CN116478569A - Double-component water-based paint filler and preparation method thereof - Google Patents

Double-component water-based paint filler and preparation method thereof Download PDF

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CN116478569A
CN116478569A CN202310504049.XA CN202310504049A CN116478569A CN 116478569 A CN116478569 A CN 116478569A CN 202310504049 A CN202310504049 A CN 202310504049A CN 116478569 A CN116478569 A CN 116478569A
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deionized water
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孙晓艳
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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
    • C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
    • 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
    • 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
    • C08K2201/002—Physical properties
    • C08K2201/005—Additives being defined by their particle size in general
    • 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
    • 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
    • C08K9/00—Use of pretreated ingredients
    • C08K9/10—Encapsulated ingredients
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
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  • Inorganic Chemistry (AREA)
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Abstract

The invention provides a double-component water-based paint filler and a preparation method thereof, which are used for preparing corrosion-resistant cadmium-doped Fe under severe (extremely high temperature) hydrothermal conditions 3 O 4 The nano ball particles are then acid washed, activated and purified to obtain high purity magnetic particles, and the magnetic nano balls are used as cores, and silica shells are directionally adsorbed on the surfaces of the magnetic nano balls to obtain a magnetic suspension with high suspension, high compatibility and good stability.

Description

Double-component water-based paint filler and preparation method thereof
Technical Field
The invention belongs to the technical field of coatings, and particularly relates to a double-component water-based coating filler, a polyurethane composite coating and a preparation method thereof.
Background
The aqueous polyurethane refers to a polyurethane emulsion in which polyurethane is dispersed by taking water as a solvent. Solvent type polyurethane has wide application, but the use of organic solvents causes air pollution and has toxicity. In recent years, people pay more attention to environmental protection, and development research of waterborne polyurethane is promoted. Waterborne polyurethane is widely applied in the fields of adhesives, coatings and the like, and is paid attention to because of the characteristics of environmental friendliness and safety. The polyurethane has the advantages of good wear resistance, high bearing capacity, high tearing strength, low temperature resistance, oil resistance, ozone resistance, diversified raw materials, adjustable molecular structure and the like, and can be further penetrated into industries such as elastomer, foamed plastic, paint, adhesive and the like. It is not acknowledged that the polyurethane itself has disadvantages of poor solvent resistance, weather resistance and heat resistance, and the width of application in the aspect of paint is greatly reduced. The current method for modifying the waterborne polyurethane can be divided into acrylic acid modification, epoxy resin modification, polysiloxane modification and natural product modification according to different modifiers. Recently, polymer composite materials have attracted great attention, and inorganic nanoparticles are capable of improving the force properties, optical properties, thermal properties, corrosion resistance, magnetic properties, etc. of polymer materials.
The magnetic nano particles have potential biomedical, industrial, military and other applications because of the inherent magnetic properties, microstructure, large specific surface area, surface charge, low toxicity and other advantages. Because of their biocompatibility and chemical stability, ferroferric oxide has been attracting attention for use in targeted drug delivery systems and the like. A wide variety of different methods are applied to develop such materials. The magnetic material can be easily polymerized due to its hydrophobicity. Surface modification helps to improve the stability of the nanoparticle and can provide additional functional groups that may be useful in other applications. One way to avoid nanoparticle agglomeration is to coat the surface with a layer of water-soluble material, typically with a core of ferroferric oxide, and a layer of other materials, typically a shell of a multi-metal oxide or other inorganic material, including titanium dioxide, silicon dioxide, aluminum oxide, zirconium dioxide, etc. The use of silica and its derivatives on the surface of magnetic nanoparticles may help to improve their surface properties and may provide good acid and alkali resistance and high temperature stability because silica is an inert compound. Meanwhile, the silicon dioxide has high permeability in the ultraviolet light region, so that the silicon dioxide can be used as an anti-reflection material, and can realize stronger electromagnetic loss performance by being compounded with ferroferric oxide.
The preparation method of the waterproof and oilproof magnetic SiO2/Fe3O4 composite particles as shown in CN102807775B comprises the following steps: feCl2.4H O, na2SO3, polyvinylpyrrolidone and NaOH are dissolved in deionized water and reacted for 8-16 hours at 100-180 ℃ to obtain Fe3O4 particles after separation, washing and drying; the Fe3O4 particles are uniformly dispersed in ethanol, ammonia water is added, ethyl orthosilicate is added while stirring, stirring is continued for 8-16 hours at 5-50 ℃, the waterproof and oilproof magnetic SiO2/Fe3O4 composite particles are obtained after separation, washing and drying, and the product prepared by wrapping fluorosilane has the advantages of improved performance, simple production process, strong producibility and high yield. The invention relates to a waterproof and oil-proof magnetic SiO 2 /Fe 3 O 4 The composite particles or the product have better water and oil resistance, and can be widely applied to the aspects of paint, medical machinery, steel corrosion resistance and the like.
