CN107353819A - One kind removes gray haze antifouling paint and preparation method thereof - Google Patents

One kind removes gray haze antifouling paint and preparation method thereof Download PDF

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Publication number
CN107353819A
CN107353819A CN201710715942.1A CN201710715942A CN107353819A CN 107353819 A CN107353819 A CN 107353819A CN 201710715942 A CN201710715942 A CN 201710715942A CN 107353819 A CN107353819 A CN 107353819A
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gray haze
antifouling paint
tio
clay
cationic surfactant
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李建生
张腾
赵洋
葸彦娇
尹浩南
刘炳光
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Tianjin Vocational Institute
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Tianjin Vocational Institute
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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
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • 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
    • C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
    • 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
    • C09D5/16—Antifouling paints; Underwater paints
    • C09D5/1606—Antifouling paints; Underwater paints characterised by the anti-fouling agent
    • C09D5/1612—Non-macromolecular compounds
    • C09D5/1618—Non-macromolecular compounds inorganic
    • 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
    • C09D5/16—Antifouling paints; Underwater paints
    • C09D5/1606—Antifouling paints; Underwater paints characterised by the anti-fouling agent
    • C09D5/1612—Non-macromolecular compounds
    • C09D5/1625—Non-macromolecular compounds organic
    • 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
    • C09D5/16—Antifouling paints; Underwater paints
    • C09D5/1687—Use of special additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
    • C08K13/06—Pretreated ingredients and ingredients covered by the main groups C08K3/00 - C08K7/00
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2237—Oxides; Hydroxides of metals of titanium
    • C08K2003/2241—Titanium dioxide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2248—Oxides; Hydroxides of metals of copper
    • 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
    • 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
    • C08K3/34—Silicon-containing compounds
    • C08K3/346—Clay
    • 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
    • C08K9/00—Use of pretreated ingredients
    • C08K9/02—Ingredients treated with inorganic substances
    • 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
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • 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
    • C08K9/00—Use of pretreated ingredients
    • C08K9/12—Adsorbed ingredients, e.g. ingredients on carriers

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

Abstract

The present invention relates to one kind to remove gray haze antifouling paint and preparation method thereof, particularly with nanometer Cu2O /TiO2Composite photoelectric catalyst and gemini cationic surfactant are made up of as the coating except haze anti-pollution function component photoelectric, antibacterial anti-fouling agent, absorption synergist, film forming agent and solvent.Composite photoelectric catalyst is reacted by the salt hydrolysis of titanium and copper forms co-precipitation, is supported on the clay adsorber by pretreatment, further reduction treatment is formed.Antibacterial anti-fouling agent is dopen Nano TiO2, nanometer Cu2O and gemini cationic surfactant.It is clay adsorber and gemini cationic surfactant to adsorb synergist.The raw material that the present invention removes gray haze antifouling paint is cheap and easy to get and one multi-purpose, both can apply to remove gray haze in indoor and outdoor air, and can is as interior/exterior decoration coating application.

Description

One kind removes gray haze antifouling paint and preparation method thereof
Technical field
The present invention relates to one kind to remove gray haze antifouling paint and preparation method thereof, particularly with nanometer Cu2O /TiO2It is compound Photoelectric and gemini cationic surfactant belong to ring as coating except haze anti-pollution function component and preparation method thereof Guarantor and field of new materials.
Background technology
In recent years, both there is Trans-Provincial/Municipal, gray haze a wide range of, seasonality is strong, the duration is short in China, also occurred Local, small range, normalization, duration very long gray haze.Gray haze particulate matter is enriched with many inorganic compounds and organic Compound, these compounds are adsorbed on the very thin solids of aerosol.Mainly there is the larger chemical composition of content in gray haze Sulfate, nitrate, ammonium salt, five kinds of compositions of organic carbon and elemental carbon, the composition of various regions gray haze is different, and gentle with season As condition is varied from.Air solid particulate matter PM is generally divided into PM by thickness10、PM2.5And PM1.0It is several, the particle diameter of gray haze Generally 0.003-10 μm, average diameter is at 0.3-1 μm.Research finds that air fine grained of the particle diameter below 2.5 μm is to lead The main reason for causing gray haze to occur, PM2.5Index can reflect the degree of gray haze pollution to a certain extent.
