CN114456685B - Water-based heat-resistant anticorrosive paint with magnetic conduction function and preparation method thereof - Google Patents

Water-based heat-resistant anticorrosive paint with magnetic conduction function and preparation method thereof Download PDF

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CN114456685B
CN114456685B CN202111680718.6A CN202111680718A CN114456685B CN 114456685 B CN114456685 B CN 114456685B CN 202111680718 A CN202111680718 A CN 202111680718A CN 114456685 B CN114456685 B CN 114456685B
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resin
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CN114456685A (en
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钱涛
刘海龙
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Hangzhou Jihua Polymer Materials 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
    • C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08—Anti-corrosive paints
    • C09D5/10—Anti-corrosive paints containing metal dust
    • 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
    • C09D5/23—Magnetisable or magnetic paints or lacquers
    • 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
    • C09D7/63—Additives non-macromolecular organic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C08K2003/0806—Silver
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C08K2003/0856—Iron
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C08K2003/0862—Nickel
    • 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
    • C08K2201/01—Magnetic additives
    • 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

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

Abstract

The invention relates to the field of high polymer materials, and discloses a water-based heat-resistant anticorrosive paint with a magnetic conduction function and a preparation method thereof, wherein the raw materials of the paint comprise: 60-80 parts of aqueous organosilicon modified polyester resin, 20-40 parts of amino resin, 10-20 parts of preservative efficacy filler, 5-10 parts of magnetic conductive metal particles, 1-3 parts of silane coupling agent, 0.1-0.3 part of tetraethyl orthosilicate, 10-20 parts of high-temperature resistant pigment, 1-3 parts of auxiliary agent, 1-3 parts of pH regulator and 10-20 parts of water. According to the invention, the aqueous organosilicon modified polyester resin is prepared firstly, then the amino resin is added, the molecular weight of the resin is increased through the reaction between the amino resin and the resin, and the crosslinking density of the resin is increased, so that the compactness of the coating is enhanced, the corrosion resistance of the coating is improved, and meanwhile, the corrosion resistance and the magnetic conductivity of the coating are further enhanced by adding the anticorrosive functional filler and the magnetic conductive metal particles subjected to the organic modification on the particle surfaces.

Description

Water-based heat-resistant anticorrosive paint with magnetic conduction function and preparation method thereof
Technical Field
The invention relates to the field of high polymer materials, in particular to a water-based heat-resistant anticorrosive paint with a magnetic conduction function and a preparation method thereof.
Background
The non-stick pan is formed by die casting an aluminum plate with good heat conduction performance, and can realize easy frying and food frying without sticking to the bottom by coating the non-stick coating, so that the oil consumption can be reduced to the greatest extent, the kitchen is clean and less in oil smoke, the intake of fat can be reduced, the consumption trend of pursuing low fat and low heat by modern people is complied, and the life quality of people is greatly improved. The induction cooker is one of main heating devices of the nonstick pan, and the pan body is induced to generate vortex by electromagnetic induction, so that a large amount of heat energy is converted as required to directly enable the pan body to quickly heat, the purpose of heating food is achieved, open fire does not exist in the heating process, and the induction cooker is high in heat efficiency, safe and sanitary and is welcomed by people.
However, the aluminum material is non-magnetic material and can not be directly used on the induction cooker, and the prior art adopts a layer of ferromagnetic composite bottom metal sheet on the bottom of the cooker so that the non-magnetic cooker can also be used on the induction cooker. The metal composite negative with magnetic permeability mainly adopts 430 or 410 series stainless steel, compared with austenitic stainless steel such as 304 and the like, other metals are adopted to replace part of nickel, the nickel can enlarge an austenitic phase region, the corrosion resistance of the stainless steel is improved, the addition of the nickel is reduced, the tissue singleness and corrosion resistance of the austenitic stainless steel can be influenced, and therefore the corrosion resistance of the existing composite negative is poor. In addition, the composite bottom plate is required to be polished and polished after the composite bottom plate is finished, the texture of the composite bottom plate is hard, abrasion can be caused by friction between the composite bottom plate and a panel when the composite bottom plate is used on a crystal panel of an electromagnetic oven at a high temperature, ferromagnetic stainless steel is easy to oxidize and turn yellow when the heating temperature is too high, and the composite bottom plate is generally protected by coating an anti-corrosion coating, so that the service life of the composite bottom plate is prolonged.
