CN111471377A - Special powder coating for aluminum profile and preparation method thereof - Google Patents

Special powder coating for aluminum profile and preparation method thereof Download PDF

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CN111471377A
CN111471377A CN202010377526.7A CN202010377526A CN111471377A CN 111471377 A CN111471377 A CN 111471377A CN 202010377526 A CN202010377526 A CN 202010377526A CN 111471377 A CN111471377 A CN 111471377A
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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
    • 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
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    • C09D5/033—Powdery paints characterised by the additives
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    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
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    • C08K2003/2206—Oxides; Hydroxides of metals of calcium, strontium or barium
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2227—Oxides; Hydroxides of metals of aluminium
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2237—Oxides; Hydroxides of metals of titanium
    • C08K2003/2241—Titanium dioxide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2265—Oxides; Hydroxides of metals of iron
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Abstract

The invention discloses a special powder coating for an aluminum profile and a preparation method thereof, wherein the special powder coating for the aluminum profile comprises the following raw materials in percentage by mass: 46.7-48.9% of saturated carboxyl polyester resin, 41.4-44.3% of modified red mud powder, 4-5.1% of curing agent, 0.8-1.4% of flatting agent, 0.2-0.4% of dispersing agent, 0.4-0.7% of defoaming agent, 0.5-1% of brightener, 0.3-0.4% of benzoin, 0.2-0.6% of wax powder and 0.3-0.6% of pigment, wherein the special powder coating for the aluminum profile is prepared by the steps of mixing raw materials, melt extrusion, grinding, crushing and the like. The powder coating has good impact resistance and weather resistance, and can be widely applied to various aluminum profiles.

Description

Special powder coating for aluminum profile and preparation method thereof
[ 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 special powder coating for an aluminum profile and a preparation method thereof.
[ background of the invention ]
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 blending materials used in iron separation of red mud and cement production, and the red mud is not well 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 BDA0002480547290000011
Since the red mud has strong alkalinity of residual attached liquid and contains a large amount of hydroxyl on the surface of the red mud, if unmodified red mud powder is directly filled into the coating, 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 such as resin of the special powder coating for the aluminum section are extremely poor, and the prepared powder coating has poor film appearance and luster.
The thermal transfer powder coating is used as an environment-friendly and highly decorative coating, and is widely applied to the field of aluminum profiles at present. However, the conventional thermal transfer powder coating, especially the low gloss coating, has a sharp decline in the mechanical properties, weather resistance and storage stability of the powder coating due to the addition of excessive physical or chemical flatting agents, and cannot meet the requirements of many outdoor aluminum profiles or aluminum alloy doors which need to be stamped.
Chinese patent application document "a low-gloss bending-resistant thermal transfer printing powder coating for aluminum profiles and a preparation method thereof" (application publication No. CN 106867371A) "discloses a low-gloss bending-resistant thermal transfer printing powder coating for aluminum profiles and a preparation method thereof. The powder coating is formed by mixing a component A and a component B; the raw materials of the component A comprise: saturated carboxyl-terminated polyester resin A, TGIC curing agent, closed isocyanate, extinction barium, flatting agent, brightening agent, benzoin, wax powder, wax-based flatting agent, rutile titanium dioxide, carbon black and iron yellow; the raw materials of the component B comprise: saturated carboxyl-terminated polyester resin B, TGIC curing agent, closed isocyanate, delustering barium, flatting agent, brightening agent, benzoin, wax powder, rutile titanium dioxide, carbon black and iron yellow. The powder coating film has the characteristics of very good bending resistance and the like, but has poor impact resistance and other properties, and cannot meet the application requirements.
The method solves the problems of the conventional powder coating special for aluminum profiles, innovatively applies the red mud to the powder coating, solves the problems of high production cost of the powder coating and the like, realizes the industrial and industrialized application of the red mud, further solves the problems of changing waste into valuable, protecting the environment, reducing the land occupation of waste slag and the like, and has important economic and environmental benefits.
[ summary of the invention ]
The invention provides a special powder coating for aluminum profiles and a preparation method thereof, which aim to solve the problems of using the traditional special powder coating for aluminum profiles, innovatively apply red mud in the powder coating, and solve the problems of poor performance, high production cost and the like of the powder coating, thereby realizing the industrial and industrialized application of the red mud.
In order to solve the technical problems, the invention adopts the following technical scheme:
the special powder coating for the aluminum profile comprises the following raw materials in percentage by mass: 46.7-48.9 percent of saturated carboxyl polyester resin, 41.4-44.3 percent of modified red mud powder, 4-5.1 percent of curing agent, 0.8-1.4 percent of flatting agent, 0.2-0.4 percent of dispersing agent, 0.4-0.7 percent of defoaming agent, 0.5-1 percent of brightener, 0.3-0.4 percent of benzoin, 0.2-0.6 percent of wax powder and 0.3-0.6 percent of pigment.
