CN111087841A - Anticorrosive coating for surface of magnesium alloy substrate - Google Patents
Anticorrosive coating for surface of magnesium alloy substrate Download PDFInfo
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- CN111087841A CN111087841A CN201911333276.0A CN201911333276A CN111087841A CN 111087841 A CN111087841 A CN 111087841A CN 201911333276 A CN201911333276 A CN 201911333276A CN 111087841 A CN111087841 A CN 111087841A
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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
- C09D5/082—Anti-corrosive paints characterised by the anti-corrosive pigment
- C09D5/084—Inorganic compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/46—Polycondensates having carboxylic or carbonic ester groups in the main chain having heteroatoms other than oxygen
- C08G18/4607—Polycondensates having carboxylic or carbonic ester groups in the main chain having heteroatoms other than oxygen having halogens
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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
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/06—Polyurethanes from polyesters
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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
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
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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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2251—Oxides; Hydroxides of metals of chromium
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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
- 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
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
Abstract
The magnesium alloy base material of the invention has the characteristics of liveness, easy corrosion and the like, and develops an anti-corrosion primer with excellent adhesion with the base material and a hydrophobic and high-crosslinking protective finish. In the using process, firstly, the magnesium alloy base material is subjected to chemical oxidation or micro-arc oxidation treatment, then the primer is sprayed within 24 hours, and finally the finish paint is used for coating, so that the long-acting anticorrosion effect of the magnesium alloy base material can be met, wherein the neutral salt spray resistance can reach 1500 hours, and the humidity resistance and heat resistance can also reach 1500 hours.
Description
Technical Field
The invention relates to an anticorrosive coating for the surface of a magnesium alloy substrate.
Background
Along with the technological progress, people have more and more requirements on the use of magnesium alloy, and the magnesium alloy as a new green novel material has many advantages which cannot be achieved by other metals, such as high strength, small density (about 1.8g/cm 3), good electromagnetic shielding, large elastic modulus, good heat dissipation, good shock absorption, larger impact load bearing capacity than aluminum alloy, good organic matter and alkali corrosion resistance and the like, and has important application value and wide application prospect in the fields of communication, automobiles, chemical industry, electronics, aerospace, rockets, weapons, national defense and the like. However, magnesium alloys have high activity and are very easy to corrode and destroy in humid, marine and Cl-containing corrosive media. Therefore, the use of magnesium alloy metal is affected, and in order to make the metal perform advantages and fully use, various protection methods such as metal plating, micro-arc oxidation, chemical conversion coating, anodic oxidation and the like are researched, but the corrosion resistance is still poor. Therefore, the surface of the magnesium alloy substrate needs to be protected by coating a special anticorrosive coating system.
Because the magnesium alloy substrate is more active and is easy to corrode in the natural environment, in order to improve the corrosion resistance of the magnesium alloy, the domestic method adopted at present mainly comprises chemical oxidation, micro-arc oxidation and protective coating, the common chemical oxidation conversion film can resist 24 hours at most and generate foaming corrosion under neutral salt fog, the selected base material after micro-arc oxidation treatment has great improvement on corrosion resistance compared with chemical oxidation, the process for carrying out surface ceramic treatment on the magnesium and the alloy material thereof has the advantages of simple process, strong processing capability, high production efficiency and the like, the processed film has high hardness, strong corrosion resistance (neutral salt spray test 192h), strong bonding force between the film and the base material, the method has the defects that micro-arc oxidation is high in power consumption and high in cost, the required performance of the magnesium alloy base material can be influenced to a certain extent in the treatment process, and micro-arc oxidation treatment of the magnesium alloy base material is forbidden by part of units. The existing magnesium alloy protective coating can not reach the neutral salt fog resistance and the damp and heat resistance performance for 1500 h.
There is therefore a need to develop coating systems which have excellent corrosion protection properties. The magnesium alloy anticorrosion coating system generally comprises a primer and a finish, wherein the primer has excellent adhesion and mechanical properties and can provide good anticorrosion performance. The finish paint has certain corrosion resistance and artificial aging resistance, so that the coating system can be used in any natural environment.
