CN112870965B - Air purification material capable of rapidly degrading formaldehyde and preparation method thereof - Google Patents
Air purification material capable of rapidly degrading formaldehyde and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of air purification, and particularly relates to an air purification material for rapidly degrading formaldehyde and a preparation method thereof, wherein an antimony trichloride hydrochloric acid solution and sodium thiosulfate are added into deionized water, the mixture is stirred and uniformly mixed, then nano cerium dioxide is added, the ultrasonic dispersion is uniform, the hydrothermal reaction is carried out, and the post-treatment is carried out to obtain a nano material; then, the nano material is modified by gamma-aminopropyltriethoxysilane to obtain a modified nano material, and then the modified nano material is compounded with polyether sulfone to obtain a compound; and finally, adding the compound into tetraethoxysilane, hydrolyzing to prepare gel, and performing polyimide modification on the gel to obtain the polyimide resin. The air purification material can realize rapid, efficient and continuous adsorption and degradation of formaldehyde, and has extremely good popularization value.
Description
Technical Field
The invention belongs to the technical field of air purification. More particularly, relates to an air purification material for rapidly degrading formaldehyde and a preparation method thereof.
Background
Formaldehyde is a common environmental pollutant and a dangerous carcinogen, is a main source of indoor air pollution and seriously affects the health of people. Formaldehyde is very easily absorbed by the respiratory tract and gastrointestinal tract due to its high water solubility in water. If a human body is exposed to low-dose formaldehyde for a long time, chronic poisoning can be caused, mucosal inflammation, skin allergy, chronic digestive tract and respiratory tract diseases appear, even cancer of the oral cavity, the nasal cavity, the respiratory tract and the skin is caused, and death is caused by more serious people. Formaldehyde can react with some substances in the air to generate carcinogenic substances, and the metabolic products of formaldehyde can destroy proteins and enzymes of the organism, so that tissue cells are subjected to irreversible coagulation and necrosis, the functions of the organism are influenced, and the human body is greatly injured. According to the civil building indoor environmental pollution control standard and the indoor air quality standard, the content of the formaldehyde is less than or equal to 0.08mg/m3Or less than or equal to 0.1mg/m3I.e.. ltoreq.80 mg/L or 100mg/L, formaldehyde in fact exceeds the above-mentioned standards severely in many indoor environments.
The research shows that the process of releasing the formaldehyde in the room can last for ten years or more, and the long-term effective formaldehyde absorption and removal are very important.
At present, two methods for removing formaldehyde mainly exist, one is physical adsorption, and the other is chemical decomposition. The physical adsorption is to absorb free formaldehyde released from the environment by using the surface structure of an adsorption filler, and common adsorption fillers comprise activated carbon, diatomite, medical stone and the like. The chemical decomposition is the function of capturing formaldehyde and absorbing and decomposing into harmless components by adding a chemical additive capable of chemically decomposing formaldehyde. If the two are combined, the adsorption and decomposition are carried out in an auxiliary way, and the effect of removing the formaldehyde is better.
Patent CN107252703B discloses a preparation method of a cellulose-based formaldehyde degradation catalytic material, which is obtained by taking a cellulose-based carrier material as a raw material, compounding active components by using an impregnation method, aging at low temperature, reducing and post-treating. The formaldehyde removal rate of the catalytic material is low, the formaldehyde removal activity can be maintained within 72 hours, and the requirement for quickly, efficiently and continuously degrading formaldehyde cannot be met.
Disclosure of Invention
The invention aims to solve the technical problem of overcoming the defects and shortcomings that the existing air purification material can not degrade formaldehyde quickly, efficiently and continuously, and provides an air purification material for quickly degrading formaldehyde and a preparation method thereof.
The invention aims to provide a preparation method of an air purification material capable of rapidly degrading formaldehyde.
The invention also aims to provide the air purification material for rapidly degrading formaldehyde, which is obtained by the preparation method.
The above purpose of the invention is realized by the following technical scheme:
the invention provides a preparation method of an air purification material for rapidly degrading formaldehyde, which comprises the following specific steps:
(1) adding an antimony trichloride hydrochloric acid solution and sodium thiosulfate into deionized water, uniformly stirring, adding nano cerium dioxide, uniformly dispersing by ultrasonic waves, carrying out hydrothermal reaction, and carrying out post-treatment to obtain a nano material;
(2) then, the nano material is modified by gamma-aminopropyltriethoxysilane to obtain a modified nano material, and then the modified nano material is compounded with polyether sulfone to obtain a compound;
(3) and finally, adding the compound into tetraethoxysilane, hydrolyzing to prepare gel, and performing polyimide modification on the gel to obtain the air purification material.
