A polymer containing an oxygen amine functional group, a preparation method thereof, a reactive adsorbent and a preparation method thereof, an application thereof, and a regeneration method thereof

Abstract

The present invention belongs to the technical field of adsorbents, and particularly relates to a polymer containing an oxoamine functional group, a preparation method thereof, a reactive adsorbent and a preparation method thereof, an application and a regeneration method. In the present invention, a polymer containing an oxime ether is hydrolyzed in an acidic environment to in-situ generate a polymer containing an oxoamine functional group; the polymer containing the oxoamine functional group is formed into a film or loaded on a porous carrier to obtain a reactive adsorbent for degrading aldehyde pollutants. The oxoamine functional group undergoes an oximation reaction with aldehydes (such as formaldehyde), and can efficiently remove aldehyde pollutants in environments such as air or solution. The completely reacted and deactivated adsorbent can be regenerated by hydrolysis in an acidic solution to obtain the oxoamine functional group, and has good recyclability. The high-molecular material for in-situ generating the oxoamine functional group proposed by the present invention has a simple preparation process, high efficiency in removing aldehydes, easy regeneration of the material, and low cost, providing a simple method for removing aldehydes, especially formaldehyde, in the environment.

Description

Technical Field

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

[0002] Aldehyde compounds are intermediates in many organic syntheses and are widely used in industrial production processes such as plastics, dyes, pharmaceuticals, and pesticides. Among them, formaldehyde (HCHO) is widely used in industries (such as plastics, resins), building materials (such as adhesives, paints), medical (such as fungicides, preservatives), etc. However, formaldehyde is also one of the most harmful gases to human health, usually associated with an increased risk of cancer, and has strong irritation 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 0.5 ppm per 8 h. How to efficiently remove formaldehyde from the environment (such as air or solution systems in industrial production) is an important topic.

[0003] Currently, the technologies for removing aldehyde pollutants such as formaldehyde from the environment mainly include plasma decomposition, biofiltration, photocatalytic oxidation, or physical adsorption. Among them, physical adsorption is widely used due to its low cost, environmental friendliness, simple operation, etc. However, due to the high vapor pressure of formaldehyde (3890 mmHg at 25 °C) and relatively low boiling point (-19.3 °C), it is prone to re-desorption affected by temperature and pollutant concentration, and physical adsorption has poor selectivity. When the adsorption equilibrium is reached, it will lose the removal effect.

[0004] In contrast, the chemical reaction elimination method is a better strategy for formaldehyde removal due to its irreversibility and high efficiency. It has been found that the oxyamine functional group (-ONH 2 ) can react with the aldehyde group to form an oxime bond, and can selectively remove aldehyde substances such as formaldehyde from the environment or reaction system; for example, the oxyamine functional group-capped compound can undergo chemical conjugation with the ketone functional group on the polymer side chain at room temperature without using a catalyst to produce an oxime bond (-C=N-O-), which can be regenerated to -ONH 2 in a weakly acidic medium. However, the preparation process of the existing oxyamine functional group-capped compounds is cumbersome, the reagents used are costly, the efficiency is low, and it does not have the feasibility of mass production, thus affecting its application in degrading aldehyde pollutants. Summary of the Invention

[0005] In view of this, the present invention provides a polymer containing an oxyamine functional group, a preparation method thereof, a reactive adsorbent, a preparation method thereof, an application and a regeneration method; the preparation method of the polymer containing an oxyamine functional group provided by the present invention is simple and easy for industrial production, and the prepared polymer containing an oxyamine functional group has high degradation efficiency for aldehyde pollutants.

[0006] To solve the above technical problems, the present invention provides a polymer containing an oxime ether functional group, having the structure shown in Formula 2:

[0007] Formula 2.

[0008] The present invention also provides a method for preparing the polymer containing an oxime ether functional group as described in the above technical solution, comprising the following steps:

[0009] Subject the polymer containing an oxime ether to acid hydrolysis to obtain the polymer containing an oxime amine functional group;

[0010] The polymer containing an oxime ether has the structure shown in Formula 1:

[0011] Formula 1;

[0012] Wherein, R 1 and R 2 are each independently an alkyl group.

