CN114591672A - Odor-removing and aldehyde-removing paint and preparation method and application thereof - Google Patents
Odor-removing and aldehyde-removing paint and preparation method and application thereof Download PDFInfo
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- CN114591672A CN114591672A CN202210291972.5A CN202210291972A CN114591672A CN 114591672 A CN114591672 A CN 114591672A CN 202210291972 A CN202210291972 A CN 202210291972A CN 114591672 A CN114591672 A CN 114591672A
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- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
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- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 2
- 238000006731 degradation reaction Methods 0.000 claims description 2
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Images
Classifications
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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
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8668—Removing organic compounds not provided for in B01D53/8603 - B01D53/8665
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
-
- 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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
- B01D2257/704—Solvents not covered by groups B01D2257/702 - B01D2257/7027
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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
- C08K3/02—Elements
- C08K3/08—Metals
- C08K2003/0806—Silver
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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
- C08K2003/2248—Oxides; Hydroxides of metals of copper
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
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Abstract
The invention discloses an odor-removing and aldehyde-removing paint and a preparation method and application thereof, wherein the odor-removing and aldehyde-removing paint is prepared by the following steps: dissolving chitosan in acetic acid solution, and adding mixture powder consisting of coconut shell carbon and diatomite to prepare a carboxylated chitosan composite carrier; the second step is that cuprous oxide and silver nitrate are loaded on the carboxylated chitosan composite material; thirdly, heating and reacting the waterborne epoxy resin, triethylene tetramine and polyethylene glycol diglycidyl ether, and then adding deionized water to dilute to obtain a waterborne epoxy resin curing agent; and finally, fully mixing the waterborne epoxy resin and the prepared corresponding curing agent, adding the silver-cuprous oxide loaded carboxylated chitosan composite material, and uniformly stirring. The odor-removing and aldehyde-removing paint provided by the invention has an excellent air purifying function at room temperature, and can completely convert various pollutants in the air, particularly formaldehyde, into carbon dioxide and water.
Description
Technical Field
The invention belongs to the technical field of formaldehyde removal purifying agents, and particularly relates to a smell-removing formaldehyde-removing paint and a preparation method and application thereof.
Background
Various volatile aldehydes, in particular formaldehyde, are one of the major sources of harm to indoor air pollution (Huang HB, Xu Y, Feng QY, et al. Low temperature catalytic oxidation of volatile organic compounds: a review [ J ] C., C.I.Technol.2015, 5(5):2649 + 2669.). They are easily released from building and furniture materials and often have various pungent and unpleasant tastes, and long-term exposure can have serious effects on human health, such as allergic reactions, dermatitis, nasopharyngeal carcinoma and leukemia. In 2017, the world health organization international agency for research on cancer has classified formaldehyde as a carcinogen. In view of their harm to human body, countries around the world have strict regulations on indoor formaldehyde concentrations. In addition, the release period of formaldehyde can be as long as 3-15 years, so that the effective removal of formaldehyde from indoor air is very important for improving the indoor air quality and ensuring the human health.
At present, the main methods for removing aldehyde in the market, including Air purifiers and various aldehyde-removing paints or coatings, mainly use various adsorbents for adsorption, however, the problem of adsorption saturation and secondary pollution exists when Formaldehyde is removed by adsorption using adsorbents, and the problem of Formaldehyde gas pollution cannot be fundamentally solved (Zhu X D, Shen J, Liu Y. Removal of formaldehydeand Volatile Organic Compounds from particulate floors by Air-Cleaning Materials [ J]Advanced Materials Research,2010, 113-. Therefore, the development of a method which not only can remove various peculiar smells in the air, but also can convert formaldehyde into CO at room temperature2And H2Aldehyde-free lacquers of O remain one of the challenging problems.
Disclosure of Invention
The invention aims to provide odor-removing and aldehyde-removing paint and a preparation method and application thereof.
