Polymer containing oxygen amine functional group, preparation method of polymer, reactive adsorbent, preparation method of reactive adsorbent, application of reactive adsorbent and regeneration method of reactive adsorbent

Abstract

The invention belongs to the technical field of adsorbents, and particularly relates to an oxyamine functional group-containing polymer and a preparation method thereof, a reactive adsorbent and a preparation method, application and regeneration method thereof. The preparation method comprises the following steps: hydrolyzing a polymer containing oxime ether in an acid environment to generate a polymer containing an oxygen amine functional group in situ; a polymer containing an oxyamine functional group is subjected to film forming or loaded on a porous carrier to obtain the reactive adsorbent for degrading the aldehyde pollutants, the oxyamine functional group and aldehydes (such as formaldehyde) are subjected to oximation reaction, and the aldehyde pollutants in environments such as air or solutions can be efficiently removed; the adsorbent which is completely reacted and inactivated can be regenerated to obtain an oxygen amine functional group after being hydrolyzed in an acid solution, and has good recycling performance. The polymer material for in-situ generation of the oxyamine functional group is simple in preparation process, high in aldehyde removal efficiency, easy to regenerate and low in cost, and a simple and convenient method is provided for removal of aldehydes, especially formaldehyde, in the environment.

Description

Technical Field

[0001] The invention belongs to the technical field of adsorbents, and in particular relates to a polymer containing an oxygenated amine functional group and a preparation method thereof, a reactive adsorbent and a preparation method, application and regeneration method thereof. Background Art

[0002] Aldehyde compounds are intermediates in many organic syntheses and are widely used in industrial production processes such as plastics, dyes, medicines, and pesticides. Among them, formaldehyde (HCHO) is widely used in industries (such as plastics and resins), building materials (such as adhesives and paints), and medical treatments (such as fungicides and preservatives). However, formaldehyde is one of the most harmful gases to human health, often associated with an increased risk of cancer, and is highly irritating to the eyes and mucous membranes. In industrial production, formaldehyde is used as a raw material or by-product, and the exposure limit of formaldehyde is set at 0.5ppm every 8 hours. How to efficiently remove formaldehyde from the environment (such as air or solution systems in industrial production) is an important issue.

[0003] At present, the technologies for removing formaldehyde and other aldehyde pollutants in the environment mainly include plasma decomposition, biofiltration, photocatalytic oxidation or physical adsorption. Among them, physical adsorption has the advantages of low cost, environmental friendliness and simple operation and is widely used. However, due to the high vapor pressure of formaldehyde (3890 mmHg at 25°C) and relatively low boiling point (-19.3°C), it is easy to desorb again due to the influence of temperature and pollutant concentration. In addition, the selectivity of physical adsorption is poor. When the adsorption equilibrium is reached, it will lose the removal effect.

[0004] In contrast, chemical reaction elimination is a better formaldehyde removal strategy due to its irreversibility and high efficiency. It has been found that the oxamine functional group (-ONH2) can react with the aldehyde group to form an oxime bond, and can highly selectively remove formaldehyde and other aldehyde substances from the environment or reaction system; for example, the oxamine functional group-terminated compound can chemically conjugate with the ketone functional group on the polymer side chain at room temperature without the use of a catalyst to produce an oxime bond (-C=NO-), which can be regenerated into -ONH2 in a weakly acidic medium. However, the preparation process of the existing oxamine functional group-terminated compounds is cumbersome, the reagents used are costly, the efficiency is low, and it is not feasible for mass production, which affects its application in the degradation of aldehyde pollutants. Summary of the invention

[0005] In view of this, the present invention provides a polymer containing oxygenated amine functional groups and a preparation method thereof, a reactive adsorbent and a preparation method, application and regeneration method thereof; the preparation method of the polymer containing oxygenated amine functional groups provided by the present invention is simple and easy to industrialize, and the prepared polymer containing oxygenated amine functional groups has a high degradation efficiency for aldehyde pollutants.

[0006] In order to solve the above technical problems, the present invention provides a polymer containing an oxygen-amine functional group, having a structure shown in Formula 2: Formula 2.

[0007] The present invention also provides a method for preparing the polymer containing oxygen-amine functional groups described in the above technical solution, comprising the following steps: Acidifying and hydrolyzing the polymer containing oxime ether to obtain the polymer containing oxygenated amine functional groups; The oxime ether-containing polymer has a structure shown in Formula 1: Formula 1; Wherein, R1 and R2 are alkyl groups respectively.

[0008] Preferably, R1 and R2 are independently methyl, ethyl, propyl, isopropyl, butyl, sec-butyl or isobutyl.

[0009] Preferably, the method for preparing the oxime ether-containing polymer comprises the following steps: The chlorinated polyolefin, alkyl ketoxime, alkali metal salt, crown ether and the first organic solvent are mixed and refluxed to obtain the oxime ether-containing polymer.