Gray haze particle all carries certain negative electrical charge or positive charge in air, also there is electroneutral, but overall negative charge Lotus.Unipolar charged gray haze particle, because it is mutually exclusive reduce its cohesion rate, tack and stability improve, cause its It is difficult to natural subsidence removing in air；For the charged gray haze particle of bipolarity because attracting each other, its cohesion rate is significantly greater than non-charged grain Son, condition is provided to condense naturally and settling removing；Non- charged gray haze particle can form dipolar nature induced electricity in the electric field, its Effect is similar to the charged gray haze particle of bipolarity.
Gray haze sweep-out method is similar to industrial dust administering method in air, mainly using gray haze charge and can oxygen What the property changed was carried out, but technical requirements are more complicated, require higher to Technical Economy, the scope of application requires wider.Sweep-out method Dry method can be divided into remove and wet method removing；Also physical removal method, chemical scavenging method and photochemical scanvenging method etc. can be divided into.In recent years A series of patents of invention that gray haze is removed by modes such as electricity, magnetic, light, sound, chemistry and photochemistries have been disclosed.
Zhejiang University patent of invention CN104815496A（2015-08-05）Use spray charged water spray with high-efficient cleaning except big Aerosol haze；China Mining University patent of invention CN106902595A（2017-06-30）The middle table that water is reduced using spray magnetized water Face tension force is to improve haze elimination effect；China University of Geosciences（Beijing）Patent of invention CN105013255A（2015-11-04）In Using sack cleaner principle, removing will be moved except haze device is installed on vehicle；Middle letter heavy industry machinery share is limited Company patent of invention CN105890074A（2016-08-24）Middle borrow electrostatic precipitation technology principle, will contain aerosol contaminants grain In the air input Large-sized Electrostatic Precipitator of son, contaminant particles is quickly collected on battery lead plate and remove, it is empty so as to export cleaning Gas；Patent of invention CN105536987A（2016-05-04）Middle borrow air purifier principle, using large-scale anion, cation It is electrically charged to neutralize aerosol contaminants institute or kation anion generator sends negative ions to the secondary inorganic aerosol of air, Accelerate its cohesion and sedimentation is removed, but these methods are required for consuming a large amount of electric energy, and high operating cost causes application It is relatively difficult.
Be exposed to the sun in the presence of photochemical catalyst is degraded and removing organic pollution most original and economic method, typical light Catalyst is dichloride in anatase type TiO2Or dopen Nano TiO2, they can produce electronics e under sunshine irradiation-With hole h+, energy The H for enough adsorbing photocatalyst surface2O、O2, organic pollution oxidation or reduction, so as to strength clear the pollution off.Dopen Nano TiO2Photochemical catalyst can be obviously improved the hydrophilic and lipophile of contaminated surface, contaminated surface is easier as water and glossy wet.Mesh It is preceding to be applied to dispel solar cell, building, motor vehicle, billboard and highway barrier surface as self-cleaning coating component Pollutant, but for air PM2.5Clearance it is not high, main cause is dopen Nano TiO2The electrically charged amount of photochemical catalyst institute Seldom, it is impossible to electrostatic attraction and actively trap the gray haze particle in air.For example, Nantong Snakes Treating Inst. is in Chinese patent Shell waste residue element anion functional nanometer environmental protection paint is disclosed in CN106893420A (2017-03-17)；Jiangsu University A kind of automatically cleaning air type exterior coating and its preparation side are disclosed in Chinese patent CN103992712A (2014-05-12) Method；Co., Ltd of Bei Si productivity promotion centers of Fanchang County is disclosed in Chinese patent CN104353421A (2014-10-21) A kind of haze adsorbent and preparation method thereof；Wuxi Qiao Yang Harmann Berstorff, Maschinenbau GmbH is in Chinese patent CN105214721A （2016-0106）In disclose it is a kind of prevent and treat haze catalyst；Tianjin Professional College application for a patent for invention 2017106944462（2017-08-15）、2017107001390（2017-08-15）With 2017107100841（2017-08- 18）The method being combined using Electrostatic Absorption and photocatalysis removes gray haze in indoor and outdoor air, is characterized in only utilizing sunshine Energy, it is not necessary to consume additional electrical energy, but the efficiency of these methods removing gray haze needs further to be improved.
