CN110373076A - A kind of environment protecting building paint and preparation method of photocatalytic degradation haze precursor - Google Patents
A kind of environment protecting building paint and preparation method of photocatalytic degradation haze precursor Download PDFInfo
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- CN110373076A CN110373076A CN201910628220.1A CN201910628220A CN110373076A CN 110373076 A CN110373076 A CN 110373076A CN 201910628220 A CN201910628220 A CN 201910628220A CN 110373076 A CN110373076 A CN 110373076A
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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
- C09D143/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing boron, silicon, phosphorus, selenium, tellurium, or a metal; Coating compositions based on derivatives of such polymers
- C09D143/04—Homopolymers or copolymers of monomers containing silicon
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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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
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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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
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- 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/65—Additives macromolecular
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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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/70—Additives characterised by shape, e.g. fibres, flakes or microspheres
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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
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
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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
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
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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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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Abstract
The invention belongs to technical field of coatings, and in particular to a kind of environment protecting building paint and preparation method of photocatalytic degradation haze precursor.The present invention is by the way that zinc oxide to be carried on inside γ-aluminum oxyhydroxide tiny balloon, its principle is using cetyl trimethylammonium bromide as pattern controlling agent, through hydrothermal synthesis γ as made of nanometer sheet self assembly-aluminum oxyhydroxide hierarchical structure tiny balloon, the microballoon possesses the hydroxyl exposure of very high percentage, it is active high, it is easy to be bonded with polyethers institute with Amino End Group, and by being closely assembled into spherical shape by spraying, overcome nano-photocatalyst be difficult in coating it is evenly dispersed, it is easy to the defect reunited, it can effectively avoid simultaneously and shedding phenomenon occur in coating, prolong the service life, improve the degradation efficiency of haze organic precursors.
Description
Technical field
The invention belongs to technical field of coatings, and in particular to a kind of environment protecting building paint of photocatalytic degradation haze precursor
And preparation method.
Background technique
With Chinese national economy sustainable growth and the continuous improvement of living standards of the people, environmental protection has become a kind of people and chases after
Seek the theme of healthy green living.And as coating requirement of the people to indoor exterior decoration is higher and higher, more people are selecting
During selecting functional coating, anti-fog haze environment-friendly type coating is considered emphatically, more and more people, which pursue, " gets close to nature, big gloomy
Fresh air as woods ", therefore, researching and developing, there is the coating of anti-fog haze effect to have great importance.
In recent years, haze pollution and indoor air quality issues were increasingly serious, and volatile organic contaminant (VOCs) is made
For one of the primary pollution source that haze and room atmosphere pollute, the extensive concern of people is also therefore received.Have and some passes through light
Catalysis reaction reaches the atmospheric cleaning exterior coating of purification air, as a kind of environment-friendly type photocatalysis exterior wall of Shanghai university application applies
Material and preparation method thereof (application No. is 200310109272.7) discloses a kind of atmospheric cleaning photocatalystic outer wall coating and its system
Preparation Method.Belong to construction material manufacturing process technology field.It is characterized in that using inorganic/organic composite emulsion as film forming matter,
By photochemical catalyst TiO2It is dispersed therein in the form of functional stuffing, then is aided with auxiliary agent and other functional additives, preparation one
The Environmental Protective Water-paint of kind normal temperature cure.Wherein photochemical catalyst be mainly made of single Anatase or by Anatase and
The titanium dioxide of Rutile Type mixing phase composition, surface coat different oxides to meet the needs of different systems, i.e. surface changes
The titanium dioxide of property.But this coating producing process is special, expensive, and used TiO2Catalyst can only be in ultraviolet light
Irradiation under the polluter that could effectively degrade in atmosphere, therefore it is universal to cannot get market.Therefore, it is difficult to carry out large area at present
Except haze.