A super-hydrophobic graphene anti-corrosion coating with a double-layer inclusion structure as in CN109627906B and a preparation method thereof belong to the technical field of super-hydrophobic anti-corrosion coatings, and can solve the problems that the structure and performance of the existing super-hydrophobic coating are unstable, the anti-corrosion performance of the super-hydrophobic coating is poor, and the large-scale preparation cannot be performed. The invention comprises the following steps: firstly, synthesizing a nanoparticle oily dispersion liquid with low surface energy and a graphene/resin composite oily dispersion liquid with good dispersibility; and secondly, spraying a graphene/resin composite oily dispersion liquid and a nanoparticle oily dispersion liquid on the metal substrate in sequence to prepare the coating with the double-layer inclusion structure. Compared with the traditional super-hydrophobic anticorrosive coating, the coating has more excellent hydrophobic performance and anticorrosive performance, more stable surface structure and performance, and can be widely controllable, thereby accelerating the engineering application of the super-hydrophobic coating in the anticorrosive field.
Disclosure of Invention
The invention provides a preparation method of a double-component water-based paint filler, which prepares corrosion-resistant cadmium-doped Fe under severe (extremely high temperature) hydrothermal conditions 3 O 4 The nano ball particles are then acid washed, activated and purified to obtain high purity magnetic particles, the magnetic nano balls are used as cores, silica shells are directionally adsorbed on the surfaces of the magnetic nano balls to obtain a magnetic suspension with high suspension, high compatibility and good stability, and when the magnetic suspension is used for water-based paint fillers, the fillers are highly dispersed in a coating, and the coating has good physical and chemical properties, such as tensile strength and corrosion resistance.
A preparation method of a two-component water-based paint filler comprises the following steps:
(1) 5-8mM FeCl 3 . 6H 2 O、0.5-1 mM CdCl 2 . 6H 2 Adding O metal salt into ethanol-deionized water solution, stirring uniformly, sequentially adding 3-4g/L tetrahydroxypropyl ethylenediamine and 1-2g/L ethylenediamine tetraacetic acid compound complexing agent, then adding 0.02-0.04 g/L2, 2' -bipyridine as stabilizer, and 10-15mL NaBH 4 Uniformly stirring the mixture serving as a reducing agent, and then adjusting pH=7.5-8.5 by taking sodium acetate as an alkali source to obtain a precursor liquid;
(2) Placing the precursor liquid into a lining-free stainless steel water heating reaction kettle, exhausting air in the reaction kettle by using nitrogen, sealing the reaction kettle, heating to 300-310 ℃ at 5-10 ℃/min, preserving heat for 24-48h, and naturally cooling to room temperature.
(3) Magnetically separating a hydrothermal product, and performing activation pickling purification: the activation pickling purification is to place the magnetic separation hydrothermal product in a volume ratio of 1-2:1 by 98wt.% H 2 SO 4 And 30wt.% H 2 O 2 Treating for 2-3min at 30 ℃, stirring by a motor, sequentially and repeatedly cleaning to neutrality by using deionized water and ethanol after activating, pickling and purifying, and preparing a suspension of 10-20wt.% magnetic particles, wherein the solvent of the suspension consists of polyether modified siloxane wetting agent, ethanol and deionized water.
(4) Adding ammonia water into the magnetic particle suspension prepared in the step (3), stirring for 10-20min, adding ethyl silicate, stirring for 12-14h by a motor at 10-14 ℃, filtering and washing the product, and vacuum drying to obtain (Cd-Fe) O x @SiO 2 And (3) filling.
In certain embodiments, the polyether modified siloxane wetting agent is present in an amount of 4 to 5wt.%.
In certain embodiments, the volume ratio of ethanol to deionized water in step (1) and step (3) is 1:7-9.
In certain embodiments, the magnetic particles after the activated acid wash purification in step (3) have a saturation magnetic strength of 62.7 emu/G, a remanence of 4.23 emu/G, and a coercivity hc=41.8g.
In some embodiments, (Cd-Fe) O x @SiO 2 The saturation magnetic strength of the filler was 25.3 emu/g.
In certain embodiments, the ethyl silicate is used in an amount of 3-4g and the aqueous ammonia is used in an amount of 5-8mL.
In some embodiments, (Cd-Fe) O x The core size is 20-70nm, siO 2 The thickness of the shell is 10-30nm.
In certain embodiments, the (Cd-Fe) O x @SiO 2 Ultrasonic dispersing filler in deionized water containing wetting agent, (Cd-Fe) O x @SiO 2 The mass concentration is 40-50wt%, and the mass concentration of the wetting agent is 1-2wt%.
The preparation method of the two-component water-based paint comprises the following steps:
(A) The preparation method of the component A comprises the following steps: the water-based hydroxyl acrylic resin, the wetting dispersant, the defoamer, the leveling agent and the deionized water are uniformly stirred according to the formula amount, the filler suspension is added, then the mixture is uniformly stirred and mixed at a high speed of 800-1200 rpm, and then the cosolvent and the thixotropic thickener are added and uniformly mixed at a medium speed of 600-800 rpm.
