CN110117451B - Processing method for enhancing powder coating by utilizing modified red mud - Google Patents

Processing method for enhancing powder coating by utilizing modified red mud Download PDF

Info

Publication number
CN110117451B
CN110117451B CN201910452975.0A CN201910452975A CN110117451B CN 110117451 B CN110117451 B CN 110117451B CN 201910452975 A CN201910452975 A CN 201910452975A CN 110117451 B CN110117451 B CN 110117451B
Authority
CN
China
Prior art keywords
red mud
powder coating
powder
prepared
coating
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201910452975.0A
Other languages
Chinese (zh)
Other versions
CN110117451A (en
Inventor
王雄
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Guangxi Fubaoxin Technology Co ltd
Original Assignee
Guangxi Fubaoxin Technology Co ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Guangxi Fubaoxin Technology Co ltd filed Critical Guangxi Fubaoxin Technology Co ltd
Priority to CN201910452975.0A priority Critical patent/CN110117451B/en
Publication of CN110117451A publication Critical patent/CN110117451A/en
Application granted granted Critical
Publication of CN110117451B publication Critical patent/CN110117451B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • 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
    • C09D167/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/03—Powdery paints
    • C09D5/033—Powdery paints characterised by the additives
    • 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
    • C08K2003/2206—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
    • C08K2003/2272—Ferric oxide (Fe2O3)
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Paints Or Removers (AREA)

Abstract

The invention discloses a processing method for reinforcing powder coating by using modified red mud, which comprises the following steps: (1) mixing modified red mud powder, epoxy resin E-12, polyester resin, a flatting agent GLP588, benzoin, a polyoxyethylene polyoxypropylene ether defoaming agent, fumed silica, lead chrome yellow PY-34, a dispersing agent NC and a brightener LD-608 according to mass percentage, respectively adding into a mixer, pre-crushing, and mixing to obtain uniformly mixed raw materials; (2) putting the uniformly mixed raw materials into an extruder, performing melt extrusion, tabletting and cooling, and then crushing into sheet materials; (3) and (3) putting the crushed sheet materials into a flour mill for milling, and obtaining the indoor powder coating after cyclone separation and screening. The invention overcomes the defects of the existing red mud in coating utilization, realizes the purposes of changing waste into valuable and comprehensively utilizing, provides a new way for preparing indoor coatings, and has important economic and environmental benefits.

