CN111440354A - Preparation method and application of bisphenol A molecularly imprinted composite membrane with through hierarchical pore structure - Google Patents
Preparation method and application of bisphenol A molecularly imprinted composite membrane with through hierarchical pore structure Download PDFInfo
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- CN111440354A CN111440354A CN202010227273.5A CN202010227273A CN111440354A CN 111440354 A CN111440354 A CN 111440354A CN 202010227273 A CN202010227273 A CN 202010227273A CN 111440354 A CN111440354 A CN 111440354A
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- bisphenol
- pore structure
- hierarchical pore
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- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 title claims abstract description 162
- 239000012528 membrane Substances 0.000 title claims abstract description 113
- 239000002149 hierarchical pore Substances 0.000 title claims abstract description 98
- 239000002131 composite material Substances 0.000 title claims abstract description 70
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 30
- 238000000926 separation method Methods 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 16
- 239000011780 sodium chloride Substances 0.000 claims abstract description 15
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims abstract description 11
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000002033 PVDF binder Substances 0.000 claims abstract description 9
- 239000013078 crystal Substances 0.000 claims abstract description 9
- 239000002245 particle Substances 0.000 claims abstract description 9
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 9
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims abstract description 9
- JOBBTVPTPXRUBP-UHFFFAOYSA-N [3-(3-sulfanylpropanoyloxy)-2,2-bis(3-sulfanylpropanoyloxymethyl)propyl] 3-sulfanylpropanoate Chemical compound SCCC(=O)OCC(COC(=O)CCS)(COC(=O)CCS)COC(=O)CCS JOBBTVPTPXRUBP-UHFFFAOYSA-N 0.000 claims abstract description 4
- 210000004379 membrane Anatomy 0.000 claims description 108
- 239000000203 mixture Substances 0.000 claims description 44
- 239000011259 mixed solution Substances 0.000 claims description 37
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 36
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 30
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 24
- 238000010438 heat treatment Methods 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 15
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 15
- 229920002554 vinyl polymer Polymers 0.000 claims description 15
- 239000000243 solution Substances 0.000 claims description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- 238000010992 reflux Methods 0.000 claims description 9
- KWVGIHKZDCUPEU-UHFFFAOYSA-N 2,2-dimethoxy-2-phenylacetophenone Chemical compound C=1C=CC=CC=1C(OC)(OC)C(=O)C1=CC=CC=C1 KWVGIHKZDCUPEU-UHFFFAOYSA-N 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 8
- 239000003480 eluent Substances 0.000 claims description 7
- 238000004140 cleaning Methods 0.000 claims description 6
- 238000007789 sealing Methods 0.000 claims description 6
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 210000002469 basement membrane Anatomy 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 238000007599 discharging Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- -1 tetra (3-mercaptopropionic acid) pentaerythritol ester Chemical class 0.000 claims description 5
- 239000011148 porous material Substances 0.000 claims description 3
- 238000002791 soaking Methods 0.000 claims description 2
- 238000001179 sorption measurement Methods 0.000 abstract description 47
- 239000000463 material Substances 0.000 abstract description 13
- 230000004907 flux Effects 0.000 abstract description 7
- 239000003431 cross linking reagent Substances 0.000 abstract description 4
- 230000007547 defect Effects 0.000 abstract description 4
- 239000004088 foaming agent Substances 0.000 abstract description 2
- 239000000178 monomer Substances 0.000 abstract description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- 230000000149 penetrating effect Effects 0.000 description 12
- 239000012466 permeate Substances 0.000 description 9
- 238000002474 experimental method Methods 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 238000004090 dissolution Methods 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 230000001678 irradiating effect Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 230000035699 permeability Effects 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000011550 stock solution Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000010170 biological method Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010828 elution Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
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- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VCCBEIPGXKNHFW-UHFFFAOYSA-N biphenyl-4,4'-diol Chemical group C1=CC(O)=CC=C1C1=CC=C(O)C=C1 VCCBEIPGXKNHFW-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000005371 permeation separation Methods 0.000 description 1
- 238000011197 physicochemical method Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
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- 238000005070 sampling Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
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- 210000002700 urine Anatomy 0.000 description 1
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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
- C08J9/36—After-treatment
- C08J9/40—Impregnation
- C08J9/405—Impregnation with polymerisable compounds
-
- 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
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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
-
- 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
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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
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
