CN111286247A - Functional environment-friendly coating and preparation method thereof - Google Patents

Functional environment-friendly coating and preparation method thereof Download PDF

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Publication number
CN111286247A
CN111286247A CN202010299582.3A CN202010299582A CN111286247A CN 111286247 A CN111286247 A CN 111286247A CN 202010299582 A CN202010299582 A CN 202010299582A CN 111286247 A CN111286247 A CN 111286247A
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tio
parts
zeolite
composite material
stirring
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赵本茂
沈少雄
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Foshan Sanshui Create Tide Co ltd
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Foshan Sanshui Create Tide Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—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 at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • 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
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2237—Oxides; Hydroxides of metals of titanium
    • C08K2003/2241—Titanium dioxide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2265—Oxides; Hydroxides of metals of iron
    • C08K2003/2272—Ferric oxide (Fe2O3)
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure

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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)
  • Inorganic Chemistry (AREA)
  • Paints Or Removers (AREA)
  • Catalysts (AREA)

Abstract

The invention discloses a functional environment-friendly coating and a preparation method thereof, wherein the coating comprises the following components in parts by weight: 30-35 parts of acrylic emulsion, 5-10 parts of resin polymer and Fe3+/TiO210-25 parts of/zeolite composite material, 5-15 parts of inorganic powder, 0.5 part of dispersant, 1-2 parts of film forming additive, 0.5-1 part of thickener, 1-2 parts of other additives and 25-30 parts of deionized water; said Fe3+/TiO2The surface of the zeolite composite material is coated with a coupling agent. The method comprises the following steps: pretreatment of zeolites, Fe3+/TiO2Preparation of/Zeolite composite, Fe3+/TiO2Surface modification of the zeolite composite material and preparation of the coating. According to the functional environment-friendly coating and the preparation method thereof provided by the invention, the obtained coating has the effect of continuously adsorbing VOCs and formaldehyde, can be used for photocatalytic degradation of VOCs and formaldehyde under the irradiation of visible light, and has excellent air purification capability.

Description

Functional environment-friendly coating and preparation method thereof
Technical Field
The invention relates to the technical field of coatings, and particularly relates to a functional environment-friendly coating and a preparation method thereof.
Background
In recent years, with the improvement of living standard of people, health consciousness is continuously enhanced, the requirement on air quality is increasingly improved, and the quality of indoor air quality directly influences the health condition of human bodies, particularly the pollution problem of Volatile Organic Compounds (VOCs) and formaldehyde, and the air conditioner is attracted by people. The VOCs and formaldehyde are mainly derived from chemical products such as artificial building materials, decoration materials, living goods and the like, and when the VOCs and formaldehyde exceed the standard, the human health is seriously harmed, so that the problem that how to reduce and eliminate the content of the VOCs and formaldehyde in indoor air is urgently needed to be solved by people is solved.
In the prior art, materials with adsorption function are often used for adsorbing VOCs, formaldehyde or other toxic and harmful gases in air, such as activated carbon, diatom ooze and the like, but the materials can only adsorb and cannot be degraded, so that the defect of reverse release exists after the adsorption saturation. Therefore, the titanium dioxide photocatalysis material is added into the coating or prepared into the air purification material, and the photocatalysis of the titanium dioxide is utilized to degrade VOCs and formaldehyde in the indoor air so as to achieve the effect of purifying the indoor air. However, titanium dioxide has a wide forbidden band and requires an ultraviolet light source, but most of indoor light is visible light, so that the photocatalytic effect is limited.
In addition, VOCs and formaldehyde in the air are in a free dispersion state, and more contact with titanium dioxide can be realized by adsorbing VOCs and formaldehyde by a wall surface or a plate. On this basis, the loading of TiO by carbon fibers has emerged2TiO loaded fly ash2Diatomite supported TiO2TiO supported on silica2And vermiculite supported TiO2The materials such as powder, these materials play the effect of collecting absorption and photocatalytic degradation in an organic whole, great improvement air purification's ability and persistence. However, the materials can adsorb VOCs and formaldehyde and simultaneously adsorb water in the air more easily, especially in southern areas with humid air, which greatly affects the adsorption amount of VOCs and formaldehyde, thereby greatly reducing the air purification capacity of the materials.
