A polymer adsorbent and its preparation method and application

Abstract

The present invention belongs to the technical field of polymer adsorption materials, and specifically relates to a polymer adsorbent, its preparation method, and application. The method for preparing the polymer adsorbent provided by the present invention comprises the following steps: mixing a stabilizer and a stabilizing aid with water to obtain an aqueous phase; mixing an alkenyl aromatic monomer, a polyalkenyl ester monomer, a halogenated olefin monomer, a porogen, and an initiator to obtain an oil phase; adding the oil phase to the aqueous phase to obtain a polymer intermediate through a suspension polymerization reaction; extracting the porogen from the polymer intermediate, drying, swelling, and adding a catalyst to carry out a cross-linking reaction to obtain the polymer adsorbent.

Description

Technical Field

[0001] The present invention belongs to the technical field of polymer adsorption materials, and in particular relates to a polymer adsorbent and a preparation method and application thereof. Background Art

[0002] Colds are common flu-like illnesses, and amantadine compounds, as antiviral drugs, are widely used clinically for the treatment and prevention of influenza viruses. However, the production of these compounds inevitably produces wastewater containing derivatives such as adamantane alcohol and adamantane. These wastewaters have high chemical oxygen demand (COD) values ​​and poor biodegradability, causing severe damage if discharged directly into rivers. Therefore, it is necessary to reduce the content of adamantane alcohol, adamantane amine, and other derivatives in these production wastewaters to a level that is acceptable for discharge, or even to zero discharge.

[0003] Conventional crystallization methods can reduce the amantadine content in water, but they cannot simultaneously treat both adamantanol and amantadine, and they produce a large amount of alkali solution that is difficult to handle. Furthermore, adsorption using activated carbon or molecular sieves is commonly used in existing technologies. While these methods can simultaneously treat both substances, they cannot be effectively separated and recovered at high purity, and the cost of adsorbent regeneration is high. Summary of the Invention

[0004] Therefore, the technical problem to be solved by the present invention is to overcome the above-mentioned defects in the prior art, thereby providing a polymer adsorbent and a preparation method and application thereof.

[0005] The present invention provides a method for preparing a polymer adsorbent, which is characterized by comprising the following steps:

[0006] S1, mixing a stabilizer, a stabilizing aid and water to obtain an aqueous phase;

[0007] S2, mixing an alkenyl aromatic monomer, a polyalkenyl ester monomer, a halogenated olefin monomer, a porogen, and an initiator to obtain an oil phase;

[0008] S3, adding the oil phase to the water phase to obtain a high molecular weight polymer intermediate through suspension polymerization;

[0009] S4, extracting the porogen from the polymer intermediate, drying, swelling, adding a catalyst to carry out a cross-linking reaction, and obtaining the polymer adsorbent.

[0010] Optionally, the preparation method of the polymer adsorbent satisfies at least one of the following:

[0011] (1) The alkenyl aromatic monomers include vinyl aromatic monomers and propenyl aromatic monomers;

[0012] (2) The vinyl aromatic monomer includes a monovinyl aromatic monomer and a polyvinyl aromatic monomer; the monovinyl aromatic monomer includes at least one of styrene and p-chloromethylstyrene; the polyvinyl aromatic monomer includes at least one of divinylbenzene and 1,3-diisopropenylbenzene;

[0013] (3) The halogenated olefin monomer includes trichloroethylene 、 At least one of chloropropylene, hexachloropropylene, and 2,3-dichloropropylene;

[0014] (4) The propenyl aromatic monomer includes at least one of 1,3-diisopropenylbenzene and 3-(1-naphthyl)-1-propene, preferably 1,3-diisopropenylbenzene;

[0015] (5) The polyalkenyl ester monomer includes at least one of triallyl isocyanurate (TAIC), triallyl cyanurate, triallyl cyanurate (TAC), bisallyl itaconate, ethylene glycol dimethacrylate, and allyl methacrylate; preferably triallyl isocyanurate or triallyl cyanurate;

[0016] (6) The catalyst includes at least one of zinc chloride, ferric chloride, tin chloride, titanium chloride, and aluminum chloride.

[0017] Optionally, the cross-linking reaction temperature is 40-80°C, and the cross-linking reaction time is 2 hours to 6 hours; and / or, the suspension polymerization reaction is carried out under the condition of staged heating, and the staged heating process includes one heating, one constant temperature, two heatings, and two constant temperatures; and / or, the first heating is to 70-80°C, the time of the first heating process is 0.2 to 5 hours, the first constant temperature time is 1 to 5 hours, the second heating is to 85-95°C, the time of the second heating process is 0.2 to 5 hours, and the second constant temperature time is 2 to 8 hours.

[0018] Optionally, the adding is carried out at 40-50° C. and the adding time is 0.1-2 hours;

[0019] and / or, the extraction of the porogen is carried out at 40-60° C., the number of extractions is 3-5 times, and each extraction time is 1-2 hours;

[0020] And / or, the porogen comprises at least one selected from n-pentanol, 200# gasoline, liquid wax, adamantane amine derivatives, and adamantane alcohol derivatives; preferably adamantane amine derivatives and / or adamantane alcohol derivatives;

[0021] And / or, the adamantane amine derivative is N-methyl-1-adamantanamine; the adamantane alcohol derivative is 3-amino-1-adamantanol;

[0022] and / or, the solvent used for extracting the porogen includes at least one of methylal (also known as dimethoxymethane), methanol, acetone, ethanol, and toluene;

[0023] The mass ratio of the amount of the extractant to the high molecular weight polymer intermediate is (1.5-3):1.