In addition, application No. is 201710788580.9 patent applications to disclose a kind of automatic absorbing haze coating, existing
On the basis of having coating, it is added surfactant-modified existing coating, the mass ratio of surfactant and coating is 1:1~1:
100, according to the environmental condition of location, pH is adjusted, coating surface can increase, to adsorb haze.It is used in the present invention
Surfactant can be cationic surface active agent, anionic surfactant, nonionic surface active agent.It uses
Coating can for the building coatings such as solvent based coating, high solid coating, no-solvent type coating, water paint, powdery paints,
Industrial coating and maintenance paint.The pH value of the adjustment coating such as acid, alkali can be added in adjustment surface.But the Paint preparation technology is multiple
It is miscellaneous, it is unable to mass market, and easily affected by environment, service life is not grown.
As it can be seen that the application efficiency in concrete of the catalyst for photocatalysis Decomposition haze in the prior art is low, outside
It is applied in coating and is easy failure and falls off, and when being used for coating, there are easy to reunite, low efficiencys, easy the disadvantages of being lost.
Summary of the invention
For current photocatalysis Decomposition haze catalyst be used for coating when, there are easy to reunite, low efficiency, easy shedding etc. lack
Point, the present invention propose the environment protecting building paint and preparation method of a kind of photocatalytic degradation haze precursor.
In order to achieve the above first purpose, a kind of environment-friendly type building painting of photocatalytic degradation haze precursor of the invention
The preparation method of material includes the following steps:
(1) it using aluminum sulfate, urea and cetyl trimethylammonium bromide as raw material, is dissolved in distilled water, stirs to get after mixing
The precursor liquid that mass concentration is 30~60%；Photocatalyst of zinc oxide is added in gained precursor liquid, high pressure hydro-thermal reaction is then moved to
In kettle, 16~36h of hydro-thermal reaction, is cooled to room temperature after the reaction was completed at 150~180 DEG C, and centrifugation collects sediment, then
Successively with dehydrated alcohol, distillation water washing precipitate, dry, natural cooling obtains the nanometer sheet self assembly of high hydroxyl exposure
Made of γ-aluminum oxyhydroxide tiny balloon, and tiny balloon internal load has photocatalyst of zinc oxide；
(2) the tiny balloon load photocatalyst of zinc oxide and amine terminated polyether polyalcohol, polyisocyanates obtained step (1)
Mixing, is warming up to 50-60 DEG C of 10~15h of reaction, is then spray-dried, the polyurethane/γ assembled-hydroxyl oxidation
Aluminium/zinc oxide spherical particle；
(3) polyurethane/γ-aluminum oxyhydroxide/zinc oxide spherical particle that step (2) is prepared and nano silica,
Nanometer wollastonite, precipitated calcium carbonate, defoaming agent, dispersing agent, coalescing agent, organic pigment, water are added in high speed disperser, are mixed
Slurry is made in conjunction；Silicone modified acrylic resin and the slurry are uniformly mixed again, thickener is added, stirs 1~3h to get institute
State can photocatalytic degradation haze precursor environment protecting building paint.
Photocatalysis oxidation technique has that oxidability is strong, energy-efficient, simple process, and it is excellent to generate secondary pollution etc.
Point, is widely used in the processing of organic wastewater, is especially difficult to biodegradable organic matter.Photocatalysis oxidation technique simultaneously
For indoor air purification.By light-catalyzed reaction, organic matter can be made to be converted to H2O、CO2, sulfate ion, nitrate anion from
The inorganic molecules such as son, phosphate anion, and then achieve the purpose that completely inorganization.Common photochemical catalyst is mainly some half
Conductor material, such as TiO2、ZnO、Cds、WO3、Fe2O3Deng.
Wherein, ZnO is as a kind of semiconductor material, its forbidden bandwidth is about 3.37eV at room temperature, is less than 378nm in wavelength
Ultraviolet light under, can be generated photohole-electronics pair, and photohole has oxidisability, therefore ZnO is urged with light
The property changed, and have the characteristics that cheap and easy to get, nontoxic and pollution-free.Therefore, the preferential selective oxidation zinc of photochemical catalyst of the present invention.