In an environment with high humidity, how to improve the photocatalytic degradation capability of titanium dioxide and the adsorption capacity of an adsorption medium to VOCs and formaldehyde becomes a problem to be solved urgently at present. It is seen that improvements and enhancements to the prior art are needed.
Disclosure of Invention
In view of the defects of the prior art, the invention aims to provide a functional environment-friendly coating and a preparation method thereof, and aims to overcome the defects that the air purification material in the prior art has small adsorption quantity on VOCs and formaldehyde in the air under the influence of water vapor, and the photocatalytic effect of titanium dioxide is low.
In order to achieve the purpose, the invention adopts the following technical scheme:
a functional environment-friendly coating comprises the following components in parts by weight: 30-35 parts of acrylic emulsion, 5-10 parts of resin polymer and Fe3+/TiO210-25 parts of/zeolite composite material, 5-15 parts of inorganic powder, 0.5 part of dispersant, 1-2 parts of film forming additive, 0.5-1 part of thickener, 1-2 parts of other additives and 25-30 parts of deionized water; said Fe3+/TiO2The surface of the zeolite composite material is coated with a coupling agent.
In the functional environment-friendly coating, the coupling agent is one of a silane coupling agent or trimethylchlorosilane.
In the functional environment-friendly coating, the silane coupling agent comprises KH550 and KH 972.
In the functional environment-friendly coating, the resin polymer is one or more of methyl methacrylate, acrylate and styrene polymer.
In the functional environment-friendly coating, the inorganic powder is a mixture of wollastonite and quartz powder.
A method for preparing the functional environment-friendly paint, wherein the method comprises the following steps: weighing the raw materials according to the proportion, and sequentially adding part of water, the dispersing agent and TiO under low-speed stirring2Stirring the zeolite composite material at a medium speed for 3-5 min, adding the thickening agent, stirring at a high speed for dispersing for 15min, and stirring at a medium speed; and then adding the acrylic emulsion, the inorganic powder, the resin polymer, the rest water and other auxiliaries, continuously stirring at a medium speed for 35-45 min, and finally filtering to obtain the environment-friendly functional coating.
In the preparation method of the functional environment-friendly coating, the rotation speed of the low-speed stirring is 500-800 rpm, the rotation speed of the medium-speed stirring is 800-1000 rpm, and the rotation speed of the high-speed stirring is 1000-1500 rpm.
In the preparation method of the functional environment-friendly coating, the method also comprises TiO2The preparation method of the/zeolite composite material specifically comprises the following steps:
step S1, pretreatment of zeolite: taking natural zeolite, and carrying out water washing, acid treatment and alkali treatment to obtain pretreated zeolite;
step S2.TiO2Preparation of zeolite composite material: mixing pretreated zeolite and deionized water in a ratio of 1:10, adding 1% of concentrated hydrochloric acid and 0.1-0.5% of ferric nitrate, uniformly stirring, adding 1-2% of titanium tetrachloride, continuously stirring, adding dilute ammonia water to adjust the pH value to 8-9, continuously stirring for 20-30 min, aging for 20-24 h, performing suction filtration and washing to neutrality, drying filter residues at 150 ℃, and roasting at 300 ℃ for 2h to obtain Fe-doped zeolite2O3Of TiO 22A zeolite composite material.
In the preparation method of the functional environment-friendly coating, TiO is also included after the step S22The surface modification of the/zeolite composite material specifically comprises the following steps: the TiO obtained in the step S22Putting the zeolite composite material into a coupling agent and ethanol/water mixed solution, stirring for 3-4 hours at 60-80 ℃, then centrifuging and washing to be neutral, and drying the precipitate at 140-160 ℃ to obtain surface modified TiO2A zeolite composite material.