[0024] And / or, the solvent used for the swelling includes at least one of methanol, ethanol, water, 1,2-dichloroethane, and N,N-dimethylformamide;

[0025] The mass ratio of the amount of solvent used to the high molecular weight polymer intermediate during the swelling process is (2-6):1.

[0026] and / or, the initiator comprises at least one of benzamide peroxide, azobisisobutyronitrile, diacyl peroxide, azobisisoheptanenitrile, and tert-butyl benzoyl peroxide;

[0027] and / or, the mass ratio of water, stabilizer, and stabilizing aid is 100:(0.1-30):(0.1-30);

[0028] And / or, the mass ratio of the water phase to the oil phase is (1-5):1.

[0029] Optionally, the stabilizer comprises at least one of polyvinyl alcohol, gelatin, cellulose, and derivatives thereof, and is used to reduce the surface tension of water, thereby preventing the oil droplets from merging and bonding. Alternatively, the stabilizing aid is adapted to reduce the solubility of the oil phase in the aqueous phase and comprises at least one of sodium chloride, magnesium chloride, and methylene blue. Optionally, the drying is performed in a vacuum drying oven or a forced air drying oven.

[0030] The mass ratio of the alkenyl aromatic monomer, the polyalkenyl ester monomer, the halogenated olefin monomer, the porogen, the initiator and the catalyst is (70-110): (0.01-20): (0.01-20): (100-180): (0.05-4): (40-80).

[0031] The present invention also provides a polymer adsorbent, which is prepared by the above preparation method.

[0032] The present invention also provides a use of the polymer adsorbent in separating adamantane alcohol and adamantane amine compounds in wastewater.

[0033] Optionally, the use of the polymer adsorbent in separating adamantane alcohol and adamantane amine compounds in wastewater comprises the following steps:

[0034] Pretreatment: remove suspended matter from wastewater and adjust pH;

[0035] Adsorption treatment: the pretreated wastewater is subjected to adsorption treatment using the polymer adsorbent to adsorb the adamantane alcohol and adamantane amine compounds in the wastewater;

[0036] Analytical separation: The adsorbed polymer adsorbent is analyzed with alcohol solvents to extract the adamantane alcohol compounds, and with alkaline solution to extract the adamantane amine compounds.

[0037] Optionally, use filter cotton, filter paper or filters to remove suspended matter.

[0038] Optionally, after removing the suspended matter, the concentration of the suspended matter is made ≤20ppm.

[0039] Optionally, the pH of the wastewater is adjusted to be weakly acidic to neutral, preferably, the pH is adjusted to 6-7.

[0040] Optionally, a 1-10% aqueous acid solution is used to adjust the pH, preferably sulfuric acid.

[0041] Optionally, the use of the polymer adsorbent in separating adamantane alcohol and adamantane amine compounds in wastewater further comprises:

[0042] Regeneration step: the polymer adsorbent separated by analytical analysis is washed with acid and then with water;

[0043] And / or, the method further includes a purification step of evaporating or distilling the decomposition solution containing the adamantane alcohol compound, cooling, filtering, and drying the hot saturated liquid after removing the alcohol solvent to obtain the adamantane alcohol compound product; and steam distilling the decomposition solution containing the adamantane amine compound, cooling, crystallizing, filtering, and drying to obtain the adamantane amine compound product.

[0044] Optionally, the adsorption treatment is normal pressure, forward adsorption.

[0045] Optionally, the water washing is a combination of forward washing and backwashing.

[0046] Optionally, in the regeneration step, pre-water washing is performed before pickling.

[0047] Optionally, the use of the polymer adsorbent in separating adamantane alcohol and adamantane amine compounds in wastewater satisfies at least one of the following conditions:

[0048] (1) The alcohol solvent is selected from at least one of methanol and ethanol;

[0049] (2) the alkali solution is at least one selected from sodium hydroxide, potassium hydroxide, sodium carbonate or ammonia water; and / or the mass fraction of the alkali solution is preferably 4%-10%;

[0050] (4) the acid solution is selected from at least one of sulfuric acid and hydrochloric acid; and / or the mass fraction of the acid solution is preferably 0.1%-10%;

[0051] (5) The purity of the adamantane alcohol compound product is 70-95%; and / or the purity of the adamantane amine compound product is 72-98%.

[0052] The use of a polymeric adsorbent in separating adamantane alcohol and adamantane amine compounds from wastewater typically, but not exclusively, involves loading the polymeric adsorbent into an adsorption column for wastewater treatment, wherein the specific treatment conditions satisfy at least one of the following:

[0053] (1) The amount of polymer adsorbent loaded in the adsorption column is 10-1000 ml; and / or the flow rate of wastewater through the adsorption column is 1-4 BV / h;

[0054] (2) The amount of the adamantane alcohol decomposing agent is 1 to 5 BV, and the flow rate through the adsorption column is 1 to 4 BV / h;

[0055] (3) The amount of the alkali solution is 1 to 5 BV, and the flow rate through the adsorption column is 1 to 4 BV / h;

[0056] (4) The amount of water used in the pre-water washing is 1 to 2 BV, and / or; the amount of the acid solution used is 0.2 to 3 BV, and the flow rate through the adsorption column is 1 to 4 BV / h; and / or, the amount of water used in the water washing is 1 to 5 BV.

