CN110256875B - Composite modifier capable of improving oxygen index and application method of composite modifier in preparation of modified red mud for coating - Google Patents

Composite modifier capable of improving oxygen index and application method of composite modifier in preparation of modified red mud for coating Download PDF

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CN110256875B
CN110256875B CN201910570036.6A CN201910570036A CN110256875B CN 110256875 B CN110256875 B CN 110256875B CN 201910570036 A CN201910570036 A CN 201910570036A CN 110256875 B CN110256875 B CN 110256875B
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red mud
composite modifier
powder
coating
oxygen index
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CN110256875A (en
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王雄
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Guangxi Fubaoxin 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
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/40—Compounds of aluminium
    • C09C1/407—Aluminium oxides or hydroxides
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/006—Combinations of treatments provided for in groups C09C3/04 - C09C3/12
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • 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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    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/12—Treatment with organosilicon compounds
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/03—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
    • C09D5/18—Fireproof paints including high temperature resistant paints
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
    • 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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant

Abstract

The invention discloses a composite modifier b capable of improving oxygen index and a use method thereof in preparing modified red mud for coating, and the use method thereof in preparing modified red mud for coating comprises the following steps: (1) adding a composite modifier a into clean red mud powder, controlling the temperature, and stirring at a speed to prepare a mixture a; (2) adding the mixture a prepared in the step (1) and the composite modifier b into a stirrer, controlling the temperature, and stirring at a speed to prepare a mixture b; (3) and (3) drying the mixture b prepared in the step (2) at a temperature, then carrying out superfine grinding and sieving to obtain the modified red mud powder. According to the invention, ammonia-terminated polydimethylsiloxane and hexa-p-carboxyphenoxy cyclotriphosphazene are adopted to carry out secondary modification on the red mud, a synergistic effect is achieved, and the oxygen index of the outdoor powder coating is improved.

Description

Composite modifier capable of improving oxygen index and application method of composite modifier in preparation of modified red mud for 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 composite modifier b capable of improving an oxygen index and a use method of the composite modifier b in preparation of modified red mud for coating.
[ background of the invention ]
Guangxi plain aluminium is honored as the aluminium of China, is the main aluminium industry production base of China, and it mainly utilizes local bauxite resource to produce aluminium oxide, annual production aluminium oxide 250 ten thousand tons, discharge 300 ten thousand tons of red mud, nowadays 3750 ten thousand tons of red mud tailings have piled up into the mountain, increase and discharge at the speed of 300 ten thousand at present gradually every year, not only cause to seal and process and spend a large amount of financial resources, material resources, manpower, but also need a large amount of land resources to pile up the red mud, make dam safety control very hard in addition.
At present, due to the great difficulty in comprehensive utilization of red mud, most of the red mud can only be stockpiled in red mud dams except a small amount of admixture used in iron separation of red mud and cement production, and the red mud is not well and fully utilized.
The waste residue discharged in the production process of alumina is red mud, and the mineral composition of the red mud mainly comprises Al2O3、Na2O、SiO2、CaO、Fe2O3、TiO2And the like. The chemical composition of red mud from some aluminum industries, Guangxi, is shown in the following table.
Figure GDA0002679088540000011
The red mud has strong alkalinity of residual attached liquid, so that the surface of the red mud contains a large amount of hydroxyl, for example, unmodified red mud powder is directly filled into the coating, and the agglomeration effect in a matrix of the red mud cannot be reduced, so that the adhesion, compatibility and wettability between the unmodified red mud powder and other raw materials of outdoor powder coating, such as resin, are extremely poor, and the prepared powder coating has poor film appearance performance and gloss.
The powder coating is a novel economic, environment-friendly and efficient environment-friendly coating. At present, organic solvent-based coatings are gradually being replaced and become an important component in the coating industry. The outdoor powder coating is a variety of powder coatings, and the traditional outdoor powder coating is used outdoors and has the problems of high production cost and the like.
Therefore, how to overcome the problems existing in the use of the traditional outdoor powder coating, the red mud is innovatively applied to the outdoor powder coating, the problems of high production cost and the like are solved, the industrial and industrialized application of the red mud is realized, the problems of changing waste into valuable, protecting the environment, reducing the land occupation of waste slag and the like are further solved, and the method has important economic and environmental benefits.
[ summary of the invention ]
The invention provides a composite modifier b capable of improving an oxygen index and a use method of the composite modifier b in modified red mud for preparing a coating, which aims to solve the problems of using the traditional outdoor powder coating, innovatively apply the red mud in the outdoor powder coating, solve the problems of high production cost, changing waste into valuable, protecting the environment, reducing the land occupation of waste slag and the like, and further realize the industrial and industrialized application of the red mud.
In order to solve the technical problems, the invention adopts the following technical scheme:
a composite modifier b capable of improving oxygen index consists of amino-terminated polydimethylsiloxane and hexa-p-carboxyphenoxy cyclotriphosphazene.
Further, the mass ratio of the amino-terminated polydimethylsiloxane to the six-p-carboxyphenoxy cyclotriphosphazene is 2.8-3.7: 5.2-7.6.
Further, the mass ratio of the amino-terminated polydimethylsiloxane to the six-p-carboxyphenoxy cyclotriphosphazene is 3.5: 6.4.
