CN110194928A - It can effectively reduce the preparation method of the outdoor powdery paints of cost - Google Patents
It can effectively reduce the preparation method of the outdoor powdery paints of cost Download PDFInfo
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- CN110194928A CN110194928A CN201910570038.5A CN201910570038A CN110194928A CN 110194928 A CN110194928 A CN 110194928A CN 201910570038 A CN201910570038 A CN 201910570038A CN 110194928 A CN110194928 A CN 110194928A
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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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- 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
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- 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
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- 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
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- 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
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Abstract
The invention discloses a kind of preparation methods of outdoor powdery paints that can effectively reduce cost, the following steps are included: (1) raw material mix: raw material is carried out ingredient by mass percentage, it is then respectively adding in mixing machine, then precrushing, then it remixes, uniformly mixed raw material is made；(2) melting extrusion: the raw material being uniformly mixed made from step (1) is put into extruder, through melting extrusion, tabletting, cooling, is then broken into sheet stock；(3) it grinds: by broken sheet stock in step (2), being placed in flour mill and be milled, after cyclonic separation and screening, indoor powdery paints is made.The present invention overcomes traditional outdoor powdery paints use there are the problem of; innovation and application red mud is in outdoor powdery paints; solves the problems such as high production cost, turn waste into wealth, protect environment, reduce dump slag land seizure, to realize red mud industrialization, industrial application.
Description
[technical field]
The invention belongs to powdery paints preparation technical fields, and in particular to a kind of outdoor powder painting that can effectively reduce cost
The preparation method of material.
[background technique]
Guangxi pingguo's aluminium is known as the aluminium of China all, is the main aluminium producing base of China, mainly utilizes local aluminium
Native ore resources produce aluminium oxide, produce 2,500,000 tons of aluminium oxide in year, discharge 3,000,000 tons of red mud, and nowadays 37,500,000 tons of red mud tailings have been
Be piled into mountain, it is now annual that discharge is gradually increased with 3,000,000 speed, not only cause Seal treatment to spend a large amount of financial resources,
Material resources, manpower, but also to occupy local land resource largely to stack red mud, it is also very difficult in addition to make dam safety management
It is huge.
At present since red mud comprehensive utilization difficulty is huge, the admixture in iron and manufacture of cement is selected in addition to being used for red mud on a small quantity
Outside, the overwhelming majority can only store up in Red Mud Dam, not made full use of preferably.
The waste residue discharged in aluminum oxide production process is red mud, and mineral composition mainly has Al2O3、Na2O、SiO2、CaO、
Fe2O3、TiO2Deng.The red mud chemical component of Guangxi Chinalco see the table below.
For red mud since residual attached liquid alkalinity is strong, great amount of hydroxy group is contained on red mud surface, in this way directly fills out unmodified red mud powder
It is charged in coating, reuniting effect in the matrix due to failing to reduce red mud, so that unmodified red mud powder and outdoor powdery paints
Caking property, compatibility and wetability between other raw materials such as resin is very poor, powdery paints film apparent property obtained and
Gloss is poor.
Powdery paints is a kind of economic, environmentally friendly, efficient novel environment-friendly coating.Currently, gradually replacing organic molten
Dosage form coating becomes a component part important in coating industry.Outdoor powdery paints is a kind of kind of powdery paints, is passed
The outdoor powdery paints of system uses the problems such as outdoors, there are high production cost.
Therefore, how to overcome the problems, such as that traditional outdoor powdery paints use exists, innovation and application red mud is applied in outdoor powder
In material, solve high production cost the problems such as, thus realize red mud industrialization, industrial application, further solve turn waste into wealth, protect
The problems such as retaining ring border, reduction dump slag land seizure, there is important economy and environmental benefit.
[summary of the invention]
The present invention provides a kind of preparation method of outdoor powdery paints that can effectively reduce cost, to solve how to overcome biography
Unite outdoor powdery paints use there are the problem of, innovation and application red mud solves high production cost, becomes and give up in outdoor powdery paints
For precious, protection environment, the problems such as reducing dump slag land seizure, to realize red mud industrialization, industrial application.
In order to solve the above technical problems, the invention adopts the following technical scheme:
A kind of preparation method for the outdoor powdery paints can effectively reduce cost, comprising the following steps:
(1) raw material mix: by changed red mud powder, polyester resin, curing agent, levelling agent, defoaming agent, optical brightener, resting in peace
Perfume, white carbon black, wax powder carry out ingredient by mass percentage, are then respectively adding in mixing machine, then precrushing, then mix again
It closes, uniformly mixed raw material is made；
(2) melting extrusion: the raw material being uniformly mixed made from step (1) is put into extruder, through melting extrusion, pressure
Piece, cooling, are then broken into sheet stock；
(3) it grinds: by broken sheet stock in step (2), being placed in flour mill and be milled, through cyclonic separation and screening
Afterwards, indoor powdery paints is made.
Further, the preparation method of changed red mud powder described in step (1), comprising the following steps:
It 1) is 8.6-9.1 by sulfuric acid washing to the pH value that red mud is 12-18wt% with concentration, then to the red mud after pickling
It is washed, red mud filters pressing after detection pH value is 7.8-8.2 is processed into clean red mud after washing, and clean red mud drying is to containing
Water≤4.7%；
2) cleaning red mud made from step 1) is subjected to super fine powder, cleaning red mud powder is made after sieving；
3) composite modifier a is added into cleaning red mud powder made from step 2), the composite modifier a is by fatty acid
Methyl ester ethoxylates sodium sulfonate, Coconut Fatty Acid Monoethanolamide sulfosuccinic acid monoesters disodium composition, the composite modifier a's
Additional amount is the 1.8-2.7% of clean red mud powder quality, the fatty acid methyl ester ethoxylate sodium sulfonate, coconut oil list second
The mass ratio of alkylolamides sulfosuccinic acid monoesters disodium is 2.6-5.4:7.8-9.2, controlled at 78-84 DEG C, and with 800-
The speed of 1000r/min stirs 26-34min, and mixture a is made；
4) mixture a made from step 3) and composite modifier b are added to the mixer, the composite modifier b is by ammonia
Auspicious dimethyl silicone polymer, six pairs of three phosphonitrile of carboxyphenoxy ring compositions, the additional amount of the composite modifier b are clean red mud
The 3.2-4.3% of powder quality, the auspicious dimethyl silicone polymer of the ammonia, six pairs of three phosphonitriles of carboxyphenoxy ring mass ratio be
2.8-3.7:5.2-7.6 stirs 35-43min controlled at 96-105 DEG C with the speed of 1000-1200r/min, is made mixed
Close object b；
5) by mixture b made from step 4) temperature be 43-48 DEG C at dry to water content≤1.2%, then carry out
Changed red mud powder is made in super fine powder after sieving.