Further, the saturated carboxyl polyester resin is a high-toughness carboxyl polyester resin, the acid value of the resin is 45-55mgKOH/g, the viscosity at 200 ℃ is 7000-8500 mPa.s, and the glass transition temperature is 65-68 ℃.
Further, the curing agent is a TGIC curing agent.
Further, the leveling agent is a PV88 leveling agent.
Further, the dispersant is an NC dispersant.
Further, the defoaming agent is TP-39 defoaming agent.
Further, the brightener is 701B brightener.
Further, the preparation method of the modified red mud powder comprises the following steps:
(1) pickling red mud with sulfuric acid with the concentration of 10-20 wt% until the pH value is 9.2-9.4, then washing the pickled red mud with water, detecting the pH value of the washed red mud to be 7.9-8.1, performing filter pressing treatment on the red mud to obtain clean red mud, and drying the clean red mud until the water content is less than or equal to 3.6%;
(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 modifier a into the clean red mud powder prepared in the step (2), wherein the modifier a consists of fatty alcohol polyoxyethylene ether ammonium sulfate and diethanol amide stearic acid monoglyceride, the addition amount of the modifier a is 2.8-3.5% of the mass of the clean red mud powder, the mass ratio of the fatty alcohol polyoxyethylene ether ammonium sulfate to the diethanol amide stearic acid monoglyceride is 5.2-7.8:2.9-4.6, the temperature is controlled to be 70-75 ℃, and the mixture is stirred at the speed of 600-900r/min for 30-50min to prepare a mixture a;
(4) adding the mixture a prepared in the step (3) and a modifier b into a mixer, wherein the modifier b consists of fatty acid methyl ester sodium sulfonate and N-trimethyl chitosan, the addition amount of the modifier b is 4.6-5.7% of the mass of the clean red mud powder, the mass ratio of the fatty acid methyl ester sodium sulfonate to the N-trimethyl chitosan is 4.3-5.4:1.8-2.5, the temperature is controlled to be 78-86 ℃, and the mixture b is prepared by stirring at the speed of 900 plus 1300r/min for 32-45 min;
(5) and (4) drying the mixture b prepared in the step (4) at the temperature of 50-53 ℃ until the water content is less than or equal to 1.5%, then carrying out superfine grinding, and sieving to obtain the modified red mud powder with the particle size of more than 300 meshes.
The invention also provides a preparation method of the special powder coating for the aluminum profile, which 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 sheet materials crushed in the step (2) into an ACM (acid-activated metal) pulverizer to pulverize, and performing cyclone separation and screening to obtain the special powder coating for the aluminum profile with the average particle size of 25-45 um.
Further, 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 invention has the following beneficial effects:
(1) the invention uses the water washing method to wash the waste red mud in the alumina production process to remove Na in the red mud2After water-soluble substances such as O and the like are washed away, the obtained clean red mud can be used as a filler of the special powder coating for the aluminum profile after being modified, so that waste can be changed into valuable, the possible environmental pollution caused by occupation of land resources and stacking loss due to stacking can be reduced, and the production cost of the powder coating can be effectively reduced. The invention provides a new way which can not only reduce the production cost of the powder coating, but also fully and effectively utilize the waste resources.
(2) The invention overcomes the problems existing in the traditional powder coating special for aluminum profiles, innovatively applies red mud in the powder coating special for aluminum profiles, and solves the problems of high production cost, waste material recycling, environmental protection, waste slag land occupation reduction and the like, thereby realizing the industrial and industrialized application of the red mud.
(3) When the filling amount of the modified red mud is 42.6%, the comprehensive performance obtained by the special powder coating for the aluminum profile is optimal, wherein the impact resistance is 60kg/cm, the adhesive force is 86.9, and the weather resistance is pulverization level 0; level 1 of chromatic aberration; the gloss retention rate is 79.3 percent, which provides basis for seeking the best process for producing the special powder coating for the aluminum profile and is beneficial to guiding production.
[ description of the drawings ]
Fig. 1 is a black and white image of a powder coating product special for aluminum profiles 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.
In an embodiment, the special powder coating for the aluminum profile comprises the following raw materials in percentage by mass: 46.7-48.9 percent of saturated carboxyl polyester resin, 41.4-44.3 percent of modified red mud powder, 4-5.1 percent of curing agent, 0.8-1.4 percent of flatting agent, 0.2-0.4 percent of dispersing agent, 0.4-0.7 percent of defoaming agent, 0.5-1 percent of brightener, 0.3-0.4 percent of benzoin, 0.2-0.6 percent of wax powder and 0.3-0.6 percent of pigment.