Preferably, in the step (1), the mass ratio of the antimony trichloride contained in the nano cerium dioxide, the deionized water and the antimony trichloride hydrochloric acid solution is 0.2-0.3: 8-10: 1, slowly adding antimony trichloride into concentrated hydrochloric acid with the mass concentration of 36-38% and the weight of 3-5 times that of the antimony trichloride, and uniformly stirring to obtain an antimony trichloride-sodium thiosulfate solution, wherein the molar ratio of the antimony trichloride to the sodium thiosulfate is 4: 3.
preferably, in the step (1), the hydrothermal reaction process conditions are as follows: hydrothermal reaction at 75-85 ℃ for 3-4 hours.
Preferably, in step (1), the post-treatment comprises: centrifuging to obtain a precipitate, washing with deionized water for 2-3 times, and vacuum drying at 70-80 ℃ for 8-10 hours.
Preferably, in the step (2), the preparation method of the modified nano material comprises the following steps: adding 1 part of gamma-aminopropyltriethoxysilane into 6-8 parts of toluene, uniformly stirring, adding 1.2-1.5 parts of a nano material, stirring and reacting at 80-90 ℃ for 6-9 hours, naturally cooling to room temperature, centrifuging, washing, and drying to obtain the modified nano material.
Preferably, in the step (2), the composite is prepared by mixing the modified nano material and the polyether sulfone according to a mass ratio of 1: 7-9, and extruding in a parallel electric field with the electric field strength of 3-4 kV/m and the direction of the electric field unchanged to obtain the mixture; wherein the polymerization degree of the polyether sulfone is 1300-1500.
Preferably, in the step (3), the preparation method of the gel comprises the following steps in parts by weight: adding 1 part of the compound into 2-2.5 parts of ethyl orthosilicate, fully stirring, adding 9-10 parts of 40-50% ethanol aqueous solution by mass concentration, uniformly stirring, adjusting the pH to 3-4, stirring for hydrolysis, adjusting the pH to 8-10, heating to 60-70 ℃, standing for curing to obtain hydrogel, and performing post-treatment to obtain the gel.
Further preferably, the process conditions of stirring hydrolysis are as follows: stirring and hydrolyzing for 50-60 minutes at 60-70 ℃; standing and curing time is 40-50 hours.
Further preferably, the post-treatment method comprises the following specific steps: and (3) fully replacing water and ethanol in the hydrogel by using n-hexane, and drying by using a carbon dioxide supercritical fluid to obtain the gel.
More preferably, the process conditions of the supercritical fluid drying by carbon dioxide are as follows: the pressure is 6-8 MPa, the temperature is 45-50 ℃, and the time is 8-10 hours.
Preferably, in the step (3), the specific method for modifying the polyimide comprises the following steps in parts by weight: adding 4,4 ' -diaminobenzanilide into N, N ' -dimethylacetamide with the weight 5-7 times of that of the diaminobenzanilide, uniformly dispersing by ultrasonic waves, adding 4,4 ' - (hexafluoroisopropylene) diphthalic anhydride, and stirring and reacting at room temperature (25 ℃) for 6-8 hours to obtain a mixed solution; adding the gel into the mixed solution, stirring and reacting for 5-7 hours at 200-220 ℃, centrifuging, washing and drying; wherein the mol ratio of the 4,4 '-diaminobenzanilide to the 4, 4' - (hexafluoroisopropylidene) diphthalic anhydride is 1: 1.
further preferably, the mass ratio of the gel to the premix is 1: 6-8.
The invention also provides the air purification material for rapidly degrading formaldehyde, which is prepared by the preparation method.
The invention has the following beneficial effects:
adding an antimony trichloride hydrochloric acid solution and sodium thiosulfate into deionized water, uniformly stirring, adding nano cerium dioxide, uniformly dispersing by ultrasonic waves, carrying out hydrothermal reaction, and carrying out post-treatment to obtain a nano material; then, the nano material is modified by gamma-aminopropyltriethoxysilane to obtain a modified nano material, and then the modified nano material is compounded with polyether sulfone to obtain a compound; and finally, adding the compound into tetraethoxysilane, hydrolyzing to prepare gel, and performing polyimide modification on the gel to obtain the air purification material. The air purification material can realize rapid, efficient and continuous adsorption and degradation of formaldehyde, and has extremely good popularization value.
Firstly, the modified nano material and the polyether sulfone have a certain adsorption effect, a plurality of pores are formed after the modified nano material and the polyether sulfone are hydrolyzed by tetraethoxysilane to prepare a gel structure, so that the adsorption effect is better, finally, the gel is modified by polyimide, the specific surface area is further increased, and the adsorption effect is further improved, so that the air purification material has better adsorption to formaldehyde, and provides a good foundation for the rapid degradation of the formaldehyde.
And secondly, the invention takes antimony trichloride, sodium thiosulfate and nano cerium dioxide as raw materials, the raw materials are prepared into a nano material through hydrothermal reaction, the electron-withdrawing action of sulfur promotes the charge transfer on antimony and cerium, the separation and transfer of carriers in a system are promoted, the photocatalytic degradation performance of formaldehyde is improved, and the rapid and efficient degradation is realized.