Further, polyester resin described in step (1) is CRYLCOAT 2437-2 polyester resin.
Further, curing agent described in step (1) is TGIC curing agent.
Further, levelling agent described in step (1) is PV88 levelling agent.
Further, defoaming agent described in step (1) is TP-39 defoaming agent.
Further, optical brightener described in step (1) is 701B optical brightener.
Further, the time of precrushing is 1min in step (1).
Further, the time remixed in step (1) is 4min.
Further, the temperature of melting extrusion is 105-110 DEG C in step (2), wherein I area's temperature is 105 DEG C, II area's temperature
Degree is 110 DEG C.
The invention has the following advantages:
(1) the present invention overcomes traditional outdoor powdery paints use there are the problem of, innovation and application red mud is in outdoor powder
In coating, solves the problems such as high production cost, turn waste into wealth, protect environment, reduce dump slag land seizure, to realize
Red mud industrialization, industrial application.
(2) present invention is filled into the outdoor powdery paints of preparation, loading is up to by modified to red mud as filler
44.6% or more, for the fillers such as conventional barium sulfate, not only filling capacity is good, but also loading is high, can have significantly
Effect reduces production cost, and in the prior art, resin content is generally no less than 50%, and amount of filler is usually no more than 40%, such as
The patent of application number 201510622727.8,201310222062.2,201610963019.5, otherwise levelability and other performances
It is all bad.And resin content of the present invention 48.1% hereinafter, amount of filler is up to 44.6% or more, in addition the present invention is using discarded
Red mud is as raw material, and by the modified changed red mud that obtains as filler, extremely low due to buying discarded red mud cost, preparation is modified
Red mud filler cost is much smaller than conventional fillers barium sulfate, about less 1320 yuan/ton or more, reduces additionally, due to amount of resin, because
This, the production cost for preparing outdoor powdery paints can be effectively reduced significantly.
[Detailed description of the invention]
Fig. 1 is the outdoor powder coating product artwork master of the embodiment of the present invention 1；
Fig. 2 is the outdoor powder coating product artwork master of the embodiment of the present invention 2；
Fig. 3 is the outdoor powder coating product artwork master of the embodiment of the present invention 3.
[specific embodiment]
To facilitate a better understanding of the present invention, it is illustrated by the following examples, these examples belong to protection of the invention
Range, but do not limit the scope of the invention.
A kind of open air powdery paints, the raw material including following mass percents: changed red mud powder 44.6-47.2%, polyester
Resin 45.4-48.1%, curing agent 3.8-5.3%, levelling agent 0.5-1.5%, defoaming agent 0.5-1%, optical brightener 0.5-
1.5%, styrax 0.3-0.8%, white carbon black 0.2-0.5%, wax powder 0.2-1%.
The polyester resin is CRYLCOAT 2437-2 polyester resin.
The curing agent is TGIC curing agent.
The levelling agent is PV88 levelling agent.
The defoaming agent is TP-39 defoaming agent.
The optical brightener is 701B optical brightener.
The preparation method of the changed red mud powder, comprising the following steps:
It (1) is 8.6-9.1 by sulfuric acid washing to the pH value that red mud is 12-18wt% with concentration, then to red after pickling
Mud is washed, and red mud filters pressing after detection pH value is 7.8-8.2 is processed into clean red mud after washing, and clean red mud drying is extremely
Water content≤4.7%；
(2) cleaning red mud made from step (1) is subjected to super fine powder, the clean red mud of 300 mesh is formed more widely than after sieving
Powder；
(3) composite modifier a is added into cleaning red mud powder made from step (2), the composite modifier a is by fat
Sour methyl ester ethoxylates sodium sulfonate, Coconut Fatty Acid Monoethanolamide sulfosuccinic acid monoesters disodium composition, the composite modifier a
Additional amount be clean red mud powder quality 1.8-2.7%, the fatty acid methyl ester ethoxylate sodium sulfonate, coconut oil list
The mass ratio of Acid Ethanolamide Sulfosuccinates disodium is 2.6-5.4:7.8-9.2, controlled at 78-84 DEG C, and with
The speed of 800-1000r/min stirs 26-34min, and mixture a is made；
(4) mixture a made from step (3) and composite modifier b are added to the mixer, the composite modifier b by
The auspicious dimethyl silicone polymer of ammonia, six pairs of three phosphonitrile of carboxyphenoxy ring compositions, the additional amount of the composite modifier b are clean red
The 3.2-4.3% of mud powder quality, the auspicious dimethyl silicone polymer of the ammonia, six pairs of three phosphonitriles of carboxyphenoxy ring mass ratio be
2.8-3.7:5.2-7.6 stirs 35-43min controlled at 96-105 DEG C with the speed of 1000-1200r/min, is made mixed
Close object b；
(5) by mixture b made from step (4) be 43-48 DEG C in temperature at dry to water content≤1.2%, then into
Row super fine powder is formed more widely than the changed red mud powder of 300 mesh after sieving.