Description

Processing method for enhancing powder coating by utilizing modified red mud
[ 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 processing method for enhancing a powder coating by using modified red mud.
[ 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 main harmful component of red mud is Na2O, the attached solution contains 2-3g/L alkali and has a pH value of 12.2-13.1. The chemical composition of red mud from some aluminum industries, Guangxi, is shown in the following table.
Figure GDA0002754759470000011
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 the indoor coating, such as resin, are extremely poor, and the prepared powder coating has poor film appearance performance and gloss.
Therefore, how to overcome the defects of the existing red mud in the utilization of indoor coating, realize the industrial and industrialized application of the red mud, solve the environmental problems caused by the Guangxi red mud tailings, and have important economic and environmental benefits.
[ summary of the invention ]
The invention provides a processing method for enhancing powder coating by utilizing modified red mud, which aims to solve the technical problem of insufficient utilization of the existing red mud in indoor coating.
In order to solve the technical problems, the invention adopts the following technical scheme:
a processing method for enhancing powder coating by utilizing modified red mud comprises the following steps:
(1) mixing raw materials: mixing modified red mud powder, epoxy resin E-12, polyester resin, a flatting agent GLP588, benzoin, a polyoxyethylene polyoxypropylene ether defoaming agent, fumed silica, lead chrome yellow PY-34, a dispersing agent NC and a brightener LD-608 according to mass percentage, respectively adding into a mixer, pre-crushing, and mixing 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 a flour mill for milling, and performing cyclone separation and screening to obtain the indoor powder coating.
Further, the preparation method of the modified red mud powder in the step (1) comprises the following steps:
1) washing the red mud with water, detecting the pH value of the washed red mud to be 8.2-9.6, performing filter pressing treatment to obtain clean red mud, and drying the clean red mud until the water content is less than or equal to 5.2%;
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 I into the clean red mud powder prepared in the step 2), wherein the modifier I is composed of diethanolamide stearic acid monoglyceride and ethylene-bis (N-ethanesulfonic acid-dodecanamide) sodium, the addition amount of the modifier I is 3.4-4.6% of the mass of the clean red mud powder, the mass ratio of the diethanolamide stearic acid monoglyceride to the ethylene-bis (N-ethanesulfonic acid-dodecanamide) sodium is 6.3-10.8:3.4-7.6, the temperature is controlled to be 56-65 ℃, and the mixture I is prepared by stirring at the speed of 1000r/min of 800-materials;
4) adding the mixture I prepared in the step 3) and a modifier II into a mixer, wherein the modifier II consists of ammonia-terminated polydimethylsiloxane, hexabromocyclotriphosphazene and N-propyl-perfluorooctylsulfonyl ammonia glutamate, the addition amount of the modifier II is 1.8-2.5% of the mass of the clean red mud powder, the mass ratio of the ammonia-terminated polydimethylsiloxane, the hexabromocyclotriphosphazene and the N-propyl-perfluorooctylsulfonyl ammonia glutamate is 4.1-6.5:1.2-2:2.8-3.9, the temperature is controlled to be 80-89 ℃, and the mixture II is prepared by stirring at the speed of 1000-;
5) drying the mixture II prepared in the step 4) at the temperature of 40-46 ℃ until the water content is less than or equal to 1%, then carrying out superfine grinding and sieving to obtain the modified red mud powder with the particle size of more than 300 meshes.
Further, the time for pre-crushing in step (1) is 1 min.
Further, the time for remixing in step (1) was 4 min.
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 ℃.
Further, the pulverizer in the step (3) is an ACM pulverizer.
Further, the mesh number of the indoor powder coating in the step (3) is more than 200.
The invention has the following beneficial effects:
(1) the invention modifies the red mud, and fills the modified red mud as a filler into the prepared indoor powder coating, the filling amount is up to more than 48.3 percent, compared with the conventional fillers such as barium sulfate and the like, the filling performance is good, the filling amount is high, and the production cost can be greatly and effectively reduced (in the prior art, the resin content is generally not less than 50 percent, the filling amount is generally not more than 40 percent, otherwise, the leveling property and other properties are not good; the resin content is below 47.3 percent, and the filling amount is up to more than 48.3 percent; in addition, the invention adopts the waste red mud as the raw material, the modified red mud is obtained after modification as the filling material, because the cost of purchasing the waste red mud is extremely low, the cost of preparing the modified red mud filling material is far less than that of the conventional filling material barium sulfate and is about 1400 yuan/ton or more, and in addition, because the resin amount is reduced, the production cost of preparing the; when the filling amount of the modified red mud reaches 49.5 percent, the indoor powder coating has the optimal comprehensive performance, wherein the impact resistance is 92kg/cm, the bending resistance is 1.9mm, the adhesive force is 100 percent, and the apparent leveling property is excellent, thereby providing a basis for seeking the optimal production process.
(2) The invention overcomes the defects of the prior red mud in the utilization of indoor coating, realizes the purposes of changing waste into valuable and comprehensively utilizing, realizes the industrial and industrialized application of the red mud by utilizing the effective components in the red mud, can solve the environmental problem caused by the red mud tailings in Pinguo county of Guangxi province, and has important economic and environmental benefits.
[ description of the drawings ]
FIG. 1 is a black and white drawing of an indoor powder coating product according to example 1 of the present invention;
FIG. 2 is a black and white drawing of an indoor powder coating product of example 2 of the present invention;
fig. 3 is a black and white image of an indoor powder coating product according to 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 indoor powder coating comprises the following raw materials in percentage by mass: 48.3 to 50.2 percent of modified red mud powder, 21.9 to 28.6 percent of epoxy resin, 18.7 to 24.3 percent of polyester resin, 1 to 3 percent of flatting agent, 0.2 to 1 percent of benzoin, 0.2 to 2 percent of defoaming agent, 0.1 to 0.3 percent of fumed silica, 0.5 to 5 percent of pigment, 0.1 to 0.5 percent of dispersing agent and 0.3 to 1 percent of brightener.
The epoxy resin is epoxy resin E-12.
The polyester resin is prepared by adopting the method disclosed in the specification example 2 of the Chinese patent document 'polyester resin for indoor powder coating and preparation method thereof (patent number: ZL 201610735896.7').
The leveling agent is a leveling agent GLP 588.
The defoaming agent is a polyoxyethylene polyoxypropylene amine ether defoaming agent.
The pigment is lead chrome yellow PY-34.
The dispersant is dispersant NC.
The brightener is brightener LD-608.
The preparation method of the modified red mud powder comprises the following steps:
(1) washing the red mud with water, detecting the pH value of the washed red mud to be 8.2-9.6, performing filter pressing treatment to obtain clean red mud, and drying the clean red mud until the water content is less than or equal to 5.2%;
(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 I into the clean red mud powder prepared in the step (2), wherein the modifier I is composed of diethanolamide stearic acid monoglyceride and ethylene-bis (N-ethanesulfonic acid-dodecanamide) sodium, the addition amount of the modifier I is 3.4-4.6% of the mass of the clean red mud powder, the mass ratio of the diethanolamide stearic acid monoglyceride to the ethylene-bis (N-ethanesulfonic acid-dodecanamide) sodium is 6.3-10.8:3.4-7.6, the temperature is controlled to be 56-65 ℃, and the mixture I is prepared by stirring at the speed of 800-charge 1000r/min for 20-30 min;