In addition, the invention carries out modification treatment on the nano material by utilizing gamma-aminopropyltriethoxysilane, introduces amino, can form hydrogen bond action with polyether sulfone, constructs a three-dimensional structure, enriches pores, further enhances the adsorbability to formaldehyde, provides more paths for carrier separation and transfer and promotes photocatalytic degradation. The polyimide modification is also beneficial to the rapid separation and transfer of current carriers, and the photocatalytic degradation efficiency of formaldehyde is further improved.
Detailed Description
The present invention is further illustrated by the following specific examples, which are not intended to limit the invention in any way. Reagents, methods and apparatus used in the present invention are conventional in the art unless otherwise indicated.
Unless otherwise indicated, reagents and materials used in the following examples are commercially available.
Example 1
A preparation method of an air purification material for rapidly degrading formaldehyde comprises the following specific steps:
(1) adding an antimony trichloride hydrochloric acid solution and sodium thiosulfate into deionized water, uniformly stirring, adding nano cerium dioxide, uniformly dispersing by ultrasonic waves, carrying out hydrothermal reaction, and carrying out post-treatment to obtain a nano material;
(2) then, the nano material is modified by gamma-aminopropyltriethoxysilane to obtain a modified nano material, and then the modified nano material is compounded with polyether sulfone to obtain a compound;
(3) and finally, adding the compound into tetraethoxysilane, hydrolyzing to prepare gel, and performing polyimide modification on the gel to obtain the air purification material.
In the step (1), the mass ratio of antimony trichloride contained in the nano cerium dioxide, the deionized water and the antimony trichloride hydrochloric acid solution is 0.3: 8: 1, slowly adding antimony trichloride into concentrated hydrochloric acid with the mass concentration of 38% and the weight of 3 times of that of the antimony trichloride, and uniformly stirring to obtain an antimony trichloride hydrochloric acid solution, wherein the molar ratio of the antimony trichloride to sodium thiosulfate is 4: 3.
in the step (1), the process conditions of the hydrothermal reaction are as follows: hydrothermal reaction at 75 deg.c for 4 hr.
In the step (1), the post-treatment comprises: centrifuging to obtain precipitate, washing with deionized water for 2 times, and vacuum drying at 80 deg.C for 8 hr.
In the step (2), the preparation method of the modified nano material comprises the following steps: firstly adding 1kg of gamma-aminopropyltriethoxysilane into 8kg of toluene, uniformly stirring, then adding 1.2kg of nano material, stirring and reacting for 6 hours at 90 ℃, naturally cooling to room temperature, centrifuging, washing and drying to obtain the modified nano material.
In the step (2), the composite is prepared by mixing the modified nano material and polyether sulfone according to the mass ratio of 1: 9, mixing, and extruding in a parallel electric field with the electric field strength of 3kV/m and the unchanged electric field direction to obtain the product; wherein the polymerization degree of the polyether sulfone is 1500.
In the step (3), the preparation method of the gel is as follows: adding 1kg of compound into 2kg of ethyl orthosilicate, fully stirring, adding 10kg of ethanol aqueous solution with the mass concentration of 40%, uniformly stirring, adjusting the pH to 4, stirring for hydrolysis, adjusting the pH to 8, heating to 70 ℃, standing for curing to obtain hydrogel, and performing post-treatment to obtain the gel.
The technological conditions of stirring hydrolysis are as follows: stirring and hydrolyzing for 60 minutes at 60 ℃; standing for aging for 40 hr.
The specific method of post-treatment is as follows: and (3) fully replacing water and ethanol in the hydrogel by using n-hexane, and drying by using a carbon dioxide supercritical fluid to obtain the gel.
The process conditions of the supercritical carbon dioxide fluid drying are as follows: the pressure is 8MPa, the temperature is 45 ℃, and the time is 10 hours.
In the step (3), the specific method for modifying the polyimide comprises the following steps: adding 4,4 ' -diaminobenzanilide into N, N ' -dimethylacetamide with the weight 5 times of that of the diaminobenzanilide, uniformly dispersing by ultrasonic waves, adding 4,4 ' - (hexafluoro-isopropylene) diphthalic anhydride, and stirring at room temperature (25 ℃) for reacting for 8 hours to obtain a mixed solution; then adding the gel into the mixed solution, stirring and reacting for 7 hours at 200 ℃, centrifuging, washing and drying to obtain the gel; wherein the mol ratio of the 4,4 '-diaminobenzanilide to the 4, 4' - (hexafluoroisopropylidene) diphthalic anhydride is 1: 1. the mass ratio of the gel to the premix is 1: 6.
example 2
A preparation method of an air purification material for rapidly degrading formaldehyde comprises the following specific steps:
(1) adding an antimony trichloride hydrochloric acid solution and sodium thiosulfate into deionized water, uniformly stirring, adding nano cerium dioxide, uniformly dispersing by ultrasonic waves, carrying out hydrothermal reaction, and carrying out post-treatment to obtain a nano material;
(2) then, the nano material is modified by gamma-aminopropyltriethoxysilane to obtain a modified nano material, and then the modified nano material is compounded with polyether sulfone to obtain a compound;
(3) and finally, adding the compound into tetraethoxysilane, hydrolyzing to prepare gel, and performing polyimide modification on the gel to obtain the air purification material.
