CN110339727B - A kind of preparation method and application of divalent lead ion imprinted composite membrane - Google Patents

A kind of preparation method and application of divalent lead ion imprinted composite membrane Download PDF

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CN110339727B
CN110339727B CN201910589870.XA CN201910589870A CN110339727B CN 110339727 B CN110339727 B CN 110339727B CN 201910589870 A CN201910589870 A CN 201910589870A CN 110339727 B CN110339727 B CN 110339727B
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CN110339727A (en
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成会玲
赵莉
刘迎梅
胡德琼
陈树梁
字富庭
胡显智
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Kunming University of Science and Technology
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
    • B01D15/08—Selective adsorption, e.g. chromatography
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0002—Organic membrane manufacture
    • B01D67/0006—Organic membrane manufacture by chemical reactions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/12—Composite membranes; Ultra-thin membranes
    • B01D69/125—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/72—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, not provided for in a single one of the groups B01D71/46 - B01D71/70 and B01D71/701 - B01D71/702
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/26—Synthetic macromolecular compounds
    • B01J20/268—Polymers created by use of a template, e.g. molecularly imprinted polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
    • B01J20/28033—Membrane, sheet, cloth, pad, lamellar or mat
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
    • C08F222/102—Esters of polyhydric alcohols or polyhydric phenols of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate

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Abstract

The invention discloses a preparation method and application of a divalent lead ion imprinting composite membrane, and belongs to the technical field of high polymer materials with adsorption and separation functions. According to the method, lead (II) ions are used as template ions, a compound which is designed and synthesized automatically is used as a functional monomer, ethylene glycol dimethacrylate is used as a cross-linking agent, azodiisobutyronitrile is used as an initiator, a commercial membrane is used as a base membrane, a mixed solution of an organic solvent and water is used as a pore-forming agent, a surface grafting imprinting method is adopted, and a polymer thin layer is imprinted on the surface of a support membrane in a thermal initiation mode. The preparation method of the lead (II) ion imprinting composite membrane provided by the invention is simple and convenient to operate and low in economic cost, and the obtained lead (II) ion imprinting composite membrane can adsorb and remove lead (II) ions in an aqueous solution with high selectivity.

Description

Preparation method and application of divalent lead ion imprinting composite membrane
Technical Field
The invention relates to a preparation method and application of a divalent lead ion imprinting composite membrane, and belongs to the technical field of high polymer materials with adsorption and separation functions.
Background
The metal ion imprinting technology is an important development direction of the molecular imprinting technology, and has important academic and application values in the fields of environment, life, material science and the like. The ion imprinting technology is characterized in that ions are used as a template, a chelate is formed by combining with a monomer through electrostatic interaction, coordination and the like, the template ions are eluted by an acidic reagent and the like after polymerization, and finally the imprinting material with a three-dimensional hole structure corresponding to a target metal ion is prepared.
The membrane separation technology is a technology for realizing selective separation of a mixture of molecules with different particle sizes on a molecular level when the mixture passes through a semipermeable membrane, and can be divided into a microfiltration Membrane (MF), an ultrafiltration membrane (UF), a nanofiltration membrane (NF), a reverse osmosis membrane (RO) and the like according to the pore size, and common organic fluorine-containing commercial membranes mainly comprise Polytetrafluoroethylene (PTFE) and polyvinylidene fluoride (PVDF). However, the current commercial membrane can not realize the selective separation of single substances, and the metal ion imprinting technology provides a feasible and effective solution for separating specific target ions from the mixture of structural analogs of the specific target ions.
Therefore, the metal ion imprinting technology is combined with the membrane separation technology, and a practical technology is provided for efficiently and specifically identifying the metal ions. Now, heavy metal pollution not only causes serious damage to the environment, but also poses serious threats to human health. Lead is a heavy metal pollutant which is relatively toxic, stable in property and difficult to degrade. Lead accumulates in the human body and damages the respiratory system, nervous system, hematopoietic system and the like, so how to effectively solve the problem of lead pollution is an important task facing human beings at present.
Disclosure of Invention
The invention provides a preparation method of a divalent lead ion imprinting composite membrane, which effectively combines an ion imprinting technology and a membrane technology to synthesize a lead (II) ion imprinting composite membrane, and has the advantages of simple and convenient operation process and mild conditions; the lead (II) ion imprinting composite membrane prepared by the method can simply, quickly and selectively identify and adsorb divalent lead ions, and has high application value.