(B) The preparation method of the component B comprises the following steps: the hydrophilic modified isocyanate curing agent and the propylene glycol diacetate are fully and uniformly mixed to prepare the modified polyurethane foam.
(C) When in use, the component A and the component B are mixed according to the mass ratio of (5.5-10): 1, uniformly mixing, and then spraying on the surface of a substrate.
The filler suspension is prepared by the following steps.
(1) 5-8mM FeCl 3 . 6H 2 O、0.5-1 mM CdCl 2 . 6H 2 Adding O metal salt into ethanol-deionized water solution, stirring uniformly, sequentially adding 3-4g/L tetrahydroxypropyl ethylenediamine and 1-2g/L ethylenediamine tetraacetic acid compound complexing agent, then adding 0.02-0.04 g/L2, 2' -bipyridine as stabilizer, and 10-15mL NaBH 4 Uniformly stirring the mixture serving as a reducing agent, and then adjusting pH=7.5-8.5 by taking sodium acetate as an alkali source to obtain a precursor liquid;
(2) Placing the precursor liquid into a lining-free stainless steel water heating reaction kettle, exhausting air in the reaction kettle by using nitrogen, sealing the reaction kettle, heating to 300-310 ℃ at 5-10 ℃/min, preserving heat for 24-48h, and naturally cooling to room temperature.
(3) Magnetically separating a hydrothermal product, and performing activation pickling purification: the activation pickling purification is to place the magnetic separation hydrothermal product in a volume ratio of 1-2:1 by 98wt.% H 2 SO 4 And 30wt.% H 2 O 2 Treating for 2-3min at 30 ℃, stirring by a motor, sequentially and repeatedly cleaning to neutrality by using deionized water and ethanol after activating, pickling and purifying, and preparing a suspension of 10-20wt.% magnetic particles, wherein the solvent of the suspension consists of polyether modified siloxane wetting agent, ethanol and deionized water.
(4) Step (3)Adding ammonia water into the magnetic particle suspension prepared in the step (a), stirring for 10-20min, adding ethyl silicate, stirring for 12-14h by a motor at 10-14 ℃, filtering and washing the product, and vacuum drying to obtain (Cd-Fe) O x @SiO 2 Fillers, the (Cd-Fe) O x @SiO 2 Ultrasonic dispersing filler in deionized water containing wetting agent to obtain filler suspension, (Cd-Fe) O x @SiO 2 The mass concentration is 40-50wt%, and the mass concentration of the wetting agent is 1-2wt%.
An aqueous two-component polyurethane coating comprises a component A and a component B; the mass ratio of the component A to the component B is (5.5-10): 1.
the component A comprises the following components in parts by mass: 40-65 parts of aqueous hydroxy acrylic resin, 0.5-3 parts of wetting dispersant, 0.5-3 parts of defoamer, 5-10 parts of cosolvent, 10-25 parts of filler suspension, 0.5-3 parts of flatting agent, 0.5-5 parts of thixotropic thickener and 15-25 parts of deionized water;
the component B comprises the following components in parts by mass: 60-80 parts of hydrophilic modified isocyanate curing agent and 10-15 parts of propylene glycol diacetate.
The wetting dispersant is at least one selected from TEGO 4100, TEGO 755W, BYK-190; the defoamer is at least one selected from BYK022, BYK093, TEGO Airex 901W and TEGO Foamex 810.
The cosolvent is at least one selected from propylene glycol methyl ether, ethylene glycol butyl ether and dipropylene glycol methyl ether.
The leveling agent is at least one of TEGO-450, BYK-381, TEGO Glide 410 and TEGO Glide 4100; the thixotropic thickener is at least one selected from the group consisting of Borchi 0620 and RHEOLATE 299.