In the step (1), the mass ratio of antimony trichloride contained in the nano cerium dioxide, the deionized water and the antimony trichloride hydrochloric acid solution is 0.2: 10: 1, slowly adding antimony trichloride into concentrated hydrochloric acid with the mass concentration of 36% and the weight of 5 times of that of the antimony trichloride, and uniformly stirring to obtain an antimony trichloride hydrochloric acid solution, wherein the molar ratio of the antimony trichloride to sodium thiosulfate is 4: 3.
in the step (1), the process conditions of the hydrothermal reaction are as follows: hydrothermal reaction at 85 deg.c for 3 hr.
In the step (1), the post-treatment comprises: centrifuging to obtain precipitate, washing with deionized water for 3 times, and vacuum drying at 70 deg.C for 10 hr.
In the step (2), the preparation method of the modified nano material comprises the following steps: firstly, adding 1kg of gamma-aminopropyltriethoxysilane into 6kg of toluene, uniformly stirring, then adding 1.5kg of nano material, stirring and reacting for 9 hours at 80 ℃, naturally cooling to room temperature, centrifuging, washing and drying to obtain the modified nano material.
In the step (2), the composite is prepared by mixing the modified nano material and polyether sulfone according to the mass ratio of 1: 7, mixing, and extruding in a parallel electric field with the electric field strength of 4kV/m and the direction of the electric field unchanged to obtain the product; wherein the polymerization degree of the polyether sulfone is 1300.
In the step (3), the preparation method of the gel is as follows: adding 1kg of compound into 2.5kg of ethyl orthosilicate, fully stirring, adding 9kg of ethanol aqueous solution with the mass concentration of 50%, uniformly stirring, adjusting the pH to 3, stirring for hydrolysis, adjusting the pH to 10, heating to 60 ℃, standing for curing to obtain hydrogel, and performing aftertreatment to obtain the gel.
The technological conditions of stirring hydrolysis are as follows: stirring and hydrolyzing for 50 minutes at 70 ℃; the standing and curing time is 50 hours.
The specific method of post-treatment is as follows: and (3) fully replacing water and ethanol in the hydrogel by using n-hexane, and drying by using a carbon dioxide supercritical fluid to obtain the gel.
The process conditions of the supercritical carbon dioxide fluid drying are as follows: the pressure is 6MPa, the temperature is 50 ℃, and the time is 8 hours.
In the step (3), the specific method for modifying the polyimide comprises the following steps: adding 4,4 ' -diaminobenzanilide into N, N ' -dimethylacetamide with the weight being 7 times that of the diaminobenzanilide, uniformly dispersing by ultrasonic waves, adding 4,4 ' - (hexafluoro-isopropylene) diphthalic anhydride, and stirring and reacting at room temperature (25 ℃) for 6 hours to obtain a mixed solution; then adding the gel into the mixed solution, stirring and reacting for 5 hours at 220 ℃, centrifuging, washing and drying to obtain the gel; wherein the mol ratio of the 4,4 '-diaminobenzanilide to the 4, 4' - (hexafluoroisopropylidene) diphthalic anhydride is 1: 1. the mass ratio of the gel to the premix is 1: 8.
example 3
A preparation method of an air purification material for rapidly degrading formaldehyde comprises the following specific steps:
(1) adding an antimony trichloride hydrochloric acid solution and sodium thiosulfate into deionized water, uniformly stirring, adding nano cerium dioxide, uniformly dispersing by ultrasonic waves, carrying out hydrothermal reaction, and carrying out post-treatment to obtain a nano material;
(2) then, the nano material is modified by gamma-aminopropyltriethoxysilane to obtain a modified nano material, and then the modified nano material is compounded with polyether sulfone to obtain a compound;
(3) and finally, adding the compound into tetraethoxysilane, hydrolyzing to prepare gel, and performing polyimide modification on the gel to obtain the air purification material.
In the step (1), the mass ratio of antimony trichloride contained in the nano cerium dioxide, the deionized water and the antimony trichloride hydrochloric acid solution is 0.25: 9: 1, slowly adding antimony trichloride into concentrated hydrochloric acid with the mass concentration of 37% and the weight of 4 times of that of the antimony trichloride, and uniformly stirring to obtain an antimony trichloride hydrochloric acid solution, wherein the molar ratio of the antimony trichloride to sodium thiosulfate is 4: 3.
in the step (1), the process conditions of the hydrothermal reaction are as follows: hydrothermal reaction at 80 deg.c for 3.5 hr.