In the prior art, the organosilicon modified polyester high-temperature resistant coating is sprayed on the outer surface of the non-stick pan, and simultaneously, the composite bottom plate is also sprayed, so that a protective coating is formed. The organosilicon modified polyester high-temperature resistant coating has high heat resistance, good hardness, good adhesive force and bright color, and has been widely applied to the outer surface coating of various cookers and small household appliances. However, most of the existing organosilicon modified polyester coating is a solvent type product, and a large amount of organic solvent enters the atmosphere during construction application, so that not only is environmental pollution caused, but also energy is wasted. The coating can be converted into an environment-friendly product in a water-based mode, but the coating is independently applied to a composite negative plate, so that the corrosion resistance is poor, and the electromagnetic heating effect of the composite negative plate can be influenced because the formed coating does not have a magnetic conduction function.
Disclosure of Invention
In order to solve the technical problems, the invention provides the water-based heat-resistant anticorrosive paint with the magnetic conduction function and the preparation method thereof.
The specific technical scheme of the invention is as follows:
in a first aspect, the invention provides an aqueous heat-resistant anticorrosive paint with a magnetic conduction function, which comprises the following raw materials in parts by mass: 60-80 parts of water-based organosilicon modified polyester resin, 20-40 parts of amino resin, 10-20 parts of flaky or scaly anticorrosive functional filler, 5-10 parts of magnetic conductive metal particles, 1-3 parts of silane coupling agent, 0.1-0.3 part of tetraethyl orthosilicate, 10-20 parts of high-temperature resistant pigment, 1-3 parts of auxiliary agent, 1-3 parts of pH regulator and 10-20 parts of water.
The invention prepares the water-based heat-resistant anticorrosive paint by taking the water-based organosilicon modified polyester resin as a main film forming substance, and can greatly reduce VOC emission.
The invention cross-links hydroxyl in the aqueous organosilicon modified polyester resin in the curing process by introducing amino resin as curing agent. Specifically, in the curing process, except that the aqueous organic silicon resin is cured by condensation reaction of alkoxy in organic silicon and hydroxyl in polyester at high temperature, the newly introduced amino resin is cured again to form dual curing, so that the compactness of the coating is enhanced, and the corrosion resistance of the coating can be effectively improved.
The invention selects the flaky or scaly anti-corrosion effect filler, and the filler is inserted in the middle of the resin by utilizing the characteristics of large specific surface area and easy accumulation of the flaky structure of the filler, so as to enhance the contact with the resin, and the problem of micro-phase interface and interface cracking of the coating after film formation can be eliminated from the source by organically modifying the particle surface of the inorganic anti-corrosion effect filler, thereby avoiding the corrosion problem caused by the interface separation and stress concentration phenomenon between the filler and the resin to form gaps in the cold-hot alternate use process of the composite negative coating.
The invention adds magnetic conductive metal particles to make the original heat-resistant anti-corrosion coating have magnetic conductive function, and besides enhancing the electromagnetic heating effect of the composite negative, the coating can be further directly coated on an aluminum substrate to form a magnetic conductive coating without using the magnetic conductive composite negative, and can be used on an electromagnetic oven.
Preferably, the aqueous organosilicon modified polyester resin comprises the following raw materials in parts by mass: 1-5 parts of neopentyl glycol, 10-20 parts of trimethylolpropane, 10-30 parts of isophthalic acid, 15-30 parts of an organosilicon intermediate, 3-6 parts of trimellitic anhydride, 3-6 parts of N, N-dimethylethanolamine, 0.01-0.02 part of tetrabutyl titanate, 10-20 parts of ethylene glycol butyl ether and 30-60 parts of water.
The invention adopts neopentyl glycol, trimethylol propane and isophthalic acid to prepare hydroxyl-terminated polyester resin, then uses monomer (trimellitic anhydride) containing carboxyl functional groups to end-cap the polyester resin, uses organosilicon intermediate containing alkoxy to modify the polyester resin, and uses amine to neutralize and salify after modification to obtain the aqueous organosilicon modified polyester resin. The water-based heat-resistant anticorrosive paint prepared by taking the water-based organosilicon modified polyester resin as a main film forming substance can greatly reduce VOC emission.
Further, the silicone intermediate is DC-3074.
Preferably, the amino resin is selected from partially methylated melamine resin and fully methylated melamine resin.
Further, the partially methylated melamine resin is selected from the group consisting of cyanogen CYMEL 373 and trimaran 5717W; the fully methylated melamine resin is selected from cyante CYMEL 350 and three wood 5847.
Preferably, the flake or scale-shaped preservative efficacy filler is selected from mica powder, graphene and glass flakes.
Preferably, the magnetic conductive metal particles are selected from silver powder, iron powder, nickel powder, neodymium iron boron powder, iron-nickel alloy powder and iron-zinc alloy powder.
Preferably, the silane coupling agent is selected from methyltrimethoxysilane, gamma- (2, 3-glycidoxy) propyltrimethoxysilane, gamma-methacryloxypropyltrimethoxysilane and gamma-aminopropyltriethoxysilane.
Preferably, the high temperature resistant pigment is selected from the group consisting of titanium dioxide, carbon black, titanium nickel yellow, titanium cobalt green, cobalt blue, copper chromium black, and iron red.