The invention adopts a hydrothermal method to prepare magnetic nano Fe3O4, which is to take water and ethanol as hydrothermal reaction medium, react in a reaction kettle in a closed inert atmosphere at a high temperature of 300-310 ℃ under the condition of about 20-40Mpa high pressure, wherein the hydrothermal filling degree is 40-80%, preferably 75%, the internal pressure of the reaction kettle is about 32MPa at 310 ℃, and FeCl is used in the reaction process 3 . 6H 2 O and CdCl 2 . 6H 2 O is a metal source, tetrahydroxypropyl ethylenediamine and ethylenediamine tetraacetic acid EDTA are used as a double-component composite complexing agent, which can effectively complex iron and cadmium ions, the distance between the two is shortened, an alloy structure is formed, then 2,2' -bipyridine is added as a stabilizer to stabilize the metal ion state, and then NaBH is added 4 As a reducing agent, a part of Fe is reduced 3+ Is Fe 2+ And Cd 2+ Reducing Cd, using sodium acetate as an alkali source, dehydrating to generate cadmium-doped Fe3O4 magnetic particles, and obtaining the cadmium-doped Fe under the conditions of extremely high hydrothermal temperature and pressure 3 O 4 The saturation magnetic strength of the magnetic particles is reduced compared with Fe 3 O 4 Or other FeO X Or CdO has extremely high corrosion resistance, and based on the above properties, fe in the CdO 3 O 4 ，FeO X Or the CdO is subjected to impurity removal, the magnetic particles obtained after purification are high-purity cadmium-doped Fe3O4 magnetic particles, and meanwhile, in order to prepare a magnetic core-shell structure, the cadmium-doped Fe is needed 3 O 4 The surface of the magnetic nano particle is introduced with active groups, the active groups are mainly hydroxyl groups, sulfuric acid can react with redundant FeOx and CdO which are easy to corrode, and the purified high-purity cadmium-doped Fe is obtained 3 O 4 The magnetic particles react with sulfuric acid and hydrogen peroxide to produce H 2 SO 4 +H 2 O 2 →H 3 O + +HSO 4 - +O, fe to realize cadmium doping 3 O 4 The hydroxylation of the surface of the magnetic particles needs to be noticed in the purification and activation process, the obtaining time cannot be longer than 4 minutes, and excessive corrosion is avoided.
Then doping Fe in subsequent hydroxylation cadmium 3 O 4 The surface of the magnetic particle is directionally adsorbed with silicon oxide, and the directional adsorption mechanism is as follows: alkaline condition is selected, ammonia water is used for providing hydroxide radical, TEOS is hydrolyzed under alkaline condition, and the mechanism is OH - Firstly, nucleophilic reaction is carried out with silicon atomic nucleus to generate silanol, hydroxyl of silanol and Fe doped with cadmium 3 O 4 Hydrogen bond is formed between hydroxyl groups on the surface of the magnetic particles, then the magnetic particles are further condensed on the basis of hydrogen bond bridging, and silanol is dehydrogenated under alkaline condition to form a roadEasy-to-sit alkali continuously reacts with other silicon atomic nuclei, and is dehydrated (or dealcoholized) and polymerized to slowly generate a reticular structure, and finally, fe doped with cadmium is obtained 3 O 4 SiO formation on the surface of magnetic particles 2 And (3) a film.
Referring to the energy spectrum of FIG. 1, it can be seen that the cadmium-doped Fe 3 O 4 Magnetic particle-SiO 2 In the form of a core-shell in which cadmium-doped Fe 3 O 4 The magnetic nano particles are core, the size is 54nm, the silicon oxide is taken as a shell, the size of the shell is 26nm, and the magnetic nano particles are uniformly dispersed in the coating layer, and no obvious agglomeration exists, and the magnetic nano particles are shown in figure 2.
Beneficial technical effects
(1) The invention firstly prepares cadmium doped Fe which is relatively corrosion resistant 3 O 4 The magnetic particles are then subjected to an acid washing activation step to effectively purify the components of the magnetic particles and simultaneously introduce hydroxyl groups on the surfaces thereof.
(2) By directional introduction of hydroxyl groups, the surface of the magnetic particle filler is coated with a silicon oxide coating film with a slight thorn shape, and the coating film can obviously improve (Cd-Fe) O x @SiO 2 The filler is water-soluble in suspension, and then is highly dispersed in the polyurethane coating, so that the coating has good compatibility, and the physical and chemical properties of polyurethane such as tensile strength and the like are obviously improved.
(3) By directional introduction of hydroxyl groups, the surface of the magnetic particle filler is coated with a silicon oxide coating film with a little thorn, and the coating film improves (Cd-Fe) O x Particularly improves the corrosion resistance of the coating and prolongs the service life of the magnetic coating.
Drawings
FIG. 1 (Cd-Fe) O x @SiO 2 Energy spectrum of the filler.
FIG. 2 (Cd-Fe) O x @SiO 2 Dispersion diagram of filler in polyurethane.