[0010] Preferably, the chlorinated polyolefin includes chlorinated polyethylene, chlorinated polypropylene or chlorinated polybutene; The chlorinated polyolefin includes a chlorinated polyolefin with a low chlorination degree or a chlorinated polyolefin with a high chlorination degree; the chlorination degree of the chlorinated polyolefin with a low chlorination degree is 20-50%, and the chlorination degree of the chlorinated polyolefin with a high chlorination degree is greater than 50% and less than or equal to 70%; the viscosity of the chlorinated polyolefin is 800-50000. , acid value is 6.0~8.0; The alkyl ketone oxime includes acetone oxime, butanone oxime, 2-pentanone oxime, 3-pentanone oxime, 3-methyl-2-butanone oxime, 2-hexanone oxime, 3-hexanone oxime, 2-methyl-3-pentanone oxime, 3-methyl-2-pentanone oxime or 4-methyl-2-pentanone oxime; The alkali metal salt includes one or more of alkali metal carbonate, alkali metal bicarbonate and alkali metal halide; The crown ether includes 12-crown-4, 15-crown-5 or 18-crown-6; The first organic solvent includes aromatic solvents, chlorinated hydrocarbon solvents, ester solvents, ketone solvents, tetrahydrofuran, pyridine or dioxane.

[0011] Preferably, the mass ratio of the chlorinated polyolefin to the alkyl ketoxime is 1:3 to 3:1; The molar ratio of the alkyl ketoxime to the alkali metal salt is 0.4:1 to 2:1; The molar ratio of the alkyl ketoxime to the crown ether is 100:1 to 10:1.

[0012] Preferably, the reflux temperature is 50-120° C. and the reflux time is 5-20 h.

[0013] Preferably, after the reflux, the method further comprises: adding an organic alcohol dropwise to the reflux system to perform solid-liquid separation after precipitation to obtain the oxime ether-containing polymer; The organic alcohol includes methanol, ethanol, isopropanol or n-butanol.

[0014] Preferably, the first acid solution for acidification and hydrolysis includes hydrochloric acid solution, sulfuric acid solution or nitric acid solution; The conditions of the acidification hydrolysis include: pH value of 1-4, temperature of 30-70° C., and time of 3-10 hours.

[0015] The present invention also provides a reactive adsorbent, including a membrane reactive adsorbent or a supported reactive adsorbent; The material of the membrane reactive adsorbent is a polymer containing oxygen-amine functional groups; The supported reactive adsorbent comprises a porous carrier and a polymer containing oxygen-containing amine functional groups supported on the surface and / or in the pores of the porous carrier; The polymer containing oxygenated amine functional groups is the polymer containing oxygenated amine functional groups described in the above technical solution or the polymer containing oxygenated amine functional groups prepared by the preparation method described in the above technical solution.

[0016] The present invention also provides a method for preparing the reactive adsorbent described in the above technical solution, comprising the following steps: The preparation method of the membrane reactive adsorbent comprises the following steps: The polymer containing oxygen amine functional group and the pore-forming agent are mixed to obtain a mixed material; The mixed product is formed and then subjected to biaxial stretching treatment to obtain the membrane reactive adsorbent; The preparation method of the supported reactive adsorbent comprises the following steps: dissolving the polymer containing oxygenated amine functional groups in a second organic solvent to obtain a polymer solution containing oxygenated amine functional groups; The porous carrier is dispersed in the polymer solution containing oxygen-containing amine functional groups for adsorption and then solid-liquid separation is performed, and the solid obtained by the solid-liquid separation is dried to obtain the supported reactive adsorbent.

[0017] The present invention also provides the use of the reactive adsorbent described in the above technical solution or the reactive adsorbent prepared by the preparation method described in the above technical solution in degrading aldehyde pollutants.

[0018] The present invention also provides a method for regenerating a reactive adsorbent, comprising the following steps: The reactive adsorbent after adsorbing the aldehyde pollutants is mixed with the second acid solution for hydrolysis to obtain a regenerated reactive adsorbent; The reactive adsorbent is the reactive adsorbent described in the above technical solution or the reactive adsorbent prepared by the preparation method described in the above technical solution.