[0013] Preferably, the R 1 and R 2 are independently methyl, ethyl, propyl, isopropyl, butyl, sec-butyl or isobutyl.

[0014] Preferably, the method for preparing the polymer containing an oxime ether comprises the following steps:

[0015] Mix chlorinated polyolefin, alkyl ketoxime, alkali metal salt, crown ether and a first organic solvent and reflux to obtain the polymer containing an oxime ether.

[0016] Preferably, the chlorinated polyolefin includes chlorinated polyethylene, chlorinated polypropylene or chlorinated polybutene;

[0017] The chlorinated polyolefin includes low-chlorinated chlorinated polyolefin or high-chlorinated chlorinated polyolefin; the chlorination degree of the low-chlorinated chlorinated polyolefin is 20-50%, and the chlorination degree of the high-chlorinated chlorinated polyolefin is greater than 50% and less than or equal to 70%; the viscosity of the chlorinated polyolefin is 800-50000 , and the acid value is 6.0-8.0;

[0018] The alkyl ketoxime 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;

[0019] The alkali metal salt includes one or more of alkali metal carbonates, alkali metal bicarbonates and alkali metal halides;

[0020] The crown ethers include 12-crown-4, 15-crown-5 or 18-crown-6;

[0021] The first organic solvent includes aromatic solvents, chlorinated hydrocarbon solvents, ester solvents, ketone solvents, tetrahydrofuran, pyridine or dioxane.

[0022] Preferably, the mass ratio of the chlorinated polyolefin to the alkyl ketoxime is 1:3 to 3:1;

[0023] The molar ratio of the alkyl ketoxime to the alkali metal salt is 0.4:1 to 2:1;

[0024] The molar ratio of the alkyl ketoxime to the crown ether is 100:1 to 10:1.

[0025] Preferably, the temperature of the reflux is 50 to 120 °C and the time is 5 to 20 h.

[0026] Preferably, after the reflux, it further includes: adding an organic alcohol dropwise to the system after the reflux for precipitation and then performing solid-liquid separation to obtain the polymer containing oxime ether;

[0027] The organic alcohol includes methanol, ethanol, isopropanol or n-butanol.

[0028] Preferably, the first acid solution for acid hydrolysis includes hydrochloric acid solution, sulfuric acid solution or nitric acid solution;

[0029] The conditions for the acid hydrolysis include: pH value is 1 to 4, temperature is 30 to 70 °C, and time is 3 to 10 h.

[0030] The present invention also provides a reactive adsorbent, including a membrane reactive adsorbent or a supported reactive adsorbent;

[0031] The material of the membrane reactive adsorbent is a polymer containing an oxygen amine functional group;

[0032] The supported reactive adsorbent includes a porous carrier and a polymer containing an oxygen amine functional group supported on the surface and / or pores of the porous carrier;

[0033] The polymer containing an oxygen amine functional group is the polymer containing an oxygen amine functional group described in the above technical solution or the polymer containing an oxygen amine functional group prepared by the preparation method described in the above technical solution.

[0034] The present invention also provides a preparation method of the reactive adsorbent described in the above technical solution, including the following steps:

[0035] The preparation method of the membrane reactive adsorbent includes the following steps:

[0036] Mixing the polymer containing an oxygen amine functional group and a pore former to obtain a mixture;

[0037] After forming the kneaded mixture, a biaxial stretching treatment is carried out to obtain the membrane reactive adsorbent;

[0038] The preparation method of the supported reactive adsorbent includes the following steps:

[0039] Dissolve the polymer with oxime ether functional groups in a second organic solvent to obtain a polymer solution with oxime ether functional groups;

[0040] Disperse the porous carrier in the polymer solution with oxime ether functional groups, carry out adsorption and then solid-liquid separation, and dry the solid obtained by the solid-liquid separation to obtain the supported reactive adsorbent.

[0041] The present invention also provides the application 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.