Detailed Description
Example 1
A preparation method of a two-component water-based paint filler comprises the following steps:
(1) 6.5mM FeCl 3 . 6H 2 O、0.75 mM CdCl 2 . 6H 2 O metal salt is added into ethanol-deionized water solution, and the volume ratio of ethanol to deionized water is 1:8, stirring uniformly, sequentially adding 3.5g/L tetrahydroxypropyl ethylenediamine and 1.5g/L ethylenediamine tetraacetic acid composite complexing agent, then adding 0.03 g/L2, 2' -bipyridine as a stabilizer, and 12.5mL NaBH 4 Uniformly stirring as a reducing agent, and then adjusting pH=8 by taking sodium acetate as an alkali source to obtain a precursor liquid;
(2) Placing the precursor liquid into a lining-free stainless steel water thermal reaction kettle, discharging air in the reaction kettle by using nitrogen, sealing the reaction kettle, heating to 305 ℃ at 7.5 ℃/min, preserving heat for 36h, and naturally cooling to room temperature;
(3) Magnetically separating a hydrothermal product, and performing activation pickling purification: the activated pickling purification is to place the magnetic separation hydrothermal product in a volume ratio of 1.5:1 by 98wt.% H 2 SO 4 And 30wt.% H 2 O 2 After the activation pickling purification, deionized water and ethanol are sequentially and repeatedly washed to be neutral by stirring in a motor at the temperature of 30 ℃ for 2.5min, wherein the saturated magnetic strength of the magnetic particles after the activation pickling purification is 62.7 emu/G, the remanence is 4.23 emu/G, the coercivity is Hc=41.8G, 15wt.% of magnetic particle suspension is prepared, the solvent of the suspension consists of 4.5wt.% of polyether modified siloxane wetting agent, ethanol and deionized water, and the volume ratio of the ethanol to deionized water is 1:8, 8;
(4) Adding 6.5mL of ammonia water into the magnetic particle suspension prepared in the step (3), stirring for 15min, adding 3.5g of ethyl silicate, stirring for 13h by a motor at the temperature of 12 ℃, filtering and washing the product, and drying in vacuum to obtain (Cd-Fe) O x @SiO 2 Filler, (Cd-Fe) O x @SiO 2 The saturation magnetic strength of the filler was 25.3 emu/g.
The (Cd-Fe) O x @SiO 2 Ultrasonic dispersing filler in deionized water containing wetting agent, (Cd-Fe) O x @SiO 2 The mass concentration was 45 wt.%, the mass concentration of wetting agent was 1.5wt.%, the filler suspension obtained.
Comparative example 1
A preparation method of a two-component water-based paint filler comprises the following steps:
(1) 6.5mM FeCl 3 . 6H 2 O、0.75 mM CdCl 2 . 6H 2 O metal salt is added into ethanol-deionized water solution, and the volume ratio of ethanol to deionized water is 1:8, stirring uniformly, then sequentially adding 5g/L tetrahydroxypropyl ethylenediamine and 12.5mL NaBH 4 As a reducing agent, stirring uniformly, and then adjusting ph=8 with sodium acetate as an alkali source to obtain a precursor liquid.
(2) And (3) placing the precursor liquid into a lining-free stainless steel water thermal reaction kettle, discharging air in the reaction kettle by using nitrogen, sealing the reaction kettle, heating to 230 ℃ at 7.5 ℃/min, preserving heat for 36h, and naturally cooling to room temperature.
(3) Magnetically separating a hydrothermal product, and performing activation pickling purification: the activated pickling purification is to place the magnetic separation hydrothermal product in a volume ratio of 1.5:1 by 98wt.% H 2 SO 4 And 30wt.% H 2 O 2 Treating for 2.5min at 30 ℃, stirring by a motor, sequentially and repeatedly cleaning to neutrality by using deionized water and ethanol after activating, pickling and purifying, and preparing 15wt.% magnetic particle suspension, wherein the solvent of the suspension consists of 4.5wt.% polyether modified siloxane wetting agent, ethanol and deionized water, and the volume ratio of the ethanol to deionized water is 1:8.
(4) Adding 6.5mL of ammonia water into the magnetic particle suspension prepared in the step (3), stirring for 15min, adding 3.5g of ethyl silicate, stirring for 13h by a motor at the temperature of 12 ℃, filtering and washing the product, and drying in vacuum to obtain (Cd-Fe) O x @SiO 2 And (3) filling.
The (Cd-Fe) O x @SiO 2 Ultrasonic dispersing filler in deionized water containing wetting agent, (Cd-Fe) O x @SiO 2 The mass concentration was 45 wt.%, the mass concentration of the wetting agent was 1.5wt.%.
Comparative example 2
A preparation method of a two-component water-based paint filler comprises the following steps:
(1) 6.5mM FeCl 3 . 6H 2 O, metalAdding salt into ethanol-deionized water solution, wherein the volume ratio of ethanol to deionized water is 1:8, stirring uniformly, sequentially adding 3.5g/L tetrahydroxypropyl ethylenediamine and 1.5g/L ethylenediamine tetraacetic acid composite complexing agent, then adding 0.03 g/L2, 2' -bipyridine as a stabilizer, and 12.5mL NaBH 4 As a reducing agent, stirring uniformly, and then adjusting ph=8 with sodium acetate as an alkali source to obtain a precursor liquid.
(2) And (3) placing the precursor liquid into a lining-free stainless steel water thermal reaction kettle, discharging air in the reaction kettle by using nitrogen, sealing the reaction kettle, heating to 305 ℃ at 7.5 ℃/min, preserving heat for 36h, and naturally cooling to room temperature.
(3) Magnetically separating a hydrothermal product, and performing activation pickling purification: the activated pickling purification is to place the magnetic separation hydrothermal product in a volume ratio of 1.5:1 by 98wt.% H 2 SO 4 And 30wt.% H 2 O 2 Treating for 2.5min at 30 ℃, stirring by a motor, sequentially and repeatedly cleaning to neutrality by using deionized water and ethanol after activating, pickling and purifying, and preparing 15wt.% magnetic particle suspension, wherein the solvent of the suspension consists of 4.5wt.% polyether modified siloxane wetting agent, ethanol and deionized water, and the volume ratio of the ethanol to deionized water is 1:8.
