CN113088108A - Preparation method of modified coal ash and application of modified coal ash in metal powder coating - Google Patents

Preparation method of modified coal ash and application of modified coal ash in metal powder coating Download PDF

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CN113088108A
CN113088108A CN202110352116.1A CN202110352116A CN113088108A CN 113088108 A CN113088108 A CN 113088108A CN 202110352116 A CN202110352116 A CN 202110352116A CN 113088108 A CN113088108 A CN 113088108A
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coal ash
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metal powder
powder coating
modified coal
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王雄
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Guangxi Fubaoxin Technology Co ltd
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Guangxi Fubaoxin Technology Co ltd
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    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
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    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
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    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/04—Physical treatment, e.g. grinding, treatment with ultrasonic vibrations
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    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
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    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
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    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/08—Treatment with low-molecular-weight non-polymer organic compounds
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    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/10—Treatment with macromolecular organic compounds
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    • C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
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    • 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
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    • 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
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    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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Abstract

The invention discloses a preparation method of modified coal ash, which comprises the following steps: the method comprises the following steps of grinding clean coal ash, and modifying by adopting a first composite modifier and a second composite modifier respectively to obtain modified coal ash, wherein the modified coal ash can be applied to a metal powder coating, and the metal powder coating comprises the following raw materials in percentage by mass: 30.4-36.5 percent of modified coal ash, 46.2-51.4 percent of polyester resin, 5.2-6.3 percent of curing agent, 1-1.5 percent of flatting agent, 0.4-0.7 percent of benzoin, 2.3-4.4 percent of wax powder, 0.8-1.2 percent of brightener and 6.5-10.2 percent of metal pigment. The metal powder coating prepared by the invention has excellent performance and is very suitable for spraying in the fields of door industry, furniture, instruments and meters and the like.

Description

Preparation method of modified coal ash and application of modified coal ash in metal powder coating
[ technical field ] A method for producing a semiconductor device
The invention belongs to the technical field of powder coating preparation, and particularly relates to a metal powder coating and a preparation method thereof.
[ background of the invention ]
Along with the improvement of the living standard of people, domestic waste slag becomes stumbling stones which influence the living quality of people, particularly furnace slag, coal slag and the like are daunting for people, coal slag becomes one of pollution sources of the environment, meanwhile, at present, all the waste limestone slag, coal slag and the like of various factories and mines are taken as waste materials to be discharged in the environment, the waste limestone slag, the coal slag and the like are accumulated like a mountain, the environment is seriously polluted, and the cost is quite high and the time and the labor are wasted when the factory and the mine are required to be treated.
Main component SiO of coal ash2、Al2O3、Fe3O4And FeO, and a small amount of CaO, MgO and the like, so that the coal ash surface contains a large amount of hydroxyl groups, and if the unmodified coal ash is directly filled into the coating, the agglomeration effect in the matrix of the coal ash cannot be reduced, so that the caking property, the compatibility and the wettability between the unmodified coal ash and other raw materials of the powder coating, such as resin, are extremely poor, the apparent property and the gloss of the prepared powder coating are poor, the weather resistance is not high, and the application requirement of the powder coating cannot be met.
The metal powder coating refers to various powder coatings containing metal pigments (such as copper-gold powder, silver-aluminum powder and the like). The metal powder coating film is metallic luster, has gorgeous multicolor effect and outstanding protection function, and provides gorgeous and colorful appearance decoration for high-grade industrial products such as door industry, furniture, instruments and meters and the like. The powder coating can be directly sprayed on an iron material or an aluminum material which is subjected to proper pretreatment, and a coating surface with excellent performance, such as the durability of the coating, can be obtained by baking, and comprises the following components: abrasion resistance, impact resistance, adherence, toughness, corrosion resistance, chemical resistance and the like, but has the problems of weak antibacterial property, high preparation cost and the like.
Chinese patent application document "metallic powder coating for enhancing decorative effect and preparation method thereof" (publication No. CN108047901A) "discloses a metallic powder coating for enhancing decorative effect, which comprises the following raw materials in parts by weight: 15-20 parts of modified polyester compound, 1-3 parts of bentonite, 0.5-1 part of electrical charge enhancer, 1.5-4.5 parts of metal pigment, 0.5-1 part of degasifier, 0.2-0.5 part of dispersant, 0.5-1 part of flexibilizer, 0.2-0.5 part of brightener, 0.1-0.5 part of wetting agent, 0.1-0.3 part of preservative, 0.1-0.3 part of antioxidant and 0.2-0.5 part of light stabilizer. The metal powder coating is prepared by preparing a modified polyester compound, adding an antioxidant and a light stabilizer, and remarkably improving the weather resistance and the impact resistance of the metal powder coating. However, the antibacterial property is not strong, and the preparation cost is high.
At present, most of coal ash is directly used as a filler to be directly applied to paint preparation without modification, for example, Chinese patent application documents 'a modified municipal sludge casting paint and a manufacturing method thereof (publication number: CN 104475670A)' and 'a dilute silicon composite heat-insulating paint (publication number: CN 1148072A)', have the problems that: firstly, the filling amount is less, and the cost cannot be effectively reduced; secondly, the problems of too much application filling amount, poor weather resistance, low mechanical property and the like exist. How to creatively apply the coal ash in the powder coating solves the problems of high production cost of the powder coating, environmental pollution caused by the coal ash and the like, thereby realizing the industrial and industrialized application of the coal ash and having important economic and environmental benefits.
[ summary of the invention ]
The invention provides a metal powder coating and a preparation method thereof, and aims to solve the problems of weak antibacterial property, high preparation cost and the like of the existing metal powder coating.