(4) adding the mixture I prepared in the step (3) and a modifier II into a mixer, wherein the modifier II consists of ammonia-terminated polydimethylsiloxane, hexabromocyclotriphosphazene and N-propyl-perfluorooctylsulfonyl ammonia glutamic acid sodium, the addition amount of the modifier II is 1.8-2.5% of the mass of the clean red mud powder, the mass ratio of the ammonia-terminated polydimethylsiloxane to the hexabromocyclotriphosphazene to the N-propyl-perfluorooctylsulfonyl ammonia glutamic acid sodium is 4.1-6.5:1.2-2:2.8-3.9, the temperature is controlled to be 80-89 ℃, and the mixture II is prepared by stirring at the speed of 1000-;
(5) and (4) drying the mixture II prepared in the step (4) at the temperature of 40-46 ℃ until the water content is less than or equal to 1%, 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 indoor 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) 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 indoor 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 indoor 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、TiO2CaO, etc., the hardness of the materials is higher, the scratch resistance of the prepared powder coating is better, and the color of the powder coating is betterThe coating is red and is also the main color of the powder coating, not only has good covering power, but also can be used as partial pigment, and reduces the manufacturing cost of the powder coating.
The composite system of the main raw material resin and the filler (red mud) of the indoor powder coating is a macroscopically 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 resin microstructure (red mud) and chemical components on the resin interface. Therefore, the key to improving the performance of the indoor powder coating is to study the interaction of the components in the interface structure and the area of the indoor powder coating system, because the interaction between two phases is carried out through intermolecular force between different substances, formation of new chemical bonds, acid-base action and even polarity, and the orientation of resin molecular chains in the indoor powder coating system and the dispersion degree of the filler in the matrix can also influence the action force. The combination of filler and resin in an indoor powder coating system 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 Na2O, the attached solution contains 2-3g/L alkali and has a pH value of 12.2-13.1. The red mud has strong alkalinity of residual attached liquid, so the surface of the red mud contains a large amount of hydroxyl, 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 the cohesiveness, compatibility and wettability between the unmodified red mud powder and other raw materials of indoor coating, such as resin, are extremely poor, and the prepared powder coating has apparent performance and optical performanceIt is of poor luster. 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 indoor coating, such as resin, are improved, the prepared powder coating has good apparent property and gloss, and the quality of the indoor coating is improved.
In order to improve the cohesiveness, compatibility and wettability between the modified red mud and other raw materials of the indoor coating, such as resin, the invention adopts diethanolamide stearic acid monoglyceride and ethylene-bis (N-ethanesulfonic acid-dodecanoic acid amide) sodium to carry out surface modification on the red mud, and the two have a synergistic effect in modification, so that the coating apparent property and the gloss of the indoor powder coating are synergistically improved; the reason is that: the epoxy resin is usually nonpolar, and the surface of the unmodified red mud powder contains a large amount of hydroxyl, so that the apparent property and the gloss of the coating film of the indoor powder coating prepared by directly filling the unmodified red mud powder into the epoxy resin are poor. The red mud is subjected to surface modification by using diethanolamide stearic acid monoglyceride and ethylene-bis (N-ethanesulfonic acid-dodecanamide) sodium, and as the diethanolamide stearic acid monoglyceride and the ethylene-bis (N-ethanesulfonic acid-dodecanamide) sodium contain long-carbon-chain fatty acid, amino, sulfonic acid and other groups, the long-carbon-chain fatty acid, the amino, the sulfonic acid and other groups can be introduced into the surfaces of the red mud particles during 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 indoor powder coating, such as epoxy resin and polyester resin, the interfacial adhesion of the indoor powder coating is improved, and the apparent performance and the gloss of a coating of the indoor powder coating are improved. The red mud is added into epoxy resin and 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 among the epoxy resin, the polyester resin and the modified red mud powder can be effectively improved, so that the apparent performance and the gloss of the indoor 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 diethanolamide stearic acid monoglyceride and ethylene-bis (N-ethanesulfonic acid-dodecanamide) sodium; then, ammonia-terminated polydimethylsiloxane, hexabromocyclotriphosphazene and N-propyl-perfluorooctyl sulfonamide sodium glutamate are adopted to carry out secondary modification on the red mud, and a synergistic effect is achieved, so that the oxygen index of the indoor powder coating is improved, and the reason 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 hexabromocyclotriphosphazene has a P-N synergistic effect, and the ammonia-end polydimethylsiloxane is matched with the hexabromocyclotriphosphazene for use, so that the flame retardant effect of the sample plate is more obvious, and the oxygen index of the sample plate is improved; in addition, the hexabromocyclotriphosphazene and the N-propyl-perfluorooctyl sulfonamide sodium glutamate contain flame retardant elements of bromine and nitrogen, and the flame retardant property and the oxygen index of the sample are further improved due to the presence of the bromine and the nitrogen elements.
The epoxy resin E-12 used in the invention accounts for a larger proportion of the raw materials in the indoor powder coating, and has the characteristics of strong film adhesion, better heat resistance and electrical insulation, and better color retention of the film.
The polyester resin used in the invention is prepared by adopting the method disclosed in the specification example 2 of Chinese patent document 'polyester resin for indoor powder coating and preparation method thereof (patent number: ZL 201610735896.7)', has the advantages of large proportion of raw materials in indoor powder coating, low specific melt viscosity, high glass transition temperature and narrow molecular weight distribution. The indoor powder coating prepared from the polyester resin selected by the invention has excellent leveling property and gloss.
The flatting agent GLP588 used in the invention can promote the coating to form a flat, smooth and uniform coating film in the drying film-forming process, can effectively reduce the surface tension of the finishing liquid, improve the leveling property and uniformity of the coating liquid, improve the permeability of the finishing liquid, reduce the possibility of generating spots and stains during brushing, increase the coverage property and enable the film to be formed uniformly and naturally.
The benzoin can eliminate the problems of pinholes, shrinkage cavities, bubbles and the like generated in the curing process of the powder coating. The presence of benzoin accelerates the gasification and discharge of trace moisture and solvent in the powder coating, and the trace moisture and solvent are completely discharged before the powder coating is not cured, so that the generation of air holes is avoided, and the performance of the coating is improved.
The indoor 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 coating effect and performance of the coating, and at the moment, a polyoxyethylene polyoxypropylene amine ether defoaming agent is required to be added for defoaming, and the method 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 refractive index of the fumed silica is 1.46, is close to that of the film-forming resin, has no influence on the color of a coating, can be transferred to the surface of the coating in the film-forming process, can generate expected roughness on the surface, obviously reduces the surface gloss, and is a good flatting agent. Fumed silica added to indoor powder coatings can provide abrasion resistance. By adding a suitable amount of fumed silica, the abrasion resistance can be improved without adversely affecting the rheological properties of the coating and the optical properties of the dry film. In addition, the fumed silica can also improve the weather resistance and the scratch resistance of the coating and improve the bonding strength between the coating and the base material, and meanwhile, the fumed silica has extremely strong ultraviolet absorption and infrared reflection characteristics and can improve the ageing resistance of the coating when added into the coating.