[0042] The present invention also provides a method for regenerating a reactive adsorbent, including the following steps:

[0043] Mix the reactive adsorbent adsorbed with aldehyde pollutants with a second acid solution for hydrolysis to obtain a regenerated reactive adsorbent;

[0044] 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.

[0045] In the present invention, a polymer with oxime ether functional groups is hydrolyzed in an acidic environment to in-situ generate a polymer with oxime ether functional groups; the polymer with oxime ether functional groups is formed into a film or loaded on a porous carrier to obtain a reactive adsorbent for degrading aldehyde pollutants. The oxime ether functional groups can carry out an oximation reaction with aldehydes (such as formaldehyde), and can efficiently remove aldehyde impurities in environments such as air or solution. The completely reacted and inactivated reactive adsorbent can be regenerated by hydrolysis in an acidic solution to obtain oxime ether functional groups, and has good recyclability. The high molecular material for in-situ generating oxime ether functional groups proposed by the present invention has a simple preparation process, high efficiency in removing aldehydes, easy regeneration of the material, and low cost, providing a simple method for removing aldehydes, especially formaldehyde, in the environment. Description of the Drawings

[0046] Figure 1 It is a reaction mechanism diagram for a polymer with oxime ether functional groups to hydrolyze in an acidic condition to generate a polymer with oxime ether functional groups;

[0047] Figure 2 It is a reaction principle diagram for using a polymer with oxime ether functional groups to absorb formaldehyde and regenerate. Detailed Embodiments

[0048] The present invention provides a polymer containing an oxime ether functional group, having the structure shown in Formula 2:

[0049] Formula 2.

[0050] The present invention also provides a method for preparing the polymer containing an oxime ether functional group according to the above technical solution, including the following steps:

[0051] Subject the polymer containing an oxime ether to acid hydrolysis to obtain the polymer containing an oxime amine functional group;

[0052] The polymer containing an oxime ether has the structure shown in Formula 1:

[0053] Formula 1;

[0054] Wherein, R 1 and R 2 are each independently an alkyl group; the R 1 and R 2 can independently be methyl, ethyl, propyl, isopropyl, butyl or isobutyl; when R 1 is methyl, R 2 can be methyl, ethyl, propyl, isopropyl, butyl, sec-butyl or isobutyl.

[0055] In the present invention, if not otherwise specified, all materials are conventional commercially available products.

[0056] As a specific embodiment of the present invention, the method for preparing the polymer containing an oxime ether may include the following steps:

[0057] Mix chlorinated polyolefin, alkyl ketoxime, alkali metal salt, crown ether and a first organic solvent and reflux to obtain the polymer containing an oxime ether.

[0058] As a specific embodiment of the present invention, the mixing may include the following steps:

[0059] Dissolve chlorinated polyolefin in a first organic solvent to obtain a chlorinated polyolefin solution;

[0060] Add an alkali metal salt, an alkyl ketoxime and a crown ether to the chlorinated polyolefin solution.

[0061] 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 low-chlorination chlorinated polyolefin or high-chlorination chlorinated polyolefin; the chlorination degree of the low-chlorination chlorinated polyolefin may be 20-50%, and may also be 25-35%; the chlorination degree of the high-chlorination chlorinated polyolefin may be greater than 50% and less than or equal to 70%, and may also be 55-68%; the viscosity of the chlorinated polyolefin may be 800-50000 and may also be 1000-20000 ; the acid value of the chlorinated polyolefin may be 6.0-8.0, and may specifically be 6.0, 7.0 or 8.0.

[0062] As a specific embodiment of the present invention, the alkyl ketoxime 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.

[0063] As a specific embodiment of the present invention, the alkali metal salt may include one or more of alkali metal carbonates, alkali metal bicarbonates and alkali metal halides, and may specifically be alkali metal carbonates, alkali metal bicarbonates or alkali metal halides; 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 serves to provide an alkaline environment and promote the ketoxime etherification.

[0064] 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 serves as a co-catalyst.