The content of the invention
It is an object of the invention to provide one kind to remove gray haze antifouling paint and preparation method thereof, particularly with nanometer Cu2O /TiO2 Composite photoelectric catalyst and gemini cationic surfactant are as the coating except haze anti-pollution function component, except haze anti-pollution function group It is point one multi-purpose, gray haze particle is actively attracted by electrostatic and surface energy, promotes that it is removed naturally after condensing and photoelectrocatalysis divides Solution；Coating sol is made up of photoelectric, antibacterial anti-fouling agent, absorption synergist, film forming agent and solvent.
The mass percent of present invention removing gray haze antifouling paint formula, which forms, is：
Nano-TiO2 0.5%-1.0%
Nanometer Cu2O 0.05%-0.2%
Surfactant 0.01-0.2%
Clay adsorber 2%-10%
Fluoboric acid 0.02-0.1%
Film forming agent 2%-5%
Balance of solvent.
It is a nanometer Cu that the present invention, which removes photoelectric in gray haze antifouling paint,2O /TiO2Composite photoelectric catalyst, composition Mol ratio is：Ti：Cu =1:0.05-0.2, co-precipitation is formed by the salt-mixture hydrolysis of titanium and copper, be supported on by pre- place On the clay adsorber of reason, further reduction treatment is formed.In fact there was only a small amount of Cu+Ion enters nano-TiO2It is real in lattice Existing nano-TiO2Doping, nano-TiO2With nanometer Cu2Also exist between O and form Cu2TiO3Reaction, make the nano-TiO after doping2 Photo-catalysis capability significantly improves, and just has good photo-catalysis capability under visible light illumination.Nanometer Cu2O is also good in itself Photochemical catalyst, with nano-TiO2Synergy can be produced, dopen Nano TiO can be significantly improved2With nanometer Cu2O photoelectricity is urged Change ability.
It is dopen Nano TiO that the present invention, which removes antibacterial anti-fouling agent in gray haze antifouling paint,2, nanometer Cu2O and Shuangzi cation Surfactant.Dopen Nano TiO2It is light-sensitive semiconductor material, with regard to light induced electron and hole pair can be generated under sunlight, Hydrone and oxygen produce hydroxyl radical free radical and negative oxygen ion in energy oxidation air, can kill microorganism and decompose its life of relying The organic nutrient substance deposited；Nanometer Cu2O has bio-toxicity, also has strong bacteriostasis even if without light irradiation；Shuangzi sun Ionic surface active agent is novel surfactant, is the bacteriostatic agent of a kind of high-efficiency low-toxicity.The Shuangzi cationic surface of selection is lived Property agent is dimethylene -1,2- didodecyldimethylammbromide bromide（12-2-12）, the double myristyls two of dimethylene -1,2- Methyl bromide ammonium（14-2-14）, ethyl dimethylene -1,2- didodecyldimethylammbromide bromide（12-4-12）With ethyl two The double dodecyldimethylamine base ammonium bromides of methylene -1,2-（14-4-14）.