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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
- C08F220/04—Acids; Metal salts or ammonium salts thereof
- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
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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
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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
- C08J2201/00—Foams characterised by the foaming process
- C08J2201/04—Foams characterised by the foaming process characterised by the elimination of a liquid or solid component, e.g. precipitation, leaching out, evaporation
- C08J2201/042—Elimination of an organic solid phase
- C08J2201/0422—Elimination of an organic solid phase containing oxygen atoms, e.g. saccharose
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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
- C08J2201/00—Foams characterised by the foaming process
- C08J2201/04—Foams characterised by the foaming process characterised by the elimination of a liquid or solid component, e.g. precipitation, leaching out, evaporation
- C08J2201/044—Elimination of an inorganic solid phase
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- C08J2201/0446—Elimination of NaCl only
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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
- C08J2327/00—Characterised by the use of homopolymers or 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 halogen; Derivatives of such polymers
- C08J2327/02—Characterised by the use of homopolymers or 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 halogen; Derivatives of such polymers not modified by chemical after-treatment
- C08J2327/12—Characterised by the use of homopolymers or 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 halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C08J2327/16—Homopolymers or copolymers of vinylidene fluoride
Abstract
The invention belongs to the technical field of functional material preparation, and particularly relates to a preparation method and application of a through hierarchical pore structure bisphenol A molecularly imprinted composite membrane; the preparation steps are as follows: the preparation method comprises the steps of taking polyvinylidene fluoride as a film preparation material, sodium chloride crystal particles as a pore-foaming agent, bisphenol A as template molecules, methacrylic acid as a functional monomer, pentaerythritol tetra (3-mercaptopropionate) as a cross-linking agent, dipentaerythritol penta-/hexa-acrylic acid as an auxiliary cross-linking agent, combining a sacrificial template film preparation process, and preparing the bisphenol A molecularly imprinted composite film with the through hierarchical pore structure based on a 'click chemistry' polymerization method; the bisphenol A molecularly imprinted composite membrane with the through hierarchical pore structure effectively overcomes the defect that the flux, the adsorption capacity and the selectivity of the conventional molecularly imprinted membrane are difficult to balance; in addition, the prepared membrane material has good specific recognition and separation capability on bisphenol A.
Description
Technical Field
The invention belongs to the technical field of functional material preparation, and particularly relates to a preparation method and application of a through hierarchical pore structure bisphenol A molecularly imprinted composite membrane.
Background
Bisphenol A, as a raw material of a large number of chemicals, is widely applied to the production of polycarbonate plastics, epoxy resin, water pipes, toys, medical equipment, electronic products and other consumer goods. With the progress of science and the progress of research, the danger of bisphenol A has been recognized. However, due to the wide use of bisphenol A in the past life and production, bisphenol A is widely present in environmental water worldwide, and even more than 90% of people can detect the presence of bisphenol A in urine. At present, methods for removing BPA in environmental water mainly comprise biological methods, advanced oxidation methods, physical and chemical methods, membrane separation methods and the like. Although the biodegradability of bisphenol a based on biological methods has been widely proven, its degradation period is long; the physicochemical method and the advanced oxidation method have a good removal effect, but have harsh application conditions, and also limit the application. In contrast, the membrane separation method has the advantages of low energy consumption, simple and convenient operation, high efficiency, changeable treatment scale, continuous process application and the like.
In the development process of over 200 years, the membrane separation technology has attracted extensive attention in the fields of separation, purification, water treatment, resource recovery and the like by virtue of the characteristics of low energy consumption, high efficiency, easy operation and the like. Considering that the water body contains a large amount of good carbon sources which need to be reserved, and the concentration of the bisphenol A is often low, the single selective separation of the bisphenol A in the water is the key for realizing the effective removal of the bisphenol A based on the membrane separation technology. In this context, the appearance of molecularly imprinted membranes has positively contributed to the solution of this problem. The molecular engram membrane is a novel selective recognition and separation material developed based on a membrane separation technology and a molecular engram technology, and the membrane material has the selective recognition and adsorption capacity on specific molecules by synthesizing molecular selective recognition sites on the surface of the membrane and the inner surface of pores, so that the permeation of the molecules is slowed down by utilizing the function, and the purpose of selectively separating the specific molecules is achieved.