The lead chrome yellow PY-34 has excellent light resistance, heat resistance, water resistance and solvent resistance, and plays an important role in corrosion resistance in an indoor powder coating besides the functions of coloring and covering.
Dispersant NC plays a very important role in the production of indoor powder coatings. The stability of the dispersion system can avoid a plurality of problems of indoor powder coating and coating defects, and if the formula is reasonable, the cost can be effectively reduced and the coating performance can be improved by adding a proper amount of dispersant NC.
1. Can improve the luster and increase the leveling effect. If the dispersant used is not appropriate, the colour becomes coarse after flocculation, which acts like a matting powder on gloss and naturally affects gloss.
2. Prevent floating color and floating color. To prevent floating color, the floating color in the can or the floating color of the coating film should be improved or eliminated by using a suitable dispersant.
3. The pigment is better dispersed and stabilized, and the tinting strength is obviously enhanced.
4. The viscosity is reduced, the pigment loading is increased, and the viscosity of the obtained color paste is obviously reduced by adopting a proper dispersant. Therefore, the loading amount of the pigment can be increased, and the production efficiency is improved.
5. Reducing flocculation, increasing workability and usability many people will conduct finger-test tests when evaluating dispersants. If the dispersant is not properly matched, the area which is not ground and the area which is ground are obviously different in color, and the coloring power of the flocculated pigment is reduced, which brings difficulty to toning and coating construction. Whether the color paste is flocculated or not can be observed by adopting a flow plate test.
6. The wetting function of the wetting dispersant, which improves the grinding efficiency and reduces the production cost, allows air and water on the pigment surface to be replaced more quickly by the liquid of the grinding medium, while the separation of the primary particles of the pigment obtained in the dispersion stage is maintained and controlled. These all improve grinding efficiency, reduce energy consumption and human cost.
7. Prevention of sedimentation many want to certainly think that anti-sedimentation must rely on anti-sedimentation agents, which are in fact faceted. If the ground color paste is flocculated, the pigment particles become larger and the density increases, and the ground color paste will settle quickly. If the color paste with the dispersant NC is selected, no anti-settling agent needs to be added, so that the cost is reduced.
The brightener LD-608 can improve the wettability of epoxy resin and polyester resin to lead chrome yellow PY-34 and modified red mud, simultaneously avoid the defects of coating such as pinholes, shrinkage cavities and the like, play a role in helping leveling, and obviously improve the appearance of the coating, thereby enabling the coating to obtain better flatness and gloss.
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 12.7 through detection.
TABLE 1 Main chemical composition Table of Red mud
Composition (I) CaO SiO2 Fe2O3 Al2O3 TiO2 Na2O
Content (%) 14.91 8.43 43.24 15.17 7.70 3.65
EXAMPLE 1
A preparation method of modified red mud powder comprises the following steps:
(1) abandoning the alumina production processWashing the red mud with water to remove Na in the red mud2Washing off water-soluble substances such as O, performing filter pressing treatment on the washed red mud after the pH value is detected to be 8.9 to obtain clean red mud, and drying the clean red mud until the water content is 5%;
(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 I into the clean red mud powder prepared in the step (2), wherein the modifier I is composed of diethanolamide stearic acid monoglyceride and ethylene-bis (N-ethanesulfonic acid-dodecanamide) sodium, the addition amount of the modifier I is 4.2% of the mass of the clean red mud powder, the mass ratio of the diethanolamide stearic acid monoglyceride to the ethylene-bis (N-ethanesulfonic acid-dodecanamide) sodium is 9.2:5.8, the temperature is controlled to be 56-60 ℃, and the mixture I is prepared by stirring at the speed of 1000r/min for 26 min;
(4) adding the mixture I prepared in the step (3) and a modifier II into a mixer, wherein the modifier II consists of ammonia-terminated polydimethylsiloxane, hexabromocyclotriphosphazene and N-propyl-perfluorooctylsulfonyl ammonia glutamic acid sodium, the addition amount of the modifier II is 2% of the mass of the clean red mud powder, the mass ratio of the ammonia-terminated polydimethylsiloxane, the hexabromocyclotriphosphazene and the N-propyl-perfluorooctylsulfonyl ammonia glutamic acid sodium is 5.3:1.8:3.5, the temperature is controlled to be 80-84 ℃, and the mixture II is prepared by stirring at the speed of 1200r/min for 40 min;
(5) and (4) drying the mixture II prepared in the step (4) at the temperature of 42-45 ℃ until the water content is 0.9%, then carrying out superfine grinding and sieving to obtain the modified red mud powder with the particle size of more than 300 meshes.
And performing infrared characterization (FTIR) and electron microscope Scanning (SEM) on the modified red mud powder prepared after modification.
Infrared characterization (FTIR): the modified red mud powder is repeatedly washed by absolute ethyl alcohol and acetone, vacuum-dried and potassium bromide tabletted, and a Nicolet 67 model Fourier infrared spectrometer produced by U.S. Thermo Nicolet company is adopted to record the surface characteristic peak of the modified red mud powder. Resolution of 1cm-1The number of scans was 16.
Through FT-IR analysis, amino groups, sulfonic groups and other groups, as well as silicon-oxygen bonds, bromine and nitrogen elements are successfully connected to the surfaces of the red mud particles.
Electron microscopy Scanning (SEM): modified red mud powder is adopted to fill resin matrix (epoxy resin and polyester resin) to obtain a sample, normal-temperature notch impact section of the sample is subjected to metal spraying treatment, and a tungsten filament scanning electron microscope is used for observing surface morphology at the voltage of 20 KV. Instrument model JSM-6490LV, manufactured by Japan.
SEM analysis shows that the compatibility of the modified red mud and a resin matrix is increased, the modified red mud is uniformly dispersed in the resin matrix and is used as a stress concentration point to induce more silver streaks and shear bands to be generated, and the impact strength of the powder coating is greatly improved.
An indoor powder coating comprises the following raw materials in percentage by mass: 49.5% of modified red mud powder, 21.9% of epoxy resin, 24.3% of polyester resin, 1.3% of flatting agent, 0.5% of benzoin, 0.7% of defoaming agent, 0.2% of fumed silica, 0.8% of pigment, 0.2% of dispersing agent and 0.6% of brightener.
The epoxy resin is epoxy resin E-12.
The polyester resin is prepared by adopting the method disclosed in the specification example 2 of the Chinese patent document 'polyester resin for indoor powder coating and preparation method thereof (patent number: ZL 201610735896.7').
The leveling agent is a leveling agent GLP 588.
The defoaming agent is a polyoxyethylene polyoxypropylene amine ether defoaming agent.
The pigment is lead chrome yellow PY-34.
The dispersant is dispersant NC.
The brightener is brightener LD-608.
The preparation method of the indoor 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 an indoor powder coating finished product with the particle size of more than 200 meshes.
EXAMPLE 2
A preparation method of modified red mud powder comprises the following steps:
(1) washing the red mud discarded in the production process of alumina with water to remove Na in the red mud2Washing off water-soluble substances such as O, performing filter pressing treatment on the washed red mud after the pH value is detected to be 8.5 to obtain clean red mud, and drying the clean red mud until the water content is 4.9%;