[0019] The present invention hydrolyzes the polymer containing oxime ether in an acidic environment to generate a polymer containing oxygen amine functional groups in situ; the polymer containing oxygen amine functional groups is formed into a film or loaded on a porous carrier to obtain a reactive adsorbent for degrading aldehyde pollutants; the oxygen amine functional groups react with aldehydes (such as formaldehyde) to efficiently remove aldehyde impurities in air or solution environments; the reactive adsorbent that has reacted completely and deactivated can be hydrolyzed in an acidic solution to regenerate the oxygen amine functional groups, and has good recycling performance. The polymer material for generating oxygen amine functional groups in situ proposed by the present invention has a simple preparation process, high efficiency in removing aldehydes, easy material regeneration, and low cost, and provides a simple method for removing aldehydes, especially formaldehyde, in the environment. BRIEF DESCRIPTION OF THE DRAWINGS

[0020] Figure 1 The diagram is a reaction mechanism diagram of the hydrolysis of oxime ether-containing polymers under acidic conditions to generate polymers containing oxygenated amine functional groups; Figure 2 The schematic diagram of the reaction for absorbing formaldehyde and regenerating it using a polymer containing oxygenated amine functional groups. DETAILED DESCRIPTION

[0021] The present invention provides a polymer containing an oxygen-amine functional group, having a structure shown in Formula 2: Formula 2.

[0022] The present invention also provides a method for preparing the polymer containing oxygen-amine functional groups described in the above technical solution, comprising the following steps: Acidifying and hydrolyzing the polymer containing oxime ether to obtain the polymer containing oxygenated amine functional groups; The oxime ether-containing polymer has a structure shown in Formula 1: Formula 1; Wherein, R1 and R2 are alkyl groups respectively; R1 and R2 can independently be methyl, ethyl, propyl, isopropyl, butyl or isobutyl; when R1 is methyl, R2 can be methyl, ethyl, propyl, isopropyl, butyl, sec-butyl or isobutyl.

[0023] In the present invention, unless otherwise specified, all materials are conventional commercially available products.

[0024] As a specific embodiment of the present invention, the method for preparing the oxime ether-containing polymer may include the following steps: The chlorinated polyolefin, alkyl ketoxime, alkali metal salt, crown ether and the first organic solvent are mixed and refluxed to obtain the oxime ether-containing polymer.

[0025] As a specific embodiment of the present invention, the mixing may include the following steps: dissolving a chlorinated polyolefin in a first organic solvent to obtain a chlorinated polyolefin solution; Alkali metal salt, alkyl ketoxime and crown ether are added to the chlorinated polyolefin solution.

[0026] As a specific embodiment of the present invention, the chlorinated polyolefin may include chlorinated polyethylene, chlorinated polypropylene or chlorinated polybutene; the chlorinated polyolefin may include a chlorinated polyolefin with a low chlorination degree or a chlorinated polyolefin with a high chlorination degree; the chlorination degree of the chlorinated polyolefin with a low chlorination degree may be 20-50%, or 25-35%; the chlorination degree of the chlorinated polyolefin with a high chlorination degree may be greater than 50% and less than or equal to 70%, or 55-68%; the viscosity of the chlorinated polyolefin may be 800-50000. , can also be 1000~20000 ; The acid value of the chlorinated polyolefin may be 6.0 to 8.0, and may specifically be 6.0, 7.0 or 8.0.

[0027] As a specific embodiment of the present invention, the alkyl ketone oxime includes acetone oxime, butanone oxime, 2-pentanone oxime, 3-pentanone oxime, 3-methyl-2-butanone oxime, 2-hexanone oxime, 3-hexanone oxime, 2-methyl-3-pentanone oxime, 3-methyl-2-pentanone oxime or 4-methyl-2-pentanone oxime.

[0028] As a specific embodiment of the present invention, the alkali metal salt may include one or more of alkali metal carbonate, alkali metal bicarbonate and alkali metal halide, which may be specifically alkali metal carbonate, alkali metal bicarbonate or alkali metal halide; the alkali metal carbonate may include lithium carbonate, sodium carbonate or potassium carbonate; the alkali metal bicarbonate may include lithium bicarbonate, sodium bicarbonate or potassium bicarbonate; the alkali metal halide may include lithium chloride, sodium chloride, potassium chloride, sodium bromide or potassium iodide. In the present invention, the alkali metal salt plays the role of providing an alkaline environment to promote the ketoxime etherification.

[0029] As a specific embodiment of the present invention, the crown ether may include 12-crown-4, 15-crown-5 or 18-crown-6. In the present invention, the crown ether plays a role of a promoter.

[0030] As a specific embodiment of the present invention, the first organic solvent may include an aromatic solvent, a chlorinated hydrocarbon solvent, an ester solvent, a ketone solvent, tetrahydrofuran, pyridine or dioxane; the aromatic solvent may include benzene, toluene or xylene; the chlorinated hydrocarbon solvent may include 1,2-dichloroethane, tetrachloroethane, chloroform, carbon tetrachloride or chlorobenzene; the ester solvent may include ethyl acetate or butyl acetate; the ketone solvent may include butanone, methyl isobutyl ketone or methyl-2-pyrrolidone.