The magnesium alloy base material is mainly composed of magnesium element and has high activity, because of the processing technology and the structure state of the magnesium alloy, the magnesium alloy base material contains impurities and alloy elements, chemical corrosion and galvanic corrosion are easy to generate in the environment, and the magnesium alloy anti-corrosion coating sold on the market cannot meet the requirements of long-time salt mist resistance and humidity and heat resistance, so that the magnesium alloy is easy to corrode when applied in a complex environment, and the wide application of the magnesium alloy base material is limited.
Disclosure of Invention
The purpose of the invention is as follows: aiming at the characteristics of liveness, easy corrosion and the like of a magnesium alloy substrate, an anti-corrosion primer with excellent adhesion with the substrate and a hydrophobic and high-crosslinking protective finish are developed. In the using process, firstly, the magnesium alloy base material is subjected to chemical oxidation or micro-arc oxidation treatment, then the primer is sprayed within 24 hours, and finally the finish paint is used for coating, so that the long-acting anticorrosion effect of the magnesium alloy base material can be met, wherein the neutral salt spray resistance can reach 1500 hours, and the humidity resistance and heat resistance can also reach 1500 hours.
The invention mainly aims at the protection requirements of the magnesium alloy substrate on heat and humidity resistance and salt mist resistance, and carries out professional technical research to prepare the anticorrosive primer with excellent adhesive force and the hydrophobic and high-crosslinking protective finish. The coating system can meet the basic performance required by the surface of the magnesium alloy substrate.
The anti-corrosion coating for the surface of the magnesium alloy substrate consists of a primer and a finish.
The primer consists of a component A and a component B, wherein the component A consists of bisphenol A modified phenolic epoxy resin, zinc chrome yellow, mica powder, talcum powder, precipitated barium sulfate, graphene, titanium dioxide, a dispersing agent, a leveling agent, an antifoaming agent, a mixed solvent and the like; the component B consists of polyamide resin and mixed solvent.
The finish paint consists of a component A and a component B, wherein the component A consists of fluorine-containing modified polyester resin, titanium dioxide, talcum powder, mica powder, a dispersing agent, a leveling agent, a defoaming agent, a catalyst, a mixed solvent and the like; the component B consists of polyisocyanate and mixed solvent.
The formula of the anti-corrosion primer A for the surface of the magnesium alloy substrate comprises the following components in percentage by mass:
the bisphenol A modified novolac epoxy resin is a mixture of any one or more than two of EPALLOY 7138, EPALLOY 7170, EPALLOY9237-70 and EPALLOY7200X90 in any proportion, contains a large amount of benzene ring structures and epoxy functional groups, and has high crosslinking density, excellent adhesive force and heat resistance after being cured.
The dispersant is at least one of BYK-110, BYK-163 and BYK-P104S.
The leveling agent is at least one of BYK-378, BYK-320 and BYK-306.
The defoaming agent is at least one of BYK-054 and BYK-066N, BYK-A530
The mixed solvent is at least one of cyclohexanone, xylene, butyl acetate and butanol.
The formula of the anti-corrosion primer B for the surface of the magnesium alloy base material comprises the following components in percentage by mass:
60 to 65 percent of polyamide resin
35 to 40 percent of mixed solvent
The polyamide resin is one or a mixture of more than two of polyamide 651, polyamide 650, polyamide D-3014 and polyamide D-3015 in any proportion.
The mixed solvent is at least one of cyclohexanone, xylene, butyl acetate and butanol.
The protective finishing coat A for the surface of the magnesium alloy substrate comprises the following components in percentage by mass:
the fluorine-containing modified polyester resin is specially synthesized, and is prepared by carrying out dehydration reaction between one or more of trifluoroethanol, tetrafluoropropanol and hexafluorobutanol and one or more of polyester 800 resin, polyester T1665 and polyester 651 resin at 200-250 ℃ and concentrated sulfuric acid as a catalyst to obtain ether, so that fluorine is introduced into the polyester resin, and fluorine-containing modified polyester resins FJ-1 (trifluoroethanol modified polyester 800), FJ-2 (tetrafluoropropanol modified polyester 651) and FJ-3 (hexafluorobutanol modified polyester 651) are synthesized, so that the synthesized fluorine-containing modified polyester resin not only contains excellent mechanical properties, chemical properties and weather resistance of the polyester resin, but also has low surface properties and hydrophobic properties, and the corrosion resistance of the resin is improved.