[0065] As a specific embodiment of the present invention, the first organic solvent may include aromatic solvents, chlorinated hydrocarbon solvents, ester solvents, ketone solvents, tetrahydrofuran, pyridine or dioxane; the aromatic solvents may include benzene, toluene or xylene; the chlorinated hydrocarbon solvents may include 1,2-dichloroethane, tetrachloroethane, chloroform, carbon tetrachloride or chlorobenzene; the ester solvents may include ethyl acetate or butyl acetate; the ketone solvents may include butanone, methyl isobutyl ketone or methyl-2-pyrrolidone.

[0066] As a specific embodiment of the present invention, the mass ratio of the chlorinated polyolefin to the alkyl ketoxime can be 1:3 to 3:1, can also be 1:2 to 2:1, and can specifically be 1.1:1 or 1.2:1; the molar ratio of the alkyl ketoxime to the alkali metal salt can be 0.4:1 to 2:1, can also be 0.8:1 to 1.2:1, and can specifically be 1:1; the molar ratio of the alkyl ketoxime to the crown ether can be 100:1 to 10:1, can also be 50:1 to 30:1, and can specifically be 50:1, 40:1 or 30:1. The present invention has no special requirements for the dosage of the first organic solvent, as long as the materials can be mixed evenly.

[0067] As a specific embodiment of the present invention, the temperature of the reflux can be 50 to 120 °C, can also be 80 to 100 °C; the time of the reflux can be 5 to 20 h, can also be 8 to 15 h. As a specific embodiment of the present invention, stirring can be accompanied during the reflux. The present invention has no special limitation on the stirring, as long as the materials can react completely.

[0068] As a specific embodiment of the present invention, after the reflux, it can also include: dropping an organic alcohol aqueous solution into the system after the reflux for precipitation and then performing solid-liquid separation to obtain the polymer containing oxime ether; the organic alcohol aqueous solution can 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 can be 20 to 80%, and can specifically be 20%, 30%, 40%, 50%, 60%, 70% or 80%; the solid-liquid separation can be filtration by suction.

[0069] As a specific embodiment of the present invention, the acid hydrolysis can be mixing the polymer containing oxime ether with a first acid solution for acid hydrolysis; the first acid solution can include a hydrochloric acid solution, a sulfuric acid solution or a 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 to 4, and can specifically be 1, 2, 3 or 4; the temperature can be 30 to 70 °C, and can specifically be 30 °C, 35 °C, 40 °C, 45 °C, 50 °C, 55 °C, 60 °C, 65 °C or 70 °C; the time can be 3 to 10 h, and can specifically be 3 h, 4 h, 5 h, 6 h, 7 h, 8 h, 9 h or 10 h. As a specific embodiment of the present invention, stirring can be accompanied during the acid hydrolysis; the present invention has no special requirements for the stirring, and the conventional methods in the art can be adopted.

[0070] As a specific embodiment of the present invention, taking butanone oxime as the alkyl ketoxime, the reaction equation for preparing the polymer containing oxygen amine functional groups through reflux (ketoxime etherification) and acid hydrolysis is as follows:

[0071] 。

[0072] 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 Figure 1 shown.

[0073] As a specific embodiment of the present invention, after the acid hydrolysis, it may further include: filtering the system after acid hydrolysis, washing the filtered solid with water and then drying it to obtain the polymer containing an oxyamine functional group. The present invention has no special requirements for the filtration, and a conventional method in the art can be used; the water for washing can be deionized water. The present invention has no special requirements for the number of times of washing, as long as the pH value of the washing liquid is neutral after washing. The present invention has no special limitation on the drying, as long as the solvent on the surface of the solid can be removed.

[0074] The present invention also provides a reactive adsorbent, including a membrane reactive adsorbent or a supported reactive adsorbent;

[0075] The material of the membrane reactive adsorbent is a polymer containing an oxyamine functional group;

[0076] The supported reactive adsorbent includes a porous carrier and a polymer containing an oxyamine functional group supported on the surface and / or pores of the porous carrier;

[0077] The polymer containing an oxyamine functional group is the polymer containing an oxyamine functional group described in the above technical solution or the polymer containing an oxyamine functional group prepared by the preparation method described in the above technical solution.

