CN115058174B - Epoxy powder coating with high adhesive force to metal substrate - Google Patents

Epoxy powder coating with high adhesive force to metal substrate Download PDF

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CN115058174B
CN115058174B CN202210808763.3A CN202210808763A CN115058174B CN 115058174 B CN115058174 B CN 115058174B CN 202210808763 A CN202210808763 A CN 202210808763A CN 115058174 B CN115058174 B CN 115058174B
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coating
powder
wollastonite powder
parts
wollastonite
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CN115058174A (en
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马腾飞
徐武斌
胡语梦
李停
刘元章
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Nantong Meiyicai New Material Technology Co ltd
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Nantong Meiyicai New Material Technology 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
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/03—Powdery paints
    • C09D5/033—Powdery paints characterised by the additives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08—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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/221—Oxides; Hydroxides of metals of rare earth metal
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/221—Oxides; Hydroxides of metals of rare earth metal
    • C08K2003/2213—Oxides; Hydroxides of metals of rare earth metal of cerium
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2227—Oxides; Hydroxides of metals of aluminium
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2265—Oxides; Hydroxides of metals of iron
    • C08K2003/2272—Ferric oxide (Fe2O3)

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

Abstract

The invention discloses an epoxy powder coating with high adhesion to metal substrates, which comprises the following components in parts by weight: 55-65 parts of epoxy resin; 3-5 parts of a curing agent; 0.5-1 part by weight of a leveling agent; 0.4-0.6 parts of benzoin; 25-30 parts of special filler; 0.5-2 parts by weight of a silane coupling agent; 5-10 parts of pigment and filler; wherein the special filler is modified wollastonite powder which is coated by a nano silicon dioxide film and a composite modified film. The epoxy powder coating with high adhesion to metal substrates provided by the invention has the advantages of high coating adhesion, excellent boiling resistance, excellent salt spray corrosion resistance and excellent ultraviolet aging resistance, and can be well applied to protection of metal substrates.

Description

Epoxy powder coating with high adhesive force to metal substrate
Technical Field
The invention relates to the field of coatings, in particular to an epoxy powder coating with high adhesion to metal substrates.
Background
In many fields of national economy, steel is used for structural design, but if a common steel material is directly exposed outside, the common steel material is easily damaged due to rusting, corrosion and the like within a period of time, the surface of the steel material is usually sprayed with paint for protection, and epoxy powder paint is widely applied as protective paint. For example, patent CN202110560685.5 discloses an ultraviolet aging resistant epoxy resin coating and a preparation method thereof, patent CN202010166712.6 discloses a texture powder coating special for ultralow temperature rapid prototyping sewing machines and a preparation method thereof, patent CN201410211298.0 discloses a high permeability resistant epoxy powder coating and a preparation method thereof, and the like.
When the coating is formed by spraying the coating, the adhesive force of the coating is easy to reduce due to the fact that the coating has larger shrinkage capacity, the number of polar groups is reduced because polymers are crosslinked in the curing process, and the like, so that the protective effect of the coating on a metal substrate is insufficient, and the protective life is short. The existing epoxy powder coating is difficult to well solve the defect of poor adhesion of the coating, so that the protective effect on the metal substrate cannot meet the use requirement. Therefore, there is a need for improvements in the art to provide a more reliable solution.
Disclosure of Invention
The technical problem to be solved by the invention is to provide an epoxy powder coating with high adhesion to metal substrates, aiming at the defects in the prior art.
In order to solve the technical problems, the invention adopts the technical scheme that: an epoxy powder coating with high adhesion to metal substrates comprises the following components in parts by weight:
55-65 parts of epoxy resin;
3-5 parts of a curing agent;
0.5-1 part of leveling agent;
0.4-0.6 parts of benzoin;
25-30 parts of special filler;
0.5-2 parts by weight of a silane coupling agent;
5-10 parts of pigment and filler;
wherein the special filler is modified wollastonite powder which is double-layer coated by a nano silicon dioxide film and a composite modified film.
Preferably, the epoxy resin is a two-step epoxy resin.
Preferably, the modified wollastonite powder is prepared by the following method:
1) Preparing a wollastonite powder dispersion;
2) Preparing wollastonite powder coated with a nano silicon dioxide film;
3) Coating the composite modified film to obtain the modified wollastonite powder coated with the nano silicon dioxide film and the composite modified film in a double-layer manner.
Preferably, the step 1) is specifically:
grinding needle-shaped or rod-shaped wollastonite into powder, adding the powder into deionized water, stirring, adding a dispersing agent and an aluminate coupling agent, and performing ultrasonic dispersion to obtain a wollastonite powder dispersion liquid.
Preferably, the step 2) is specifically:
2-1) adding sodium silicate into the wollastonite powder dispersion liquid, and uniformly stirring;
2-2) heating the mixed solution obtained in the step 2-1) to 50-75 ℃, then dropwise adding a hydrochloric acid solution into the solution under continuous stirring, stopping dropwise adding until the pH value of the solution is 6-6.5, and aging for 1-4h;
2-3) filtering, washing and drying the solid product, and grinding to obtain the wollastonite powder coated with the nano silicon dioxide.
Preferably, the step 3) is specifically:
3-1) preheating the nano silicon dioxide coated wollastonite powder obtained in the step 2) to 110-150 ℃, and keeping the temperature for 0.5-2h;
3-2) reacting AlCl 3 ·6H 2 O、FeCl 3 ·6H 2 Adding O, cerium acetate and erbium acetate tetrahydrate into a reaction container, mixing, uniformly stirring and grinding;
3-3) adding the wollastonite powder coated with the nano silicon dioxide treated in the step 3-1) into a reaction vessel to be mixed with the product obtained in the step 3-2), and uniformly stirring;
3-4) heating to 185-350 ℃ under continuous stirring, and reacting for 1-8 hours;
3-5) heating to 750-950 ℃, and calcining for 1-6 hours;
3-6) cooling to room temperature, and grinding to obtain the modified wollastonite powder double-layer coated by the nano silicon dioxide film and the composite modified film.