The invention also provides a use method of the composite modifier b capable of improving the oxygen index in preparing the modified red mud for the coating, which comprises the following steps:
(1) adding a composite modifier a into clean red mud powder, wherein the composite modifier a consists of sodium fatty acid methyl ester ethoxylate sulfonate and disodium coconut monoethanolamide sulfosuccinate monoester, controlling the temperature, and stirring at a high speed to prepare a mixture a;
(2) adding the mixture a prepared in the step (1) and a composite modifier b into a stirrer, wherein the composite modifier b consists of amino-terminated polydimethylsiloxane and hexa-p-carboxyphenoxy cyclotriphosphazene, and stirring at a speed under the condition of controlling the temperature to prepare a mixture b;
(3) and (3) drying the mixture b prepared in the step (2) at a temperature, then carrying out superfine grinding and sieving to obtain the modified red mud powder.
Further, it is characterized in that the temperature in the step (1) is 78-84 ℃.
Further, stirring is carried out at a speed of 800-1000r/min for 26-34min in the step (1).
Further, the temperature in the step (2) is 96-105 ℃.
Further, in the step (2), stirring is carried out for 35-43min at the speed of 1000-1200 r/min.
Further, the mixture b prepared in the step (3) is dried at the temperature of 43-48 ℃ until the water content is less than or equal to 1.2 percent.
Further, the modified red mud powder in the step (3) has a mesh number larger than 300 meshes.
The invention has the following beneficial effects:
according to the invention, ammonia-terminated polydimethylsiloxane and hexa-p-carboxyphenoxy cyclotriphosphazene are adopted to carry out secondary modification on the red mud, and the ammonia-terminated polydimethylsiloxane is of an organic-inorganic hybrid structure and contains silicon-oxygen bonds and amino groups, so that the silicon-oxygen bonds and the amino groups can be introduced to the surfaces of the red mud particles after the primary modification during modification, and when a sample plate is ignited, the siloxane rapidly migrates to the surface of the sample plate to form a protective layer, thereby playing the roles of heat insulation and oxygen isolation and further preventing the sample plate from burning; in addition, the six pairs of carboxyl phenoxy cyclotriphosphazenes have a P-N synergistic effect, and the ammonia-end polydimethylsiloxane is matched with the six pairs of carboxyl phenoxy cyclotriphosphazenes, so that the flame retardant effect of the sample plate is more obvious, and the oxygen index of the sample plate is improved.
[ description of the drawings ]
FIG. 1 is a black and white image of an outdoor powder coating product of example 1 of the present invention;
FIG. 2 is a black and white image of an outdoor powder coating product of example 2 of the present invention;
FIG. 3 is a black and white image of an outdoor powder coating product of example 3 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.
An outdoor powder coating comprises the following raw materials in percentage by mass: 44.6 to 47.2 percent of modified red mud powder, 45.4 to 48.1 percent of polyester resin, 3.8 to 5.3 percent of curing agent, 0.5 to 1.5 percent of flatting agent, 0.5 to 1 percent of defoaming agent, 0.5 to 1.5 percent of brightener, 0.3 to 0.8 percent of benzoin, 0.2 to 0.5 percent of white carbon black and 0.2 to 1 percent of wax powder.
The polyester resin is CRYLCOAT 2437-2 polyester resin.
The curing agent is TGIC curing agent.
The leveling agent is a PV88 leveling agent.
The defoaming agent is TP-39 defoaming agent.
The brightener is 701B brightener.
The preparation method of the modified red mud powder comprises the following steps:
(1) pickling red mud with sulfuric acid with the concentration of 12-18 wt% until the pH value is 8.6-9.1, then washing the pickled red mud with water, detecting the pH value of the washed red mud to be 7.8-8.2, performing filter pressing treatment on the washed red mud to obtain clean red mud, and drying the clean red mud until the water content is less than or equal to 4.7%;
(2) carrying out superfine grinding on the clean red mud prepared in the step (1), and sieving to obtain clean red mud powder with the particle size of more than 300 meshes;
(3) adding a composite modifier a into the clean red mud powder prepared in the step (2), wherein the composite modifier a consists of sodium fatty acid methyl ester ethoxylate sulfonate and disodium coconut monoethanolamide sulfosuccinate monoester, the addition amount of the composite modifier a is 1.8-2.7% of the clean red mud powder by mass, the mass ratio of the sodium fatty acid methyl ester ethoxylate sulfonate to the disodium coconut monoethanolamide sulfosuccinate monoester is 2.6-5.4:7.8-9.2, the temperature is controlled to be 78-84 ℃, and the mixture a is prepared by stirring at the speed of 800-1000r/min for 26-34 min;
(4) adding the mixture a prepared in the step (3) and a composite modifier b into a mixer, wherein the composite modifier b is composed of amino-terminated polydimethylsiloxane and hexa-p-carboxyphenoxy cyclotriphosphazene, the addition amount of the composite modifier b is 3.2-4.3% of the mass of the clean red mud powder, the mass ratio of the amino-terminated polydimethylsiloxane to the hexa-p-carboxyphenoxy cyclotriphosphazene is 2.8-3.7:5.2-7.6, the temperature is controlled to be 96-105 ℃, and the mixture b is prepared by stirring at the speed of 1000-1200 r/min;
(5) and (4) drying the mixture b prepared in the step (4) at the temperature of 43-48 ℃ until the water content is less than or equal to 1.2%, then carrying out superfine grinding and sieving to obtain the modified red mud powder with the particle size of more than 300 meshes.
