CN110776596A - Para-hydroxybenzoic acid selective resin and preparation method thereof - Google Patents
Para-hydroxybenzoic acid selective resin and preparation method thereof Download PDFInfo
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- 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
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- 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
- B01J20/22—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
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- 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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/26—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a solid phase from a macromolecular composition or article, e.g. leaching out
Abstract
The invention discloses a p-hydroxybenzoic acid selective resin and a preparation method thereof, wherein the exchange capacity of the resin is 2.26-2.65 mmol/g, and the preparation method comprises the following steps: 1) putting p-hydroxybenzoic acid and diethylaminoethyl methacrylate in acetonitrile, uniformly mixing, and performing self-assembly to obtain an assembly solution; 2) adding a carrier, a cross-linking agent, an initiator, a catalyst and a reducing agent into the self-assembly solution for reaction to prepare a polymer; 3) and (3) washing and removing the polymer by using an eluent, washing the material to be neutral by sequentially adopting 1-3 wt% of hydrochloric acid solution, deionized water, 2-8 wt% of sodium hydroxide solution and deionized water, extracting by using ethanol, and drying in an oven to constant weight to obtain the polymer. The selective resin has a cavity matched with the template molecule in shape, size and recognition site, so that the selective resin has stronger adsorption function and good specific selectivity on p-hydroxybenzoic acid.
Description
Technical Field
The invention relates to a p-hydroxybenzoic acid selective resin and a preparation method thereof, belonging to the field of molecular imprinting polymers.
Background
The phenolic acid compound is a compound containing a hydroxyl group and a carboxyl group on an aromatic ring, and is an organic substance having certain toxicity and bioaccumulation properties. The phenolic acid wastewater has large harm and wide pollution range, and is widely applied to multiple fields, such as fluorescent indicators, scorch retarders, rubber, preservatives, bactericides, dyes, pesticides, pharmaceutical industry and the like. Generally, phenolic acid compounds are prepared by taking phenol as a raw material, a large amount of raw material phenol and a product phenolic acid are contained in production wastewater, and if the wastewater is directly discharged, the wastewater pollutes atmosphere, water and soil and causes harm to the environment. At present, research methods related to the treatment of phenolic acid organic wastewater include electrochemical coagulation, advanced oxidation, biofilm, enzyme catalysis, membrane extraction and resin adsorption. The resin adsorption method is to utilize resin to adsorb phenolic acid compounds in phenolic acid wastewater so as to recover or remove the substances, thereby achieving the purpose of sewage purification. The resin has large specific surface, proper pores and surface structures, high adsorption efficiency, easy regeneration and wide application. However, most commercial resins have the disadvantages of weak inorganic salt interference resistance, poor specific selectivity and the like, and cannot realize specific adsorption of specific pollutants. At present, a large amount of industrial wastewater always appears in the production process of various chemical drugs, the characteristics of the wastewater are high concentration and complex components, and part of pollutants are chemicals capable of recycling resources, such as raw material phenol and product p-hydroxybenzoic acid in the p-hydroxybenzoic acid production wastewater, if the substances can be taken out from the production wastewater, the wastewater can be treated cleanly, and the separation, purification and recycling of the two substances can be realized.
The Molecular Imprinting Technology (MIT) is a technology for preparing a material having specific selectivity to a template molecule, and has the characteristics of predetermination, identification and practicability, i.e., different Molecularly Imprinted Polymers (MIPs) can be prepared according to different purposes to meet various special requirements, the imprinted molecules can be specifically identified, and the technology has higher stability and longer service life. The surface imprinting polymerization is to modify active functional groups with amino groups and olefinic bonds on the surface of a carrier, and the imprinting sites of the prepared polymer are basically on the surface of the carrier, so that the phenomenon of over-deep embedding of template molecules can be prevented, and the template molecules can be removed quickly. The surface imprinting process reduces the imprinting difficulty of template molecules, improves the adsorption and desorption efficiency, and improves the adsorption capacity and the specific recognition selectivity of the material.
The atom transfer free radical polymerization is to apply the transfer free radical addition reaction catalyzed by transition metal to the synthesis of high molecular materials, mainly takes organic halide as an initiator and a transition metal complexing agent as a catalyst, achieves the transfer of halogen atoms through the redox reaction of a metal catalyst, forms dynamic balance between dormant species and active species, and further realizes the control of polymerization reaction.