The preparation method of the open air powdery paints, comprising the following steps:
(1) raw material mix: all kinds of raw materials being carried out ingredient by above-mentioned mass percent, are then respectively adding mixing machine
In, then precrushing 1min, then remixes 4min, and uniformly mixed raw material is made；
(2) melting extrusion: the raw material being uniformly mixed made from step (1) is put into extruder, through melting extrusion, pressure
Piece, cooling, are then broken into sheet stock；
(3) grind: by broken sheet stock in step (2), being placed in ACM flour mill and be milled, through cyclonic separation and
After screening, it is formed more widely than the outdoor powdery paints of 200 mesh.
The temperature of melting extrusion is 105-110 DEG C in step (2), wherein I area's temperature is 105 DEG C, II area's temperature is 110
℃。
The mesh number of open air powdery paints described in step (3) is greater than 200.
Technical principle of the invention: red mud is the sediment to precipitate when by dropping slot in aluminum oxide production process,
Granularity very little, partial size correspond to 210-1000 mesh in 0.001-0.07mm, are highly suitable as filler and prepare more good powder
Last coating.The main ingredient of red mud is Al2O3、Fe2O3、SiO2、TiO2, CaO etc., the hardness of these materials is relatively high, makes
The scratch resistance capability of the powdery paints come also can be more preferable, its color is the primary color of redness of the skin or complexion and powdery paints, not only
Covering power is good, and can also be used as the use of part pigment, reduces the cost of manufacture of powdery paints.
The compound system of the primary raw material polyester resin of outdoor powdery paints and filler (red mud) is macroscopically uneven
System is two-phase system, i.e., the multiple groups being made of filler (red mud) the continuous phase that the dispersed phase and resin of component are matrix
Fission system, and influence chemical constituent and resin circle that the adhesion strength between two-phase is that in resin microstructure on (red mud)
Interaction on face between chemical constituent.Therefore the key for promoting outdoor performance powder coating is that the outdoor powder of research applies
Each component interacts in Material system interfacial structure and region, because the interaction between two-phase is by between different material
Intermolecular force forms new chemical bond, acid-base function even polarity to carry out, and resin point in outdoor powder coating systems
Degree of scatter can also influence this active force to subchain orientation in the base with filler.It usually can will be in outdoor powder coating systems
The bonding state of filler and resin is divided into following a few classes: (1) simple mechanical mixture；(2) two-phase has relatively uniform physics mixed
It closes；(3) two alternate form new chemical bond by chemical reaction to making bond strength be significantly increased.Since resin generally shows
For hydrophobicity, and red mud surface is rich in a large amount of polar hydroxyl group, so that red mud is shown as alkalinity, hydrophilicity is strong, if by red
Mud necessarily causes to be combined weakness at two-phase interface with the simple physical mixed of resin, and compatibility is not high and red mud is caused to be reunited
Effect is easily broken off at fault in material in the case where stress is concentrated, therefore is surface-treated to red mud just seems ten in advance
Divide important.
Red mud main ingredient also contains Na2The attached liquid of O, pH value is 12.2 or more.Red mud is red since residual attached liquid alkalinity is strong
Great amount of hydroxy group is contained on mud surface, and directly unmodified red mud powder is filled into coating in this way, due to failing the matrix of reduction red mud
Middle reuniting effect, so that caking property, compatibility between unmodified red mud powder and other raw materials such as resin of outdoor powdery paints
And wetability is very poor, powdery paints film apparent property and gloss obtained are poor.Therefore it needs to carry out red mud except alkali, drop
Low ph value reduces surface hydroxyl, while needing to carry out surface to red mud to be modified, so that improving changed red mud and outdoor powdery paints
Other raw materials such as resin between caking property, compatibility and wetability, the powdery paints film apparent property prepared by
It is preferable with gloss, improve the quality of outdoor powdery paints.
In order to improve the caking property between changed red mud and other raw materials such as resin of outdoor powdery paints, compatibility and
Wetability, the present invention use fatty acid methyl ester ethoxylate sodium sulfonate, Coconut Fatty Acid Monoethanolamide sulfosuccinic acid monoesters two
Sodium carries out red mud surface, synergistic effect to be played in the two modification, and collaboration improves the apparent property of film of outdoor powdery paints
Energy and gloss；The reason is that: polyester resin is nonpolar, and great amount of hydroxy group is contained on unmodified red mud powder surface, therefore directly will not
It is poor that changed red mud powder is filled into open air powdery paints film apparent property and gloss obtained in polyester resin.Red mud fat
Sour methyl ester ethoxylates sodium sulfonate, Coconut Fatty Acid Monoethanolamide sulfosuccinic acid monoesters disodium carry out surface and are modified, due to rouge
Contain sulfonic group, oleic acid in fatty acid methyl esters ethoxylate sodium sulfonate, Coconut Fatty Acid Monoethanolamide sulfosuccinic acid monoesters disodium
Base, amino groups can make red mud particle surface introduce sulfonic group, oleic acid base, amino groups when modified, not only can be with
The dispersibility and processing fluidity of changed red mud powder are improved, so that other raw materials of modified red mud and outdoor powdery paints are such as poly-
Ester resin compatible is more preferable, improves outdoor powdery paints coating interface cohesive force, and then improves the film table of outdoor powdery paints
See performance and gloss.Red mud is added in polyester resin reuniting effect in the matrix that red mud can be effectively reduced after surface modification,
Caking property, compatibility and the wetability that can be effectively improved between polyester resin and changed red mud powder, to increase substantially family
Outer powdery paints film apparent property and gloss.
In order to improve flame retardant property and oxygen index (OI), red mud uses fatty acid methyl ester ethoxylate sodium sulfonate, coconut oil list
It is modified that Acid Ethanolamide Sulfosuccinates disodium carries out first step surface to red mud；Then the auspicious polydimethylsiloxanes of ammonia are used
Alkane, six pairs of three phosphonitriles of carboxyphenoxy ring carry out second to red mud and are modified, and play synergistic effect, improve outdoor powder
The oxygen index (OI) of coating, the reason is that: since the auspicious dimethyl silicone polymer of ammonia is hybrid inorganic-organic structure, contain silicon oxygen bond, ammonia
Base can introduce silicon oxygen bond, amino, when template is ignited, silicon oxygen in modified red mud particle surface for the first time when modified
Alkane fast transferring forms protective layer to specimen surface, to play the role of burning that is heat-insulated, oxygen-impermeable, and then preventing template；This
Outside, six pairs of three phosphonitriles of carboxyphenoxy ring make it have P-N synergistic effect, and the auspicious dimethyl silicone polymer of ammonia cooperates six pairs of carboxyl benzene
The use of three phosphonitrile of oxygroup ring, keeps the flame retardant effect of template more significant, to improve the oxygen index (OI) of template.
