Double-monomer tungsten ion imprinted polymer as well as preparation method and application thereof

Abstract

The invention relates to the technical field of tungsten ion adsorbents, in particular to a double-monomer tungsten ion imprinted polymer and a preparation method and application thereof. The method comprises the following steps: by taking 4-vinylpyridine and chitosan as organic functional monomers and tungstate radicals as template ions, carrying out polymerization reaction and template ion elution to obtain the double-monomer tungsten ion imprinted polymer. The preparation method of the double-monomer tungsten ion imprinted polymer is simple, the adsorption capacity is high, the double-monomer tungsten ion imprinted polymer is prepared by adopting relatively common medicines and methods, tungsten and molybdenum metal ions can be selectively separated, and the double-monomer tungsten ion imprinted polymer is an adsorption material with application prospects.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of tungsten ion adsorbent, in particular to a bimonomer tungsten ion imprinted polymer and a preparation method and application thereof. BACKGROUND

[0002] Tungsten (W) and molybdenum (Mo) are both rare high-melting-point metals, which are indispensable in industrial development. Due to their excellent characteristics in hardness, electrical conductivity, fire resistance, thermal expansion, and corrosion resistance, they are widely used in important fields such as hard alloy, electronics, medical treatment, chemical industry, national defense industry, aerospace, etc., and are essential basic raw materials for guaranteeing economic construction, maintaining national security, and promoting the development of high-tech. With the development of economy and society, the demand for tungsten and molybdenum is increasing. Therefore, the recycling of tungsten and molybdenum has become a research hotspot.

[0003] In the current tungsten recovery process, tungsten-molybdenum separation is a research difficulty. Tungsten and molybdenum belong to the same group VI B in the periodic table of elements, and due to the influence of lanthanide contraction, their physicochemical properties are similar, making them difficult to separate. The traditional processes for separating tungsten and molybdenum are pyrometallurgy and hydrometallurgy, among which the effective hydrometallurgical methods for separating tungsten and molybdenum include organic solvent extraction, precipitation, and ion exchange, etc. These methods have problems such as flammability and explosiveness, generation of harmful gases, complex process, and secondary pollution, etc.

[0004] Ion imprinting technology is attractive due to its specific selectivity for template ions. Ion imprinted polymers developed by ion imprinting technology have made great progress in the field of heavy metal adsorption and separation. In view of the low adsorption capacity and selectivity coefficient of the current ion imprinted polymers for separating W / Mo, the present application provides a method for preparing a bimonomer tungsten ion imprinted polymer. SUMMARY

[0005] In order to solve the above technical problems, the present application provides a bimonomer tungsten ion imprinted polymer and a preparation method and application thereof. The bimonomer tungsten ion imprinted polymer of the present application has a simple preparation method, high adsorption capacity, and is prepared by using commonly used drugs and methods, which can selectively separate tungsten and molybdenum metal ions, and is an adsorbent material with application prospect.

[0006] In a first aspect, the present application provides a preparation method of a bimonomer tungsten ion imprinted polymer, comprising: using 4-vinylpyridine and chitosan as organic functional monomers, tungstate as template ions, performing a polymerization reaction and template ion elution to obtain a bimonomer tungsten ion imprinted polymer. The present application solves the problem of relatively low adsorption capacity and selective adsorption of a monomer ion imprinted polymer by using an optimized scheme of a specific bimonomer ion imprinted polymer. The bimonomer ion imprinted polymer of 4-vinylpyridine and chitosan not only increases the types of functional monomers and improves the number of functional monomer binding sites, but also significantly improves the specific surface area, porosity and adsorption performance of the ion imprinted polymer through the synergistic effect of the two monomers.

[0007] Preferably, the molar ratio of 4-vinylpyridine to chitosan is 1-3:1-3. By controlling the ratio of 4-vinylpyridine to chitosan, a higher tungsten adsorption capacity and tungsten-molybdenum separation coefficient can be achieved, especially when the molar ratio of 4-vinylpyridine to chitosan is 1:1.

[0008] Preferably, the molar ratio of the template ions to the organic functional monomers is 1-5:8-24.

[0009] Preferably, the metal salt of tungstate is sodium tungstate dihydrate.

[0010] Preferably, the preparation method further comprises a crosslinking agent; the crosslinking agent is ethylene glycol dimethacrylate; preferably, the molar ratio of the organic functional monomer to ethylene glycol dimethacrylate is 4-12:15-35.

[0011] Further preferably, the molar ratio of sodium tungstate dihydrate, 4-vinylpyridine and chitosan is 1-5:4-12:4-12; and / or, the molar ratio of 4-vinylpyridine, chitosan and ethylene glycol dimethacrylate is 4-12:4-12:30-70.

[0012] Preferably, the preparation method further comprises an initiator, and the initiator is purified azobisisobutyronitrile; preferably, the ratio of the crosslinking agent to the purified azobisisobutyronitrile is 6-16 mol:5-14 g.