The mass ratio of aluminum sulfate, urea and cetyl trimethylammonium bromide and photocatalyst of zinc oxide is to lithium sulphur electricity
The quality of pond graphene composite sulfur positive plate be also it is most important, the variation of proportion between each component, obtained product quality can
It can be very well, it is also possible to it is very poor, it finds after study, when the mass ratio of aluminum sulfate, urea and cetyl trimethylammonium bromide is 8
The property of product when the mass ratio of~10:10~12:30~35 and photocatalyst of zinc oxide and precursor liquid is 5~10:60~75
It can be preferably.Therefore, it is further preferred that the mass ratio of step (1) aluminum sulfate, urea and cetyl trimethylammonium bromide
For 8~10:10~12:30~35；The mass ratio of the photocatalyst of zinc oxide and precursor liquid is 5~10:60~75.
The present invention is using aluminum sulfate as silicon source, using urea as pore-foaming agent, controls by pattern of cetyl trimethylammonium bromide
Agent, photocatalyst of zinc oxide, after mixing, by hydro-thermal reaction, so that aluminum sulfate formation γ-aluminum oxyhydroxide is hollow micro-
Ball, and make tiny balloon internal load have photocatalyst of zinc oxide in water-heat process, obtain tiny balloon load zinc oxide
Photochemical catalyst.
It is further preferred that the temperature of step (1) described hydro-thermal reaction is 160 DEG C, the reaction time is for 24 hours.
It is further preferred that the number of step (1) dehydrated alcohol, distillation water washing precipitate is respectively 3~5 times,
Washing removes the impurity such as unreacted urea, aluminum sulfate in reaction process, it is ensured that it is empty to obtain the higher γ of purity-aluminum oxyhydroxide
Heart microballoon.
Spray drying refers to that through mechanism, the material that will need to be dried is dispersed into the very thin particle as mist,
(increasing moisture disengagement area, accelerate drying process) and hot air, most of moisture is removed, make in moment in material
Solid matter is dried to powder.Spray drying is broadly divided into (1) pressure spray dryer method；(2) centrifugal spray drying method；(3) gas
Three kinds of flow type spray seasoning.Present invention spray drying is without limiting specific drying means, three kinds of drying means when practical application
?.
It is further preferred that step (2) tiny balloon load photocatalyst of zinc oxide and amine terminated polyether polyalcohol,
The mass ratio of polyisocyanates are as follows: 5~15:35~50:40~60.
It is further preferred that step (3) polyurethane/γ-aluminum oxyhydroxide/zinc oxide spherical particle and nano-silica
SiClx, nanometer wollastonite, precipitated calcium carbonate, defoaming agent, dispersing agent, coalescing agent, organic pigment, water mass ratio are as follows: 5-10:
2~8:5~15:6~15:2~5:2~8:7~10:3~8:50~60.
It is further preferred that step (3) defoaming agent be dimethicone, tributyl phosphate, in silicone emulsion extremely
Few one kind；The dispersing agent is at least one of oxidized polyethylene wax, calgon, alkyl phenol polyoxyethylene ether；It is described
Coalescing agent is at least one of propandiol butyl ether, alcohol ester 12, propylene glycol methyl ether acetate, benzoglycols；It is described organic
Pigment is at least one of metal azo pigments, heterocyclic pigment, condensed ring ketone pigment, phthalocyanine pigment.
It is further preferred that 10~20:50 of mass ratio of step (3) silicone modified acrylic resin, slurry, thickener
~75:3~10；The thickener is at least one of aluminium-magnesium silicate, sodium carboxymethylcellulose.
A second object of the present invention is to provide a kind of environment protecting building paints of photocatalytic degradation haze precursor.
In order to reach second object of the present invention, a kind of environment protecting building paint of photocatalytic degradation haze precursor
It is prepared using a kind of preparation method of the environment protecting building paint of above-mentioned photocatalytic degradation haze precursor.