In order to solve the technical problems, the invention adopts the following technical scheme:
a preparation method of modified coal ash comprises the following steps:
the method comprises the following steps: washing the coal ash with hydrochloric acid with the mass concentration of 25.2-30% until the pH value of the coal ash is 8.6-9.0, then washing the washed coal ash with water, detecting the pH value of the washed coal ash to be 7.2-7.5, and performing filter pressing treatment to obtain clean coal ash, wherein the clean coal ash is dried at the temperature of 70-76 ℃ until the water content is less than or equal to 2.3%;
step two: grinding the clean coal ash obtained in the step one, and sieving to obtain clean coal ash with the particle size of more than 400 meshes;
step three: adding a first compound modifier into the clean coal ash obtained in the step two, wherein the first compound modifier consists of coconut oil fatty acid diethylamide, hexa-polyglycerol monostearate and N-oleoyl-N-methyl sodium taurate, the adding amount of the first compound modifier is 4.2-4.8% of the mass of the clean coal ash, the mass ratio of the coconut oil fatty acid diethylamide to the hexa-polyglycerol monostearate to the N-oleoyl-N-methyl sodium taurate is 3.6-4.3:1:7.1-9.2, stirring for 1-1.5 hours at the microwave power of 100-200W and the rotation speed of 300-500r/min at the temperature of 60-64 ℃ to obtain a first mixture;
step four: adding the first mixture prepared in the step three, the second composite modifier and methyl ethyl ketone peroxide into a mixer, the second composite modifier consists of 2-methyl-5-vinylpyridine, lauroyl sulfate deacetylated chitosan and trihydroxy triethylamine, the adding amount of the second composite modifier is 2.3-3% of the mass of the clean coal ash, the addition amount of the methyl ethyl ketone peroxide is 0.4 to 0.5 percent of the mass of the clean coal ash, the mass ratio of the 2-methyl-5-vinylpyridine to the lauroyl sulfate chitosan to the trihydroxy triethylamine is 1:2.1-3.4:5.3-7.8, stirring for 2-3h at the microwave power of 150-;
step five: and (3) drying the second mixture prepared in the fourth step at the temperature of 58-62 ℃ until the water content is less than or equal to 1.2%, grinding the dried second mixture into powder, and sieving the powder to obtain the modified coal ash with the particle size of more than 400 meshes.
Further, the modified coal ash prepared by the method is applied to a metal powder coating, and the metal powder coating comprises the following raw materials in percentage by mass: 30.4-36.5 percent of modified coal ash, 46.2-51.4 percent of polyester resin, 5.2-6.3 percent of curing agent, 1-1.5 percent of flatting agent, 0.4-0.7 percent of benzoin, 2.3-4.4 percent of wax powder, 0.8-1.2 percent of brightener and 6.5-10.2 percent of metal pigment.
Further, the metal powder coating comprises the following raw materials in percentage by mass: 34.2 percent of modified coal ash, 47.6 percent of polyester resin, 5.6 percent of curing agent, 1.2 percent of flatting agent, 0.5 percent of benzoin, 2.7 percent of wax powder, 0.9 percent of brightener and 7.3 percent of metal pigment.
Further, the curing agent is a TGIC curing agent.
Further, the leveling agent is a leveling agent GLP 588.
Further, the brightener is brightener LD-608.
Further, the metal pigment comprises one or more of pearlescent pigment, copper gold powder and silver aluminum powder.
Further, the preparation method of the metal powder coating comprises the following steps:
a. mixing raw materials: the preparation method comprises the following steps of (1) mixing various raw materials according to mass percentage, adding the raw materials into a mixer respectively, pre-crushing, and mixing to obtain uniformly mixed raw materials;
b. melt extrusion: b, putting the uniformly mixed raw materials prepared in the step a into an extruder, performing melt extrusion, tabletting and cooling, and then crushing into sheet materials;
c. grinding and crushing: and c, placing the sheet materials crushed in the step b into an ACM (acid-activated metal) pulverizer to pulverize, and performing cyclone separation and screening to obtain the metal powder coating.
Further, the temperature of the melt extrusion in step b was 105-110 ℃.
Further, the metal powder coating is applied to the fields of door industry, furniture and automobiles.
The technical principle of the metal powder coating of the invention is as follows: the coal ash is powder formed after coal combustion, and the main component of the coal ash is SiO2、Al2O3、Fe3O4FeO, a small amount of CaO, MgO and the like, and the hardness of the materials is higher, so that the scratch resistance of the prepared powder coating is better, and the manufacturing cost of the powder coating can be effectively reduced by using the waste coal ash.
The composite system of polyester resin and stuffing (coal ash) as main material for preparing metal powder paint is one inhomogeneous macroscopical system and one two-phase system with stuffing (coal ash) as componentAnd the resin as the matrix, and the strength of the bond between the two phases is affected by the interaction between the chemical components on the resin microstructure (coal ash) and the chemical components on the resin interface. Therefore, the key point for improving the performance of the metal powder coating is to research the interaction of each component in the interface structure and the area of the metal powder coating system, because the interaction between two phases is carried out through intermolecular force, polarity and the like between different substances, and the acting force can be influenced by the orientation of resin molecular chains and the dispersion degree of fillers in a matrix in the metal powder coating system. The binding of fillers to resins in metal powder coating systems can be generally classified into the following categories: (1) pure mechanical mixing; (2) the two phases are relatively uniformly physically mixed; (3) the two phases form a new chemical bond through chemical reaction, so that the bonding strength is greatly increased. Since polyester resin exhibits hydrophobicity and carbon ash has SiO as a main component2、Al2O3、Fe3O4FeO, a small amount of CaO, MgO, and the like make coal ash be alkaline, and have strong hydrophilic performance, and if the coal ash is simply and physically mixed with polyester resin, the combination of the two phase interfaces is necessarily weak, the compatibility is not high, and the coal ash is agglomerated, and the material defects are easily broken under the condition of stress concentration, so that the weather resistance is extremely poor, and thus it is very important to perform surface treatment on the coal ash.
In order to improve the cohesiveness, compatibility and wettability between the coal ash and other raw materials of the powder coating, such as resin, the coconut oil fatty acid diethylamide, the hexa-polyglycerol monostearate and the N-oleoyl-N-methyl sodium taurate are adopted to modify the surface of the coal ash, and the modification of the coconut oil fatty acid diethylamide, the hexa-polyglycerol monostearate and the N-oleoyl-N-methyl sodium taurate play a synergistic role, so that the apparent property and the gloss of a coating film of the metal powder coating are improved in a synergistic manner; this is:
the polyester resin is non-polar, and the unmodified coal ash is alkaline, contains a large amount of hydroxyl on the surface, and has a complex result, so that the metal powder coating prepared by directly filling the unmodified coal ash into the polyester resin has poor appearance and luster. The coal ash is subjected to surface modification by coconut oil fatty acid diethylamide, hexa-polyglycerol monostearate and N-oleoyl-N-methyl sodium taurate under certain microwave and temperature, because the coconut oil fatty acid diacetyl amide, the hexa-polyglycerol monostearate and the N-oleoyl-N-methyl sodium taurate contain amide, long-carbon-chain fatty acid, carbonyl, sulfonic acid group and other groups, can introduce amide, long-carbon-chain fatty acid, carbonyl, sulfonic group and other groups into the surface of the coal ash particles during the first modification, not only can improve the processing fluidity and the dispersibility of the modified coal ash, the modified coal ash is changed from hydrophilicity to lipophilicity, so that the modified coal ash and other raw materials of the metal powder coating, such as polyester resin, have better cohesiveness, wettability and compatibility, the interfacial cohesive force of the metal powder coating is improved, and the apparent performance and the gloss of a coating film of the metal powder coating are further improved.