(4) Adding 6.5mL of ammonia water into the magnetic particle suspension prepared in the step (3), stirring for 15min, adding 3.5g of ethyl silicate, stirring for 13h by a motor at the temperature of 12 ℃, filtering and washing the product, and drying in vacuum to obtain (Cd-Fe) O x @SiO 2 And (3) filling.
The (Cd-Fe) O x @SiO 2 Ultrasonic dispersing filler in deionized water containing wetting agent, (Cd-Fe) O x @SiO 2 The mass concentration was 45 wt.%, the mass concentration of the wetting agent was 1.5wt.%.
Comparative example 3
A preparation method of a two-component water-based paint filler comprises the following steps:
(1) 6.5mM FeCl 3 . 6H 2 O、0.75 mM CdCl 2 . 6H 2 Adding O metal salt into ethanol-deionized water solution, and adding ethanol and deionized waterThe volume ratio is 1:8, stirring uniformly, sequentially adding 3.5g/L tetrahydroxypropyl ethylenediamine and 1.5g/L ethylenediamine tetraacetic acid composite complexing agent, then adding 0.03 g/L2, 2' -bipyridine as a stabilizer, and 12.5mL NaBH 4 As a reducing agent, stirring uniformly, and then adjusting ph=8 with sodium acetate as an alkali source to obtain a precursor liquid.
(2) And (3) placing the precursor liquid into a lining-free stainless steel water thermal reaction kettle, discharging air in the reaction kettle by using nitrogen, sealing the reaction kettle, heating to 305 ℃ at 7.5 ℃/min, preserving heat for 36h, and naturally cooling to room temperature.
(3) Magnetically separating the hydrothermal product to prepare 15wt.% of a magnetic particle suspension, wherein the solvent of the suspension consists of 4.5wt.% of polyether-modified siloxane wetting agent, ethanol and deionized water, and the volume ratio of the ethanol to deionized water is 1:8.
(4) Adding 6.5mL of ammonia water into the magnetic particle suspension prepared in the step (3), stirring for 15min, adding 3.5g of ethyl silicate, stirring for 13h by a motor at the temperature of 12 ℃, filtering and washing the product, and drying in vacuum to obtain (Cd-Fe) O x @SiO 2 And (3) filling.
The (Cd-Fe) O x @SiO 2 Ultrasonic dispersing filler in deionized water containing wetting agent, (Cd-Fe) O x @SiO 2 The mass concentration was 45 wt.%, the mass concentration of wetting agent was 1.5wt.%, the filler suspension obtained.
The preparation processes of the example 1 and the comparative examples 1-3 are not substantially different, the main difference is that the comparative document 1 is free of complexing agent and stabilizer, the comparative document 2 is free of cadmium salt, the comparative document 3 is free of an activation step, after the magnetic separation hydrothermal products of the step (3) of the example 1 and the comparative examples 1-3 are dried in vacuum, corrosion tests are carried out, equal mass samples are soaked in 5wt.% of saline solution for 15min, the corrosion rates of the example 1 and the comparative examples 1-3 are 93.5wt.%, 78.5wt.%, 80.2wt.%, 93.4wt.%, and the corrosion rates of the comparative examples 1-3 are 91.2wt.%, 65.5wt.%, 66.2wt.%, 91.3wt.%, respectively, wherein the corrosion rates of the example 1 are not substantially different, and the products are obviously proved to be corrosion-resistant magnetic particles, the corrosion resistance is derived from cadmium doping under high-pressure hydrothermal conditions, the corrosion rates of the example 1 and the comparative examples are respectively 93.5wt.%, 78.5wt.%, 93.4wt.%, and the corrosion rates of the comparative examples 1-3 are not different from the thermal conditions, and the corrosion rates of the comparative examples are not different from the thermal conditions, and the corrosion rates of the thermal alloy is not stable, and the corrosion effects of the iron alloy is formed by the comparative examples 2. Furthermore, comparative example 3 is not substantially different from example 1 in that the treatment steps before activation are similar.
Example 2
The suspensions prepared in example 1 and comparative example 3 are fillers for polyurethanes.
A preparation method of a two-component water-based paint,
(A) The preparation method of the component A comprises the following steps: the water-based hydroxyl acrylic resin, the wetting dispersant, the defoamer, the leveling agent and the deionized water are uniformly stirred according to the formula amount, the filler suspension is added, the mixture is uniformly stirred at a high speed of 1000rpm, and then the cosolvent and the thixotropic thickener are added and uniformly mixed at a medium speed of 700 rpm.
(B) The preparation method of the component B comprises the following steps: the hydrophilic modified isocyanate curing agent and the propylene glycol diacetate are fully and uniformly mixed to prepare the modified polyurethane foam.