The saturated carboxyl polyester resin is high-toughness carboxyl polyester resin, the acid value of the resin is 45-55mgKOH/g, the viscosity at 200 ℃ is 7000-8500 mPa.s, and the glass transition temperature is 65-68 ℃.
The curing agent is TGIC curing agent.
The leveling agent is a PV88 leveling agent.
The dispersant is an NC dispersant.
The defoaming agent is TP-39 defoaming agent.
The brightener is 701B brightener.
The wax powder is polytetrafluoroethylene wax modified polyethylene micro powder wax.
The pigment is iron yellow.
The preparation method of the modified red mud powder comprises the following steps:
(1) pickling red mud with sulfuric acid with the concentration of 10-20 wt% until the pH value is 9.2-9.4, then washing the pickled red mud with water, detecting the pH value of the washed red mud to be 7.9-8.1, performing filter pressing treatment on the red mud to obtain clean red mud, and drying the clean red mud until the water content is less than or equal to 3.6%;
(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 modifier a into the clean red mud powder prepared in the step (2), wherein the modifier a consists of fatty alcohol polyoxyethylene ether ammonium sulfate and diethanol amide stearic acid monoglyceride, the addition amount of the modifier a is 2.8-3.5% of the mass of the clean red mud powder, the mass ratio of the fatty alcohol polyoxyethylene ether ammonium sulfate to the diethanol amide stearic acid monoglyceride is 5.2-7.8:2.9-4.6, the temperature is controlled to be 70-75 ℃, and the mixture is stirred at the speed of 600-900r/min for 30-50min to prepare a mixture a;
(4) adding the mixture a prepared in the step (3) and a modifier b into a mixer, wherein the modifier b consists of fatty acid methyl ester sodium sulfonate and N-trimethyl chitosan, the addition amount of the modifier b is 4.6-5.7% of the mass of the clean red mud powder, the mass ratio of the fatty acid methyl ester sodium sulfonate to the N-trimethyl chitosan is 4.3-5.4:1.8-2.5, the temperature is controlled to be 78-86 ℃, and the mixture b is prepared by stirring at the speed of 900 plus 1300r/min for 32-45 min;
(5) and (4) drying the mixture b prepared in the step (4) at the temperature of 50-53 ℃ until the water content is less than or equal to 1.5%, 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 special powder coating for the aluminum profile 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 sheet materials crushed in the step (2) into an ACM (acid-activated metal) pulverizer to pulverize, and performing cyclone separation and screening to obtain the powder coating special for the aluminum profile.
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 average particle size of the special powder coating for the aluminum profile in the step (3) is 25-45 um.
The technical principle of the invention is as follows: the red mud is a precipitate precipitated during the process of alumina production and passes through the precipitation tank, has small granularity, 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、TiO2CaO, etc., which have higher hardness, and the prepared powder coating has better scratch resistance, and the color of the powder coating is red, which is the main color of the powder coating, but the powder coating can not cover the powder coatingThe powder coating has good strength, can be used as partial pigment, and reduces the manufacturing cost of the powder coating.
The composite system of saturated carboxyl polyester resin and filler (red mud) which is the main raw material of the special powder coating for the aluminum profile 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 a resin microstructure and chemical components on a resin interface. Therefore, the key point for improving the performance of the special powder coating for the aluminum profile is to research the interaction of each component in the interface structure and the area of the special powder coating system for the aluminum profile, because the interaction between two phases is carried out through the acting force between molecules of different substances, the formation of new chemical bonds, the acid-base action and even the polarity, 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 special powder coating system for the aluminum profile. The combination of fillers and resins in powder coating systems for aluminum profiles can be generally classified into the following categories: (1) mechanical mixing of pure form; (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 surface of the red mud is rich in a large number 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 Na2And (4) liquid attachment of O. The red mud has strong alkalinity of residual attached liquid, so that the surface of the red mud contains a large amount of hydroxyl groups, 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 such as resin of the special powder coating for the aluminum profile are extremely poor, and the apparent performance and the gloss of the prepared powder coating are poor.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 such as resin of the powder coating special for the aluminum profile are improved, the prepared powder coating has good apparent property and luster, and the quality of the powder coating special for the aluminum profile is improved.