The 2-methyl-5-vinylpyridine, lauroyl sulfate chitosan and trihydroxy triethylamine are adopted to play a synergistic role in the modification of coal ash, so that the antibacterial rate of the powder coating is improved, and the antibacterial rate is as follows:
after the coal ash is modified for the first time, 2-methyl-5-vinylpyridine, lauroyl sulfate deacetylated chitosan and trihydroxy triethylamine are adopted for carrying out secondary modification, and the 2-methyl-5-vinylpyridine, the lauroyl sulfate deacetylated chitosan and the trihydroxy triethylamine contain groups such as pyridyl and amino, so that antibacterial groups such as pyridyl and amino can be introduced to the surface of coal ash particles during secondary modification, under the mutual cooperation of the components, the antibacterial components are contacted with staphylococcus aureus and then adsorbed to the surface of the bacteria to penetrate cell walls, the composition of cell membranes is disturbed through the change of osmotic pressure and the decomposition of organic matters, the leakage of intracellular substances (DNA and RNA) is promoted, and the staphylococcus aureus can be effectively killed. In addition, the introduced antibacterial groups such as pyridyl, amino and the like are concentrated on the surface of the coal ash, so that the concentration is increased, the sterilization time is shortened, and the effect is effectively improved.
The polyester resin used in the invention is prepared by the method disclosed in the specification example 2 of Chinese patent document 'polyester resin for indoor powder coating and preparation method thereof (patent number: ZL 201610735896.7)', has the advantages of large proportion of raw materials in metal powder coating, low specific melt viscosity, high glass transition temperature and narrow molecular weight distribution. The metal powder coating prepared from the polyester resin selected by the invention has excellent leveling property and luster.
The TGIC curing agent used in the invention has good heat resistance, fluidity, weather resistance and adhesion, excellent high-temperature performance, good decorative performance and overbaking yellowing resistance.
The flatting agent GLP588 used in the invention can promote the coating to form a flat, smooth and uniform coating film in the drying film-forming process, can effectively reduce the surface tension of the finishing liquid, improve the leveling property and uniformity of the coating liquid, improve the permeability of the finishing liquid, reduce the possibility of generating spots and stains during brushing, increase the coverage property and enable the film to be formed uniformly and naturally.
The benzoin can eliminate the problems of pinholes, shrinkage cavities, bubbles and the like generated in the curing process of the powder coating. The presence of benzoin accelerates the gasification and discharge of trace moisture and solvent in the powder coating, and the trace moisture and solvent are completely discharged before the powder coating is not cured, so that the generation of air holes is avoided, and the performance of the coating is improved.
The wax powder used in the invention is distributed on the surface of the coating film so as to protect the coating film, prevent scratches and grazes and provide abrasion resistance; in addition, the existence of the wax powder enables the modified coal ash to have better wettability, so that the leveling property of the metal powder coating is better.
The brightener LD-608 used in the invention can improve the wettability of polyester resin to metal pigment and modified coal ash, simultaneously avoid the defects of coating such as pinholes, shrinkage cavities and the like, play a role in helping leveling, and obviously improve the appearance of the coating, thereby enabling the coating to obtain better flatness and gloss.
The metallic pigment can make the coating film have metallic luster, and has gorgeous multicolor effect and outstanding protection function.
The invention has the following beneficial effects:
(1) according to the invention, after the coal ash is modified, the problem of poor weather resistance of the powder coating obtained by using the traditional coal ash as the filler is effectively solved, the powder coating is filled into the prepared metal powder coating as the filler, the filling amount is up to more than 30.4%, and compared with the conventional white carbon black filler, the filling amount is about 400 yuan/ton less, so that the production cost for preparing the metal powder coating can be effectively reduced.
(2) Compared with the powder coating prepared by unmodified coal ash, the metal powder coating prepared by the modified coal ash has the advantages that the apparent performance of the coating is improved, and the gloss is improved by at least 85.5 percent.
(3) The impact property of the metal powder coating is 60.9-63.8kg/cm, which is at least 10.3% higher than that of the prior art; the antibacterial rate is 93.18% -96.24%, and is at least 43.2% higher than that of the prior art; the cupping is 6.3-6.6mm, which is at least 10.5% higher than the prior art; the weather resistance is 1824-1902h, which is at least 11.3 percent higher than that of the prior art, and the comprehensive performance of the metal powder coating is better than that of the prior art, thereby having remarkable progress.
(4) The metal powder coating disclosed by the invention is bright in optical effect, good in metal luster, high in powder applying rate and high in recycling rate.
[ description of the drawings ]
FIG. 1 is a black and white image of a metal powder coating product of preferred embodiment 2 of the present invention.
[ detailed description ] embodiments
In order to facilitate a better understanding of the invention, the following examples are given to illustrate, but not to limit the scope of the invention.
In an embodiment, the metal powder coating comprises the following raw materials in percentage by mass: 30.4-36.5 percent of modified coal ash, 46.2-51.4 percent of polyester resin, 5.2-6.3 percent of curing agent, 1-1.5 percent of flatting agent, 0.4-0.7 percent of benzoin, 2.3-4.4 percent of wax powder, 0.8-1.2 percent of brightener and 6.5-10.2 percent of metal pigment.
The polyester resin is prepared by adopting the method disclosed in the specification example 2 of the Chinese patent document 'polyester resin for indoor powder coating and preparation method thereof (patent number: ZL 201610735896.7').
The curing agent is TGIC curing agent.
The leveling agent is a leveling agent GLP 588.
The brightener is brightener LD-608.
The metal pigment comprises one or more of pearlescent pigment, copper gold powder and silver aluminum powder.