Has the advantages that:
the invention provides a functional environment-friendly coating and a preparation method thereof3+/TiO2Zeolite composite material, in which Fe is doped3+Of nano TiO2Has wider wavelength response range, has excellent photocatalysis effect under the irradiation of visible light, and greatly improves the TiO2Photocatalytic effect of (1), and Fe3+/TiO2The coupling agent coated on the surface of the zeolite composite material can improve Fe3+/TiO2The compatibility and dispersibility of the/zeolite composite material in the coating can be reduced, and Fe can be reduced3+/TiO2The zeolite composite material has the adsorption effect on water, so that the adsorption quantity of the material on VOCs and formaldehyde is greatly improved. Doped TiO2In synergistic action with surface modifiers, on the one hand, TiO2The photocatalysis effect can make VOCs and formaldehyde in the zeolite obtain the degradation clearance, and then impel zeolite can adsorb more VOCs and formaldehyde, and on the other hand, the surfactant can block the absorption of water to make zeolite have more selective absorption to VOCs and formaldehyde, both combine together, thereby great improvement the coating to the lasting purifying effect of air.
Detailed Description
The invention provides a functional environment-friendly coating and a preparation method thereof, and in order to make the purpose, technical scheme and effect of the invention clearer and clearer, the invention is further described in detail by the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The invention provides a functional environment-friendly coating, which comprises the following components in parts by weight: the coating comprises the following components in parts by weight: 30-35 parts of acrylic emulsion, 5-10 parts of resin polymer and Fe3+/TiO210-25 parts of/zeolite composite material, 5-15 parts of inorganic powder, 0.5 part of dispersing agent, 1-2 parts of film forming additive, 0.5-1 part of thickening agent, 1-2 parts of other additives and 25-30 parts of deionized water; said Fe3+/TiO2The surface of the zeolite composite material is coated with a coupling agent.
The functional environment-friendly coating prepared by the above proportion is prepared by adding Fe3+/TiO2The zeolite composite material not only has the function of adsorbing VOCs and formaldehyde, but also has the function of photocatalytic degradation of VOCs and formaldehyde by titanium dioxide attached to the surface of zeolite, thereby realizing continuous adsorption and catalytic degradation of VOCs and formaldehyde and achieving the function of continuous air purification. And by the presence of nano-TiO2Middle doped Fe2O3By Fe3+The generated oxygen vacancy enables TiO2The band gap is narrowed, thereby making TiO2The light response range of the composite material is expanded to a visible light area, the composite material is better suitable for indoor lighting environment, and the photocatalytic degradation effect on VOCs and formaldehyde is greatly improved.
In the functional environment-friendly coating with the proportion, the Fe3+/TiO2The surface of the/zeolite composite material is also coated with a coupling agent. In Fe3+/TiO2The coupling agent coated by the zeolite composite material can improve Fe3+/TiO2The compatibility of the zeolite composite material and the coating enables the dispersion to be more uniform, and on the other hand, the coupling agent is a non-polar organic matter and can change the surface polarity of the zeolite, so that the adsorption capacity of the zeolite on water can be reduced, and the adsorption quantity of the zeolite on VOCs and formaldehyde can be greatly improved.
Preferably, in the functional environment-friendly coating material in the above ratio, the coupling agent is one of a silane coupling agent or trimethylchlorosilane, and specifically, the silane coupling agent includes KH550 and KH 972. The silane coupling agent and the trimethylchlorosilane have good compatibility with acrylic emulsion, weak polarity and poor compatibility with water, thereby greatly reducing the adsorption capacity of the zeolite to water.
Specifically, in the functional environment-friendly coating material prepared according to the above ratio, the resin polymer is one or more of methyl methacrylate, acrylate and styrene polymer.
Specifically, in the functional environment-friendly coating prepared according to the above ratio, the inorganic powder is a mixture of wollastonite and quartz powder. The inorganic powder is used as a filler of the coating, has the function of improving the hardness and the strength of the coating, and preferably has higher hardness when being a mixture of wollastonite and quartz powder, and can be suitable for places with higher requirements on hardness.