[0057] The technical solution of the present invention has the following advantages:

[0058] 1. The present invention provides a method for preparing a polymeric adsorbent, comprising the following steps: S1, mixing a stabilizer and a stabilizing aid with water to obtain an aqueous phase; S2, mixing an alkenyl aromatic monomer, a polyalkenyl ester monomer, a halogenated olefin monomer, a porogen, and an initiator to obtain an oil phase; S3, adding the oil phase to the aqueous phase to obtain a polymer intermediate through suspension polymerization; S4, extracting the porogen from the polymer intermediate, drying, swelling it, and adding a catalyst to carry out a cross-linking reaction to obtain the polymeric adsorbent. The adsorbent material prepared by the suspension polymerization and cross-linking reaction described above has a high specific surface area and a suitable pore structure. In particular, polyolefin ester monomers are added to the raw materials, which also act as cross-linking agents and selective adsorbents, so that a partial cross-linking reaction occurs in the S3 suspension polymerization reaction, and a high-molecular polymer intermediate with a tight network structure is obtained. The addition of halogenated olefin monomers to the raw materials cooperates with the cross-linking reaction of S4, and finally a high-molecular adsorbent with a three-dimensional network structure with a higher degree of cross-linking is obtained. While the physical and mechanical properties are improved, its pore structure is more suitable for the adsorption of adamantane alcohol and adamantane amine compounds. In addition, the hydrophilic groups contained therein (lipid compounds on the skeleton structure) enable the prepared adsorbent to adsorb adamantane alcohol and adamantane amine compounds to the surface or pores of its molecular structure through hydrogen bonds or van der Waals forces.

[0059] 2. The present invention provides a method for preparing a polymeric adsorbent. The method comprises selecting appropriate monomers, porogens, crosslinkers, and catalysts, adding them in a specific ratio, and conducting polymerization and crosslinking reactions under specific conditions. By controlling the molecular size, a highly selective polymeric adsorbent capable of adsorbing adamantane alcohol and adamantane amine at room temperature and pressure is prepared.

[0060] Among them, vinyl aromatics are used as the main monomer for initial polymerization, and metal chloride is subsequently added as a catalyst for post-crosslinking reaction. The halogen atoms on the skeleton structure and the benzene rings on the alkenyl aromatic monomer undergo Friedel-Strauss reaction to further crosslink the macromolecules, thereby preparing an adsorbent material with a higher specific surface area and a higher yield.

[0061] The suspension polymerization reaction adopts a staged heating method. The polymer adsorbent prepared by controlling the temperature has higher mechanical strength and better adsorbent repeatability.

[0062] Alternatively, adamantane amine derivatives and / or adamantane alcohol derivatives themselves can be selected as porogens, which neither react with the monomer nor can be extracted by the porogen solvent, thereby obtaining a molecularly imprinted adsorption material with a suitable pore size. Such a material has an optimally suitable pore size for the target substance to be extracted.

[0063] 3. The polymer adsorbent provided by the present invention is prepared by the above method, has a high adsorption capacity regulated by molecular size, has high adsorption properties for two types of substances, adamantane alcohol and adamantane amine compounds, and has excellent recycling and regeneration performance.

[0064] 4. The polymer adsorbent provided by the present invention is used to separate adamantane alcohol and adamantane amine compounds from wastewater. The polymer adsorbent synthesized by the preparation method provided by the present invention can adsorb both adamantane alcohol and adamantane amine compounds in the wastewater. The physical and chemical properties of the two substances are then used to perform elution and step-by-step analysis to separate the two substances. The treated water can be discharged in compliance with the discharge standards.

[0065] 5. The polymer adsorbent provided by the present invention is used to separate adamantane alcohol and adamantane amine compounds from wastewater. After the adamantane alcohol and adamantane amine compounds are separated by decomposition, the respective decomposition solutions are purified to obtain high-purity recovered adamantane alcohol and adamantane amine compounds, which can be directly reused. The polymer adsorbent is regenerated through decomposition, regeneration, and water washing steps, with low regeneration cost. The regenerated adsorbent is then recycled for the next adsorption cycle.

[0066] 6. The polymer adsorbent provided by the present invention is used to separate adamantane alcohol and adamantane amine compounds from wastewater. The separation and purification yields adamantane alcohol and adamantane amine compound products with purities of 70-95% and 72-98%, respectively. After recovery, the compounds can be used as raw materials for pharmaceutical preparation.