The red mud is subjected to first-step surface modification by adopting fatty alcohol-polyoxyethylene ether ammonium sulfate and diethanol amide stearic acid monoglyceride; and then, carrying out secondary modification on the red mud by adopting fatty acid methyl ester sodium sulfonate and N-trimethyl chitosan, wherein long-carbon-chain fatty acids, hydroxyl, carbonyl, sulfonic group, amino group and other groups are successfully grafted to the surface of the red mud particles, so that the cohesiveness, compatibility and wettability between saturated carboxyl polyester resin and modified red mud powder in the powder coating are effectively improved, and the apparent property, the gloss and the like of a coating are obviously improved.
The resin used in the invention adopts saturated carboxyl polyester resin, and the resin can obviously improve the bending resistance and the impact resistance of the coating film;
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.
NC dispersants play a very important role in the production of powder coatings. The stability of the dispersion system can avoid a plurality of problems of powder coating and defects of film coating, and if the formula is reasonable, the proper amount of the dispersant NC can effectively reduce the cost and improve the performance of the coating.
The special powder coating for the aluminum profile 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 saturated carboxyl polyester resin to pigment and modified red mud, simultaneously avoid the defects of coating such as pinholes, shrinkage cavities and the like, and also play a role in helping leveling and obviously improve the appearance of the coating, thereby ensuring that the coating has 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 wax powder is polytetrafluoroethylene modified polyethylene micro powder wax, has good compatibility in the system, and can improve the hardness and smoothness of the surface of a coating film and improve the paper tearing effect of heat transfer printing.
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 of the red mud are shown in a table 1, and the pH value is 12.8 through detection.
TABLE 1 Main chemical composition Table of Red mud
Composition (I) CaO SiO2 Fe2O3 Al2O3 TiO2 Na2O
Content (%) 15.73 8.04 41.57 16.39 7.02 3.87
EXAMPLE 1
The special powder coating for the aluminum profile comprises the following raw materials in percentage by mass: 47.2 percent of saturated carboxyl polyester resin, 43.5 percent of modified red mud powder, 4.5 percent of curing agent, 1.3 percent of flatting agent, 0.4 percent of dispersing agent, 0.6 percent of defoaming agent, 1 percent of brightener, 0.4 percent of benzoin, 0.6 percent of wax powder and 0.5 percent of pigment.
The saturated carboxyl polyester resin is high-toughness carboxyl polyester resin, the acid value of the resin is 46mgKOH/g, the viscosity of the resin is 7500mPa & s at 200 ℃, and the glass transition temperature of the resin is 67 ℃.
The curing agent is TGIC curing agent.
The leveling agent is a PV88 leveling agent.
The dispersant is an NC dispersant.
The defoaming agent is TP-39 defoaming agent.
The brightener is 701B brightener.
The wax powder is polytetrafluoroethylene wax modified polyethylene micro powder wax.
The pigment is iron yellow.
The preparation method of the modified red mud powder comprises the following steps:
(1) washing red mud with 16 wt% sulfuric acid until the pH value is 9.4, washing the washed red mud with water, detecting the pH value of the washed red mud to be 7.9, performing filter pressing treatment to obtain clean red mud, and drying the clean red mud until the water content is 3.1%;
(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 modifier a into the clean red mud powder prepared in the step (2), wherein the modifier a is composed of fatty alcohol polyoxyethylene ether ammonium sulfate and diethanol amide stearic acid monoglyceride, the addition amount of the modifier a is 3.3% of the mass of the clean red mud powder, the mass ratio of the fatty alcohol polyoxyethylene ether ammonium sulfate to the diethanol amide stearic acid monoglyceride is 7.2:4.3, the temperature is controlled to be 73 ℃, and the mixture is stirred at the speed of 900r/min for 30min to prepare a mixture a;
(4) adding the mixture a prepared in the step (3) and a modifier b into a mixer, wherein the modifier b is composed of fatty acid methyl ester sodium sulfonate and N-trimethyl chitosan, the addition amount of the modifier b is 5.3% of the mass of the clean red mud powder, the mass ratio of the fatty acid methyl ester sodium sulfonate to the N-trimethyl chitosan is 5.2:2.3, the temperature is controlled to be 82 ℃, and the mixture b is prepared by stirring at the speed of 1200r/min for 42 min;
(5) and (3) drying the mixture b prepared in the step (4) at the temperature of 52 ℃ until the water content is 1.5%, 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 special powder coating for the aluminum profile 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 special aluminum profile powder coating with the average particle size of 29 um.
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 ℃.