[0013] Further preferably, the preparation method comprises: mixing sodium tungstate dihydrate and organic functional monomers to perform a chelation reaction to obtain a metal coordination compound; mixing the metal coordination compound, a crosslinking agent and an initiator to perform a polymerization reaction to obtain a bimonomer tungsten ion imprinted polymer precursor; and performing template ion elution on the bimonomer tungsten ion imprinted polymer precursor; the polymerization reaction is performed in an argon atmosphere, and preferably in a methanol aqueous solution.

[0014] Further preferably, the preparation method comprises the following steps: 1) Sodium tungstate dihydrate, 4-vinylpyridine and chitosan were mixed and subjected to isothermal shaking to obtain a metal coordination compound.

[0015] 2) Ethylene glycol dimethacrylate, initiator, methanol aqueous solution and the metal coordination compound are mixed, and dried under constant temperature shaking in an inert atmosphere to obtain a dual-monomer tungsten ion imprinted polymer precursor.

[0016] 3) The dual-monomer tungsten ion-imprinted polymer precursor was mixed with a methanol solution of acetic acid and extracted, then washed with an aqueous methanol solution and dried.

[0017] Preferably, in step 2), the inert gas is argon.

[0018] Preferably, in step 1), the isothermal oscillation temperature is 60~70 ℃ and the time is 2.5~3.5 h.

[0019] Preferably, in step 2), the constant temperature oscillation temperature is 60~70 ℃ and the time is 20~30 h, and the drying temperature is 60±10℃ and the time is 12~24 h.

[0020] Preferably, in step 3), the extraction temperature is 110~130 ℃, the extraction time is 6~10 h, and the cycle is repeated 2~3 times; the drying temperature is 66~65 ℃.

[0021] Preferably, in the methanol-water solution, the volume ratio of methanol to water is 1:0.5-1.5, more preferably 1:1.

[0022] Preferably, in the acetic acid methanol solution, the volume ratio of acetic acid to methanol is 1:5-10, more preferably 1:9.

[0023] Preferably, the degree of deacetylation of the chitosan is 70% to 99%. In this invention, the percentage of deacetylation of the chitosan used is not limited, and chitosan with high deacetylation (91.5%, etc.) or low deacetylation (70%, etc.) can be used.

[0024] Secondly, the present invention provides a dual-monomer tungsten ion-imprinted polymer, which is prepared by the above-described preparation method.

[0025] Thirdly, the present invention provides the application of the dual-monomer tungsten ion imprinted polymer prepared by the preparation method described above, or the application of the dual-monomer tungsten ion imprinted polymer described above in the selective separation of tungsten and molybdenum metal ions.

[0026] In some embodiments of the present invention, the preparation method of the dual-monomer tungsten ion imprinted polymer involves using a methanol aqueous solution with the metal template ion tungstate WO4. 2-The interaction between the N-pyridine-containing group of 4-vinylpyridine and the active group of chitosan forms a coordination bond, resulting in a stable complex. The initiator azobisisobutyronitrile generates free radicals at 70 °C, initiating the polymerization of the obtained complex and the crosslinking agent methyl glycol diacrylate to form a bimonomer tungsten ion-imprinted polymer. The bimonomer tungsten ion-imprinted polymer is then eluted in a methanol solution of acetic acid to remove the template ion WO4. 2- This process creates ion-imprinted cavities with specific spatial dimensions and binding sites in the tungsten ion-imprinted polymer. The eluted dual-monomer tungsten ion-imprinted polymer is then placed as an adsorbent in a tungsten-molybdenum ion mixed solution, where the cavities containing binding sites and spatial dimensions can selectively adsorb tungsten ions.

[0027] The preparation method of the dual-monomer tungsten ion-imprinted polymer described in some embodiments of the present invention includes a molar ratio of n(template ion):n(4-vinylpyridine):n(chitosan):n(crosslinking agent) = (1~5):(4~12):(4~12):(30~70), with argon protection during polymerization, and polymerization reaction in methanol aqueous solution; the preferred preparation method includes: 1) placing (1~5) mmol of sodium tungstate dihydrate (Na2WO4∙2H2O), (4~12) mmol of 4-vinylpyridine (4-VP) and (4~12) mmol of chitosan (CTS) in a reaction vessel and dissolving them in methanol aqueous solution (V 甲醇 V 水 =1:1), seal the container. Place the container in a constant temperature shaking water bath, set the temperature to 60~70 ℃, and shake for 3h; 2) Add (30~70) mmol of ethylene glycol dimethacrylate (EDGMA), 0.25 mg of purified azobis(2-methylpropionitrile) (AIBN), and part of methanol aqueous solution to (1), and purify the solution with argon (Ar) for about 15 min to remove oxygen (O2) from the solution, and seal the container. Place the container in a constant temperature shaking water bath at 60-70 ℃ and shake for 24 h to obtain a white polymer; 3) Place the polymer in a glass petri dish and put it in an oven at 60 ℃ for 12-24 h to obtain a dried bimonomer tungsten ion-imprinted polymer; 4) Place the dried bimonomer tungsten ion-imprinted polymer from 3) in a Soxhlet extractor and use a methanol solution of acetic acid as the extraction solvent (V 乙酸 V 甲醇=1:9). The extraction temperature was set at 120 ℃ and the extraction time was 8 h. The cycle was repeated 3 times to obtain the eluted dual-monomer tungsten ion imprinted polymer; 5) The dual-monomer tungsten ion imprinted polymer was obtained by washing (4) with methanol aqueous solution to remove excess acetic acid. Then it was placed in an oven at 60 ℃ to dry thoroughly and the product was sealed in a glass desiccator for later use. The dual-monomer tungsten ion imprinted polymer was placed in a tungsten-molybdenum ion mixed solution as an adsorbent and shaken to adsorb by dynamic method.