[0067] In addition, after the alkali solution is used to elute the adamantane compounds, the adsorbent becomes an alkaline system. Only water washing will produce 10 to 20 BV of alkaline water. However, after pre-washing the alkali with a small amount (1-2 BV) of water, a low-concentration acid solution (adjustable concentration) is used for forward washing, and then water washing is performed again. The pH of the effluent can be controlled at 6-7, which greatly reduces the generation of alkaline water and ensures the use effect of the adsorbent (the resin is better used under weak acidic conditions than under alkaline conditions). BRIEF DESCRIPTION OF THE DRAWINGS

[0068] In order to more clearly illustrate the specific embodiments of the present invention or the technical solutions in the prior art, the following briefly introduces the drawings required for use in the specific embodiments or the description of the prior art. Obviously, the drawings described below are some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying any creative work.

[0069] Figure 1 The present invention provides a process flow chart for separating adamantane alcohol and adamantane amine compounds from wastewater. DETAILED DESCRIPTION

[0070] The following examples are provided for a better understanding of the present invention and are not intended to limit the best mode of implementation. They do not limit the content and scope of protection of the present invention. Any product identical or similar to the present invention obtained by anyone under the guidance of the present invention or by combining the features of the present invention with other prior arts shall fall within the scope of protection of the present invention.

[0071] If no specific experimental steps or conditions are specified in the examples, the conventional experimental steps or conditions described in the literature in this field can be used. If the manufacturer of the reagents or instruments is not specified, they are all commercially available conventional reagents.

[0072] Example 1

[0073] This embodiment provides a method for preparing a polymer adsorbent, comprising the following steps:

[0074] 32.5 g of sodium chloride, 6.5 g of polyvinyl alcohol (manufactured by MacLean; alcoholysis degree: 87.0-89.0%, the same below), and 0.01 g of methylene blue were added to 610 g of water and mixed to obtain an aqueous phase;

[0075] Monomers (74 g styrene, 2 g 1,3-diisopropenylbenzene, 10 g p-chloromethylstyrene, 4 g divinylbenzene, 4 g allyl chloride, 4 g triallyl isocyanurate), a porogen (40 g 200# gasoline, 40 g liquid wax, 80 g 3-amino-1-adamantanol), and an initiator (0.5 g benzamide peroxide, 0.5 g azobisisobutyronitrile) were mixed to obtain an oil phase;

[0076] The oil phase was added to the aqueous phase at 45°C for 0.2 h, and then the temperature was raised to 75°C for 1.5 h, and the reaction was carried out at 75°C for 2 h. Then, the temperature was further raised to 90°C for 1 h, and the reaction was carried out at 90°C for 6 h. The temperature was then lowered to room temperature, filtered, and washed to obtain a high molecular weight polymer intermediate in the form of white spherical particles.

[0077] 90 g of the polymer intermediate obtained above was subjected to porogen extraction 5 times with methylal solvent at 40° C., each extraction for 2 h, with 180 g of methylal used for each extraction. The product was then dried in a blast drying oven, swollen with 360 g of 1,2-dichloroethane solvent, and finally, 60 g of zinc chloride catalyst was added. The product was cross-linked at 40° C. for 3 h, and washed with water after the reaction to obtain a polymer adsorbent.

[0078] Example 2

[0079] This embodiment provides a method for preparing a polymer adsorbent, comprising the following steps:

[0080] 20 g of magnesium chloride, 5 g of polyvinyl alcohol, and 0.01 g of methylene blue were added to 500 g of water and mixed to obtain an aqueous phase;

[0081] The monomers (85 g styrene, 2 g p-chloromethylstyrene, 4 g divinylbenzene, 6 g hexachloropropylene, 0.5 g triallyl isocyanurate), a porogen (50 g 200# gasoline, 50 g 3-amino-1-adamantanol), and an initiator (0.5 g azobisisobutyronitrile) were mixed to obtain an oil phase;

[0082] The oil phase was added to the aqueous phase at 50°C over a period of 0.1 h, and then the temperature was raised to 70°C for a single heating process of 0.2 h, followed by a constant temperature reaction at 70°C for 2 h. Subsequently, the temperature was raised to 88°C for a second time of 1.5 h, followed by a constant temperature reaction at 88°C for 2 hours, and then the temperature was lowered to room temperature, filtered, and washed to obtain a high molecular weight polymer intermediate in the form of white spherical particles.

[0083] 90 g of the polymer intermediate obtained above was subjected to porogen extraction 4 times with methanol solvent at 60° C., each extraction lasting 1 h, with 140 g of methanol used each time. The product was then dried in a blast drying oven, swollen with 160 g of 1,2-dichloroethane and 100 g of water solvent, and finally, 50 g of zinc chloride catalyst was added. The product was cross-linked at 40° C. for 4 h, and washed with water after the reaction to obtain a polymer adsorbent.

[0084] Example 3

[0085] This embodiment provides a preparation method of a polymer adsorbent. Compared with Example 1, the only difference is that liquid wax is used in the porogen instead of 3-amino-1-adamantanol.