The preparation method of the outdoor powder coating comprises the following steps:
(1) 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;
(2) melt extrusion: putting the uniformly mixed raw materials prepared in the step (1) into an extruder, performing melt extrusion, tabletting and cooling, and then crushing into sheet materials;
(3) grinding and crushing: and (3) placing the crushed sheet materials in the step (2) into an ACM (acid-activated metal) pulverizer to pulverize, and performing cyclone separation and screening to obtain the outdoor powder coating with the particle size of more than 200 meshes.
The temperature of the melt extrusion in the step (2) is 105-110 ℃, wherein the temperature of the zone I is 105 ℃, and the temperature of the zone II is 110 ℃.
The mesh number of the outdoor powder coating in the step (3) is more than 200.
The technical principle of the invention is as follows: the red mud is a precipitate precipitated during the process of lowering the trough in the production process of alumina, has small granularity, the grain diameter is 0.001-0.07mm, corresponds to 1000 meshes of 210-fold sand, and is very suitable for being used as a filler to prepare a powder coating with higher quality. The main component of the red mud is Al2O3、Fe2O3、SiO2、TiO2And CaO and the like, the hardness of the materials is higher, the scratch resistance of the prepared powder coating is better, the color of the powder coating is red and is the main color of the powder coating, the covering power is good, and the powder coating can be used as a part of pigment, so that the manufacturing cost of the powder coating is reduced.
The composite system of polyester resin and filler (red mud) as main raw materials of outdoor powder coating is a macroscopic inhomogeneous system and is a two-phase system, namely a multi-component system consisting of a dispersed phase taking the filler (red mud) as a component and a continuous phase taking the resin as a matrix, and the influence on the bonding strength between the two phases is the interaction between chemical components on the (red mud) in the resin microstructure and chemical components on the resin interface. Therefore, the key point for improving the performance of the outdoor powder coating is to research the interaction of each component in the interface structure and the area of the outdoor powder coating system, because the interaction between two phases is carried out through intermolecular acting force between different substances, formation of new chemical bonds, acid-base action and even polarity, and the acting force can be influenced by the orientation of resin molecular chains and the dispersion degree of the filler in a matrix in the outdoor powder coating system. The bonding of fillers to resins in outdoor 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. Because the resin is generally hydrophobic, and the red mud surface is rich in a large amount of polar hydroxyl groups, the red mud is alkaline and has strong hydrophilic performance, if the red mud and the resin are simply and physically mixed, the combination of two-phase interfaces is necessarily weak, the compatibility is not high, the red mud is agglomerated, and the material defect is easy to break under the condition of stress concentration, so that the surface treatment of the red mud is very important in advance.
The main component of the red mud also contains Na2The pH value of the attached solution of O is more than 12.2. The red mud has strong alkalinity of residual attached liquid, so that the surface of the red mud contains a large amount of hydroxyl, for example, unmodified red mud powder is directly filled into the coating, and the agglomeration effect in a matrix of the red mud cannot be reduced, so that the adhesion, compatibility and wettability between the unmodified red mud powder and other raw materials of outdoor powder coating, such as resin, are extremely poor, and the prepared powder coating has poor film appearance performance and gloss. Therefore, the red mud needs to be subjected to alkali removal, the pH value is reduced, the surface hydroxyl groups are reduced, and meanwhile, the red mud needs to be subjected to surface modification, so that the cohesiveness, compatibility and wettability between the modified red mud and other raw materials of the outdoor powder coating, such as resin, are improved, the prepared powder coating has good apparent property and gloss, and the quality of the outdoor powder coating is improved.
In order to improve the cohesiveness, compatibility and wettability between the modified red mud and other raw materials of the outdoor powder coating, such as resin, the invention adopts sodium fatty acid methyl ester ethoxylate sulfonate and disodium coconut monoethanolamide sulfosuccinate monoester to carry out surface modification on the red mud, and the two have a synergistic effect in modification, so that the apparent performance and gloss of a coating film of the outdoor powder coating are synergistically improved; the reason is that: the polyester resin is nonpolar, and the surface of the unmodified red mud powder contains a large amount of hydroxyl, so the outdoor powder coating prepared by directly filling the unmodified red mud powder into the polyester resin has poor apparent property and luster. The red mud is subjected to surface modification by using sodium fatty acid methyl ester ethoxylate sulfonate and disodium coconut monoethanolamide sulfosuccinate, and because the sodium fatty acid methyl ester ethoxylate sulfonate and the disodium coconut monoethanolamide sulfosuccinate contain groups such as sulfonic acid groups, oleic acid groups and amino groups, the groups such as the sulfonic acid groups, the oleic acid groups and the amino groups can be introduced into the surfaces of the red mud particles during modification, so that the dispersibility and the processing flowability of the modified red mud powder can be improved, the modified red mud has better compatibility with other raw materials of outdoor powder coating such as polyester resin, the interfacial adhesion of the outdoor powder coating is improved, and the apparent performance and the gloss of the coating of the outdoor powder coating are improved. The modified red mud is added into the polyester resin after the surface of the red mud is modified, so that the agglomeration effect in a matrix of the red mud can be effectively reduced, the cohesiveness, the compatibility and the wettability between the polyester resin and the modified red mud powder can be effectively improved, and the apparent performance and the gloss of an outdoor powder coating film are greatly improved.