[0028] This invention uses tungstate ions (WO4) 2- Using 4-vinylpyridine and chitosan as templates, ethylene glycol dimethacrylate as a crosslinking agent, azobisisobutyronitrile as an initiator, and methanol-water solution as a solvent (porogen), tungsten ion-imprinted polymers were prepared using the mechanism and technology of ion-imprinted polymers. Chitosan, as an abundant biopolymer adsorbent, is biodegradable, environmentally friendly, and widely available, making it an ideal adsorbent for metal ions and attracting increasing attention in the field of separation and enrichment. Because chitosan exhibits good adsorption selectivity for specific metal ions, it shows promising application prospects for solving and treating various wastewaters containing heavy metal ions. The chitosan skeleton contains abundant active groups such as hydroxyl (-OH) and amino (-NH2), which endows chitosan with excellent biological functions, metal ion adsorption performance, and chemical modifiability. Compared with chitosan, ion-imprinted polymers have a relatively smaller specific surface area and lower porosity, resulting in lower adsorption efficiency. Chitosan has a relatively large specific surface area and relatively high porosity. By using chitosan as a second functional monomer and co-preparing it with 4-vinylpyridine, a dual-monomer tungsten ion-imprinted polymer can be prepared, thereby improving the adsorption capacity and selective adsorption of the ion-imprinted polymer.

[0029] The preparation process of the tungsten ion-imprinted polymer of this invention is simple, the reaction conditions are mild and relatively easy to control, and the production cost is low. The tungsten ion-imprinted polymer of this invention exhibits good physicochemical stability and simple adsorption operation. The specifically selective adsorbent obtained by this invention is a dual-monomer tungsten ion-imprinted polymer, with WO4 as the primary adsorbent. 2- Using ions as imprinted templates, organic functional monomers and crosslinking agents are added, dissolved in methanol-water solution, and bulk polymerization is carried out under the action of an initiator to prepare tungsten ion-imprinted polymers. The ion-imprinted polymers prepared by the above method contain specific adsorption sites and cavities of specific spatial dimensions, and are effective against WO4. 2- Possessing specific recognition capabilities and selective adsorption, the dual-monomer tungsten ion-imprinted polymer combines the advantages of chitosan and monomonomer ion-imprinted polymers. The tungsten ion-imprinted polymer of this invention, as an adsorbent, exhibits strong selective adsorption and high efficiency, achieving an adsorption capacity of Qe = 227 mg / g for W(VI), and a selectivity of up to β = 35.6 in a tungsten-molybdenum mixed solution at 75 °C. Attached Figure Description

[0030] To more clearly illustrate the technical solutions in this invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are some embodiments of this invention. For those skilled in the art, other drawings can be obtained from these drawings without creative effort.

[0031] Figure 1 The images show the XRD patterns of the dual-monomer tungsten ion-imprinted polymer obtained in the embodiments of the present invention before and after elution. Detailed Implementation

[0032] To make the objectives, technical solutions, and advantages of this invention clearer, the technical solutions of this invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of this invention, not all embodiments. Based on the embodiments of this invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of this invention.

[0033] The endpoints and any values ​​of the ranges disclosed in this invention are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed in this invention.

[0034] Unless otherwise specified, the techniques or conditions described in the embodiments of this invention shall be performed in accordance with the techniques or conditions described in the literature in this field, or in accordance with the product instructions. Devices, instruments, reagents, etc., without specified manufacturers, are all conventional products that can be purchased through legitimate channels. All experimental reagents and raw materials involved are commercially available products, and all reagents are analytical grade products.

[0035] The relevant calculation formulas involved in the embodiments are as follows: The formula for calculating the adsorption capacity Qe is: In the formula, C0 is the initial concentration of W or Mo in the solution, C e denoted as the concentration after adsorption equilibrium, m is the mass of the adsorbent, and V is the volume of the solution.

[0036] The separation efficiency of tungsten and molybdenum can be represented by the separation coefficient β, which is calculated using the following formula: In the formula, and Let Mo and W represent the distribution coefficients, respectively. and The calculation formula is: In the examples, the degree of deacetylation of the chitosan used was 91.5%.

[0037] Example 1 This embodiment provides a dual-monomer tungsten ion-imprinted polymer, the preparation method of which is as follows: (1) Place 3 mmol of sodium tungstate dihydrate, 12 mmol of 4-vinylpyridine and 12 mmol of chitosan in a reaction vessel and dissolve them in an aqueous methanol solution (V). 甲醇 V 水 =1:1), seal the container. Place the container in a constant temperature shaking water bath, set the temperature to 70 ℃, and shake for 3 h.