A method for preparing the functional environment-friendly paint, which comprises the following steps: weighing the raw materials according to the proportion, and sequentially adding part of water, the dispersing agent and Fe under low-speed stirring3+/TiO2Stirring the zeolite composite material at a medium speed for 3-5 min, adding the thickening agent, stirring at a high speed for dispersing for 15min, and stirring at a medium speed; then adding acrylic emulsion and inorganic powderAnd continuously stirring the resin polymer, the rest water and other auxiliary agents at a medium speed for 35-45 min, and finally filtering to obtain the environment-friendly functional coating. The rotating speed of the low-speed stirring is 500-800 rpm, the rotating speed of the medium-speed stirring is 800-1000 rpm, and the rotating speed of the high-speed stirring is 1000-1500 rpm.
The preparation method of the functional environment-friendly coating is simple to operate, and the materials are uniformly dispersed through different stirring speeds, so that the obtained coating has the characteristics of good dispersibility and uniform and stable performance.
In the preparation method of the functional environment-friendly coating, the method also comprises Fe3+/TiO2The preparation method of the/zeolite composite material specifically comprises the following steps:
step S1, pretreatment of zeolite: taking natural zeolite, performing wet ball milling on the natural zeolite, sieving the natural zeolite with a 200-mesh sieve, washing the natural zeolite with water, centrifuging the natural zeolite, placing the natural zeolite in 0.2mol/L hydrochloric acid solution, and stirring the natural zeolite for 2 to 4 hours at the temperature of between 60 and 70 ℃; then adding 2mol/L NaOH solution to adjust the pH value to 7, and continuously stirring for 2-4 h; then adding 2mol/L NaOH solution to adjust the pH value to 14, and continuously stirring for 2-4 h; and then centrifugally separating, washing the precipitate to be neutral, and drying at 200-250 ℃ to obtain the pretreated zeolite. The pretreatment of the zeolite removes impurities on the surface and in the pore diameter of the zeolite through water washing, acid treatment and alkali treatment, and modifies the polarity of the zeolite by performing ion exchange on the zeolite and NaOH.
Step S2.Fe3+/TiO2Preparation of zeolite composite material: stirring and mixing pretreated zeolite and deionized water in a ratio of 1:10, adding 1% of concentrated hydrochloric acid and 0.1-0.5% of ferric nitrate, stirring uniformly, adding 1-2% of titanium tetrachloride, continuing stirring for 1h, adding dilute ammonia water to adjust the pH value to 8-9, continuing stirring for 20-30 min, aging for 20-24 h, performing suction filtration and washing to neutrality, drying filter residues at 150 ℃, and roasting at 300 ℃ for 2h to obtain Fe3+/TiO2A zeolite composite material. Said Fe3+/TiO2The preparation of the zeolite composite material adopts a hydrothermal coprecipitation method, and the obtained titanium dioxide is nano titanium dioxide and Fe3+Can be better doped into TiO2In the crystal lattice, thereby effectively changingTiO2The forbidden band width of the material is enlarged, the range of light wave is enlarged, and TiO is improved2The photocatalytic efficiency of (c). On the other hand, TiO2Loaded on the surface of zeolite, and can greatly improve TiO through the adsorption effect of zeolite2The photocatalytic effect of (2), correspondingly, due to TiO2VOCs and formaldehyde adsorbed by zeolite can be degraded, so that the adsorption quantity of zeolite is greatly increased, and the two are mutually synergistic to make Fe3+/TiO2The zeolite composite material has higher air purifying capacity.