In order to improve the flame retardant property and the oxygen index, the red mud is subjected to first-step surface modification by adopting sodium fatty acid methyl ester ethoxylate sulfonate and disodium coconut monoethanolamide sulfosuccinate; then, ammonia-terminated polydimethylsiloxane and six pairs of carboxyl phenoxy cyclotriphosphazene are adopted to carry out secondary modification on the red mud, a synergistic effect is achieved, and the oxygen index of the outdoor powder coating is improved because: because the ammonia-end polydimethylsiloxane is of an organic-inorganic hybrid structure and contains silicon-oxygen bonds and amino groups, the silicon-oxygen bonds and the amino groups can be introduced to the surfaces of the red mud particles after the first modification during the modification, and when the sample plate is ignited, the siloxane quickly migrates to the surface of the sample plate to form a protective layer, thereby playing the roles of heat insulation and oxygen isolation and further preventing the sample plate from burning; in addition, the six pairs of carboxyl phenoxy cyclotriphosphazenes have a P-N synergistic effect, and the ammonia-end polydimethylsiloxane is matched with the six pairs of carboxyl phenoxy cyclotriphosphazenes, so that the flame retardant effect of the sample plate is more obvious, and the oxygen index of the sample plate is improved.
According to the invention, fatty acid methyl ester ethoxylate sodium sulfonate and coconut oil acid monoethanolamide sulfosuccinic acid monoester disodium are adopted to carry out first-step surface modification on red mud; and then, ammonia-terminated polydimethylsiloxane and six-pair carboxyl phenoxy cyclotriphosphazene are adopted to carry out secondary modification on the red mud, wherein sulfonic groups, oleic acid groups, amino groups, silicon-oxygen bonds and the like are successfully connected to the surfaces of red mud particles, so that the cohesiveness, the compatibility and the wettability between the polyester resin and the modified red mud powder are effectively improved, and the oxygen index is improved.
The polyester resin used in the invention is a carboxyl functional polyester resin without TMA, and the prepared outdoor powder coating has the advantages of no blooming, good leveling property and good outdoor weather resistance by adopting the CRYLCOAT 2437-2 brand.
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 PV88 leveling agent used in the invention is a white free-flowing powdery leveling agent, which 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 coating film, improve the leveling property and uniformity of the coating film, and can obviously reduce or basically remove craters, pinholes and fish eyes.
The outdoor powder coating is easy to generate bubbles in the production and use processes, a large number of stable bubbles are not beneficial to smooth production of the coating and the coating effect and performance of the coating, and the TP-39 defoaming agent used in the invention mainly has two functions: 1. suppressing the generation of bubbles; 2. accelerating the destruction of the generated bubbles. Thus, defoaming effect can be achieved.
The 701B brightener used in the invention can improve the wettability of polyester resin to white carbon black and modified red mud, simultaneously avoids the defects of coating such as pinholes, shrinkage cavities and the like, can also play a role in helping leveling, and obviously improves the appearance of the coating, thereby enabling the coating to obtain better flatness and gloss.
The benzoin used in the invention 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 white carbon black used in the invention can be used as a loose flowing agent in the powder coating, prevents agglomeration and improves the spraying efficiency, has thixotropic property, and can eliminate the phenomenon of liquid drop sedimentation by adding a small amount of white carbon black in the coating.
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 white carbon black and the modified red mud to have better wettability, thereby enabling the leveling property of the powder coating to be better.
In order to further illustrate the present invention and make the disclosure more complete, more specific embodiments are described below.
The red mud adopted in the embodiment and the comparative example of the invention is Bayer process red mud provided by a certain aluminum industry company in Guangxi, the main components and the mass percentage thereof are shown in Table 1, and the pH value is 12.5 through detection.