EXAMPLE 2
The special powder coating for the aluminum profile comprises the following raw materials in percentage by mass: 48.7 percent of saturated carboxyl polyester resin, 43.9 percent of modified red mud powder, 4.2 percent of curing agent, 0.9 percent of flatting agent, 0.2 percent of dispersing agent, 0.5 percent of defoaming agent, 0.6 percent of brightener, 0.3 percent of benzoin, 0.4 percent of wax powder and 0.3 percent of pigment.
The saturated carboxyl polyester resin is high-toughness carboxyl polyester resin, the acid value of the resin is 50mgKOH/g, the viscosity of the resin is 7800 mPa.s at 200 ℃, and the glass transition temperature of the resin is 68 ℃.
The curing agent is TGIC curing agent.
The leveling agent is a PV88 leveling agent.
The dispersant is an NC dispersant.
The defoaming agent is TP-39 defoaming agent.
The brightener is 701B brightener.
The wax powder is polytetrafluoroethylene wax modified polyethylene micro powder wax.
The pigment is iron yellow.
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 wt% until the pH value is 9.2, then washing the pickled red mud with water, detecting the pH value of the washed red mud to be 7.9, performing filter pressing treatment on the red mud to obtain clean red mud, and drying the clean red mud until the water content is 3.6%;
(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 modifier a into the clean red mud powder prepared in the step (2), wherein the modifier a is composed of fatty alcohol polyoxyethylene ether ammonium sulfate and diethanol amide stearic acid monoglyceride, the addition amount of the modifier a is 2.9% of the mass of the clean red mud powder, the mass ratio of the fatty alcohol polyoxyethylene ether ammonium sulfate to the diethanol amide stearic acid monoglyceride is 5.7:3.1, the temperature is controlled to be 71 ℃, and the mixture is stirred at the speed of 600r/min for 50min to prepare a mixture a;
(4) adding the mixture a prepared in the step (3) and a modifier b into a mixer, wherein the modifier b is composed of fatty acid methyl ester sodium sulfonate and N-trimethyl chitosan, the addition amount of the modifier b is 4.8% of the mass of the clean red mud powder, the mass ratio of the fatty acid methyl ester sodium sulfonate to the N-trimethyl chitosan is 4.7:1.9, the temperature is controlled to be 82 ℃, and the mixture b is prepared by stirring at the speed of 1000r/min for 42 min;
(5) drying the mixture b prepared in the step (4) at the temperature of 50 ℃ until the water content is 1.5%, 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 special powder coating for the aluminum profile 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 sheet materials crushed in the step (2) into an ACM (acid-activated metal) pulverizer to pulverize, and performing cyclone separation and screening to obtain the special aluminum profile powder coating with the average particle size of 32 um.
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 ℃.
EXAMPLE 3
The special powder coating for the aluminum profile comprises the following raw materials in percentage by mass: 48.6 percent of saturated carboxyl polyester resin, 42.6 percent of modified red mud powder, 4.4 percent of curing agent, 1.2 percent of flatting agent, 0.3 percent of dispersing agent, 0.6 percent of defoaming agent, 0.9 percent of brightener, 0.3 percent of benzoin, 0.5 percent of wax powder and 0.6 percent of pigment.
The saturated carboxyl polyester resin is high-toughness carboxyl polyester resin, the acid value of the resin is 47mgKOH/g, the viscosity of the resin is 7700mPa & s at 200 ℃, and the glass transition temperature of the resin is 67 ℃.
The curing agent is TGIC curing agent.
The leveling agent is a PV88 leveling agent.
The dispersant is an NC dispersant.
The defoaming agent is TP-39 defoaming agent.
The brightener is 701B brightener.
The wax powder is polytetrafluoroethylene wax modified polyethylene micro powder wax.
The pigment is iron yellow.
The preparation method of the modified red mud powder comprises the following steps:
(1) washing red mud with 16 wt% sulfuric acid until the pH value is 9.3, washing the washed 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 3.2%;
(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 modifier a into the clean red mud powder prepared in the step (2), wherein the modifier a is composed of fatty alcohol polyoxyethylene ether ammonium sulfate and diethanol amide stearic acid monoglyceride, the addition amount of the modifier a is 3.2% of the mass of the clean red mud powder, the mass ratio of the fatty alcohol polyoxyethylene ether ammonium sulfate to the diethanol amide stearic acid monoglyceride is 6.5:3.8, the temperature is controlled to be 73 ℃, and the mixture is stirred at the speed of 800r/min for 42min to prepare a mixture a;
(4) adding the mixture a prepared in the step (3) and a modifier b into a mixer, wherein the modifier b is composed of fatty acid methyl ester sodium sulfonate and N-trimethyl chitosan, the addition amount of the modifier b is 5.2% of the mass of the clean red mud powder, the mass ratio of the fatty acid methyl ester sodium sulfonate to the N-trimethyl chitosan is 4.8:2.3, the temperature is controlled to be 82 ℃, and the mixture b is prepared by stirring at the speed of 1200r/min for 42 min;
(5) and (4) drying the mixture b prepared in the step (4) at the temperature of 52 ℃ 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.