The dispersant is at least one of BYK-110, BYK-163 and BYK-P104S.
The leveling agent is at least one of BYK-378, BYK-320 and BYK-331.
The defoaming agent is at least one of BYK-054 and BYK-066N, BYK-A530.
The catalyst is at least one of dibutyltin dilaurate, stannous octoate and dibutyltin diacetate.
The mixed solvent is at least one of cyclohexanone, xylene, butyl acetate and propylene glycol monomethyl ether acetate.
The formula of the protective finish paint B for the surface of the magnesium alloy substrate comprises the following components in percentage by mass:
75 to 85 percent of polyisocyanate
15 to 25 percent of mixed solvent
The polyisocyanate is an isocyanate compound with the functionality of 2 or more than 2, and the NCO content of the polyisocyanate is 10-15%. .
The mixed solvent is at least one of propylene glycol methyl ether acetate, xylene, butyl acetate and cyclohexanone.
The preparation method of the anti-corrosion primer for the surface of the magnesium alloy substrate prepares materials according to the formula, and the preparation process of the component A comprises the following steps:
dissolving bisphenol A modified novolac epoxy resin: putting the mixed solvent and the bisphenol A modified novolac epoxy resin into a dissolving container, heating to a reflux temperature, and stirring to dissolve the bisphenol A modified novolac epoxy resin. And after the solution is uniformly dissolved, continuing stirring for 1h to prepare the bisphenol A modified novolac epoxy resin solution.
Preparing the component A. Sequentially adding bisphenol A modified phenolic epoxy resin solution, zinc chrome yellow, mica powder, talcum powder, precipitated barium sulfate, titanium dioxide, a leveling agent, a defoaming agent and part of mixed solvent into a pulling cylinder under a stirring state, uniformly stirring, grinding until the fineness is less than 40 mu m, then adding graphene, a dispersing agent and the rest of mixed solvent, continuously grinding until the fineness is less than 30 mu m, filtering and discharging to obtain the component A.
The preparation method of the anti-corrosion primer for the surface of the magnesium alloy substrate prepares materials according to the formula, and the preparation process of the component B comprises the following steps:
and sequentially adding the polyamide resin and the mixed solvent into the pulling cylinder under the stirring state, uniformly stirring, filtering and discharging to obtain the component B.
The preparation method of the protective finishing coat for the surface of the magnesium alloy substrate prepares materials according to the formula, and the preparation process of the component A comprises the following steps:
synthesis of fluorine-containing modified polyester resin: the fluorine-containing alcohol monomers such as trifluoroethanol, tetrafluoropropanol and hexafluorobutanol are subjected to dehydration reaction with hydroxyl groups in polyester resins such as polyester 800, polyester T1665 and polyester 651 at the temperature of 200-250 ℃ and concentrated sulfuric acid as a catalyst, and then fluorine-containing polyester resins FJ-1 (trifluoroethanol modified polyester 800), FJ-2 (tetrafluoropropanol modified polyester 651) and FJ-3 (hexafluorobutanol modified polyester 651) are synthesized, wherein the fluorine monomers account for 6-10% of the polyester resins.
Preparing the component A. Sequentially adding fluorine-containing modified polyester resin, titanium dioxide, talcum powder, mica powder, a dispersing agent, a flatting agent, a defoaming agent, a catalyst and a mixed solvent into a drawn cylinder under a stirring state, uniformly stirring, grinding until the fineness is less than 30 mu m, filtering and discharging to obtain the component A.
The preparation method of the protective finishing coat for the surface of the magnesium alloy substrate prepares materials according to the formula, and the preparation process of the component B comprises the following steps:
firstly, adding polyol resin and a solvent into a reaction bottle for reflux dehydration, then adding diisocyanate for heat preservation reaction, taking the percentage content of NCO as a final control index, filtering and discharging to obtain a component B.
The key points of the technology of the invention are as follows:
(1) preparing an anticorrosive primer A component for the surface of the magnesium alloy substrate;
(2) preparing protective finish paint for the surface of the magnesium alloy substrate.