(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 modifier I into the clean red mud powder prepared in the step (2), wherein the modifier I is composed of diethanolamide stearic acid monoglyceride and ethylene-bis (N-ethanesulfonic acid-dodecanamide) sodium, the addition amount of the modifier I is 3.8% of the mass of the clean red mud powder, the mass ratio of the diethanolamide stearic acid monoglyceride to the ethylene-bis (N-ethanesulfonic acid-dodecanamide) sodium is 7.5:3.7, the temperature is controlled to be 62-65 ℃, and the mixture I is prepared by stirring at the speed of 900r/min for 22 min;
(4) adding the mixture I prepared in the step (3) and a modifier II into a mixer, wherein the modifier II consists of ammonia-terminated polydimethylsiloxane, hexabromocyclotriphosphazene and N-propyl-perfluorooctylsulfonyl ammonia glutamic acid sodium, the addition amount of the modifier II is 2.2% of the mass of the clean red mud powder, the mass ratio of the ammonia-terminated polydimethylsiloxane to the hexabromocyclotriphosphazene to the N-propyl-perfluorooctylsulfonyl ammonia glutamic acid sodium is 4.5:1.3:3.6, the temperature is controlled to be 85-89 ℃, and the mixture II is prepared by stirring at the speed of 1000r/min for 42 min;
(5) and (4) drying the mixture II prepared in the step (4) at the temperature of 44-46 ℃ until the water content is 0.7%, then carrying out superfine grinding and sieving to obtain the modified red mud powder with the particle size of more than 300 meshes.
And performing infrared characterization (FTIR) and electron microscope Scanning (SEM) on the modified red mud powder prepared after modification.
Infrared characterization (FTIR): the modified red mud powder is repeatedly washed by absolute ethyl alcohol and acetone, vacuum-dried and potassium bromide tabletted, and a Nicolet 67 model Fourier infrared spectrometer produced by U.S. Thermo Nicolet company is adopted to record the surface characteristic peak of the modified red mud powder. Resolution of 1cm-1The number of scans was 16.
Through FT-IR analysis, amino groups, sulfonic groups and other groups, as well as silicon-oxygen bonds, bromine and nitrogen elements are successfully connected to the surfaces of the red mud particles.
Electron microscopy Scanning (SEM): modified red mud powder is adopted to fill resin matrix (epoxy resin and polyester resin) to obtain a sample, normal-temperature notch impact section of the sample is subjected to metal spraying treatment, and a tungsten filament scanning electron microscope is used for observing surface morphology at the voltage of 20 KV. Instrument model JSM-6490LV, manufactured by Japan.
SEM analysis shows that the compatibility of the modified red mud and a resin matrix is increased, the modified red mud is uniformly dispersed in the resin matrix and is used as a stress concentration point to induce more silver streaks and shear bands to be generated, and the impact strength of the powder coating is greatly improved.
An indoor powder coating comprises the following raw materials in percentage by mass: 48.3 percent of modified red mud powder, 28.6 percent of epoxy resin, 18.7 percent of polyester resin, 1.2 percent of flatting agent, 0.8 percent of benzoin, 0.4 percent of defoaming agent, 0.1 percent of gas-phase silicon dioxide, 1.4 percent of pigment, 0.2 percent of dispersing agent and 0.3 percent of brightener.
The epoxy resin is epoxy resin E-12.
The polyester resin is prepared by adopting the method disclosed in the specification example 2 of the Chinese patent document 'polyester resin for indoor powder coating and preparation method thereof (patent number: ZL 201610735896.7').
The leveling agent is a leveling agent GLP 588.
The defoaming agent is a polyoxyethylene polyoxypropylene amine ether defoaming agent.
The pigment is lead chrome yellow PY-34.
The dispersant is dispersant NC.
The brightener is brightener LD-608.
The preparation method of the indoor 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 an indoor powder coating finished product with the particle size of more than 200 meshes.
EXAMPLE 3
A preparation method of modified red mud powder comprises the following steps:
(1) washing the red mud discarded in the production process of alumina with water to remove Na in the red mud2Washing off water-soluble substances such as O, performing filter pressing treatment on the washed red mud after the pH value is detected to be 9.5 to obtain clean red mud, and drying the clean red mud until the water content is 4.2%;
(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 I into the clean red mud powder prepared in the step (2), wherein the modifier I is composed of diethanolamide stearic acid monoglyceride and ethylene-bis (N-ethanesulfonic acid-dodecanamide) sodium, the addition amount of the modifier I is 4.6% of the mass of the clean red mud powder, the mass ratio of the diethanolamide stearic acid monoglyceride to the ethylene-bis (N-ethanesulfonic acid-dodecanamide) sodium is 9.7:6.8, the temperature is controlled to be 59-63 ℃, and the mixture I is prepared by stirring at the speed of 800r/min for 28 min;
(4) adding the mixture I prepared in the step (3) and a modifier II into a mixer, wherein the modifier II consists of ammonia-terminated polydimethylsiloxane, hexabromocyclotriphosphazene and N-propyl-perfluorooctylsulfonyl ammonia glutamic acid sodium, the addition amount of the modifier II is 2.4% of the mass of the clean red mud powder, the mass ratio of the ammonia-terminated polydimethylsiloxane to the hexabromocyclotriphosphazene to the N-propyl-perfluorooctylsulfonyl ammonia glutamic acid sodium is 6.3:1.2:3.5, the temperature is controlled to be 85-88 ℃, and the mixture II is prepared by stirring at the speed of 1100r/min for 36 min;
(5) and (4) drying the mixture II prepared in the step (4) at the temperature of 41-46 ℃ until the water content is 0.7%, then carrying out superfine grinding and sieving to obtain the modified red mud powder with the particle size of more than 300 meshes.
And performing infrared characterization (FTIR) and electron microscope Scanning (SEM) on the modified red mud powder prepared after modification.
Infrared characterization (FTIR): the modified red mud powder is repeatedly washed by absolute ethyl alcohol and acetone, vacuum-dried and potassium bromide tabletted, and a Nicolet 67 model Fourier infrared spectrometer produced by U.S. Thermo Nicolet company is adopted to record the surface characteristic peak of the modified red mud powder. Resolution of 1cm-1The number of scans was 16.
Through FT-IR analysis, amino groups, sulfonic groups and other groups, as well as silicon-oxygen bonds, bromine and nitrogen elements are successfully connected to the surfaces of the red mud particles.
Electron microscopy Scanning (SEM): modified red mud powder is adopted to fill resin matrix (epoxy resin and polyester resin) to obtain a sample, normal-temperature notch impact section of the sample is subjected to metal spraying treatment, and a tungsten filament scanning electron microscope is used for observing surface morphology at the voltage of 20 KV. Instrument model JSM-6490LV, manufactured by Japan.
SEM analysis shows that the compatibility of the modified red mud and a resin matrix is increased, the modified red mud is uniformly dispersed in the resin matrix and is used as a stress concentration point to induce more silver streaks and shear bands to be generated, and the impact strength of the powder coating is greatly improved.
An indoor powder coating comprises the following raw materials in percentage by mass: 50.2% of modified red mud powder, 22.8% of epoxy resin, 22.5% of polyester resin, 1% of flatting agent, 0.7% of benzoin, 0.5% of defoaming agent, 0.3% of fumed silica, 0.6% of pigment, 0.5% of dispersing agent and 0.9% of brightener.
The epoxy resin is epoxy resin E-12.
The polyester resin is prepared by adopting the method disclosed in the specification example 2 of the Chinese patent document 'polyester resin for indoor powder coating and preparation method thereof (patent number: ZL 201610735896.7').
The leveling agent is a leveling agent GLP 588.
The defoaming agent is a polyoxyethylene polyoxypropylene amine ether defoaming agent.
The pigment is lead chrome yellow PY-34.
The dispersant is dispersant NC.
The brightener is brightener LD-608.
The preparation method of the indoor 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 an indoor powder coating finished product with the particle size of more than 200 meshes.
Comparative example 1