[0031] As a specific embodiment of the present invention, the mass ratio of the chlorinated polyolefin to the alkyl ketoxime can be 1:3-3:1, or 1:2-2:1, and can be specifically 1.1:1 or 1.2:1; the molar ratio of the alkyl ketoxime to the alkali metal salt can be 0.4:1-2:1, or 0.8:1-1.2:1, and can be specifically 1:1; the molar ratio of the alkyl ketoxime to the crown ether can be 100:1-10:1, or 50:1-30:1, and can be specifically 50:1, 40:1 or 30:1. The present invention has no special requirements for the amount of the first organic solvent, as long as the materials can be mixed evenly.

[0032] As a specific embodiment of the present invention, the reflux temperature can be 50-120°C, or 80-100°C; the reflux time can be 5-20h, or 8-15h. As a specific embodiment of the present invention, the reflux process can be accompanied by stirring. The present invention has no special limitation on the stirring as long as the material can react completely.

[0033] As a specific embodiment of the present invention, the reflux may further include: adding an organic alcohol aqueous solution to the reflux system to precipitate and then perform solid-liquid separation to obtain the oxime ether-containing polymer; the organic alcohol aqueous solution may include a methanol aqueous solution, an ethanol aqueous solution, an isopropanol aqueous solution or a n-butanol aqueous solution, and the mass concentration of the organic alcohol aqueous solution may be 20-80%, specifically 20%, 30%, 40%, 50%, 60%, 70% or 80%; the solid-liquid separation may be suction filtration.

[0034] As a specific embodiment of the present invention, the acid hydrolysis can be acid hydrolysis by mixing the oxime ether-containing polymer and the first acid solution; the first acid solution can include hydrochloric acid solution, sulfuric acid solution or nitric acid solution. The present invention has no special requirements for the concentration of the first acid solution, as long as the pH value of the acid hydrolysis system can meet the requirements. As a specific embodiment of the present invention, the conditions of the acid hydrolysis can include: the pH value can be 1~4, specifically 1, 2, 3 or 4; the temperature can be 30~70℃, specifically 30℃, 35℃, 40℃, 45℃, 50℃, 55℃, 60℃, 65℃ or 70℃; the time can be 3~10h, specifically 3h, 4h, 5h, 6h, 7h, 8h, 9h or 10h. As a specific embodiment of the present invention, the acid hydrolysis process can be accompanied by stirring; the present invention has no special requirements for the stirring, and the conventional method in the art can be used.

[0035] As a specific embodiment of the present invention, taking butanone oxime as an example, the reaction equation for preparing a polymer containing an oxygenated amine functional group by refluxing (ketoxime etherification) and acid hydrolysis is as follows: .

[0036] As a specific embodiment of the present invention, the reaction mechanism of the hydrolysis reaction of the oxime ether-containing polymer under acidic conditions is as follows: Figure 1 shown.

[0037] As a specific embodiment of the present invention, the acid hydrolysis may further include: filtering the acid hydrolysis system, washing the filtered solid with water and then drying it to obtain the polymer containing oxygenated amine functional groups. The present invention has no special requirements for the filtration, and conventional methods in the art can be used; the water used for the washing can be deionized water. The present invention has no special requirements for the number of washings, as long as the pH value of the washing liquid after washing is neutral. The present invention has no special limitation on the drying, as long as the solvent on the surface of the solid can be removed.

[0038] The present invention also provides a reactive adsorbent, including a membrane reactive adsorbent or a supported reactive adsorbent; The material of the membrane reactive adsorbent is a polymer containing oxygen-amine functional groups; The supported reactive adsorbent comprises a porous carrier and a polymer containing oxygen-containing amine functional groups supported on the surface and / or in the pores of the porous carrier; The polymer containing oxygenated amine functional groups is the polymer containing oxygenated amine functional groups described in the above technical solution or the polymer containing oxygenated amine functional groups prepared by the preparation method described in the above technical solution.

[0039] The present invention also provides a method for preparing the reactive adsorbent described in the above technical solution, comprising the following steps: The preparation method of the membrane reactive adsorbent comprises the following steps: The polymer containing oxygen amine functional group and the pore-forming agent are mixed to obtain a mixed material; The kneaded product is molded and then subjected to biaxial stretching treatment to obtain the membrane reactive adsorbent.

[0040] The present invention mixes a polymer containing oxygen amine functional groups and a pore former to obtain a mixed material. As a specific embodiment of the present invention, the pore former may be polyethylene glycol (PEG), polyvinyl pyrrolidone (PVP) or polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer (P123); the molecular weight of the polyethylene glycol may be 2000-8000 g / mol. As a specific embodiment of the present invention, the mass percentage of the polymer containing oxygen amine functional groups in the mixed material may be 60-90%, or may be 70-80%. The present invention has no special limitation on the mixing, and the conventional method in the art may be used.