The utility model has the advantages that
For the present invention by the way that zinc oxide to be carried on inside γ-aluminum oxyhydroxide tiny balloon, principle is with cetyl front three
Base ammonium bromide is pattern controlling agent, hollow through hydrothermal synthesis γ as made of nanometer sheet self assembly-aluminum oxyhydroxide hierarchical structure
Microballoon, the hierarchical structure of the microballoon possess the hydroxyl exposure of very high percentage, and activity is high, are easy to and the band Amino End Group generation of polyethers institute
Bonding, and by being closely assembled into spherical shape by spraying, overcome nano-photocatalyst be difficult in coating it is evenly dispersed, be easy to reunite
Defect, while can effectively avoid coating occur shedding phenomenon, prolong the service life, be easy to catalytic degradation organic matter.
Specific embodiment
In the following, the present invention will be further described in detail by way of specific embodiments, but this should not be interpreted as to the present invention
Range be only limitted to example below.Without departing from the idea of the above method of the present invention, according to ordinary skill
The various replacements or change that knowledge and customary means are made, should be included in the scope of the present invention.
Embodiment 1
(1) using aluminum sulfate, urea and cetyl trimethylammonium bromide as raw material, wherein aluminum sulfate, urea and cetyl three
The mass ratio of methyl bromide ammonium is 9:11:32, is dissolved in distilled water after mixing, and the precursor liquid that mass concentration is 45% is stirred to get；
Photocatalyst of zinc oxide is added in gained precursor liquid, the mass ratio of photocatalyst of zinc oxide and precursor liquid is 8:65, is then moved to
In high-pressure hydrothermal reaction kettle, hydro-thermal reaction for 24 hours, is cooled to room temperature after the reaction was completed at 160 DEG C, and centrifugation collects sediment, so
4 sediments are successively washed respectively with dehydrated alcohol, distilled water afterwards, and dry, natural cooling obtains the nanometer of high hydroxyl exposure
γ made of piece self assembly-aluminum oxyhydroxide tiny balloon, and tiny balloon internal load has photocatalyst of zinc oxide；
(2) the tiny balloon load photocatalyst of zinc oxide and amine terminated polyether polyalcohol, polyisocyanates obtained step (1)
It is mixed according to mass ratio 10:40:50, is warming up to 55 DEG C of reaction 12h, is then spray-dried, the polyurethane assembled/
γ-aluminum oxyhydroxide/zinc oxide spherical particle；
(3) polyurethane/γ-aluminum oxyhydroxide/zinc oxide spherical particle that step (2) is prepared and nano silica,
Nanometer wollastonite, precipitated calcium carbonate, defoaming agent, dispersing agent, coalescing agent, organic pigment, water are according to mass ratio 8:5:10:10:
3:5:8:5:55 is added in high speed disperser, is mixed and made into slurry；Silicone modified acrylic resin and the slurry are mixed again
Uniformly, be added thickener, stir 2h to get it is described can photocatalytic degradation haze precursor environment protecting building paint；The defoaming
Agent is tributyl phosphate；The dispersing agent is oxidized polyethylene wax；The coalescing agent is propandiol butyl ether；The organic pigment
For metal azo pigments.The silicone modified acrylic resin, slurry, thickener mass ratio 15:65:6；The thickener is silicon
Sour magnalium.
The coating that embodiment 1 is obtained is coated on 150mm × 100mm × 5mm cement asbestos board, and coating thickness is
Photocatalysis coating sample is placed in circulation tubular type reaction unit as photocatalysis coating test sample by 0.2mm, air drying 2d
It is interior, it is passed through the NO that concentration is 100ppm into reactor, ultraviolet radioactive Continuous irradiation 30min can be launched using xenon short-act lamp,
NO removal efficiency is 72.65%.