(C) When in use, the component A and the component B are mixed according to the mass ratio of (7.5): 1, uniformly mixing, and then spraying on the surface of a substrate.
Example 3
An aqueous two-component polyurethane coating comprises a component A and a component B; the mass ratio of the component A to the component B is 7.5:1.
the component A comprises the following components in parts by mass: 52 parts of aqueous hydroxy acrylic resin, 1.5 parts of wetting dispersant, 1.5 parts of defoamer, 7.5 parts of cosolvent, 20 parts of filler suspension, 1.5 parts of flatting agent, 2.5 parts of thixotropic thickener and 20 parts of deionized water;
the component B comprises the following components in parts by mass: 70 parts of hydrophilic modified isocyanate curing agent and 12.5 parts of propylene glycol diacetate.
The wetting dispersant is selected from BYK-190.
The defoamer is selected from BYK 093.
The cosolvent is selected from ethylene glycol butyl ether.
The leveling agent is selected from TEGO Glide 4100.
The thixotropic thickener is selected from RHEOLATE 299.
The suspension prepared in example 1 was used as filler for polyurethane.
Comparative example 4
An aqueous two-component polyurethane coating comprises a component A and a component B; the mass ratio of the component A to the component B is 7.5:1.
the component A comprises the following components in parts by mass: 52 parts of aqueous hydroxy acrylic resin, 1.5 parts of wetting dispersant, 1.5 parts of defoamer, 7.5 parts of cosolvent, 20 parts of filler suspension, 1.5 parts of flatting agent, 2.5 parts of thixotropic thickener and 20 parts of deionized water;
the component B comprises the following components in parts by mass: 70 parts of hydrophilic modified isocyanate curing agent and 12.5 parts of propylene glycol diacetate.
The wetting dispersant is selected from BYK-190.
The defoamer is selected from BYK 093.
The cosolvent is selected from ethylene glycol butyl ether.
The leveling agent is selected from TEGO Glide 4100.
The thixotropic thickener is selected from RHEOLATE 299.
The suspension prepared in comparative example 3 was used as filler for polyurethane.
Comparative example 5
An aqueous two-component polyurethane coating comprises a component A and a component B; the mass ratio of the component A to the component B is (7.5): 1.
the component A comprises the following components in parts by mass: 52 parts of aqueous hydroxy acrylic resin, 1.5 parts of wetting dispersant, 1.5 parts of defoamer, 7.5 parts of cosolvent, 20 parts of filler suspension, 1.5 parts of flatting agent, 2.5 parts of thixotropic thickener and 20 parts of deionized water;
the component B comprises the following components in parts by mass: 70 parts of hydrophilic modified isocyanate curing agent and 12.5 parts of propylene glycol diacetate.
The wetting dispersant is selected from BYK-190.
The defoamer is selected from BYK 093.
The cosolvent is selected from ethylene glycol butyl ether.
The leveling agent is selected from TEGO Glide 4100.
The thixotropic thickener is selected from RHEOLATE 299.
The filler suspension was prepared as follows: the method comprises the following steps:
(1) 6.5mM FeCl 3 . 6H 2 O、0.75 mM CdCl 2 . 6H 2 O metal salt is added into ethanol-deionized water solution, and the volume ratio of ethanol to deionized water is 1:8, stirring uniformly, sequentially adding 3.5g/L tetrahydroxypropyl ethylenediamine and 1.5g/L ethylenediamine tetraacetic acid composite complexing agent, then adding 0.03 g/L2, 2' -bipyridine as a stabilizer, and 12.5mL NaBH 4 Uniformly stirring as a reducing agent, and then adjusting pH=8 by taking sodium acetate as an alkali source to obtain a precursor liquid;
(2) Placing the precursor liquid into a lining-free stainless steel water thermal reaction kettle, discharging air in the reaction kettle by using nitrogen, sealing the reaction kettle, heating to 305 ℃ at 7.5 ℃/min, preserving heat for 36h, and naturally cooling to room temperature;
(3) Magnetically separating a hydrothermal product, and performing activation pickling purification: the activated pickling purification is to place the magnetic separation hydrothermal product in a volume ratio of 1.5:1 by 98wt.% H 2 SO 4 And 30wt.% H 2 O 2 Treating in the mixed solution for 2.5min at 30 ℃, stirring by a motor, activating, pickling and purifying, and sequentially and repeatedly cleaning to be neutral by using deionized water and ethanol.
The (Cd-Fe) O x The filler was ultrasonically dispersed in deionized water containing a wetting agent, the mass concentration of (Cd-Fe) O was 45 wt.%, and the mass concentration of the wetting agent was 1.5wt.%, to obtain a filler suspension.