In the step (1), the post-treatment comprises: centrifuging to obtain precipitate, washing with deionized water for 3 times, and vacuum drying at 75 deg.C for 9 hr.
In the step (2), the preparation method of the modified nano material comprises the following steps: firstly adding 1kg of gamma-aminopropyltriethoxysilane into 7kg of toluene, uniformly stirring, adding 1.3kg of nano material, stirring and reacting for 8 hours at 85 ℃, naturally cooling to room temperature, centrifuging, washing and drying to obtain the modified nano material.
In the step (2), the composite is prepared by mixing the modified nano material and polyether sulfone according to the mass ratio of 1: 8, mixing, and extruding in a parallel electric field with the electric field strength of 3.5kV/m and the direction of the electric field unchanged to obtain the mixture; wherein the polymerization degree of the polyether sulfone is 1400.
In the step (3), the preparation method of the gel is as follows: adding 1kg of compound into 2.2kg of ethyl orthosilicate, fully stirring, adding 9.5kg of 45% ethanol aqueous solution with mass concentration, uniformly stirring, adjusting the pH to 4, stirring for hydrolysis, adjusting the pH to 9, heating to 65 ℃, standing for curing to obtain hydrogel, and performing aftertreatment to obtain the gel.
The technological conditions of stirring hydrolysis are as follows: stirring and hydrolyzing for 55 minutes at 65 ℃; the standing and curing time is 45 hours.
The specific method of post-treatment is as follows: and (3) fully replacing water and ethanol in the hydrogel by using n-hexane, and drying by using a carbon dioxide supercritical fluid to obtain the gel.
The process conditions of the supercritical carbon dioxide fluid drying are as follows: the pressure is 7MPa, the temperature is 48 ℃, and the time is 9 hours.
In the step (3), the specific method for modifying the polyimide comprises the following steps: adding 4,4 ' -diaminobenzanilide into 6 times of N, N ' -dimethylacetamide, uniformly dispersing by ultrasonic wave, adding 4,4 ' - (hexafluoro-isopropylene) diphthalic anhydride, and stirring at room temperature (25 ℃) for reaction for 7 hours to obtain a mixed solution; then adding the gel into the mixed solution, stirring and reacting for 6 hours at 210 ℃, centrifuging, washing and drying to obtain the gel; wherein the mol ratio of the 4,4 '-diaminobenzanilide to the 4, 4' - (hexafluoroisopropylidene) diphthalic anhydride is 1: 1. the mass ratio of the gel to the premix is 1: 7.
comparative example 1
A preparation method of an air purification material comprises the following specific steps:
(1) adding an antimony trichloride hydrochloric acid solution and sodium thiosulfate into deionized water, stirring until the antimony trichloride hydrochloric acid solution and the sodium thiosulfate are completely dissolved, carrying out hydrothermal reaction, and carrying out post-treatment to obtain a nano material;
(2) then, the nano material is modified by gamma-aminopropyltriethoxysilane to obtain a modified nano material, and then the modified nano material is compounded with polyether sulfone to obtain a compound;
(3) and finally, adding the compound into tetraethoxysilane, hydrolyzing to prepare gel, and performing polyimide modification on the gel to obtain the air purification material.
In the step (1), the mass ratio of antimony trichloride contained in the nano cerium dioxide, the deionized water and the antimony trichloride hydrochloric acid solution is 0.3: 8: 1, slowly adding antimony trichloride into concentrated hydrochloric acid with the mass concentration of 38% and the weight of 3 times of that of the antimony trichloride, and uniformly stirring to obtain an antimony trichloride hydrochloric acid solution, wherein the molar ratio of the antimony trichloride to sodium thiosulfate is 4: 3.
in the step (1), the process conditions of the hydrothermal reaction are as follows: hydrothermal reaction at 75 deg.c for 4 hr.
In the step (1), the post-treatment comprises: centrifuging to obtain precipitate, washing with deionized water for 2 times, and vacuum drying at 80 deg.C for 8 hr.
In the step (2), the preparation method of the modified nano material comprises the following steps: firstly adding 1kg of gamma-aminopropyltriethoxysilane into 8kg of toluene, uniformly stirring, then adding 1.2kg of nano material, stirring and reacting for 6 hours at 90 ℃, naturally cooling to room temperature, centrifuging, washing and drying to obtain the modified nano material.
In the step (2), the composite is prepared by mixing the modified nano material and polyether sulfone according to the mass ratio of 1: 9, mixing, and extruding in a parallel electric field with the electric field strength of 3kV/m and the unchanged electric field direction to obtain the product; wherein the polymerization degree of the polyether sulfone is 1500.