The present invention uses fatty acid methyl ester ethoxylate sodium sulfonate, Coconut Fatty Acid Monoethanolamide sulfosuccinic acid monoesters two
It is modified that sodium carries out first step surface to red mud；Then the auspicious dimethyl silicone polymer of ammonia, six pairs of three phosphonitriles of carboxyphenoxy ring are used
Red mud is carried out second modified, sulfonic group therein, oleic acid base, amino, silicon oxygen bond etc. are successfully connected to red mud particle surface,
Caking property, compatibility and the wetability between polyester resin and changed red mud powder are effectively improved, oxygen index (OI) is improved.
The polyester resin that the present invention uses is the polyester resin using trade mark CRYLCOAT 2437-2, which is a kind of
Carboxyl functionality polyester resin without TMA, manufactured open air powdery paints is non-blooming, and levelability is good, outdoor weathe resistance is good.
The TGIC curing agent that the present invention uses has good heat-resisting, mobility, weatherability, cementability and excellent height
Warm nature energy, have good decorative performance and it is anti-bake excessively it is yellowing.
The PV88 levelling agent that the present invention uses is the free flowable powdered levelling agent of white, and coating can be promoted dry
A smooth, smooth, uniform film is formed in dry film forming procedure, and film coated surface tension can be effectively reduced, improve its levelability
And uniformity, it can significantly reduce or remove substantially volcanic crater, pin hole and flake.
Outdoor powdery paints is producing and is being easy to produce bubble in use process, and largely stable bubble is unfavorable for coating material production
Go on smoothly with the film effect and performance when paint spraying, mainly there are two effects for TP-39 defoaming agent that the present invention uses:
1, inhibit the generation of bubble；2, accelerate vanishing for the bubble generated.It thus can achieve the effect of defoaming.
Polyester resin can be improved to the wetability of white carbon black, changed red mud in the 701B optical brightener that the present invention uses, and keeps away simultaneously
Exempt from the paint marketings such as pin hole and shrinkage cavity occur, moreover it is possible to play the role of helping levelling, hence it is evident that appearance of film is improved, to make coating
Obtain preferable flatness and gloss.
The problems such as styrax that the present invention uses can eliminate the pin hole generated during powder coating solidification, shrinkage cavity, bubble.
Benzoic presence makes moisture and solvent micro in powdery paints accelerate gasification discharge, before powdery paints not yet solidifies
It is all drained, to avoid the generation of stomata, improve coating property.
The white carbon black that the present invention uses can be used as loose flowable in powdery paints, prevent from agglomerating and improving spraying effect
Rate, white carbon black have thixotropic property, a small amount of white carbon black are added in coating, and coating can be made to eliminate droplet settling phenomenon.
The wax powder that the present invention uses be distributed in film coated surface protect whereby film, prevent from scratching, abrade and providing it is wear-resistant
Property；In addition the presence of wax powder makes the better wetability of white carbon black, changed red mud, to keep the levelability of powdery paints more preferable.
In order to be further illustrated to the present invention, it is allowed to open abundant, more specific embodiment is described below.
The red mud used in the embodiment of the present invention and comparative example is the Bayer process red mud provided by Guangxi Chinalco,
Main component and its shared mass percent are to be shown in Table 1, through detecting, pH value 12.5.
1 red mud main chemical compositions table of table
| Ingredient | CaO | SiO2 | Fe2O3 | Al2O3 | TiO2 | Na2O |
| Content (%) | 15.34 | 8.10 | 42.86 | 16.09 | 7.39 | 3.46 |
Implement 1
A kind of preparation method of changed red mud powder, comprising the following steps:
(1) it is 8.9 by sulfuric acid washing to the pH value that red mud is 13wt% with concentration, water then is carried out to the red mud after pickling
It washes, red mud filters pressing after detection pH value is 8.1 is processed into clean red mud after washing, and clean red mud drying to water content is
4.6%；
(2) cleaning red mud made from step (1) is subjected to super fine powder, the clean red mud of 300 mesh is formed more widely than after sieving
Powder；
(3) composite modifier a is added into cleaning red mud powder made from step (2), the composite modifier a is by fat
Sour methyl ester ethoxylates sodium sulfonate, Coconut Fatty Acid Monoethanolamide sulfosuccinic acid monoesters disodium composition, the composite modifier a
Additional amount be the 2.1% of clean red mud powder quality, the fatty acid methyl ester ethoxylate sodium sulfonate, coconut oil monoethanol
The mass ratio of amide sulfosuccinic acid monoesters disodium is 3.6:9.1, controlled at 80-83 DEG C, and with the speed of 800r/min
33min is stirred, mixture a is made；
(4) mixture a made from step (3) and composite modifier b are added to the mixer, the composite modifier b by
The auspicious dimethyl silicone polymer of ammonia, six pairs of three phosphonitrile of carboxyphenoxy ring compositions, the additional amount of the composite modifier b are clean red
The 3.3% of mud powder quality, the auspicious dimethyl silicone polymer of the ammonia, six pairs of three phosphonitriles of carboxyphenoxy ring mass ratio be 2.9:
5.7, controlled at 96-102 DEG C, 41min is stirred with the speed of 1000r/min, mixture b is made；
(5) by mixture b made from step (4) be 43-46 DEG C in temperature at dry to water content be 1.2%, then into
Row super fine powder is formed more widely than the changed red mud powder of 300 mesh after sieving.