The method specifically comprises the following steps:
(1) preparation of prepolymerization solution: dissolving template ions Pb (II) in a pore-forming solvent according to the proportion of 0.005-0.01 g/L, adding a functional monomer, oscillating for 2-3 h at room temperature, finally sequentially adding a crosslinking agent ethylene glycol dimethacrylate and an initiator azobisisobutyronitrile, and carrying out ultrasonic degassing treatment for 5-10 min to obtain a prepolymerization solution.
(2) Preparing a lead (II) ion imprinting composite membrane: and (2) placing the base membrane into the prepolymerization solution obtained in the step (1), soaking at normal temperature for 3-60 min, heating to 60-70 ℃, reacting for 24-48 h to obtain the lead (II) ion imprinted composite membrane, and finally eluting with a mixed solution of methanol and acetic acid to remove template ions to obtain the lead (II) ion imprinted composite membrane with a three-dimensional cavity.
Preferably, in the step (1) of the invention, the molar ratio of the template ions, the functional monomer and the cross-linking agent is 1 (4-10) to (20-50), and the mass molar ratio of the initiator to the functional monomer is 1 (10-15).
Preferably, the porogen is a mixed solution of an organic solvent and water, the volume ratio of the organic solvent to the water is (1:3) - (3:1), wherein the organic solvent is one of methanol, ethanol, acetonitrile, N-dimethylformamide and isopropanol.
Preferably, the preparation method of the functional monomer of the invention is as follows:
(1) weighing 10-20 mmol of compound N-hydroxyethyl pyrrolidine in a reaction container, dissolving with 50-70 mL of HCl, reacting to generate 1- (2-vinyl chloride) pyrrolidine, heating and refluxing for 2-5 h, cooling with an ice-water bath, adding 5-10 mmol of acrylamide into the reaction, continuing heating and stirring for reaction for 5-10 h, cooling to room temperature after the reaction is completed, dropwise adding 10-30 mL of acryloyl chloride into the cooled mixed solution, removing the ice-water bath after the reaction is completed, and reacting at room temperature for 12-24 h;
(2) and (3) post-treatment: after the reaction is finished, filtering, extracting the filtrate by using chloroform, washing the filtrate with water until the pH value is neutral, drying the filtrate by using anhydrous sodium sulfate, filtering, concentrating in vacuum, performing column chromatography on the residue by using a mixed solution of petroleum ether and ethyl acetate, wherein the volume ratio of the petroleum ether to the ethyl acetate is (20-30) to (1-5), and separating to obtain a light yellow oily liquid.
Preferably, the volume ratio of methanol to acetic acid in the mixed solution of methanol and acetic acid in the step (2) is (1-9): 1.
Preferably, the base membrane in step (2) of the present invention is one of a polytetrafluoroethylene microporous filter membrane (PTFE), a polyvinylidene fluoride microporous filter membrane (PVDF), and a Nylon-6 microporous filter membrane (Nylon-6), and the base membrane is a commercially available product.
The invention also aims to provide the lead (II) ion imprinting composite membrane prepared by the method for adsorbing and separating the divalent lead ions in the solution.
The invention has the beneficial effects that:
(1) the method adopts a surface grafting imprinting technology, takes the compound which is automatically designed and synthesized as a functional monomer, and takes a commercial microporous filter membrane as a support membrane, thereby overcoming the defects of difficult preparation, complex operation and the like of the traditional divalent lead ion adsorbing material.
(2) The ion imprinting composite membrane prepared by the method disclosed by the invention has the advantages that the recognition sites are exposed on the surface of the membrane, so that the specific recognition performance of the ion imprinting composite membrane can be improved, and the adsorption capacity of the ion imprinting composite membrane on divalent lead ions can be improved.
Detailed Description
The present invention will be described in further detail with reference to specific examples, but the scope of the present invention is not limited to the examples.