TABLE 1 Main chemical composition Table of Red mud
Composition (I) CaO SiO2 Fe2O3 Al2O3 TiO2 Na2O
Content (%) 15.34 8.10 42.86 16.09 7.39 3.46
EXAMPLE 1
A preparation method of modified red mud powder comprises the following steps:
(1) washing red mud with sulfuric acid with the concentration of 13 wt% until the pH value is 8.9, then washing the washed red mud with water, detecting the pH value of the washed red mud to be 8.1, performing filter pressing treatment to obtain clean red mud, and drying the clean red mud until the water content is 4.6%;
(2) carrying out superfine grinding on the clean red mud prepared in the step (1), and sieving to obtain clean red mud powder with the particle size of more than 300 meshes;
(3) adding a composite modifier a into the clean red mud powder prepared in the step (2), wherein the composite modifier a consists of sodium fatty acid methyl ester ethoxylate sulfonate and disodium coconut monoethanolamide sulfosuccinate monoester, the addition amount of the composite modifier a is 2.1% of the mass of the clean red mud powder, the mass ratio of the sodium fatty acid methyl ester ethoxylate sulfonate to the disodium coconut monoethanolamide sulfosuccinate monoester is 3.6:9.1, the temperature is controlled to be 80-83 ℃, and the mixture is stirred at the speed of 800r/min for 33min to prepare a mixture a;
(4) adding the mixture a prepared in the step (3) and a composite modifier b into a mixer, wherein the composite modifier b is composed of amino-terminated polydimethylsiloxane and six pairs of carboxyphenoxy cyclotriphosphazenes, the adding amount of the composite modifier b is 3.3% of the mass of the clean red mud powder, the mass ratio of the amino-terminated polydimethylsiloxane to the six pairs of carboxyphenoxy cyclotriphosphazenes is 2.9:5.7, the temperature is controlled to be 96-102 ℃, and the mixture is stirred at the speed of 1000r/min for 41min to prepare a mixture b;
(5) and (4) drying the mixture b prepared in the step (4) at the temperature of 43-46 ℃ until the water content is 1.2%, then carrying out superfine grinding and sieving to obtain the modified red mud powder with the particle size of more than 300 meshes.
An outdoor powder coating comprises the following raw materials in percentage by mass: 44.6 percent of modified red mud powder, 48.1 percent of polyester resin, 3.8 percent of curing agent, 0.5 percent of flatting agent, 0.7 percent of defoaming agent, 1.1 percent of brightener, 0.5 percent of benzoin, 0.3 percent of white carbon black and 0.4 percent of wax powder.
The polyester resin is CRYLCOAT 2437-2 polyester resin.
The curing agent is TGIC curing agent.
The leveling agent is a PV88 leveling agent.
The defoaming agent is TP-39 defoaming agent.
The brightener is 701B brightener.
The preparation method of the outdoor powder coating comprises the following steps
(1) 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;
(2) melt extrusion: putting the uniformly mixed raw materials prepared in the step (1) 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 slices;
(3) grinding and crushing: and (3) putting the crushed sheet materials in the step (2) into an ACM (activated carbon model) pulverizer to pulverize, and performing cyclone separation and screening to obtain an outdoor powder coating finished product with the particle size of more than 200 meshes, wherein the outdoor powder coating finished product is shown in figure 1.
EXAMPLE 2
A preparation method of modified red mud powder comprises the following steps:
(1) washing red mud with 16 wt% sulfuric acid until the pH value is 8.7, washing the washed red mud with water, detecting the pH value of the washed red mud to be 7.8, performing filter pressing treatment to obtain clean red mud, and drying the clean red mud until the water content is 3.9%;
(2) carrying out superfine grinding on the clean red mud prepared in the step (1), and sieving to obtain clean red mud powder with the particle size of more than 300 meshes;
(3) adding a composite modifier a into the clean red mud powder prepared in the step (2), wherein the composite modifier a consists of sodium fatty acid methyl ester ethoxylate sulfonate and disodium coconut monoethanolamide sulfosuccinate monoester, the addition amount of the composite modifier a is 2.4% of the mass of the clean red mud powder, the mass ratio of the sodium fatty acid methyl ester ethoxylate sulfonate to the disodium coconut monoethanolamide sulfosuccinate monoester is 5.2:8.7, the temperature is controlled to be 80-84 ℃, and the mixture is stirred at the speed of 1000r/min for 27min to prepare a mixture a;
(4) adding the mixture a prepared in the step (3) and a composite modifier b into a mixer, wherein the composite modifier b is composed of amino-terminated polydimethylsiloxane and six pairs of carboxyphenoxy cyclotriphosphazenes, the adding amount of the composite modifier b is 4.1% of the mass of the clean red mud powder, the mass ratio of the amino-terminated polydimethylsiloxane to the six pairs of carboxyphenoxy cyclotriphosphazenes is 3.5:6.4, the temperature is controlled to be 102-105 ℃, and the mixture is stirred at the speed of 1200r/min for 36min to prepare a mixture b;
(5) and (4) drying the mixture b prepared in the step (4) at the temperature of 43-45 ℃ until the water content is 1.1%, then carrying out superfine grinding and sieving to obtain the modified red mud powder with the particle size of more than 300 meshes.
An outdoor powder coating comprises the following raw materials in percentage by mass: 46.3 percent of modified red mud powder, 47.1 percent of polyester resin, 3.9 percent of curing agent, 0.6 percent of flatting agent, 0.7 percent of defoaming agent, 0.5 percent of brightener, 0.4 percent of benzoin, 0.2 percent of white carbon black and 0.3 percent of wax powder.
The polyester resin is CRYLCOAT 2437-2 polyester resin.
The curing agent is TGIC curing agent.
The leveling agent is a PV88 leveling agent.
The defoaming agent is TP-39 defoaming agent.
The brightener is 701B brightener.
The preparation method of the outdoor powder coating comprises the following steps
(1) 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;
(2) melt extrusion: putting the uniformly mixed raw materials prepared in the step (1) 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 slices;
(3) grinding and crushing: and (3) putting the crushed sheet materials in the step (2) into an ACM (acid-activated metal) pulverizer to pulverize, and performing cyclone separation and screening to obtain the outdoor powder coating finished product with the particle size of more than 200 meshes shown in figure 2.