In the above method for preparing the functional environmental protection coating, after the step S2, Fe is further included3+/TiO2The surface modification of the/zeolite composite material specifically comprises the following steps: fe obtained in step S23+/TiO2The zeolite composite material is placed in ethanol/water mixed solution containing 10% of coupling agent, stirred for 3-4 h at 60-80 ℃, then centrifuged and washed to be neutral, and the precipitate is dried at 140-160 ℃ to obtain surface modified Fe3+/TiO2A zeolite composite material. Said Fe3+/TiO2Surface modification of/zeolite composite material, mainly through surface coating modification, to make Fe3+/TiO2The polarity of the/zeolite composite material is changed, so that the dispersibility of the/zeolite composite material in the coating is improved, and the water adsorption capacity of the/zeolite composite material is reduced. Due to non-surface-modified Fe3+/TiO2The zeolite composite material is an inorganic material with polarity, has strong water adsorption capacity, and is unmodified Fe when VOCs, formaldehyde and water in the air simultaneously appear3+/TiO2The zeolite composite material preferentially adsorbs water, the adsorption capacity is limited, the adsorption capacity of the zeolite composite material on VOCs and formaldehyde is greatly reduced under the condition of large water adsorption capacity, and particularly in southern humid areas, water almost occupies the whole Fe3+/TiO2The zeolite composite material has an internal pore diameter, so that the adsorption and degradation effects on VOCs and formaldehyde are almost negligible. And surface modified Fe3+/TiO2The nonpolar surface of the zeolite composite material greatly reduces the adsorption effect of the zeolite composite material on water, thereby improving the adsorption capacity of the zeolite composite material on VOCs and formaldehyde and improving the air purification effect.
Example 1
A preferable functional environment-friendly coating comprises the following components in parts by weight: 33 parts of acrylic emulsion, 8 parts of resin polymer and Fe3+/TiO220 parts of/zeolite composite material, 10 parts of inorganic powder, 0.5 part of dispersant, 2 parts of film-forming additive, 0.8 part of thickening agent, 2 parts of other additives and 28 parts of deionized water.
The coating is prepared by the following steps:
pretreatment of zeolite: taking natural zeolite, performing wet ball milling on the natural zeolite, sieving the natural zeolite with a 200-mesh sieve, washing the natural zeolite with water, centrifuging the natural zeolite, placing the natural zeolite in 0.2mol/L hydrochloric acid solution, and stirring the natural zeolite for 3.5 hours at 68 ℃; then adding 2mol/L NaOH solution to adjust the pH value to 7, and continuing stirring for 3 hours; then, continuously adding 2mol/L NaOH solution to adjust the pH value to 14, and continuously stirring for 3 hours; then centrifugally separating, washing the precipitate to be neutral, and then drying at 230 ℃ to obtain the pretreated zeolite.
Fe3+/TiO2Preparation of zeolite composite: mixing pretreated zeolite and deionized water at a ratio of 1:10, adding 1% concentrated hydrochloric acid and 0.4% ferric nitrate, stirring uniformly, adding 1.6% titanium tetrachloride, stirring for 1h, adding dilute ammonia water to adjust pH to 8.6, stirring for 25min, aging for 24h, filtering, washing to neutrality, drying the filter residue at 150 deg.C, and calcining at 300 deg.C for 2h to obtain Fe3+/TiO2A zeolite composite material.
Fe3+/TiO2Surface modification of zeolite composite: mixing Fe3+/TiO2Putting the zeolite composite material into ethanol/water mixed solution containing 10% of coupling agent, stirring for 3.5h at 72 ℃, then centrifuging and washing to be neutral, and drying the precipitate at 150 ℃ to obtain surface modified Fe3+/TiO2A zeolite composite material.
Preparation of the coating: weighing the components in the raw materials according to the proportion, and sequentially adding part of water, the dispersing agent and the surface modified Fe under the stirring of the rotating speed of 600rpm3+/TiO2Stirring the zeolite composite material at 800rpm for 4min, adding the thickening agent, stirring and dispersing at 1200rpm for 15min, and changing to 900rpm and thenAnd (3) continuously stirring, then adding the acrylic emulsion, the inorganic powder, the resin polymer, the rest water and other auxiliary agents, continuously stirring at 900rpm for 40min, and finally filtering to obtain the environment-friendly functional coating.
Example 2
A functional environment-friendly coating comprises the following components in parts by weight: 30 parts of acrylic emulsion, 5 parts of resin polymer and Fe3+/TiO210 parts of/zeolite composite material, 5 parts of inorganic powder, 0.5 part of dispersant, 1 part of film-forming additive, 0.5 part of thickening agent, 1 part of other additives and 25 parts of deionized water.