For membrane-based separation materials, the higher the membrane flux, the larger the required membrane pore size, and the smaller the corresponding specific surface area of the membrane material, so that the number of imprinted recognition sites that can be formed on the membrane is small, which will result in the low adsorption capacity of the obtained molecularly imprinted membrane on target molecules, thereby indirectly affecting the overall selectivity of the molecularly imprinted membrane. Therefore, the balance between flux, adsorption capacity and selectivity is always the biggest challenge facing molecularly imprinted membranes. It has been reported that an interpenetrating hierarchical pore structure can balance membrane flux and specific surface area. Based on the above, the construction of the molecularly imprinted membrane with a through hierarchical pore structure is expected to solve the above-mentioned contradiction.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to overcome the technical defects in the prior art, solve the problem that the flux, the adsorption capacity and the selectivity of the traditional molecularly imprinted membrane are difficult to balance, ensure that the molecularly imprinted membrane has high selectivity and high adsorption capacity on target molecules (bisphenol A), and greatly improve the permeation flux of the molecularly imprinted membrane.
The present invention achieves the above-described object by the following technical means.
A preparation method of a bisphenol A molecularly imprinted composite membrane with a through hierarchical pore structure comprises the following steps:
s1, preparing a through hierarchical pore structure base film: uniformly mixing polyvinylidene fluoride powder and sodium chloride crystal particles, placing the mixture in a film forming container, heating the mixture for a period of time to melt the mixture, cooling the mixture, taking out the formed mixture from the container, soaking and cleaning the mixture in water at a certain temperature, replacing the water solution for multiple times, taking out the formed mixture, and drying the formed mixture to obtain a through hierarchical pore structure base film;
s2, preparing a through hierarchical pore structure vinyl modified membrane: preparing a mixed solution of ethanol and water, adding the penetrating hierarchical pore structure basement membrane prepared in S1, immersing a certain amount of 3- (methacryloyloxy) propyl trimethoxy silane, heating and refluxing the mixture, cleaning with ethanol, and drying to obtain a penetrating hierarchical pore structure vinyl modified membrane;
s3, penetrating the bisphenol A molecularly imprinted composite membrane with the hierarchical pore structure: firstly dissolving bisphenol A and methacrylic acid in acetonitrile, stirring for a period of time to obtain a prepolymerization system, adding dipentaerythritol penta-/hexa-acrylic acid, tetra (3-mercaptopropionic acid) pentaerythritol ester and 2, 2-dimethoxy-2-phenylacetophenone to obtain a mixed solution, finally immersing the through hierarchical pore structure vinyl modified membrane prepared in S2 into the mixed solution, discharging oxygen by using nitrogen, sealing, carrying out imprinting polymerization reaction under ultraviolet irradiation, washing with alcohol and water, eluting template molecules by using an eluent, and drying to obtain the through hierarchical pore structure bisphenol A molecularly imprinted composite membrane.
Preferably, in step S1, the usage ratio of the polyvinylidene fluoride powder to the sodium chloride crystal particles is 1-4 g: 8 g.
Preferably, in step S1, the heating time is 0.5-2h, and the heating temperature is 200 ℃.
Preferably, in step S1, the certain temperature is 90 ℃; the water solution is replaced for 3-5 times.
Preferably, in step S2, the volume ratio of ethanol, water and 3- (methacryloyloxy) propyltrimethoxysilane in the mixed solution is 80: 20: 3.
preferably, in step S2, the heating reflux temperature is 80 ℃; the heating reflux time is 9-27 h.
Preferably, in step S3, the usage ratio of the bisphenol A, the methacrylic acid and the acetonitrile is 0.5-1.5 mmol: 2 mmol: 60m L.
Preferably, in step S3, the ratio of the methacrylic acid, dipentaerythritol penta-/hexa-acrylic acid, pentaerythritol tetrakis (3-mercaptopropionate), and 2, 2-dimethoxy-2-phenylacetophenone is 2 mmol: 1 mmol: 2 mmol: 10-30 mg.
Preferably, in step S3, the wavelength of the ultraviolet light is 365 nm; the time of the imprinting polymerization reaction is 1-4 h.