EXAMPLE 3
A preparation method of modified red mud powder comprises the following steps:
(1) pickling red mud with 17 wt% sulfuric acid until the pH value is 9.1, washing the pickled red mud with water, detecting the pH value of the washed red mud to be 8, performing filter pressing treatment to obtain clean red mud, and drying the clean red mud until the water content is 4.3%;
(2) carrying out superfine grinding on the clean red mud prepared in the step (1), and sieving to obtain clean red mud powder with the particle size of more than 300 meshes;
(3) adding a composite modifier a into the clean red mud powder prepared in the step (2), wherein the composite modifier a consists of sodium fatty acid methyl ester ethoxylate sulfonate and disodium coconut monoethanolamide sulfosuccinate monoester, the addition amount of the composite modifier a is 2.6% of the mass of the clean red mud powder, the mass ratio of the sodium fatty acid methyl ester ethoxylate sulfonate to the disodium coconut monoethanolamide sulfosuccinate monoester is 2.9:9.1, the temperature is controlled to be 78-82 ℃, and the mixture is stirred at the speed of 900r/min for 31min to prepare a mixture a;
(4) adding the mixture a prepared in the step (3) and a composite modifier b into a mixer, wherein the composite modifier b is composed of amino-terminated polydimethylsiloxane and six pairs of carboxyphenoxy cyclotriphosphazenes, the adding amount of the composite modifier b is 4.2% of the mass of the clean red mud powder, the mass ratio of the amino-terminated polydimethylsiloxane to the six pairs of carboxyphenoxy cyclotriphosphazenes is 3.2:6.7, the temperature is controlled to be 97-103 ℃, and the mixture is stirred at the speed of 1100r/min for 39min to prepare a mixture b;
(5) and (4) drying the mixture b prepared in the step (4) at the temperature of 43-46 ℃ until the water content is 1%, then carrying out superfine grinding and sieving to obtain the modified red mud powder with the particle size of more than 300 meshes.
An outdoor powder coating comprises the following raw materials in percentage by mass: 47.2 percent of modified red mud powder, 45.4 percent of polyester resin, 4.1 percent of curing agent, 0.8 percent of flatting agent, 0.5 percent of defoaming agent, 0.7 percent of brightener, 0.6 percent of benzoin, 0.3 percent of white carbon black and 0.4 percent of wax powder.
The polyester resin is CRYLCOAT 2437-2 polyester resin.
The curing agent is TGIC curing agent.
The leveling agent is a PV88 leveling agent.
The defoaming agent is TP-39 defoaming agent.
The brightener is 701B brightener.
The preparation method of the outdoor powder coating comprises the following steps
(1) 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;
(2) melt extrusion: putting the uniformly mixed raw materials prepared in the step (1) 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 slices;
(3) grinding and crushing: and (3) putting the crushed sheet materials in the step (2) into an ACM (activated carbon model) pulverizer to pulverize, and performing cyclone separation and screening to obtain an outdoor powder coating finished product with the particle size of more than 200 meshes, wherein the outdoor powder coating finished product is shown in figure 3.
Comparative example 1
The outdoor powder coating preparation process was substantially the same as that of example 2, except that only the modification of step (4) was carried out in the preparation of the modified red mud powder, and the modification of step (3) was not carried out.
Comparative example 2
The outdoor powder coating preparation process was essentially the same as that of example 2, except that the composite modifier a used in the preparation of the modified red mud powder lacked sodium fatty acid methyl ester ethoxylate sulfonate.
Comparative example 3
The outdoor powder coating preparation process was essentially the same as that of example 2, except that the complex modifier a used in the preparation of the modified red mud powder lacked disodium coco monoethanolamide sulfosuccinate.
Comparative example 4
The outdoor powder coating preparation process was substantially the same as that of example 2, except that only the modification of step (3) was carried out in the preparation of the modified red mud powder, and the modification of step (4) was not carried out.
Comparative example 5
The preparation process of the outdoor powder coating is basically the same as that of example 2, except that the composite modifier b used in the preparation of the modified red mud powder lacks an amino-terminated polydimethylsiloxane.
Comparative example 6
The preparation process of the outdoor powder coating is basically the same as that of example 2, except that the composite modifier b used in the preparation of the modified red mud powder lacks six pairs of carboxyphenoxy cyclotriphosphazenes.
Comparative example 7
The preparation process of the outdoor powder coating is basically the same as that of example 2, except that the modified red mud powder is prepared without modification in the steps (3) and (4).
Comparative example 8
The outdoor powder coating is prepared by the process of example 1 of Chinese patent application document 'an outdoor pattern powder coating with metal texture and a production method thereof (patent number: ZL 201510622727.8').
Comparative example 9
China patent application document ZL201510622727.8, which discloses an outdoor pattern powder coating with metal texture and a production method thereof, is adopted to prepare the outdoor powder coating by the process of example 1, except that fillers (kaolin and precipitated barium sulfate) in the outdoor pattern powder coating are replaced by the modified red mud with the same weight as that prepared in example 2.