Preferably, the pH adjustor is selected from the group consisting of AMP-95, triethylamine, N-dimethylethanolamine, and triethanolamine.
Preferably, the auxiliary agent comprises one or more of a dispersing agent, a leveling agent, an antifoaming agent and a thickening agent.
In a second aspect, the invention provides a preparation method of an aqueous heat-resistant anticorrosive paint with a magnetic conduction function, which comprises the following steps:
1) Preparation of aqueous organosilicon modified polyester resin: neopentyl glycol, trimethylolpropane and isophthalic acid are put into a reaction kettle, the temperature is raised to 160-180 ℃ for heat preservation and esterification for 1-2 hours, then the temperature is raised to 200-220 ℃, the reaction is continued for 2-4 hours until the acid value is reduced to below 10mgKOH/g, then the reaction is stopped, xylene is used as a water carrying agent for keeping reflux in the reaction process, ethylene glycol butyl ether and trimellitic anhydride are added after the temperature is reduced to 140-160 ℃, the reaction is continued until the acid value is 60-80mgKOH/g, the temperature is reduced to 110-130 ℃, tetrabutyl titanate and an organosilicon intermediate are added, the reaction is carried out for 1-2 hours until the reaction is transparent, the temperature is reduced to 80-90 ℃, N-dimethylethanolamine is added for neutralization, and finally water is added for dispersion.
2) Preparation of organic modified anti-corrosion effect filler: dispersing flaky or scaly anticorrosive effect filler in water accounting for 40-60% of the total amount to form slurry, adding a silane coupling agent, stirring at room temperature for reaction for 4-6 hours, filtering, and adding tetraethyl orthosilicate accounting for 40-60% of the total amount to obtain the organic modified anticorrosive effect filler. 3) Preparation of water-based heat-resistant anticorrosive paint with magnetic conduction function: uniformly mixing the water-based organic silicon modified polyester resin prepared in the step 1), amino resin and the residual tetraethyl orthosilicate, sequentially adding the organic modified anti-corrosion effect filler prepared in the step 2), magnetic conductive metal particles, high-temperature resistant pigment, auxiliary agent, pH regulator and residual water, and grinding to obtain the water-based heat-resistant anti-corrosion coating with magnetic conductive function.
In the step 1), neopentyl glycol, trimethylolpropane, isophthalic acid and trimellitic anhydride are taken as raw materials to prepare hydroxyl-containing aqueous polyester resin, and then the hydroxyl-containing aqueous polyester resin is reacted with an organosilicon intermediate to prepare the aqueous organosilicon modified polyester resin.
In the step 2), the flaky or scaly preservative efficacy filler is dispersed in water to form slurry, so that the filler particles which are possibly agglomerated originally are dispersed, and the modification is facilitated. In the modification process, part of alkoxy on the silane coupling agent is hydrolyzed to form silanol, part of hydroxyl exists on the surface of the filler particles, the silanol can react with the silanol to form covalent bonds, and the hydroxyl on the surface of the filler particles can not be metered, so that tetraethyl orthosilicate is continuously added into the product to enhance the effect of organic modification, hydrolysis condensation reaction further occurs to form an inorganic three-dimensional network structure, and the filler particles are wrapped to obtain the organic modified anti-corrosion effect filler.
In step 3), tetraethyl orthosilicate is also added to the mixture of the aqueous organosilicon modified polyester resin and the amino resin; on the one hand, the condensation of the amino resin and the aqueous organic silicon modified polyester resin and the self-condensation of the amino resin form dual curing, so that the crosslinking density of the resin is enhanced; on the other hand, the tetraethyl orthosilicate added in two steps further generates hydrolysis condensation reaction in the preparation process of the coating, the tetraethyl orthosilicate plays a role in linking, an inorganic three-dimensional network structure of filler particles and an interpenetrating network structure of organic network of film-forming resin are formed, in the structure, the filler particles are locked in pores of the network structure, even if the silane coupling agent is used for physically wrapping the modification of the filler particles, the filler particles can be anchored by the network structure, after the filler particles are mixed with an organic coating system, the uniformly dispersed state of the filler particles is not changed, the problem that inorganic filler particles are agglomerated again does not occur, and the corrosion resistance of the coating can be effectively improved.
Preferably, in step 2), the stirring rate is 200-300rpm.
Compared with the prior art, the invention has the beneficial effects that:
(1) According to the invention, the water-based heat-resistant anticorrosive paint is prepared by taking the water-based organosilicon modified polyester resin as a main film forming substance, so that the VOC emission is greatly reduced.
(2) According to the invention, the amino resin is selected as the curing agent of the aqueous organosilicon modified polyester resin, and double curing is formed by condensation of the amino resin and the aqueous organosilicon modified polyester resin and self-condensation of the amino resin, so that the crosslinking density of the resin is enhanced, and the corrosion resistance of the resin is greatly improved.