In the step (3), the preparation method of the gel is as follows: adding 1kg of compound into 2kg of ethyl orthosilicate, fully stirring, adding 10kg of ethanol aqueous solution with the mass concentration of 40%, uniformly stirring, adjusting the pH to 4, stirring for hydrolysis, adjusting the pH to 8, heating to 70 ℃, standing for curing to obtain hydrogel, and performing post-treatment to obtain the gel.
The technological conditions of stirring hydrolysis are as follows: stirring and hydrolyzing for 60 minutes at 60 ℃; standing for aging for 40 hr.
The specific method of post-treatment is as follows: and (3) fully replacing water and ethanol in the hydrogel by using n-hexane, and drying by using a carbon dioxide supercritical fluid to obtain the gel.
The process conditions of the supercritical carbon dioxide fluid drying are as follows: the pressure is 8MPa, the temperature is 45 ℃, and the time is 10 hours.
In the step (3), the specific method for modifying the polyimide comprises the following steps: adding 4,4 ' -diaminobenzanilide into N, N ' -dimethylacetamide with the weight 5 times of that of the diaminobenzanilide, uniformly dispersing by ultrasonic waves, adding 4,4 ' - (hexafluoro-isopropylene) diphthalic anhydride, and stirring at room temperature (25 ℃) for reacting for 8 hours to obtain a mixed solution; then adding the gel into the mixed solution, stirring and reacting for 7 hours at 200 ℃, centrifuging, washing and drying to obtain the gel; wherein the mol ratio of the 4,4 '-diaminobenzanilide to the 4, 4' - (hexafluoroisopropylidene) diphthalic anhydride is 1: 1. the mass ratio of the gel to the premix is 1: 6.
comparative example 2
A preparation method of an air purification material comprises the following specific steps:
(1) adding an antimony trichloride hydrochloric acid solution and sodium thiosulfate into deionized water, uniformly stirring, adding nano cerium dioxide, uniformly dispersing by ultrasonic waves, carrying out hydrothermal reaction, and carrying out post-treatment to obtain a nano material;
(2) then, the nano material is modified by gamma-aminopropyltriethoxysilane to obtain a modified nano material;
(3) and finally, adding the modified nano material into tetraethoxysilane, hydrolyzing to prepare gel, and performing polyimide modification on the gel to obtain the air purification material.
In the step (1), the mass ratio of antimony trichloride contained in the nano cerium dioxide, the deionized water and the antimony trichloride hydrochloric acid solution is 0.3: 8: 1, slowly adding antimony trichloride into concentrated hydrochloric acid with the mass concentration of 38% and the weight of 3 times of that of the antimony trichloride, and uniformly stirring to obtain an antimony trichloride hydrochloric acid solution, wherein the molar ratio of the antimony trichloride to sodium thiosulfate is 4: 3.
in the step (1), the process conditions of the hydrothermal reaction are as follows: hydrothermal reaction at 75 deg.c for 4 hr.
In the step (1), the post-treatment comprises: centrifuging to obtain precipitate, washing with deionized water for 2 times, and vacuum drying at 80 deg.C for 8 hr.
In the step (2), the preparation method of the modified nano material comprises the following steps: firstly adding 1kg of gamma-aminopropyltriethoxysilane into 8kg of toluene, uniformly stirring, then adding 1.2kg of nano material, stirring and reacting for 6 hours at 90 ℃, naturally cooling to room temperature, centrifuging, washing and drying to obtain the modified nano material.
In the step (3), the preparation method of the gel is as follows: adding 1kg of modified nano material into 2kg of ethyl orthosilicate, fully stirring, adding 10kg of ethanol aqueous solution with the mass concentration of 40%, uniformly stirring, adjusting the pH to 4, stirring for hydrolysis, adjusting the pH to 8, heating to 70 ℃, standing for curing to obtain hydrogel, and performing aftertreatment to obtain the gel.
The technological conditions of stirring hydrolysis are as follows: stirring and hydrolyzing for 60 minutes at 60 ℃; standing for aging for 40 hr.
The specific method of post-treatment is as follows: and (3) fully replacing water and ethanol in the hydrogel by using n-hexane, and drying by using a carbon dioxide supercritical fluid to obtain the gel.
The process conditions of the supercritical carbon dioxide fluid drying are as follows: the pressure is 8MPa, the temperature is 45 ℃, and the time is 10 hours.