Preferably, in step S3, the sealing method is to seal with a vacuum plug, a degreasing tape and a preservative film; the eluent is a mixed solution of methanol and acetic acid, and the volume ratio of the methanol to the acetic acid is 95: 5; the elution mode is that the shaking is carried out at room temperature, the eluent is changed every 12 hours, and the elution process lasts for 3 days.
The polyvinylidene fluoride powder in the technical scheme is used as a film making material.
The sodium chloride crystal particles in the technical scheme are used as pore-foaming agents.
The 3- (methacryloyloxy) propyl trimethoxysilane in the technical scheme is used as a film surface vinyl modification reagent.
The ethanol in the technical scheme is used as a solvent.
The bisphenol A in the technical scheme is used as a template molecule.
The methacrylic acid in the technical scheme is used as a functional monomer.
The acetonitrile in the technical scheme is used as a solvent.
The pentaerythritol tetrakis (3-mercaptopropionate) described in the above technical scheme acts as a cross-linking agent.
The dipentaerythritol penta-/hexa-acrylic acid in the technical scheme is used as an auxiliary crosslinking agent.
The 2, 2-dimethoxy-2-phenylacetophenone in the technical scheme has the function of a photoinitiator.
The invention also comprises the application of the through hierarchical pore structure bisphenol A molecular imprinting composite membrane in the selective adsorption and separation of bisphenol A in a bisphenol A mixed solution, in particular to the selective adsorption and separation of bisphenol A in a mixed solution of bisphenol A, 4' -dihydroxybiphenyl and hydroquinone.
And (3) testing the material performance:
(1) isothermal adsorption experiment
Weighing 8 parts of bisphenol A molecular imprinting composite membrane with a through hierarchical pore structure, respectively placing the composite membrane into test tubes, respectively adding 10m of mixed solution of bisphenol A, 4 '-dihydroxybiphenyl and hydroquinone with the concentration of L being 5, 10, 25, 50, 75, 100, 150 and 200 mg/L, standing and adsorbing for 3 hours at room temperature, measuring the concentration of the unadsorbed bisphenol A, 4' -dihydroxybiphenyl and hydroquinone in the solution by a high performance liquid chromatograph after adsorption is finished, and calculating the adsorption capacity (Q) according to the resulte，mg/g)：
Qe＝(C0-Ce)×V/m (1)
Wherein C is0(mg/L) and Ce(mg/L) is the concentration of the same molecule in the solution before and after adsorption, V (m L) is the volume of the adsorption solution, and m (g) is the mass of the bisphenol A molecularly imprinted composite membrane with the through hierarchical pore structure.
(2) Dynamic adsorption experiment
Respectively weighing 8 parts of bisphenol A molecular imprinting composite membrane with a through hierarchical pore structure, putting the composite membrane into a test tube, respectively adding 10m of mixed solution of L bisphenol A, 4 '-dihydroxybiphenyl and hydroquinone with the concentration of 75 mg/L, standing and adsorbing for 5, 10, 15, 30, 60, 90, 120 and 180min at room temperature, measuring the concentration of the unadsorbed bisphenol A, 4' -dihydroxybiphenyl and hydroquinone in the solution by a high performance liquid chromatograph after adsorption is finished, and calculating the adsorption capacity (Q) according to the resultt，mg/g)：
Qt＝(C0-Ct)×V/m (2)
Wherein C is0(mg/L) and Ct(mg/L) is the concentration of the same molecule in the solution before and after adsorption, V (m L) is the volume of the adsorption solution, and m (g) is the mass of the bisphenol A molecularly imprinted composite membrane with the through hierarchical pore structure.
(3) Permselectivity experiments
The prepared through hierarchical pore structure bisphenol A molecularly imprinted composite membrane is placed in the center of an H-shaped permeation device, so that an H-shaped glass tube is divided into two identical cavities by the prepared through hierarchical pore structure bisphenol A molecularly imprinted composite membrane, a 100m L mixed solution of bisphenol A, 4 '-dihydroxybiphenyl and hydroquinone with the concentration of 75 mg/L is added into one cavity, a 100m L pure solvent is added into the other cavity, 2m L solution (permeation solution) is taken from the pure solvent cavity and is backfilled with 2m 2 pure solvent at 5 min, 10 min, 15 min, 30 min, 60 min, 90 min, 120 min, 180min, 360 min and 720min, so that no height difference exists between the two cavities, and the concentrations of bisphenol A, 4' -dihydroxybiphenyl and hydroquinone in the sampling permeation solution are measured by a high performance liquid chromatograph 539.