Example 1
A preparation method of a divalent lead ion imprinting composite membrane specifically comprises the following steps:
(1) preparing a functional monomer: weighing 10mmol of compound N-hydroxyethyl pyrrolidine in a three-necked bottle, dissolving with 50m LHCl, reacting to generate 1- (2-vinyl chloride) pyrrolidine, heating and refluxing for 2h, cooling with ice water bath, adding 5mmol of acrylamide into the reaction, continuing heating and stirring for reaction for 6h, cooling to room temperature after the reaction is completed, dropwise adding 12ml of acryloyl chloride into the cooled mixed solution, removing the ice water bath after the reaction is completed, and reacting at room temperature for 12 h. After the reaction is finished, filtering, extracting the filtrate by using chloroform, washing the filtrate with water until the pH value is neutral, drying the filtrate by using anhydrous sodium sulfate, filtering, concentrating in vacuum, performing column chromatography on the residue by using a mixed solution of petroleum ether and ethyl acetate, wherein the volume ratio of the petroleum ether to the ethyl acetate is 20:1, and separating to obtain a light yellow oily liquid.
(2) Adding 0.1mmol Pb (NO)3)2Adding the mixture into a pore-foaming agent of a mixed solution of methanol and water with the volume ratio of 1:1, adding 0.4mmol of functional monomer after the mixture is completely dissolved, oscillating at normal temperature for 3 hours to uniformly mix the mixture, then adding 2mmol of cross-linking agent ethylene glycol dimethacrylate and 15mg of initiator azobisisobutyronitrile, shaking up, and carrying out ultrasonic degassing treatment for 10 minutes to obtain the pre-polymerization solution.
(3) And (2) placing the polyvinylidene fluoride microporous filter membrane into the pre-polymerization solution obtained in the step (1), soaking for 3min at normal temperature, and then carrying out thermal initiation reaction for 24h at the temperature of 60 ℃.
(4) Eluting the template ions by using a mixed solution of methanol and acetic acid with the volume ratio of 9:1, and washing the template ions to be neutral by using methanol to obtain the lead (II) ion imprinted composite membrane with the shape and the size matched with those of the template ions and a three-dimensional cavity.
The 20.00mg of lead (II) ion imprinting composite membrane prepared by the embodiment is applied to a solution with the lead (II) concentration of 18mg/mL for isothermal adsorption; the results show that: the adsorption capacity of the lead (II) ion imprinting composite membrane is 990.49 mu mol/g, and the imprinting factor is 1.78.
Example 2
A preparation method of a divalent lead ion imprinting composite membrane specifically comprises the following steps:
(1) preparing a functional monomer: weighing 17mmol of compound N-hydroxyethyl pyrrolidine in a three-necked bottle, dissolving with 72m of HCl, reacting to generate 1- (2-vinyl chloride) pyrrolidine, heating and refluxing for 3h, cooling with ice water bath, adding 10mmol of acrylamide into the reaction, continuing heating and stirring for reaction for 7h, cooling to room temperature after the reaction is completed, dropwise adding 13ml of acryloyl chloride into the cooled mixed solution, removing the ice water bath after the reaction is completed, and reacting at room temperature for 14 h. After the reaction is finished, filtering, extracting the filtrate by using chloroform, washing the filtrate with water until the pH value is neutral, drying the filtrate by using anhydrous sodium sulfate, filtering, concentrating in vacuum, performing column chromatography on the residue by using a mixed solution of petroleum ether and ethyl acetate, wherein the volume ratio of the petroleum ether to the ethyl acetate is 30:5, and separating to obtain a light yellow oily liquid.
(2) Adding 0.1mmol Pb (NO)3)2Adding into a pore-foaming agent of a mixed solution of ethanol and water with the volume ratio of 1:1Dissolving completely, adding 0.6mmol of functional monomer, oscillating at normal temperature for 3h to mix uniformly, then adding 3mmol of cross-linking agent ethylene glycol dimethacrylate and 15mg of initiator azobisisobutyronitrile, shaking uniformly, and carrying out ultrasonic degassing treatment for 10min to obtain the pre-polymerization solution.
(3) And (2) placing a polytetrafluoroethylene microporous filter membrane (PTFE) in the pre-polymerization solution obtained in the step (1), soaking at normal temperature for 10min, and then carrying out thermal initiation reaction at 60 ℃ for 24 h.
(4) Eluting the template ions by using a mixed solution of methanol and acetic acid with the volume ratio of 9:1, and washing the template ions to be neutral by using methanol to obtain the lead (II) ion imprinted composite membrane with the shape and the size matched with those of the template ions and a three-dimensional cavity.
The 20.00mg of lead (II) ion imprinting composite membrane prepared by the embodiment is applied to a solution with the lead (II) concentration of 18mg/mL for isothermal adsorption; the results show that: the adsorption capacity of the lead (II) ion imprinting composite membrane is 1010.31 mu mol/g imprinting factor of 2.01.