[0078] The present invention also provides a preparation method of the reactive adsorbent described in the above technical solution, including the following steps:

[0079] The preparation method of the membrane reactive adsorbent includes the following steps:

[0080] Mixing the polymer containing an oxyamine functional group and a pore former to obtain a mixture;

[0081] Forming the mixture and then performing a biaxial stretching treatment to obtain the membrane reactive adsorbent.

[0082] The present invention kneads a polymer containing an oxyamine functional group and a pore former to obtain a kneaded product. As a specific embodiment of the present invention, the pore former can be polyethylene glycol (PEG), polyvinylpyrrolidone (PVP), or polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer (P123); the molecular weight of the polyethylene glycol can be 2000-8000 g / mol. As a specific embodiment of the present invention, the mass percentage content of the polymer containing an oxyamine functional group in the kneaded product can be 60-90%, and can also be 70-80%. The present invention has no special limitation on the kneading, and the conventional method in the art can be adopted.

[0083] After obtaining the kneaded product, the present invention forms the kneaded product and then performs a biaxial stretching treatment to obtain the membrane reactive adsorbent. As a specific embodiment of the present invention, the forming method can be extruding the kneaded product into a sheet-like membrane through a screw extruder or extruding the kneaded product into a tubular shape through a cylindrical mold. As a specific embodiment of the present invention, the biaxial stretching treatment can be performing a biaxial stretching treatment by water bath impregnation on the formed product to remove the water-soluble pore former, thereby obtaining the membrane reactive adsorbent.

[0084] The preparation method of the supported reactive adsorbent includes the following steps:

[0085] Dissolve the polymer containing an oxyamine functional group in a second organic solvent to obtain a polymer solution containing an oxyamine functional group;

[0086] Disperse the porous support in the polymer solution containing an oxyamine functional group, perform adsorption and then solid-liquid separation, and dry the solid obtained by the solid-liquid separation to obtain the supported reactive adsorbent.

[0087] The present invention dissolves the polymer containing an oxyamine functional group in a second organic solvent to obtain a polymer solution containing an oxyamine functional group. 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.

[0088] After obtaining the polymer solution containing oxygenated amine functional groups, the present invention disperses a porous support in the polymer solution containing oxygenated amine functional groups for adsorption and then performs solid-liquid separation. The solid obtained from the solid-liquid separation is dried to obtain the supported reactive adsorbent. As a specific embodiment of the present invention, the porous support can be activated carbon or graphene; the adsorption time can be 0.5 to 10 h, specifically 0.5 h, 1 h, 2 h, 3 h, 4 h, 5 h, 6 h, 7 h, 8 h, 9 h or 10 h. As a specific embodiment of the present invention, the solid-liquid separation can be evaporation or filtration; the drying temperature can be 30 to 120 °C, and can also be 60 to 100 °C; the drying time can be 0.5 to 5 h, and can also be 1.5 to 3 h.

[0089] The present invention also provides an application of the reactive adsorbent described in the above technical solution in degrading aldehyde pollutants. As a specific embodiment of the present invention, the aldehyde pollutants can include formaldehyde, acetaldehyde, propionaldehyde or acrolein; the aldehyde pollutants can be aldehyde pollutants in the air or aldehyde pollutants in the waste liquid.

[0090] The present invention also provides a method for regenerating a reactive adsorbent, including the following steps:

[0091] Mix the reactive adsorbent after adsorbing aldehyde pollutants with a second acid solution for hydrolysis to obtain a regenerated reactive adsorbent.

[0092] 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 to 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 to 60 °C, specifically 40 °C, 45 °C, 50 °C, 55 °C or 60 °C; the hydrolysis time can be 7 to 8 h, specifically 7 h, 7.5 h or 8 h.