[0086] Example 4

[0087] This embodiment provides a method for preparing a polymer adsorbent, comprising the following steps:

[0088] 20 g of sodium chloride, 4 g of polyvinyl alcohol, and 0.01 g of methylene blue were added to 800 g of water and mixed to obtain an aqueous phase;

[0089] Monomers (92 g styrene, 8 g p-chloromethylstyrene, 2 g divinylbenzene, 1 g allyl chloride, 6 g triallyl cyanurate, 4 g triallyl isocyanurate), a porogen (20 g 200# gasoline, 40 g liquid wax, 100 g 3-amino-1-adamantanol), and an initiator (2 g tert-butyl benzoyl peroxide, 2 g azobisisobutyronitrile) were mixed to obtain an oil phase;

[0090] The oil phase was added to the aqueous phase at 40°C for 1 hour, and then the temperature was raised to 72°C for 1 hour, and the reaction was kept at 72°C for 1 hour. Then, the temperature was raised to 90°C for 4 hours, and the reaction was kept at 90°C for 8 hours. The temperature was then lowered to room temperature, filtered, and washed to obtain a high molecular weight polymer intermediate in the form of white spherical particles.

[0091] 90 g of the polymer intermediate obtained above was subjected to porogen extraction 5 times with acetone solvent at 45° C., each extraction lasting 2 h, with an amount of 260 g of acetone solvent used for each extraction. The product was then dried in a blast drying oven, swollen with 400 g of methanol solvent, and finally, 40 g of aluminum chloride catalyst was added. The product was cross-linked at 55° C. for 6 h, and washed with water to obtain a polymer adsorbent.

[0092] Example 5

[0093] This embodiment provides a method for preparing a polymer adsorbent, comprising the following steps:

[0094] 20 g of sodium chloride, 4 g of polyvinyl alcohol, 5 g of gelatin, and 0.01 g of methylene blue were added to 1000 g of water and mixed to obtain an aqueous phase;

[0095] Monomers (81 g styrene, 10 g p-chloromethylstyrene, 4 g divinylbenzene, 4 g 3-(1-naphthyl)-1-propylene, 8 g triallyl isocyanurate, 10 g trichloroethylene, 10 g diallyl itaconate), a porogen (20 g 200# gasoline, 50 g liquid wax, 80 g N-methyl-1-adamantanamine), and an initiator (1.0 g benzamide peroxide, 0.5 g azobisisobutyronitrile) were mixed to obtain an oil phase;

[0096] The oil phase was added to the aqueous phase at 45°C for 2 hours, and then the temperature was raised to 78°C for 3 hours, and the reaction was carried out at 78°C for 3.5 hours. Then, the temperature was raised to 95°C for 5 hours, and the reaction was carried out at 95°C for 4 hours. The temperature was then lowered to room temperature, filtered, and washed to obtain a high molecular weight polymer intermediate in the form of white spherical particles.

[0097] 90 g of the polymer intermediate obtained above was subjected to porogen extraction 4 times using methylal solvent at 51° C., each extraction lasting 1.5 h, with 250 g of methylal used for each extraction. The product was then dried in a blast drying oven, swollen with 380 g of N,N-dimethylformamide solvent, and finally, 80 g of zinc chloride catalyst was added. The product was cross-linked at 70° C. for 5 h, and washed with water to obtain a polymer adsorbent.

[0098] Example 6

[0099] This embodiment provides a method for preparing a polymer adsorbent, comprising the following steps:

[0100] 20 g of sodium chloride, 5 g of polyvinyl alcohol, and 0.01 g of methylene blue were added to 610 g of water and mixed to obtain an aqueous phase;

[0101] Monomers (90 g styrene, 4 g divinylbenzene, 3 g 1,3-diisopropenylbenzene, 2 g hexachloropropylene, 2 g triallyl isocyanurate), a porogen (40 g 200# gasoline, 40 g liquid wax, 40 g 3-amino-1-adamantanol), and an initiator (0.5 g benzamide peroxide, 0.5 g azobisisobutyronitrile) were mixed to obtain an oil phase;

[0102] The oil phase was added to the aqueous phase at 48°C over a period of 1.5 hours, and then the temperature was raised to 80°C for a single heating process of 5 hours, followed by a constant temperature reaction at 80°C for 5 hours. Subsequently, the temperature was raised to 85°C for a second time of 0.2 hours, followed by a constant temperature reaction at 85°C for 6 hours, and then the temperature was lowered to room temperature, filtered, and washed to obtain a high molecular weight polymer intermediate in the form of white spherical particles.

[0103] 90 g of the polymer intermediate obtained above was subjected to porogen extraction three times using methylal solvent at 56° C., each extraction for 2 h, with 260 g of methylal used for each extraction. The product was then dried in a blast drying oven, then swollen with 260 g of methanol and 200 g of ethanol solvent, and finally, 60 g of ferric chloride catalyst was added. The product was cross-linked at 80° C. for 2 h, and washed with water after the reaction to obtain a polymer adsorbent.