Example 3
A preparation method of a divalent lead ion imprinting composite membrane specifically comprises the following steps:
(1) preparing a functional monomer: weighing 14mmol of compound N-hydroxyethyl pyrrolidine in a three-necked bottle, dissolving the compound N-hydroxyethyl pyrrolidine in 60m of LHCl, reacting to generate 1- (2-vinyl chloride) pyrrolidine, heating and refluxing for 4h, cooling in an ice water bath, adding 8mmol of acrylamide into the reaction, continuing heating and stirring for reaction for 7h, cooling to room temperature after the reaction is completed, dropwise adding 15ml of acryloyl chloride into the cooled mixed solution, removing the ice water bath after the reaction is completed, and reacting at room temperature for 18 h. After the reaction is finished, filtering, extracting the filtrate by using chloroform, washing the filtrate with water until the pH value is neutral, drying the filtrate by using anhydrous sodium sulfate, filtering, concentrating in vacuum, performing column chromatography on the residue by using a mixed solution of petroleum ether and ethyl acetate, wherein the volume ratio of the petroleum ether to the ethyl acetate is 25:4, and separating to obtain a light yellow oily liquid.
(2) 0.1mmol of Pb (NO)3)2Adding into a pore-foaming agent of a mixed solution of acetonitrile and water with the volume ratio of 1:1, adding 0.4mmol of functional monomer after the pore-foaming agent is completely dissolved, oscillating for 3 hours at normal temperature to uniformly mix the functional monomer,then adding 4mmol of crosslinking agent ethylene glycol dimethacrylate and 15mg of initiator azobisisobutyronitrile, shaking up, and carrying out ultrasonic degassing treatment for 10min to obtain the pre-polymerization solution.
(3) And (2) placing a Nylon-6 microporous filter membrane (Nylon-6) in the pre-polymerization solution obtained in the step (1), soaking at normal temperature for 20min, and then carrying out thermal initiation reaction at 60 ℃ for 24 h.
(4) Eluting the template ions by using a mixed solution of methanol and acetic acid with the volume ratio of 9:1, and washing the template ions to be neutral by using methanol to obtain the lead (II) ion imprinted composite membrane with the shape and the size matched with those of the template ions and a three-dimensional cavity.
The 20.00mg of lead (II) ion imprinting composite membrane prepared in the example is applied to a solution with the lead (II) concentration of 18mg/mL for isothermal adsorption. The results show that: the adsorption capacity of the lead (II) ion imprinting composite membrane is 957.43 mu mol/g, and the imprinting factor is 1.60.
Example 4
A preparation method of a divalent lead ion imprinting composite membrane specifically comprises the following steps:
(1) preparing a functional monomer: weighing 15mmol of compound N-hydroxyethyl pyrrolidine in a three-necked bottle, dissolving with 65m LHCl, reacting to generate 1- (2-vinyl chloride) pyrrolidine, heating and refluxing for 5h, cooling with an ice water bath, adding 7mmol of acrylamide into the reaction, continuing heating and stirring for reaction for 9h, cooling to room temperature after the reaction is completed, dropwise adding 11ml of acryloyl chloride into the cooled mixed solution, removing the ice water bath after the reaction is completed, and reacting at room temperature for 20 h. After the reaction is finished, filtering, extracting the filtrate by using chloroform, washing the filtrate with water until the pH value is neutral, drying the filtrate by using anhydrous sodium sulfate, filtering, concentrating the filtrate in vacuum, performing column chromatography on the residue by using a mixed solution of petroleum ether and ethyl acetate, wherein the volume ratio of the petroleum ether to the ethyl acetate is 28:3, and separating to obtain a light yellow oily liquid.
(2) 0.1mmol of Pb (NO)3)2Adding into a pore-foaming agent of a mixed solution of N, N-dimethylformamide and water with the volume ratio of 1:1, adding 0.6mmol of functional monomer after the functional monomer is completely dissolved, oscillating at normal temperature for 3h to mix the functional monomer uniformly, and then adding 5mmol of cross-linking agent ethylene glycol dimethacrylate and 15mg of initiatorUniformly shaking azodiisobutyronitrile as an agent, and performing ultrasonic degassing treatment for 10min to obtain a pre-polymerization solution;
(3) placing a polyvinylidene fluoride microporous filter membrane in the pre-polymerization solution obtained in the step (1), soaking for 30min at normal temperature, and then carrying out thermal initiation reaction for 24h at 60 ℃;
(4) eluting the template ions by using a mixed solution of methanol and acetic acid with the volume ratio of 9:1, and washing the template ions to be neutral by using methanol to obtain the lead (II) ion imprinted composite membrane with the shape and the size matched with those of the template ions and a three-dimensional cavity.