[0093] As a specific embodiment of the present invention, after the hydrolysis, it may further include: filtering the hydrolyzed system, washing the solid obtained by filtration with water and drying it in sequence to obtain the regenerated reactive adsorbent. The present invention has no special requirements for the filtration, and the conventional methods in the art can be used; the water for washing can be deionized water. The present invention has no special requirements for the number of washing times, as long as the pH value of the washing liquid is neutral after washing. The present invention has no special limitations on the drying, as long as the solvent on the surface of the solid can be removed.

[0094] As a specific embodiment of the present invention, the reaction principle of absorbing formaldehyde and regenerating by using the polymer containing oxygenated amine functional groups is as Figure 2 shown.

[0095] The present invention briefly modifies existing chlorinated polyolefins through two steps of ketoxime etherification and acid hydrolysis, and can quickly prepare a highly active polymer material containing an oximeamine functional group (-ONH 2 ). The contained oximeamine functional group has specific high reactivity towards aldehyde compounds and can react rapidly, so that aldehyde compounds can be efficiently removed under ambient temperature conditions; in the examples of the present invention, the reactive adsorbent can remove more than 99.5% of free formaldehyde from the environment. In addition, after the saturation reaction and complete consumption of the oximeamine functional group, the reactive adsorbent can be regenerated by repeating the acid hydrolysis step. The regeneration step is fast, and the activity retention rate after regeneration is high, and it can be reused multiple times. The preparation process of this method is simple, the efficiency of removing aldehyde compound impurities is high, the material is easy to regenerate, and the cost is low, providing a simple method for removing aldehydes, especially formaldehyde, in the environment.

[0096] To further illustrate the present invention, the technical solutions provided by the present invention will be described in detail below in conjunction with examples, but they cannot be construed as limiting the protection scope of the present invention.

[0097] Examples 1-2 are for preparing oxime ether-containing polymers by ketoxime etherification, Examples 3-4 are for preparing polymers containing oximeamine functional groups by acid hydrolysis reaction, Examples 5-6 are for preparing aldehyde-reactive adsorbents, Examples 7-12 are for removing formaldehyde pollutants in the air using the reactive adsorbent, Examples 13-16 are for removing acetaldehyde in aqueous solution using the reactive adsorbent, and Example 17 is for regenerating the reactive adsorbent after adsorbing aldehyde pollutants.

[0098] Example 1

[0099] Dissolve 20 g of chlorinated polyethylene with a chlorine content of 30%, a viscosity of 10000 , and an acid value of 7.0 in 200 mL of toluene, add solid potassium carbonate (0.2 mol, 27.6 g), methyl ethyl ketoxime (0.2 mol, 17.4 g), potassium iodide (0.3 mol, 49.8 g), and 18-crown-6 (5 mmol, 1.32 g), and add them to a flask equipped with a condenser, a thermometer, and a magnetic stirrer. Stir and reflux in a constant temperature water bath at 100 °C for 8 h; after the reaction is completed, cool to 30 °C and then dropwise add a 50% methanol aqueous solution to the reaction system for precipitation, and separate by suction filtration to obtain a methyl ethyl ketoxime etherified polyethylene polymer; by detecting the replaced chloride ions, the calculated yield (substitution etherification degree) is 80%.

[0100] Example 2

[0101] Dissolve 20 g of chlorinated polyethylene with a chlorine content of 40% and a viscosity of 15000 , 25 g of chlorinated polypropylene with an acid value of 7.0 was dissolved in 250 mL of xylene. 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 and placed into a flask equipped with a condenser, a thermometer, and a magnetic stirrer. The mixture was refluxed and stirred in a constant-temperature water bath at 100 °C for 8 h. After the reaction ended, it was cooled to 30 °C, and then an aqueous ethanol solution with a mass concentration of 50% was added dropwise to the reaction system for precipitation. The precipitate was separated by filtration to obtain a polypropylene polymer etherified with butanone oxime. The chloride ions displaced were detected, and the calculated yield (degree of substitution by etherification) was 77%.