Embodiment 2
(1) using aluminum sulfate, urea and cetyl trimethylammonium bromide as raw material, wherein aluminum sulfate, urea and cetyl three
The mass ratio of methyl bromide ammonium is 10:12:30, is dissolved in distilled water after mixing, and the forerunner that mass concentration is 35% is stirred to get
Liquid；Photocatalyst of zinc oxide is added in gained precursor liquid, the mass ratio of photocatalyst of zinc oxide and precursor liquid is 6:70, then is moved
Into high-pressure hydrothermal reaction kettle, hydro-thermal reaction for 24 hours, is cooled to room temperature after the reaction was completed at 160 DEG C, and sediment is collected in centrifugation,
Then 5 sediments are successively washed respectively with dehydrated alcohol, distilled water, dry, natural cooling obtains receiving for high hydroxyl exposure
γ-aluminum oxyhydroxide tiny balloon made of rice piece self assembly, and tiny balloon internal load has photocatalyst of zinc oxide；
(2) the tiny balloon load photocatalyst of zinc oxide and amine terminated polyether polyalcohol, polyisocyanates obtained step (1)
It is mixed according to mass ratio 12:35:45, is warming up to 50 DEG C of reaction 15h, is then spray-dried, the polyurethane assembled/
γ-aluminum oxyhydroxide/zinc oxide spherical particle；
(3) polyurethane/γ-aluminum oxyhydroxide/zinc oxide spherical particle that step (2) is prepared and nano silica,
Nanometer wollastonite, precipitated calcium carbonate, defoaming agent, dispersing agent, coalescing agent, organic pigment, water are according to mass ratio 6:2:8:12:2:
8:7:6:58 is added in high speed disperser, is mixed and made into slurry；Silicone modified acrylic resin and the slurry are mixed again equal
It is even, be added thickener, stir 3h to get it is described can photocatalytic degradation haze precursor environment protecting building paint；The defoaming agent
For silicone emulsion；The dispersing agent is alkyl phenol polyoxyethylene ether；The coalescing agent is propandiol butyl ether；The organic pigment
For heterocyclic pigment.The silicone modified acrylic resin, slurry, thickener mass ratio 10:50:10；The thickener is silicon
Sour magnalium.
The coating that embodiment 2 is obtained is coated on 150mm × 100mm × 5mm cement asbestos board, and coating thickness is
Photocatalysis coating sample is placed in circulation tubular type reaction unit as photocatalysis coating test sample by 0.2mm, air drying 2d
It is interior, it is passed through the NO that concentration is 100ppm into reactor, ultraviolet radioactive Continuous irradiation 30min can be launched using xenon short-act lamp,
NO removal efficiency is 76.62%.
Embodiment 3
(1) using aluminum sulfate, urea and cetyl trimethylammonium bromide as raw material, wherein aluminum sulfate, urea and cetyl three
The mass ratio of methyl bromide ammonium is 8:10:32, is dissolved in distilled water after mixing, and the precursor liquid that mass concentration is 55% is stirred to get；
Photocatalyst of zinc oxide is added in gained precursor liquid, the mass ratio of photocatalyst of zinc oxide and precursor liquid is 6:65, is then moved to
In high-pressure hydrothermal reaction kettle, hydro-thermal reaction 36h, is cooled to room temperature after the reaction was completed at 150 DEG C, and centrifugation collects sediment, so
3 sediments are successively washed respectively with dehydrated alcohol, distilled water afterwards, and dry, natural cooling obtains the nanometer of high hydroxyl exposure
γ made of piece self assembly-aluminum oxyhydroxide tiny balloon, and tiny balloon internal load has photocatalyst of zinc oxide；
(2) the tiny balloon load photocatalyst of zinc oxide and amine terminated polyether polyalcohol, polyisocyanates obtained step (1)
It is mixed according to mass ratio 15:40:55, is warming up to 58 DEG C of reaction 12h, is then spray-dried, the polyurethane assembled/
γ-aluminum oxyhydroxide/zinc oxide spherical particle；
(3) polyurethane/γ-aluminum oxyhydroxide/zinc oxide spherical particle that step (2) is prepared and nano silica,
Nanometer wollastonite, precipitated calcium carbonate, defoaming agent, dispersing agent, coalescing agent, organic pigment, water are according to mass ratio 8:2:6:8:3:
7:8:8:50 is added in high speed disperser, is mixed and made into slurry；Silicone modified acrylic resin and the slurry are mixed again equal
It is even, be added thickener, stir 2h to get it is described can photocatalytic degradation haze precursor environment protecting building paint；The defoaming agent
For dimethicone；The dispersing agent is alkyl phenol polyoxyethylene ether；The coalescing agent is alcohol ester 12；The organic pigment
For phthalocyanine pigment.The silicone modified acrylic resin, slurry, thickener mass ratio 20:75:9；The thickener is silicic acid
Magnalium.