As shown in the above table, the main difference between example 3 and comparative example 4 is whether the filler is different, and the further difference is whether the filler is subjected to the purification activation treatment, the difference between example 3 and comparative example 5In whether the coating treatment is performed. The coating was applied to the surface of a metal substrate and then subjected to a polarization potential test to convert it to a corrosion current density, which is significantly orders of magnitude higher than that of comparative examples 4 and 5, example 3, comparative example 5 differing primarily in the presence or absence of purification activation, which resulted in a hydrothermal product having relatively heterogeneous composition, and more importantly no functional groups on the surface, affecting the subsequent directional coating of silica, and, in addition, as shown in comparative example 5, no silica coating, alone (Cd-Fe) O x The filler has poor corrosion resistance, and (Cd-Fe) O x Poor dispersibility in the coating, filler agglomeration, which is most directly reflected by a decrease in tensile strength, all affect the corrosion resistance of the coating, as indicated above.
The foregoing embodiments have been described in some detail by way of illustration of the principles of the invention, and it is to be understood that this invention is not limited to the specific embodiments described herein, but is intended to cover modifications and improvements made within the spirit and scope of the invention.

Claims (9)

1. The preparation method of the two-component water-based paint filler is characterized by comprising the following steps of:
(1) 5-8mM FeCl 3 . 6H 2 O、0.5-1 mM CdCl 2 . 6H 2 Adding O metal salt into ethanol-deionized water solution, stirring uniformly, sequentially adding 3-4g/L tetrahydroxypropyl ethylenediamine and 1-2g/L ethylenediamine tetraacetic acid compound complexing agent, then adding 0.02-0.04 g/L2, 2' -bipyridine as stabilizer, and 10-15mL NaBH 4 Uniformly stirring the mixture serving as a reducing agent, and then adjusting pH=7.5-8.5 by taking sodium acetate as an alkali source to obtain a precursor liquid;
(2) Placing the precursor liquid into a lining-free stainless steel water thermal reaction kettle, exhausting air in the reaction kettle by using nitrogen, sealing the reaction kettle, heating to 300-310 ℃ at 5-10 ℃/min, preserving heat for 24-48h, and naturally cooling to room temperature;
(3) Magnetically separating a hydrothermal product, and performing activation pickling purification: the activated acid washingThe purification is that the magnetic separation hydrothermal product is placed in a volume ratio of 1-2:1 by 98wt.% H 2 SO 4 And 30wt.% H 2 O 2 Treating for 2-3min at 30 ℃, stirring by a motor, sequentially and repeatedly cleaning to neutrality by using deionized water and ethanol after activating, pickling and purifying, and preparing a suspension of 10-20wt.% magnetic particles, wherein the solvent of the suspension consists of polyether modified siloxane wetting agent, ethanol and deionized water;
(4) Adding ammonia water into the magnetic particle suspension prepared in the step (3), stirring for 10-20min, adding ethyl silicate, stirring for 12-14h by a motor at 10-14 ℃, filtering and washing the product, and vacuum drying to obtain (Cd-Fe) O x @SiO 2 And (3) filling.
2. A method of preparing a two-component waterborne coating filler according to claim 1, wherein the polyether modified siloxane wetting agent is present in an amount of from 4 to 5wt.%.
3. The method for preparing a two-component water-based paint filler according to claim 1, wherein the volume ratio of ethanol to deionized water in the step (1) and the step (3) is 1:7-9.
4. The method for preparing a two-component water-based paint filler according to claim 1, wherein the saturated magnetic strength of the magnetic particles after the activated acid washing purification in the step (3) is 62.7 emu/G, the remanence is 4.23 emu/G, and the coercive force is hc=41.8g.
5. The process for preparing a two-component aqueous coating filler according to claim 1, wherein (Cd-Fe) O x @SiO 2 The saturation magnetic strength of the filler was 25.3 emu/g.
6. The method for preparing a two-component water-based paint filler according to claim 1, wherein the amount of ethyl silicate is 3-4g and the amount of ammonia water is 5-8mL.
7. The process for preparing a two-component aqueous coating filler according to claim 1, wherein (Cd-Fe) O x The core size is 20-70nm, siO 2 The thickness of the shell is 10-30nm.
8. A process for preparing a two-component aqueous coating filler according to claim 1, wherein the (Cd-Fe) O x @SiO 2 Ultrasonic dispersing filler in deionized water containing wetting agent, (Cd-Fe) O x @SiO 2 The mass concentration is 40-50wt%, and the mass concentration of the wetting agent is 1-2wt%.
9. A two-component aqueous coating filler characterized by being obtained by a two-component aqueous coating filler preparation method as claimed in claims 1 to 8.
CN202310504049.XA 2023-05-06 2023-05-06 Double-component water-based paint filler and preparation method thereof Pending CN116478569A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2024056109A1 (en) * 2023-08-28 2024-03-21 常州大学 "brick-mortar" layered structure corrosion-resistant phosphate composite coating, and preparation method and use therefor

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2024056109A1 (en) * 2023-08-28 2024-03-21 常州大学 "brick-mortar" layered structure corrosion-resistant phosphate composite coating, and preparation method and use therefor

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