[0104] Example 7

[0105] This embodiment provides a method for preparing a polymer adsorbent, comprising the following steps:

[0106] 32.5 g of sodium chloride, 6.5 g of polyvinyl alcohol, and 0.01 g of methylene blue were added to 610 g of water and mixed to obtain an aqueous phase;

[0107] Monomers (74 g styrene, 2 g 1,3-diisopropenylbenzene, 10 g p-chloromethylstyrene, 4 g divinylbenzene, 4 g allyl chloride, 4 g triallyl isocyanurate), a porogen (40 g 200# gasoline, 40 g liquid wax, 80 g 3-amino-1-adamantanol), and an initiator (0.5 g benzamide peroxide, 0.5 g azobisisobutyronitrile) were mixed to obtain an oil phase;

[0108] The oil phase was added to the aqueous phase at 45°C for 0.2h; the polymerization reaction was then carried out at 80°C for 12h, and then the temperature was lowered to room temperature, filtered, and washed to obtain a high molecular weight polymer intermediate in the form of white spherical particles;

[0109] 90 g of the polymer intermediate obtained above was subjected to porogen extraction 5 times with methylal solvent at 40° C., each extraction for 2 h, and the amount of methylal used for each extraction was 180 g. The product was then dried in a blast drying oven, and then swollen with 300 g of 1,2-dichloroethane solvent. Finally, 60 g of zinc chloride catalyst was added, and a cross-linking reaction was carried out at 40° C. for 3 h. After the reaction was completed, the product was washed with water to obtain a polymer adsorbent.

[0110] Comparative Example 1

[0111] This comparative example provides a preparation method of a polymer adsorbent. Compared with Example 1, the only difference is that styrene is used instead of triallyl isocyanurate.

[0112] Comparative Example 2

[0113] This comparative example provides a method for preparing a polymer adsorbent, comprising the following steps:

[0114] 32.5 g of sodium chloride, 6.5 g of polyvinyl alcohol, and 0.01 g of methylene blue were added to 610 g of water and mixed to obtain an aqueous phase;

[0115] Monomers (74 g styrene, 2 g 1,3-diisopropenylbenzene, 10 g p-chloromethylstyrene, 4 g divinylbenzene, 4 g allyl chloride, 4 g triallyl isocyanurate), a porogen (40 g 200# gasoline, 40 g liquid wax, 80 g 3-amino-1-adamantanol), and an initiator (0.5 g benzamide peroxide, 0.5 g azobisisobutyronitrile) were mixed to obtain an oil phase;

[0116] The oil phase was added to the aqueous phase at 45°C for 0.2h, wherein the mass ratio of aqueous phase to oil phase was 2.5:1; the temperature was then raised to 75°C for 1.5h, and the reaction was continued at 75°C for 2h. The temperature was then raised to 90°C for 1h, and the reaction was continued at 90°C for 6h. The temperature was then lowered to room temperature, filtered, and washed to obtain 90g (dry basis) of a high molecular weight polymer intermediate in the form of white spherical particles.

[0117] 90 g of the polymer intermediate obtained above was subjected to porogen extraction 5 times with methylal solvent at 40° C., each extraction lasting 2 h. The amount of methylal used in each extraction was 200 g. After the porogen extraction was completed, the polymer adsorbent was washed with water to obtain the polymer adsorbent.

[0118] Test Example 1

[0119] For the polymer adsorbents prepared in Examples 1-7 and Comparative Examples 1-2, the specific surface area and pore volume / pore diameter were measured using the mercury intrusion method (Micromeritics AutoPore IV equipment); the mechanical strength of the resin (expressed by the post-grinding roundness rate) was measured using the GB / T 12598-2001 ion exchange resin infiltration roundness rate and post-grinding roundness rate method (which complies with the resin wear resistance test method, and the laboratory has its own ball mill); the water content of the test resin was tested using the GB5757-86 method, and the adsorption capacity was tested using the phenol meter method (using phenol as a reference, the phenol concentration was 6.5 g / l, and 10 ml of the adsorbent was transferred to The resin was adsorbed in a glass sand core adsorption column. Phenol was detected in the adsorbed water using the indicator method (the resin was considered saturated). The resin's adsorption capacity was tested according to the formula: adsorption capacity (g / l) = C1 * V1 / 10, where C1 = 6.5 g / l; V1 is the volume of the adsorbed water at which no phenol was detected, expressed in L. The results are shown in Table 1 below.

[0120] Table 1

[0121]

[0122]

[0123] Note: The lower the water content of the polymer adsorbent, the higher the degree of cross-linking of the polymer molecular skeleton structure and the better the mechanical strength performance.

[0124] By conducting physicochemical analysis on the polymer adsorbents synthesized in the examples and comparative examples 1-2, it can be concluded that the examples have the characteristics of suitable pore size, high specific surface area, large mechanical strength, high cross-linking degree and good adsorption performance. Among them, the polymer adsorbent prepared in Example 1 has the best performance. In Example 3, since no adamantane alcohol derivatives were added as porogens, the pore size, specific surface area, adsorption performance, etc. were slightly worse than those in Example 1. In Example 7, since the staged heating method was not adopted, the mechanical strength, adsorption performance, etc. were reduced. In Comparative Example 1, no polyalkenyl ester monomers were added. Therefore, not only the cross-linking degree of the obtained polymer adsorbent molecules was reduced, but also the mechanical strength, adsorption performance, specific surface area, pore size, etc. were all worse than those in the examples. In Comparative Example 2, no cross-linking reaction was carried out, and all properties were also deteriorated.

[0125] Test Example 2

[0126] The purity of adamantane alcohol and adamantane amine in the above embodiments and comparative examples, as well as the composition and proportion of the substances contained in the wastewater after adsorption treatment, were respectively detected by using the DB37 / T4299-2020 high performance liquid chromatography method to compare the adsorption and separation effects of each adsorbent on adamantane alcohol and adamantane amine.

[0127] Experimental group: Examples 1-7 and Comparative Examples 1-2. The process flow of the treatment method is as follows Figure 1 As shown, the specific operation is as follows: 4000g of pharmaceutical wastewater (pH ≈ 9) containing adamantanol (0.05%), amantadine (0.08%), and sodium sulfate (1%) is passed through a precision filter (security filter) for suspended solids treatment, reducing the inlet suspended solids concentration to ≤ 20ppm. 10% sulfuric acid is then added to adjust the pH to 6.8. The pretreated wastewater is passed through an adsorption column containing 50ml of a polymer adsorbent via a metering pump at a flow rate of 2 BV / h (BV is the volume of the resin bed in the adsorption column) for 30 hours. The adsorption column is backwashed with methanol (99.5%) at a flow rate of 1 BV / h for 2 hours. The eluent containing adamantanol is collected in sections (i.e., once every 0.5 hours). The eluents are evaporated with methanol in evaporators, filtered, and dried to obtain the adamantanol product. The adsorption column is backwashed with 6% sodium hydroxide solution at a flow rate of 1 BV / h for 2 hours. The eluate containing amantadine is collected in sections (i.e., once every 0.5 hours) and steam distilled (distillation is stopped if crystals precipitate). The product is then cooled, filtered, and dried to obtain the amantadine product. The qualified water after the adsorption treatment is discharged; the adsorption column is prewashed with 2 BV of pure water, then forward-washed with 0.5% sulfuric acid solution at a flow rate of 1 BV / h. The resin column is then washed with 3 BV of pure water. The regenerated adsorbent is then recycled.

[0128] Control group: Adsorption using granular activated carbon. Treatment method: Except for replacing 50ml of polymer adsorbent with 50mL of granular activated carbon for the adsorption test, the adsorption treatment, analytical separation, purification methods, and parameter conditions were the same as those of the experimental group. The adsorption effluent test showed that the adamantane alcohol content in the adsorption effluent was 0.04% adamantane alcohol and 0.06% adamantane amine. The effluent failed the test. Because the activated carbon requires regeneration under high temperature conditions for analytical separation and purification, regeneration and recovery were not performed in this experiment, and it could not meet the requirements of analytical separation and purification at normal temperature and pressure. The results are shown in Table 2 below.

[0129] Table 2

[0130]

[0131]

[0132] Qualitative and quantitative analysis of the recovered adamantane alcohol and adamantane amine revealed that the results of the examples were superior to those of the comparative examples. Example 1 exhibited superior specific surface area and pore size, good separation and recovery effects, and high product purity. Example 3, which did not incorporate an adamantane alcohol derivative as a porogen, exhibited slightly inferior separation effects compared to Example 1. Comparative Example 1 lacked the addition of a polyalkenyl ester monomer, and Comparative Example 2 did not undergo a cross-linking reaction, resulting in a decreased degree of crosslinking and a poorer separation effect. Comparative Example 3 employed activated carbon as an adsorbent, and while this adsorption of adamantane alcohol and adamantane amine was also possible, the adsorption effect was far inferior to that of the examples, and the separation and recovery effects of both were not achieved.

[0133] Test Example 3

[0134] The adsorption capacity of the polymer adsorbents prepared in the examples and comparative examples after regeneration was tested. The specific method was as follows: the regenerated adsorbent of the experimental group of Test Example 2 and the activated carbon treated with high-temperature steam in the control group were subjected to secondary adsorption treatment, analytical separation, and purification of the wastewater (composition as above) according to the method in Test Example 2, and the composition of the wastewater after the second adsorption treatment and the situation of the separated products were tested. The specific parameters of the treatment remained unchanged (the same as in Test Example 2). The results are shown in Table 3 below.

[0135] Table 3

[0136]

[0137]

[0138] By comparing the data in the table, it is found that the results of the embodiments are better than those of the comparative examples to varying degrees, indicating that the recycling effect of the polymer adsorbent of the present invention is also good.

[0139] Obviously, the above embodiments are merely examples for clarity of explanation and are not intended to limit the implementation methods. Those skilled in the art will readily appreciate that other variations or modifications based on the above descriptions are possible. It is not necessary and impossible to enumerate all implementation methods here. Obvious variations or modifications arising therefrom remain within the scope of protection of the present invention.

Claims

1. A method for preparing a polymer adsorbent, characterized in that: The following steps are involved: S1, mixing a stabilizer, a stabilizing aid and water to obtain an aqueous phase; S2, mixing an alkenyl aromatic monomer, a polyalkenyl ester monomer, a halogenated olefin monomer, a porogen, and an initiator to obtain an oil phase; the porogen comprises at least one of an adamantane amine derivative and an adamantane alcohol derivative; S3, adding the oil phase to the water phase to obtain a high molecular weight polymer intermediate through suspension polymerization; S4, extracting the porogen from the polymer intermediate, drying, swelling, adding a catalyst to carry out a cross-linking reaction, and obtaining the polymer adsorbent; The cross-linking reaction temperature is 40-80°C, and the cross-linking reaction time is 2 hours to 6 hours; The suspension polymerization reaction is carried out under the condition of staged temperature increase, and the staged temperature increase process includes a first temperature increase, a first constant temperature, a second temperature increase, and a second constant temperature; The first heating process is to 70-80°C, the first heating process takes 0.2 to 5 hours, the first constant temperature time is 1 to 5 hours, the second heating process is to 85-95°C, the second heating process takes 0.2 to 5 hours, and the second constant temperature time is 2 to 8 hours.

2. The method for preparing a polymer adsorbent according to claim 1, wherein: The alkenyl aromatic monomer includes at least one of a vinyl aromatic monomer and a propenyl aromatic monomer; And / or, the halogenated olefin monomer includes at least one of trichloroethylene, chloropropylene, hexachloropropylene, and 2,3-dichloropropylene; And / or, the polyalkenyl ester monomer includes at least one of triallyl isocyanurate, triallyl cyanurate, diallyl cyanurate, diallyl itaconate, ethylene glycol dimethacrylate, and allyl methacrylate; And / or, the catalyst includes at least one of zinc chloride, ferric chloride, tin chloride, titanium chloride, and aluminum chloride.

3. The method for preparing a polymer adsorbent according to claim 2, wherein: The vinyl aromatic monomer includes at least one of a monovinyl aromatic monomer and a polyvinyl aromatic monomer; the monovinyl aromatic monomer includes at least one of styrene and p-chloromethylstyrene; the polyvinyl aromatic monomer includes at least one of divinylbenzene; And / or, the propenyl aromatic monomer includes at least one of 1,3-diisopropenylbenzene and 3-(1-naphthyl)-1-propene.

4. The method for preparing a polymer adsorbent according to any one of claims 1 to 3, characterized in that: The feeding is carried out at 40-50°C for 0.1-2 hours; and / or, the extraction of the porogen is carried out at 40-60° C., the number of extractions is 3-5 times, and each extraction time is 1-2 hours; And / or, the porogen further comprises at least one selected from n-pentanol, 200# gasoline, and liquid wax; And / or, the adamantane amine derivative is N-methyl-1-adamantanamine; the adamantane alcohol derivative is 3-amino-1-adamantanol; and / or, the solvent used in the extraction of the porogen comprises at least one of methylal, methanol, acetone, ethanol, and toluene; and / or, the solvent used in the swelling step comprises at least one of methanol, ethanol, water, 1,2-dichloroethane, and N,N-dimethylformamide; And / or, the initiator comprises at least one of benzamide peroxide, azobisisobutyronitrile, azobisisoheptanenitrile, and tert-butyl benzoyl peroxide; and / or, the mass ratio of water, stabilizer, and stabilizing aid is 100:(0.1-30):(0.1-30); and / or, the stabilizer comprises at least one of polyvinyl alcohol, gelatin, cellulose and derivatives thereof; And / or, the stabilizing agent includes at least one of sodium chloride, magnesium chloride, and methylene blue; And / or, the mass ratio of the water phase to the oil phase is (1~5):

1.

5. The method for preparing a polymer adsorbent according to any one of claims 1 to 3, characterized in that: The mass ratio of the alkenyl aromatic monomer, the polyalkenyl ester monomer, the halogenated olefin, the porogen, the initiator and the catalyst is (70-110): (0.01-20): (0.01-20): (100-180): (0.05-4): (40-80).

6. A polymer adsorbent, characterized in that: The method is prepared according to any one of claims 1 to 5.

7. Use of the polymer adsorbent according to claim 6 for separating adamantane alcohol and adamantane amine compounds from wastewater.

8. The use according to claim 7, characterized in that The following steps are involved: Pretreatment: remove suspended matter from wastewater and adjust pH; Adsorption treatment: the pretreated wastewater is subjected to adsorption treatment using the polymer adsorbent to adsorb the adamantane alcohol and adamantane amine compounds in the wastewater; Analytical separation: The adsorbed polymer adsorbent is analyzed with alcohol solvents to extract the adamantane alcohol compounds, and with alkaline solution to extract the adamantane amine compounds.

9. The use according to claim 8, characterized in that Also includes: Regeneration step: the polymer adsorbent separated by analytical analysis is washed with acid and water; And / or, the method further includes a purification step of evaporating or distilling the decomposition solution containing the adamantane alcohol compound, cooling, filtering, and drying the hot saturated liquid after removing the alcohol solvent to obtain the adamantane alcohol compound product, and steam distilling the decomposition solution containing the adamantane amine compound, cooling, filtering, and drying to obtain the adamantane amine compound product.

10. The use according to claim 9, characterized in that Meet at least one of the following: (1) The alcohol solvent is selected from at least one of methanol and ethanol; (2) the alkali solution is at least one selected from sodium hydroxide, potassium hydroxide, sodium carbonate or ammonia water; and / or the mass fraction of the alkali solution is 4%-10%; (3) The acid solution used in the pickling step is selected from at least one of sulfuric acid and hydrochloric acid; and / or the mass fraction of the acid solution is 0.1%-10%; (4) The purity of the adamantane alcohol compound product is 70-95%; and / or the purity of the adamantane amine compound product is 72-98%.

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