The coating is prepared by the following steps:
pretreatment of zeolite: taking natural zeolite, performing wet ball milling on the natural zeolite, sieving the natural zeolite with a 200-mesh sieve, then washing the natural zeolite with water, centrifuging the natural zeolite, placing the natural zeolite in 0.2mol/L hydrochloric acid solution, and stirring the natural zeolite for 2 hours at 60 ℃; then adding 2mol/L NaOH solution to adjust the pH value to 7, and continuing stirring for 2 h; then, continuously adding 2mol/L NaOH solution to adjust the pH value to 14, and continuously stirring for 2 hours; then centrifugally separating, washing the precipitate to be neutral, and then drying at 200 ℃ to obtain the pretreated zeolite.
Fe3+/TiO2Preparation of zeolite composite: mixing pretreated zeolite and deionized water at a ratio of 1:10, adding 1% concentrated hydrochloric acid and 0.1% ferric nitrate, stirring uniformly, adding 1% titanium tetrachloride, stirring for 1h, adding dilute ammonia water to adjust pH value to 8, stirring for 20min, aging for 20h, suction-filtering, washing to neutrality, drying filter residue at 150 deg.C, and calcining at 300 deg.C for 2h to obtain Fe-doped zeolite2O3Of TiO 22A zeolite composite material.
Fe3+/TiO2Surface modification of zeolite composite material: mixing Fe3+/TiO2The zeolite composite material is put into ethanol/water mixed solution containing 10 percent of coupling agent, stirred for 3 hours at the temperature of 60 ℃, then centrifuged and washed to be neutral, and the precipitate is dried at the temperature of 140 ℃ to obtain Fe after surface modification3+/TiO2A zeolite composite material.
Preparation of the coating: weighing the raw materials according to the proportion, adding part of water and part of water in turn under the stirring of 500rpmPowder and surface-modified Fe3+/TiO2The zeolite composite material is stirred at 800rpm for 3min, then the thickening agent is added, and the mixture is stirred at 1000rpm for 15min and then is stirred at 800rpm at medium speed; then adding acrylic emulsion, inorganic powder, resin polymer, residual water and other auxiliary agents, continuing stirring at the speed of 800rpm for 35min, and finally filtering to obtain the environment-friendly functional coating.
Example 3
A functional environment-friendly coating comprises the following components in parts by weight: 35 parts of acrylic emulsion, 10 parts of resin polymer and Fe3+/TiO225 parts of/zeolite composite material, 15 parts of inorganic powder, 0.5 part of dispersant, 2 parts of film-forming additive, 1 part of thickening agent, 2 parts of other additives and 30 parts of deionized water.
The coating is prepared by the following steps:
pretreatment of zeolite: taking natural zeolite, performing wet ball milling on the natural zeolite, sieving the natural zeolite with a 200-mesh sieve, then washing the natural zeolite with water, centrifuging the natural zeolite, placing the natural zeolite in 0.2mol/L hydrochloric acid solution, and stirring the natural zeolite for 4 hours at 70 ℃; then adding 2mol/L NaOH solution to adjust the pH value to 7, and continuing stirring for 4 hours; then, continuously adding 2mol/L NaOH solution to adjust the pH value to 14, and continuously stirring for 4 hours; then centrifugally separating, washing the precipitate to be neutral, and then drying at 250 ℃ to obtain the pretreated zeolite.
Fe3+/TiO2Preparation of zeolite composite material: mixing pretreated zeolite and deionized water at a ratio of 1:10, adding 1% concentrated hydrochloric acid and 0.5% ferric nitrate, stirring uniformly, adding 2% titanium tetrachloride, stirring for 1h, adding dilute ammonia water to adjust pH to 9, stirring for 30min, aging for 24h, vacuum-filtering, washing to neutrality, drying the filter residue at 150 deg.C, and calcining at 300 deg.C for 2h to obtain Fe3+/TiO2A zeolite composite material.
Fe3+/TiO2Surface modification of zeolite composite: mixing Fe3+/TiO2The zeolite composite material is put into ethanol/water mixed solution containing 10 percent of coupling agent, stirred for 4 hours at 80 ℃, then centrifuged and washed to be neutral, and the precipitate is dried at 160 ℃ to obtain Fe after surface modification3+/TiO2A zeolite composite material.