The 20.00mg of lead (II) ion imprinting composite membrane prepared in the example is applied to a solution with the lead (II) concentration of 18mg/mL for isothermal adsorption. The results show that: the adsorption capacity of the lead (II) ion imprinting composite membrane is 960.76 mu mol/g, and the imprinting factor is 1.58.
Example 5
A preparation method of a divalent lead ion imprinting composite membrane specifically comprises the following steps:
(1) preparing a functional monomer: weighing 20mmol of compound N-hydroxyethyl pyrrolidine in a three-necked bottle, dissolving with 55m LHCl, reacting to generate 1- (2-vinyl chloride) pyrrolidine, heating and refluxing for 4h, cooling with an ice water bath, adding 7mmol of acrylamide into the reaction, continuing heating and stirring for reaction for 10h, cooling to room temperature after the reaction is completed, dropwise adding 30ml of acryloyl chloride into the cooled mixed solution, removing the ice water bath after the reaction is completed, and reacting at room temperature for 24 h. After the reaction is finished, filtering, extracting the filtrate by using chloroform, washing the filtrate with water until the pH value is neutral, drying the filtrate by using anhydrous sodium sulfate, filtering, concentrating in vacuum, performing column chromatography on the residue by using a mixed solution of petroleum ether and ethyl acetate, wherein the volume ratio of the petroleum ether to the ethyl acetate is 25:5, and separating to obtain a light yellow oily liquid.
(2) Adding 0.1mmol Pb (NO)3)2Adding the mixture into a pore-foaming agent of a mixed solution of isopropanol and water with the volume ratio of 1:1, adding 0.4mmol of functional monomer after the mixture is completely dissolved, oscillating at normal temperature for 3 hours to mix the mixture evenly, then adding 2mmol of cross-linking agent ethylene glycol dimethacrylate and 15mg of initiator azobisisobutyronitrile, shaking up, and carrying out ultrasonic degassing treatment for 10 minutes to obtain the pre-polymerization solution.
(3) And (3) placing the polyvinylidene fluoride microporous filter membrane into the prepolymerization liquid obtained in the first step, soaking for 60min at normal temperature, and then carrying out thermal initiation reaction for 24h at 60 ℃.
(4) Eluting the template ions by using a mixed solution of methanol and acetic acid with the volume ratio of 9:1, and washing the template ions to be neutral by using methanol to obtain the lead (II) ion imprinted composite membrane with the shape and the size matched with those of the template ions and a three-dimensional cavity.
The 20.00mg of lead (II) ion imprinting composite membrane prepared in the example is applied to a solution with the lead (II) concentration of 18mg/mL for isothermal adsorption. The results show that: the adsorption capacity of the lead (II) ion imprinting composite membrane is 1020.89 mu mol/g, and the imprinting factor is 1.77.
While the present invention has been described in detail with reference to the specific embodiments thereof, the present invention is not limited to the embodiments described above, and various changes can be made without departing from the spirit of the present invention within the knowledge of those skilled in the art.