[0041] After obtaining the mixture, the present invention performs biaxial stretching treatment after molding the mixture to obtain the membrane reactive adsorbent. As a specific embodiment of the present invention, the molding method can be to extrude the mixture into a sheet film through a screw extruder or to extrude the mixture into a tube through a cylindrical mold. As a specific embodiment of the present invention, the biaxial stretching treatment can be to perform biaxial stretching treatment on the molded product by water bath immersion to remove the water-soluble pore-forming agent to obtain the membrane reactive adsorbent.

[0042] The preparation method of the supported reactive adsorbent comprises the following steps: dissolving the polymer containing oxygenated amine functional groups in a second organic solvent to obtain a polymer solution containing oxygenated amine functional groups; The porous carrier is dispersed in the polymer solution containing oxygen-containing amine functional groups for adsorption and then solid-liquid separation is performed, and the solid obtained by the solid-liquid separation is dried to obtain the supported reactive adsorbent.

[0043] The present invention dissolves the polymer containing oxygen amine functional groups in a second organic solvent to obtain a polymer solution containing oxygen amine functional groups. As a specific embodiment of the present invention, the second organic solvent can be carbon tetrachloride, chloroform, benzene, toluene, xylene, n-hexane, heptane or octane. The present invention has no special requirements for the dissolution, as long as it can be completely dissolved.

[0044] After obtaining the polymer solution containing oxygenated amine functional groups, the present invention disperses the porous carrier in the polymer solution containing oxygenated amine functional groups for solid-liquid separation after adsorption, and dries the solid obtained by the solid-liquid separation to obtain the supported reactive adsorbent. As a specific embodiment of the present invention, the porous carrier can be activated carbon or graphene; the adsorption time can be 0.5~10h, and can be specifically 0.5h, 1h, 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h or 10h. As a specific embodiment of the present invention, the solid-liquid separation can be evaporation or filtration; the drying temperature can be 30~120℃, and can also be 60~100℃; the drying time can be 0.5~5h, and can also be 1.5~3h.

[0045] The present invention also provides the use of the reactive adsorbent described in the above technical solution in the degradation of aldehyde pollutants. As a specific embodiment of the present invention, the aldehyde pollutants may include formaldehyde, acetaldehyde, propionaldehyde or acrolein; the aldehyde pollutants may be aldehyde pollutants in the air or aldehyde pollutants in waste liquid.

[0046] The present invention also provides a method for regenerating a reactive adsorbent, comprising the following steps: The reactive adsorbent after adsorbing the aldehyde pollutants is mixed with the second acid solution for hydrolysis to obtain a regenerated reactive adsorbent.

[0047] As a specific embodiment of the present invention, the second acid solution can be a hydrochloric acid solution, a sulfuric acid solution or a nitric acid solution; the pH value of the second acid solution can be 1-4, specifically 1, 2, 2.5, 3, 3.5 or 4. As a specific embodiment of the present invention, the hydrolysis temperature can be 40-60°C, specifically 40°C, 45°C, 50°C, 55°C or 60°C; the hydrolysis time can be 7-8h, specifically 7h, 7.5h or 8h.

[0048] As a specific embodiment of the present invention, the hydrolysis may further include: filtering the hydrolyzed system, washing and drying the filtered solids in sequence to obtain the regenerated reactive adsorbent. The present invention has no special requirements for the filtration, and conventional methods in the art can be used; the water used for the washing can be deionized water. The present invention has no special requirements for the number of washings, as long as the pH value of the washing liquid after washing is neutral. The present invention has no special limitation on the drying, as long as the solvent on the surface of the solid can be removed.

[0049] As a specific embodiment of the present invention, the reaction principle of using a polymer containing oxygenated amine functional groups to absorb formaldehyde and regenerate is as follows Figure 2 shown.

[0050] The present invention performs two simple steps of ketoxime etherification and acid hydrolysis on the existing chlorinated polyolefins, and can quickly prepare a high-activity polymer material containing an oxamine functional group (-ONH2). The oxamine functional group contained has a specific high reactivity to aldehyde compounds and can react quickly, so that the aldehyde compounds can be efficiently removed under ambient room temperature conditions; in an embodiment of the present invention, the reactive adsorbent can remove more than 99.5% of free formaldehyde from the environment. In addition, after the saturated reaction and the complete consumption of the oxamine functional groups, the reactive adsorbent can be regenerated by the acid hydrolysis step again. The regeneration step is fast, the activity retention rate after regeneration is high, and it can be reused many times. The method has a simple preparation process, high efficiency in removing impurities of aldehyde compounds, easy material regeneration, and low cost, and provides a simple method for removing aldehydes, especially formaldehyde, from the environment.

[0051] In order to further illustrate the present invention, the technical solutions provided by the present invention are described in detail below in conjunction with embodiments, but they should not be construed as limiting the protection scope of the present invention.

