parts of solvent A5; the component B comprises, by weight, 0-20 parts of a solvent B and 80-100 parts of a curing agent. The high-solid-content rust-conversion acid-resistant coating solves the problems of low solid content, environmental pollution, poor resistance to high-concentration acid, high attachment difficulty to rusty base materials after acid corrosion, difficult maintenance and the like of the conventional coating.
Description
Technical Field
The invention relates to application in the field of anticorrosive paint, in particular to high-solid rust-conversion acid-resistant anticorrosive paint and a preparation method thereof.
Background
With the continuous development of industry, the environmental protection consciousness of people is continuously enhanced, the environmental protection coating is more and more emphasized by the nation, the discharge limit of VOC of each country is more and more strict, and the environmental protection coating is more and more favored by people. High solid content anticorrosive coatings have become the trend of the current coatings.
The acidic corrosive environment is a common corrosive environment in industrial production, and the corrosion to the base material is relatively serious, and mainly comprises hydrogen evolution corrosion and oxidation corrosion. The economic loss caused by acid-base corrosion is increasingly serious, and people pay attention to the economic loss. Therefore, the development and the use of the acid-resistant anticorrosive paint are very important. The acid-resistant coating can well protect the base material, prolong the service life of the base material and reduce the maintenance cost of the anticorrosion project in an acid environment.
Steel structure equipment of some chemical plants is corroded by acidic gases such as sulfide, water vapor, oxynitride, hydrogen chloride and the like all the year round, meanwhile, the acidic solution of the chemical plants seriously corrodes the steel structure of the chemical plants, a plurality of chemical plants have the problem that the corroded steel structure is difficult to maintain, and the acid-resistant rust-converting anticorrosive paint can solve the problem of maintaining the steel structure of the chemical plants.
Aiming at the defects of the traditional coating, the requirements of environmental protection and rust conversion and acid-proof environment, the invention adopts the modified special functional resin, improves the acid-proof property of the resin, has the advantages of good acid resistance, good adhesive force, good corrosion resistance, capability of being coated with rust and the like, and has good application prospect.
Disclosure of Invention
The invention provides an acid-resistant anticorrosive paint based on high-solid rust conversion and a preparation method thereof.
In order to realize the problems, the invention adopts the following technical scheme:
the high-solid rust-conversion acid-resistant anticorrosive paint comprises A, B two components in a mass ratio of 10: 1-15: the paint comprises a component A, wherein the component A comprises, by weight, 0-30 parts of epoxy resin, 0-20 parts of modified special acid-resistant resin, 30-50 parts of pigment/filler, 0.5-2 parts of auxiliary agent and 0.78-20 parts of solvent A5; the component B comprises, by weight, 0-20 parts of a solvent B and 80-100 parts of a curing agent. The solid content of the rust-conversion acid-resistant coating is more than or equal to 80 percent.
The modified special acid-resistant resin is prepared by carrying out etherification reaction on fluorine-containing bisphenol A (BPAF) and Epichlorohydrin (ECH) under the catalysis of tetraethylammonium chloride (PTA), and then closing a ring of an etherification product by alkali to obtain the fluorine-containing bisphenol A epoxy resin.
Further, the modified special acid-resistant resin is prepared by mixing BPAF and ECH under a dry condition, adding PTA, and reacting at 70-100 ℃ for 50-60min to obtain an etherified product; then dropwise adding NaOH solution into the etherification product, cooling and refluxing for 100-120min to enable the etherification product to be closed-loop, carrying out reduced pressure distillation for 100-120min, and then carrying out water washing and extraction to obtain fluorine-containing epoxy resin; wherein, the mol ratio of the BPAF to the ECH is 1:4-1:12, and the PTA is 0.5% -2% (mol/BPAF).
The epoxy resin comprises one or two of bisphenol A type epoxy resin, bisphenol F type epoxy resin and novolac epoxy resin;
the bisphenol A type epoxy resin is a high molecular compound prepared by condensing bisphenol A and epoxy chloropropane under an alkaline condition, washing with water, and removing a solvent.
The bisphenol F type epoxy resin is bisphenol F diglycidyl ether, and is prepared by reacting phenol with formaldehyde under acid catalysis to generate bisphenol F, and then carrying out polycondensation reaction with epichlorohydrin in the presence of sodium hydroxide, wherein the epoxy equivalent is 160-170, and the viscosity is 2600-4000 cps.
The novolac epoxy resin comprises one of phenol novolac epoxy resin, o-cresol novolac epoxy resin and bisphenol A novolac epoxy resin.