In order to achieve the above purpose, the solution of the invention is:
the preparation method of the odor-removing and aldehyde-removing paint is characterized by comprising the following steps of:
(1) dissolving chitosan in an acetic acid solution, adding mixture powder consisting of coconut shell carbon and diatomite, uniformly stirring, filtering the obtained mixture, washing the obtained solid with deionized water, and drying the obtained solid to obtain a carboxylated chitosan composite carrier;
(2) adding the carboxylated chitosan composite carrier prepared in the step (1) into an acetic acid solution, then adding a copper salt solution, uniformly stirring, continuously stirring, adding an ascorbic acid solution, adjusting the pH value of the solution by using diluted ammonia water, carrying out hydrothermal reaction on the obtained mixture, collecting the obtained solid after the reaction is finished, washing the obtained solid and drying to prepare the cuprous oxide loaded carboxylated chitosan composite material;
(3) adding the cuprous oxide loaded carboxylated chitosan composite material prepared in the step (2) into deionized water, then adding a silver nitrate solution, carrying out microwave reaction, and filtering to obtain a silver-cuprous oxide loaded carboxylated chitosan composite material;
(4) heating and reacting waterborne epoxy resin and triethylene tetramine, then adding polyethylene glycol diglycidyl ether, continuing heating and reacting, and adding deionized water for diluting to obtain a waterborne epoxy resin curing agent;
(5) and (5) fully mixing the water-based epoxy resin with the corresponding curing agent prepared in the step (4), then adding the silver-cuprous oxide loaded carboxylated chitosan composite material prepared in the step (3), and uniformly stirring to obtain the odor-removing and aldehyde-removing paint.
Preferably, the mass ratio of the chitosan, the coconut shell charcoal and the diatomite in the step (1) is 4:1: 1-5: 1: 1.
Preferably, the hydrothermal reaction temperature in the step (2) is 200-300 ℃, and the hydrothermal reaction time is 1-2 h.
Preferably, the pH value of the adjusting solution in the step (2) is 5.5-6.5.
Preferably, the copper salt in step (2) is selected from one of copper nitrate, copper chloride or copper sulfate.
Preferably, the microwave reaction temperature in the step (3) is 50-80 ℃, and the microwave reaction time is 0.5-1 h.
Preferably, the heating reaction temperature in the step (4) is 40-80 ℃, and the heating reaction time is 0.5-2 h.
The odor-removing and aldehyde-removing paint prepared by the preparation method of the odor-removing and aldehyde-removing paint has the mass content of silver ions of 0.1-0.5%; the weight content of the cuprous oxide is 1.0 to 5.0 percent.
The application of the odor-removing aldehyde-removing paint in degrading formaldehyde.
The principle of the invention is as follows:
various pollutants in the air, particularly harmful gases such as formaldehyde and the like, can be adsorbed and decomposed into CO through catalytic oxidation2And H2And O, so as to achieve the purpose of purifying the air. The invention fully utilizes the silver-cuprous oxide loaded carboxylated chitosan composite material as a catalyst to catalyze and oxidize formaldehyde at room temperature and lower temperature, so that the formaldehyde is completely converted into CO2And H2O, and can completely convert toluene into CO at a lower temperature (150 ℃ C. and 200 ℃ C.) relative to other catalysts2And H2And O, the defects of secondary pollution and the like are avoided, and the purification efficiency is improved. The specific mechanism is as follows: formaldehyde or toluene gas is adsorbed on metal atom silver or copper and can be easily activated by surrounding hydroxyl groups, and oxygen holes are generated and further activate O in the air2While the adsorbed reactant molecules and active oxygen react to form CO2And H2O。
Compared with the prior odor-removing and aldehyde-removing paint method, the method has the following beneficial effects:
1. the odor-removing and aldehyde-removing paint provided by the invention has an excellent air purification function at room temperature, and can completely convert various pollutants in the air, particularly formaldehyde, into CO2And H2O；
2. The odor-removing and aldehyde-removing paint provided by the invention can effectively degrade and remove formaldehyde gas and prevent secondary pollution.
Detailed Description
The present invention will be described in further detail with reference to examples. It is also to be understood that the following examples are intended to illustrate the present invention and are not to be construed as limiting the scope of the invention, and that the particular materials, reaction times and temperatures, process parameters, etc. listed in the examples are exemplary only and are intended to be exemplary of suitable ranges, and that insubstantial modifications and adaptations of the invention by those skilled in the art in light of the foregoing description are intended to be within the scope of the invention.
All reagents were commercial reagents unless otherwise indicated and were not further purified prior to use.
The UV-vis absorption spectrometer used in the examples section of this invention was shimadzu UV 2550.