(3) The invention selects the flaky or scaly anti-corrosion effect filler, and the filler is inserted in the middle of the resin by utilizing the characteristics of large specific surface area and easy accumulation of the flaky structure of the filler, so as to enhance the contact with the resin, and the problem of micro-phase interface and interface cracking of the coating after film formation is eliminated from the source by organically modifying the particle surface of the inorganic anti-corrosion effect filler, so that the corrosion problem caused by the interface separation and stress concentration phenomenon between the filler and the resin in the cold-hot alternate use process of the composite negative coating is avoided.
(4) According to the invention, tetraethyl orthosilicate is added step by step, so that hydrolysis condensation reaction can be further carried out in the preparation process of the coating, a linking effect is achieved, an interpenetrating network structure of an inorganic three-dimensional network structure of filler particles and an organic network of film-forming resin are formed, the filler particles are locked in pores of the network structure, re-agglomeration is avoided, and the corrosion resistance of the coating can be further improved.
(5) The invention adds magnetic conductive metal particles to make the original non-magnetic conductive heat-resistant anticorrosive coating have magnetic conductive function, and besides enhancing the electromagnetic heating effect of the composite bottom plate, the coating can be further directly coated on an aluminum substrate to form a magnetic conductive coating without using a magnetic conductive composite bottom plate, and can be used on an electromagnetic oven.
Detailed Description
The invention is further described below with reference to examples.
General examples
1) Preparation of aqueous organosilicon modified polyester resin: 1-5 parts (by mass parts, the same applies below) of neopentyl glycol, 10-20 parts of trimethylolpropane and 10-30 parts of isophthalic acid are put into a reaction kettle, the temperature is raised to 160-180 ℃ for heat preservation and esterification for 1-2 hours, then the temperature is raised to 200-220 ℃, the reaction is continued for 2-4 hours until the acid value is reduced to below 10mgKOH/g, the reaction is stopped, 5-10 parts of dimethylbenzene is used as a water carrying agent for keeping reflux during the reaction, 10-20 parts of ethylene glycol butyl ether and 3-6 parts of trimellitic anhydride are added after the temperature is lowered to 140-160 ℃, the reaction is continued until the acid value is 60-80mgKOH/g, the temperature is lowered to 110-130 ℃, 0.01-0.02 part of tetrabutyl titanate and 15-30 parts of organosilicon intermediate are added, the reaction is carried out for 1-2 hours until the reaction is transparent, the temperature is lowered to 80-90 ℃, 3-6 parts of N, N-dimethylethanolamine is added for neutralization, and finally 30-60 parts of water is added for dispersion.
2) Preparation of organic modified anti-corrosion effect filler: dispersing 10-20 parts of anti-corrosion effect filler in 5-10 parts of water to form slurry, adding 1-3 parts of silane coupling agent, mechanically stirring (200-300 rpm) in a reaction bottle, reacting for 4-6 hours at room temperature, filtering, and adding 0.05-0.15 part of tetraethyl orthosilicate to obtain the organized modified anti-corrosion effect filler.
3) Preparation of water-based heat-resistant anticorrosive paint with magnetic conduction function: uniformly mixing 60-80 parts of the aqueous organosilicon modified polyester resin prepared in the step 1), 20-40 parts of amino resin and 0.05-0.15 part of tetraethyl orthosilicate, sequentially adding the organic modified anti-corrosion effect filler prepared in the step 2), 5-10 parts of magnetic conductive metal particles, 10-20 parts of high temperature resistant pigment, 1-3 parts of auxiliary agent, 1-3 parts of pH regulator and 5-10 parts of water, and grinding to obtain the aqueous heat-resistant anti-corrosion coating with a magnetic conductive function.
Preferably, the amino resin is selected from partially methylated melamine resin and fully methylated melamine resin; further preferably, the partially methylated melamine resin is selected from the group consisting of CYMEL 373 and trimaran 5717W, and the fully methylated melamine resin is selected from the group consisting of CYMEL 350 and trimaran 5847. The anti-corrosion effect filler is selected from mica powder, graphene and glass flakes. The magnetic conductive metal particles are selected from silver powder, iron powder, nickel powder, neodymium iron boron powder, iron-nickel alloy powder and iron-zinc alloy powder. The silane coupling agent is selected from methyltrimethoxysilane, gamma- (2, 3-epoxypropoxy) propyl trimethoxysilane, gamma-methacryloxypropyl trimethoxysilane and gamma-aminopropyl triethoxysilane. The high temperature resistant pigment is selected from titanium dioxide, carbon black, titanium nickel yellow, titanium cobalt green, cobalt blue, copper chromium black and iron red. The pH regulator is selected from AMP-95, triethylamine, N-dimethylethanolamine and triethanolamine. The auxiliary agent comprises a dispersing agent, a leveling agent, a defoaming agent and a thickening agent.