The invention has the advantages and technical effects that:
(1) compared with the existing bisphenol A selective separation material, the through hierarchical pore structure bisphenol A molecularly imprinted composite membrane prepared by the invention has the advantages that the material is easy to recover, the phase change is not needed in the separation process, no reagent is additionally added, no secondary pollution is caused to the separated substances, the membrane can be applied to the continuous separation process, and the like, and the defects of difficult recovery, easy generation of secondary pollution, high energy consumption and the like of the existing bisphenol A selective separation material are effectively overcome; in addition, the through hierarchical pore structure bisphenol A molecularly imprinted composite membrane prepared by the invention has higher selectivity on bisphenol A, and can effectively separate bisphenol A molecules from bisphenol A structural analogues such as 4, 4' -dihydroxybiphenyl, hydroquinone and the like.
(2) Compared with the existing molecularly imprinted membrane, the invention prepares and synthesizes the efficient and stable bisphenol A molecularly imprinted composite membrane with the through hierarchical pore structure by taking the porous membrane with the through hierarchical pore structure as a substrate and combining the imprinted polymerization technology; the prepared bisphenol A molecularly imprinted composite membrane with the through hierarchical pore structure has the advantages of high selectivity, strong stability and stable regeneration performance, so that the selective separation efficiency of the bisphenol A in a complex mixed system is greatly improved; in addition, due to the design of the through hierarchical pore structure, the prepared through hierarchical pore structure bisphenol A molecularly imprinted composite membrane can ideally balance the contradiction among flux, adsorption capacity and selectivity, and greatly improves the permeation separation efficiency while ensuring high selectivity and high adsorption capacity.
Drawings
FIG. 1 is a schematic flow chart of the experimental procedure of the present invention.
In fig. 2, a, b and c are respectively an isothermal adsorption curve, a kinetic adsorption curve and a permeate concentration curve of the through hierarchical pore structure bisphenol a molecularly imprinted composite membrane in example 1.
In fig. 3, a, b and c are respectively an isothermal adsorption curve, a kinetic adsorption curve and a permeate concentration curve of the through hierarchical pore structure bisphenol a molecularly imprinted composite membrane in example 2.
In fig. 4, a, b and c are respectively an isothermal adsorption curve, a kinetic adsorption curve and a permeate concentration curve of the through hierarchical pore structure bisphenol a molecularly imprinted composite membrane in example 3.
Detailed Description
The invention is further described with reference to the drawings and the detailed description.
Example 1:
s1, preparing a through hierarchical pore structure base film: uniformly mixing 1g of polyvinylidene fluoride powder and 8g of sodium chloride crystal particles, placing the mixture in a film forming container, heating the mixture for 0.5h at 200 ℃ to melt the mixture, cooling the mixture, taking out the shaped mixture from the container, placing the mixture in water at 90 ℃ to dissolve sodium chloride, changing water for many times to ensure complete dissolution of sodium chloride, and drying to obtain a through hierarchical pore structure basement membrane;
s2, preparing a through hierarchical pore structure vinyl modified membrane, namely preparing a mixed solution from 80m L ethanol and 20m L water, adding the through hierarchical pore structure base membrane prepared in S1, adding 3m L3- (methacryloyloxy) propyl trimethoxy silane, heating and refluxing the mixture at 80 ℃ for 9 hours, and cleaning and drying the mixture by using ethanol to obtain the through hierarchical pore structure vinyl modified membrane;
s3, dissolving 0.5mmol of bisphenol A and 2mmol of methacrylic acid in 60m L acetonitrile, stirring for a period of time to obtain a prepolymerization system, adding 1mmol of dipentaerythritol penta-/hexan-acrylic acid, 2mmol of tetra (3-mercaptopropionic acid) pentaerythritol ester and 10mg of 2, 2-dimethoxy-2-phenylacetophenone to obtain a mixed solution, immersing the penetrating hierarchical pore structure vinyl modified membrane prepared in S2 in the mixed solution, discharging oxygen by using nitrogen, sealing, irradiating for 1h by using ultraviolet light with the wavelength of 365nm for carrying out imprinting polymerization reaction, washing with alcohol, washing with water, eluting template molecules by using an eluent (a mixed solution of methanol and acetic acid with the volume ratio of 95: 5), and drying to obtain the penetrating hierarchical pore structure bisphenol A molecularly imprinted composite membrane.