A kind of open air powdery paints, the raw material including following mass percents: changed red mud powder 44.6%, polyester resin
48.1%, curing agent 3.8%, levelling agent 0.5%, defoaming agent 0.7%, optical brightener 1.1%, styrax 0.5%, white carbon black
0.3%, wax powder 0.4%.
The polyester resin is CRYLCOAT 2437-2 polyester resin.
The curing agent is TGIC curing agent.
The levelling agent is PV88 levelling agent.
The defoaming agent is TP-39 defoaming agent.
The optical brightener is 701B optical brightener.
The preparation method of above-mentioned open air powdery paints, includes the following steps
(1) raw material mix: all kinds of raw materials being carried out ingredient by above-mentioned mass percent, are then respectively adding mixing machine
In, then precrushing 1min, then remixes 4min, and uniformly mixed raw material is made；
(2) melting extrusion: the raw material being uniformly mixed made from step (1) is put into extruder, I area's temperature of Jing is
105 DEG C, II area's temperature is melting extrusion, tabletting, cooling at 110 DEG C, is then broken into sheet stock；
(3) grind: by broken sheet stock in step (2), being placed in ACM flour mill and be milled, through cyclonic separation and
After screening, it is formed more widely than the outdoor powdery paints finished product of 200 mesh, sees Fig. 1.
Implement 2
A kind of preparation method of changed red mud powder, comprising the following steps:
(1) it is 8.7 by sulfuric acid washing to the pH value that red mud is 16wt% with concentration, water then is carried out to the red mud after pickling
It washes, red mud filters pressing after detection pH value is 7.8 is processed into clean red mud after washing, and clean red mud drying to water content is
3.9%；
(2) cleaning red mud made from step (1) is subjected to super fine powder, the clean red mud of 300 mesh is formed more widely than after sieving
Powder；
(3) composite modifier a is added into cleaning red mud powder made from step (2), the composite modifier a is by fat
Sour methyl ester ethoxylates sodium sulfonate, Coconut Fatty Acid Monoethanolamide sulfosuccinic acid monoesters disodium composition, the composite modifier a
Additional amount be the 2.4% of clean red mud powder quality, the fatty acid methyl ester ethoxylate sodium sulfonate, coconut oil monoethanol
The mass ratio of amide sulfosuccinic acid monoesters disodium is 5.2:8.7, controlled at 80-84 DEG C, and with the speed of 1000r/min
27min is stirred, mixture a is made；
(4) mixture a made from step (3) and composite modifier b are added to the mixer, the composite modifier b by
The auspicious dimethyl silicone polymer of ammonia, six pairs of three phosphonitrile of carboxyphenoxy ring compositions, the additional amount of the composite modifier b are clean red
The 4.1% of mud powder quality, the auspicious dimethyl silicone polymer of the ammonia, six pairs of three phosphonitriles of carboxyphenoxy ring mass ratio be 3.5:
6.4, controlled at 102-105 DEG C, 36min is stirred with the speed of 1200r/min, mixture b is made；
(5) by mixture b made from step (4) be 43-45 DEG C in temperature at dry to water content be 1.1%, then into
Row super fine powder is formed more widely than the changed red mud powder of 300 mesh after sieving.
A kind of open air powdery paints, the raw material including following mass percents: changed red mud powder 46.3%, polyester resin
47.1%, curing agent 3.9%, levelling agent 0.6%, defoaming agent 0.7%, optical brightener 0.5%, styrax 0.4%, white carbon black
0.2%, wax powder 0.3%.
The polyester resin is CRYLCOAT 2437-2 polyester resin.
The curing agent is TGIC curing agent.
The levelling agent is PV88 levelling agent.
The defoaming agent is TP-39 defoaming agent.
The optical brightener is 701B optical brightener.
The preparation method of above-mentioned open air powdery paints, includes the following steps
(1) raw material mix: all kinds of raw materials being carried out ingredient by above-mentioned mass percent, are then respectively adding mixing machine
In, then precrushing 1min, then remixes 4min, and uniformly mixed raw material is made；
(2) melting extrusion: the raw material being uniformly mixed made from step (1) is put into extruder, I area's temperature of Jing is
105 DEG C, II area's temperature is melting extrusion, tabletting, cooling at 110 DEG C, is then broken into sheet stock；
(3) grind: by broken sheet stock in step (2), being placed in ACM flour mill and be milled, through cyclonic separation and
After screening, the outdoor powdery paints finished product for being formed more widely than 200 mesh is shown in Fig. 2.
Implement 3
A kind of preparation method of changed red mud powder, comprising the following steps:
(1) it is 9.1 by sulfuric acid washing to the pH value that red mud is 17wt% with concentration, water then is carried out to the red mud after pickling
It washes, red mud filters pressing after detection pH value is 8 is processed into clean red mud after washing, and clean red mud drying to water content is 4.3%；
(2) cleaning red mud made from step (1) is subjected to super fine powder, the clean red mud of 300 mesh is formed more widely than after sieving
Powder；
(3) composite modifier a is added into cleaning red mud powder made from step (2), the composite modifier a is by fat
Sour methyl ester ethoxylates sodium sulfonate, Coconut Fatty Acid Monoethanolamide sulfosuccinic acid monoesters disodium composition, the composite modifier a
Additional amount be the 2.6% of clean red mud powder quality, the fatty acid methyl ester ethoxylate sodium sulfonate, coconut oil monoethanol
The mass ratio of amide sulfosuccinic acid monoesters disodium is 2.9:9.1, controlled at 78-82 DEG C, and with the speed of 900r/min
31min is stirred, mixture a is made；
(4) mixture a made from step (3) and composite modifier b are added to the mixer, the composite modifier b by
The auspicious dimethyl silicone polymer of ammonia, six pairs of three phosphonitrile of carboxyphenoxy ring compositions, the additional amount of the composite modifier b are clean red
The 4.2% of mud powder quality, the auspicious dimethyl silicone polymer of the ammonia, six pairs of three phosphonitriles of carboxyphenoxy ring mass ratio be 3.2:
6.7, controlled at 97-103 DEG C, 39min is stirred with the speed of 1100r/min, mixture b is made；
(5) by mixture b made from step (4) be 43-46 DEG C in temperature to dry to water content be 1%, then carry out
Super fine powder is formed more widely than the changed red mud powder of 300 mesh after sieving.