The pigment/filler is one or more of carbon black, graphite, precipitated barium sulfate, mica, micaceous iron oxide, aluminum tripolyphosphate, zinc oxide, zinc phosphate and organic bentonite;
the carbon black is a black pigment, and has high blackness and tinting strength, stable performance, and good weather resistance and chemical resistance.
Preferably, the graphite is an allotrope of carbon, has a gray black sheet layered structure, is an opaque solid, and has a density of 2.25g/cm3The conductive coating has stable chemical properties, good corrosion resistance, difficult reaction with acid, good shielding performance and good conductive performance.
The precipitated barium sulfate is 800 meshes, has good acid and alkali resistance, is insoluble in water and has low oil absorption. The mica comprises one or more of muscovite, sericite and mica iron oxide, has good chemical stability, and has a lamellar structure capable of preventing water and chemical reagents from penetrating.
The aluminum tripolyphosphate, the zinc oxide and the zinc phosphate have good rust conversion performance. The zinc phosphate is on metal surface and Fe3+Form a firmly adhering complex Fe [ Zn ]3(PO4)3]The precipitation layer inhibits the anode reaction, and simultaneously can be complexed with hydroxyl and carboxyl in the paint, so that chemical combination is formed among the pigment, the coating and the base material, the adhesive force and the impermeability of the coating are improved, and harmful ions in the rust can be inactivated. The aluminum tripolyphosphate can dissociate to obtain tripolyphosphate radical ion P with strong chelating ability3O10 5-The coating has chelation with iron ions of a metal base material to passivate the surface of the metal, so that the coating has high hardness and good adhesive force, can better protect the base material from being corroded, and has strong and long-acting antirust effects. The zinc oxide is an alkaline substance, is beneficial to improving the corrosion resistance of the coating, has good heat resistance and weather resistance, and can realize long-acting and efficient corrosion prevention of a system by reacting the alkaline zinc oxide with hydrogen ions in the aluminum tripolyphosphate to obtain a proper pH value.
The organic bentonite is modified by organic ammonium salt, and comprises high-viscosity organic bentonite, easily dispersible organic bentonite and self-activated organic bentonite.
The auxiliary agent is a dispersing agent, a defoaming agent, a flatting agent and a thickening agent;
wherein the dispersant is one or more of modified polyurethane polymer, modified polyester polymer compound, high molecular weight block copolymer and acid group-containing copolymer; such as AFCONA 4071 modified polyurethane polymer, AFCONA-PF502 modified polyurethane polymer, AFCONA 4053 modified polyester polymer, BYK-163 high molecular weight block copolymer, Disponer 9250 copolymer with acid group.
The defoaming agent is one or more of modified organic silicon, polymerized organic silicon-free polysiloxane and two fluorine modified polysiloxanes; such as AFCONA 2726 modified silicone defoamer, AFCONA2270 silicone free polymeric defoamer, BYK-066N two-fluoro modified polysiloxane.
The flatting agent is one or more of fluorocarbon modified polypropylene ester compound and polyether modified polysiloxane; such as AFCONA-S373 fluorocarbon modified polypropylene ester and AFCONA3030 polyether modified polysiloxane.
The thickener is one or more of polyethylene wax and modified urea solution, such as Disponer202p polyethylene wax, Disponer 201p polyethylene wax, BYK410 modified urea solution.
The curing agent is one or more of an aliphatic amine modified amine curing agent, a polyamide curing agent, a modified Mannich base curing agent and a phenolic amine curing agent.
The solvent A and the solvent B can be the same or different and are selected from one or more of dimethylbenzene, n-butanol, propylene glycol methyl ether, propylene glycol butyl ether and cyclohexanone.
A preparation method of a high-solid rust-conversion acid-resistant anticorrosive paint comprises the following steps:
1) preparation of the component A: under stirring, adding the auxiliary agent into the mixed solvent A, adding the epoxy resin and the modified special acid-resistant resin after stirring to fully dissolve the resin, adding the pigment/filler into the mixture, stirring and mixing uniformly, and grinding the materials until the fineness is less than or equal to 50 mu m to obtain a component A;
2) b, preparation of a component: feeding the curing agent and the solvent B according to a required proportion, and uniformly mixing to obtain a component B;
3) when in use, A, B bi-component is mixed according to the mass ratio of 10: 1-15: 1 and mixing.
The invention has the advantages that:
the high-solid-content rust-conversion acid-resistant coating solves the problems of the existing coating, such as low solid content, environmental pollution, poor resistance to high-concentration acid, high attachment difficulty to rusty base materials after acid corrosion, difficult maintenance and the like; the method comprises the following steps:
1. the high-solid rust-transferring acid-resistant coating has good rust-transferring performance due to the fact that the special acid-resistant resin has good acid resistance, and the aluminum tripolyphosphate, the zinc oxide and the zinc phosphate have good rust-transferring performance, so that the high-solid rust-transferring acid-resistant coating has good salt spray resistance, good corrosion resistance, excellent chemical medium resistance such as acid resistance, salt water resistance and solvent resistance.