The invention relates to an anticorrosive coating for the surface of a magnesium alloy substrate. The anticorrosive primer adopts composite bisphenol A modified novolac epoxy resin solution as main resin, polyamide solution as component B, flaky mica powder and graphene as pigment and filler, and zinc chrome as passivation pigment as anticorrosive pigment and filler. The primer combines a high-degree cross-linking structure with good flexibility, and improves the anti-corrosion performance of the coating. The protective finish paint adopts hydrophobic and high-crosslinking fluorine-containing modified polyester resin as base resin, isocyanate resin as a curing agent and mica powder as shielding filler to prepare the finish paint which is not only anticorrosive but also weather-resistant. Under the synergistic effect of the primer and the finish paint, the magnesium alloy base material is well protected, so that the magnesium alloy base material can be used in a complex environment for a long time. The method has the following beneficial effects:
(1) the primer adopts bisphenol A modified novolac epoxy resin with higher epoxy value and the like as base resin, and the formed paint film has high crosslinking density, good adhesive force and better corrosion resistance. The pigment and the filler are selected from zinc chrome yellow, mica powder, graphene and the like, wherein the zinc chrome yellow has an anode protection and passivation effect, and the mica powder and the graphene are of sheet structures and have the effect of preventing water vapor and media from penetrating through a paint film to enter a base material. Therefore, the primer has excellent anti-corrosion performance under the synergistic action of the high-crosslinking resin and the anti-corrosion pigment and filler.
(2) The finish paint selects fluorine-containing modified polyester resin with higher hydroxyl value, the resin has certain hydrophobicity, higher crosslinking density, ultrahigh weather resistance, solvent resistance, heat resistance and the like, compared with the existing fluorine-containing polyester resin in the market, the performance of the fluorine-containing monomer and Bayer-containing polyester resin selected by people is relatively stable, then the crosslinking density and the hydrophobic performance reach certain balance under the modification of the fluorine-containing monomer in a certain proportion, finally the required anti-corrosion performance can be achieved, the existing fluorine-containing polyester resin in the market is taken as base resin, the salt mist resistance and the humidity resistance performance on a magnesium alloy base material are difficult to reach 1500h, and the performance of each batch is not stable.
The pigment and the filler are selected from rutile titanium dioxide with good weather resistance and mica powder with higher shielding performance, so that the formed paint film can further improve the corrosion resistance and weather resistance of the primer, the bottom surface matching coating system improves the corrosion resistance of the base material to a great extent, the safety of equipment using the magnesium alloy base material is improved, and the actual service life of the equipment is prolonged.
Detailed Description
This example demonstrates the preparation of an anti-corrosive coating for the surface of a magnesium alloy substrate.
The first embodiment is as follows:
(1) preparing an anticorrosive primer A component for the surface of the magnesium alloy substrate: adding 4kg of cyclohexanone, 8.4kg of xylene and 3.6kg of butanol into a reaction kettle, adding 12kg of modified novolac epoxy EPALLOY 7138 and 4kg of modified novolac epoxy EPALLOY 7170, heating to a reflux state, and keeping the temperature for 2 hours in the reflux state to obtain the bisphenol A modified novolac epoxy resin solution. Adding 2kg of dispersant BYK-110, 0.3kg of flatting agent BYK-320, 0.5kg of defoaming agent BYK-A530, 4.64kg of cyclohexanone, 9.74kg of dimethylbenzene, 4.18kg of butanol, 15kg of zinc chrome yellow, 3kg of titanium dioxide, 3kg of talcum powder, 4kg of precipitated barium sulfate and 6kg of mica powder into an epoxy resin solution in sequence under the stirring state, stirring for 30 minutes, grinding and dispersing until the fineness is less than 40 mu m, continuously adding 1kg of graphene, 1kg of dispersant and 6kg of dimethylbenzene, grinding until the fineness is less than 30 mu m, filtering and discharging to obtain a component A
(2) Preparing an anti-corrosion primer B component for the surface of the magnesium alloy substrate: adding 60kg of polyamide 651 resin, 10kg of cyclohexanone, 21kg of xylene and 9kg of butanol into a drawn cylinder under the stirring state, stirring for 25 minutes, and filtering and discharging to obtain the component B.