Disclosure of Invention
The technical problem is as follows: the invention aims to provide a p-hydroxybenzoic acid selective resin and a preparation method thereof, the selective resin synthesized by the method has higher adsorption capacity and excellent adsorption selectivity to the p-hydroxybenzoic acid in aqueous solution; the selective resin has simple preparation process and easily obtained raw materials, and effectively overcomes the defects of poor selection performance, few recognition sites and low binding speed of the existing adsorption material.
The technical scheme is as follows: the invention provides a preparation method of p-hydroxybenzoic acid selective resin, which comprises the following steps:
1) placing template molecules of p-hydroxybenzoic acid and a functional monomer of diethylaminoethyl methacrylate in an organic solvent of acetonitrile, uniformly mixing, and carrying out self-assembly to obtain a self-assembly solution;
2) adding a carrier, a cross-linking agent, an initiator, a catalyst and a reducing agent into the self-assembly solution for reaction to prepare a polymer;
3) and (3) washing the polymer prepared in the step 2) by using an eluent to remove template molecules, washing the material to be neutral by sequentially adopting 1-3 wt% hydrochloric acid solution, deionized water, 2-8 wt% sodium hydroxide solution and deionized water, extracting by using ethanol, and drying in an oven to constant weight to obtain the p-hydroxybenzoic acid selective resin.
Wherein:
the mass of the template molecule p-hydroxybenzoic acid in the step 1) is 0.6-0.75 time of that of the carrier before swelling, and the molar ratio of the p-hydroxybenzoic acid to the functional monomer diethyl aminoethyl methacrylate is 1: 4-1: 8.
The mass of the organic solvent acetonitrile in the step 1) is 8-12 times of the mass of the organic solvent acetonitrile added before swelling of the carrier.
The self-assembly temperature of the template molecule p-hydroxybenzoic acid and the functional monomer diethylaminoethyl methacrylate in the step 1) is 30-35 ℃, and the self-assembly time is 120-150 min.
The carrier in the step 2) is polystyrene chlorine balls, the chlorine balls are washed to be neutral before use, then the chlorine balls are placed in absolute ethyl alcohol, are vibrated and washed for 8-12 h, and are placed in an oven to be dried for later use at 40-45 ℃, and the dried chlorine balls are firstly swelled in N, N-dimethylformamide for 10-12 h when in use.
The cross-linking agent in the step 2) is ethylene glycol dimethacrylate, and the molar ratio of the functional monomer diethylaminoethyl methacrylate to the cross-linking agent ethylene glycol dimethacrylate is 1: 0.5-1: 3.
The initiator in the step 2) is ethyl 2-bromoisobutyrate, and the dosage of the initiator is 0.03-0.05 time of the mass of the carrier before swelling.
The catalyst in the step 2) is a mixture of 2,2 '-bipyridyl and copper bromide, the dosage of the 2, 2' -bipyridyl is 0.09-0.15 times of the mass of the carrier before swelling, and the dosage of the copper bromide is 0.05-0.1 times of the mass of the carrier before swelling.
The reducing agent in the step 2) is glycol, and the mass of the reducing agent is 0.05-0.085 times of the mass of the carrier before swelling.
Adding the carrier, the cross-linking agent, the initiator catalyst and the reducing agent into the self-assembly solution for reaction in the step 2), namely introducing nitrogen to remove oxygen in the self-assembly solution after the self-assembly solution is added, heating in a water bath at 60-65 ℃, and stirring for reaction for 24-28 h to obtain the p-hydroxybenzoic acid selective resin.
The eluent in the step 3) is methanol-concentrated hydrochloric acid solution, wherein the volume ratio of methanol to hydrochloric acid is 8: 1-12: 1, and the mass concentration of concentrated hydrochloric acid is 36-38%.
And 3) extracting with ethanol, drying in an oven to constant weight, wherein the ethanol extraction time is 5-6 h, and the temperature of the oven is 40-45 ℃.