2. Compared with the traditional oil paint, the high-solid rust-conversion acid-resistant paint has the advantages of higher solid content, less solvent content, low VOC (volatile organic compound) emission and less environmental pollution.
3. The high-solid-content rust-conversion acid-resistant coating can be coated on a low-surface treatment, reduces the treatment cost of a base material before construction, and is convenient to use for rust base material and equipment maintenance.
4. The paint provided by the invention can be used under a harsh corrosive environment, so that the service life of equipment is prolonged, and the paint is particularly suitable for surface coating protection of newly-built equipment and equipment maintenance in an acidic environment in the field of chemical corrosion prevention.
Detailed Description
The technical solution of the present invention is clearly and completely described below with reference to the following examples. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The formula of the anticorrosive paint of each embodiment is calculated by weight fraction.
Examples 1 to 20
The modified special acid-resistant resin is specifically prepared from fluorine-containing epoxy resin: adding BPAF and ECH into a drying flask, mixing the BPAF and the ECH according to a molar ratio of 1:10, adding PTA (tetraethylammonium chloride) with the mass of the mixture of 1% (mol/BPAF) as a catalyst, and reacting at 70 ℃ for 60min to obtain an etherification product. And then, dropwise adding a NaOH solution with the mass fraction of 28.57% into the etherification product, and cooling and refluxing for 120min to enable the etherification product to be closed. And after the reaction is finished, removing unreacted ECH monomers by adopting a reduced pressure distillation method, dropwise adding a NaOH solution, cooling and refluxing for 120min, and extracting and washing to obtain a fluorine-containing epoxy resin solution which is used in the coating of each embodiment.
Examples preparation of coatings (see tables 1-3):
1) preparation of a component A: adding 18 parts of solvent, 0-30 parts of epoxy resin and 0-10 parts of modified special acid-resistant resin into a moving cylinder, dispersing for 30min by using a high-speed dispersion machine, adding 2 parts of mixed auxiliary agent, after uniform dispersion, sequentially adding 0.5 part of carbon black, 0-10 parts of graphite, 0-25 parts of precipitated barium sulfate, 15 parts of mica, 0-10 parts of mica iron oxide, 0-3 parts of aluminum tripolyphosphate, 0-5 parts of zinc oxide, 0-5 parts of zinc phosphate and 0.5 part of organic bentonite, dispersing for 10-15 min at a high speed of 800-1000r/min, grinding to the fineness of less than or equal to 50 mu m by using a sand mill, and filtering and discharging to obtain the component A. Wherein the mixed auxiliary agent is a mixture of a dispersing agent, a defoaming agent, a flatting agent and a thickening agent. The dispersing agent is AFCONA-PF502 modified polyurethane high polymer, the defoaming agent is AFCONA2270 silicone-free polymerization type defoaming agent, the leveling agent is AFCONA-S373 fluorocarbon modified polypropylene ester, and the thickening agent is Disponer202p polyethylene wax.
2) B, preparation of a component: and mixing the curing agent and the solvent B according to the proportion, adding the mixture into a dispersion cylinder, dispersing for 10min at the rotating speed of 800-1000r/min, filtering and discharging to obtain the component B.
3) Coating: and (3) homogenizing the obtained component A and component B according to the mass ratio of 13: 1 and mixing.
The coating is coated on a standard test carbon steel plate, and performance tests are carried out according to HG/T4564-2013 epoxy coating with low surface treatment tolerance and HG/T5572-2019 acid-resistant anticorrosive coating for inner walls of petrochemical equipment, wherein the coating has the advantages of adhesive force, flexibility, impact resistance, neutral salt mist resistance and medium resistance (see table 4). The data in the table show that the performance index of each example exceeds the standard.
TABLE 1 examples 1-20 ingredient A formulation tables (based on 100g of ingredient A)
Table 2 examples 1-20 amount of resin used in component a formulations
Table 3 examples 1-20 amount of mixing aid in component a formulation
Table 4 table of properties of the components of examples 1-20
Claims (8)
1. The high-solid rust-conversion acid-resistant anticorrosive paint is A, B bi-component, and is characterized in that: the anticorrosive paint is prepared from A, B two components according to the mass ratio of 10: 1-15: the paint comprises a component A, wherein the component A comprises, by weight, 0-30 parts of epoxy resin, 0-20 parts of modified special acid-resistant resin, 30-50 parts of pigment/filler, 0.5-2 parts of auxiliary agent and 0.78-20 parts of solvent A5; the component B comprises, by weight, 0-20 parts of a solvent B and 80-100 parts of a curing agent.