It is clay adsorber and gemini cationic surfactant that the present invention, which removes absorption synergist in gray haze antifouling paint,. The clay adsorber of selection is natural montmorillonite, sepiolite and attapulgite, specific surface area 100-300m2/g.Clay adsorption Cooperative effect between agent and gemini cationic surfactant be present, the clay handled by gemini cationic surfactant is inhaled The attached dose of adsorption capacity to gray haze greatly improves；Gemini cationic surfactant absorption is dispersed on clay adsorber, makes it Surface is positively charged, has strong electrostatic attraction to generally negatively charged gray haze；The scattered Shuangzi cation form of absorption Face activating agent enters inside clay adsorber, makes it have lasting bacteriostasis.
The fluoboric acid used in present invention removing gray haze antifouling paint is one multi-purpose, can be used as clay adsorber surface active Agent, the clay adsorber by fluoboric acid pretreatment is easier and Cu2O dopen Nanos TiO2With nanometer Cu2O stable bonds；Simultaneously Hydrolyst and film forming curing agent as organo-silicon coupling agent.
The present invention remove gray haze antifouling paint in organosilicon film forming agent be organo-silicon coupling agent, particularly tetraethyl orthosilicate, One of MTMS, coupling agent KH550, coupling agent KH560, coupling agent KH570 or its mixture, their hydrolysis- The film coating to form dense uniform can be bonded after polymerization with photoelectric, antibacterial anti-fouling agent and clay adsorber.
It is hydrone that the present invention, which removes solvent in gray haze antifouling paint, can be with insoluble film-forming components surfactant It is scattered to form oil-in-water emulsion.
The mass percentage concentration that the present invention removes gray haze antifouling paint solid constituent is 3%-5%, and colloidal sol is coated on structures Formed on surface it is firm remove gray haze nonpolluting coating, coated film thickness is 10-50 μm, in weight haze weather and indoor illumination Gray haze clearance rate is 65%-80% in lower 2h.
The raw material clay adsorber that the present invention uses is commercially available prod, specific surface area 100-300m2/ g, particle diameter are less than 2 μ M, proportion 2.7-2.9g/ ㎝3.The raw material sulphuric acid oxygen titanium of use, copper nitrate, fluoboric acid, organo-silicon coupling agent etc. are chemical examination Agent.
It is a further object to provide a kind of preparation method for removing gray haze antifouling paint, the technical scheme taken It is with step：
（1）Chemical reagent titanyl sulfate and copper sulphate are dissolved in the solution that 1mol/L is configured in deionized water respectively；Stirring Lower add copper-bath in titanyl sulfate solution forms mixing salt solution, controls the molar ratio to be：Ti：Cu=1:0.05- 0.2；
（2）Clay adsorber is added in the aqueous solution containing gemini cationic surfactant and fluoboric acid, controls the matter that feeds intake Measuring ratio is：Clay adsorber：Surfactant：HBF4：H2O=1：0.001-0.02：0.02-0.05：30-50, at 40-50 DEG C Lower stirring makes clay adsorber surface active 4-8h, to improve adsorption capacity and adhesive force；
（3）Titanyl sulfate and copper sulphate mixing salt solution are added into above suspension under agitation, continues to stir 1- after adding 2h, the ion of Titanium and copper is set to be exchanged for clay adsorber；Ammoniacal liquor to the pH value of solution for being then slowly added into 1mol/L is 11 to be Only, TiO (OH) is made2With Cu (OH)2Co-precipitation controls the mass ratio that feeds intake to be in clay adsorber micropore：Clay adsorber： (TiO2+CuO)=1：0.05-0.2；
（4）The hydrazine hydrate solution that mass percentage concentration is 20% is added under agitation, the CuO particles of absorption is reduced to nanometer Cu2O particles, the mass ratio that feeds intake for controlling pure material are：CuO：N2H4=1:0.1-0.15；Precipitation is separated by filtration, uses deionized water It is washed till in wash water untill no longer containing sulfate ion；
（5）Precipitation is dispersed in the aqueous solution containing gemini cationic surfactant and fluoboric acid, controls the throwing of pure material Expect that mass ratio is：(TiO2+CuO)：Surfactant：Fluoboric acid：H2O=1：0.01-0.2：0.02-0.05:20-50, in 60- Peptization 1-2h is carried out at 70 DEG C, makes precipitation dispersed in aqueous；
（6）Add organosilicon film forming agent and reaction 4-8h, then being positioned to 12-24h at room temperature is hydrolyzed, form uniform apply Expect colloidal sol, control the mass ratio that feeds intake to be：Clay adsorber：Organosilicon：Water=1：0.2-0.5；
（7）It is 5%-10% to be diluted with water colloidal sol to solid constituent mass percentage concentration, obtains removing gray haze antifouling paint；Brushed It is coated on structures surface, the removing gray haze nonpolluting coating of firm attachment is formed after solvent volatilization, coated film thickness is 10-50 μ M, available for gray haze in removing indoor and outdoor air.