[0038] (2) Add 30 mmol of ethylene glycol dimethacrylate, 25 mg of purified azobisisobutyronitrile, and a portion of methanol aqueous solution to (1). Purge the solution with argon gas for about 15 min to remove oxygen from the solution, and seal the container. Place the container in a constant temperature shaking water bath, set the temperature to 70 °C, and shake for 24 h to obtain a white polymer.

[0039] (3) Place the polymer in a glass petri dish, put it in an oven, set the temperature to 60 °C, and dry for 12-24 h to obtain a dry dual-monomer tungsten ion imprinted polymer.

[0040] (4) Place the dried tungsten ion-imprinted polymer from (3) into a Soxhlet extractor, and use a methanol solution of acetic acid as the extraction solvent (V). 乙酸 V 甲醇 =1:9). The extraction temperature was set at 120 ℃, the extraction time was 8 h, and the cycle was repeated 3 times to obtain the eluted dual-monomer tungsten ion imprinted polymer.

[0041] (5) Use methanol aqueous solution (V) 甲醇 V 水 =1:1) Washing 4) yields a dual-monomer tungsten ion imprinted polymer. Excess acetic acid is removed, and then the polymer is thoroughly dried in an oven at 60 °C to obtain the target product.

[0042] The XRD patterns of the dual-monomer tungsten ion-imprinted polymer obtained in this embodiment before and after elution are shown below. Figure 1 As shown in the figure, the peaks of the tungsten ion-imprinted polymer before and after elution are both peaks resembling steamed buns, proving that it is an organic compound; the tungsten ion-imprinted polymer has obvious Na2WO4 characteristic peaks before elution, but not after elution, proving that it was completely eluted.

[0043] A W(VI) / Mo(VI) solution with a concentration of 1 mmol / L was prepared using Na₂WO₄∙2H₂O, Na₂MoO₄∙2H₂O, and deionized water. 25 mg of the tungsten ion-imprinted polymer obtained in this example was weighed and added to 50 mL of the above solution. The mixture was shaken at 25 °C for 5 h, and a selective adsorption experiment was performed, yielding Qe(W) = 320 mg / g, Qe(Mo) = 38 mg / g, and β(W / Mo) = 9.5.

[0044] Example 2 This embodiment provides a dual-monomer tungsten ion-imprinted polymer, the preparation method of which is as follows: (1) Place 3 mmol of sodium tungstate dihydrate, 8 mmol of 4-vinylpyridine, and 16 mmol of chitosan in a reaction vessel and dissolve them in an aqueous methanol solution (V). 甲醇 V 水 =1:1), sealed container. Place the container in a constant temperature shaking water bath, set the temperature to 70℃, and shake for 3 hours.

[0045] (2) Add 30 mmol of ethylene glycol dimethacrylate, 25 mg of purified azobisisobutyronitrile and some methanol aqueous solution to step (1), purify the solution with argon gas for about 15 min, remove the oxygen in the solution, and seal the container.

[0046] (3) Place the container in a constant temperature shaking water bath, set the temperature to 70 ℃, and shake for 24 h to obtain a white polymer. Place the polymer in a glass petri dish, put it in an oven, set the temperature to 60 ℃, and dry for 24 h to obtain a dried polymer.

[0047] (4) Place the dried tungsten ion-imprinted polymer obtained in step (3) into a Soxhlet extractor, and the extraction solution is a methanol solution of acetic acid (V). 乙酸 V 甲醇 =1:9), the extraction temperature was set to 120 ℃, the extraction time was 8 h, and the cycle was repeated 3 times to obtain the eluted tungsten ion imprinted polymer.

[0048] (5) Use methanol aqueous solution (V) 甲醇 V 水 =1:1) In the cleaning step (4), the tungsten ion imprinted polymer is obtained, excess acetic acid is removed, and then it is dried in an oven at 60 °C to obtain the target product.

[0049] A W(VI) / Mo(VI) solution with a concentration of 1 mmol / L was prepared using Na₂WO₄∙2H₂O, Na₂MoO₄∙2H₂O, and deionized water. 10 mg of the tungsten ion-imprinted polymer obtained in this example was weighed and added to 20 mL of the above solution. The mixture was shaken at 25 °C for 5 h, and a selective adsorption experiment was conducted. The results showed an adsorption capacity of Qe(W) = 333 mg / g, Qe(Mo) = 56 mg / g, and a separation coefficient β(W / Mo) = 6.5.

[0050] Example 3 This embodiment provides a dual-monomer tungsten ion-imprinted polymer, the preparation method of which is as follows: (1) Place 3 mmol of sodium tungstate dihydrate, 16 mmol of 4-vinylpyridine, and 8 mmol of chitosan in a reaction vessel and dissolve them in an aqueous methanol solution (V). 甲醇 V 水 =1:1), sealed container. Place the container in a constant temperature shaking water bath, set the temperature to 70℃, and shake for 3 hours.

[0051] (2) Add 30 mmol of ethylene glycol dimethacrylate, 25 mg of purified azobisisobutyronitrile and some methanol aqueous solution to step (1), purify the solution with argon gas for about 15 min, remove the oxygen in the solution, and seal the container.