Preferably, the curing agent is dicyandiamide.
Preferably, the leveling agent is a silica-adsorbed acrylate leveling agent.
Preferably, the pigment and filler is one or more of carbon black, iron oxide red, iron oxide yellow and phthalocyanine blue.
Preferably, the preparation method of the epoxy powder coating with high adhesion to metal substrates comprises the following steps:
s1, weighing raw materials according to the weight part ratio, pouring the raw materials into a premixing container, and uniformly mixing;
s2, adding the uniformly mixed raw materials into a double-screw extruder for melt extrusion, wherein the melt temperature of the extruder is controlled to be 80-100 ℃;
and S3, cooling the extruded material by a compression roller, tabletting, grinding and sieving to obtain the epoxy powder coating.
The invention has the beneficial effects that:
the epoxy powder coating with high adhesion to a metal substrate provided by the invention has the advantages that the prepared coating has high adhesion, excellent boiling resistance, excellent salt spray corrosion resistance and excellent ultraviolet aging resistance, and can be well applied to the protection of the metal substrate;
according to the invention, the nanometer silicon dioxide film and the composite modified film are coated in a double-layer manner to modify the wollastonite powder, so that on one hand, the dispersibility of the wollastonite powder and the compatibility with a polymer material can be obviously improved, and the reinforcing effect of the wollastonite powder on enhancing the adhesive force and the mechanical property of the coating can be fully exerted; on the other hand, the composite modified film can also play a role in remarkably improving the comprehensive performance of the epoxy resin base material, and can further enhance the adhesion strength and durability of the formed coating; a (c)
In the invention, rare earth elements Ce and Er, and Fe 2 O 3 、Al 2 O 3 The introduction of the rare earth elements Ce, er and Fe can improve the dispersion performance of the wollastonite powder and the adhesive force, the anti-stripping performance and the aging resistance of the coating, and the rare earth elements Ce, er and Fe are introduced in a modified wollastonite powder loading mode 2 O 3 、Al 2 O 3 The components can be uniformly dispersed in a coating system, so that the effects of complementary and synergistic enhancement are achieved, and the enhancement effect of each component on the coating can be favorably exerted.
Detailed Description
The present invention is further described in detail below with reference to examples so that those skilled in the art can practice the invention with reference to the description.
It will be understood that terms such as "having," "including," and "comprising," as used herein, do not preclude the presence or addition of one or more other elements or groups thereof.
The test methods used in the following examples are all conventional methods unless otherwise specified. The materials and reagents used in the following examples are commercially available unless otherwise specified. The following examples, in which specific conditions are not specified, were carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The invention provides an epoxy powder coating with high adhesion to a metal substrate, which comprises the following components in parts by weight:
55-65 parts of epoxy resin;
3-5 parts of a curing agent;
0.5-1 part of leveling agent;
0.4-0.6 parts of benzoin;
25-30 parts of special filler;
0.5-2 parts by weight of a silane coupling agent;
5-10 parts of pigment and filler;
in a preferred embodiment, the epoxy resin is a two-step epoxy resin. In a further preferred embodiment, the epoxy resin has an epoxy value of between 0.115 and 0.125mol/100g and a molecular weight of between 800 and 1500. The epoxy resin is not suitable for being selected to have too low relative molecular weight, because the low relative molecular weight is favorable for improving the adhesive force of the coating and the metal substrate although the hydroxyl content is high, but the toughness of the cured coating is lower; it is not preferable to use a coating having a relatively high molecular weight because the cured coating has a low hydroxyl content and poor adhesion to the substrate, although it has high toughness. Therefore, the epoxy resin with medium/medium molecular weight is selected in the invention, and the coating has better coating adhesion and coating toughness. The two-step epoxy resin is prepared by synthesizing low-molecular-weight basic epoxy resin, and then performing chain extension reaction to synthesize high-molecular epoxy resin with a softening point of 90-98 ℃, and in a more preferred embodiment, 90-92 ℃; the method for producing the epoxy resin by the two-step method adopts a synthetic route which is well known in the field, for example, the document of 'Wangsun' two-step method for synthesizing the epoxy resin [ J ] with medium and high molecular weight, 2009, 32 (6): 35-36. For example, E-51, E-54, E-10, E-06, E-03 epoxy resins and the like are all conventional two-step epoxy resins, and the conventional two-step epoxy resins can be selected as long as the requirements of the parameters are met.
In a preferred embodiment, the curing agent is dicyandiamide. The leveling agent is an acrylate leveling agent adsorbed by silicon dioxide. The degassing agent is benzoin, namely benzoin.
The silane coupling agent is an organic compound with one end of the molecule being organophilic and the other being inorganophilic, and the general formula of the molecule is Y-R-Si (OR) 3 Y is an organic functional group, siOR is a siloxy group, is a hydrolyzable group, and is a group indispensable for reaction with an inorganic material. In a preferred embodiment, the silane coupling agent is NH 2 (CH 2 ) 3 Si(OCH 3 ) 3 . The silane coupling agent is between the inorganic and organic interfaces, and can form a bonding layer of an organic matrix, the silane coupling agent and the inorganic matrix, so that the inorganic filler is tightly bonded with the organic matter, and the adhesive force of the coating is improved.
In a preferred embodiment, the pigment and filler is one or more of carbon black, iron oxide red, iron oxide yellow and phthalocyanine blue, and can be selected according to the use requirements.
In a preferred embodiment, the special filler is modified wollastonite powder which is double-layer coated by a nano silicon dioxide film and a composite modified film. Among them, the wollastonite is preferably needle-shaped or rod-shaped wollastonite which is easy to form an intercrossed three-dimensional structure in the stacking process, and can form a more compact coating just corresponding to a three-dimensional network structure formed in the epoxy resin crosslinking and curing process.