[0102] Example 3

[0103] The polymer containing oxime ether prepared in Example 1 (polyethylene polymer etherified with butanone oxime) was stirred in an aqueous HCl solution with a pH value of 2 and subjected to acid hydrolysis at 40 °C for 3 h. The hydrochloric acid aqueous solution was filtered off, and the solid obtained by filtration was washed with deionized water until neutral, and then dried to obtain a polymer containing an oxyamine functional group, with a yield of 98%.

[0104] Example 4

[0105] The polymer containing oxime ether prepared in Example 2 (polypropylene polymer etherified with butanone oxime) was stirred in an aqueous HCl solution with a pH value of 3 and subjected to acid hydrolysis at 50 °C for 6 h. The hydrochloric acid aqueous solution was filtered off, and the solid obtained by filtration was washed with deionized water until neutral, and then dried to obtain a polymer containing an oxyamine functional group, with a yield of 98.2%.

[0106] Example 5

[0107] Preparation of aldehyde-based membrane reactive adsorbent: The polymer containing oxyamine functional group prepared in Example 3 and the pore-forming agent poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) triblock copolymer (P123) were kneaded in a mass ratio of 8:2 to form a kneaded product, which was then extruded into a sheet-like membrane through a screw extruder. Then, the sheet-like membrane was subjected to a two-way stretching treatment by water bath impregnation to remove the water-soluble pore-forming agent, obtaining a reactive adsorbent 1 of a polymer porous membrane containing an oxyamine functional group.

[0108] Example 6

[0109] Preparation of aldehyde-based supported reactive adsorbent: The polymer containing oxyamine functional group prepared in Example 4 was dissolved in n-hexane and stirred evenly to obtain a polymer solution containing oxyamine functional group;

[0110] Activated carbon was added to the polymer solution containing oxyamine functional group. After dispersion for 2 h, n-hexane was evaporated by heating, and then dried at 70 °C for 2 h to obtain a reactive adsorbent 2 of a polymer containing oxyamine functional group supported on graphene.

[0111] Examples 7 - 12

[0112] Inject nitrogen into formalin to produce gaseous formaldehyde. Place the formalin in a constant temperature water bath at 24°C. Then, inject the gaseous formaldehyde and nitrogen simultaneously into a previously evacuated 1L mixing box, in which there is placed 10g of the aldehyde - reactive adsorbent sample prepared in Example 5 or 6, and a fan is placed for air circulation inside the box. Finally, use a real - time formaldehyde analyzer to record the formaldehyde concentration before and after adsorption. The initial formaldehyde concentration in the test system is controlled by the nitrogen flow rate, and the nitrogen flow rate is adjusted by a mass flow meter. After a reaction time of 2 - 10h, analyze the formaldehyde concentration before and after the reaction, and the results are shown in Table 1.

[0113] Table 1 Results of formaldehyde removal efficiency in air

[0114]

[0115] As can be seen from Table 1, the reactive adsorbent provided by the present invention can efficiently remove formaldehyde in the air; the formaldehyde removal ability in the air increases with the increase of the nitrogen flow rate and temperature. At an N 2 flow rate of 0.2L / min at ambient temperature, 10g of the modified aldehyde - reactive adsorbent 1 can basically remove formaldehyde after 4h, and its content drops from 9ppm to 0.3ppm, with a removal rate of 96.7%. The removal efficiency of aldehyde - reactive adsorbent 2 reaches 99.5% after 10h.

[0116] Examples 13 - 16

[0117] Test on the aldehyde removal ability in an aqueous solution environment. In the examples of removing formaldehyde from the solution, the amount of free formaldehyde in the sample is determined by titration. In a typical treatment process, a known amount of hydroxylammonium chloride is added to the sample before or after removing formaldehyde, which reacts with the residual free formaldehyde in the solution. After the reaction of hydroxylammonium chloride, an equimolar amount of hydrochloric acid is released, and the amount of hydrochloric acid is titrated with NaOH to measure the accurate amount of hydrochloric acid, which is equivalent to the amount of formaldehyde that reacted in the original sample (i.e., the amount of free formaldehyde). The automatic titrator 888Titrando can be used for this analysis.