[0052] (3) Place the container in a constant temperature shaking water bath, set the temperature to 70 ℃, and shake for 24 h to obtain a white polymer. Place the polymer in a glass petri dish, put it in an oven, set the temperature to 60 ℃, and dry for 24 h to obtain a dried polymer.

[0053] (4) Place the dried tungsten ion-imprinted polymer obtained in step (3) into a Soxhlet extractor, and the extraction solution is a methanol solution of acetic acid (V). 乙酸 V 甲醇 =1:9), the extraction temperature was set to 120 ℃, the extraction time was 8 h, and the cycle was repeated 3 times to obtain the eluted tungsten ion imprinted polymer.

[0054] (5) Use methanol aqueous solution (V) 甲醇 V 水 =1:1) In the cleaning step (4), the tungsten ion imprinted polymer is obtained, excess acetic acid is removed, and then it is dried in an oven at 60 °C to obtain the target product.

[0055] A W(VI) / Mo(VI) solution with a concentration of 1 mmol / L was prepared using Na₂WO₄∙2H₂O, Na₂MoO₄∙2H₂O, and deionized water. 10 mg of the tungsten ion-imprinted polymer obtained in this example was weighed and added to 20 mL of the above solution. The mixture was shaken at 25 °C for 5 h, and a selective adsorption experiment was conducted. The results showed an adsorption capacity of Qe(W) = 180 mg / g, Qe(Mo) = 11 mg / g, and a separation coefficient β(W / Mo) = 11.4.

[0056] Example 4 This embodiment provides a dual-monomer tungsten ion-imprinted polymer, the preparation method of which is as follows: (1) Place 3 mmol of sodium tungstate dihydrate, 6 mmol of 4-vinylpyridine, and 18 mmol of chitosan in a reaction vessel and dissolve them in an aqueous methanol solution (V). 甲醇 V 水 =1:1), sealed container. Place the container in a constant temperature shaking water bath, set the temperature to 70℃, and shake for 3 hours.

[0057] (2) Add 30 mmol of ethylene glycol dimethacrylate, 25 mg of purified azobisisobutyronitrile and some methanol aqueous solution to step (1), purify the solution with argon gas for about 15 min, remove the oxygen in the solution, and seal the container.

[0058] (3) Place the container in a constant temperature shaking water bath, set the temperature to 70 ℃, and shake for 24 h to obtain a white polymer. Place the polymer in a glass petri dish, put it in an oven, set the temperature to 60 ℃, and dry for 24 h to obtain a dried polymer.

[0059] (4) Place the dried tungsten ion-imprinted polymer obtained in step (3) into a Soxhlet extractor, and the extraction solution is a methanol solution of acetic acid (V). 乙酸 V 甲醇 =1:9), the extraction temperature was set to 120 ℃, the extraction time was 8 h, and the cycle was repeated 3 times to obtain the eluted tungsten ion imprinted polymer.

[0060] (5) Use methanol aqueous solution (V) 甲醇 V 水 =1:1) In the cleaning step (4), the tungsten ion imprinted polymer is obtained, excess acetic acid is removed, and then it is dried in an oven at 60 °C to obtain the target product.

[0061] A W(VI) / Mo(VI) solution with a concentration of 1 mmol / L was prepared using Na₂WO₄∙2H₂O, Na₂MoO₄∙2H₂O, and deionized water. 10 mg of the tungsten ion-imprinted polymer obtained in this example was weighed and added to 20 mL of the above solution. The mixture was shaken at 25 °C for 5 h, and a selective adsorption experiment was conducted. The adsorption capacities were Qe(W) = 338 mg / g, Qe(Mo) = 53 mg / g, and the separation coefficient β(W / Mo) = 7.4.

[0062] Example 5 This embodiment provides a dual-monomer tungsten ion-imprinted polymer, the preparation method of which is as follows: (1) Place 3 mmol of sodium tungstate dihydrate, 18 mmol of 4-vinylpyridine, and 6 mmol of chitosan in a reaction vessel and dissolve them in an aqueous methanol solution (V). 甲醇 V 水 =1:1), sealed container. Place the container in a constant temperature shaking water bath, set the temperature to 70℃, and shake for 3 hours.

[0063] (2) Add 30 mmol of ethylene glycol dimethacrylate, 25 mg of purified azobisisobutyronitrile and some methanol aqueous solution to step (1), purify the solution with argon gas for about 15 min, remove the oxygen in the solution, and seal the container.

[0064] (3) Place the container in a constant temperature shaking water bath, set the temperature to 70 ℃, and shake for 24 h to obtain a white polymer. Place the polymer in a glass petri dish, put it in an oven, set the temperature to 60 ℃, and dry for 24 h to obtain a dried polymer.

[0065] (4) Place the dried tungsten ion-imprinted polymer obtained in step (3) into a Soxhlet extractor, and the extraction solution is a methanol solution of acetic acid (V). 乙酸 V 甲醇 =1:9), the extraction temperature was set to 120 ℃, the extraction time was 8 h, and the cycle was repeated 3 times to obtain the eluted tungsten ion imprinted polymer.