In the invention, the modified wollastonite powder is prepared by the following method:
1) Preparing a wollastonite powder dispersion:
grinding needle-shaped or rod-shaped wollastonite into powder, then adding the powder into deionized water, stirring, adding a dispersing agent and an aluminate coupling agent, and performing ultrasonic dispersion to obtain a wollastonite powder dispersion liquid. In a preferred embodiment, the dispersant is sodium hexametaphosphate and the aluminate coupling agent is distearoyl oxide isopropyl aluminate.
2) Preparing wollastonite powder coated with a nano silicon dioxide film:
2-1) adding sodium silicate into the wollastonite powder dispersion liquid, and uniformly stirring;
2-2) heating the mixed solution obtained in the step 2-1) to 50-75 ℃, then dropwise adding a hydrochloric acid solution into the solution under continuous stirring until the pH value of the solution is 6-6.5, stopping dropwise adding, and aging for 1-4h;
2-3) filtering, washing and drying the solid product, and grinding to obtain the wollastonite powder coated with the nano silicon dioxide.
3) Coating a composite modified film:
3-1) preheating the nano silicon dioxide coated wollastonite powder obtained in the step 2) to 110-150 ℃, and keeping the temperature for 0.5-2h;
3-2) reacting AlCl 3 ·6H 2 O、FeCl 3 ·6H 2 O, cerium (C) acetate 2 H 3 CeO 2 ) And erbium acetate tetrahydrate (C) 6 H 17 ErO 10 ) Adding into a reaction vessel, mixing, stirring uniformly, and grinding;
3-3) adding the nanometer silica coated wollastonite powder treated in the step 3-1) into a reaction vessel to be mixed with the product obtained in the step 3-2), and uniformly stirring;
3-4) heating to 185-350 ℃ under continuous stirring, and reacting for 1-8 hours;
3-5) heating to 750-950 ℃, and calcining for 1-6 hours;
3-6) cooling to room temperature, and grinding to obtain the modified wollastonite powder double-layer coated by the nano silicon dioxide film and the composite modified film.
Wollastonite has the characteristics of chemical corrosion resistance, good thermal stability, excellent mechanical property and the like, is widely applied to be used as a reinforcing filler of a polymer material, and can play a remarkable reinforcing role in a formed coating by adding the wollastonite into an epoxy powder coating, improve the adhesive force of the coating and improve the mechanical property of the coating. However, the wollastonite has the defects of poor dispersibility and poor compatibility with polymer materials, so that the practical application effect is greatly reduced, and the reinforcing effect cannot be fully exerted.
According to the invention, the nanometer silicon dioxide film and the composite modified film are coated in a double-layer manner to modify the wollastonite powder, so that on one hand, the dispersibility of the wollastonite powder and the compatibility with a polymer material can be obviously improved, and the reinforcing effect of the wollastonite powder on enhancing the adhesive force and the mechanical property of the coating can be fully exerted; on the other hand, the composite modified film can also play a role in remarkably improving the comprehensive performance of the epoxy resin base material, and can further enhance the adhesion strength and durability of the formed coating; therefore, the composite modified film can improve the epoxy powder coating from at least two aspects, and the two aspects of improvement can be mutually and synergistically enhanced, so that the comprehensive performance of the epoxy powder coating is improved.
Specifically, the modification of the wollastonite powder in the invention comprises the following two steps:
1. nano SiO produced by reaction 2 Coating the surface of the wollastonite powder; by depositing nano SiO on the surface of the wollastonite powder 2 Particle formation of nano SiO 2 The layer can improve sharp edges and corners formed when wollastonite powder is crushed and flatten the cleavage surface of the wollastonite, so that the strength of the wollastonite powder is improved to a certain extent, the bonding interface of the wollastonite and an epoxy resin base material is improved, and the compatibility of the wollastonite powder and the base material is enhanced.
2. Single nano SiO 2 The improvement of the mechanical strength and the adhesive force of the coating is limited by the modification of the coating, mainly because the nano SiO obtained by adopting an inorganic nano coating method 2 The thickness uniformity of the film is difficult to control, and the density of the film layer is not enough. In the invention, through the second step, the rare earth element-doped aluminum oxide-iron oxide composite modified film is coated outside the wollastonite powder coated by the nano silicon dioxide film, so that the nano SiO film can be compensated 2 The film shortage has a further enhancement effect on the performance of the wollastonite powder and the whole epoxy powder coating.
The forming and coating principle of the composite modified film is as follows:
AlCl 3 ·6H 2 O、FeCl 3 ·6H 2 decomposition of O to AlCl under heating 3 、FeCl 3 And steam, further heating to remove AlCl 3 、FeCl 3 Sublimed into gas (AlCl) 3 Sublimating at about 183 deg.C to obtain FeCl 3 Sublimable at about 300 deg.C), alCl 3 Combined with steam to form Al (OH) 3 Adsorbing to the surface of wollastonite powder, feCl 3 Combined with steam to produce Fe (OH) 2 、Fe(OH) 3 Also adsorbed to the surface of the wollastonite powder; cerium acetate and tetrahydrateErbium acetate decomposes to cerium oxide (CeO) under heating 2 ) Erbium oxide (Er) 2 O 3 ）、CO 2 And water vapor, etc., acting on these gas streams and Al (OH) 3 、Fe(OH) 2 、Fe(OH) 3 Under the entrainment effect of the particles, cerium oxide and erbium oxide are also adsorbed on the surface of the wollastonite powder; thereby forming Al (OH) contained in the wollastonite powder 3 、Fe(OH) 2 、Fe(OH) 3 、CeO 2 、Er 2 O 3 A composite modified film of a plurality of compounds;
under further heating, al (OH) 3 Conversion to Al 2 O 3 ，Fe(OH) 2 、Fe(OH) 3 Then dehydrated and oxidized to form Fe 2 O 3 Finally, the surface of the wollastonite powder is coated to form dense CeO-doped silica 2 And Er 2 O 3 Al of (2) 2 O 3 -Fe 2 O 3 The composite modified film has obvious enhancement effects on the dispersibility and the flowability of wollastonite powder, the compatibility with an epoxy resin base material and the improvement on the adhesive force of a coating.