The preparation method of the special powder coating for the aluminum profile 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) putting the crushed sheet materials in the step (2) into an ACM (Acetomine) pulverizer for pulverizing, and performing cyclone separation and screening to obtain the special aluminum profile powder coating with the average particle size of 40um, wherein a black-white picture of the product is shown in figure 1.
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 ℃.
Comparative example 1
The preparation process of the special powder coating for the aluminum profile is basically the same as that of the embodiment 3, except that only the modification of the step (4) is carried out in the preparation of the modified red mud powder, and the modification of the step (3) is not carried out.
Comparative example 2
The preparation process of the powder coating special for the aluminum profile is basically the same as that of the preparation process in the embodiment 3, except that the modifier a used in the preparation of the modified red mud powder lacks fatty alcohol-polyoxyethylene ether ammonium sulfate.
Comparative example 3
The preparation process of the special powder coating for the aluminum profile is basically the same as that of the preparation process of the example 3, except that the modifier a used for preparing the modified red mud powder lacks diethanolamide stearic acid monoglyceride.
Comparative example 4
The preparation process of the special powder coating for the aluminum profile is basically the same as that of the embodiment 3, except that only the modification of the step (3) is carried out in the preparation of the modified red mud powder, and the modification of the step (4) is not carried out.
Comparative example 5
The preparation process of the special powder coating for the aluminum profile is basically the same as that of the preparation process in the example 3, except that the modifier b used in the preparation of the modified red mud powder is lack of fatty acid methyl ester sodium sulfonate.
Comparative example 6
The preparation process of the special powder coating for the aluminum profile is basically the same as that of the preparation process of the example 3, except that the modifier b used in the preparation of the modified red mud powder lacks N-trimethyl chitosan.
Comparative example 7
The preparation process of the powder coating special for the aluminum profile is basically the same as that of the preparation process of the embodiment 3, except that the modification of the step (3) and the step (4) is not carried out in the preparation of the modified red mud powder.
Comparative example 8
The powder coating for aluminum profiles prepared by the process of examples 1-5 was prepared by using the Chinese patent application document "a low gloss bending resistant thermal transfer powder coating for aluminum profiles and a preparation method thereof" (application publication No. CN 106867371A) ".
And (3) performance detection:
preparing a coating layer: the powder coatings special for aluminum profiles of examples 1-3 and comparative examples 1-7 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 cured at 200 ℃/10min to obtain coating layers corresponding to examples 1-3 and comparative examples 1-7.
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
Experimental project Apparent appearance of coating film Gloss (60 degree specular gloss),% of
Example 1 Smooth and pore-free 56.3
Example 2 Smooth and pore-free 58.7
Example 3 Smooth and pore-free 61.4
Comparative example 1 Rough, unsmooth and porous 42.5
Comparative example 2 Basically flat and smooth without air holes 54.9
Comparative example 3 Basically flat and smooth without air holes 53.8
Comparative example 4 Basically flat and smooth without air holes 44.6
Comparative example 5 Basically flat and smooth without air holes 55.7
Comparative example 6 Basically flat and smooth without air holes 54.5
Comparative example 7 Rough, unsmooth and porous 19.8
As can be seen from Table 2: (1) as can be seen from the data of the example 3 and the comparative examples 1 to 3, the fatty alcohol polyoxyethylene ether ammonium sulfate and the diethanol amide stearic acid monoglyceride have a synergistic effect in the red mud modification, and the apparent performance and the gloss of the coating film of the powder coating special for the aluminum profile are synergistically improved; this is:
the saturated carboxyl polyester resin is nonpolar, and the surface of the unmodified red mud powder contains a large amount of hydroxyl, so the coating film appearance performance and the luster of the special powder coating for the aluminum profile prepared by directly filling the unmodified red mud powder into the saturated carboxyl polyester resin are poor. The red mud is subjected to surface modification by using fatty alcohol-polyoxyethylene ether ammonium sulfate and diethanol amide stearic acid monoglyceride, and as the fatty alcohol-polyoxyethylene ether ammonium sulfate and the diethanol amide stearic acid monoglyceride contain long-carbon-chain fatty acid, hydroxyl, carbonyl, amino and other groups, the long-carbon-chain fatty acid, hydroxyl, carbonyl, amino and other groups can be introduced into the surfaces of the red mud particles during first 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 the powder coating special for the aluminum profile, such as saturated carboxyl polyester resin, the interfacial adhesion of the powder coating special for the aluminum profile is improved, and the film appearance performance and the gloss of the powder coating special for the aluminum profile are improved. The red mud is added into the saturated carboxyl polyester resin after surface modification, so that the agglomeration effect in a red mud matrix can be effectively reduced, and the cohesiveness, compatibility and wettability between the saturated carboxyl polyester resin and the modified red mud powder can be effectively improved, thereby greatly improving the apparent performance and gloss of the powder coating special for the aluminum profile.