Embodiment 4
(1) using aluminum sulfate, urea and cetyl trimethylammonium bromide as raw material, wherein aluminum sulfate, urea and cetyl three
The mass ratio of methyl bromide ammonium is 9:11:33, is dissolved in distilled water after mixing, and the precursor liquid that mass concentration is 40% is stirred to get；
Photocatalyst of zinc oxide is added in gained precursor liquid, the mass ratio of photocatalyst of zinc oxide and precursor liquid is 5:68, is then moved to
In high-pressure hydrothermal reaction kettle, hydro-thermal reaction 16h, is cooled to room temperature after the reaction was completed at 180 DEG C, and centrifugation collects sediment, so
5 sediments are successively washed respectively with dehydrated alcohol, distilled water afterwards, and dry, natural cooling obtains the nanometer of high hydroxyl exposure
γ made of piece self assembly-aluminum oxyhydroxide tiny balloon, and tiny balloon internal load has photocatalyst of zinc oxide；
(2) the tiny balloon load photocatalyst of zinc oxide and amine terminated polyether polyalcohol, polyisocyanates obtained step (1)
It is mixed according to mass ratio 5:36:50, is warming up to 56 DEG C of reaction 14h, is then spray-dried, the polyurethane/γ-assembled
Aluminum oxyhydroxide/zinc oxide spherical particle；
(3) polyurethane/γ-aluminum oxyhydroxide/zinc oxide spherical particle that step (2) is prepared and nano silica,
Nanometer wollastonite, precipitated calcium carbonate, defoaming agent, dispersing agent, coalescing agent, organic pigment, water are according to mass ratio 10:3:14:13:
2:5:7:6:56 is added in high speed disperser, is mixed and made into slurry；Silicone modified acrylic resin and the slurry are mixed again
Uniformly, be added thickener, stir 2h to get it is described can photocatalytic degradation haze precursor environment protecting building paint；The defoaming
Agent is tributyl phosphate；The dispersing agent is calgon；The coalescing agent is propylene glycol methyl ether acetate；It is described organic
Pigment is condensed ring ketone pigment.The silicone modified acrylic resin, slurry, thickener mass ratio 17:66:8；The thickener
For sodium carboxymethylcellulose.