The function ingredients raw material that the present invention removes gray haze antifouling paint is cheap and easy to get and one multi-purpose, can remove room with high-efficient cleaning Gray haze particle in inner air and outer air；The present invention removes gray haze antifouling paint and both can apply to remove gray haze in indoor and outdoor air, and can As interior/exterior decoration coating application；The present invention, which removes gray haze antifouling paint, can be coated on indoor and outdoor metope, roof, advertisement Board, decorative panel, guardrail and automotive surfaces, which are used to removing in indoor and outdoor air gray haze and make to be applied surface, realizes automatically cleaning.
Embodiment
Embodiment 1
Respectively by chemical reagent titanyl sulfate 16.0g（0.1mol）With copper sulphate 3.2g（0.02mol）It is dissolved in deionized water and matches somebody with somebody 1mol/L solution is made；Copper-bath is added in titanyl sulfate solution under agitation and forms mixing salt solution；By activity Carclazyte 50g adds the aqueous solution containing gemini cationic surfactant (12-2-12) 0.5g, fluoboric acid 2.5g and water 250g In, being stirred at 40-50 DEG C makes atlapulgite surface active 4-8h.
The titanyl sulfate and copper sulphate mixing salt solution of preparation are added into above suspension under agitation, is continued after adding 1h is stirred, titanium and copper ion is exchanged for atlapulgite；1mol/L ammoniacal liquor is then slowly added into untill pH value of solution is 11, is made TiO(OH)2With Cu (OH)2Co-precipitation is in atlapulgite micropore.The hydrazine hydrate that mass percentage concentration is 20% is added under agitation Solution 1.2g, the CuO particles of absorption are made to be reduced to a nanometer Cu2O particles；Precipitation is separated by filtration, is washed with deionized water into wash water Untill no longer containing sulfate ion.
Precipitation is dispersed in containing gemini cationic surfactant 0.5g and fluoboric acid 0.4g and water the 400g aqueous solution In, peptization 2h is carried out at 60-70 DEG C, makes precipitation dispersed in aqueous；Add organo-silicon coupling agent KH560 20g Reaction 4h, then being positioned to 24h at room temperature is hydrolyzed, forms uniform coating sol.Colloidal sol is diluted with water to solid group It is 10% to divide mass percentage concentration, obtains removing gray haze antifouling paint 800g.
Gray haze antifouling paint will be removed to brush in a 15m2, formed on floor height 2.7m room metope, after drying firm Removing gray haze nonpolluting coating, 50 μm of coated film thickness.In the test that a certain gray haze day noon is carried out, door and window is first opened Make indoor and outdoor PM2.5Concentration balance, indoor PM is measured under natural light after being then shut off door and window2.5Concentration is 285 μ g/m3, in door PM when 0.5h, 1.0h and 2.0h after window is closed2.5Concentration is respectively 112 μ g/m3、78μg/m3With 46 μ g/m3；Corresponding gray haze is clear Except rate is respectively 60.7%, 72.6% and 83.8%；PM in the control room for removing gray haze nonpolluting coating is not brushed2.5Concentration is without notable Change.