Example 1
1) Preparation of aqueous organosilicon modified polyester resin: 5 parts of neopentyl glycol, 20 parts of trimethylolpropane and 30 parts of isophthalic acid are put into a reaction kettle, the temperature is raised to 180 ℃ for heat preservation and esterification for 1 hour, then the temperature is raised to 220 ℃, the reaction is continued for 2 hours until the acid value is reduced to 8.9mgKOH/g, the reaction is stopped, 10 parts of dimethylbenzene is used as a water carrying agent for keeping reflux in the reaction process, 20 parts of ethylene glycol butyl ether and 6 parts of trimellitic anhydride are added, the reaction is continued until the acid value is 68.6mgKOH/g, the temperature is reduced to 130 ℃, 0.02 part of tetrabutyl titanate and 30 parts of organosilicon intermediate DC-3074 are added, the reaction is carried out for 1 hour until the reaction is transparent, the temperature is reduced to 90 ℃, 6 parts of N, N-dimethylethanolamine is added for neutralization, and finally 60 parts of water is added.
2) Preparation of organic modified anti-corrosion effect filler: after dispersing 20 parts of glass flakes in 10 parts of water to form slurry, adding 3 parts of gamma- (2, 3-glycidoxy) propyl trimethoxy silane, mechanically stirring (300 rpm) in a reaction bottle, reacting for 6 hours at room temperature, filtering, and adding 0.15 part of tetraethyl orthosilicate to obtain the organic modified anti-corrosion effect filler.
3) Preparation of water-based heat-resistant anticorrosive paint with magnetic conduction function: uniformly mixing 80 parts of the aqueous organosilicon modified polyester resin prepared in the step 1), 40 parts of cyanogen CYMEL 350 amino resin and 0.15 part of tetraethyl orthosilicate, sequentially adding the organic modified anti-corrosion effect filler prepared in the step 2), 10 parts of silver powder, 20 parts of iron oxide red, 2 parts of dispersing agent BYK-190, 1 part of defoaming agent BYK-028, 3 parts of N, N-dimethylethanolamine and 10 parts of water, and grinding to obtain the aqueous heat-resistant anti-corrosion coating with a magnetic conduction function.
Example 2
1) Preparation of aqueous organosilicon modified polyester resin: 1 part of neopentyl glycol, 10 parts of trimethylolpropane and 10 parts of isophthalic acid are put into a reaction kettle, the temperature is raised to 160 ℃ for heat preservation and esterification for 2 hours, then the temperature is raised to 200 ℃, the reaction is continued for 4 hours until the acid value is reduced to 9.2mgKOH/g, the reaction is stopped, 5 parts of dimethylbenzene is used as a water carrying agent for keeping reflux in the reaction process, 10 parts of ethylene glycol butyl ether and 3 parts of trimellitic anhydride are added, the reaction is continued until the acid value is 72.8mgKOH/g, the temperature is reduced to 110 ℃, 0.01 part of tetrabutyl titanate and 15 parts of organosilicon intermediate DC-3074 are added, the reaction is carried out for 2 hours until the reaction is transparent, the temperature is reduced to 80 ℃,3 parts of N, N-dimethylethanolamine is added for neutralization, and finally 30 parts of water is added.
2) Preparation of organic modified anti-corrosion effect filler: after 10 parts of graphene is dispersed in 10 parts of water to form slurry, 1 part of methyltrimethoxysilane is added, the mixture is mechanically stirred (300 rpm) in a reaction bottle for reaction for 6 hours at room temperature, then the reaction bottle is filtered, and 0.05 part of tetraethyl orthosilicate is added to obtain the organic modified anti-corrosion effect filler.
3) Preparation of water-based heat-resistant anticorrosive paint with magnetic conduction function: uniformly mixing 60 parts of the aqueous organosilicon modified polyester resin prepared in the step 1), 20 parts of the three-wood 5847 amino resin and 0.05 part of tetraethyl orthosilicate, sequentially adding the organic modified anticorrosive effect filler prepared in the step 2), 3 parts of iron powder, 2 parts of neodymium iron boron powder, 10 parts of carbon black, 0.8 part of dispersing agent UNIQ-690W, 0.2 part of defoaming agent UNIQ-265W, 1 part of AMP-95 and 5 parts of water, and grinding to obtain the aqueous heat-resistant anticorrosive paint with a magnetic conduction function.