[0052] Examples 1-2 are for preparing oxime ether-containing polymers by ketoxime etherification, Examples 3-4 are for preparing polymers containing oxygenated amine functional groups by acidification and hydrolysis reaction, Examples 5-6 are for preparing aldehyde reactive adsorbents, Examples 7-12 are for removing formaldehyde pollutants from the air by using reactive adsorbents, Examples 13-16 are for removing acetaldehyde from aqueous solutions by using reactive adsorbents, and Example 17 is for regenerating the reactive adsorbent after adsorbing aldehyde pollutants.

[0053] Example 1 The chlorination degree is 30% and the viscosity is 10000 20 g of chlorinated polyethylene with an acid value of 7.0 was dissolved in 200 mL of toluene, and solid potassium carbonate (0.2 mol, 27.6 g), butanone oxime (0.2 mol, 17.4 g), potassium iodide (0.3 mol, 49.8 g), and 18-crown-6 (5 mmol, 1.32 g) were added. The mixture was added to a flask with a condenser, a thermometer, and a magnet, and refluxed in a constant temperature water bath at 100°C with stirring for 8 hours. After the reaction was completed, the system was cooled to 30°C and a 50% methanol aqueous solution was added dropwise to the reaction system for precipitation. The system was separated by suction to obtain a butanone oxime-etherified polyethylene polymer. The substituted chloride ions were detected, and the calculated yield (substitution degree of etherification) was 80%.

[0054] Example 2 The chlorination degree is 40% and the viscosity is 15000 25 g of chlorinated polypropylene with an acid value of 7.0 was dissolved in 250 mL of xylene, and solid potassium carbonate (0.2 mol, 27.6 g), butanone oxime (0.2 mol, 17.4 g), potassium iodide (0.3 mol, 49.8 g), and 18-crown-6 (5 mmol, 1.32 g) were added to a flask with a condenser, a thermometer, and a magnet, and refluxed in a constant temperature water bath at 100°C with stirring for 8 hours; after the reaction was completed, the system was cooled to 30°C and a 50% ethanol aqueous solution was added dropwise to the reaction system for precipitation, and the system was separated by suction to obtain a butanone oxime-etherified polypropylene polymer; the substituted chloride ions were detected, and the calculated yield (substitution degree of etherification) was 77%.

[0055] Example 3 The oxime ether-containing polymer (butanone oxime etherified polyethylene polymer) prepared in Example 1 was stirred in an aqueous HCl solution with a pH value of 2 at 40°C for acid hydrolysis for 3 hours, the aqueous hydrochloric acid solution was filtered out, and the filtered solid was washed with deionized water until neutral, and dried to obtain a polymer containing an oxamine functional group with a yield of 98%.

[0056] Example 4 The polymer containing oxime ether prepared in Example 2 (butanone oxime etherified polypropylene polymer) was stirred in an aqueous HCl solution with a pH value of 3 at 50°C for acid hydrolysis for 6 hours, the aqueous hydrochloric acid solution was filtered out, and the filtered solid was washed with deionized water until neutral, and dried to obtain a polymer containing an oxamine functional group with a yield of 98.2%.

[0057] Example 5 Preparation of reactive adsorbent for aldehyde membrane: The polymer containing oxygen amine functional groups prepared in Example 3 and the pore-forming agent polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer (P123) are mixed in a mass ratio of 8:2 to form a mixture, which is then extruded into a sheet film by a screw extruder. The sheet film is then immersed in a water bath and subjected to biaxial stretching treatment to remove the water-soluble pore-forming agent to obtain reactive adsorbent 1 of a porous polymer membrane containing oxygen amine functional groups.

[0058] Example 6 Preparation of aldehyde-supported reactive adsorbent: dissolving the polymer containing oxygenated amine functional groups prepared in Example 4 in n-hexane and stirring the mixture to obtain a polymer solution containing oxygenated amine functional groups; The activated carbon was added to the polymer solution containing oxygen-amine functional groups, dispersed for 2 hours, and then heated to evaporate the n-hexane, and dried at 70° C. for 2 hours to obtain the reactive adsorbent 2 of the polymer containing oxygen-amine functional groups supported on graphene.

[0059] Embodiments 7 to 12 Nitrogen was injected into formalin to produce gaseous formaldehyde. Formalin was placed in a constant temperature water bath at 24°C. Then, gaseous formaldehyde and nitrogen were simultaneously injected into a 1L mixing box that had been evacuated in advance, in which 10g of the aldehyde reactive adsorbent sample prepared by Example 5 or 6 was placed, and a fan was placed for air circulation in the box. Finally, a real-time formaldehyde analyzer was used to record the formaldehyde concentration before and after adsorption. The initial formaldehyde concentration in the test system was controlled by the nitrogen flow rate, which was adjusted by a mass flow meter. After a reaction time of 2 to 10 hours, the formaldehyde concentration before and after the reaction was analyzed, and the results are shown in Table 1.