Embodiment 5
(1) using aluminum sulfate, urea and cetyl trimethylammonium bromide as raw material, wherein aluminum sulfate, urea and cetyl three
The mass ratio of methyl bromide ammonium is 9:12:35, is dissolved in distilled water after mixing, and the precursor liquid that mass concentration is 55% is stirred to get；
Photocatalyst of zinc oxide is added in gained precursor liquid, the mass ratio of photocatalyst of zinc oxide and precursor liquid is 8:70, is then moved to
In high-pressure hydrothermal reaction kettle, hydro-thermal reaction 30h, is cooled to room temperature after the reaction was completed at 170 DEG C, and centrifugation collects sediment, so
4 sediments are successively washed respectively with dehydrated alcohol, distilled water afterwards, and dry, natural cooling obtains the nanometer of high hydroxyl exposure
γ made of piece self assembly-aluminum oxyhydroxide tiny balloon, and tiny balloon internal load has photocatalyst of zinc oxide；
(2) the tiny balloon load photocatalyst of zinc oxide and amine terminated polyether polyalcohol, polyisocyanates obtained step (1)
It is mixed according to mass ratio 12:45:42, is warming up to 56 DEG C of reaction 13h, is then spray-dried, the polyurethane assembled/
γ-aluminum oxyhydroxide/zinc oxide spherical particle；
(3) polyurethane/γ-aluminum oxyhydroxide/zinc oxide spherical particle that step (2) is prepared and nano silica,
Nanometer wollastonite, precipitated calcium carbonate, defoaming agent, dispersing agent, coalescing agent, organic pigment, water are according to mass ratio 10:4:8:10:
3:5:9:4:55 is added in high speed disperser, is mixed and made into slurry；Silicone modified acrylic resin and the slurry are mixed again
Uniformly, be added thickener, stir 3h to get it is described can photocatalytic degradation haze precursor environment protecting building paint；The defoaming
Agent is silicone emulsion；The dispersing agent is calgon；The coalescing agent is alcohol ester 12；The organic pigment is metal
Azo pigments.The silicone modified acrylic resin, slurry, thickener mass ratio 16:73:8；The thickener is magnesium silicate
Aluminium.
Comparative example 1
(1) photocatalyst of zinc oxide is mixed with amine terminated polyether polyalcohol, polyisocyanates according to mass ratio 10:40:50, is risen
Then temperature is spray-dried, the polyurethane assembled/zinc oxide spherical particle to 55 DEG C of reaction 12h；
(2) by the polyurethane being prepared/zinc oxide spherical particle and nano silica, nanometer wollastonite, precipitated calcium carbonate,
Defoaming agent, dispersing agent, coalescing agent, organic pigment, water are added to high speed point according to mass ratio 8:5:10:10:3:5:8:5:55
It dissipates in device, is mixed and made into slurry；Silicone modified acrylic resin and the slurry are uniformly mixed again, thickener is added, stirs 2h,
Up to it is described can photocatalytic degradation haze precursor environment protecting building paint；The defoaming agent is tributyl phosphate；The dispersion
Agent is oxidized polyethylene wax；The coalescing agent is propandiol butyl ether；The organic pigment is metal azo pigments.It is described organic
Silicone acrylic resin, slurry, thickener mass ratio 15:65:6；The thickener is aluminium-magnesium silicate.
The coating that comparative example 1 is obtained is coated on 150mm × 100mm × 5mm cement asbestos board, and coating thickness is
Photocatalysis coating sample is placed in circulation tubular type reaction unit as photocatalysis coating test sample by 0.2mm, air drying 2d
It is interior, it is passed through the NO that concentration is 100ppm into reactor, ultraviolet radioactive Continuous irradiation 30min can be launched using xenon short-act lamp,
NO removal efficiency is 51.45%.
Claims (10)
1. a kind of preparation method of the environment protecting building paint of photocatalytic degradation haze precursor, which is characterized in that the preparation side
Method includes the following steps:
(1) it using aluminum sulfate, urea and cetyl trimethylammonium bromide as raw material, is dissolved in distilled water, stirs to get after mixing
The precursor liquid that mass concentration is 30~60%；Photocatalyst of zinc oxide is added in gained precursor liquid, high pressure hydro-thermal reaction is then moved to
In kettle, 16~36h of hydro-thermal reaction, is cooled to room temperature after the reaction was completed at 150~180 DEG C, and centrifugation collects sediment, then
Successively with dehydrated alcohol, distillation water washing precipitate, dry, natural cooling obtains the nanometer sheet self assembly of high hydroxyl exposure
Made of γ-aluminum oxyhydroxide tiny balloon, and tiny balloon internal load has photocatalyst of zinc oxide；
(2) the tiny balloon load photocatalyst of zinc oxide and amine terminated polyether polyalcohol, polyisocyanates obtained step (1)
Mixing, is warming up to 50~60 DEG C of 10~15h of reaction, is then spray-dried, the polyurethane/γ assembled-hydroxyl oxidation
Aluminium/zinc oxide spherical particle；
(3) polyurethane/γ-aluminum oxyhydroxide/zinc oxide spherical particle that step (2) is prepared and nano silica,
Nanometer wollastonite, precipitated calcium carbonate, defoaming agent, dispersing agent, coalescing agent, organic pigment, water are added in high speed disperser, are mixed
Slurry is made in conjunction；Silicone modified acrylic resin and the slurry are uniformly mixed again, thickener is added, stirs 1~3h to get institute
State can photocatalytic degradation haze precursor environment protecting building paint.