And (3) performance detection:
preparing a coating layer: the outdoor powder coatings of examples 1-3 and comparative examples 1-7 were sprayed on the surface-treated cold-rolled steel sheets using an electrostatic spray gun, and the thickness of the coating films was substantially uniform, and cured at 200 deg.C/10 min to obtain coating layers corresponding to examples 1-3 and comparative examples 1-7.
The detection basis of the coating indexes is as follows: GB/T21776 2008 Standard guidelines for testing powder coatings and coatings thereof; the test pieces obtained in examples 1 to 3 and comparative examples 1 to 7 were examined for oxygen index according to: GB 8624 and 2012 'grading of combustion properties of building materials and products'.
The coating test results of examples 1 to 3 and comparative examples 1 to 7 are shown in Table 2.
TABLE 2 coating test results of examples 1 to 3 and comparative examples 1 to 7
Figure GDA0002679088540000121
Figure GDA0002679088540000131
As can be seen from Table 2: (1) as can be seen from the data of example 2 and comparative examples 1-3, the sodium fatty acid methyl ester ethoxylate sulfonate and disodium coconut monoethanolamide sulfosuccinate have a synergistic effect in red mud modification, and the apparent performance and gloss of the coating film of the outdoor powder coating are synergistically improved; this is:
the polyester resin is nonpolar, and the surface of the unmodified red mud powder contains a large amount of hydroxyl, so the outdoor powder coating prepared by directly filling the unmodified red mud powder into the polyester resin has poor apparent property and luster. The red mud is subjected to surface modification by using sodium fatty acid methyl ester ethoxylate sulfonate and disodium coconut monoethanolamide sulfosuccinate, and because the sodium fatty acid methyl ester ethoxylate sulfonate and the disodium coconut monoethanolamide sulfosuccinate contain groups such as sulfonic acid groups, oleic acid groups and amino groups, the groups such as the sulfonic acid groups, the oleic acid groups and the amino groups can be introduced into the surfaces of the red mud particles during modification, so that the dispersibility and the processing flowability of the modified red mud powder can be improved, the modified red mud has better compatibility with other raw materials of outdoor powder coating such as polyester resin, the interfacial adhesion of the outdoor powder coating is improved, and the apparent performance and the gloss of the coating of the outdoor powder coating are improved. The modified red mud is added into the polyester resin after the surface of the red mud is modified, so that the agglomeration effect in a matrix of the red mud can be effectively reduced, the cohesiveness, the compatibility and the wettability between the polyester resin and the modified red mud powder can be effectively improved, and the apparent performance and the gloss of an outdoor powder coating film are greatly improved.
(2) As can be seen from the data of example 2 and comparative examples 4 to 6, the amino-terminated polydimethylsiloxane and the hexa-p-carboxyphenoxy cyclotriphosphazene play a synergistic role in red mud modification, and the oxygen index of the outdoor powder coating is improved, which is that:
because the ammonia-end polydimethylsiloxane is of an organic-inorganic hybrid structure and contains silicon-oxygen bonds and amino groups, the silicon-oxygen bonds and the amino groups can be introduced to the surfaces of the red mud particles after the first modification during the modification, and when the sample plate is ignited, the siloxane quickly migrates to the surface of the sample plate to form a protective layer, thereby playing the roles of heat insulation and oxygen isolation and further preventing the sample plate from burning; in addition, the six pairs of carboxyl phenoxy cyclotriphosphazenes have a P-N synergistic effect, and the ammonia-end polydimethylsiloxane is matched with the six pairs of carboxyl phenoxy cyclotriphosphazenes, so that the flame retardant effect of the sample plate is more obvious, and the oxygen index of the sample plate is improved.
(3) As can be seen from the data of examples 1-3, example 2 is the most preferred example; as can be seen from the data of examples 1-3 and comparative example 7, the outdoor powder coating prepared from the modified red mud has obviously improved apparent performance, gloss and oxygen index of the coating film, which are as follows:
according to the invention, fatty acid methyl ester ethoxylate sodium sulfonate and coconut oil acid monoethanolamide sulfosuccinic acid monoester disodium are adopted to carry out first-step surface modification on red mud; then, ammonia-terminated polydimethylsiloxane and six-pair carboxyl phenoxy cyclotriphosphazene are adopted to carry out secondary modification on the red mud, wherein sulfonic groups, oleic acid groups, amino groups, silicon-oxygen bonds and the like are successfully connected to the surfaces of red mud particles, so that the cohesiveness, compatibility and wettability between polyester resin and modified red mud powder in the powder coating are effectively improved, and the apparent property, the gloss and the oxygen index of a coating are obviously improved.
In addition, as can be seen from the data of examples 1-3 and comparative example 7, the outdoor powder coating prepared by using the modified red mud has improved film appearance performance and improved gloss and oxygen index by at least 47.88% and 62.96% respectively compared with the outdoor powder coating prepared by using the unmodified red mud.
The outdoor powder coatings prepared in examples 1-3 and comparative examples 8 and 9 were tested for impact resistance, adhesion, acid resistance, and weathering resistance, wherein impact resistance was tested using GB/T1732-19; the adhesive force is detected by GB/T9286-1998; the acid resistance is detected by a GB/T9274-1988A method; artificial weathering resistance was determined using operating equation A in Table 3 of GB/T1865-1997 and the evaluation was performed according to GB/T1766-1995, with the results shown in Table 3 below.