[0060] Table 1 Results of formaldehyde removal efficiency in air

[0061] As can be seen from Table 1, the reactive adsorbent provided by the present invention can efficiently remove formaldehyde in the air; the ability to remove formaldehyde in the air increases with the increase of nitrogen flow rate and temperature. At an ambient temperature and N2 flow rate of 0.2L / min, 10g of the modified aldehyde reactive adsorbent 1 can basically remove formaldehyde after 4 hours, and its content is reduced from 9ppm to 0.3ppm, and the removal rate reaches 96.7%. The removal efficiency of the aldehyde reactive adsorbent 2 reaches 99.5% after 10 hours.

[0062] Embodiments 13 to 16 Aldehyde removal capability test in aqueous solution environment. In the embodiment of removing formaldehyde from solution, the amount of free formaldehyde in the sample is determined by titration. In a typical process, a known amount of hydroxyammonium chloride is added to the sample before or after formaldehyde removal, which reacts with the free formaldehyde remaining in the solution. The hydroxyammonium chloride releases an equimolar amount of hydrochloric acid after the reaction. The amount of hydrochloric acid is titrated with NaOH to measure the exact amount of hydrochloric acid, which is equivalent to the amount of formaldehyde reacted in the original sample (i.e., the amount of free formaldehyde). The automatic titrator 888Titrando can be used for this analysis.

[0063] The experiment was conducted using 100 g of formaldehyde aqueous solution (2000 ppm), to which 50 g of the aldehyde remover prepared in Example 5 or 6 was added. The adsorption was performed at 70°C for 1 to 10 hours. The sample was taken out, cooled, and its formaldehyde residue was analyzed. The results are shown in Table 2 below.

[0064] Table 2 Results of formaldehyde removal efficiency in aqueous solution

[0065] It can be seen from Table 2 that the reactive adsorbent provided by the present invention can efficiently remove formaldehyde in aqueous solution; in aqueous solution, when the base formaldehyde content is as high as 2000ppm, the reactive adsorbent provided by the present invention also has a high formaldehyde absorption efficiency. After 2 to 10 hours of absorption, the formaldehyde is reduced by more than 95%. When the reaction time reaches 10 hours, the formaldehyde absorption efficiency can reach more than 99.35%.

[0066] Embodiment 17 Regeneration of aldehyde reactive adsorbent: The reactive adsorbents of Examples 7 to 16 that were completely adsorbed and saturated were stirred in an aqueous HCl solution with a pH value of 3 and hydrolyzed at 50° C. for 8 h, and then the aqueous hydrochloric acid solution was filtered to remove it, and then washed with deionized water until it was neutral, and dried to obtain a regenerated reactive adsorbent.

[0067] The corresponding regenerated reactive adsorbents were subjected to formaldehyde adsorption according to Examples 7 to 16, and the results are listed in Tables 3 and 4.

[0068] Table 3 Results of the removal efficiency of formaldehyde in air by regenerated reactive adsorbent

[0069] Table 4 Results of formaldehyde removal efficiency of regenerated reactive adsorbent in aqueous solution

[0070] It can be seen from the results in Tables 3 and 4 that the regenerated reactive adsorbent can restore its good removal rate for formaldehyde.

[0071] The present invention directly performs a two-step simple modification of chlorinated polyolefins by ketoxime etherification-acid hydrolysis, and can conveniently prepare a high-activity polymer material containing an oxamine functional group (-ONH2). The contained oxamine functional group has a specific high reactivity to aldehyde compounds and can react quickly, so that the aldehyde compounds can be efficiently removed under ambient room temperature conditions. In some embodiments, the system can remove more than 99.5% of free formaldehyde from the environment. In addition, after the saturated reaction and the complete consumption of the oxamine functional groups, the polymer material can be regenerated by the acidification and hydrolysis step again. The regeneration step is fast, the activity retention rate after regeneration is high, and it can be reused many times. The method has a simple preparation process, high efficiency in removing impurities of aldehyde compounds, easy material regeneration, and low cost, and provides a simple method for removing aldehydes, especially formaldehyde, in the environment.

[0072] Although the above embodiment describes the present invention in detail, it is only a part of the embodiments of the present invention, not all of the embodiments. People can also obtain other embodiments based on this embodiment without creativity, and these embodiments all fall within the protection scope of the present invention.

Claims

1. A polymer containing oxygenated amine functional groups, characterized in that: It has the structure shown in formula 2: Formula 2.

2. The method for preparing a polymer containing oxygen-amine functional groups according to claim 1, characterized in that: The following steps are involved: Acidifying and hydrolyzing the polymer containing oxime ether to obtain the polymer containing oxygenated amine functional groups; The oxime ether-containing polymer has a structure shown in Formula 1: Formula 1; Wherein, R1 and R2 are alkyl groups respectively.