A kind of open air powdery paints, the raw material including following mass percents: changed red mud powder 47.2%, polyester resin
45.4%, curing agent 4.1%, levelling agent 0.8%, defoaming agent 0.5%, optical brightener 0.7%, styrax 0.6%, white carbon black
0.3%, wax powder 0.4%.
The polyester resin is CRYLCOAT 2437-2 polyester resin.
The curing agent is TGIC curing agent.
The levelling agent is PV88 levelling agent.
The defoaming agent is TP-39 defoaming agent.
The optical brightener is 701B optical brightener.
The preparation method of above-mentioned open air powdery paints, includes the following steps
(1) raw material mix: all kinds of raw materials being carried out ingredient by above-mentioned mass percent, are then respectively adding mixing machine
In, then precrushing 1min, then remixes 4min, and uniformly mixed raw material is made；
(2) melting extrusion: the raw material being uniformly mixed made from step (1) is put into extruder, I area's temperature of Jing is
105 DEG C, II area's temperature is melting extrusion, tabletting, cooling at 110 DEG C, is then broken into sheet stock；
(3) grind: by broken sheet stock in step (2), being placed in ACM flour mill and be milled, through cyclonic separation and
After screening, it is formed more widely than the outdoor powdery paints finished product of 200 mesh, sees Fig. 3.
Comparative example 1
The preparation process of outdoor powdery paints preparation process and embodiment 2 are essentially identical, have only the difference is that changing in preparation
Only carry out the modification of step (4) in property red mud powder, and the modification without step (3).
Comparative example 2
The preparation process of outdoor powdery paints preparation process and embodiment 2 are essentially identical, have only the difference is that changing in preparation
Composite modifier a used in property red mud powder lacks fatty acid methyl ester ethoxylate sodium sulfonate.
Comparative example 3
The preparation process of outdoor powdery paints preparation process and embodiment 2 are essentially identical, have only the difference is that changing in preparation
Composite modifier a used in property red mud powder lacks Coconut Fatty Acid Monoethanolamide sulfosuccinic acid monoesters disodium.
Comparative example 4
The preparation process of outdoor powdery paints preparation process and embodiment 2 are essentially identical, have only the difference is that changing in preparation
Only carry out the modification of step (3) in property red mud powder, and the modification without step (4).
Comparative example 5
The preparation process of outdoor powdery paints preparation process and embodiment 2 are essentially identical, have only the difference is that changing in preparation
Composite modifier b used in property red mud powder lacks the auspicious dimethyl silicone polymer of ammonia.
Comparative example 6
The preparation process of outdoor powdery paints preparation process and embodiment 2 are essentially identical, have only the difference is that changing in preparation
Composite modifier b used in property red mud powder lacks six pairs of three phosphonitriles of carboxyphenoxy ring.
Comparative example 7
The preparation process of outdoor powdery paints preparation process and embodiment 2 are essentially identical, have only the difference is that changing in preparation
Without the modification of step (3) and step (4) in property red mud powder.
Comparative example 8
Using a kind of Chinese patent application document " outdoor TEXTURE POWDER COATING and its production method with metal-like
The technique of (patent No.: ZL201510622727.8) " embodiment 1 prepares outdoor powdery paints.
Comparative example 9
Using a kind of Chinese patent application document " outdoor TEXTURE POWDER COATING and its production method with metal-like
The technique of (patent No.: ZL201510622727.8) " embodiment 1 prepares outdoor powdery paints, has only the difference is that therein
Filler (kaolin, blanc fixe) such as changes made of embodiment 2 at the changed red mud of weight.
Performance detection:
The preparation of paint coatings: the outdoor powdery paints of embodiment 1-3 and comparative example 1-7 are sprayed on using electrostatic gun
On cold-rolled steel sheet after surface treated, the thickness of film is almost the same, solidifies through 200 DEG C/10min, obtains corresponding to and implement
The paint coatings of example 1-3 and comparative example 1-7.
Coating Indexs measure foundation: GB/T 21776-2008 " the examination criteria guide of powdery paints and its coating "；Implement
The template oxygen index (OI) detection foundation that example 1-3 and comparative example 1-7 is obtained: GB 8624-2012 " construction material and product burns performance
Classification ".
The coating testing result of embodiment 1-3 and comparative example 1-7 is as shown in table 2.
The coating testing result table of table 2 embodiment 1-3 and comparative example 1-7
| Experimental project | Film is apparent | Gloss (60 ° of angles) | Oxygen index (OI) (%) |
| Embodiment 1 | It is smooth | 90.8 | 36.4 |
| Embodiment 2 | It is smooth | 93.7 | 39.1 |
| Embodiment 3 | It is smooth | 91.6 | 35.2 |
| Comparative example 1 | It is coarse | 68.5 | 33.7 |
| Comparative example 2 | It is substantially smooth | 81.3 | 34.6 |
| Comparative example 3 | It is substantially smooth | 84.6 | 34.1 |
| Comparative example 4 | It is substantially smooth | 89.4 | 23.9 |
| Comparative example 5 | It is substantially smooth | 87.9 | 32.1 |
| Comparative example 6 | It is substantially smooth | 88.7 | 33.5 |
| Comparative example 7 | It is coarse | 61.4 | 21.6 |
As shown in Table 2: (1) by embodiment 2 and the data of comparative example 1-3 as it can be seen that fatty acid methyl ester ethoxylate sulfonic acid
Sodium, Coconut Fatty Acid Monoethanolamide sulfosuccinic acid monoesters disodium play synergistic effect in red mud is modified, and collaboration improves family
The film apparent property and gloss of outer powdery paints；This is:
Polyester resin is nonpolar, and great amount of hydroxy group is contained on unmodified red mud powder surface, therefore directly by unmodified red mud
It is poor that powder is filled into open air powdery paints film apparent property and gloss obtained in polyester resin.Red mud fatty acid methyl ester second
Oxygroup compound sodium sulfonate, Coconut Fatty Acid Monoethanolamide sulfosuccinic acid monoesters disodium carry out surface and are modified, due to fatty acid methyl ester
Contain sulfonic group, oleic acid base, amino etc. in ethoxylate sodium sulfonate, Coconut Fatty Acid Monoethanolamide sulfosuccinic acid monoesters disodium
Group can make red mud particle surface introduce sulfonic group, oleic acid base, amino groups when modified, modification not only can be improved
The dispersibility and processing fluidity of red mud powder, so that other raw materials such as polyester resin phase of modified red mud and outdoor powdery paints
Capacitive is more preferable, improves outdoor powdery paints coating interface cohesive force, so improve outdoor powdery paints film apparent property and
Gloss.Red mud is added in polyester resin reuniting effect in the matrix that red mud can be effectively reduced after surface modification, can effectively be changed
Caking property, compatibility and wetability between kind polyester resin and changed red mud powder apply to increase substantially outdoor powder
Expect film apparent property and gloss.