Due to AlCl in the gas phase formed by sublimation 3 、FeCl 3 Combined with steam to form Al (OH) 3 、Fe(OH) 2 、Fe(OH) 3 The aluminum and iron compounds can be more uniformly and fully coated on the surface of the wollastonite powder in the form of nanoparticles, and compared with single Al 2 O 3 Film, fe 2 O 3 The compounding of the silicon dioxide-containing composite material can improve the viscosity of the film layer so that the film layer is firmly coated on the surface of the wollastonite powder, and meanwhile, the toughness of the film layer is also improved; then, the nano fine particles obtained by high-temperature calcination dehydration can form a sufficiently compact composite modified film; the rare earth elements Ce and Er are doped in the composite modified film, and the Ce and Er atoms have a vacancy bond orbit, so that the composite modified film has active chemical properties and large contact surface with other atoms, and can form a network structure taking the Ce and the Er as centers, thereby increasing the polymerization force of the composite modified film, improving the compactness and strength of the composite modified film, and improving the acid-base corrosion resistance of a coating; on the other hand, ce and Er can also refine grains and can form one with Al and FeSome compounds, e.g. Al 3 Er can further improve the compactness of the composite modified film; and the introduction of Ce and Er also has obvious improvement effect on the compatibility of the wollastonite powder and the epoxy resin base material.
The nano silicon dioxide film and the composite modified film are subjected to double-layer coating modification, so that the comprehensive properties such as dispersibility, strength and the like of wollastonite powder are remarkably improved, the improvement of the performance of the wollastonite powder can be acted on a finally formed coating, the adhesion property, mechanical strength and the like of the coating are improved, and meanwhile, various doped compounds introduced by the composite modified film can also be acted on the coating, so that the acid-base corrosion resistance, ageing resistance and the like of the coating are further improved.
The modified wollastonite powder coated with the nano silicon dioxide film and the composite modified film in a double-layer manner is blended into the epoxy powder coating to finally form a coating, and by means of the characteristics that the rare earth elements Ce and Er have high reaction activity and can react with epoxy resin to obtain a compound with extremely strong bond energy, the compactness of the coating and the binding force between the coating and a base body can be improved, the oxidation rate of the coating is reduced, the anti-stripping performance of the coating is improved, the drying of the coating can be promoted, and the adhesion performance of the coating is improved.
In addition, ceO 2 Has better ultraviolet shielding performance and Fe 2 O 3 The coating has a certain ultraviolet shielding performance, and after the ultraviolet shielding performance and the ultraviolet shielding performance are compounded and introduced into the epoxy resin system, the obtained coating has excellent ultraviolet shielding performance, so that the aging resistance of the coating can be improved. In addition, fe 2 O 3 The bonding strength between the coating and the metal substrate can be improved, and the adhesive force is improved.
In the present invention, the rare earth elements Ce and Er, and Fe 2 O 3 、Al 2 O 3 The introduction of the rare earth element can improve the dispersion performance of the wollastonite powder, and the rare earth elements Ce, er and Fe are introduced in a modified wollastonite powder loading mode 2 O 3 、Al 2 O 3 The components can be uniformly dispersed in a coating system, so that the effects of complementary and synergistic enhancement are achieved, and the enhancement of the components on the coating can be facilitated.
In a preferred embodiment, the preparation method of the epoxy powder coating with high adhesion to the metal substrate comprises the following steps:
s1, weighing raw materials according to the weight part ratio, pouring the raw materials into a premixing container, and uniformly mixing the raw materials for 3 to 5 minutes at the speed of 1000 to 2000 r/min;
s2, adding the uniformly mixed raw materials into a double-screw extruder for melt extrusion, wherein the rotating speed frequency of an extrusion screw of the extruder is 40-60Hz, the melt temperature of the extruder is controlled at 80-90 ℃, and the temperature of a discharge port of the extruder is not higher than 100 ℃;
and S3, cooling the extruded material by a compression roller, tabletting, grinding and sieving to obtain the epoxy powder coating.
The present invention is further illustrated by the following examples and comparative examples, which are given above as a general idea of the present invention.
Example 1
An epoxy powder coating with high adhesion to a metal substrate comprises the following components in parts by weight:
60 parts by weight of epoxy resin;
4 parts of a curing agent;
0.8 part of leveling agent;
0.4 part by weight of benzoin;
25 parts of special filler;
1 part by weight of a silane coupling agent;
and 10 parts of pigment and filler.
The preparation method of the epoxy powder coating with high adhesion to metal substrates comprises the following steps:
s1, weighing raw materials according to the weight part ratio, pouring the raw materials into a premixing container, and uniformly mixing the raw materials for 5 minutes at the speed of 1500 rpm;
s2, adding the uniformly mixed raw materials into a double-screw extruder for melt extrusion, wherein the rotating speed frequency of an extrusion screw of the extruder is 50Hz, the melt temperature of the extruder is controlled at 85 ℃, and the temperature of a discharge port of the extruder is not higher than 100 ℃;
and S3, cooling the extruded material by a compression roller, tabletting, grinding by an ACM (Acrylonitrile-butadiene-styrene) pulverizer, removing the ultrafine particle part by using a cyclone separator, sieving by a 160-mesh sieve to obtain the epoxy powder coating, and packaging.