[0118] The experiment is carried out using 100g of formaldehyde aqueous solution (2000ppm), 50g of the aldehyde remover prepared in Example 5 or 6 is added, the adsorption is carried out at 70°C for 1 - 10h, the sample is taken out, cooled, and its formaldehyde residue is analyzed. The results are shown in Table 2 below.

[0119] Table 2 Results of formaldehyde removal efficiency in aqueous solution

[0120]

[0121] As can be seen from Table 2, the reactive adsorbent provided by the present invention can efficiently remove formaldehyde in aqueous solution; in aqueous solution, when the substrate formaldehyde content is as high as 2000 ppm, the reactive adsorbent provided by the present invention also has a high formaldehyde absorption efficiency. After absorption for 2 to 10 hours, formaldehyde is reduced by more than 95%. When the reaction time reaches 10 hours, the formaldehyde absorption efficiency can reach more than 99.35%.

[0122] Example 17

[0123] Regeneration of aldehyde reactive adsorbent. The reactive adsorbent after being completely adsorbed and saturated in Examples 7 to 16 was hydrolyzed in an aqueous HCl solution with a pH value of 3 at 50 °C for 8 hours, then filtered to remove the hydrochloric acid aqueous solution, washed with deionized water to neutrality, and dried to obtain a regenerated reactive adsorbent.

[0124] The corresponding regenerated reactive adsorbent was used for formaldehyde adsorption according to Examples 7 to 16, and the results are listed in Tables 3 and 4.

[0125] Table 3 Results of the formaldehyde removal efficiency of the regenerated reactive adsorbent in air

[0126]

[0127] Table 4 Results of the formaldehyde removal efficiency of the regenerated reactive adsorbent in aqueous solution

[0128]

[0129] As can be seen from the results in Tables 3 and 4, the regenerated reactive adsorbent can restore its good formaldehyde removal rate.

[0130] The present invention can conveniently prepare a highly active polymer material containing an oxyamine functional group (-ONH 2 ) by a two-step brief modification of direct ketoxime etherification-acid hydrolysis of chlorinated polyolefin. The oxyamine functional group contained has specific high reactivity towards aldehyde compounds and can react rapidly, so that aldehyde compounds can be efficiently removed at ambient temperature. In some embodiments, this system can remove more than 99.5% of free formaldehyde from the environment. In addition, after the saturated reaction and complete consumption of the oxyamine functional group, the polymer material can be regenerated by a re-acid hydrolysis step. The regeneration step is fast, and the activity retention rate after regeneration is high, and it can be reused multiple times. This method has a simple preparation process, high efficiency in removing aldehyde compound impurities, easy regeneration of the material, and low cost, providing a simple method for removing aldehydes, especially formaldehyde, in the environment.

[0131] Although the above embodiments have described the present invention in detail, they are only a part of the embodiments of the present invention, rather than all embodiments. People can also obtain other embodiments based on this embodiment without creative efforts, 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: The preparation method of the polymer containing oxygen-amine functional groups 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 an oxime ether-containing polymer; The polymer containing oxime ether is subjected to acid hydrolysis to obtain the polymer containing oxygenated amine functional groups.

2. The method for preparing a polymer containing oxygen-amine functional groups according to claim 1, characterized in that: The following steps are involved: The chlorinated polyolefin, alkyl ketoxime, alkali metal salt, crown ether and the first organic solvent are mixed and refluxed to obtain an oxime ether-containing polymer; The polymer containing oxime ether is subjected to acid hydrolysis to obtain the polymer containing oxygenated amine functional groups.

3. The preparation method according to claim 2, characterized in that: The chlorinated polyolefin includes chlorinated polyethylene, chlorinated polypropylene or chlorinated polybutylene.

4. The preparation method according to claim 3, characterized in that: 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. , the acid value is 6.0~8.

0.

5. The preparation method according to claim 2, characterized in that: 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 any one of claims 2 to 5, 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 2, 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 adsorbing 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.

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