(3) Preparing a protective finish A component for the surface of the magnesium alloy substrate:
synthesis of fluorine-containing modified polyester resin: carrying out dehydration reaction between 0.9kg of trifluoroethanol and 9.1kg of hydroxyl in polyester 800 resin at the temperature of 230 ℃ and concentrated sulfuric acid as a catalyst to synthesize fluorine-containing polyester resin FJ-1; the polyester resin FJ-2 containing fluorine was synthesized by dehydration reaction between 1.4kg of tetrafluoropropanol and 18.6kg of hydroxyl group in polyester 651 resin at 230 ℃ with concentrated sulfuric acid as a catalyst.
Adding 10kg of fluorine-containing polyester resin FJ-1, 20kg of fluorine-containing polyester resin FJ-2, 16kg of titanium dioxide, 20kg of mica powder, 4kg of talcum powder, 2kg of BYK-163, 0.3kg of BYK-320, 0.4kg of BYK-054, 0.03kg of dibutyltin dilaurate, 10kg of dimethylbenzene, 10kg of cyclohexanone and 10kg of propylene glycol methyl ether acetate into a drawn cylinder in sequence under the stirring state, stirring for 30 minutes, grinding and dispersing until the fineness is less than 30 mu m, filtering and discharging to obtain the component A.
(4) Preparing a protective finish paint component B for the surface of the magnesium alloy substrate: 75kg of polyisocyanate with the NCO content of 18 percent and 25kg of butyl acetate are added into a pulling cylinder under the stirring state, and after stirring for 25 minutes, the mixture is filtered and discharged, thus obtaining the component B.
Example two:
(1) preparing an anticorrosive primer A component for the surface of the magnesium alloy substrate: adding 4kg of cyclohexanone, 8.4kg of xylene and 3.6kg of butanol into a reaction kettle, adding 16kg of modified novolac epoxy EPALLOY 7170, heating to a reflux state, and keeping the temperature for 2 hours in the reflux state to obtain a modified novolac epoxy resin solution. Adding 2kg of dispersant BYK-110, 0.3kg of flatting agent BYK-320, 0.5kg of defoaming agent BYK-A530, 4.64kg of cyclohexanone, 9.74kg of dimethylbenzene, 4.18kg of butanol, 15kg of zinc chrome yellow, 3kg of titanium dioxide, 3kg of talcum powder, 4kg of precipitated barium sulfate and 8kg of mica powder into an epoxy resin solution in sequence under a stirring state, stirring for 30 minutes, grinding and dispersing until the fineness is less than 40 mu m, continuously adding 1kg of graphene, 1kg of dispersant and 6kg of dimethylbenzene, grinding until the fineness is less than 30 mu m, filtering and discharging to obtain the component A.
(2) Preparing an anti-corrosion primer B component for the surface of the magnesium alloy substrate: adding 40kg of polyamide 651 resin, 20kg of polyamide D-3014, 10kg of cyclohexanone, 21kg of xylene and 9kg of butanol into a drawn cylinder under the stirring state, stirring for 25 minutes, and filtering and discharging to obtain the component B.
(3) Preparing a protective finish A component for the surface of the magnesium alloy substrate:
synthesis of fluorine-containing modified polyester resin: the polyester resin FJ-2 containing fluorine was synthesized by dehydration reaction between 2.1kg of tetrafluoropropanol and 27.9kg of hydroxyl group in polyester 651 resin at 230 ℃ with concentrated sulfuric acid as a catalyst.
Adding 30kg of fluorine-containing polyester resin FJ-2, 16kg of titanium dioxide, 25kg of mica powder, 4kg of talcum powder, 2kg of BYK-163, 0.3kg of BYK-320, 0.4kg of BYK-054, 0.03kg of dibutyltin dilaurate, 10kg of dimethylbenzene, 10kg of cyclohexanone and 10kg of propylene glycol monomethyl ether acetate into a drawn cylinder in sequence under the stirring state, stirring for 30 minutes, grinding and dispersing until the fineness is less than 30 mu m, filtering and discharging to obtain the component A.
(4) Preparing a protective finish paint component B for the surface of the magnesium alloy substrate: 75kg of polyisocyanate with the NCO content of 18 percent and 25kg of butyl acetate are added into a pulling cylinder under the stirring state, and after stirring for 25 minutes, the mixture is filtered and discharged, thus obtaining the component B.