In the step (3), the specific method for modifying the polyimide comprises the following steps: adding 4,4 ' -diaminobenzanilide into N, N ' -dimethylacetamide with the weight 5 times of that of the diaminobenzanilide, uniformly dispersing by ultrasonic waves, adding 4,4 ' - (hexafluoro-isopropylene) diphthalic anhydride, and stirring at room temperature (25 ℃) for reacting for 8 hours to obtain a mixed solution; then adding the gel into the mixed solution, stirring and reacting for 7 hours at 200 ℃, centrifuging, washing and drying to obtain the gel; wherein the mol ratio of the 4,4 '-diaminobenzanilide to the 4, 4' - (hexafluoroisopropylidene) diphthalic anhydride is 1: 1. the mass ratio of the gel to the premix is 1: 6.
comparative example 3
A preparation method of an air purification material comprises the following specific steps:
(1) adding an antimony trichloride hydrochloric acid solution and sodium thiosulfate into deionized water, uniformly stirring, adding nano cerium dioxide, uniformly dispersing by ultrasonic waves, carrying out hydrothermal reaction, and carrying out post-treatment to obtain a nano material;
(2) then, the nano material is modified by gamma-aminopropyltriethoxysilane to obtain a modified nano material, and then the modified nano material is compounded with polyether sulfone to obtain a compound;
(3) and finally, adding the compound into tetraethoxysilane, and hydrolyzing to prepare gel, namely the air purification material.
In the step (1), the mass ratio of antimony trichloride contained in the nano cerium dioxide, the deionized water and the antimony trichloride hydrochloric acid solution is 0.3: 8: 1, slowly adding antimony trichloride into concentrated hydrochloric acid with the mass concentration of 38% and the weight of 3 times of that of the antimony trichloride, and uniformly stirring to obtain an antimony trichloride hydrochloric acid solution, wherein the molar ratio of the antimony trichloride to sodium thiosulfate is 4: 3.
in the step (1), the process conditions of the hydrothermal reaction are as follows: hydrothermal reaction at 75 deg.c for 4 hr.
In the step (1), the post-treatment comprises: centrifuging to obtain precipitate, washing with deionized water for 2 times, and vacuum drying at 80 deg.C for 8 hr.
In the step (2), the preparation method of the modified nano material comprises the following steps: firstly adding 1kg of gamma-aminopropyltriethoxysilane into 8kg of toluene, uniformly stirring, then adding 1.2kg of nano material, stirring and reacting for 6 hours at 90 ℃, naturally cooling to room temperature, centrifuging, washing and drying to obtain the modified nano material.
In the step (2), the composite is prepared by mixing the modified nano material and polyether sulfone according to the mass ratio of 1: 9, mixing, and extruding in a parallel electric field with the electric field strength of 3kV/m and the unchanged electric field direction to obtain the product; wherein the polymerization degree of the polyether sulfone is 1500.
The specific method of the step (3) is as follows: adding 1kg of compound into 2kg of ethyl orthosilicate, fully stirring, adding 10kg of ethanol aqueous solution with the mass concentration of 40%, uniformly stirring, adjusting the pH to 4, stirring for hydrolysis, adjusting the pH to 8, heating to 70 ℃, standing for curing to obtain hydrogel, and performing post-treatment to obtain the gel.
The technological conditions of stirring hydrolysis are as follows: stirring and hydrolyzing for 60 minutes at 60 ℃; standing for aging for 40 hr.
The specific method of post-treatment is as follows: and (3) fully replacing water and ethanol in the hydrogel by using n-hexane, and drying by using a carbon dioxide supercritical fluid to obtain the gel.
The process conditions of the supercritical carbon dioxide fluid drying are as follows: the pressure is 8MPa, the temperature is 45 ℃, and the time is 10 hours.
Test examples
Using formaldehyde generator to reach 10m3Formaldehyde is generated in the test chamber, the initial concentration of the formaldehyde in the test chamber is 10mg/L through stirring by a stirring fan, the air purification material obtained in examples 1-3 or comparative examples 1-3 is placed in the middle position in the test chamber, the air purification material is stirred for 5 minutes at 25 ℃ under the condition of natural light, a formaldehyde tester is used for detecting the concentration of the formaldehyde after treatment, the degradation rate of the formaldehyde is calculated, and the result is shown in table 1, wherein the degradation rate (%) (concentration before treatment-concentration after treatment)/concentration before treatment x 100%.
Generating formaldehyde into the test chamber at 8 am every day to ensure that the initial concentration of the formaldehyde in the test chamber is 10mg/L, and stirring for 5 minutes by a stirring fan at 25 ℃ under the condition of natural light; after the circulation and the continuous treatment for one month, the formaldehyde degradation rate is examined, and the results are shown in Table 2.
TABLE 1 examination of Formaldehyde degradation
| Degradation Rate (%) | |
| Example 1 | 98.32 |
| Example 2 | 98.57 |
| Example 3 | 99.15 |
| Comparative example 1 | 87.69 |
| Comparative example 2 | 92.38 |
| Comparative example 3 | 93.04 |
TABLE 2 examination of Formaldehyde degradation after 1 month of continued use
As can be seen from tables 1 and 2, the air purification materials obtained in examples 1 to 3 can efficiently degrade formaldehyde within 5 minutes, and have a high formaldehyde degradation rate after long-term use, which indicates that the air purification material of the present invention can rapidly, efficiently, and continuously remove formaldehyde.