Wherein the epoxy resin is a two-step epoxy resin with the epoxy value of 0.115-0.125mol/100g, and the molecular weight is 1000-1200. The two-step method epoxy resin is characterized in that low molecular weight basic epoxy resin is firstly synthesized, then chain growth reaction is carried out to synthesize high molecular epoxy resin, and the softening point of the high molecular epoxy resin is 90-92 ℃; and the two-step process for producing epoxy resins employs synthetic routes well known in the art.
Wherein the silane coupling agent is NH 2 (CH 2 ) 3 Si(OCH 3 ) 3 The curing agent is dicyandiamide, the flatting agent is an acrylate flatting agent adsorbed by silicon dioxide, the degassing agent is benzoin, namely benzoin, and the pigment and filler are carbon black.
The special filler is modified wollastonite powder which is double-layer coated by a nano silicon dioxide film and a composite modified film, and is prepared by the following method:
1) Preparing a wollastonite powder dispersion liquid:
grinding needle-shaped wollastonite into powder, adding the powder into deionized water, stirring, and adding a dispersing agent: sodium hexametaphosphate and aluminate coupling agent: and (3) carrying out ultrasonic dispersion on distearoyl isopropyl aluminate for 30min to obtain wollastonite powder dispersion liquid.
2) Preparing wollastonite powder coated with a nano silicon dioxide film:
2-1) adding sodium silicate into the wollastonite powder dispersion liquid, and uniformly stirring;
2-2) heating the mixed solution obtained in the step 2-1) to 55 ℃, then dropwise adding a hydrochloric acid solution into the solution under continuous stirring until the pH value of the solution is 6.5, stopping dropwise adding, and aging for 3 hours;
2-3) filtering, washing the solid product, drying at 80 ℃, and grinding to obtain the wollastonite powder coated with the nano silicon dioxide.
3) Coating a composite modified film:
3-1) preheating the nano silicon dioxide coated wollastonite powder obtained in the step 2) to 130 ℃, and keeping the temperature for 1h;
3-2) mixingAlCl 3 ·6H 2 O、FeCl 3 ·6H 2 Adding O, cerium acetate and erbium acetate tetrahydrate into a reaction container, mixing, uniformly stirring and grinding;
3-3) adding the nanometer silica coated wollastonite powder treated in the step 3-1) into a reaction vessel to be mixed with the product obtained in the step 3-2), and uniformly stirring; wherein, the nanometer silicon dioxide coated wollastonite powder: alCl 3 ·6H 2 O：FeCl 3 ·6H 2 O: cerium acetate: erbium acetate tetrahydrate at mass ratio = 25;
3-4) heating to 310 ℃ under continuous stirring, and reacting for 5 hours;
3-5) heating to 850 ℃, and calcining for 3 hours;
3-6) cooling to room temperature, and grinding to obtain the modified wollastonite powder double-layer coated by the nano silicon dioxide film and the composite modified film.
Example 2
An epoxy powder coating with high adhesion to metal substrates comprises the following components in parts by weight:
60 parts by weight of epoxy resin;
4 parts of a curing agent;
0.8 part of leveling agent;
0.4 part by weight of benzoin;
21 parts of special filler;
1 part by weight of a silane coupling agent;
and 10 parts of pigment and filler.
The preparation method of the epoxy powder coating with high adhesion to metal substrates comprises the following steps:
s1, weighing raw materials according to the weight part ratio, pouring the raw materials into a premixing container, and uniformly mixing the raw materials for 5 minutes at the speed of 1500 rpm;
s2, adding the uniformly mixed raw materials into a double-screw extruder for melt extrusion, wherein the rotating speed frequency of an extrusion screw of the extruder is 50Hz, the melt temperature of the extruder is controlled at 85 ℃, and the temperature of a discharge port of the extruder is not higher than 100 ℃;
and S3, cooling the extruded material by a compression roller, tabletting, grinding by an ACM (Acrylonitrile-butadiene-styrene) pulverizer, removing the ultramicron part by using a cyclone separator, sieving by a 160-mesh sieve to obtain the epoxy powder coating, and packaging.
Wherein the epoxy resin is a two-step epoxy resin with the epoxy value of 0.115-0.125mol/100g, and the molecular weight is 1000-1200. The two-step method epoxy resin is characterized in that low molecular weight basic epoxy resin is firstly synthesized, then chain growth reaction is carried out to synthesize high molecular epoxy resin, and the softening point of the high molecular epoxy resin is 90-92 ℃; and the two-step process for producing epoxy resins employs synthetic routes well known in the art.
Wherein the silane coupling agent is NH 2 (CH 2 ) 3 Si(OCH 3 ) 3 The curing agent is dicyandiamide, the flatting agent is an acrylate flatting agent adsorbed by silicon dioxide, the degassing agent is benzoin, namely benzoin, and the pigment and filler are carbon black.
The special filler is modified wollastonite powder which is double-layer coated by a nano silicon dioxide film and a composite modified film, and is prepared by the following method:
1) Preparing a wollastonite powder dispersion:
grinding needle-shaped wollastonite into powder, adding the powder into deionized water, stirring, and adding a dispersing agent: sodium hexametaphosphate and aluminate coupling agent: and (3) carrying out ultrasonic dispersion on distearoyl oxygen isopropyl aluminate for 30min to obtain a wollastonite powder dispersion liquid.
2) Preparing wollastonite powder coated with a nano silicon dioxide film:
2-1) adding sodium silicate into the wollastonite powder dispersion liquid, and uniformly stirring;
2-2) heating the mixed solution obtained in the step 2-1) to 55 ℃, then dropwise adding a hydrochloric acid solution into the solution under continuous stirring until the pH value of the solution is 6.5, stopping dropwise adding, and aging for 3 hours;
2-3) filtering, washing the solid product, drying at 80 ℃, and grinding to obtain the wollastonite powder coated with the nano silicon dioxide.