Example three:
(1) preparing an anticorrosive primer A component for the surface of the magnesium alloy substrate: adding 4kg of cyclohexanone, 8.4kg of xylene and 3.6kg of butanol into a reaction kettle, adding 8kg of modified novolac epoxy EPALLOY 7170, heating to a reflux state, keeping the temperature for 2 hours in the reflux state, cooling, and adding 8kg of modified novolac epoxy EPALLOY7200X90 to obtain the modified novolac epoxy resin solution. Adding 2kg of dispersant BYK-110, 0.3kg of flatting agent BYK-320, 0.5kg of defoaming agent BYK-A530, 4.64kg of cyclohexanone, 9.74kg of dimethylbenzene, 4.18kg of butanol, 13kg of zinc chrome yellow, 3kg of titanium dioxide, 3kg of talcum powder, 4kg of precipitated barium sulfate and 8kg of mica powder into an epoxy resin solution in sequence under a stirring state, stirring for 30 minutes, grinding and dispersing until the fineness is less than 40 mu m, continuously adding 0.8kg of graphene, 1kg of dispersant and 6kg of dimethylbenzene, grinding until the fineness is less than 30 mu m, filtering and discharging to obtain the component A.
(2) Preparing an anti-corrosion primer B component for the surface of the magnesium alloy substrate: adding 40kg of polyamide 651 resin, 20kg of polyamide D-3014, 10kg of cyclohexanone, 21kg of xylene and 9kg of butanol into a drawn cylinder under the stirring state, stirring for 25 minutes, and filtering and discharging to obtain the component B.
(3) Preparing a protective finish A component for the surface of the magnesium alloy substrate:
synthesis of fluorine-containing modified polyester resin: the polyester resin FJ-3 containing fluorine was synthesized by dehydration reaction between 1.8kg of hexafluorobutanol and 28.2kg of hydroxyl groups in polyester 651 resin at 230 ℃ in the presence of concentrated sulfuric acid as a catalyst.
Adding 30kg of fluorine-containing polyester resin FJ-3, 16kg of titanium dioxide, 25kg of mica powder, 4kg of talcum powder, 2kg of BYK-163, 0.3kg of BYK-320, 0.4kg of BYK-054, 0.03kg of dibutyltin dilaurate, 10kg of dimethylbenzene, 10kg of cyclohexanone and 10kg of propylene glycol monomethyl ether acetate into a drawn cylinder in sequence under the stirring state, stirring for 30 minutes, grinding and dispersing until the fineness is less than 30 mu m, filtering and discharging to obtain the component A.
(4) Preparing a protective finish paint component B for the surface of the magnesium alloy substrate: 75kg of polyisocyanate with the NCO content of 18 percent and 25kg of butyl acetate are added into a pulling cylinder under the stirring state, and after stirring for 25 minutes, the mixture is filtered and discharged, thus obtaining the component B.
The products of examples 1-3 were coated on a magnesium alloy substrate and subjected to wet heat resistance and neutral salt spray resistance tests after 7 days of drying. The test results were as follows:
Claims (10)
1. the anti-corrosion coating for the surface of the magnesium alloy substrate is characterized by comprising a primer and a finish: the formula of the anti-corrosion primer A for the surface of the magnesium alloy substrate comprises the following components in percentage by mass:
2. the anticorrosion coating for the surface of a magnesium alloy substrate according to claim 1, wherein the bisphenol A modified novolac epoxy resin is one or a mixture of two or more of EPALLOY 7138, EPALLOY 7170, EPALLOY9237-70 and EPALLOY7200X90 at any ratio.
3. The anticorrosion coating for the surface of a magnesium alloy substrate as recited in claim 1, wherein the dispersant is at least one of BYK-110, BYK-163 and BYK-P104S, the leveling agent is at least one of BYK-378, BYK-320 and BYK-306, the defoaming agent is at least one of BYK-054 and BYK-066N, BYK-A530, and the mixed solvent is at least one of cyclohexanone, xylene, butyl acetate and butanol.
4. The magnesium alloy substrate surface anticorrosion coating, according to claim 1, characterized in that the formula of the magnesium alloy substrate surface anticorrosion primer B component is, by mass percent:
60 to 65 percent of polyamide resin
35 to 40 percent of mixed solvent.