Example 3
1) Preparation of aqueous organosilicon modified polyester resin: 3 parts of neopentyl glycol, 15 parts of trimethylolpropane and 18 parts of isophthalic acid are put into a reaction kettle, the temperature is raised to 170 ℃ for heat preservation and esterification for 1 hour, then the temperature is raised to 210 ℃, the reaction is continued for 3 hours until the acid value is reduced to 8.5mgKOH/g, the reaction is stopped, 7 parts of dimethylbenzene is used as a water carrying agent for keeping reflux, 15 parts of ethylene glycol butyl ether and 5 parts of trimellitic anhydride are added when the temperature is reduced to 150 ℃, the reaction is continued until the acid value is 70.8mgKOH/g, the temperature is reduced to 120 ℃, 0.01 part of tetrabutyl titanate and 20 parts of organosilicon intermediate DC-3074 are added, the reaction is carried out for 1.5 hours until the reaction is transparent, the temperature is reduced to 85 ℃, 5 parts of N, N-dimethylethanolamine is added for neutralization, and finally 45 parts of water is added.
2) Preparation of organic modified anti-corrosion effect filler: 15 parts of mica powder is dispersed in 10 parts of water to form slurry, 2 parts of gamma-aminopropyl triethoxysilane is added, the mixture is mechanically stirred (200 rpm) in a reaction bottle for reaction for 4 hours at room temperature, the reaction is filtered, and 0.1 part of tetraethyl orthosilicate is added to obtain the organic modified anti-corrosion effect filler.
3) Preparation of water-based heat-resistant anticorrosive paint with magnetic conduction function: uniformly mixing 80 parts of the aqueous organosilicon modified polyester resin prepared in the step 1), 30 parts of cyanogen CYMEL 373 amino resin and 0.1 part of tetraethyl orthosilicate, sequentially adding the organic modified anti-corrosion effect filler prepared in the step 2), 5 parts of nickel powder, 3 parts of iron-nickel alloy powder, 5 parts of titanium nickel yellow, 5 parts of titanium cobalt green, 5 parts of cobalt blue, 1 part of dispersing agent UNIQ-690W, 0.5 part of flatting agent UNIQ-495U, 0.5 part of defoaming agent BYK-028, 2 parts of triethylamine and 8 parts of water, and grinding to obtain the aqueous heat-resistant anti-corrosion coating with a magnetic conduction function.
Example 4
1) Preparation of aqueous organosilicon modified polyester resin: 2 parts of neopentyl glycol, 12 parts of trimethylolpropane and 15 parts of isophthalic acid are put into a reaction kettle, the temperature is raised to 170 ℃ for heat preservation and esterification for 1.5 hours, then the temperature is raised to 220 ℃, the reaction is continued until the acid value is reduced to 7.6mgKOH/g or lower, the reaction is stopped, 7 parts of dimethylbenzene is used as a water carrying agent for keeping reflux in the reaction process, 15 parts of ethylene glycol butyl ether and 4 parts of trimellitic anhydride are added, the reaction is continued until the acid value is 70.1mgKOH/g, the temperature is reduced to 120 ℃, 0.02 part of tetrabutyl titanate and 25 parts of organosilicon intermediate DC-3074 are added, the reaction is carried out for 1.5 hours until the reaction is transparent, the temperature is reduced to 85 ℃, 4 parts of N, N-dimethylethanolamine is added for neutralization, and finally 48 parts of water dispersion is added.
2) Preparation of organic modified anti-corrosion effect filler: after 16 parts of glass flakes are dispersed in 8 parts of water to form slurry, 2 parts of gamma-methacryloxypropyl trimethoxy silane is added, the mixture is mechanically stirred (250 rpm) in a reaction bottle for reaction for 5 hours, then the reaction solution is filtered, and 0.1 part of tetraethyl orthosilicate is added to obtain the organic modified anti-corrosion effect filler.
3) Preparation of water-based heat-resistant anticorrosive paint with magnetic conduction function: uniformly mixing 70 parts of the aqueous organosilicon modified polyester resin prepared in the step 1), 30 parts of the three wood 5717W amino resin and 0.1 part of tetraethyl orthosilicate, sequentially adding the organic modified anti-corrosion effect filler prepared in the step 2), 6 parts of iron powder, 2 parts of iron-zinc alloy powder, 15 parts of titanium dioxide, 0.8 part of dispersant BYK-190, 0.5 part of defoamer UNIQ-265W, 0.1 part of thickener ASE-60, 2 parts of triethanolamine and 8 parts of water, and grinding to obtain the aqueous heat-resistant anti-corrosion coating with a magnetic conduction function.
Comparative example 1
The only difference from example 1 is that step 2) is not added with the preservative efficacy filler glass flake, and the remaining steps and materials and compositions are identical to those of example 1.
Comparative example 2
The only difference from example 1 is that step 2) was not added with the silane coupling agent γ - (2, 3-glycidoxy) propyltrimethoxysilane, and the remaining steps and materials and compositions were the same as those of example 1.