Fig. 2(a) is an isothermal adsorption curve of the prepared through hierarchical pore structure bisphenol a molecularly imprinted composite membrane, and the adsorption amounts of the prepared through hierarchical pore structure bisphenol a molecularly imprinted composite membrane to bisphenol a, 4' -dihydroxybiphenyl and hydroquinone in a mixed solution with concentrations of 5, 10, 25, 50, 75, 100, 150 and 200 mg/L for 3 hours are shown in table 1 (a).
TABLE 1(a) isothermal adsorption data for bisphenol A molecularly imprinted composite membrane with through hierarchical pore structure
Fig. 2(b) is a kinetic adsorption curve of the prepared through hierarchical pore structure bisphenol a molecularly imprinted composite membrane, and the adsorption amounts of the prepared through hierarchical pore structure bisphenol a molecularly imprinted composite membrane to bisphenol a, 4' -dihydroxybiphenyl and hydroquinone in a mixed solution with a concentration of 75 mg/L at 5 min, 10 min, 15 min, 30 min, 60 min, 90 min, 120 min and 180min are shown in table 1 (b).
TABLE 1(b) dynamic adsorption data of bisphenol A molecularly imprinted composite membrane with through hierarchical pore structure
Fig. 2(c) is a concentration curve of a permeate obtained by the prepared through hierarchical pore structure bisphenol a molecularly imprinted composite membrane in a selective permeation experiment, a mixed solution with a concentration of 75 mg/L is used as a stock solution, the prepared through hierarchical pore structure bisphenol a molecularly imprinted composite membrane is used as a permeation medium, and the concentrations of bisphenol a, 4' -dihydroxybiphenyl and hydroquinone in the permeate are shown in table 1(c) at 5 min, 10 min, 15 min, 30 min, 60 min, 90 min, 120 min, 180min, 360 min and 720 min.
TABLE 1(c) Permeability data of bisphenol A molecularly imprinted composite membrane with through hierarchical pore structure
Example 2:
s1, preparing a through hierarchical pore structure base film: uniformly mixing 2g of polyvinylidene fluoride powder and 8g of sodium chloride crystal particles, placing the mixture in a film forming container, heating the mixture for 1 hour at 200 ℃ to melt the mixture, cooling the mixture, taking out the shaped mixture from the container, placing the mixture in water at 90 ℃ to dissolve sodium chloride, changing water for many times to ensure complete dissolution of sodium chloride, and drying the mixture to obtain a through hierarchical pore structure basement membrane;
s2, preparing a through hierarchical pore structure vinyl modified membrane, namely preparing a mixed solution from 80m L ethanol and 20m L water, adding the through hierarchical pore structure base membrane prepared in S1, adding 3m L3- (methacryloyloxy) propyl trimethoxy silane, heating and refluxing the mixture at 80 ℃ for 18 hours, and cleaning and drying the mixture by using ethanol to obtain the through hierarchical pore structure vinyl modified membrane;
s3, dissolving 1mmol of bisphenol A and 2mmol of methacrylic acid in 60m L acetonitrile, stirring for a period of time to obtain a prepolymerization system, adding 1mmol of dipentaerythritol penta-/hexan-acrylic acid, 2mmol of tetra (3-mercaptopropionic acid) pentaerythritol ester and 20mg of 2, 2-dimethoxy-2-phenylacetophenone to obtain a mixed solution, immersing the penetrating hierarchical pore structure vinyl modified membrane prepared in S2 in the mixed solution, discharging oxygen by using nitrogen, sealing, irradiating for 1h by using ultraviolet light with the wavelength of 365nm for carrying out imprinting polymerization reaction, washing with alcohol, washing with water, eluting the template molecules by using an eluent (a mixed solution of methanol and acetic acid with the volume ratio of 95: 5), and drying to obtain the hierarchical pore structure bisphenol A molecularly imprinted composite membrane.