2. a kind of preparation method of the environment protecting building paint of photocatalytic degradation haze precursor according to claim 1,
Be characterized in that, the mass ratio of aluminum sulfate, urea and cetyl trimethylammonium bromide described in step (1) be 8~10:10~
12:30~35.
3. a kind of preparation method of the environment protecting building paint of photocatalytic degradation haze precursor according to claim 1,
It is characterized in that, the mass ratio of step (1) photocatalyst of zinc oxide and precursor liquid are as follows: 5~10:60~75.
4. a kind of preparation method of the environment protecting building paint of photocatalytic degradation haze precursor according to claim 1,
It is characterized in that, the temperature of step (1) described hydro-thermal reaction is 160 DEG C, and the reaction time is for 24 hours.
5. a kind of preparation method of the environment protecting building paint of photocatalytic degradation haze precursor according to claim 1,
It is characterized in that, step (1) dehydrated alcohol, the number for distilling water washing precipitate are respectively 3~5 times.
6. a kind of preparation method of the environment protecting building paint of photocatalytic degradation haze precursor according to claim 1,
It is characterized in that, step (2) tiny balloon load photocatalyst of zinc oxide and amine terminated polyether polyalcohol, polyisocyanates
Mass ratio are as follows: 5~15:35~50:40~60.
7. a kind of preparation method of the environment protecting building paint of photocatalytic degradation haze precursor according to claim 1,
It is characterized in that, step (3) polyurethane/γ-aluminum oxyhydroxide/zinc oxide spherical particle and nano silica, nano-silicon
Lime stone, precipitated calcium carbonate, defoaming agent, dispersing agent, coalescing agent, organic pigment, water mass ratio are as follows: 5-10:2~8:5~15:
6~15:2~5:2~8:7~10:3~8:50~60.
8. a kind of preparation method of the environment protecting building paint of photocatalytic degradation haze precursor according to claim 1,
It is characterized in that, step (3) defoaming agent is at least one of dimethicone, tributyl phosphate, silicone emulsion；Described point
Powder is at least one of oxidized polyethylene wax, calgon, alkyl phenol polyoxyethylene ether；The coalescing agent is the third two
At least one of alcohol butyl ether, alcohol ester 12, propylene glycol methyl ether acetate, benzoglycols；The organic pigment is metal azo
At least one of pigment, heterocyclic pigment, condensed ring ketone pigment, phthalocyanine pigment.
9. a kind of preparation method of the environment protecting building paint of photocatalytic degradation haze precursor according to claim 1,
It is characterized in that, 10~20:50 of mass ratio~75:3~10 of step (3) silicone modified acrylic resin, slurry, thickener；
The thickener is at least one of aluminium-magnesium silicate, sodium carboxymethylcellulose.
10. a kind of environment protecting building paint of photocatalytic degradation haze precursor, which is characterized in that a kind of photocatalytic degradation mist
The environment protecting building paint of haze precursor uses a kind of ring of photocatalytic degradation haze precursor according to any one of claims 1 to 9
The preparation method of guarantor's type building coating is prepared.
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| US20040209084A1 (en) * | 2003-04-18 | 2004-10-21 | Masaaki Yamaya | Protective coat-forming coating composition, coated article, and multilayer laminate |
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