Preparation of the coating: weighing the raw materials according to the proportion, and sequentially adding part of water, the dispersing agent and the surface modified Fe under the stirring of the rotating speed of 800rpm3+/TiO2And stirring the zeolite composite material at the rotating speed of 1000rpm for 5min, adding a thickening agent, stirring and dispersing at the high speed of 1500rpm for 15min, then stirring at the medium speed of 1000rpm, then adding the acrylic emulsion, the inorganic powder, the resin polymer, the rest water and other auxiliaries, stirring at the speed of 1000rpm for 45min, and finally filtering to obtain the environment-friendly functional coating.
Comparative example 1
A coating comprises the following components in parts by weight: 33 parts of acrylic emulsion, 8 parts of resin polymer and TiO220 parts of/zeolite composite material, 10 parts of inorganic powder, 0.5 part of dispersant, 2 parts of film-forming additive, 0.8 part of thickening agent, 2 parts of other additives and 28 parts of deionized water. The TiO is2The zeolite composite material is loaded with nano TiO on the surface2But not doped with Fe3 +And the surface is not coated with the coupling agent.
The coating was prepared by the same method as in example 1, but TiO2Fe is not doped in the preparation process of the zeolite composite material3+。
Comparative example 2
A coating comprises the following components in parts by weight: 33 parts of acrylic emulsion, 8 parts of resin polymer and Fe3+/TiO220 parts of/zeolite composite material, 10 parts of inorganic powder, 0.5 part of dispersant, 2 parts of film-forming additive, 0.8 part of thickening agent, 2 parts of other additives and 28 parts of deionized water. Said Fe3+/TiO2Zeolite with doped Fe supported on its surface3+Of nano TiO2But the surface is not coated with a coupling agent.
The coating was prepared by the same method as in example 1, but without the inclusion of Fe3+/TiO2Surface modification of/zeolite composite materials.
Testing the adsorption and photocatalytic degradation capacities:
the coatings described in examples 1 to 3 and the coatings described in comparative examples 1 to 2 were subjected to adsorption tests and photocatalytic degradation tests of VOCs, formaldehyde and toluene, respectively, and the specific test designs were as follows:
1. formaldehyde removal capacity test:
preparation of a sample: the coatings obtained in examples 1-3 and comparative examples 1-2 were uniformly applied to both sides of 5 adhesive sheets (measured to have no formaldehyde emission) of 100cm × 100cm × 0.55cm, respectively, and the coating thicknesses were the same, and after drying at room temperature, the sheets were cut into samples of 15cm × 15cm × 0.55cm, and the edges of the samples were sealed with a formaldehyde-free glue, and then the test was sealed and stored for use.
And (3) testing: the same sample is randomly divided into 3 groups, which are marked as group 1, group 2 and group 3, and vertically placed in a 20L transparent closed container containing formaldehyde respectively, the humidity of the closed containers of the group 1 and the group 2 is 60 percent, the container humidity of the group 3 is 80 percent, the group 1 and the group 3 are respectively irradiated by ultraviolet light, the group 2 is irradiated by visible light, the test process is ensured that one side of the sample is aligned with a light source, and the container is rotated once every 12h, so that the two sides of the sample alternately face the light source. Test procedure the formaldehyde concentration value in the closed vessel was measured and recorded every 12 hours, and compared with the initial concentration, 3d and 5d, and the results are shown in table 1. It should be noted that the intensity of the light source and other test conditions used in the same set of tests are the same and will not be described in detail here.
Formaldehyde concentration detection instrument: the formaldehyde monitoring instrument of the American 4160 type, which is recognized by national standard measurement, detects and displays concentration value figures (the concentration deviation range is less than or equal to +/-5 percent).
TABLE 1 Performance test results of coatings for formaldehyde removal
Figure BDA0002453468630000111
2. P-toluene removal capability test:
the preparation and test procedures of the test specimens were the same as those of the test procedure for formaldehyde described above, and the test gas was replaced with toluene, and the results are shown in Table 2. Toluene concentration detection apparatus: the detection range of the MIC-600 type toluene monitor is 0-1000ppm and the precision is 0.01ppm, which are determined by national standard measurement.