3) Coating a composite modified film:
3-1) preheating the nano silicon dioxide coated wollastonite powder obtained in the step 2) to 130 ℃, and keeping the temperature for 1h;
3-2）mixing AlCl 3 ·6H 2 O、FeCl 3 ·6H 2 Adding O, cerium acetate and erbium acetate tetrahydrate into a reaction container, mixing, uniformly stirring and grinding;
3-3) adding the nanometer silica coated wollastonite powder treated in the step 3-1) into a reaction vessel to be mixed with the product obtained in the step 3-2), and uniformly stirring; wherein, the nanometer silicon dioxide coated wollastonite powder: alCl 3 ·6H 2 O：FeCl 3 ·6H 2 O: cerium acetate: erbium acetate tetrahydrate at mass ratio = 25;
3-4) heating to 310 ℃ under continuous stirring, and reacting for 5 hours;
3-5) heating to 850 ℃, and calcining for 3 hours;
3-6) cooling to room temperature, and grinding to obtain the modified wollastonite powder double-layer coated by the nano silicon dioxide film and the composite modified film.
Example 3
An epoxy powder coating with high adhesion to a metal substrate comprises the following components in parts by weight:
60 parts by weight of epoxy resin;
4 parts of a curing agent;
0.8 part of leveling agent;
0.4 part by weight of benzoin;
25 parts of special filler;
1 part by weight of a silane coupling agent;
and 10 parts of pigment and filler.
The preparation method of the epoxy powder coating with high adhesion to metal substrates comprises the following steps:
s1, weighing raw materials according to the weight part ratio, pouring the raw materials into a premixing container, and uniformly mixing the raw materials for 5 minutes at the speed of 1500 rpm;
s2, adding the uniformly mixed raw materials into a double-screw extruder for melt extrusion, wherein the rotating speed frequency of an extrusion screw of the extruder is 50Hz, the melt temperature of the extruder is controlled at 85 ℃, and the temperature of a discharge port of the extruder is not higher than 100 ℃;
and S3, cooling the extruded material by a compression roller, tabletting, grinding by an ACM (Acrylonitrile-butadiene-styrene) pulverizer, removing the ultramicron part by using a cyclone separator, sieving by a 160-mesh sieve to obtain the epoxy powder coating, and packaging.
Wherein the epoxy resin is a two-step epoxy resin with the epoxy value of 0.115-0.125mol/100g, and the molecular weight is 1000-1200. The two-step method epoxy resin is characterized in that low-molecular-weight basic epoxy resin is firstly synthesized, then chain extension reaction is carried out to synthesize high-molecular epoxy resin, and the softening point of the high-molecular-weight basic epoxy resin is 90-92 ℃; and the two-step process for producing epoxy resins employs synthetic routes well known in the art.
Wherein the silane coupling agent is NH 2 (CH 2 ) 3 Si(OCH 3 ) 3 The curing agent is dicyandiamide, the leveling agent is an acrylate leveling agent adsorbed by silicon dioxide, the degassing agent is benzoin, namely benzoin, and the pigment and filler are carbon black.
The special filler is modified wollastonite powder which is double-layer coated by a nano silicon dioxide film and a composite modified film, and is prepared by the following method:
1) Preparing a wollastonite powder dispersion liquid:
grinding needle-shaped wollastonite, adding the ground needle-shaped wollastonite into deionized water, stirring, and adding a dispersing agent: sodium hexametaphosphate and aluminate coupling agent: and (3) carrying out ultrasonic dispersion on distearoyl isopropyl aluminate for 30min to obtain wollastonite powder dispersion liquid.
2) Preparing wollastonite powder coated with a nano-silica film:
2-1) adding sodium silicate into the wollastonite powder dispersion liquid, and uniformly stirring;
2-2) heating the mixed solution obtained in the step 2-1) to 55 ℃, then dropwise adding a hydrochloric acid solution into the solution under continuous stirring until the pH value of the solution is 6.5, stopping dropwise adding, and aging for 3 hours;
2-3) filtering, washing the solid product, drying at 80 ℃, and grinding to obtain the wollastonite powder coated with the nano silicon dioxide.
3) Coating a composite modified film:
3-1) preheating the nano silicon dioxide coated wollastonite powder obtained in the step 2) to 130 ℃, and keeping the temperature for 1h;
3-2) Mixing AlCl 3 ·6H 2 O、FeCl 3 ·6H 2 Adding O, cerium acetate and erbium acetate tetrahydrate into a reaction container, mixing, uniformly stirring and grinding;
3-3) adding the wollastonite powder coated with the nano silicon dioxide treated in the step 3-1) into a reaction vessel to be mixed with the product obtained in the step 3-2), and uniformly stirring; wherein, the nanometer silicon dioxide coated wollastonite powder: alCl 3 ·6H 2 O：FeCl 3 ·6H 2 O: cerium acetate: erbium acetate tetrahydrate at mass ratio = 23;
3-4) heating to 310 ℃ under continuous stirring, and reacting for 5 hours;
3-5) heating to 850 ℃, and calcining for 3 hours;
3-6) cooling to room temperature, and grinding to obtain the modified wollastonite powder coated with the nano silicon dioxide film and the composite modified film.
Comparative example 1
This example is substantially the same as example 1, except that: the epoxy resin in this example is a one-shot epoxy resin E-44.
Comparative example 2
This example is substantially the same as example 1, except that: no special filler was added in this example.
Comparative example 3
This example is substantially the same as example 1, except that: in this example, NH was used as the non-silane coupling agent 2 (CH 2 ) 3 Si(OCH 3 ) 3 。
Comparative example 4
This example is substantially the same as example 1, except that: the special filler in this example is acicular wollastonite powder, i.e., unmodified.