[0066] (5) Use methanol aqueous solution (V) 甲醇 V 水 =1:1) In the cleaning step (4), the tungsten ion imprinted polymer is obtained, excess acetic acid is removed, and then it is dried in an oven at 60 °C to obtain the target product.

[0067] A W(VI) / Mo(VI) solution with a concentration of 1 mmol / L was prepared using Na₂WO₄∙2H₂O, Na₂MoO₄∙2H₂O, and deionized water. 10 mg of the tungsten ion-imprinted polymer obtained in this example was weighed and added to 20 mL of the above solution. The mixture was shaken at 25 °C for 5 h, and a selective adsorption experiment was conducted. The results showed an adsorption capacity of Qe(W) = 268 mg / g, Qe(Mo) = 61 mg / g, and a separation coefficient β(W / Mo) = 3.4.

[0068] Example 6 This embodiment provides a dual-monomer tungsten ion-imprinted polymer, the preparation method of which is as follows: (1) Place 3 mmol of sodium tungstate dihydrate, 12 mmol of 4-vinylpyridine, and 0 mmol of chitosan in a reaction vessel and dissolve them in an aqueous methanol solution (V methanol:V water = 1:1). Seal the vessel. Place the vessel in a constant temperature shaking water bath at 70°C and shake for 3 h.

[0069] (2) Add 30 mmol of ethylene glycol dimethacrylate, 25 mg of purified azobisisobutyronitrile and some methanol aqueous solution to step (1), purify the solution with argon gas for about 15 min, remove the oxygen in the solution, and seal the container.

[0070] (3) Place the container in a constant temperature shaking water bath, set the temperature to 70 ℃, and shake for 24 h to obtain a white polymer. Place the polymer in a glass petri dish, put it in an oven, set the temperature to 60 ℃, and dry for 24 h to obtain a dried polymer.

[0071] (4) Place the dried tungsten ion imprinted polymer obtained in step (3) into a Soxhlet extractor. The extraction solution is a methanol solution of acetic acid (Vacetic acid:V methanol = 1:9). Set the extraction temperature to 120 °C and the extraction time to 8 h. Repeat the cycle 3 times to obtain the eluted tungsten ion imprinted polymer.

[0072] (5) The tungsten ion imprinted polymer in step (4) was washed with methanol aqueous solution (V methanol:V water = 1:1) to remove excess acetic acid, and then dried in an oven at 60 °C to obtain the target product.

[0073] A W(VI) / Mo(VI) solution with a concentration of 100 mg / L was prepared using Na₂WO₄∙2H₂O, Na₂MoO₄∙2H₂O, and deionized water. 10 mg of the tungsten ion-imprinted polymer obtained in this example was weighed and added to 20 mL of the above solution. The mixture was shaken at 75 °C for 5 h to conduct a selective adsorption experiment. The results showed adsorption capacities of Qe(W) = 63.8 mg / g and Qe(Mo) = 1.68 mg / g, indicating relatively low adsorption capacities.

[0074] Example 7 This embodiment provides a dual-monomer tungsten ion-imprinted polymer, the preparation method of which is as follows: (1) Place 3 mmol of sodium tungstate dihydrate, 12 mmol of 4-vinylpyridine, and 0 mmol of chitosan in a reaction vessel and dissolve them in an aqueous methanol solution (V methanol:V water = 1:1). Seal the vessel. Place the vessel in a constant temperature shaking water bath at 70°C and shake for 3 h.

[0075] (2) Add 30 mmol of ethylene glycol dimethacrylate, 25 mg of purified azobisisobutyronitrile and some methanol aqueous solution to step (1), purify the solution with argon gas for about 15 min, remove the oxygen in the solution, and seal the container.

[0076] (3) Place the container in a constant temperature shaking water bath, set the temperature to 70 ℃, and shake for 24 h to obtain a white polymer. Place the polymer in a glass petri dish, put it in an oven, set the temperature to 60 ℃, and dry for 24 h to obtain a dried polymer.

[0077] (4) Place the dried tungsten ion imprinted polymer obtained in step (3) into a Soxhlet extractor. The extraction solution is a methanol solution of acetic acid (Vacetic acid:V methanol = 1:9). Set the extraction temperature to 120 °C and the extraction time to 8 h. Repeat the cycle 3 times to obtain the eluted tungsten ion imprinted polymer.

[0078] (5) The tungsten ion imprinted polymer in step (4) was washed with methanol aqueous solution (V methanol:V water = 1:1) to remove excess acetic acid, and then dried in an oven at 60 °C to obtain the target product.

[0079] A W(VI) / Mo(VI) solution with a concentration of 100 mg / L was prepared using Na₂WO₄∙2H₂O, Na₂MoO₄∙2H₂O, and deionized water. 10 mg of the tungsten ion-imprinted polymer obtained in this example was weighed and added to 20 mL of the above solution. The mixture was shaken at 25 °C for 5 h, and a selective adsorption experiment was conducted. The results showed an adsorption capacity of Qe(W) = 94.68 mg / g, Qe(Mo) = 33.14 mg / g, and a separation coefficient β(W / Mo) = 4.8.