(2) As can be seen from the data of the example 3 and the comparative examples 4 to 6, the sodium fatty acid methyl ester sulfonate and the N-trimethyl chitosan play a synergistic role in the red mud modification, and the apparent performance and the gloss of the coating film of the powder coating special for the aluminum profile are improved, which are as follows:
because the sodium fatty acid methyl ester sulfonate and the N-trimethyl chitosan contain groups such as long-carbon-chain fatty acid, sulfonic group, amino group and the like, the groups such as the long-carbon-chain fatty acid, the sulfonic group, the amino group and the like can be introduced into the surfaces of the red mud particles during the second modification, so that the dispersibility and the processing fluidity of the modified red mud powder can be improved, the modified red mud has better compatibility with other raw materials of the powder coating special for the aluminum profile, such as saturated carboxyl polyester resin, the interfacial adhesion of the powder coating special for the aluminum profile is improved, and the film appearance performance and the gloss of the powder coating special for the aluminum profile are further improved. The red mud is added into the saturated carboxyl polyester resin after surface modification, so that the agglomeration effect in a red mud matrix can be effectively reduced, and the cohesiveness, compatibility and wettability between the saturated carboxyl polyester resin and the modified red mud powder can be effectively improved, so that the apparent performance and the gloss of a coating film of the powder coating special for the aluminum profile are greatly improved.
(3) As can be seen from the data of examples 1-3, example 3 is the most preferred example; as can be seen from the data of examples 1-3 and comparative example 7, the special powder coating for aluminum profiles prepared by using the modified red mud has obviously improved apparent performance and gloss of the coating film, which is that:
the red mud is subjected to first-step surface modification by adopting fatty alcohol-polyoxyethylene ether ammonium sulfate and diethanol amide stearic acid monoglyceride; and then, carrying out secondary modification on the red mud by adopting fatty acid methyl ester sodium sulfonate and N-trimethyl chitosan, wherein long-carbon-chain fatty acids, hydroxyl, carbonyl, sulfonic group, amino group and other groups are successfully grafted to the surface of the red mud particles, so that the cohesiveness, compatibility and wettability between saturated carboxyl polyester resin and modified red mud powder in the powder coating are effectively improved, and the apparent property and the gloss of a coating are obviously improved.
In addition, as can be seen from the data of examples 1-3 and comparative example 7, the powder coating special for aluminum profiles prepared by using the modified red mud has improved apparent performance of the coating film and improved gloss by at least 210.1% compared with the powder coating special for aluminum profiles prepared by using the unmodified red mud.
The impact resistance, the adhesive force and the weather resistance of the special powder coating for the aluminum profile prepared in the examples 1 to 3 and the comparative example 8 are detected, wherein the impact resistance is detected by GB/T1732-1993; the adhesive force is detected by GB/T9286-1998; the weather resistance was measured by GB/T1865-1997, and the results are shown in Table 3 below.
TABLE 3 table of performance test results of the powder coating for aluminum profiles prepared in examples 1 to 3 and comparative example 8
Figure BDA0002480547290000151
As can be seen from Table 3:
(1) the special powder coating for the aluminum profile has the impact resistance of 52-60kg/cm, the adhesion force of 82.1-86.9, and the impact resistance and the adhesion force are at least improved by 13.04 percent and 14.66 percent compared with the prior art (comparative example 8); the weather resistance is pulverization 0 grade; 1 grade of chromatic aberration; the light retention rate is 74.6-79.3%, and is improved by at least 20.91% compared with the light retention rate of the prior art (comparative example 8), and the special powder coating for the aluminum profile is excellent in performance and superior to the prior art (comparative example 8).
(2) The red mud is modified and then filled into the special powder coating for preparing the aluminum profile as the filler, the filling amount is up to more than 41.4 percent, compared with the conventional barium sulfate and other fillers, the special 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, for example, the patent of application publication No. CN 106867371A, otherwise, the leveling property and other properties are not good, but the resin content of the special powder coating is less than 48.9 percent, and the filler consumption is up to more than 41.4 percent, in addition, the invention adopts the waste red mud as the raw material, the modified red mud is obtained as the filler after modification, because the cost for purchasing the waste red mud is extremely low, the cost for preparing the modified red mud filler is far less than the conventional barium sulfate filler, at, therefore, the production cost of the special powder coating for preparing the aluminum profile can be greatly and effectively reduced.