The preparation process of the indoor powder coating is basically the same as that of example 1, except that only the modification of step (4) is carried out in the preparation of the modified red mud powder, and the modification of step (3) is not carried out.
Comparative example 2
The indoor powder coating was prepared by a procedure substantially identical to that of example 1 except that modifier i used in the preparation of the modified red mud powder was devoid of diethanolamide stearic acid monoglyceride.
Comparative example 3
The indoor powder coating was prepared by a procedure substantially identical to that of example 1 except that modifier I used in the preparation of the modified red mud powder was devoid of ethylene-bis (N-ethanesulfonic acid-dodecanoamide) sodium.
Comparative example 4
The preparation process of the indoor powder coating is basically the same as that of example 1, except that only the modification of step (3) is carried out in the preparation of the modified red mud powder, and the modification of step (4) is not carried out.
Comparative example 5
The indoor powder coating was prepared by a procedure substantially identical to that of example 1 except that modifier II used in the preparation of the modified red mud powder was devoid of aminoterminal polydimethylsiloxane.
Comparative example 6
The indoor powder coating preparation process was essentially the same as that of example 1 except that modifier II used in the preparation of the modified red mud powder was devoid of hexabromocyclotriphosphazene.
Comparative example 7
The preparation of the indoor powder coating was essentially the same as that of example 1 except that modifier II used in the preparation of the modified red mud powder lacked sodium N-propyl-perfluorooctylsulfonyl amide glutamate.
Comparative example 8
The preparation process of the indoor powder coating is basically the same as that of the preparation process of the example 1, except that the modification of the modified red mud powder in the steps (3) and (4) is not carried out.
And (3) performance detection:
preparing a coating layer: the powder coatings of examples 1-3 and comparative examples 1-8 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 deg.C/10 min to obtain coating layers corresponding to examples 1-3 and comparative examples 1-8.
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 8 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 8 are shown in Table 2.
TABLE 2 coating test results of examples 1 to 3 and comparative examples 1 to 8
Experimental project Apparent appearance of coating film Gloss (60 degree angle) Oxygen index (%)
Example 1 Leveling 96.8 52.6
Example 2 Leveling 95.4 51.7
Example 3 Leveling 96.2 50.4
Comparative example 1 Roughness of 79.1 48.3
Comparative example 2 Is substantially flat 90.4 50.1
Comparative example 3 Is substantially flat 92.1 49.5
Comparative example 4 Is substantially flat 94.6 30.1
Comparative example 5 Is substantially flat 93.6 45.6
Comparative example 6 Is substantially flat 94.1 46.5
Comparative example 7 Is substantially flat 92.9 47.7
Comparative example 8 Roughness of 70.6 27.3
As can be seen from Table 2: (1) as can be seen from the data of the example 1 and the comparative examples 1 to 3, the diethanolamide stearic acid monoglyceride and ethylene-bis (N-ethanesulfonic acid-dodecanoamide) sodium salt play a synergistic role in red mud modification, and the apparent performance and the gloss of the coating of the indoor powder coating are synergistically improved; this is:
the epoxy resin is usually nonpolar, and the surface of the unmodified red mud powder contains a large amount of hydroxyl, so that the apparent property and the gloss of the coating film of the indoor powder coating prepared by directly filling the unmodified red mud powder into the epoxy resin are poor. The red mud is subjected to surface modification by using diethanolamide stearic acid monoglyceride and ethylene-bis (N-ethanesulfonic acid-dodecanamide) sodium, and as the diethanolamide stearic acid monoglyceride and the ethylene-bis (N-ethanesulfonic acid-dodecanamide) sodium contain long-carbon-chain fatty acid, amino, sulfonic acid and other groups, the long-carbon-chain fatty acid, the amino, the sulfonic acid and other groups can be introduced into the surfaces of the red mud particles during 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 indoor powder coating, such as epoxy resin and polyester resin, the interfacial adhesion of the indoor powder coating is improved, and the apparent performance and the gloss of a coating of the indoor powder coating are improved. The red mud is added into epoxy resin and 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 among the epoxy resin, the polyester resin and the modified red mud powder can be effectively improved, so that the apparent performance and the gloss of the indoor powder coating film are greatly improved.
(2) As can be seen from the data of example 1 and comparative examples 4-7, the ammonia-terminated polydimethylsiloxane, hexabromocyclotriphosphazene and sodium N-propyl-perfluorooctylsulfonyl amide glutamate play a synergistic role in red mud modification, and the oxygen index of the indoor 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 hexabromocyclotriphosphazene has a P-N synergistic effect, and the ammonia-end polydimethylsiloxane is matched with the hexabromocyclotriphosphazene for use, so that the flame retardant effect of the sample plate is more obvious, and the oxygen index of the sample plate is improved; in addition, the hexabromocyclotriphosphazene and the N-propyl-perfluorooctyl sulfonamide sodium glutamate contain flame retardant elements of bromine and nitrogen, and the flame retardant property and the oxygen index of the sample are further improved due to the presence of the bromine and the nitrogen elements.
(3) As can be seen from the data of examples 1-3, example 1 is the most preferred example; as can be seen from the data of examples 1-3 and comparative example 8, the indoor powder coating prepared from the modified red mud has obviously improved film appearance performance, gloss and oxygen index, and the film appearance performance is improved and the gloss and oxygen index are respectively improved by 37.11% and 92.67% compared with the indoor powder coating prepared from the unmodified red mud.
The impact resistance, bending resistance, adhesion and apparent leveling of the indoor powder coatings prepared in examples 1-3 were measured according to GB/T21776-2008 "Standard guidelines for testing powder coatings and coatings thereof", and the results are shown in Table 3.
TABLE 3 table of the results of the performance tests of the indoor powder coatings prepared in examples 1-3
Figure GDA0002754759470000161
Figure GDA0002754759470000171
As can be seen from Table 3:
(1) the indoor powder coating disclosed by the invention has the advantages of impact resistance of 85-92kg/cm, bending resistance of 1.8-2.0mm, adhesion of 100%, excellent apparent leveling property and excellent performance.
(2) The invention modifies the red mud, and fills the modified red mud as a filler into the prepared indoor powder coating, the filling amount is up to more than 48.3 percent, compared with the conventional fillers such as barium sulfate and the like, the filling performance is good, the filling amount is high, and the production cost can be greatly and effectively reduced (in the prior art, the resin content is generally not less than 50 percent, the filling amount is generally not more than 40 percent, otherwise, the leveling property and other properties are not good; the resin content is below 47.3 percent, and the filling amount is up to more than 48.3 percent; in addition, the invention adopts the waste red mud as the raw material, the modified red mud is obtained after modification as the filling material, because the cost of purchasing the waste red mud is extremely low, the cost of preparing the modified red mud filling material is far less than that of the conventional filling material barium sulfate and is about 1400 yuan/ton or more, and in addition, because the resin amount is reduced, the production cost of preparing the; when the filling amount of the modified red mud reaches 49.5 percent, the indoor powder coating has the optimal comprehensive performance, wherein the impact resistance is 92kg/cm, the bending resistance is 1.9mm, the adhesive force is 100 percent, and the apparent leveling property is excellent, thereby providing a basis for seeking the optimal production process.
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 (6)