Embodiment 2
Respectively by chemical reagent titanyl sulfate 16.0g（0.1mol）With copper sulphate 1.6g（0.01mol）It is dissolved in deionized water and matches somebody with somebody 1mol/L solution is made；Copper-bath is added in titanyl sulfate solution under agitation and forms mixing salt solution；By bumps Rod soil 80g adds the aqueous solution containing gemini cationic surfactant C16-4-16 0.2g, fluoboric acid 1.0g and water 250g In, being stirred at 40-50 DEG C makes attapulgite's surface activate 4-8h.
The titanyl sulfate and copper sulphate mixing salt solution of preparation are added into above suspension under agitation, is continued after adding 1h is stirred, titanium and copper ion is exchanged for attapulgite；1mol/L ammoniacal liquor is then slowly added into untill pH value of solution is 11, is made TiO(OH)2With Cu (OH)2Co-precipitation is in attapulgite micropore.The hydrazine hydrate that mass percentage concentration is 20% is added under agitation Solution 0.8g（0.0075mol）, the CuO particles of absorption is reduced to a nanometer Cu2O particles；Precipitation is separated by filtration, uses deionized water It is washed till in wash water untill no longer containing sulfate ion.
Precipitation is dispersed in containing gemini cationic surfactant 0.3g and fluoboric acid 0.4g and water the 600g aqueous solution In, peptization 2h is carried out at 60-70 DEG C, makes precipitation dispersed in aqueous；MTMS 20g is added to enter Row hydrolysis 4h, then being positioned to 24h at room temperature, form uniform coating sol.）Colloidal sol is diluted with water to solid constituent Mass percentage concentration is 10%, obtains removing gray haze antifouling paint 1100g.Gray haze antifouling paint will be removed to brush in a 15m2, Firm removing gray haze nonpolluting coating, 20 μm of coated film thickness are formed on floor height 2.7m room metope, after drying.In a certain ash In the test that haze day noon is carried out, first opening door and window makes indoor and outdoor PM2.5Concentration balance, it is then shut off after door and window in nature Indoor PM is measured under light2.5Concentration is 260 μ g/m3, PM when 0.5h, 1.0h and 2.0h after door and window closing2.5Concentration is respectively 112 μg/m3、74μg/m3With 43 μ g/m3；Corresponding gray haze clearance rate is respectively 56.9%, 71.5% and 83.5%；Removing gray haze is not brushed PM in the control room of nonpolluting coating2.5Concentration is without significant changes.

Claims (5)

1. one kind removes gray haze antifouling paint, it is characterised in that by photoelectric, antibacterial anti-fouling agent, absorption synergist, film forming Agent and solvent composition, the mass percent composition of formulation for coating material are：
Nano-TiO2 0.5%-1.0%
Nanometer Cu2O 0.05%-0.2%
Surfactant 0.01-0.2%
Clay adsorber 2%-10%
Fluoboric acid 0.02-0.1%
Film forming agent 2%-5%
Balance of solvent.
2. the removing gray haze antifouling paint as described in claim 1, it is characterised in that photoelectric is a nanometer Cu in coating2O / TiO2Composite photoelectric catalyst, constitutive molar ratio are：Ti：Cu =1:0.05-0.2, by the salt-mixture hydrolysis shape of titanium and copper Into co-precipitation, it is supported on the clay adsorber by pretreatment, further reduction treatment is formed.
3. the removing gray haze antifouling paint as described in claim 1, it is characterised in that antibacterial anti-fouling agent is dopen Nano in coating TiO2, nanometer Cu2O and gemini cationic surfactant, the gemini cationic surfactant are that dimethylene -1,2- is double The double dodecyldimethylamine base ammonium bromides of Dodecydimethylammonium bronides, dimethylene -1,2-, ethyl dimethylene -1,2- are double Dodecydimethylammonium bronides and the double dodecyldimethylamine base ammonium bromides of ethyl dimethylene -1,2-.