Example 1:
the preparation steps of the odor-removing aldehyde-removing paint are as follows:
(1) dissolving 1.5g of chitosan in 125mL of 9% acetic acid solution, stirring for reaction for 1h, adding mixture powder consisting of 1.5g of coconut shell carbon and 1.5g of diatomite, continuing stirring for 1h, filtering, washing the obtained solid with deionized water until the pH value of the collected eluent is close to 7, and drying the washed solid at 110 ℃ to prepare the carboxylated chitosan composite carrier;
(2) adding the carboxylated chitosan composite carrier prepared in the step (1) into 20ml of acetic acid solution with the mass concentration of 5%, then slowly dropping 8ml of copper salt solution with the molar concentration of 50mmol/L, uniformly stirring, continuously stirring, adding 2ml of ascorbic acid solution with the mass concentration of 10%, adjusting the pH value to 6.5 by using dilute ammonia water, carrying out hydrothermal reaction on the obtained mixture at 200 ℃ for 2h, cooling, centrifuging the solution, washing 3 times by using 25ml of deionized water, washing 3 times by using 25ml of absolute ethyl alcohol, freezing, drying and collecting the obtained solid to prepare the cuprous oxide loaded carboxylated chitosan composite material;
(3) adding the cuprous oxide loaded carboxylated chitosan composite material prepared in the step (2) into 50mL of deionized water, slowly dropping 4mL of silver nitrate solution with the molar concentration of 50mmol/L, carrying out microwave reaction at 200 ℃ for 5min, and filtering to obtain the silver-cuprous oxide loaded carboxylated chitosan composite material;
(4) adding 5g of waterborne epoxy resin E-51 and 5ml of triethylene tetramine into a four-neck flask with a condensation reflux device, heating to 50 ℃ for reaction for 45min, then adding 2.5g of polyethylene glycol diglycidyl ether, heating to 60 ℃, continuing to react for 2h, and adding 20ml of deionized water to dilute after the reaction is finished to obtain a waterborne epoxy resin curing agent which is light yellow transparent liquid, has the solid content of 30 percent and the active hydrogen equivalent of 220;
(5) and (3) fully mixing 5g of waterborne epoxy resin E-51 and 5g of the curing agent prepared in the step (4), adding the silver-cuprous oxide loaded carboxylated chitosan composite material prepared in the step (3), and uniformly stirring to obtain the odor-removing and aldehyde-removing paint.
Example 2
The odor-removing and aldehyde-removing paint prepared in the example 1 is prepared into a coating and then is subjected to a performance test; wherein, the preparation of the odor-removing and aldehyde-removing coating is prepared according to the method provided in GB/T1727-1992, and the specific steps are as follows: the tinplate sheet meeting the GB/T2520-2017 specification is cut into test plates with the size of 50mm multiplied by 120mm multiplied by 0.3mm, and the test plates are cleaned according to the specification of GB 9271-1988. The formaldehyde purification effect of the odorless aldehyde-removing paint in the actual environment is tested after the odorless aldehyde-removing paint is placed on a tinplate test plate by a knife coater and is finally kept stand and cured for 2 days under the conditions of 23 ℃ and 50% of relative humidity:
placing the tinplate coated with the odor-removing aldehyde-removing paint at room temperature of 20 + -2 deg.C, relative humidity of 80%, and low formaldehyde concentration of 2 + -0.5 mg/m3Decontamination tests were performed in a simulated chamber (30 cm. times.28 cm. times.33 cm). The glass watch glass was placed on the bottom of the simulation chamber, the test chamber was closed, then 3 μ L of analytically pure formaldehyde solution was taken with a micro-syringe, dropped into the glass watch glass through the injection hole, the injection hole was closed and the fan in the chamber was opened. And (5) collecting the gas in the cabin after the cabin is sealed for 1 hour to test the concentration of the gas, wherein the concentration is the initial concentration. And then putting the tinplate test plate coated with the odor-removing and aldehyde-removing paint into a simulation cabin for formaldehyde purification, and collecting gas in the cabin every 10min and testing the formaldehyde concentration of the gas.
The results of formaldehyde degradation of the odor-free formaldehyde-removing paint are shown in fig. 1, and the results show that: the odor-removing and aldehyde-removing paint provided by the invention can quickly purify formaldehyde in actual low-concentration formaldehyde, and the initial concentration of the odor-removing and aldehyde-removing paint is 2.14mg/m3In the simulation cabin, only 90min is needed to quickly assemble the simulation cabinFormaldehyde purification less than 0.08mg/m3I.e. the national standard.