The preparation method of the modified coal ash comprises the following steps:
the method comprises the following steps: washing the coal ash with hydrochloric acid with the mass concentration of 25.2-30% until the pH value of the coal ash is 8.6-9.0, then washing the washed coal ash with water, detecting the pH value of the washed coal ash to be 7.2-7.5, and performing filter pressing treatment to obtain clean coal ash, wherein the clean coal ash is dried at the temperature of 70-76 ℃ until the water content is less than or equal to 2.3%;
step two: grinding the clean coal ash obtained in the step one, and sieving to obtain clean coal ash with the particle size of more than 400 meshes;
step three: adding a first compound modifier into the clean coal ash obtained in the step two, wherein the first compound modifier consists of coconut oil fatty acid diethylamide, hexa-polyglycerol monostearate and N-oleoyl-N-methyl sodium taurate, the adding amount of the first compound modifier is 4.2-4.8% of the mass of the clean coal ash, the mass ratio of the coconut oil fatty acid diethylamide to the hexa-polyglycerol monostearate to the N-oleoyl-N-methyl sodium taurate is 3.6-4.3:1:7.1-9.2, stirring for 1-1.5 hours at the microwave power of 100-200W and the rotation speed of 300-500r/min at the temperature of 60-64 ℃ to obtain a first mixture;
step four: adding the first mixture prepared in the step three, the second composite modifier and methyl ethyl ketone peroxide into a mixer, the second composite modifier consists of 2-methyl-5-vinylpyridine, lauroyl sulfate deacetylated chitosan and trihydroxy triethylamine, the adding amount of the second composite modifier is 2.3-3% of the mass of the clean coal ash, the addition amount of the methyl ethyl ketone peroxide is 0.4 to 0.5 percent of the mass of the clean coal ash, the mass ratio of the 2-methyl-5-vinylpyridine to the lauroyl sulfate chitosan to the trihydroxy triethylamine is 1:2.1-3.4:5.3-7.8, stirring for 2-3h at the microwave power of 150-;
step five: and (3) drying the second mixture prepared in the fourth step at the temperature of 58-62 ℃ until the water content is less than or equal to 1.2%, grinding the dried second mixture into powder, and sieving the powder to obtain the modified coal ash with the particle size of more than 400 meshes.
The preparation method of the metal powder coating comprises the following steps:
a. mixing raw materials: mixing the raw materials according to the mass percentage, respectively adding the raw materials into a mixing machine, pre-crushing for 1min, and then mixing for 4min to obtain uniformly mixed raw materials;
b. melt extrusion: b, putting the uniformly mixed raw materials prepared in the step a into an extruder, performing melt extrusion, tabletting and cooling, and then crushing into sheet materials, wherein the melt extrusion temperature is 105-110 ℃, and the temperature in the area I is 105 ℃ and the temperature in the area II is 110 ℃;
c. grinding and crushing: and c, placing the crushed sheet materials in the step b into an ACM (acid-activated metal) pulverizer for pulverizing, and performing cyclone separation and screening to obtain the metal powder coating with the average particle size of 35.3-40.6 mu m.
In order to further illustrate the present invention and make the disclosure more complete, more specific embodiments are described below.
EXAMPLE 1
The metal powder coating comprises the following raw materials in percentage by mass: 31.5% of modified coal ash, 49.2% of polyester resin, 5.7% of curing agent, 1.4% of flatting agent, 0.6% of benzoin, 3% of wax powder, 1% of brightener and 7.6% of metal pigment.
The polyester resin is prepared by adopting the method disclosed in the specification example 2 of the Chinese patent document 'polyester resin for indoor powder coating and preparation method thereof (patent number: ZL 201610735896.7').
The curing agent is TGIC curing agent.
The leveling agent is a leveling agent GLP 588.
The brightener is brightener LD-608.
The metal pigment comprises 5.2% of pearlescent pigment and 2.4% of copper gold powder.
The preparation method of the modified coal ash comprises the following steps:
the method comprises the following steps: washing the coal ash with hydrochloric acid with the mass concentration of 27.9% until the pH value of the coal ash is 8.7, then washing the washed coal ash with water, detecting the pH value of the washed coal ash to be 7.4, and performing filter pressing treatment to obtain clean coal ash, wherein the clean coal ash is dried at the temperature of 75 ℃ until the water content is 1.6%;
step two: grinding the clean coal ash obtained in the step one, and sieving to obtain clean coal ash with the particle size of more than 400 meshes;
step three: adding a first compound modifier into the clean coal ash prepared in the second step, wherein the first compound modifier consists of coconut oil fatty acid diethylamide, hexa-polyglycerol monostearate and N-oleoyl-N-methyl sodium taurate, the adding amount of the first compound modifier is 4.5% of the mass of the clean coal ash, the mass ratio of the coconut oil fatty acid diethylamide to the hexa-polyglycerol monostearate to the N-oleoyl-N-methyl sodium taurate is 3.9:1:8.7, and stirring is carried out for 1.1h at the microwave power of 200W and the temperature of 63 ℃ and the rotating speed of 500r/min to prepare a first mixture;
step four: adding the first mixture prepared in the third step, a second composite modifier and methyl ethyl ketone peroxide into a mixer, wherein the second composite modifier consists of 2-methyl-5-vinylpyridine, lauroyl sulfuric acid deacetylated chitosan and trihydroxy triethylamine, the addition amount of the second composite modifier is 2.7% of the mass of the clean coal ash, the addition amount of the methyl ethyl ketone peroxide is 0.42% of the mass of the clean coal ash, the mass ratio of the 2-methyl-5-vinylpyridine to the lauroyl sulfuric acid deacetylated chitosan to the trihydroxy triethylamine is 1:2.6:6.5, and stirring for 2.5 hours at the microwave power of 230W, the temperature of 108 ℃ and the rotating speed of 500r/min to prepare a second mixture;
step five: and (3) drying the second mixture prepared in the fourth step at the temperature of 60 ℃ until the water content is 1%, grinding the dried second mixture into powder, and sieving the powder to obtain the modified coal ash with the particle size of more than 400 meshes.
The modified coal ash prepared above was subjected to infrared characterization (FTIR) and electron microscopy Scanning (SEM).
Infrared characterization (FTIR): will be provided withThe modified coal ash is repeatedly washed by absolute ethyl alcohol and acetone, vacuum-dried and potassium bromide tabletted, and a Nicolet 67 model Fourier infrared spectrometer produced by the American Thermo Nicolet company is adopted to record the characteristic peak of the surface of the modified coal ash. Resolution of 1cm-1The number of scans was 16.
FT-IR analysis shows that the amido, carbonyl, sulfonic acid, pyridyl, amino and other groups are successfully grafted to the surface of the coal ash particle.