TABLE 3 table of the results of the performance tests of the outdoor powder coatings prepared in examples 1-3 and comparative examples 8 and 9
Figure GDA0002679088540000141
Figure GDA0002679088540000151
As can be seen from Table 3:
(1) the impact resistance of the outdoor powder coating is 68-81kg/cm, which is improved by at least 25.93 percent compared with the prior art (comparative example 8); the adhesion is 0 grade, which is equivalent to the level of the prior art (comparative example 8); the acid resistance is 323-376h without abnormality, which is improved by at least 33.47 percent compared with the prior art (comparative example 8); the artificial weathering resistance is 1562-.
(2) It can be seen from the data of comparative examples 9 and 8 that the impact resistance and weather resistance can be significantly improved by using the modified red mud prepared by the present invention as a filler under the condition that the filler is different.
(3) The red mud is modified and then filled into outdoor powder coating as a filler, the filling amount is more than 44.6 percent, compared with the conventional barium sulfate and other fillers, the red mud modified outdoor powder coating has good filling performance and high filling amount, and can greatly and effectively reduce the production cost (in the prior art, the resin content is generally not less than 50 percent, the filler consumption is generally not more than 40 percent, such as the patents of application numbers 201510622727.8, 201310222062.2 and 201610963019.5, otherwise, the leveling property and other properties are not good, but the resin content of the modified red mud modified by the invention is less than 48.1 percent, and the filler consumption is more than 44.6 percent, in addition, the modified red mud is obtained as a raw material after modification, and as the cost for purchasing the waste red mud is extremely low, the cost for preparing the modified red mud filler is far less than that the conventional filler barium sulfate and is about more than 1320 yuan/ton, and in addition, the resin consumption is, the production cost for preparing the outdoor powder coating can be greatly and 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 when the modified red mud loading in example 2 is 46.3%, the outdoor powder coating has the best overall performance, wherein the impact resistance is 81kg/cm, the adhesion is 0 grade, the acid resistance is 359h without abnormality, the artificial weathering resistance is 1704h without abnormal phenomena such as chalking, foaming, cracking and peeling, which provides the basis for seeking the best process for producing outdoor 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 (7)

1. A use method of a composite modifier b for improving an oxygen index in preparing modified red mud for a coating is characterized by comprising the following steps:
(1) pickling red mud with sulfuric acid with the concentration of 12-18 wt% until the pH value is 8.6-9.1, then washing the pickled red mud with water, detecting the pH value of the washed red mud to be 7.8-8.2, performing filter pressing treatment on the washed red mud to obtain clean red mud, and drying the clean red mud until the water content is less than or equal to 4.7%;
(2) carrying out superfine grinding on the clean red mud prepared in the step (1), and sieving to obtain clean red mud powder with the particle size of more than 300 meshes;
(3) adding a composite modifier a into clean red mud powder, wherein the composite modifier a consists of sodium fatty acid methyl ester ethoxylate sulfonate and disodium coconut monoethanolamide sulfosuccinate monoester, the addition amount of the composite modifier a is 1.8-2.7% of the clean red mud powder by mass, the mass ratio of the sodium fatty acid methyl ester ethoxylate sulfonate to the disodium coconut monoethanolamide sulfosuccinate monoester is 2.6-5.4:7.8-9.2, controlling the temperature, and stirring at a high speed to prepare a mixture a;
(4) adding the mixture a prepared in the step (3) and a composite modifier b into a stirrer, wherein the composite modifier b consists of amino-terminated polydimethylsiloxane and six-p-carboxyphenoxy cyclotriphosphazene, the mass ratio of the amino-terminated polydimethylsiloxane to the six-p-carboxyphenoxy cyclotriphosphazene is 2.8-3.7:5.2-7.6, controlling the temperature, and stirring at a speed to prepare a mixture b;
(5) and (4) drying the mixture b prepared in the step (4), then carrying out superfine grinding and sieving to obtain the modified red mud powder.
2. The use method of the composite modifier b for improving the oxygen index in preparing the modified red mud for coating according to claim 1, wherein the temperature in the step (3) is 78-84 ℃.
3. The use method of the composite modifier b for improving the oxygen index in preparing the modified red mud for coating according to claim 1, wherein the stirring in the step (3) is carried out at a speed of 800-1000r/min for 26-34 min.
4. The use method of the composite modifier b for improving the oxygen index in the preparation of the modified red mud for coating according to claim 1, wherein the temperature in the step (4) is 96-105 ℃.
5. The use method of the composite modifier b for improving the oxygen index in preparing the modified red mud for coating according to claim 1, wherein the stirring in the step (4) is carried out at a speed of 1000-1200r/min for 35-43 min.
6. The use method of the composite modifier b for improving the oxygen index in preparing the modified red mud for coating according to claim 1, wherein the mixture b prepared in the step (5) is dried at a temperature of 43-48 ℃ until the water content is less than or equal to 1.2%.
7. The use method of the composite modifier b for improving the oxygen index in preparing the modified red mud for coating according to claim 1, wherein the modified red mud powder in the step (5) has a mesh number of more than 300 meshes.
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