Comparative example 3
The only difference from example 1 is that step 3) does not add the amino resin cyanohydrin 350, the remaining steps and materials and compositions are identical to those of example 1.
Comparative example 4
The difference from example 1 is only that step 3) does not add the silver powder of the magnetically conductive metal particles, and the rest of the steps and materials and compositions are the same as those of example 1.
Comparative example 5
The only difference from example 1 is that in steps 2) and 3) no tetraethyl orthosilicate is added, the remaining steps and materials and compositions are identical to example 1.
Comparative example 6
The only difference from example 1 is that in step 2) all tetraethyl orthosilicate is added at once, step 3) tetraethyl orthosilicate is not added, and the remaining steps and materials and compositions are identical to example 1.
The aqueous heat-resistant anticorrosive paint with magnetic conduction function prepared in examples 1-4 and the paint prepared in comparative examples 1-6 are respectively coated on a non-stick pan composite negative film (the thickness of the coating film is controlled to be 20 mu m), and then the performances of hardness, adhesive force, acid resistance, salt water resistance, heat resistance, electromagnetic heating efficiency and the like are tested, wherein the hardness test is carried out according to the GB/T6739 rule, and the result is evaluated: paint film scratch; the adhesive force test is carried out according to the specification of GB/T9286, and the interval is 1mm; the acid resistance test is carried out according to the specification of a soaking method in GB/T9274, and the medium is acetic acid solution with the mass fraction of 3%; the salt water resistance test is carried out according to the specification of a soaking method in GB/T9274, and the medium is 10% NaCl solution by mass percent; the heat resistance was measured according to GB/T1735-1979, test conditions: 280 ℃ for 1h, evaluation of the results: the chromatic aberration is less than or equal to 0.5 and is qualified; electromagnetic heating efficiency test the percentage value of the actual output power and the input power is measured to be the electromagnetic heating efficiency by carrying out heating test on the non-stick pan composite bottom sheet coated with the coating on an electromagnetic oven; the test results are shown in Table 1.
Table 1 results of product performance tests for examples 1-4 and comparative examples 1-6:
from the data analysis of the above table, it can be seen that:
the comparative example 1, which is not added with the anti-corrosion effect filler glass flake, has the advantages that compared with the example 1, the salt water resistance can be achieved, but the acid resistance is poor, which means that the compactness of the coating is poor and the anti-corrosion performance is poor; in addition, the reduced addition of filler also reduces the hardness of the coating.
In comparative example 2, the silane coupling agent gamma- (2, 3-glycidoxy) propyltrimethoxysilane is not added, and compared with example 1, the acid resistance is poor, the electromagnetic heating efficiency is reduced, because the filler is not organically modified, the compatibility problem exists with resin, the filler is not easy to disperse, the interface separation problem exists after film formation, the compactness of the coating and the dispersion uniformity of magnetic conductive metal particles in the coating are affected, and the corrosion resistance and the electromagnetic heating effect are reduced; in addition, the coating layer has uneven filler particles and reduced adhesive force.
Comparative example 3, in which the amino resin cyanogen CYMEL 350 was not added, had an insufficient degree of crosslinking of the film-forming resin compared with example 1, and the film compactness was significantly lowered, and thus the acid resistance, salt water resistance and heat resistance were significantly lowered.
In comparative example 4, no silver powder of magnetic conductive metal particles was added, and the electromagnetic heating efficiency was significantly reduced as compared with example 1, indicating that the coating itself without magnetic conductive metal particles had no magnetic conductive function, and the effect of electromagnetic heating was seriously affected.
In comparative example 5, tetraethyl orthosilicate is not added in steps 2) and 3), and compared with example 1, although the anticorrosive effect filler has been organically modified by the silane coupling agent and has a certain compatibility with the film-forming resin, the filler is not locked by a three-dimensional network structure formed by tetraethyl orthosilicate, and has a certain agglomeration phenomenon, so that the filler particles of the coating are unevenly distributed, the adhesive force is reduced, the acid resistance is poor, and the electromagnetic heating efficiency is reduced.
Comparative example 6 in step 2) all tetraethyl orthosilicate was added at one time, and step 3) tetraethyl orthosilicate was not added, and there was a certain decrease in acid resistance and little change in other properties as compared with example 1, because the organized modified filler particles locked by the three-dimensional network structure could be uniformly dispersed in the film-forming resin, but there was no interpenetrating network structure with the film-forming resin, and the preservative function of the flaky or flaky filler particles could not be maximized.