(2) by embodiment 2 and the data of comparative example 4-6 as it can be seen that the auspicious dimethyl silicone polymer of ammonia, six pairs of carboxyphenoxy rings
Three phosphonitriles play synergistic effect in red mud is modified, improve the oxygen index (OI) of outdoor powdery paints, this is:
It, can when modified containing silicon oxygen bond, amino since the auspicious dimethyl silicone polymer of ammonia is hybrid inorganic-organic structure
Silicon oxygen bond, amino, when template is ignited, siloxanes fast transferring to sample are introduced in modified red mud particle surface for the first time
Plate surface forms protective layer, to play the role of burning that is heat-insulated, oxygen-impermeable, and then preventing template；In addition, six pairs of carboxyl benzene
Three phosphonitrile of oxygroup ring makes it have P-N synergistic effect, and the auspicious dimethyl silicone polymer of ammonia cooperates six pairs of three phosphonitriles of carboxyphenoxy ring
Use, keep the flame retardant effect of template more significant, to improve the oxygen index (OI) of template.
(3) by the data of embodiment 1-3 as it can be seen that embodiment 2 is optimum embodiment；By the number of embodiment 1-3 and comparative example 7
According to as it can be seen that using open air powdery paints made of modified red mud, film apparent property and gloss, oxygen index (OI), which have, significantly to be mentioned
Height, this is:
The present invention uses fatty acid methyl ester ethoxylate sodium sulfonate, Coconut Fatty Acid Monoethanolamide sulfosuccinic acid monoesters two
It is modified that sodium carries out first step surface to red mud；Then the auspicious dimethyl silicone polymer of ammonia, six pairs of three phosphonitriles of carboxyphenoxy ring are used
Red mud is carried out second modified, sulfonic group therein, oleic acid base, amino, silicon oxygen bond etc. are successfully connected to red mud particle surface,
Caking property, compatibility and the wetability in powdery paints between polyester resin and changed red mud powder are effectively improved, to make
Film apparent property and gloss, oxygen index (OI) are significantly increased.
In addition from the data of embodiment 1-3 and comparative example 7 as it can be seen that using open air powdery paints ratio made of modified red mud
Using open air powdery paints made of unmodified red mud, film apparent property is improved, and gloss, oxygen index (OI) at least improve respectively
47.88% and 62.96%.
To the impact resistance of open air powdery paints made from embodiment 1-3 and comparative example 8,9, adhesive force, acid resistance, resistance to people
Work weathering aging is detected, and wherein impact resistance is detected using GB/T1732-19；Adhesive force uses GB/T9286-
1998 are detected；Acid resistance is detected using GB/T9274-1988 first method；Resistance to artificial weathering aging uses GB/T1865-
It operates formula A in 1997 tables 3 to carry out, evaluation is carried out by GB/T1766-1995, as a result as shown in table 3 below.
The performance test results table of open air powdery paints made from 3 embodiment 1-3 of table and comparative example 8,9
As shown in Table 3:
(1) outdoor powdery paints impact resistance of the invention is 68-81kg/cm, is improved extremely than the prior art (comparative example 8)
Few 25.93%；Adhesive force is that 0 grade and the prior art (comparative example 8) are on close level；Acid resistance is that 323-376h is without exception, than existing
There is technology (comparative example 8) to improve at least 33.47%；Resistance to artificial weathering aging is 1562-1704h without dusting, blisters, cracks, stripping
It the abnormal phenomenon such as falls, improves at least 55.73% than the prior art (comparative example 8), it is seen that outdoor performance powder coating of the invention
It is excellent and be better than the prior art (comparative example 8).
(2) from the data of comparative example 9 and comparative example 8 as it can be seen that changing in the case where filler difference using made of the present invention
Property red mud is remarkably improved impact resistance and weatherability as filler.
(3) present invention is filled into the outdoor powdery paints of preparation, loading is up to by modified to red mud as filler
44.6% or more, for the fillers such as conventional barium sulfate, not only filling capacity is good, but also loading is high, can have significantly
Effect reduce production cost (in the prior art, resin content is generally no less than 50%, and amount of filler is usually no more than 40%, such as
The patent of application number 201510622727.8,201310222062.2,201610963019.5, otherwise levelability and other performances
It is all bad.And resin content of the present invention 48.1% hereinafter, amount of filler is up to 44.6% or more, in addition the present invention is using discarded
Red mud is as raw material, and by the modified changed red mud that obtains as filler, extremely low due to buying discarded red mud cost, preparation is modified
Red mud filler cost is much smaller than conventional fillers barium sulfate, about less 1320 yuan/ton or more, reduces additionally, due to amount of resin, because
This, the production cost for preparing outdoor powdery paints can be effectively reduced significantly.).