Claims (4)

1.一种二价铅离子印迹复合膜的制备方法，其特征在于，具体包括以下步骤：1. a preparation method of divalent lead ion imprinted composite membrane, is characterized in that, specifically comprises the following steps: （1）预聚合溶液的制备：按0.005～0.01g/L的比例将模板离子Pb(II)溶于致孔溶剂中，再加入功能单体，在室温下振荡2～3h，最后依次加入交联剂乙二醇二甲基丙烯酸酯，引发剂偶氮二异丁腈，超声脱气处理5～10min，即形成预聚合溶液；(1) Preparation of prepolymerization solution: Dissolve the template ion Pb(II) in the pore-forming solvent at a ratio of 0.005-0.01 g/L, then add the functional monomer, shake at room temperature for 2-3 hours, and finally add the cross-linking solution in sequence. The linking agent ethylene glycol dimethacrylate, the initiator azobisisobutyronitrile, and ultrasonic degassing for 5-10min, that is, a prepolymerization solution is formed; （2）铅(II)离子印迹复合膜的制备：将基膜置于上述步骤（1）中的预聚合溶液，常温下浸泡3～60min，然后升温至60～70℃下反应24～48h，即制得铅(II)离子印迹复合膜，最后用甲醇和醋酸混合溶液洗脱除去模板离子，即制得具有立体空穴的铅(II)离子印迹复合膜；(2) Preparation of lead (II) ion-imprinted composite membrane: place the base membrane in the prepolymerized solution in the above step (1), soak it at room temperature for 3-60 minutes, and then raise the temperature to 60-70°C for 24-48 hours of reaction, That is, the lead (II) ion-imprinted composite membrane is prepared, and finally the template ions are removed by elution with a methanol and acetic acid mixed solution, that is, a lead (II) ion-imprinted composite membrane with three-dimensional holes is prepared; 步骤（1）中所述模板离子、功能单体和交联剂摩尔比为1:(4～10):(20～50)，引发剂与功能单体的质量摩尔比为1:(10～15)；In step (1), the molar ratio of template ion, functional monomer and crosslinking agent is 1:(4～10):(20～50), and the mass molar ratio of initiator and functional monomer is 1:(10～ 15); 所述功能单体的制备方法如下：The preparation method of the functional monomer is as follows: （1）称取10～20mmol化合物N-羟乙基吡咯烷于反应容器中，并用50～70mL HCl溶解，反应生成1-(2-乙烯基氯)吡咯烷，加热回流2～5h，之后用冰水浴冷却，再将5～10mmol丙烯酰胺加入上述反应中，继续加热搅拌反应5～10h，反应完全后，冷却至室温，将10～30ml丙烯酰氯逐滴加到上述冷却后的混合液中，滴完移去冰水浴，室温反应12～24h；(1) Weigh 10-20 mmol of the compound N-hydroxyethylpyrrolidine into the reaction vessel, and dissolve it with 50-70 mL of HCl, the reaction generates 1-(2-vinyl chloride)pyrrolidine, heat under reflux for 2-5 h, and then use Cool in an ice-water bath, then add 5-10 mmol of acrylamide to the above reaction, continue to heat and stir for 5 to 10 hours, after the reaction is complete, cool to room temperature, and add 10 to 30 ml of acryloyl chloride dropwise to the cooled mixture, After dropping, remove the ice-water bath and react at room temperature for 12-24 hours; （2）后处理：反应完毕后，先过滤，滤液用氯仿萃取，水洗pH到中性，无水硫酸钠干燥后过滤，真空浓缩后，残留物以石油醚和乙酸乙酯的混合溶液进行柱层析，石油醚和乙酸乙酯的体积比为(20～30):(1～5)，分离得到淡黄色油状液体，即为功能单体。(2) Post-treatment: After the reaction is completed, filter first, extract the filtrate with chloroform, wash with water to neutralize pH, dry with anhydrous sodium sulfate, filter, and concentrate in vacuo. Chromatography, the volume ratio of petroleum ether and ethyl acetate is (20～30):(1～5), and the light yellow oily liquid is obtained by separation, which is the functional monomer. 2.根据权利要求1所述方法，其特征在于：所述致孔剂为有机溶剂和水的混合溶液，有机溶剂和水的体积比为(1:3)～(3:1)，其中有机溶剂为甲醇、乙醇、乙腈、N,N-二甲基甲酰胺、异丙醇中的一种。2. The method according to claim 1, wherein the porogen is a mixed solution of an organic solvent and water, and the volume ratio of the organic solvent and water is (1:3)～(3:1), wherein the organic solvent The solvent is one of methanol, ethanol, acetonitrile, N,N-dimethylformamide and isopropanol. 3.根据权利要求1所述方法，其特征在于，步骤（2）中甲醇和醋酸混合溶液中甲醇和醋酸的体积比为(1～9):1。3. The method according to claim 1, wherein the volume ratio of methanol and acetic acid in the methanol and acetic acid mixed solution in step (2) is (1～9):1. 4.根据权利要求1所述方法，其特征在于：步骤（2）所述基膜为聚四氟乙烯微孔滤膜(PTFE)、聚偏氟乙烯微孔滤膜(PVDF)、尼龙-6微孔滤膜(Nylon-6)中的一种。4. The method according to claim 1, characterized in that: in step (2), the base film is a polytetrafluoroethylene microporous membrane (PTFE), a polyvinylidene fluoride microporous membrane (PVDF), nylon-6 One of the microporous membranes (Nylon-6).
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