Electron microscopy Scanning (SEM): the modified coal ash is filled in a resin matrix (polyester resin) to obtain a sample, the normal-temperature notch impact section of the sample is subjected to metal spraying treatment, a tungsten filament scanning electron microscope is used for observing the surface morphology, and the voltage is 20 KV. Instrument model JSM-6490LV, manufactured by Japan.
SEM analysis shows that the modified coal ash has increased compatibility with resin matrix (polyester resin), and the modified coal ash is well dispersed in the resin matrix (polyester resin).
The preparation method of the metal powder coating comprises the following steps:
a. mixing raw materials: mixing the raw materials according to the mass percentage, respectively adding the raw materials into a mixing machine, pre-crushing for 1min, and then mixing for 4min to obtain uniformly mixed raw materials;
b. melt extrusion: b, putting the uniformly mixed raw materials prepared in the step a into an extruder, performing melt extrusion, tabletting and cooling at the temperature of 105 ℃ in a region I and 110 ℃ in a region II, and crushing into tablets;
c. grinding and crushing: and c, placing the crushed sheet materials in the step b into an ACM (acid-activated metal) pulverizer for pulverizing, and performing cyclone separation and screening to obtain the metal powder coating with the average particle size of 36.7 mu m.
EXAMPLE 2
The metal powder coating comprises the following raw materials in percentage by mass: 34.2 percent of modified coal ash, 47.6 percent of polyester resin, 5.6 percent of curing agent, 1.2 percent of flatting agent, 0.5 percent of benzoin, 2.7 percent of wax powder, 0.9 percent of brightener and 7.3 percent of metal pigment.
The polyester resin is prepared by adopting the method disclosed in the specification example 2 of the Chinese patent document 'polyester resin for indoor powder coating and preparation method thereof (patent number: ZL 201610735896.7').
The curing agent is TGIC curing agent.
The leveling agent is a leveling agent GLP 588.
The brightener is brightener LD-608.
The metal pigment comprises 2.5% of pearlescent pigment and 4.8% of silver aluminum powder.
The preparation method of the modified coal ash comprises the following steps:
the method comprises the following steps: washing the coal ash with hydrochloric acid with the mass concentration of 27.9% until the pH value of the coal ash is 8.7, then washing the washed coal ash with water, detecting the pH value of the washed coal ash to be 7.4, and performing filter pressing treatment to obtain clean coal ash, wherein the clean coal ash is dried at the temperature of 75 ℃ until the water content is 1.6%;
step two: grinding the clean coal ash obtained in the step one, and sieving to obtain clean coal ash with the particle size of more than 400 meshes;
step three: adding a first compound modifier into the clean coal ash prepared in the second step, wherein the first compound modifier consists of coconut oil fatty acid diethylamide, hexa-polyglycerol monostearate and N-oleoyl-N-methyl sodium taurate, the adding amount of the first compound modifier is 4.5% of the mass of the clean coal ash, the mass ratio of the coconut oil fatty acid diethylamide to the hexa-polyglycerol monostearate to the N-oleoyl-N-methyl sodium taurate is 3.9:1:8.7, and stirring is carried out for 1.1h at the microwave power of 200W and the temperature of 63 ℃ and the rotating speed of 500r/min to prepare a first mixture;
step four: adding the first mixture prepared in the third step, a second composite modifier and methyl ethyl ketone peroxide into a mixer, wherein the second composite modifier consists of 2-methyl-5-vinylpyridine, lauroyl sulfuric acid deacetylated chitosan and trihydroxy triethylamine, the addition amount of the second composite modifier is 2.7% of the mass of the clean coal ash, the addition amount of the methyl ethyl ketone peroxide is 0.42% of the mass of the clean coal ash, the mass ratio of the 2-methyl-5-vinylpyridine to the lauroyl sulfuric acid deacetylated chitosan to the trihydroxy triethylamine is 1:2.6:6.5, and stirring for 2.5 hours at the microwave power of 230W, the temperature of 108 ℃ and the rotating speed of 500r/min to prepare a second mixture;
step five: and (3) drying the second mixture prepared in the fourth step at the temperature of 60 ℃ until the water content is 1%, grinding the dried second mixture into powder, and sieving the powder to obtain the modified coal ash with the particle size of more than 400 meshes.
The modified coal ash prepared above was subjected to infrared characterization (FTIR) and electron microscopy Scanning (SEM).
Infrared characterization (FTIR): the modified coal ash is repeatedly washed by absolute ethyl alcohol and acetone, vacuum-dried and potassium bromide tabletted, and a Nicolet 67 model Fourier infrared spectrometer produced by the American Thermo Nicolet company is adopted to record the characteristic peak of the surface of the modified coal ash. Resolution of 1cm-1The number of scans was 16.
FT-IR analysis shows that the amido, carbonyl, sulfonic acid, pyridyl, amino and other groups are successfully grafted to the surface of the coal ash particle.
Electron microscopy Scanning (SEM): the modified coal ash is filled in a resin matrix (polyester resin) to obtain a sample, the normal-temperature notch impact section of the sample is subjected to metal spraying treatment, a tungsten filament scanning electron microscope is used for observing the surface morphology, and the voltage is 20 KV. Instrument model JSM-6490LV, manufactured by Japan.
SEM analysis shows that the modified coal ash has increased compatibility with resin matrix (polyester resin), and the modified coal ash is well dispersed in the resin matrix (polyester resin).
The preparation method of the metal powder coating comprises the following steps:
a. mixing raw materials: mixing the raw materials according to the mass percentage, respectively adding the raw materials into a mixing machine, pre-crushing for 1min, and then mixing for 4min to obtain uniformly mixed raw materials;
b. melt extrusion: b, putting the uniformly mixed raw materials prepared in the step a into an extruder, performing melt extrusion, tabletting and cooling at the temperature of 105 ℃ in a region I and 110 ℃ in a region II, and crushing into tablets;
c. grinding and crushing: and c, putting the crushed sheet materials in the step b into an ACM (Acetobacter xylinum) mill for milling, and obtaining the metal powder coating with the average particle size of 38.2 mu m after cyclone separation and screening, wherein the black and white picture of the product is shown in figure 1.
EXAMPLE 3
The metal powder coating comprises the following raw materials in percentage by mass: 36.2% of modified coal ash, 46.8% of polyester resin, 5.4% of curing agent, 1% of flatting agent, 0.6% of benzoin, 2.5% of wax powder, 0.8% of brightener and 6.7% of metal pigment.