4. the removing gray haze antifouling paint as described in claim 1, it is characterised in that it is clay adsorption that synergist is adsorbed in coating Agent and gemini cationic surfactant, the clay adsorber are natural montmorillonite, sepiolite and attapulgite, specific surface area For 100-300m2/g。
5. a kind of preparation method for removing gray haze antifouling paint, it is characterised in that technology of preparing scheme and step are：
（1）Chemical reagent titanyl sulfate and copper sulphate are dissolved in the solution that 1mol/L is configured in deionized water respectively；Stirring Lower add copper-bath in titanyl sulfate solution forms mixing salt solution, controls the molar ratio to be：Ti：Cu=1:0.05- 0.2；
（2）Clay adsorber is added in the aqueous solution containing gemini cationic surfactant and fluoboric acid, controls the matter that feeds intake Measuring ratio is：Clay adsorber：Surfactant：HBF4：H2O=1：0.001-0.02：0.02-0.05：30-50, at 40-50 DEG C Lower stirring makes clay adsorber surface active 4-8h, to improve adsorption capacity and adhesive force；
（3）Titanyl sulfate and copper sulphate mixing salt solution are added into above suspension under agitation, continues to stir 1- after adding 2h, Titanium and copper ion is set to be exchanged for clay adsorber；1mol/L ammoniacal liquor is then slowly added into untill pH value of solution is 11, Make TiO (OH)2With Cu (OH)2Co-precipitation controls the mass ratio that feeds intake to be in clay adsorber micropore：Clay adsorber：(TiO2 +CuO)=1：0.05-0.2；
（4）The hydrazine hydrate solution that mass percentage concentration is 20% is added under agitation, the CuO particles of absorption is reduced to a nanometer Cu2O Particle, the mass ratio that feeds intake for controlling pure material are：CuO：N2H4=1:0.1-0.15；Be separated by filtration precipitation, be washed with deionized water to Untill no longer containing sulfate ion in wash water；
（5）Precipitation is dispersed in the aqueous solution containing gemini cationic surfactant and fluoboric acid, controls the throwing of pure material Expect that mass ratio is：(TiO2+CuO)：Surfactant：Fluoboric acid：H2O=1：0.01-0.2：0.02-0.05:20-50, in 60- Peptization 1-2h is carried out at 70 DEG C, makes precipitation dispersed in aqueous；
（6）Add organosilicon film forming agent and reaction 4-8h, then being positioned to 12-24h at room temperature is hydrolyzed, form uniform apply Expect colloidal sol, control the mass ratio that feeds intake to be：Clay adsorber：Organosilicon：Water=1：0.2-0.5；
（7）It is 5%-10% to be diluted with water colloidal sol to solid constituent mass percentage concentration, obtains removing gray haze antifouling paint；Brushed It is coated on structures surface, the removing gray haze nonpolluting coating of firm attachment is formed after drying, coated film thickness is 10-50 μm, can For removing gray haze in indoor and outdoor air.
CN201710715942.1A 2017-08-21 2017-08-21 One kind removes gray haze antifouling paint and preparation method thereof Pending CN107353819A (en)

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CN111534162A (en) * 2020-04-15 2020-08-14 华南理工大学 Montmorillonite-based photocatalytic super-hydrophobic coating and preparation method thereof
CN115895407A (en) * 2022-12-29 2023-04-04 张红江 Preparation method of high-performance water-based paint
CN115895408A (en) * 2022-12-29 2023-04-04 张红江 Water-based paint composition

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111534162A (en) * 2020-04-15 2020-08-14 华南理工大学 Montmorillonite-based photocatalytic super-hydrophobic coating and preparation method thereof
CN111534162B (en) * 2020-04-15 2021-06-08 华南理工大学 Montmorillonite-based photocatalytic super-hydrophobic coating and preparation method thereof
CN115895407A (en) * 2022-12-29 2023-04-04 张红江 Preparation method of high-performance water-based paint
CN115895408A (en) * 2022-12-29 2023-04-04 张红江 Water-based paint composition
CN115895407B (en) * 2022-12-29 2023-11-10 江苏云丝亮新材料科技有限公司 Preparation method of high-performance water-based paint

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Application publication date: 20171117