Comparative example 1 nano ceria was omitted in step (1), comparative example 2 was omitted in step (2) and compounded with polyethersulfone, comparative example 3 was omitted in step (3) and modified with polyimide, the degradation effect of the obtained air purification material on formaldehyde was significantly poor, which indicates that the synergistic photocatalytic degradation effect of the nanomaterial and the synergistic adsorption effect of polyethersulfone, gel structure and polyimide improve the formaldehyde degradation effect of the product together, and in addition, the formaldehyde degradation effect was poor after the use of comparative example 2 and comparative example 3 for a long time, which indicates that the surface modification of the nanomaterial helps to maintain the degradation activity and avoid formaldehyde degradation failure.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (7)
1. A preparation method of an air purification material capable of rapidly degrading formaldehyde is characterized by comprising the following specific steps:
(1) adding an antimony trichloride hydrochloric acid solution and sodium thiosulfate into deionized water, uniformly stirring, adding nano cerium dioxide, uniformly dispersing by ultrasonic waves, carrying out hydrothermal reaction, and carrying out post-treatment to obtain a nano material;
(2) then, the nano material is modified by gamma-aminopropyltriethoxysilane to obtain a modified nano material, and then the modified nano material is compounded with polyether sulfone to obtain a compound;
(3) finally, adding the compound into tetraethoxysilane, hydrolyzing to prepare gel, and performing polyimide modification on the gel to obtain the air purification material;
in the step (1), the mass ratio of antimony trichloride contained in the nano cerium dioxide, deionized water and antimony trichloride hydrochloric acid solution is 0.2-0.3: 8-10: 1, slowly adding antimony trichloride into concentrated hydrochloric acid with the mass concentration of 36-38% and the weight of 3-5 times that of the antimony trichloride, and uniformly stirring to obtain an antimony trichloride hydrochloric acid solution; the molar ratio of the antimony trichloride to the sodium thiosulfate is 4: 3;
in the step (2), the composite is prepared by mixing the modified nano material and polyether sulfone according to the mass ratio of 1: 7-9, and extruding in a parallel electric field with the electric field strength of 3-4 kV/m and the direction of the electric field unchanged to obtain the mixture; wherein the polymerization degree of the polyether sulfone is 1300-1500;
in the step (3), the specific method for modifying the polyimide comprises the following steps in parts by weight: adding 4,4 ' -diaminobenzanilide into N, N ' -dimethylacetamide with the weight 5-7 times of that of the diaminobenzanilide, uniformly dispersing by ultrasonic waves, adding 4,4 ' - (hexafluoroisopropylene) diphthalic anhydride, and stirring and reacting at room temperature for 6-8 hours to obtain a mixed solution; adding the gel into the mixed solution, stirring and reacting for 5-7 hours at 200-220 ℃, centrifuging, washing and drying; wherein the mol ratio of the 4,4 '-diaminobenzanilide to the 4, 4' - (hexafluoroisopropylidene) diphthalic anhydride is 1: 1.
2. the preparation method according to claim 1, wherein in the step (1), the hydrothermal reaction is carried out under the following process conditions: hydrothermal reaction at 75-85 ℃ for 3-4 hours.
3. The method according to claim 1, wherein in the step (1), the post-treatment comprises: centrifuging to obtain a precipitate, washing with deionized water for 2-3 times, and vacuum drying at 70-80 ℃ for 8-10 hours.
4. The preparation method according to claim 1, wherein in the step (2), the modified nanomaterial is prepared by the following method in parts by weight: adding 1 part of gamma-aminopropyltriethoxysilane into 6-8 parts of toluene, uniformly stirring, adding 1.2-1.5 parts of a nano material, stirring and reacting at 80-90 ℃ for 6-9 hours, naturally cooling to room temperature, centrifuging, washing, and drying to obtain the modified nano material.
5. The method according to claim 1, wherein in the step (3), the gel is prepared by the following method in parts by weight: adding 1 part of the compound into 2-2.5 parts of ethyl orthosilicate, fully stirring, adding 9-10 parts of 40-50% ethanol water solution with mass concentration, uniformly stirring, adjusting pH = 3-4, stirring for hydrolysis, adjusting pH = 8-10, heating to 60-70 ℃, standing for curing to obtain hydrogel, and performing aftertreatment to obtain the gel.
6. The preparation method according to claim 5, wherein the process conditions of stirring hydrolysis are as follows: stirring and hydrolyzing for 50-60 minutes at 60-70 ℃; standing and curing time is 40-50 hours.
7. An air purification material capable of rapidly degrading formaldehyde, which is obtained by the preparation method of any one of claims 1-6.
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