(4) As can be seen from the data of the examples 1 to 3, the example 3 of the invention is the best example, and when the filling amount of the modified red mud is 42.6 percent in the example 3, the comprehensive performance of the special powder coating for the aluminum profile is the best, wherein the impact resistance is 60kg/cm, the adhesive force is 86.9, and the weather resistance is pulverization 0 grade; 1 grade of chromatic aberration; the light retention rate is 79.3%, which provides basis for seeking the best process for producing the special powder coating for the aluminum profile and is beneficial to guiding production.
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, numerous modifications and variations are possible without departing from the spirit of the invention.

Claims (10)

1. The special powder coating for the aluminum profile is characterized by comprising the following raw materials in percentage by mass: 46.7-48.9 percent of saturated carboxyl polyester resin, 41.4-44.3 percent of modified red mud powder, 4-5.1 percent of curing agent, 0.8-1.4 percent of flatting agent, 0.2-0.4 percent of dispersing agent, 0.4-0.7 percent of defoaming agent, 0.5-1 percent of brightener, 0.3-0.4 percent of benzoin, 0.2-0.6 percent of wax powder and 0.3-0.6 percent of pigment.
2. The special powder coating for aluminum profiles as claimed in claim 1, wherein the saturated carboxyl polyester resin is a high-toughness carboxyl polyester resin with an acid value of 45-55mgKOH/g, a viscosity of 7000-8500 mPa-s at 200 ℃ and a glass transition temperature of 65-68 ℃.
3. The special powder coating for aluminum profiles as claimed in claim 1, wherein the curing agent is TGIC curing agent.
4. The powder coating special for the aluminum profile as claimed in claim 1, wherein the leveling agent is a PV88 leveling agent.
5. The special powder coating for aluminum profiles as claimed in claim 1, wherein the dispersant is NC dispersant.
6. The special powder coating for aluminum profiles as claimed in claim 1, wherein the defoamer is TP-39 defoamer.
7. The special powder coating for aluminum profiles as claimed in claim 1, wherein the brightener is 701B brightener.
8. The special powder coating for the aluminum profile as claimed in claim 1, wherein the preparation method of the modified red mud powder comprises the following steps:
(1) pickling red mud with sulfuric acid with the concentration of 10-20 wt% until the pH value is 9.2-9.4, then washing the pickled red mud with water, detecting the pH value of the washed red mud to be 7.9-8.1, 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 3.6%;
(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 modifier a into the clean red mud powder prepared in the step (2), wherein the modifier a consists of fatty alcohol-polyoxyethylene ether ammonium sulfate and diethanol amide stearic acid monoglyceride, the addition amount of the modifier a is 2.8-3.5% of the mass of the clean red mud powder, the mass ratio of the fatty alcohol-polyoxyethylene ether ammonium sulfate to the diethanol amide stearic acid monoglyceride is 5.2-7.8:2.9-4.6, the temperature is controlled to be 70-75 ℃, and the mixture is stirred at the speed of 600-900r/min for 30-50min to prepare a mixture a;
(4) adding the mixture a prepared in the step (3) and a modifier b into a mixer, wherein the modifier b is composed of fatty acid methyl ester sodium sulfonate and N-trimethyl chitosan, the addition amount of the modifier b is 4.6-5.7% of the mass of the clean red mud powder, the mass ratio of the fatty acid methyl ester sodium sulfonate to the N-trimethyl chitosan is 4.3-5.4:1.8-2.5, the temperature is controlled to be 78-86 ℃, and the mixture b is prepared by stirring at the speed of 900 and 1300r/min for 32-45 min;
(5) and (4) drying the mixture b prepared in the step (4) at the temperature of 50-53 ℃ until the water content is less than or equal to 1.5%, then carrying out superfine grinding, and sieving to obtain the modified red mud powder with the particle size of more than 300 meshes.
9. The preparation method of the special powder coating for the aluminum profile according to any one of claims 1 to 8, characterized by comprising 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 sheet materials crushed in the step (2) into an ACM (acid-activated metal) pulverizer to pulverize, and performing cyclone separation and screening to obtain the special powder coating for the aluminum profile with the average particle size of 25-45 um.
10. The preparation method of the powder coating special for aluminum profiles as claimed in claim 9, wherein 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 ℃.
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