5. The anticorrosion coating for the surface of a magnesium alloy substrate according to claim 1, wherein the polyamide resin is one of polyamide 651, polyamide 650, polyamide D-3014 and polyamide D-3015, or a mixture of two or more of them at any ratio, and the mixed solvent is at least one of cyclohexanone, xylene, butyl acetate and butanol.
6. The anticorrosive coating for the surface of the magnesium alloy substrate according to claim 1, wherein the formula of the component A of the protective finish for the surface of the magnesium alloy substrate is as follows by mass percent:
7. the anticorrosion coating for the surface of a magnesium alloy substrate according to claim 6, wherein the fluorine-containing modified polyester resin is obtained by a dehydration reaction between one or a mixture of more of trifluoroethanol, tetrafluoropropanol and hexafluorobutanol and one or a mixture of more of polyester 800 resin, polyester T1665 and polyester 651 resin at a temperature of 200-250 ℃ and concentrated sulfuric acid as a catalyst.
8. The anticorrosion coating for the surface of a magnesium alloy substrate as recited in claim 6, wherein the dispersant is at least one of BYK-110, BYK-163 and BYK-P104S, the leveling agent is at least one of BYK-378, BYK-320 and BYK-331, the defoamer is at least one of BYK-054 and BYK-066N, BYK-a530, the catalyst is at least one of dibutyltin dilaurate, stannous octoate and dibutyltin diacetate, and the mixed solvent is at least one of cyclohexanone, xylene, butyl acetate and propylene glycol methyl ether acetate.
9. The anticorrosive coating for the surface of the magnesium alloy substrate according to claim 6, wherein the formula of the protective finish paint B for the surface of the magnesium alloy substrate comprises the following components in percentage by mass:
75 to 85 percent of polyisocyanate
15 to 25 percent of mixed solvent
10. The anticorrosion coating for the surface of a magnesium alloy base material according to claim 9, wherein the polyisocyanate is an isocyanate compound having a functionality of 2 or more, and has an NCO content of 10% to 15%, and the mixed solvent is at least one of propylene glycol methyl ether acetate, xylene, butyl acetate, and cyclohexanone.
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| CN111073448A (en) * | 2019-12-03 | 2020-04-28 | 北京卫星制造厂有限公司 | Antistatic and anticorrosive coating and preparation method thereof |
| CN111100493A (en) * | 2019-12-03 | 2020-05-05 | 北京卫星制造厂有限公司 | Graphene anti-corrosion-thermal control-anti-static integrated functional coating and preparation method thereof |
| CN112029394A (en) * | 2020-08-04 | 2020-12-04 | 航天材料及工艺研究所 | Composition for forming magnesium-lithium alloy surface anticorrosive coating system and preparation method of anticorrosive coating system |
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| CN103360585A (en) * | 2012-03-31 | 2013-10-23 | 上海富臣化工有限公司 | Fluorine-modified high scratch resistance light resin and preparation method thereof |
| CN103849293A (en) * | 2012-12-03 | 2014-06-11 | 上海开林造漆厂 | Anticorrosion thermal insulation heat reflecting paint for storage tank and preparation method thereof |
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| CN103360585A (en) * | 2012-03-31 | 2013-10-23 | 上海富臣化工有限公司 | Fluorine-modified high scratch resistance light resin and preparation method thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111073448A (en) * | 2019-12-03 | 2020-04-28 | 北京卫星制造厂有限公司 | Antistatic and anticorrosive coating and preparation method thereof |
| CN111100493A (en) * | 2019-12-03 | 2020-05-05 | 北京卫星制造厂有限公司 | Graphene anti-corrosion-thermal control-anti-static integrated functional coating and preparation method thereof |
| CN111100493B (en) * | 2019-12-03 | 2021-10-01 | 北京卫星制造厂有限公司 | Graphene anti-corrosion-thermal control-anti-static integrated functional coating and preparation method thereof |
| CN112029394A (en) * | 2020-08-04 | 2020-12-04 | 航天材料及工艺研究所 | Composition for forming magnesium-lithium alloy surface anticorrosive coating system and preparation method of anticorrosive coating system |
| CN112029394B (en) * | 2020-08-04 | 2022-03-04 | 航天材料及工艺研究所 | Composition for forming magnesium-lithium alloy surface anticorrosive coating system and preparation method of anticorrosive coating system |
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