Example 3
The odor-removing and aldehyde-removing paint prepared in example 1 was prepared into a coating and then subjected to a performance test; the preparation method of the odor-removing and aldehyde-removing coating is provided by GB/T1727-1992, and comprises the following steps: the tinplate sheet meeting the GB/T2520-2017 specification is cut into test plates with the size of 50mm multiplied by 120mm multiplied by 0.3mm, and the test plates are cleaned according to the specification of GB 9271-1988. The formaldehyde purification effect of the odorless aldehyde-removing paint in the actual environment is tested after the odorless aldehyde-removing paint is placed on a tinplate test plate by a knife coater and is finally kept stand and cured for 2 days under the conditions of 23 ℃ and 50% of relative humidity:
placing the tinplate coated with the odor-removing aldehyde-removing paint at room temperature of 20 + -2 deg.C, relative humidity of 80%, and low toluene concentration of 2 + -0.5 mg/m3Decontamination tests were performed in a simulated chamber (30 cm. times.28 cm. times.33 cm). The glass watch glass was placed on the bottom of the simulation chamber, the test chamber was closed, then 3 μ L of analytically pure toluene solution was taken with a micro-syringe, dropped into the glass watch glass through the injection hole, the injection hole was closed and the fan in the chamber was opened. And (5) collecting the gas in the cabin after the cabin is sealed for 1 hour to test the concentration of the gas, wherein the concentration is the initial concentration. The tinplate test panel coated with the odor and aldehyde removing paint was then placed in a simulated chamber, the temperature in the simulated chamber was set at 170 ℃, and the gas in the chamber was collected and tested for concentration every 10 min.
The results of the evaluation of the tinplate coated with the odor-free formaldehyde-removing paint are shown in FIG. 2, which shows that: the odor-removing and aldehyde-removing paint provided by the invention can quickly purify toluene in the actual low-concentration toluene, and the initial concentration of the odor-removing and aldehyde-removing paint is 2.35mg/m3In the simulation cabin, the toluene can be quickly purified to be less than 0.20mg/m in 60min3I.e. the national standard.
Claims (9)
1. The preparation method of the odor-removing and aldehyde-removing paint is characterized by comprising the following steps of:
(1) dissolving chitosan in an acetic acid solution, adding mixture powder consisting of coconut shell carbon and diatomite, uniformly stirring, filtering the obtained mixture, washing the obtained solid with deionized water, and drying the obtained solid to obtain a carboxylated chitosan composite carrier;
(2) adding the carboxylated chitosan composite carrier prepared in the step (1) into an acetic acid solution, then adding a copper salt solution, uniformly stirring, continuously stirring, adding an ascorbic acid solution, adjusting the pH value of the solution by using diluted ammonia water, carrying out hydrothermal reaction on the obtained mixture, collecting the obtained solid after the reaction is finished, washing the obtained solid and drying to prepare the cuprous oxide loaded carboxylated chitosan composite material;
(3) adding the carboxylated chitosan composite material loaded with cuprous oxide prepared in the step (2) into deionized water, then adding a silver nitrate solution, carrying out microwave reaction, and filtering to obtain a silver-cuprous oxide loaded carboxylated chitosan composite material;
(4) heating and reacting waterborne epoxy resin and triethylene tetramine, then adding polyethylene glycol diglycidyl ether, continuing heating and reacting, and adding deionized water for diluting to obtain a waterborne epoxy resin curing agent;
(5) and (3) fully mixing the water-based epoxy resin with the corresponding curing agent prepared in the step (4), adding the silver-cuprous oxide loaded carboxylated chitosan composite material prepared in the step (3), and uniformly stirring to obtain the odor-removing aldehyde-removing paint.
2. The preparation method of the odor-free and aldehyde-removal paint as claimed in claim 1, wherein the mass ratio of the chitosan, the coconut shell carbon and the diatomite in the step (1) is 4:1: 1-5: 1: 1.
3. The method for preparing the odor-free and aldehyde-free paint as claimed in claim 1, wherein the hydrothermal reaction temperature in the step (2) is 200-300 ℃ and the hydrothermal reaction time is 1-2 h.
4. The method for preparing the odor-free and aldehyde-removing paint as claimed in claim 1, wherein the pH value of the adjusting solution in the step (2) is 5.5-6.5.
5. The method for preparing paint with odor and aldehyde removed as claimed in claim 1, wherein the copper salt in step (2) is selected from one of copper nitrate, copper chloride or copper sulfate.
6. The method for preparing the odor-free and aldehyde-removing paint as claimed in claim 1, wherein the microwave reaction temperature in the step (3) is 50-80 ℃ and the microwave reaction time is 0.5-1.5 h.
7. The method for preparing the odor-free and aldehyde-removing paint as claimed in claim 1, wherein the heating reaction temperature in the step (4) is 40-80 ℃ and the heating reaction time is 0.5-2 h.
8. The odor-removing and aldehyde-removing paint prepared by the preparation method of the odor-removing and aldehyde-removing paint as claimed in any one of claims 1 to 7 is characterized in that: wherein the mass content of silver ions is 0.1-0.5%; the mass content of the cuprous oxide is 1.0-5.0%.
9. The application of the odor-removing and aldehyde-removing paint prepared by the preparation method of the odor-removing and aldehyde-removing paint as claimed in any one of claims 1 to 7 in formaldehyde degradation.
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