TABLE 2 paint vs. toluene removal Performance test results
Figure BDA0002453468630000121
As is clear from the experimental data in tables 1 and 2, Fe was added3+/TiO2The coating of the zeolite composite material has strong removal capability to formaldehyde and toluene, the removal capability to formaldehyde and toluene can still keep high level under the condition of high humidity, and even under the irradiation of visible light, the removal rate (5d) to formaldehyde can still reach more than 90 percent, and the removal rate (5d) to toluene can reach 97.5 percent.
It should be understood that equivalents and modifications of the technical solution and inventive concept thereof may occur to those skilled in the art, and all such modifications and alterations should fall within the scope of the appended claims.

Claims (9)

1. The functional environment-friendly coating is characterized by comprising the following components in parts by weight: 30-35 parts of acrylic emulsion, 5-10 parts of resin polymer and Fe3+/TiO210-25 parts of/zeolite composite material, 5-15 parts of inorganic powder, 0.5 part of dispersant, 1-2 parts of film forming additive, 0.5-1 part of thickener, 1-2 parts of other additives and 25-30 parts of deionized water; said Fe3+/TiO2The surface of the zeolite composite material is coated with a coupling agent.
2. The functional environmental-friendly coating as recited in claim 1, wherein the coupling agent is one of a silane coupling agent or trimethylchlorosilane.
3. The functional, environmentally friendly coating of claim 2, wherein the silane coupling agent comprises KH550, KH 972.
4. The functional environmental-friendly coating according to claim 1, wherein the resin polymer is one or more of methyl methacrylate, acrylate and styrene polymer.
5. The functional environment-friendly paint as claimed in claim 1, wherein the inorganic powder is a mixture of wollastonite and quartz powder.
6. A method for preparing the functional environmental protection coating according to any one of claims 1 to 5, wherein the method comprises the following steps: weighing the raw materials according to the proportion, and sequentially adding part of water, the dispersing agent and TiO under low-speed stirring2Stirring the zeolite composite material at a medium speed for 3-5 min, adding the thickening agent, stirring at a high speed for dispersing for 15min, and stirring at a medium speed; and then adding the acrylic emulsion, the inorganic powder, the resin polymer, the rest water and other auxiliaries, continuously stirring at a medium speed for 35-45 min, and finally filtering to obtain the environment-friendly functional coating.
7. The preparation method of the functional environment-friendly coating as claimed in claim 6, wherein the rotation speed of the low-speed stirring is 500-800 rpm, the rotation speed of the medium-speed stirring is 800-1000 rpm, and the rotation speed of the high-speed stirring is 1000-1500 rpm.
8. The method for preparing the functional environmental protection coating according to claim 6, wherein the method further comprises TiO2The preparation method of the/zeolite composite material specifically comprises the following steps:
step S1, pretreatment of zeolite: taking natural zeolite, and carrying out water washing, acid treatment and alkali treatment to obtain pretreated zeolite;
step S2.Fe3+/TiO2Preparation of zeolite composite: mixing pretreated zeolite and deionized water in a ratio of 1:10, adding 1% of concentrated hydrochloric acid and 0.1% -0.5% of ferric nitrate, uniformly stirring, adding 1% -2% of titanium tetrachloride, continuously stirring, adding dilute ammonia water to adjust the pH value to 8-9, continuously stirring for 20-30 min, and aging for 20-24 hFiltering, washing with water to neutrality, drying the filter residue at 150 deg.C, and calcining at 300 deg.C for 2 hr to obtain Fe-doped product2O3Of TiO 22A zeolite composite material.
9. The method for preparing the functional environmental protection coating according to claim 8, further comprising TiO 22The surface modification of the/zeolite composite material specifically comprises the following steps: the TiO obtained in the step S22Putting the zeolite composite material into a coupling agent and ethanol/water mixed solution, stirring for 3-4 hours at 60-80 ℃, then centrifuging and washing to be neutral, and drying the precipitate at 140-160 ℃ to obtain surface modified TiO2A zeolite composite material.
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Application publication date: 20200616