1. A processing method for reinforcing powder coating by using modified red mud is characterized by comprising the following steps:
(1) mixing raw materials: mixing modified red mud powder, epoxy resin E-12, polyester resin, a flatting agent GLP588, benzoin, a polyoxyethylene polyoxypropylene ether defoaming agent, fumed silica, lead chrome yellow PY-34, a dispersing agent NC and a brightener LD-608 according to mass percentage, respectively adding into a mixer, pre-crushing, and mixing to obtain uniformly mixed raw materials;
the preparation method of the modified red mud powder comprises the following steps:
1) washing the red mud with water, detecting the pH value of the washed red mud to be 8.2-9.6, performing filter pressing treatment to obtain clean red mud, and drying the clean red mud until the water content is less than or equal to 5.2%;
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 I into the clean red mud powder prepared in the step 2), wherein the modifier I is composed of diethanolamide stearic acid monoglyceride and ethylene-bis (N-ethanesulfonic acid-dodecanamide) sodium, the addition amount of the modifier I is 3.4-4.6% of the mass of the clean red mud powder, the mass ratio of the diethanolamide stearic acid monoglyceride to the ethylene-bis (N-ethanesulfonic acid-dodecanamide) sodium is 6.3-10.8:3.4-7.6, the temperature is controlled to be 56-65 ℃, and the mixture I is prepared by stirring at the speed of 1000r/min of 800-materials;
4) adding the mixture I prepared in the step 3) and a modifier II into a mixer, wherein the modifier II consists of ammonia-terminated polydimethylsiloxane, hexabromocyclotriphosphazene and N-propyl-perfluorooctylsulfonyl ammonia glutamate, the addition amount of the modifier II is 1.8-2.5% of the mass of the clean red mud powder, the mass ratio of the ammonia-terminated polydimethylsiloxane, the hexabromocyclotriphosphazene and the N-propyl-perfluorooctylsulfonyl ammonia glutamate is 4.1-6.5:1.2-2:2.8-3.9, the temperature is controlled to be 80-89 ℃, and the mixture II is prepared by stirring at the speed of 1000-;
5) drying the mixture II prepared in the step 4) at the temperature of 40-46 ℃ until the water content is less than or equal to 1%, then carrying out superfine grinding and sieving to obtain modified red mud powder with the particle size of more than 300 meshes;
(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 a flour mill for milling, and performing cyclone separation and screening to obtain the indoor powder coating.
2. The processing method for reinforcing powder coating by using modified red mud as claimed in claim 1, wherein the time for pre-crushing in step (1) is 1 min.
3. The processing method for reinforcing powder coating by using modified red mud as claimed in claim 1, wherein the remixing time in step (1) is 4 min.
4. The processing method for reinforcing powder coating by using modified red mud as claimed in claim 1, 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 ℃.
5. The processing method for reinforcing powder coating by using modified red mud according to claim 1, wherein the mill in the step (3) is an ACM mill.
6. The processing method for reinforcing powder coating by using modified red mud as claimed in claim 1, wherein the mesh number of the indoor powder coating in the step (3) is more than 200.
CN201910452975.0A 2019-05-28 2019-05-28 Processing method for enhancing powder coating by utilizing modified red mud Active CN110117451B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201910452975.0A CN110117451B (en) 2019-05-28 2019-05-28 Processing method for enhancing powder coating by utilizing modified red mud