[0080] Example 8 This embodiment provides a dual-monomer tungsten ion-imprinted polymer, the preparation method of which is as follows: (1) Place 3 mmol of sodium tungstate dihydrate, 12 mmol of 4-vinylpyridine, and 12 mmol of chitosan in a reaction vessel and dissolve them in an aqueous methanol solution (V). 甲醇 V水 =1:1), sealed container. Place the container in a constant temperature shaking water bath, set the temperature to 70℃, and shake for 3 hours.

[0081] (2) Add 30 mmol of ethylene glycol dimethacrylate, 25 mg of purified azobisisobutyronitrile and some methanol aqueous solution to step (1), purify the solution with argon gas for about 15 min, remove the oxygen in the solution, and seal the container.

[0082] (3) Place the container in a constant temperature shaking water bath, set the temperature to 70 ℃, and shake for 24 h to obtain a white polymer. Place the polymer in a glass petri dish, put it in an oven, set the temperature to 60 ℃, and dry for 24 h to obtain a dried polymer.

[0083] (4) Place the dried tungsten ion-imprinted polymer obtained in step (3) into a Soxhlet extractor, and the extraction solution is a methanol solution of acetic acid (V). 乙酸 V 甲醇 =1:9), the extraction temperature was set to 120 ℃, the extraction time was 8 h, and the cycle was repeated 3 times to obtain the eluted tungsten ion imprinted polymer.

[0084] (5) Use methanol aqueous solution (V) 甲醇 V 水 =1:1) In the cleaning step (4), the tungsten ion imprinted polymer is obtained, excess acetic acid is removed, and then it is dried in an oven at 60 °C to obtain the target product.

[0085] A W(VI) / Mo(VI) solution with a concentration of 1 mmol / L was prepared using Na₂WO₄∙2H₂O, Na₂MoO₄∙2H₂O, and deionized water. 10 mg of the tungsten ion-imprinted polymer obtained in this example was weighed and added to 20 mL of the above solution. The mixture was shaken at 75 °C for 5 h, and a selective adsorption experiment was conducted. The results showed an adsorption capacity of Qe(W) = 227 mg / g, Qe(Mo) = 7.6 mg / g, and a separation coefficient β(W / Mo) = 35.6.

[0086] Example 9 This embodiment provides a dual-monomer tungsten ion-imprinted polymer, the preparation method of which is as follows: (1) Place 3 mmol of sodium tungstate dihydrate, 12 mmol of 4-vinylpyridine, and 12 mmol of chitosan in a reaction vessel and dissolve them in an aqueous methanol solution (V). 甲醇 V 水 =1:1), sealed container. Place the container in a constant temperature shaking water bath, set the temperature to 70℃, and shake for 3 hours.

[0087] (2) Add 30 mmol of ethylene glycol dimethacrylate, 25 mg of purified azobisisobutyronitrile and some methanol aqueous solution to step (1), purify the solution with argon gas for about 15 min, remove the oxygen in the solution, and seal the container.

[0088] (3) Place the container in a constant temperature shaking water bath, set the temperature to 70 ℃, and shake for 24 h to obtain a white polymer. Place the polymer in a glass petri dish, put it in an oven, set the temperature to 60 ℃, and dry for 24 h to obtain a dried polymer.

[0089] (4) Place the dried tungsten ion-imprinted polymer obtained in step (3) into a Soxhlet extractor, and the extraction solution is a methanol solution of acetic acid (V). 乙酸 V 甲醇 =1:9), the extraction temperature was set to 120 ℃, the extraction time was 8 h, and the cycle was repeated 3 times to obtain the eluted tungsten ion imprinted polymer.

[0090] (5) Use methanol aqueous solution (V) 甲醇 V 水 =1:1) In the cleaning step (4), the tungsten ion imprinted polymer is obtained, excess acetic acid is removed, and then it is dried in an oven at 60 °C to obtain the target product.

[0091] A W(VI) / Mo(VI) solution with a concentration of 1 mmol / L was prepared using Na₂WO₄∙2H₂O, Na₂MoO₄∙2H₂O, and deionized water. 10 mg of the tungsten ion-imprinted polymer obtained in this example was weighed and added to 20 mL of the above solution. The mixture was shaken at 65 °C for 5 h to perform selective adsorption experiments, yielding adsorption capacities Qe(W) = 242.1 mg / g, Qe(Mo) = 16.4 mg / g, and a separation coefficient β(W / Mo) = 18.2.

[0092] Example 10 This embodiment provides a dual-monomer tungsten ion-imprinted polymer, the preparation method of which is as follows: (1) Place 3 mmol of sodium tungstate dihydrate, 12 mmol of 4-vinylpyridine, and 12 mmol of chitosan in a reaction vessel and dissolve them in an aqueous methanol solution (V). 甲醇 V 水 =1:1), sealed container. Place the container in a constant temperature shaking water bath, set the temperature to 70℃, and shake for 3 hours.

[0093] (2) Add 30 mmol of ethylene glycol dimethacrylate, 25 mg of purified azobisisobutyronitrile and some methanol aqueous solution to step (1), purify the solution with argon gas for about 15 min, remove the oxygen in the solution, and seal the container.