Before the step of washing and removing the template molecules from the polymer prepared in the step 2) by using the eluent in the step 3), deionized water and 0.1mol/L EDTA aqueous solution are added to wash and remove copper bromide in the catalyst.
The invention also provides the p-hydroxybenzoic acid selective resin prepared by the method, wherein the p-hydroxybenzoic acid selective resin belongs to mesoporous resin, the average pore diameter of the resin is 33.16-36.57 nm, and the BET surface area of the resin is 26.91-28.22 m
2Per gram, pore volume 0.24-0.27 cm
3The exchange capacity is 2.26-2.65 mmol/g, and the adsorption equilibrium time is as short as 6.5 h.
Has the advantages that: compared with the prior art, the invention has the following advantages:
1. the p-hydroxybenzoic acid imprinted polymer prepared by the invention has a specific recognition function on p-hydroxybenzoic acid, can be applied to selective separation and removal of p-hydroxybenzoic acid in an aqueous solution, the imprinted material is placed in a mixed solution with the concentrations of both p-hydroxybenzoic acid and phenol of 5mmol/L, and the selective adsorption coefficient on p-hydroxybenzoic acid can reach 5.74;
2. when the p-hydroxybenzoic acid selective resin prepared by the invention adsorbs p-hydroxybenzoic acid in an aqueous solution, the adsorption capacity is large, the maximum adsorption capacity can reach 1.9299mmol/g, the adsorption speed is high, the adsorption balance can be reached within 6.5h, and the adsorption selectivity is excellent;
3. the p-hydroxybenzoic acid selective resin provided by the invention is simple in preparation method and low in cost, and has wide application prospect in the field of treatment of waste water in production of hydroxybenzoic acid.
Detailed Description
The invention provides a p-hydroxybenzoic acid selective resin and a preparation method thereof, which apply the molecular imprinting technical principle and atom transfer radical polymerization, self-assemble by template molecule p-hydroxybenzoic acid and functional monomer diethylaminoethyl methacrylate, then add carrier, initiator, cross-linking agent, catalyst and reducing agent into the self-assembly solution, carry out polymerization reaction on the surface of the carrier; and then repeatedly washing the reacted material by using an eluent methanol-concentrated hydrochloric acid solution, washing the material to be neutral by sequentially using 1-3 wt% of hydrochloric acid solution, deionized water, 2-8 wt% of sodium hydroxide solution and deionized water, then extracting by using ethanol, and drying in an oven at 40-45 ℃ to constant weight to obtain the p-hydroxybenzoic acid selective resin. Because the obtained imprinted polymer has cavities matched with the template molecules in shape, size and recognition sites, the obtained imprinted material has stronger adsorption function and good specific selectivity on p-hydroxybenzoic acid; the adsorption selectivity of the resin on the target compound is utilized to separate and purify substances in the wastewater, so that pollutants can be removed, the wastewater can be purified, and the resource can be recycled.
The present invention will be further explained with reference to examples. The following examples are provided only for illustrating the present invention and are not intended to limit the scope of the present invention.
Example 1:
a preparation method of p-hydroxybenzoic acid selective resin comprises the following steps:
(1) washing 20g of chlorine balls to be neutral, then placing the chlorine balls in absolute ethyl alcohol, washing the chlorine balls in a shaking table for 10 hours in a shaking way, and finally placing the chlorine balls in an oven to be dried at 40 ℃;
(2) 14.368g of p-hydroxybenzoic acid, 111.12ml of diethylaminoethyl methacrylate (PDEAEMA) and 200ml of acetonitrile are taken, mixed uniformly and reacted in a beaker at 30 ℃ for 120min for self-assembly to obtain a self-assembly solution;
(3) the chlorine spheres were swelled in N, N-dimethylformamide for 10h, and then charged into a 500ml three-necked flask, followed by addition of 117.7ml of Ethylene Glycol Dimethacrylate (EGDMA), 0.693g of ethyl 2-bromoisobutyrate (EBMP), 1.87g of 2, 2' -Bpy, and 1.34g of CuBr
21ml of glycol and the self-assembly solution in the step (2), introducing nitrogen to remove oxygen in the solution, reacting for 25 hours in a water bath at 60 ℃, and pouring off the solution to obtain the productTo a polymer;
(4) adding deionized water and 0.1mol/L EDTA aqueous solution into the polymer for washing, adding a mixed solution of methanol and hydrochloric acid (the volume ratio is 9:1, wherein the mass concentration of the hydrochloric acid is 38 percent) to remove template molecules;
(5) and (3) washing the polymer without the template molecules with 3 wt% of hydrochloric acid, distilled water, NaOH with the mass fraction of 2 wt% and distilled water in sequence until the polymer is neutral, extracting the polymer with ethanol for 5 hours, taking the polymer out, putting the polymer into a 45 ℃ oven, and drying the polymer until the weight of the polymer is constant to prepare the novel 4-HB imprinted resin MIP, namely the p-hydroxybenzoic acid selective resin.
Detection of p-hydroxybenzoic acid selective resin prepared by the above method resulted in an exchange capacity of 2.65mmol/g, an average pore size of 33.16nm, and a BET surface area of 28.22m
2Per g, pore volume 0.24cm
3And/g, the product is placed in a mixed solution of p-hydroxybenzoic acid and p-phenol with the concentration of 5mmol/L, and the selective adsorption coefficient of the p-hydroxybenzoic acid reaches 5.74.
Example 2:
a preparation method of p-hydroxybenzoic acid selective resin comprises the following steps:
(1) washing 20g of chlorine balls to be neutral, then placing the chlorine balls in absolute ethyl alcohol, shaking and washing the chlorine balls in a shaking table for 8 hours, and finally placing the chlorine balls in an oven to be dried at 42 ℃;
(2) mixing p-hydroxybenzoic acid 12g, diethylaminoethyl methacrylate (PDEAEMA) 112.62ml and acetonitrile 220ml, reacting in a beaker at 35 deg.C for 120min to obtain self-assembly solution;
(3) the chlorine spheres were swollen in N, N-dimethylformamide for 10 hours, and then the chlorine spheres were charged into a 500ml three-necked flask, followed by addition of 90.39ml of Ethylene Glycol Dimethacrylate (EGDMA), 0.6g of ethyl 2-bromoisobutyrate (EBMP), 2.4g of 2, 2' -Bpy, and 1.2g of CuBr
21ml of ethylene glycol and the self-assembly solution in the step (2), introducing nitrogen to remove oxygen in the solution, reacting for 24 hours in a water bath at 60 ℃, and pouring out the solution to obtain a polymer;
(4) adding deionized water and 0.1mol/L EDTA aqueous solution into the polymer for washing, adding a mixed solution of methanol and hydrochloric acid (the volume ratio is 10:1, wherein the mass concentration of the hydrochloric acid is 36 percent) to remove template molecules;
(5) and (3) washing the polymer without the template molecules with 1 wt% of hydrochloric acid, distilled water, 3 wt% of NaOH and distilled water in sequence to be neutral, extracting with ethanol for 5 hours, taking out, putting into a 40 ℃ oven, and drying to constant weight to prepare the novel 4-HB imprinted resin MIP, namely the p-hydroxybenzoic acid selective resin.
Detection of p-hydroxybenzoic acid selective resin prepared by the above method gave an exchange capacity of 2.60mmol/g, an average pore size of 33.52nm, and a BET surface area of 27.96m
2G, pore volume 0.249cm
3And/g, placing the mixture in a mixed solution of p-hydroxybenzoic acid and p-phenol with the concentration of 5mmol/L, wherein the selective adsorption coefficient of the p-hydroxybenzoic acid reaches 5.02.
Example 3:
a preparation method of p-hydroxybenzoic acid selective resin comprises the following steps:
(1) washing 20g of chlorine balls to be neutral, then placing the chlorine balls in absolute ethyl alcohol, shaking and washing the chlorine balls in a shaking table for 8 hours, and finally placing the chlorine balls in an oven to be dried at 42 ℃;
(2) taking 13g of p-hydroxybenzoic acid, 139.44ml of diethylaminoethyl methacrylate (PDEAEMA) and 240ml of acetonitrile, uniformly mixing, reacting in a beaker at 35 ℃ for 120min, and carrying out a self-assembly process to obtain a self-assembly solution;
(3) the chlorine spheres were swollen in N, N-dimethylformamide for 10h, and then added to a 500ml three-necked flask, followed by Ethylene Glycol Dimethacrylate (EGDMA)298.46ml, 0.65g of ethyl 2-bromoisobutyrate (EBMP), 2g of 2, 2' -Bpy, 2g of CuBr
21.2ml of ethylene glycol and the self-assembly solution in the step (2), introducing nitrogen to remove oxygen in the solution, reacting for 26 hours in a water bath at 62 ℃, and pouring out the solution to obtain a polymer;
(4) adding deionized water and 0.1mol/L EDTA aqueous solution into the polymer, washing, adding a mixed solution of methanol and hydrochloric acid (the volume ratio is 8:1, wherein the mass concentration of the hydrochloric acid is 37 percent), and removing template molecules;
(5) and (3) washing the polymer without the template molecules with 3 wt% hydrochloric acid, distilled water, 3 wt% NaOH and distilled water in sequence to be neutral, extracting with ethanol for 5 hours, taking out, and drying in a 42 ℃ oven to constant weight to prepare the novel 4-HB imprinted resin MIP, namely the p-hydroxybenzoic acid selective resin.
Detection of p-hydroxybenzoic acid selective resin prepared by the above method gave an exchange capacity of 2.52mmol/g, an average pore size of 34.39nm, and a BET surface area of 27.61m
2Per g, pore volume 0.252cm
3(ii)/g; the solution is placed in a mixed solution of p-hydroxybenzoic acid and p-phenol with the concentration of 5mmol/L, and the selective adsorption coefficient of the p-hydroxybenzoic acid reaches 4.53.
Example 4:
a preparation method of p-hydroxybenzoic acid selective resin comprises the following steps:
(1) washing 20g of chlorine balls to be neutral, then placing the chlorine balls in absolute ethyl alcohol, washing the chlorine balls in a shaking table in a shaking way for 11 hours, and finally placing the chlorine balls in an oven to be dried at the temperature of 40 ℃;
(2) 14.368g of p-hydroxybenzoic acid, 92.60ml of diethylaminoethyl methacrylate (PDEAEMA) and 280ml of acetonitrile are taken, mixed uniformly and reacted in a beaker at 35 ℃ for 130min for self-assembly to obtain a self-assembly solution;
(3) the chlorine spheres were swollen in N, N-dimethylformamide for 11 hours, and then the chlorine spheres were charged into a 500ml three-necked flask, followed by addition of Ethylene Glycol Dimethacrylate (EGDMA)46.3ml, ethyl 2-bromoisobutyrate (EBMP) 0.8g, 2g of 2, 2' -Bpy, and CuBr 1.2g
21.5ml of ethylene glycol and the self-assembly solution in the step (2), introducing nitrogen to remove oxygen in the solution, reacting for 25 hours in a water bath at 63 ℃, and pouring out the solution to obtain a polymer;
(4) adding deionized water and 0.1mol/L EDTA aqueous solution into the polymer for washing, and adding a mixed solution of methanol and hydrochloric acid (the volume ratio is 11:1) to remove template molecules;
(5) and (3) washing the polymer without the template molecules with 2 wt% of hydrochloric acid, distilled water, 4 wt% of NaOH and distilled water in sequence to be neutral, extracting with ethanol for 5 hours, taking out, putting into a 43 ℃ oven, and drying to constant weight to prepare the novel 4-HB imprinted resin MIP, namely the p-hydroxybenzoic acid selective resin.
Detection of p-hydroxybenzoic acid selective resin prepared by the above method gave an exchange capacity of 2.41mmol/g, an average pore diameter of 35.94nm, and a BET surface area of 27.15m
2Per g, pore volume 0.264cm
3(ii)/g; the solution is placed in a mixed solution of p-hydroxybenzoic acid and p-phenol with the concentration of 5mmol/L, and the selective adsorption coefficient of the p-hydroxybenzoic acid reaches 3.78.
Example 5:
a preparation method of p-hydroxybenzoic acid selective resin comprises the following steps:
(1) washing 20g of chlorine balls to be neutral, then placing the chlorine balls in absolute ethyl alcohol, washing the chlorine balls in a shaking table in a shaking way for 12 hours, and finally placing the chlorine balls in an oven to be dried at the temperature of 45 ℃;
(2) taking 15g of p-hydroxybenzoic acid, 80.45ml of diethylaminoethyl methacrylate (PDEAEMA) and 300ml of acetonitrile, uniformly mixing, reacting in a beaker at 35 ℃ for 150min, and carrying out a self-assembly process to obtain a self-assembly solution;
(3) the chlorine spheres were swollen in N, N-dimethylformamide for 12 hours, and then the chlorine spheres were charged into a 500ml three-necked flask, followed by Ethylene Glycol Dimethacrylate (EGDMA)258.29ml, 1.0g of ethyl 2-bromoisobutyrate (EBMP), 3g of 2, 2' -Bpy, and 1.2g of CuBr
2Introducing 1.5ml of ethylene glycol and the self-assembly product in the step (2), introducing nitrogen to remove oxygen in the solution, reacting for 28 hours in water bath at 65 ℃, and pouring out the solution to obtain a polymer;
(4) adding deionized water and 0.1mol/L EDTA aqueous solution into the polymer for washing, and adding a mixed solution of methanol and hydrochloric acid (the volume ratio is 12:1) to remove template molecules;
(5) and (3) washing the polymer without the template molecules with 3 wt% hydrochloric acid, distilled water, 8 wt% NaOH and distilled water in sequence to be neutral, extracting with ethanol for 5 hours, taking out, and drying in a 44 ℃ oven to constant weight to prepare the novel 4-HB imprinted resin MIP, namely the p-hydroxybenzoic acid selective resin.
The p-hydroxybenzoic acid selective resin prepared by the method is detected to obtain the p-hydroxybenzoic acid selective resin with the exchange capacity of 2.26mmol/g, the average pore diameter of 35.94nm and the BET tableArea of 27.15m
2Per g, pore volume 0.264cm
3(ii)/g; the solution is placed in a mixed solution of p-hydroxybenzoic acid and p-phenol with the concentration of 5mmol/L, and the selective adsorption coefficient of the p-hydroxybenzoic acid reaches 2.96.
Claims (10)
1. A preparation method of p-hydroxybenzoic acid selective resin is characterized by comprising the following steps: the method comprises the following steps:
1) placing template molecules of p-hydroxybenzoic acid and a functional monomer of diethylaminoethyl methacrylate in an organic solvent of acetonitrile, uniformly mixing, and carrying out self-assembly to obtain a self-assembly solution;
2) adding a carrier, a cross-linking agent, an initiator, a catalyst and a reducing agent into the self-assembly solution for reaction to prepare a polymer;
3) and (2) washing the polymer prepared in the step 2) by using an eluent to remove template molecules, washing the material to be neutral by sequentially adopting 1-3 wt% hydrochloric acid solution, deionized water, 2-8 wt% sodium hydroxide solution and deionized water, extracting by using ethanol, and drying in an oven to constant weight to obtain the p-hydroxybenzoic acid selective resin.
2. The method for preparing a p-hydroxybenzoic acid selective resin according to claim 1, wherein: the mass of the template molecule p-hydroxybenzoic acid is 0.6-0.75 time of that of the carrier before swelling, the molar ratio of the p-hydroxybenzoic acid to the functional monomer diethyl aminoethyl methacrylate is 1: 4-1: 8, and the mass of the organic solvent acetonitrile is 8-12 times of that of the carrier before swelling.
3. The method for preparing a p-hydroxybenzoic acid selective resin according to claim 1, wherein: uniformly mixing the components in the step 1), and then carrying out self-assembly to obtain a self-assembly solution, wherein the temperature in the self-assembly process is 30-35 ℃, and the time duration is 120-150 min.
4. The method for preparing a p-hydroxybenzoic acid selective resin according to claim 1, wherein: and 2) washing the carrier in the step 2 to be neutral, then placing the carrier in absolute ethyl alcohol, oscillating and washing the carrier for 8 to 12 hours, then placing the carrier in an oven to be dried at the temperature of 40 to 45 ℃, and swelling the dried polystyrene chloride balls in N, N-dimethylformamide for 10 to 12 hours when the carrier is used.
5. The method for preparing a p-hydroxybenzoic acid selective resin according to claim 1, wherein: the cross-linking agent in the step 2) is ethylene glycol dimethacrylate, and the molar ratio of the functional monomer diethylaminoethyl methacrylate to the cross-linking agent ethylene glycol dimethacrylate is 1: 0.5-1: 3; the initiator is 2-bromoisobutyric acid ethyl ester, and the dosage of the initiator is 0.03-0.05 time of the mass of the carrier before swelling; the reducing agent in the step 2) is glycol, and the mass of the reducing agent is 0.05-0.085 times of the mass of the carrier before swelling.
6. The method for preparing a p-hydroxybenzoic acid selective resin according to claim 1, wherein: the catalyst in the step 2) is a mixture of 2,2 '-bipyridyl and copper bromide, wherein the dosage of the 2, 2' -bipyridyl is 0.09-0.15 times of the mass of the carrier before swelling, and the dosage of the copper bromide is 0.05-0.1 times of the mass of the carrier before swelling.
7. The method for preparing a p-hydroxybenzoic acid selective resin according to claim 1, wherein: adding the carrier, the cross-linking agent, the initiator catalyst and the reducing agent into the self-assembly solution for reaction in the step 2), namely adding the components into the self-assembly solution, introducing nitrogen to remove oxygen in the self-assembly solution, heating in a water bath at 60-65 ℃, and stirring for reaction for 24-28 hours to obtain the polymer.
8. The method for preparing a p-hydroxybenzoic acid selective resin according to claim 1, wherein: the eluent in the step 3) is methanol-concentrated hydrochloric acid solution, wherein the volume ratio of methanol to hydrochloric acid is 8: 1-12: 1, the mass concentration of concentrated hydrochloric acid is 36% -38%, the eluent in the step 3) is extracted by ethanol and then placed in an oven to be dried to constant weight, the ethanol extraction time is 5-6 h, and the temperature of the oven is 40-45 ℃.
9. The method for preparing a p-hydroxybenzoic acid selective resin according to claim 1, wherein: before the step of washing and removing the template molecules from the polymer prepared in the step 2) by using the eluent in the step 3), deionized water and 0.1mol/L EDTA aqueous solution are added to wash and remove copper bromide in the catalyst.
10. A p-hydroxybenzoic acid selective resin prepared according to any of the methods of claims 1 to 9, wherein: the p-hydroxybenzoic acid selective resin belongs to mesoporous resin, the average pore diameter of the p-hydroxybenzoic acid selective resin is 33.16-36.57 nm, and the BET surface area of the p-hydroxybenzoic acid selective resin is 26.91-28.22 m
2Per gram, pore volume 0.24-0.27 cm
3The exchange capacity is 2.26-2.65 mmol/g, and the adsorption equilibrium time is as short as 6.5 h.
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| CN114275966A (en) * | 2021-11-30 | 2022-04-05 | 浙江圣效化学品有限公司 | Recycling method of nipagin ester wastewater |
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| CN102585113A (en) * | 2012-03-01 | 2012-07-18 | 南开大学 | Preparation method and application of molecularly imprinted polymer for directionally protecting functional groups |
| CN104231303A (en) * | 2014-08-27 | 2014-12-24 | 江苏大学 | Preparation method and applications of molecular imprinting composite membrane |
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| CN102585113A (en) * | 2012-03-01 | 2012-07-18 | 南开大学 | Preparation method and application of molecularly imprinted polymer for directionally protecting functional groups |
| CN104231303A (en) * | 2014-08-27 | 2014-12-24 | 江苏大学 | Preparation method and applications of molecular imprinting composite membrane |
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| BAGGIANI, C.等: "Molecularly imprinted solid-phase extraction method for the high-performance liquid chromatographicanalysis of fungicide pyrimethanil in wine", 《JOURNAL OF CHROMATOGRAPHY A》 * |
| HU, LUCY YUE等: "Molecular Imprinting by 4-Hydroxybenzoic Acid: A Two-Site Model", 《SEPARATION SCIENCE AND TECHNOLOGY 》 * |
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| CN114275966A (en) * | 2021-11-30 | 2022-04-05 | 浙江圣效化学品有限公司 | Recycling method of nipagin ester wastewater |
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