3. The preparation method according to claim 2, characterized in that: The R1 and R2 are independently methyl, ethyl, propyl, isopropyl, butyl, sec-butyl or isobutyl.

4. The preparation method according to claim 2 or 3, characterized in that: The preparation method of the polymer containing oxime ether comprises the following steps: The chlorinated polyolefin, alkyl ketoxime, alkali metal salt, crown ether and the first organic solvent are mixed and refluxed to obtain the oxime ether-containing polymer.

5. The preparation method according to claim 4, characterized in that: The chlorinated polyolefin includes chlorinated polyethylene, chlorinated polypropylene or chlorinated polybutylene; The chlorinated polyolefin includes a chlorinated polyolefin with a low chlorination degree or a chlorinated polyolefin with a high chlorination degree; the chlorination degree of the chlorinated polyolefin with a low chlorination degree is 20-50%, and the chlorination degree of the chlorinated polyolefin with a high chlorination degree is greater than 50% and less than or equal to 70%; the viscosity of the chlorinated polyolefin is 800-50000. , acid value is 6.0~8.0; The alkyl ketone oxime includes acetone oxime, butanone oxime, 2-pentanone oxime, 3-pentanone oxime, 3-methyl-2-butanone oxime, 2-hexanone oxime, 3-hexanone oxime, 2-methyl-3-pentanone oxime, 3-methyl-2-pentanone oxime or 4-methyl-2-pentanone oxime; The alkali metal salt includes one or more of alkali metal carbonate, alkali metal bicarbonate and alkali metal halide; The crown ether includes 12-crown-4, 15-crown-5 or 18-crown-6; The first organic solvent includes aromatic solvents, chlorinated hydrocarbon solvents, ester solvents, ketone solvents, tetrahydrofuran, pyridine or dioxane.

6. The preparation method according to claim 4, characterized in that: The mass ratio of the chlorinated polyolefin to the alkyl ketoxime is 1:3 to 3:1; The molar ratio of the alkyl ketoxime to the alkali metal salt is 0.4:1 to 2:1; The molar ratio of the alkyl ketoxime to the crown ether is 100:1 to 10:

1.

7. The preparation method according to claim 4, characterized in that: The reflux temperature is 50-120° C. and the reflux time is 5-20 h.

8. The preparation method according to claim 7, characterized in that: After the reflux, the method further comprises: adding an organic alcohol dropwise to the reflux system to perform solid-liquid separation after precipitation to obtain the oxime ether-containing polymer; The organic alcohol includes methanol, ethanol, isopropanol or n-butanol.

9. The preparation method according to claim 2, characterized in that: The first acid solution for acidification and hydrolysis includes hydrochloric acid solution, sulfuric acid solution or nitric acid solution; The conditions of the acidification hydrolysis include: pH value of 1-4, temperature of 30-70° C., and time of 3-10 hours.

10. A reactive adsorbent, characterized in that: Including membrane reactive adsorbent or supported reactive adsorbent; The material of the membrane reactive adsorbent is a polymer containing oxygen-amine functional groups; The supported reactive adsorbent comprises a porous carrier and a polymer containing oxygen-containing amine functional groups supported on the surface and / or in the pores of the porous carrier; The polymer containing oxygenated amine functional groups is the polymer containing oxygenated amine functional groups according to claim 1 or the polymer containing oxygenated amine functional groups prepared by the preparation method according to any one of claims 2 to 9.

11. The method for preparing the reactive adsorbent according to claim 10, characterized in that: The following steps are involved: The preparation method of the membrane reactive adsorbent comprises the following steps: The polymer containing oxygen amine functional group and the pore-forming agent are mixed to obtain a mixed material; The mixed material is formed and then biaxially stretched to obtain the membrane reactive adsorbent; The preparation method of the supported reactive adsorbent comprises the following steps: dissolving the polymer containing oxygenated amine functional groups in a second organic solvent to obtain a polymer solution containing oxygenated amine functional groups; The porous carrier is dispersed in the polymer solution containing oxygen-containing amine functional groups for adsorption and then solid-liquid separation is performed, and the solid obtained by the solid-liquid separation is dried to obtain the supported reactive adsorbent.

12. Use of the reactive adsorbent according to claim 10 or the reactive adsorbent prepared by the preparation method according to claim 11 in degrading aldehyde pollutants.

13. A method for regenerating a reactive adsorbent, comprising the steps of: The reactive adsorbent after adsorbing the aldehyde pollutants is mixed with the second acid solution for hydrolysis to obtain a regenerated reactive adsorbent; The reactive adsorbent is the reactive adsorbent according to claim 10 or the reactive adsorbent prepared by the preparation method according to claim 11.

Images