[0094] (3) Place the container in a constant temperature shaking water bath, set the temperature to 70 ℃, and shake for 24 h to obtain a white polymer. Place the polymer in a glass petri dish, put it in an oven, set the temperature to 60 ℃, and dry for 24 h to obtain a dried polymer.

[0095] (4) Place the dried tungsten ion-imprinted polymer obtained in step (3) into a Soxhlet extractor, and the extraction solution is a methanol solution of acetic acid (V). 乙酸 V 甲醇 =1:9), the extraction temperature was set to 120 ℃, the extraction time was 8 h, and the cycle was repeated 3 times to obtain the eluted tungsten ion imprinted polymer.

[0096] (5) Use methanol aqueous solution (V) 甲醇 V 水 =1:1) In the cleaning step (4), the tungsten ion imprinted polymer is obtained, excess acetic acid is removed, and then it is dried in an oven at 60 °C to obtain the target product.

[0097] A tungsten alloy waste was mixed with NaOH at a mass ratio of 1:2 and calcined at 700 °C for 2 h. The calcined mixture was then dissolved in deionized water to prepare mol... W(Ⅵ) The extract with a concentration of 1 mmol is shown in Table 1. 10 mg of the tungsten ion-imprinted polymer obtained in this example was weighed and added to 20 mL of the above solution. The mixture was shaken at 25 °C for 5 h to perform selective adsorption experiments, and the adsorption capacities are shown in Table 2.

[0098] Table 1 Elemental content in tungsten alloy scrap

[0099] Table 2 Selective adsorption of tungsten alloy leachate by dual-monomer tungsten ion-imprinted polymers

[0100] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, and not to limit them; although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some of the technical features; and these modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the spirit and scope of the technical solutions of the embodiments of the present invention.

Claims

1. A method for preparing a dual monomer tungsten ion imprinted polymer, characterized by, Comprising: The polymerization reaction and template ion elution are carried out by using 4-vinylpyridine and chitosan as organic functional monomers and tungstate as template ion to obtain a bimonomer tungsten ion imprinted polymer.

2. The production method according to claim 1, characterized by, The molar ratio of 4-vinylpyridine to chitosan is 1-3:1-3; And / or, the molar ratio of the template ion to the organic functional monomer is 1-5:8-24; And / or, the metal salt of tungstate is sodium tungstate dihydrate.

3. The production method according to claim 1 or 2, characterized by, Further comprising a crosslinking agent; the crosslinking agent is ethylene glycol dimethacrylate; preferably, the molar ratio of the organic functional monomer to ethylene glycol dimethacrylate is 4-12:15-35.

4. The production method according to any one of claims 1 to 3, characterized by, Further comprising an initiator, the initiator is purified azobisisobutyronitrile; preferably, the ratio of the crosslinking agent to the purified azobisisobutyronitrile is 6-16 mol:5-14 g.

5. The production method according to claim 4, characterized by, Comprising: The metal coordination compound is obtained by mixing sodium tungstate dihydrate and organic functional monomers and carrying out chelation reaction; the bimonomer tungsten ion imprinted polymer precursor is obtained by mixing the metal coordination compound, crosslinking agent and initiator and carrying out polymerization reaction; the template ion elution is carried out on the bimonomer tungsten ion imprinted polymer precursor; the polymerization reaction is carried out in an argon atmosphere, preferably in a methanol aqueous solution.

6. The production method according to claim 5, wherein Comprising the following steps: 1) mixing sodium tungstate dihydrate, 4-vinylpyridine and chitosan and then carrying out constant temperature oscillation to obtain a metal coordination compound; 2) mixing ethylene glycol dimethacrylate, initiator, methanol aqueous solution and the metal coordination compound, drying after constant temperature oscillation in an inert atmosphere to obtain a bimonomer tungsten ion imprinted polymer precursor; 3) mixing the bimonomer tungsten ion imprinted polymer precursor with a methanol solution of acetic acid and extracting, then washing with a methanol aqueous solution and drying.

7. The preparation method according to claim 6, characterized in that, In step 1), the constant temperature oscillation temperature is 60-70 ℃, and the time is 2.5-3.5 h; And / or, in step 2), the constant temperature oscillation temperature is 60-70 ℃, the time is 20-30 h, the drying temperature is 60±10 ℃, and the time is 12-24 h; And / or, in step 3), the extraction temperature is 110-130 ℃, the extraction time is 6-10 h, and the cycle is repeated 2-3 times; the drying temperature is 66-65 ℃.

8. The production method according to claim 6 or 7, characterized by, In the methanol aqueous solution, the volume ratio of methanol to water is 1:0.5-1.5, preferably 1:1; And / or, in the methanol solution of acetic acid, the volume ratio of acetic acid to methanol is 1:5-10, preferably 1:

9.

9. A dual monomer tungsten ion imprinted polymer, characterized in that, Prepared by the preparation method of any one of claims 1-8.

10. The application of the bimonomer tungsten ion imprinted polymer prepared by the preparation method of any one of claims 1-8 or the bimonomer tungsten ion imprinted polymer of claim 9 in selectively separating tungsten and molybdenum metal ions.

Images