The polyester resin is prepared by adopting the method disclosed in the specification example 2 of the Chinese patent document 'polyester resin for indoor powder coating and preparation method thereof (patent number: ZL 201610735896.7').
The curing agent is TGIC curing agent.
The leveling agent is a leveling agent GLP 588.
The brightener is brightener LD-608.
The metal pigment comprises 2.8% of pearlescent pigment and 3.9% of silver aluminum powder.
The preparation method of the modified coal ash comprises the following steps:
the method comprises the following steps: washing the coal ash with hydrochloric acid with the mass concentration of 27.9% until the pH value of the coal ash is 8.7, then washing the washed coal ash with water, detecting the pH value of the washed coal ash to be 7.4, and performing filter pressing treatment to obtain clean coal ash, wherein the clean coal ash is dried at the temperature of 75 ℃ until the water content is 1.6%;
step two: grinding the clean coal ash obtained in the step one, and sieving to obtain clean coal ash with the particle size of more than 400 meshes;
step three: adding a first compound modifier into the clean coal ash prepared in the second step, wherein the first compound modifier consists of coconut oil fatty acid diethylamide, hexa-polyglycerol monostearate and N-oleoyl-N-methyl sodium taurate, the adding amount of the first compound modifier is 4.5% of the mass of the clean coal ash, the mass ratio of the coconut oil fatty acid diethylamide to the hexa-polyglycerol monostearate to the N-oleoyl-N-methyl sodium taurate is 3.9:1:8.7, and stirring is carried out for 1.1h at the microwave power of 200W and the temperature of 63 ℃ and the rotating speed of 500r/min to prepare a first mixture;
step four: adding the first mixture prepared in the third step, a second composite modifier and methyl ethyl ketone peroxide into a mixer, wherein the second composite modifier consists of 2-methyl-5-vinylpyridine, lauroyl sulfuric acid deacetylated chitosan and trihydroxy triethylamine, the addition amount of the second composite modifier is 2.7% of the mass of the clean coal ash, the addition amount of the methyl ethyl ketone peroxide is 0.42% of the mass of the clean coal ash, the mass ratio of the 2-methyl-5-vinylpyridine to the lauroyl sulfuric acid deacetylated chitosan to the trihydroxy triethylamine is 1:2.6:6.5, and stirring for 2.5 hours at the microwave power of 230W, the temperature of 108 ℃ and the rotating speed of 500r/min to prepare a second mixture;
step five: and (3) drying the second mixture prepared in the fourth step at the temperature of 60 ℃ until the water content is 1%, grinding the dried second mixture into powder, and sieving the powder to obtain the modified coal ash with the particle size of more than 400 meshes.
The modified coal ash prepared above was subjected to infrared characterization (FTIR) and electron microscopy Scanning (SEM).
Infrared characterization (FTIR): the modified coal ash is repeatedly washed by absolute ethyl alcohol and acetone, vacuum-dried and potassium bromide tabletted, and a Nicolet 67 model Fourier infrared spectrometer produced by the American Thermo Nicolet company is adopted to record the characteristic peak of the surface of the modified coal ash. Resolution of 1cm-1The number of scans was 16.
FT-IR analysis shows that the amido, carbonyl, sulfonic acid, pyridyl, amino and other groups are successfully grafted to the surface of the coal ash particle.
Electron microscopy Scanning (SEM): the modified coal ash is filled in a resin matrix (polyester resin) to obtain a sample, the normal-temperature notch impact section of the sample is subjected to metal spraying treatment, a tungsten filament scanning electron microscope is used for observing the surface morphology, and the voltage is 20 KV. Instrument model JSM-6490LV, manufactured by Japan.
SEM analysis shows that the modified coal ash has increased compatibility with resin matrix (polyester resin), and the modified coal ash is well dispersed in the resin matrix (polyester resin).
The preparation method of the metal powder coating comprises the following steps:
a. mixing raw materials: mixing the raw materials according to the mass percentage, respectively adding the raw materials into a mixing machine, pre-crushing for 1min, and then mixing for 4min to obtain uniformly mixed raw materials;
b. melt extrusion: b, putting the uniformly mixed raw materials prepared in the step a into an extruder, performing melt extrusion, tabletting and cooling at the temperature of 105 ℃ in a region I and 110 ℃ in a region II, and crushing into tablets;
c. grinding and crushing: and c, placing the crushed sheet materials in the step b into an ACM (acid-activated metal) pulverizer for pulverizing, and performing cyclone separation and screening to obtain the metal powder coating with the average particle size of 40.3 mu m.
Comparative example 1
The preparation process of the metal powder coating is basically the same as that of example 2, except that only the modification of step four is performed in the preparation of the modified coal ash, and the modification of step three is not performed.
Comparative example 2
The metal powder coating preparation process was essentially the same as that of example 2, except that the first composite modifier used in the preparation of the modified coal ash lacked coconut oil fatty acid diethylamide.
Comparative example 3
The metal powder coating preparation process was essentially the same as that of example 2, except that the first composite modifier used in the preparation of the modified coal ash lacked hexaglycerol monostearate.
Comparative example 4
The metal powder coating preparation process was essentially the same as that of example 2, except that the first composite modifier used in the preparation of the modified coal ash lacked N-oleoyl-N-methyltaurate.
Comparative example 5
The preparation process of the metal powder coating is basically the same as that of example 2, except that only the modification of the third step is performed in the preparation of the modified coal ash, and the modification of the fourth step is not performed.
Comparative example 6
The process for preparing the metal powder coating was substantially the same as that of example 2, except that the second composite modifier used in the preparation of the modified coal ash lacked 2-methyl-5-vinylpyridine.
Comparative example 7
The metal powder coating preparation process was essentially the same as that of example 2, except that the second composite modifier used in the preparation of the modified coal ash lacked lauroyl chitosan sulfate.
Comparative example 8
The preparation process of the metal powder coating is basically the same as that of example 2, except that the second composite modifier used in the preparation of the modified coal ash lacks trihydroxy triethylamine.
Comparative example 9
The preparation process of the metal powder coating is basically the same as that of example 2, except that the modified coal ash is not modified in the third step and the fourth step.
Comparative example 10
The metal powder coating prepared by the process of examples 1-4 was prepared by using the Chinese patent application document "decorative effect-enhancing metal powder coating and preparation method thereof" (publication No. CN108047901A) ".