In summary, it is clear that the aqueous heat-resistant anticorrosive paint with magnetic conduction function obtained in examples 1 to 4 has excellent hardness, adhesion, acid resistance, brine resistance, heat resistance and electromagnetic heating efficiency compared with the coating formed in comparative examples, and shows that the aqueous paint with the added amino resin and the organically modified anticorrosive effect filler has excellent heat-resistant anticorrosive performance, and after the magnetic conduction metal particles are added, the original non-magnetic conduction heat-resistant anticorrosive coating has magnetic conduction function, so that the reduction of the electromagnetic heating effect of the composite negative plate after coating is avoided.
The raw materials and equipment used in the invention are common raw materials and equipment in the field unless specified otherwise; the methods used in the present invention are conventional in the art unless otherwise specified.
The foregoing description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and any simple modification, variation and equivalent transformation of the above embodiment according to the technical substance of the present invention still fall within the scope of the technical solution of the present invention.

Claims (6)

1. The application of the amino resin in improving the corrosion resistance of the water-based heat-resistant anticorrosive paint with the magnetic conduction function is characterized in that the water-based heat-resistant anticorrosive paint with the magnetic conduction function comprises the following raw materials in parts by mass:
60-80 parts of water-based organic silicon modified polyester resin,
20-40 parts of amino resin, wherein the amino resin is selected from partially methylated melamine resin and fully methylated melamine resin;
10-20 parts of scale-shaped anti-corrosion effect filler selected from mica powder, graphene and glass flakes;
5-10 parts of magnetic conductive metal particles,
1-3 parts of a silane coupling agent selected from methyltrimethoxysilane, gamma- (2, 3-glycidoxy) propyltrimethoxysilane, gamma-methacryloxypropyltrimethoxysilane and gamma-aminopropyltriethoxysilane;
0.1 to 0.3 part of tetraethyl orthosilicate,
10-20 parts of high-temperature resistant pigment,
1-3 parts of an auxiliary agent,
1-3 parts of pH regulator,
10-20 parts of water;
the aqueous organosilicon modified polyester resin comprises the following raw materials in parts by mass: 1-5 parts of neopentyl glycol, 10-20 parts of trimethylolpropane, 10-30 parts of isophthalic acid, 15-30 parts of an organosilicon intermediate, 3-6 parts of trimellitic anhydride, 3-6 parts of N, N-dimethylethanolamine, 0.01-0.02 part of tetrabutyl titanate, 10-20 parts of ethylene glycol butyl ether and 30-60 parts of water;
the preparation method of the water-based heat-resistant anticorrosive paint comprises the following steps:
1) Preparation of aqueous organosilicon modified polyester resin: putting neopentyl glycol, trimethylolpropane and isophthalic acid into a reaction kettle, heating to 160-180 ℃, preserving heat and esterifying for 1-2h, heating to 200-220 ℃, continuing to react for 2-4h until the acid value is reduced to below 10mgKOH/g, stopping the reaction, keeping refluxing by taking dimethylbenzene as a water carrying agent in the reaction process, cooling to 140-160 ℃, adding ethylene glycol butyl ether and trimellitic anhydride, continuing to react until the acid value is 60-80mgKOH/g, cooling to 110-130 ℃, adding tetrabutyl titanate and an organosilicon intermediate, reacting for 1-2h until the reaction is transparent, cooling to 80-90 ℃, adding N, N-dimethylethanolamine for neutralization, and finally adding water for dispersion;
2) Preparation of organic modified anti-corrosion effect filler: dispersing the anticorrosive effect filler in water accounting for 40-60% of the total amount to form slurry, adding a silane coupling agent, stirring at room temperature for reaction for 4-6 hours, filtering, and adding tetraethyl orthosilicate accounting for 40-60% of the total amount to obtain an organized modified anticorrosive effect filler;
3) Preparation of water-based heat-resistant anticorrosive paint with magnetic conduction function: uniformly mixing the water-based organic silicon modified polyester resin prepared in the step 1), amino resin and the residual tetraethyl orthosilicate, sequentially adding the organic modified anti-corrosion effect filler prepared in the step 2), magnetic conductive metal particles, high-temperature resistant pigment, auxiliary agent, pH regulator and residual water, and grinding to obtain the water-based heat-resistant anti-corrosion coating with magnetic conductive function.
2. The use according to claim 1, wherein: the magnetic conductive metal particles are selected from silver powder, iron powder, nickel powder, neodymium iron boron powder, iron-nickel alloy powder and iron-zinc alloy powder.
3. The use according to claim 1, wherein: the high temperature resistant pigment is selected from titanium dioxide, carbon black, titanium nickel yellow, titanium cobalt green, cobalt blue, copper chromium black and iron red.
4. The use according to claim 1, wherein: the pH regulator is selected from AMP-95, triethylamine, N-dimethylethanolamine and triethanolamine.
5. The use according to claim 1, wherein: the auxiliary agent comprises one or more of dispersing agent, leveling agent, defoaming agent and thickening agent.
6. The use according to claim 1, wherein: in step 2), the stirring rate is 200-300rpm.
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