Comparative example 5
This example is substantially the same as example 1, except that:
the special filler in the embodiment is modified wollastonite powder coated with a nano silica film, and is prepared by the following method:
1) Preparing a wollastonite powder dispersion:
grinding needle-shaped wollastonite into powder, adding the powder into deionized water, stirring, and adding a dispersing agent: sodium hexametaphosphate and aluminate coupling agent: and (3) carrying out ultrasonic dispersion on distearoyl isopropyl aluminate for 30min to obtain wollastonite powder dispersion liquid.
2) Preparing wollastonite powder coated with a nano silicon dioxide film:
2-1) adding sodium silicate into the wollastonite powder dispersion liquid, and uniformly stirring;
2-2) heating the mixed solution obtained in the step 2-1) to 55 ℃, then dropwise adding a hydrochloric acid solution into the solution under continuous stirring until the pH value of the solution is 6.5, stopping dropwise adding, and aging for 3 hours;
2-3) filtering, washing the solid product, drying at 80 ℃, and grinding to obtain the wollastonite powder coated with the nano silicon dioxide.
Comparative example 6
This example is substantially the same as example 1, except that:
the special filler in the embodiment is modified wollastonite powder compositely coated by a nano silicon dioxide film and an aluminum dioxide film, and is prepared by the following method:
1) Preparing a wollastonite powder dispersion liquid:
grinding needle-shaped wollastonite into powder, adding the powder into deionized water, stirring, and adding a dispersing agent: sodium hexametaphosphate and aluminate coupling agent: and (3) carrying out ultrasonic dispersion on distearoyl isopropyl aluminate for 30min to obtain wollastonite powder dispersion liquid.
2) Preparing wollastonite powder coated with a nano silicon dioxide film:
2-1) adding sodium silicate into the wollastonite powder dispersion liquid, and uniformly stirring;
2-2) heating the mixed solution obtained in the step 2-1) to 55 ℃, then dropwise adding a hydrochloric acid solution into the solution under continuous stirring until the pH value of the solution is 6.5, stopping dropwise adding, and aging for 3 hours;
2-3) filtering, washing the solid product, drying at 80 ℃, and grinding to obtain the wollastonite powder coated with the nano silicon dioxide.
3) Coating a composite modified film:
3-1) preheating the nano silicon dioxide coated wollastonite powder obtained in the step 2) to 130 ℃, and keeping the temperature for 1h;
3-2) reacting AlCl 3 ·6H 2 Adding O into a reaction container, and grinding;
3-3) adding the nanometer silica coated wollastonite powder treated in the step 3-1) into a reaction vessel to be mixed with the product obtained in the step 3-2), and uniformly stirring; wherein, the nanometer silicon dioxide coated wollastonite powder: alCl 3 ·6H 2 O mass ratio = 25;
3-4) heating to 310 ℃ under continuous stirring, and reacting for 5 hours;
3-5) heating to 850 ℃, and calcining for 3 hours;
3-6) cooling to room temperature, and grinding to obtain the modified wollastonite powder coated with the nano silicon dioxide film-aluminum dioxide film in a composite manner.
Comparative example 7
This example is substantially the same as example 1, except that:
the special filler in the embodiment is modified wollastonite powder which is compositely coated by a nano silicon dioxide film and an aluminum dioxide film doped with rare earth cerium and erbium, and is prepared by the following method:
1) Preparing a wollastonite powder dispersion liquid:
grinding needle-shaped wollastonite, adding the ground needle-shaped wollastonite into deionized water, stirring, and adding a dispersing agent: sodium hexametaphosphate and aluminate coupling agent: and (3) carrying out ultrasonic dispersion on distearoyl isopropyl aluminate for 30min to obtain wollastonite powder dispersion liquid.
2) Preparing wollastonite powder coated with a nano silicon dioxide film:
2-1) adding sodium silicate into the wollastonite powder dispersion liquid, and uniformly stirring;
2-2) heating the mixed solution obtained in the step 2-1) to 55 ℃, then dropwise adding a hydrochloric acid solution into the solution under continuous stirring until the pH value of the solution is 6.5, stopping dropwise adding, and aging for 3 hours;
2-3) filtering, washing the solid product, drying at 80 ℃, and grinding to obtain the wollastonite powder coated with nano silicon dioxide.
3) Coating a composite modified film:
3-1) preheating the nano silicon dioxide coated wollastonite powder obtained in the step 2) to 130 ℃, and keeping the temperature for 1h;
3-2) reacting AlCl 3 ·6H 2 Adding O, cerium acetate and erbium acetate tetrahydrate into a reaction container, mixing, uniformly stirring and grinding;
3-3) adding the wollastonite powder coated with the nano silicon dioxide treated in the step 3-1) into a reaction vessel to be mixed with the product obtained in the step 3-2), and uniformly stirring; wherein, the nanometer silicon dioxide coated wollastonite powder: alCl 3 ·6H 2 O: cerium acetate: erbium acetate tetrahydrate at mass ratio = 25;
3-4) heating to 310 ℃ under continuous stirring, and reacting for 5 hours;
3-5) heating to 850 ℃, and calcining for 3 hours;
3-6) cooling to room temperature, and grinding to obtain the modified wollastonite powder compositely coated with the nano silicon dioxide film and the rare earth cerium and erbium-doped aluminum dioxide film.
Coating samples prepared from the epoxy powder coatings prepared in examples 1 to 3 and comparative examples 1 to 6 were tested for their properties. Applying the epoxy powder coating on the surface of a metal substrate by electrostatic spraying, wherein the voltage is as follows: 60-80KV, 2-3KG/CM 2 And obtaining a coating sample for testing.
The detection items comprise:
1. adhesive force detection (at normal temperature), and inspection standard and method GB/T9286-2014;
2. boiling adhesion force (2 h), and testing standard and method GB/T9286-2014;
3. neutral salt spray test, test standard and method GB/T91771-2007;
4. ultraviolet aging resistance test, the following standards are referred to for detection: GB 14522-2008 mechanical industry products, plastic, paint and rubber materials artificial weathering test method fluorescence ultraviolet.