2. The high-solid rust-conversion acid-resistant anticorrosive paint according to claim 1, characterized in that: the modified special acid-resistant resin is prepared by carrying out etherification reaction on fluorine-containing bisphenol A (BPAF) and Epichlorohydrin (ECH) under the catalysis of tetraethylammonium chloride (PTA), and then closing a ring of an etherification product by alkali to obtain the fluorine-containing bisphenol A epoxy resin.
3. The high-solid rust-conversion acid-resistant anticorrosive paint according to claim 2, characterized in that: the modified special acid-resistant resin is prepared by mixing BPAF and ECH under a dry condition, adding PTA, and reacting at 70-100 ℃ for 50-60min to obtain an etherified product; then dropwise adding NaOH solution into the etherification product, cooling and refluxing for 100-120min to enable the etherification product to be closed-loop, carrying out reduced pressure distillation for 100-120min, and then carrying out water washing and extraction to obtain fluorine-containing epoxy resin; wherein, the mol ratio of the BPAF to the ECH is 1:4-1:12, and the PTA is 0.5% -2% (mol/BPAF).
4. The high-solid rust-conversion acid-resistant anticorrosive paint according to claim 1, characterized in that: the epoxy resin comprises one or two of bisphenol A type epoxy resin, bisphenol F type epoxy resin and novolac epoxy resin; the pigment/filler is one or more of carbon black, graphite, precipitated barium sulfate, mica, micaceous iron oxide, aluminum tripolyphosphate, zinc oxide, zinc phosphate and organic bentonite; the auxiliary agent is a dispersing agent, a defoaming agent, a wetting agent, a flatting agent and a thickening agent; the curing agent is one or more of an aliphatic amine modified amine curing agent, a polyamide curing agent, a modified Mannich base curing agent and a phenolic amine curing agent.
5. The high-solid rust-conversion acid-resistant anticorrosive paint according to claim 1, characterized in that: the solvent A and the solvent B can be the same or different and are selected from one or more of dimethylbenzene, n-butanol, propylene glycol methyl ether, propylene glycol butyl ether and cyclohexanone.
6. The preparation method of the high-solid rust-conversion acid-resistant anticorrosive paint as claimed in claim 1, characterized in that:
1) preparation of the component A: under stirring, adding the auxiliary agent into the mixed solvent A, adding the epoxy resin and the modified special acid-resistant resin after stirring to fully dissolve the resin, adding the pigment/filler into the mixture, stirring and mixing uniformly, and grinding the materials until the fineness is less than or equal to 50 mu m to obtain a component A;
2) b, preparation of a component: feeding the curing agent and the solvent B according to a required proportion, and uniformly mixing to obtain a component B;
3) when in use, A, B bi-component is mixed according to the mass ratio of 10: 1-15: 1 and mixing.
7. The method for preparing the high-solid rust-conversion acid-resistant anticorrosive paint according to claim 6, characterized in that:
the modified special acid-resistant resin is prepared by carrying out etherification reaction on fluorine-containing bisphenol A (BPAF) and Epichlorohydrin (ECH) under the catalysis of tetraethylammonium chloride (PTA), and then closing a ring of an etherification product by alkali to obtain the fluorine-containing bisphenol A epoxy resin.
8. The method for preparing the high-solid rust-conversion acid-resistant anticorrosive paint according to claim 7, characterized in that: the modified special acid-resistant resin is prepared by mixing BPAF and ECH under a dry condition, adding PTA, and reacting at 70-100 ℃ for 50-60min to obtain an etherified product; then dropwise adding NaOH solution into the etherification product, cooling and refluxing for 100-120min to enable the etherification product to be closed-loop, carrying out reduced pressure distillation for 100-120min, and then carrying out water washing and extraction to obtain fluorine-containing epoxy resin; wherein, the mol ratio of the BPAF to the ECH is 1:4-1:12, and the PTA is 0.5% -2% (mol/BPAF).
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| CN115466562A (en) * | 2022-09-06 | 2022-12-13 | 安徽先进建筑材料研究院有限公司 | Wharf steel column anti-corrosion coating and preparation method thereof |
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| CN114133832A (en) * | 2021-12-30 | 2022-03-04 | 安徽省金盾涂料有限责任公司 | Acid-resistant paint for ships |
| CN114605892A (en) * | 2022-03-22 | 2022-06-10 | 厦门双瑞船舶涂料有限公司 | Organosilicon quaternary ammonium salt modified epoxy anticorrosive paint and preparation method thereof |
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Application publication date: 20210209 |