(4) by the data of embodiment 1-3 it is found that the embodiment of the present invention 2 is optimum embodiment, when modification is red in embodiment 2
When mud loading is 46.3%, the comprehensive performance that outdoor powdery paints obtains is optimal, and wherein impact resistance is 81kg/cm, attachment
Power is 0 grade, and acid resistance is that 359h is without exception, and resistance to artificial weathering aging is 1704h without dusting, is blistered, cracking, and peeling etc. is abnormal existing
As this provides foundation to seek most preferably to produce outdoor powder coating technology.
The above content is it cannot be assumed that present invention specific implementation is only limited to these instructions, for the technical field of the invention
Those of ordinary skill for, under the premise of not departing from present inventive concept, a number of simple deductions or replacements can also be made, all answers
When being considered as belonging to present invention scope of patent protection determined by the appended claims.
Claims (10)
1. a kind of preparation method for the outdoor powdery paints that can effectively reduce cost, which comprises the following steps:
(1) raw material mix: by changed red mud powder, polyester resin, curing agent, levelling agent, defoaming agent, optical brightener, styrax, white
Carbon black, wax powder carry out ingredient by mass percentage, are then respectively adding in mixing machine, then precrushing, then remix, and are made
Uniformly mixed raw material；
(2) melting extrusion: the raw material being uniformly mixed made from step (1) is put into extruder, through melting extrusion, tabletting, cold
But, then it is broken into sheet stock；
(3) it grinds: by broken sheet stock in step (2), being placed in flour mill and be milled, after cyclonic separation and screening,
Indoor powdery paints is made.
2. the preparation method of the outdoor powdery paints according to claim 1 that can effectively reduce cost, which is characterized in that step
Suddenly the preparation method of changed red mud powder described in (1), comprising the following steps:
1) it is 8.6-9.1 by sulfuric acid washing to the pH value that red mud is 12-18wt% with concentration, then the red mud after pickling is carried out
Washing, red mud filters pressing after detection pH value is 7.8-8.2 is processed into clean red mud, clean red mud drying to water content after washing
≤ 4.7%；
2) cleaning red mud made from step 1) is subjected to super fine powder, cleaning red mud powder is made after sieving；
3) composite modifier a is added into cleaning red mud powder made from step 2), the composite modifier a is by fatty acid methyl ester
Ethoxylate sodium sulfonate, Coconut Fatty Acid Monoethanolamide sulfosuccinic acid monoesters disodium composition, the addition of the composite modifier a
1.8-2.7% of the amount for clean red mud powder quality, the fatty acid methyl ester ethoxylate sodium sulfonate, coconut oil monoethanol acyl
The mass ratio of amine sulfosuccinic acid monoesters disodium is 2.6-5.4:7.8-9.2, controlled at 78-84 DEG C, and with 800-
The speed of 1000r/min stirs 26-34min, and mixture a is made；
4) mixture a made from step 3) and composite modifier b are added to the mixer, the composite modifier b is auspicious poly- by ammonia
Dimethyl siloxane, six pairs of three phosphonitrile of carboxyphenoxy ring compositions, the additional amount of the composite modifier b are clean red mud powder
The 3.2-4.3% of quality, the auspicious dimethyl silicone polymer of the ammonia, six pairs of three phosphonitriles of carboxyphenoxy ring mass ratio be 2.8-
3.7:5.2-7.6 stirs 35-43min with the speed of 1000-1200r/min, mixture is made controlled at 96-105 DEG C
b；
5) by mixture b made from step 4) temperature be 43-48 DEG C at dry to water content≤1.2%, then carry out ultra-fine
Changed red mud powder is made in milling after sieving.
3. the preparation method of the outdoor powdery paints according to claim 1 that can effectively reduce cost, which is characterized in that step
Suddenly polyester resin described in (1) is CRYLCOAT 2437-2 polyester resin.
4. the preparation method of the outdoor powdery paints according to claim 1 that can effectively reduce cost, which is characterized in that step
Suddenly curing agent described in (1) is TGIC curing agent.
5. the preparation method of the outdoor powdery paints according to claim 1 that can effectively reduce cost, which is characterized in that step
Suddenly levelling agent described in (1) is PV88 levelling agent.
6. the preparation method of the outdoor powdery paints according to claim 1 that can effectively reduce cost, which is characterized in that step
Suddenly defoaming agent described in (1) is TP-39 defoaming agent.
7. the preparation method of the outdoor powdery paints according to claim 1 that can effectively reduce cost, which is characterized in that step
Suddenly optical brightener described in (1) is 701B optical brightener.
8. the preparation method of the outdoor powdery paints according to claim 1 that can effectively reduce cost, which is characterized in that step
Suddenly the time of precrushing is 1min in (1).
9. the preparation method of the outdoor powdery paints according to claim 1 that can effectively reduce cost, which is characterized in that step
Suddenly the time remixed in (1) is 4min.
10. the preparation method of the outdoor powdery paints according to claim 1 that can effectively reduce cost, which is characterized in that
The temperature of melting extrusion is 105-110 DEG C in step (2), wherein I area's temperature is 105 DEG C, II area's temperature is 110 DEG C.
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| CN104387927A (en) * | 2014-10-31 | 2015-03-04 | 安徽神剑新材料股份有限公司 | Powder coating |
| CN105969109A (en) * | 2016-06-27 | 2016-09-28 | 广西平果宝信涂料有限公司 | Super-weather-resistant polyester type powder coating and preparation method thereof |
| CN106433414A (en) * | 2016-08-31 | 2017-02-22 | 苏州翰晨商贸有限公司 | Outdoor highlight powdery paint |
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| JPH05139727A (en) * | 1991-11-22 | 1993-06-08 | Kawai Kaken Kogyo:Yugen | Method for utilizing red mud produced in aluminum refining process |
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| CN104387927A (en) * | 2014-10-31 | 2015-03-04 | 安徽神剑新材料股份有限公司 | Powder coating |
| CN105969109A (en) * | 2016-06-27 | 2016-09-28 | 广西平果宝信涂料有限公司 | Super-weather-resistant polyester type powder coating and preparation method thereof |
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