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201910452975.0A CN110117451B (en) 2019-05-28 2019-05-28 Processing method for enhancing powder coating by utilizing modified red mud

Publications (2)

Publication Number Publication Date
CN110117451A CN110117451A (en) 2019-08-13
CN110117451B true CN110117451B (en) 2021-03-23

Family

ID=67523410

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201910452975.0A Active CN110117451B (en) 2019-05-28 2019-05-28 Processing method for enhancing powder coating by utilizing modified red mud

Country Status (1)

Country Link
CN (1) CN110117451B (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111440509A (en) * 2020-05-07 2020-07-24 广西福宝信科技有限公司 Powder coating special for aluminum wheel hub and preparation method thereof
CN117165145A (en) * 2023-09-08 2023-12-05 广西福宝信科技有限公司 High-performance powder coating for insulating coating of new energy automobile battery and production process thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20010084694A (en) * 2000-02-28 2001-09-06 차호선 Sprayable fireproofing composition
CN101157816A (en) * 2007-11-12 2008-04-09 徐州正菱涂装有限公司 Indoor decorative metal powdery paints
CN103483880A (en) * 2013-10-09 2014-01-01 张釜维 Production method of red mud filler

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20010084694A (en) * 2000-02-28 2001-09-06 차호선 Sprayable fireproofing composition
CN101157816A (en) * 2007-11-12 2008-04-09 徐州正菱涂装有限公司 Indoor decorative metal powdery paints
CN103483880A (en) * 2013-10-09 2014-01-01 张釜维 Production method of red mud filler

Also Published As

Publication number Publication date
CN110117451A (en) 2019-08-13

Similar Documents

Publication Publication Date Title
CN110079130B (en) Modified red mud for coating and preparation method thereof
CN110093095B (en) Modifier and application method thereof in preparing coating
CN110272650B (en) Composite modifier for improving compatibility and application thereof in preparation of powder coating
CN110205003B (en) High impact resistance outdoor powder coating
CN110117451B (en) Processing method for enhancing powder coating by utilizing modified red mud
CN110105850B (en) Indoor powder coating
CN110093096B (en) Flame-retardant modifier, method for treating red mud surface and application of flame-retardant modifier in powder coating
CN106833272A (en) A kind of high-strength tasteless abrasion proof pure water-base epoxy paint and preparation method thereof
CN111440515A (en) Antibacterial powder coating and preparation method thereof
CN110408311B (en) Weather-resistant powder coating and preparation method thereof
EP1914275B1 (en) Improved particulate mineral materials
CN111440509A (en) Powder coating special for aluminum wheel hub and preparation method thereof
CN110172265B (en) High-performance modified red mud for preparing coating and application thereof
CN110922806A (en) Water-based high-transparency filler for woodware and preparation method thereof
CN113045956B (en) Production process of electrical insulation powder coating
CN110183896A (en) Technique red mud modified composite modifier and its be surface-treated in coating filling with red mud
CN110194928B (en) Preparation method of outdoor powder coating capable of effectively reducing cost
CN110256875B (en) Composite modifier capable of improving oxygen index and application method of composite modifier in preparation of modified red mud for coating
CN1186414C (en) Preparation method of high scratch resistance nano compound polyurethane paint
CN112940591A (en) High-performance antibacterial powder coating and preparation method thereof
CN110105834B (en) Water-based acrylic asphalt anticorrosive paint and preparation process thereof
CN111471377A (en) Special powder coating for aluminum profile and preparation method thereof
CN109401572B (en) Weather-resistant powder coating for concrete mixing tank truck
US9637620B2 (en) Preparation of refined pigment from elastomer
JP2021050316A (en) Water-based coating composition

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant