CN107641174B - Copper (II) ion surface imprinted polymer with double exchange of anions and cations and preparation method thereof - Google Patents
Copper (II) ion surface imprinted polymer with double exchange of anions and cations and preparation method thereof Download PDFInfo
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Abstract
The invention provides a copper (II) ion surface imprinted polymer with anion and cation double exchange supported by polystyrene, which is prepared by taking salicylaldoxime copper (II) complex modified by unsaturated quaternary ammonium cation as a functional monomer and polyallyl ammonium salt as a cross-linking agent through copolymerization reaction with a skeleton monomer on the surface of polyallyl ammonium polystyrene, is used as a solid phase imprinted double-site extractant of copper (II), is used for selective enrichment and separation of copper (II) ions in various water systems, and has the function and the characteristic of simultaneously extracting counter anions; an effective method is provided for removing copper (II) ions in various water systems and assisting in detection, separation and enrichment of the copper (II) ions in the various water systems; the copper (II) ion surface imprinted polymer with double exchanged anions and cations can be in the form of foam, membrane plate, fibril or particle.
Description
Technical Field
The invention relates to an imprinted polymer, in particular to a copper (II) ion surface imprinted polymer with anion-cation double exchange, which is prepared by taking a salicylaldoxime copper (II) complex modified by unsaturated quaternary ammonium cation as a functional monomer and polyallyl ammonium salt as a cross-linking agent through copolymerization reaction with a skeleton monomer on the surface of polyallyl ammonium polystyrene, is used for selective enrichment and extraction separation of copper (II) ions in various water systems as a solid-phase imprinted double-position extraction agent of copper (II), has the function and characteristic of simultaneously extracting counter anions, and belongs to the field of functional polymer materials.
Background
The existing extraction separation of copper (II) ions in a water system mostly adopts a liquid-liquid extraction agent 5-alkyl salicylaldoxime and a compound thereof, the copper-iron separation coefficient is as high as 450-550, the extraction capacity is large, and the extraction performance is good. The high selectivity of 5-alkyl salicylaldoxime on copper ions is due to the fact that the coordination atoms of the 5-alkyl salicylaldoxime are N and O, when two 5-alkyl salicylaldoxime and Cu (II) generate a chelate, H of phenolic hydroxyl (O-H) of the 5-alkyl salicylaldoxime forms a planar tetragonal structure+Exchange with Cu (II) to produce a neutral extract. And in addition, the hydrogen bond between the oxime hydroxyl (O-H) of the 5-alkyl salicylaldoxime and the phenol oxygen anion further increases the stability of the chelate. Therefore, the salicylaldoxime extractant has high selectivity chelating performance for Cu (II). However, the 5-alkyl salicylaldoxime has the disadvantage that when the concentration of the 5-alkyl salicylaldoxime copper (II) chelate is higher, precipitation is easy to occur; and the problem of a small amount of emulsion can also occur due to the entrainment of free acid during the back extraction of the regenerated organic phase, and the oil-water two-phase chromatographic separation time is long, so that the problems of complicated and variable wet-process copper smelting process control, severe production environment, serious waste pollution and the like are caused.
In addition, the liquid-liquid extraction process is a proton exchange process of copper (II) ions and an extracting agent, so that the acid concentration of the water phase of the extraction system is gradually increased after the extraction is circulated for many times; at the same time, non-extracted anions (e.g. SO) in the aqueous phase4 2-、PO4 3-And NO3 -And Cl-Etc.) also form waste acid solution to be discharged. In order to reduce the environmental pollution caused by the discharge of waste acid liquor, scientists at home and abroad have studied a class of salicylaldoxime or salicylaldehyde Schiff base containing tertiary amino in the molecular structure as a solvent extractant or a solid phase extractant of copper (II) ions, which is called a two-site extractant of the copper (II) ions. Compared with the traditional copper (II) ion solution extractant, the extractant can simultaneously extract copper (II) ions and counter anions associated with the copper (II) ions, so that the extraction can be more fully maintainedMaterial balance in the process. However, the synthesis technology of the copper (II) ion extracting agent containing tertiary amino salicylaldoxime or salicylaldehyde Schiff base is complex, the raw material price is high, and the use performance needs to be improved.
The ion imprinted polymer is a branch of imprinted polymers, has identification, high selectivity and affinity for specific ions as a solid phase extractant, and is used for separation, enrichment and analytical detection of certain trace heavy metal ions in medicines, foods, drinking water and the environment. The functional monomer for preparing the ion imprinted polymer is a polymerizable ligand or a chelating ligand. The polymerizable ligand or chelating ligand can form a stable complex with the transition metal ion. The ionic bond and the dative bond between the polymerizable ligand or the chelating ligand and the transition metal ion have stronger acting force relative to hydrogen bond, van der Waals force, electrostatic action, hydrophobic action and the like, have stable spatial structure and strong chelating directionality, and are favorable for preparing the imprinted polymer with high selectivity and stable imprinting function; the recognition process by coordination has the advantage of rapid and reversible binding; the coordination between the metal ions and the ligand or the chelate ligand has good thermodynamic stability, is easy to reach kinetic balance, and has wide application range; however, most of the used cross-linking agents are ethylene glycol diacrylate or bisacrylamide methane, and the prepared ion imprinted polymer material is easy to generate hydrolysis reaction in an acid-base aqueous solution, so that the ion imprinted polymer material loses due stability and cannot be recycled for a long time. Meanwhile, the ion imprinted polymer material has fewer imprinted sites, deep ion imprinted particle pore channels and large diffusion resistance of template ions close to the recognition sites, and the ion imprinted polymer material has prolonged equilibrium ion exchange time.
Based on the defects of the prior art, the inventor develops a transition metal ion imprinted polymer material containing quaternary ammonium cation and salicylaldehyde Schiff base according to the molecular synthesis design principle, see CN102924656, CN103193928, CN104356298, CN105646827 and CN105126909, wherein the structure of the transition metal ion imprinted polymer contains three functional groups, namely salicylaldoxime, amino and quaternary ammonium cation, as the functional groupsThe copper (II) solid phase imprinting double-position extractant can rapidly extract copper (II) ions and counter anions along with the copper (II) ions, realize material balance in the extraction process and eliminate SO4 2-、PO4 3-And NO3 -And Cl-And the like, environmental pollution; compared with the existing solution extracting agent, the extraction agent has the advantages of convenient use, low loss and little pollution. On the basis, the inventor further innovates and optimizes, and provides a cation and anion double-exchange copper (II) ion surface imprinted polymer taking polystyrene as a substrate material.
Disclosure of Invention
The invention provides a copper (II) ion surface imprinted polymer with anion and cation double exchange, which is prepared by taking a salicylaldoxime copper (II) complex modified by unsaturated quaternary ammonium cations as a functional monomer and allyl ammonium salt as a cross-linking agent and carrying out copolymerization reaction with a skeleton monomer on the surface of a polystyrene material; characterized in that the polystyrene material is a cross-linked or non-cross-linked allylammoniumalted polystyrene material;
wherein the crosslinked or non-crosslinked allylammoniumalted polystyrene material can be prepared by classical nucleophilic substitution reaction using triallylamine, N-methyldiallylamine, N-ethyldiallylamine, N-propyldiallylamine, N-butyldiallylamine or N-benzyldiallylamine, N-dimethylallylamine, N-diallylamine, N-dipropylallylamine, N-dibutylallylamine or N, N-dibenzylallylamine and crosslinked or non-crosslinked chloromethylated polystyrene material or crosslinked or non-crosslinked chloroacetylated polystyrene material, as schematically shown in equation 1 or equation 2:
wherein R in the reaction formula 1 or the reaction formula 23And R4One or more than two of methyl, ethyl, propyl, butyl, benzyl or allyl;
the unsaturated quaternary ammonium cation modified salicylaldoxime copper (II) complex functional monomer is selected from a structure shown in a general formula (IA), a general formula (IB) or a general formula (IC):
r in the general formula (IA), the general formula (IB) or the general formula (IC)1And R2Are respectively selected from C1～C18One of the hydrocarbon radicals, X-Selected from Cl-、Br-、SO4 2-、NO3 -、CH3COO-、p-CH3C6H4SO3 -、BF4 -、PF6 -、SbF6 -、CF3SO3 -、C3F7COO-、C4F9SO3 -、(CF3SO2)3C-Or (CF)3SO2)2N-One of (1);
the allylammonium salt crosslinker is triallylamine, N-methyldiallylamine, N-ethyldiallylamine, N-propyldiallylamine, N-butyldiallylamine, N-benzyldiallylamine, N, N '-diallylpiperazine, N, N, N', N '-tetraallylethylenediamine, N-methyl-N, N', N '-triallylethylenediamine, N-ethyl-N, N', N '-triallylethylenediamine, N-benzyl-N, N', N '-triallylethylenediamine, N, N' -dimethyl-N, N '-diallylethylenediamine, N, N' -diethyl-N, N '-diallylethylenediamine or N, N' -dibenzyl-N, one or more than two of hydrochloride, sulfate, phosphate, acetate, tetrafluoroborate, hexafluorophosphate, hexafluoroantimonate, trifluoromethanesulfonate, perfluorobutanesulfonate or bis-trifluoromethanesulfonimide salt of N' -diallyl ethylenediamine;
the skeleton monomer refers to one of styrene, acrylic acid, acrylate, acrylonitrile and acrylamide.
The unsaturated quaternary ammonium cation modified salicylaldoxime copper (II) complex functional monomer with the structure shown in the general formula (IA), the general formula (IB) or the general formula (IC): allyl ammonium salt crosslinker: framework monomer: the mass ratio of the polystyrene material is 20-200: 0-80: 100.
As is well known to those skilled in the art, if the condensed state of the copper (II) ion surface imprinted polymer subjected to cation and anion double exchange is in a foam, fiber, film or hollow sphere shape, the specific surface area of the copper (II) ion surface imprinted polymer can be significantly increased, and the adsorption capacity of the copper (II) ion surface imprinted polymer can be effectively increased. Therefore, a pore-foaming agent is added in the process of preparing the copper (II) ion surface imprinted polymer. The pore-forming agent is selected from one or more of water, ethanol, methanol, pentaerythritol, ethylene glycol, inositol, polyethylene glycol, 1, 4-dioxane, chlorobenzene, N-dimethylacetamide, N-dimethylformamide, dimethyl sulfoxide or hexamethylphosphoramide, and the dosage of the pore-forming agent is 0-10 times of the total mass of the functional monomer, the cross-linking agent and the skeleton monomer.
The invention has the beneficial effects that ester bonds and amido bonds do not exist in the structure of the copper (II) ion surface imprinted polymer with double exchange of anions and cations, the stability in acid-base solution is high, and the chemical stability and the mechanical stability of the copper (II) ion surface imprinted polymer can be continuously maintained.
And secondly, the quaternary ammonium cation unit in the copper (II) ion surface imprinted polymer structure with cation and anion double exchange has strong hydrophilicity, can obviously improve the water wettability and the charge density of the copper (II) ion surface imprinted polymer, is beneficial to the rapid diffusion of copper (II) in a water system in the copper (II) ion surface imprinted polymer, quickly achieves adsorption balance, and overcomes the defects of strong hydrophobicity and long adsorption balance time in the cavity of the existing ion chelated polymer. Meanwhile, the copper (II) ion surface imprinted polymer subjected to cation and anion double exchange also has an anion exchange function and an adsorption function.
And thirdly, after the copper (II) ion surface imprinted polymer subjected to cation and anion double exchange is eluted and recovered, the copper (II) ion surface imprinted polymer is easily converted into a zwitterion surface imprinted polymer in an alkaline solution, and the zwitterion surface imprinted polymer not only can be used for selectively chelating and extracting copper (II) ions, but also can be used for adsorbing counter anions and keeping the cation and anion material balance in the extraction process.
The specific method for preparing the copper (II) ion surface imprinted polymer with double exchange of anions and cations comprises the following steps: according to the using amount and mass ratio of the unsaturated quaternary ammonium cation modified salicylaldoxime copper (II) complex functional monomer, the allylammonium salt cross-linking agent, the skeleton monomer and the polystyrene material with the structure shown in the general formula (IA), the general formula (IB) or the general formula (IC), in a reactor, firstly adding a pore-forming agent and an initiator, stirring, then sequentially adding the functional monomer containing the quaternary ammonium cation and the salicylaldoxime copper (II) complex, the polyallylammonium salt cross-linking agent and the skeleton monomer, stirring uniformly, then adding the polystyrene material, filling nitrogen for deoxidizing for 30 minutes, after a polymerization reaction system is dispersed uniformly, heating to 55-95 ℃, carrying out polymerization reaction for 6-12 hours, cooling and filtering to obtain a copper (II) chelate polymer; sequentially using deionized water and ethyl acetate to perform Soxhlet extraction to remove the pore-foaming agent and unreacted monomers in the copper (II) chelate polymer; secondly, leaching the copper (II) chelate polymer by using hydrochloric acid, sulfuric acid or phosphoric acid with the molar concentration of 1-3 mol/L, and removing copper (II) ions to prepare the copper (II) ion surface imprinted polymer with double exchange of anions and cations;
wherein the unsaturated quaternary ammonium cation modified salicylaldoxime copper (II) complex functional monomer has a structure shown by a general formula (IA), a general formula (IB) or a general formula (IC):
r in the general formula (IA), the general formula (IB) or the general formula (IC)1And R2Are respectively selected from C1～C18One of the hydrocarbon radicals, X-Selected from Cl-、Br-、SO4 2-、NO3 -、CH3COO-、p-CH3C6H4SO3 -、BF4 -、PF6 -、SbF6 -、CF3SO3 -、 C3F7COO-、C4F9SO3 -、(CF3SO2)3C-Or (CF)3SO2)2N-One kind of (1).
The allylammonium salt crosslinker is selected from triallylamine, N-methyldiallylamine, N-ethyldiallylamine, N-propyldiallylamine, N-butyldiallylamine, N-benzyldiallylamine, N, N '-diallylpiperazine, N, N, N', N '-tetraallylethylenediamine, N-methyl-N, N', N '-triallylethylenediamine, N-ethyl-N, N', N '-triallylethylenediamine, N-benzyl-N, N', N '-triallylethylenediamine, N, N' -dimethyl-N, N '-diallylethylenediamine, N, N' -diethyl-N, N '-diallylethylenediamine or N, N' -dibenzyl-N, one or more than two of hydrochloride, sulfate, phosphate, acetate, tetrafluoroborate, hexafluorophosphate, hexafluoroantimonate, trifluoromethanesulfonate, perfluorobutanesulfonate or bis-trifluoromethanesulfonimide salt of N' -diallyl ethylenediamine;
the skeleton monomer refers to one of styrene, acrylic acid, acrylate, acrylonitrile and acrylamide.
The polystyrene material refers to a cross-linked or non-cross-linked allylammoniumted polystyrene material; the crosslinked or uncrosslinked allylammoniumalted polystyrene material can be prepared by classical nucleophilic substitution reactions starting from triallylamine, N-methyldiallylamine, N-ethyldiallylamine, N-propyldiallylamine, N-butyldiallylamine or N-benzyldiallylamine, N-dimethylallylamine, N-diallylamine, N-dipropylallylamine, N-dibutylallylamine or N, N-dibenzylallylamine and crosslinked or uncrosslinked chloromethylated polystyrene materials or crosslinked or uncrosslinked chloroacetylated polystyrene materials.
The unsaturated quaternary ammonium cation modified salicylaldoxime copper (II) complex functional monomer with the structure shown in the general formula (IA), the general formula (IB) or the general formula (IC): framework monomer: polyallyl ammonium salt crosslinker: the mass ratio of the polystyrene material is 20-200: 0-80: 20-200: 100.
The pore-forming agent is selected from one or more of water, ethanol, methanol, pentaerythritol, ethylene glycol, inositol, polyethylene glycol, 1, 4-dioxane, chlorobenzene, N-dimethylacetamide, N-dimethylformamide, dimethyl sulfoxide or hexamethylphosphoramide, and the dosage of the pore-forming agent is 0-10 times of the total mass of the functional monomer, the skeleton monomer and the crosslinking agent.
The initiator is selected from one or more than two of hydrogen peroxide, ammonium persulfate, potassium persulfate, benzoyl peroxide, lauroyl peroxide, tert-butyl peroxide, methyl ethyl ketone peroxide, azobisisobutyronitrile, azobisisoheptonitrile, dimethyl azobisisobutyrate, azobisisobutylamidine hydrochloride, azobisisobutylimidazoline hydrochloride, azobiscyanovaleric acid or azobisdiisopropylimidazoline, and the dosage of the initiator is 1-7% of the total mass of the functional monomer, the cross-linking agent and the skeleton monomer.
Detailed Description
The present invention provides a copper (II) ion imprinted polymer with double exchange of anions and cations and a preparation method thereof, which are further illustrated by the following examples, aiming to better understand the content of the present invention.
Example 1 preparation of hollow spherical anion and cation double exchanged copper (II) ion surface imprinted polymer (IA-1)
Putting 50 g (chlorine content is 13.4%) of chloromethyl polystyrene macroporous crosslinked resin balls with the average particle size of 1.8 mm and 80 g of chlorobenzene into a dry reaction bottle, swelling for 2 hours at room temperature, controlling the temperature to be 30-60 ℃, adding 20 g of triallylamine, reacting for 4 hours, cooling, filtering out polystyrene resin balls, washing to be neutral, and carrying out vacuum drying to obtain 66.2 g of triallylamine salinized crosslinked polystyrene hollow resin balls. Adding 100 g of N, N-dimethylacetamide and 3.8 g of azobisisobutyronitrile into a reaction bottle, starting stirring, adding 50 g of functional monomer (Ia-1), 20 g of triallylamine hydrochloride, 10 g of N, N-dimethylacrylamide and 50 g of triallylammonium salinized crosslinked polystyrene hollow spherical resin ball under stirring, filling nitrogen to remove oxygen for 30 minutes, adjusting the stirring rate, uniformly dispersing the system, heating to 60-65 ℃, carrying out polymerization reaction for 4 hours, raising the temperature to 90-95 ℃, carrying out polymerization reaction for 3 hours, cooling, and filtering to obtain a copper (II) chelate polymer ball; sequentially carrying out Soxhlet extraction on the copper (II) chelate polymer spheres by using ethanol and ethyl acetate, removing a pore-forming agent and unreacted monomers to the greatest extent, and then leaching the copper (II) chelate polymer spheres by using 1.5mol/L hydrochloric acid to remove copper (II) ions; then, neutralizing and leaching the chelate polymer ball by using 5mol/L ammonia water, and drying to obtain 132.5 g of light yellow copper (II) surface imprinted polymer (IA-1) with double exchanged anions and cations.
Thermogravimetric analysis showed that 132.5 g of a pale yellow, anion-and-cation double exchanged copper (II) surface imprinted polymer (IA-1) contained 15.5 g of water. 132.5 g of pale yellow cation and anion double-exchanged copper (II) surface imprinted polymer (IA-1) was continuously leached at 25 ℃ under constant temperature using a copper sulfate solution with a pH of 4.5, and as a result, it was found that the copper (II) surface imprinted polymer (IA-1) had a saturated adsorption time of copper (II) ions of 1.8 minutes and a saturated adsorption capacity of copper (II) ions of 38.7 mg/g.
EXAMPLE 2 preparation of hollow resin spherical anion and cation double exchanged copper (II) solid phase imprinting two-site extractant (IB-1)
According to the method and the operation steps of the example 1, the functional monomer (Ia-1) of the example 1 is changed into the functional monomer (Ib-1), and the hollow resin ball of the copper (II) surface imprinted polymer (IB-1) with double exchange of anions and cations is prepared. According to the experimental result, at the temperature of 25 ℃, the time for the copper (II) ion saturation adsorption of the copper (II) surface imprinted polymer (IB-1) subjected to cation and anion double exchange is 1.7 minutes, and the copper (II) ion saturation adsorption capacity is 38.8 mg/g.
EXAMPLE 3 preparation of hollow resin spherical anion and cation double exchanged copper (II) surface imprinted polymer (IC-1)
According to the method and the operation steps of example 1, the functional monomer (Ia-1) of example 1 is changed into the functional monomer (Ic-1), and the hollow resin sphere of the copper (II) surface imprinted polymer (IC-1) with double exchange of anions and cations is prepared. The saturated adsorption time of copper (II) ions of the copper (II) surface imprinted polymer (IC-1) subjected to cation and anion double exchange at 25 ℃ is 1.1 min through experiment measurement, and the saturated adsorption capacity of the copper (II) ions is 40.1 mg/g.
EXAMPLE 4 preparation of hollow resin spherical anion and cation double exchanged copper (II) surface imprinted polymer (IC-2)
The functional monomer (Ia-1) of example 1 was changed to the functional monomer (Ic-2) according to the procedure and operation of example 1 to prepare an anion and cation double-exchanged copper (II) surface imprinted polymer (IC-2). The saturated adsorption time of copper (II) ions of the copper (II) surface imprinted polymer (IC-2) subjected to cation and anion double exchange at 25 ℃ is 1.9 minutes, and the saturated adsorption capacity of the copper (II) ions is 40.0 mg/g.
Example 5 preparation of short-fiber anion-cation double exchanged copper (II) surface imprinted polymer (IA-2)
According to the method and the operation steps of the example 1, the chloromethyl polystyrene macroporous cross-linked resin sphere of the example 1 is changed into chloroacetyl cross-linked polystyrene short fiber, and the short fiber-shaped anion-cation double-exchanged copper (II) surface imprinted polymer (IA-2) is prepared. Experiments show that at 25 ℃, the saturated adsorption time of copper (II) ions of the short-fiber cation-anion double-exchange copper (II) surface imprinted polymer (IA-2) is 1.6 minutes, and the adsorption capacity of the copper (II) ions is 38.8 mg/g.
Claims (2)
1. A copper (II) ion surface imprinted polymer with anion and cation double exchange is prepared by taking salicylaldoxime copper (II) complex modified by unsaturated quaternary ammonium cation as a functional monomer and allyl ammonium salt as a cross-linking agent and carrying out copolymerization reaction with a skeleton monomer on the surface of a polystyrene material, and is characterized in that the polystyrene material refers to a crosslinked or non-crosslinked polyallyl ammonium salt polystyrene material; the crosslinked or non-crosslinked polyallylamine salified polystyrene material is prepared by taking triallylamine, N-methyldiallylamine, N-ethyldiallylamine, N-propyldiallylamine, N-butyldiallylamine or N-benzyldiallylamine, N-dimethylallylamine, N-diallylamine, N-dipropylallylamine, N-dibutylallylamine or N, N-dibenzylallylamine and a crosslinked or non-crosslinked chloromethylated polystyrene material or a crosslinked or non-crosslinked chloroacetylated polystyrene material as raw materials through classical nucleophilic substitution reaction;
wherein the unsaturated quaternary ammonium cation modified salicylaldoxime copper (II) complex functional monomer is selected from the structures shown in the general formula (IA), the general formula (IB) or the general formula (IC):
wherein R in the general formula (IA), the general formula (IB) or the general formula (IC)1And R2Are respectively selected from C1～C18One of the hydrocarbon radicals, X-Selected from Cl-、Br-、SO4 2-、NO3 -、CH3COO-、p-CH3C6H4SO3 -、BF4 -、PF6 -、SbF6 -、CF3SO3 -、C3F7COO-、C4F9SO3 -、(CF3SO2)3C-Or (CF)3SO2)2N-One of (1);
the allylammonium salt crosslinker is triallylamine, N-methyldiallylamine, N-ethyldiallylamine, N-propyldiallylamine, N-butyldiallylamine, N-benzyldiallylamine, N, N '-diallylpiperazine, N, N, N', N '-tetraallylethylenediamine, N-methyl-N, N', N '-triallylethylenediamine, N-ethyl-N, N', N '-triallylethylenediamine, N-benzyl-N, N', N '-triallylethylenediamine, N, N' -dimethyl-N, N '-diallylethylenediamine, N, N' -diethyl-N, N '-diallylethylenediamine or N, N' -dibenzyl-N, one or more than two of hydrochloride, sulfate, phosphate, acetate, tetrafluoroborate, hexafluorophosphate, hexafluoroantimonate, trifluoromethanesulfonate, perfluorobutanesulfonate or bis-trifluoromethanesulfonimide salt of N' -diallyl ethylenediamine;
the skeleton monomer refers to one of styrene, acrylic acid, acrylate, acrylonitrile or acrylamide;
the unsaturated quaternary ammonium cation modified salicylaldoxime copper (II) complex functional monomer with the structure shown in the general formula (IA), the general formula (IB) or the general formula (IC): allyl ammonium salt crosslinker: framework monomer: the mass ratio of the polystyrene material is 20-200: 0-80: 100.
2. The preparation method of the copper (II) ion surface imprinted polymer with double exchange of anions and cations is characterized by comprising the following preparation steps: sequentially weighing a pore-foaming agent, an initiator, the unsaturated quaternary ammonium cation modified salicylaldoxime copper (II) complex functional monomer with the structure shown in the general formula (IA), the general formula (IB) or the general formula (IC) in claim 1, an allylammonium salt cross-linking agent, a skeleton monomer and a polystyrene material, putting into a polymerization reactor, stirring, filling nitrogen to remove oxygen for 30 minutes, heating to 55-95 ℃ after a polymerization reaction system is uniformly dispersed, carrying out polymerization reaction for 6-12 hours, cooling, and filtering to obtain a copper (II) chelate polymer; sequentially using deionized water and ethanol for Soxhlet extraction to remove the pore-foaming agent and unreacted monomers in the copper (II) chelate polymer; secondly, leaching the copper (II) chelate polymer by using hydrochloric acid, sulfuric acid or phosphoric acid with the molar concentration of 1-3 mol/L, and removing copper (II) ions to prepare the copper (II) ion surface imprinted polymer with double exchange of anions and cations;
the pore-forming agent is selected from one or more of water, ethanol, methanol, pentaerythritol, ethylene glycol, inositol, polyethylene glycol, 1, 4-dioxane, chlorobenzene, N-dimethylacetamide, N-dimethylformamide, dimethyl sulfoxide or hexamethylphosphoramide, and the dosage of the pore-forming agent is 0-10 times of the total mass of the functional monomer, the skeleton monomer and the cross-linking agent;
the initiator is selected from one or more than two of hydrogen peroxide, ammonium persulfate, potassium persulfate, benzoyl peroxide, lauroyl peroxide, tert-butyl alcohol peroxide, methyl ethyl ketone peroxide, azobisisobutyronitrile, azobisisoheptonitrile, dimethyl azobisisobutyrate, azobisisobutylamidine hydrochloride, azobisisobutylimidazoline hydrochloride, azobiscyanovaleric acid or azobisdiisopropylimidazoline, and the dosage of the initiator is 1-7% of the total mass of the functional monomer, the cross-linking agent and the skeleton monomer;
the unsaturated quaternary ammonium cation modified salicylaldoxime copper (II) complex functional monomer has a structure shown in a general formula (IA), a general formula (IB) or a general formula (IC):
wherein R in the general formula (IA), the general formula (IB) or the general formula (IC)1And R2Are respectively selected from C1～C18One of the hydrocarbon radicals, X-Selected from Cl-、Br-、SO4 2-、NO3 -、CH3COO-、p-CH3C6H4SO3 -、BF4 -、PF6 -、SbF6 -、CF3SO3 -、C3F7COO-、C4F9SO3 -、(CF3SO2)3C-Or (CF)3SO2)2N-One of (1);
the allylammonium salt crosslinker is triallylamine, N-methyldiallylamine, N-ethyldiallylamine, N-propyldiallylamine, N-butyldiallylamine, N-benzyldiallylamine, N, N '-diallylpiperazine, N, N, N', N '-tetraallylethylenediamine, N-methyl-N, N', N '-triallylethylenediamine, N-ethyl-N, N', N '-triallylethylenediamine, N-benzyl-N, N', N '-triallylethylenediamine, N, N' -dimethyl-N, N '-diallylethylenediamine, N, N' -diethyl-N, N '-diallylethylenediamine or N, N' -dibenzyl-N, one or more than two of hydrochloride, sulfate, phosphate, acetate, tetrafluoroborate, hexafluorophosphate, hexafluoroantimonate, trifluoromethanesulfonate, perfluorobutanesulfonate or bis-trifluoromethanesulfonimide salt of N' -diallyl ethylenediamine;
the skeleton monomer refers to one of styrene, acrylic acid, acrylate, acrylonitrile or acrylamide;
the polystyrene material refers to crosslinked or non-crosslinked polyallyl ammoniumized polystyrene material, which is prepared by taking triallylamine, N-methyldiallylamine, N-ethyldiallylamine, N-propyldiallylamine, N-butyldiallylamine or N-benzyldiallylamine, N-dimethylallylamine, N-diallylamine, N-dipropylallylamine, N-dibutylallylamine or N, N-dibenzylallylamine and crosslinked or non-crosslinked chloromethylated polystyrene material or crosslinked or non-crosslinked chloroacetylated polystyrene material as raw materials through classical nucleophilic substitution reaction;
the unsaturated quaternary ammonium cation modified salicylaldoxime copper (II) complex functional monomer with the structure shown in the general formula (IA), the general formula (IB) or the general formula (IC): allyl ammonium salt crosslinker: framework monomer: the mass ratio of the polystyrene material is 20-200: 0-80: 100.
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