The results of the measurements are shown in Table 1 below.
TABLE 1
Figure 547924DEST_PATH_IMAGE002
The adhesive force is classified into grades, the grade 0 is best, the grade 1 is the highest, and the larger the number is, the worse the adhesive force is; the above-mentioned powdering grades are classified into 0 grade, the best, and 1 grade, and the larger the number is, the worse the ultraviolet ray aging resistance is.
From the above test results, it can be seen that the epoxy powder coatings provided in examples 1-3 of the present invention have high adhesion, excellent boiling resistance, excellent salt spray corrosion resistance, and excellent ultraviolet aging resistance.
The specialty filler can be represented by a comparison of comparative example 2 with example 1: the nano silicon dioxide film and the composite modified film double-layer coated modified wollastonite powder play a role in strengthening the comprehensive performance of a coating system.
As can be seen from comparison of the results of comparative examples 4, 5, 6 and 1, the effect of coating the modified wollastonite powder with the nano-silica film without modifying the wollastonite powder and coating the modified wollastonite powder with the nano-silica film-alumina film is significantly worse than that of coating the modified wollastonite powder with the nano-silica film and the composite modified film in a double layer manner.
Compared with the results of the embodiment 1, the introduction of the rare earth elements cerium and erbium can obviously improve the adhesion, boiling resistance, salt spray corrosion resistance and ultraviolet aging resistance of the coating; it also indicates Fe in the coating system 2 O 3 The introduction of the rare earth element can be cooperated with rare earth elements of cerium and erbium, and the ultraviolet aging resistance is obviously improved.
While embodiments of the invention have been disclosed above, it is not intended to be limited to the details shown in the description and the examples, which are set forth, but are fully applicable to various fields of endeavor as are suited to the particular use contemplated, and further modifications will readily occur to those skilled in the art, since the invention is not limited to the details shown and described without departing from the general concept as defined by the appended claims and their equivalents.

Claims (8)

1. The epoxy powder coating with high adhesion to a metal substrate is characterized by comprising the following components in parts by weight:
55-65 parts of epoxy resin;
3-5 parts of a curing agent;
0.5-1 part by weight of a leveling agent;
0.4-0.6 parts of benzoin;
25-30 parts of special filler;
0.5-2 parts by weight of a silane coupling agent;
5-10 parts of pigment and filler;
wherein the special filler is modified wollastonite powder which is double-layer coated by a nano silicon dioxide film and a composite modified film;
the modified wollastonite powder is prepared by the following method:
1) Preparing wollastonite powder dispersion;
2) Preparing wollastonite powder coated with a nano-silica film;
3) Coating the composite modified film to obtain modified wollastonite powder coated with the nano-silica film and the composite modified film;
the step 3) is specifically as follows:
3-1) preheating the nano silicon dioxide coated wollastonite powder obtained in the step 2) to 110-150 ℃, and keeping the temperature for 0.5-2h;
3-2) reacting AlCl 3 ·6H 2 O、FeCl 3 ·6H 2 Adding O, cerium acetate and erbium acetate tetrahydrate into a reaction container, mixing, uniformly stirring and grinding;
3-3) adding the nanometer silica coated wollastonite powder treated in the step 3-1) into a reaction vessel to be mixed with the product obtained in the step 3-2), and uniformly stirring;
3-4) heating to 185-350 ℃ under continuous stirring, and reacting for 1-8 hours;
3-5) heating to 750-950 ℃, and calcining for 1-6 hours;
3-6) cooling to room temperature, and grinding to obtain the modified wollastonite powder double-layer coated by the nano silicon dioxide film and the composite modified film.
2. The epoxy powder coating having high adhesion to a metal substrate of claim 1, wherein the epoxy resin is a two-step epoxy resin.
3. The epoxy powder coating with high adhesion to metal substrates as claimed in claim 2, wherein the step 1) is specifically:
grinding needle-shaped or rod-shaped wollastonite into powder, adding the powder into deionized water, stirring, adding a dispersing agent and an aluminate coupling agent, and performing ultrasonic dispersion to obtain a wollastonite powder dispersion liquid.
4. The epoxy powder coating with high adhesion to metal substrates as claimed in claim 3, wherein the step 2) is specifically:
2-1) adding sodium silicate into the wollastonite powder dispersion liquid, and uniformly stirring;
2-2) heating the mixed solution obtained in the step 2-1) to 50-75 ℃, then dropwise adding a hydrochloric acid solution into the solution under continuous stirring, stopping dropwise adding until the pH value of the solution is 6-6.5, and aging for 1-4h;
2-3) filtering, washing and drying the solid product, and grinding to obtain the wollastonite powder coated with the nano silicon dioxide.
5. The epoxy powder coating having high adhesion to metal substrates of claim 1, wherein the curing agent is dicyandiamide.
6. The epoxy powder coating with high adhesion to a metal substrate of claim 1, wherein the leveling agent is an acrylate leveling agent adsorbed by silica.
7. The epoxy powder coating with high adhesion to metal substrates of claim 1, wherein the pigment and filler is one or more of carbon black, red iron oxide, yellow iron oxide, and phthalocyanine blue.
8. The epoxy powder coating with high adhesion to metal substrates according to any one of claims 1 to 7, characterized in that its preparation method comprises the following steps:
s1, weighing raw materials according to the weight part ratio, pouring the raw materials into a premixing container, and mixing the raw materials uniformly;
s2, adding the uniformly mixed raw materials into a double-screw extruder for melt extrusion, wherein the melt temperature of the extruder is controlled to be 80-100 ℃;
and S3, cooling the extruded material by a compression roller, tabletting, grinding and sieving to obtain the epoxy powder coating.
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