And (3) performance detection:
preparing a coating layer: the metallic powder coatings of examples 1-3 and comparative examples 1-4, 9 were sprayed on the surface-treated cold-rolled steel sheets using an electrostatic spray gun, the thickness of the coating films was substantially uniform, and the coatings were cured at 180 ℃/10min to give coating layers corresponding to examples 1-3 and comparative examples 1-4, 9, the gloss being measured using GB/T1743-1979.
The results of coating tests of examples 1 to 3 and comparative examples 1 to 4 and 9 are shown in Table 1.
TABLE 1 coating test results of examples 1-3 and comparative examples 1-4, 9
Figure BDA0003002640960000141
As can be seen from Table 1: (1) as can be seen from the data of example 2 and comparative examples 1-4, coconut oil fatty acid diethylamide, hexa-polyglycerol monostearate, and sodium N-oleoyl-N-methyltaurate act synergistically in coal ash modification, and synergistically improve the apparent performance and gloss of the coating film of the metal powder coating; this is:
the polyester resin is non-polar, and the unmodified coal ash is alkaline, has a large amount of hydroxyl on the surface, and has a complex result, so that the metal powder coating prepared by directly filling the unmodified coal ash into the polyester resin has poor appearance and luster. The coal ash is subjected to surface modification by coconut oil fatty acid diethylamide, hexa-polyglycerol monostearate and N-oleoyl-N-methyl sodium taurate under certain microwave and temperature, because the coconut oil fatty acid diacetyl amide, the hexa-polyglycerol monostearate and the N-oleoyl-N-methyl sodium taurate contain amide, long-carbon-chain fatty acid, carbonyl, sulfonic acid group and other groups, can introduce amide, long-carbon-chain fatty acid, carbonyl, sulfonic group and other groups into the surface of the coal ash particles during the first modification, not only can improve the processing fluidity and the dispersibility of the modified coal ash, the modified coal ash is changed from hydrophilicity to lipophilicity, so that the modified coal ash and other raw materials of the metal powder coating, such as polyester resin, have better cohesiveness, wettability and compatibility, the interfacial cohesive force of the metal powder coating is improved, and the apparent performance and the gloss of a coating film of the metal powder coating are further improved.
(2) As can be seen from the data of examples 1-3 and comparative example 9, the metal powder coating using the modified coal ash has improved film appearance and gloss by at least 85.5% as compared to the powder coating using the unmodified coal ash.
The impact resistance, antibacterial rate, cupping and weather resistance of the metal powder coatings prepared in examples 1-3 and comparative examples 5-8 and 10 were tested, wherein the impact resistance was tested by GB/T1732-1993; the antibacterial rate is detected by GB/T21866-2008, wherein the bacteria are staphylococcus aureus; the cupping process is detected by GB/T9753-1988; the weather resistance was measured by irradiation with a GB/T1865-2009 xenon lamp, and the results are shown in Table 2 below.
TABLE 2 tables of results of performance tests of the powder coatings obtained in examples 1 to 3 and comparative examples 5 to 8 and 10
Figure BDA0003002640960000151
Figure BDA0003002640960000161
As can be seen from Table 2:
(1) as can be seen from the data of example 2 and comparative examples 5-8, 2-methyl-5-vinylpyridine, lauroyl chitosan sulfate, trihydroxy triethylamine have a synergistic effect in the modification of coal ash, increasing the antibacterial rate of the metal powder coating, which is:
after the coal ash is modified for the first time, 2-methyl-5-vinylpyridine, lauroyl sulfate deacetylated chitosan and trihydroxy triethylamine are adopted for carrying out secondary modification, and the 2-methyl-5-vinylpyridine, the lauroyl sulfate deacetylated chitosan and the trihydroxy triethylamine contain groups such as pyridyl and amino, so that antibacterial groups such as pyridyl and amino can be introduced to the surface of coal ash particles during secondary modification, under the mutual cooperation of the components, the antibacterial components are contacted with staphylococcus aureus and then adsorbed to the surface of the bacteria to penetrate cell walls, the composition of cell membranes is disturbed through the change of osmotic pressure and the decomposition of organic matters, the leakage of intracellular substances (DNA and RNA) is promoted, and the staphylococcus aureus can be effectively killed. In addition, the introduced antibacterial groups such as pyridyl, amino and the like are concentrated on the surface of the coal ash, so that the concentration is increased, the sterilization time is shortened, and the effect is effectively improved.
(2) As can be seen from the data of examples 1-3, the impact resistance of the metal powder coating of the present invention is 60.9-63.8kg/cm, which is at least 10.3% higher than that of the prior art (comparative example 10); the antibacterial rate is 93.18-96.24%, and is improved by at least 43.2% compared with the prior art (comparative example 10); the cupping is 6.3-6.6mm, which is improved by at least 10.5% compared with the prior art (comparative example 10); the weather resistance is 1824-1902h, which is improved by at least 11.3 percent compared with the prior art (comparative example 10); it can be seen that the overall performance of the metal powder coating of the present invention is superior to that of the prior art (comparative example 10), with a significant improvement.
(3) According to the invention, after the coal ash is modified, the problem of poor weather resistance of the powder coating obtained by using the traditional coal ash as the filler is effectively solved, the coal ash is used as the filler to be filled into the prepared metal powder coating, the filling amount is up to more than 30.4%, compared with the conventional white carbon black and other fillers, the filling performance is good, and the production cost can be effectively reduced (as the cost for purchasing the waste coal ash is extremely low, the waste coal ash is used as the raw material, and the modified coal ash is obtained after modification and used as the filler, the cost for preparing the modified coal ash filler is far less than that of the conventional white carbon black filler and is about 400 yuan/ton less, so that the production cost for preparing the metal powder coating can be effectively reduced).
(4) From the data of examples 1-3, it can be seen that example 2 of the present invention is the most preferred example, and that the overall performance of the metal powder coating obtained in example 2 is the most preferred when the modified coal ash loading is 34.2%, wherein the impact resistance is 63.8kg/cm, the antibacterial performance is 96.24%, the cupping is 6.5mm, and the weather resistance is 1902h, which provides the basis for seeking the best process for producing the metal powder coating.
The above description should not be taken as limiting the invention to the embodiments, but rather, as will be apparent to those skilled in the art to which the invention pertains, numerous simplifications or substitutions may be made without departing from the spirit of the invention, which shall be deemed to fall within the scope of the invention as defined by the claims appended hereto.

Claims (10)

1. The preparation method of the modified coal ash is characterized by comprising the following steps:
the method comprises the following steps: washing the coal ash with hydrochloric acid with the mass concentration of 25.2-30% until the pH value of the coal ash is 8.6-9.0, then washing the washed coal ash with water, detecting the pH value of the washed coal ash to be 7.2-7.5, and performing filter pressing treatment to obtain clean coal ash, wherein the clean coal ash is dried at the temperature of 70-76 ℃ until the water content is less than or equal to 2.3%;
step two: grinding the clean coal ash obtained in the step one, and sieving to obtain clean coal ash with the particle size of more than 400 meshes;
step three: adding a first compound modifier into the clean coal ash obtained in the step two, wherein the first compound modifier consists of coconut oil fatty acid diethylamide, hexa-polyglycerol monostearate and N-oleoyl-N-methyl sodium taurate, the adding amount of the first compound modifier is 4.2-4.8% of the mass of the clean coal ash, the mass ratio of the coconut oil fatty acid diethylamide to the hexa-polyglycerol monostearate to the N-oleoyl-N-methyl sodium taurate is 3.6-4.3:1:7.1-9.2, stirring for 1-1.5 hours at the microwave power of 100-200W and the rotation speed of 300-500r/min at the temperature of 60-64 ℃ to obtain a first mixture;
step four: adding the first mixture prepared in the step three, the second composite modifier and methyl ethyl ketone peroxide into a mixer, the second composite modifier consists of 2-methyl-5-vinylpyridine, lauroyl sulfate deacetylated chitosan and trihydroxy triethylamine, the adding amount of the second composite modifier is 2.3-3% of the mass of the clean coal ash, the addition amount of the methyl ethyl ketone peroxide is 0.4 to 0.5 percent of the mass of the clean coal ash, the mass ratio of the 2-methyl-5-vinylpyridine to the lauroyl sulfate chitosan to the trihydroxy triethylamine is 1:2.1-3.4:5.3-7.8, stirring for 2-3h at the microwave power of 150-;
step five: and (3) drying the second mixture prepared in the fourth step at the temperature of 58-62 ℃ until the water content is less than or equal to 1.2%, grinding the dried second mixture into powder, and sieving the powder to obtain the modified coal ash with the particle size of more than 400 meshes.
2. The application of the modified coal ash prepared by the method according to claim 1 in metal powder coating, wherein the metal powder coating comprises the following raw materials in percentage by mass: 30.4-36.5 percent of modified coal ash, 46.2-51.4 percent of polyester resin, 5.2-6.3 percent of curing agent, 1-1.5 percent of flatting agent, 0.4-0.7 percent of benzoin, 2.3-4.4 percent of wax powder, 0.8-1.2 percent of brightener and 6.5-10.2 percent of metal pigment.
3. The application of the modified coal ash prepared by the method according to claim 2 in metal powder coating, wherein the metal powder coating comprises the following raw materials in percentage by mass: 34.2 percent of modified coal ash, 47.6 percent of polyester resin, 5.6 percent of curing agent, 1.2 percent of flatting agent, 0.5 percent of benzoin, 2.7 percent of wax powder, 0.9 percent of brightener and 7.3 percent of metal pigment.
4. Use of the modified coal ash prepared according to the method of claim 2 or 3 in metal powder coatings, wherein the curing agent is TGIC curing agent.
5. Use of a modified coal ash prepared according to the method of claim 2 or 3 in a metal powder coating, wherein the leveling agent is a leveling agent GLP 588.
6. The use of the modified coal ash prepared according to the method of claim 2 or 3 in metal powder coatings, wherein the brightener is brightener LD-608.
7. The use of the modified coal ash prepared by the method according to claim 2 or 3 in metal powder coating, wherein the metal pigment comprises one or more of pearlescent pigment, copper gold powder and silver aluminum powder.
8. The use of the modified coal ash prepared according to the method of claim 2 or 3 in a metal powder coating, wherein the preparation method of the metal powder coating comprises the following steps:
a. mixing raw materials: the preparation method comprises the following steps of (1) mixing various raw materials according to mass percentage, adding the raw materials into a mixer respectively, pre-crushing, and mixing to obtain uniformly mixed raw materials;
b. melt extrusion: b, putting the uniformly mixed raw materials prepared in the step a into an extruder, performing melt extrusion, tabletting and cooling, and then crushing into sheet materials;
c. grinding and crushing: and c, placing the sheet materials crushed in the step b into an ACM (acid-activated metal) pulverizer to pulverize, and performing cyclone separation and screening to obtain the metal powder coating.
9. The use of the modified coal ash prepared by the method of claim 8 in metal powder coating, wherein the temperature of the melt extrusion in step b is 105-110 ℃.
10. Use of the modified coal ash prepared according to the method of claim 2 or 3 in metal powder coatings, wherein the metal powder coatings are used in fields including door industry, furniture, and automobiles.
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000053892A (en) * 1998-08-04 2000-02-22 Seishin Enterprise Co Ltd Powder coating material produced from pet resin product and production thereof
CN110079130A (en) * 2019-05-28 2019-08-02 广西福宝信科技有限公司 Coating changed red mud and preparation method thereof
CN110272650A (en) * 2019-06-27 2019-09-24 广西福宝信科技有限公司 Improve the composite modifier of compatibility and its in the application for preparing powdery paints
CN111440509A (en) * 2020-05-07 2020-07-24 广西福宝信科技有限公司 Powder coating special for aluminum wheel hub and preparation method thereof
CN111440515A (en) * 2020-05-07 2020-07-24 广西福宝信科技有限公司 Antibacterial powder coating and preparation method thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000053892A (en) * 1998-08-04 2000-02-22 Seishin Enterprise Co Ltd Powder coating material produced from pet resin product and production thereof
CN110079130A (en) * 2019-05-28 2019-08-02 广西福宝信科技有限公司 Coating changed red mud and preparation method thereof
CN110272650A (en) * 2019-06-27 2019-09-24 广西福宝信科技有限公司 Improve the composite modifier of compatibility and its in the application for preparing powdery paints
CN111440509A (en) * 2020-05-07 2020-07-24 广西福宝信科技有限公司 Powder coating special for aluminum wheel hub and preparation method thereof
CN111440515A (en) * 2020-05-07 2020-07-24 广西福宝信科技有限公司 Antibacterial powder coating and preparation method thereof

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