Fig. 3(a) is an isothermal adsorption curve of the prepared through hierarchical pore structure bisphenol a molecularly imprinted composite membrane, and the adsorption amounts of the prepared through hierarchical pore structure bisphenol a molecularly imprinted composite membrane to bisphenol a, 4' -dihydroxybiphenyl and hydroquinone in a mixed solution with concentrations of 5, 10, 25, 50, 75, 100, 150 and 200 mg/L for 3 hours are shown in table 2 (a).
TABLE 2(a) isothermal adsorption data for bisphenol A molecularly imprinted composite membrane with through hierarchical pore structure
Fig. 3(b) is a kinetic adsorption curve of the prepared through hierarchical pore structure bisphenol a molecularly imprinted composite membrane, and the adsorption amounts of the prepared through hierarchical pore structure bisphenol a molecularly imprinted composite membrane to bisphenol a, 4' -dihydroxybiphenyl and hydroquinone in a mixed solution with a concentration of 75 mg/L at 5 min, 10 min, 15 min, 30 min, 60 min, 90 min, 120 min and 180min are shown in table 2 (b).
TABLE 2(b) dynamic adsorption data of bisphenol A molecularly imprinted composite membrane with through hierarchical pore structure
Fig. 3(c) is a concentration curve of a permeate obtained by the prepared penetrating hierarchical pore structure bisphenol a molecularly imprinted composite membrane in a selective permeation experiment, a mixed solution with a concentration of 75 mg/L is used as a stock solution, the prepared penetrating hierarchical pore structure bisphenol a molecularly imprinted composite membrane is used as a permeation medium, and the concentrations of bisphenol a, 4' -dihydroxybiphenyl and hydroquinone in the permeate are shown in table 2(c) at 5 min, 10 min, 15 min, 30 min, 60 min, 90 min, 120 min, 180min, 360 min and 720 min.
TABLE 2(c) Permeability data of bisphenol A molecularly imprinted composite membrane with through hierarchical pore structure
Example 3:
s1, preparing a through hierarchical pore structure base film: uniformly mixing 4g of polyvinylidene fluoride powder and 8g of sodium chloride crystal particles, placing the mixture in a film forming container, heating the mixture for 2 hours at 200 ℃ to melt the mixture, cooling the mixture, taking out the shaped mixture from the container, placing the mixture in water at 90 ℃ to dissolve sodium chloride, changing water for many times to ensure complete dissolution of sodium chloride, and drying the mixture to obtain a through hierarchical pore structure basement membrane;
s2, preparing a through hierarchical pore structure vinyl modified membrane, namely preparing a mixed solution from 80m L ethanol and 20m L water, adding the through hierarchical pore structure base membrane prepared in S1, adding 3m L3- (methacryloyloxy) propyl trimethoxy silane, heating and refluxing the mixture at 80 ℃ for 27 hours, and cleaning and drying the mixture with ethanol to obtain the through hierarchical pore structure vinyl modified membrane;
s3, dissolving 1.5mmol of bisphenol A and 2mmol of methacrylic acid in 60m L acetonitrile, stirring for a period of time to obtain a prepolymerization system, adding 1mmol of dipentaerythritol penta-/hexan-acrylic acid, 2mmol of tetra (3-mercaptopropionic acid) pentaerythritol ester and 30mg of 2, 2-dimethoxy-2-phenylacetophenone to obtain a mixed solution, immersing the penetrating hierarchical pore structure vinyl modified membrane prepared in S2 in the mixed solution, discharging oxygen by using nitrogen, sealing, irradiating for 1h by using ultraviolet light with the wavelength of 365nm for carrying out imprinting polymerization reaction, washing with alcohol, washing with water, eluting template molecules by using an eluent (a mixed solution of methanol and acetic acid with the volume ratio of 95: 5), and drying to obtain the penetrating hierarchical pore structure bisphenol A molecularly imprinted composite membrane.
Fig. 4 (a) is an isothermal adsorption curve of the prepared through hierarchical pore structure bisphenol a molecularly imprinted composite membrane, and the adsorption amounts of the prepared through hierarchical pore structure bisphenol a molecularly imprinted composite membrane to bisphenol a, 4' -dihydroxybiphenyl and hydroquinone in a mixed solution with concentrations of 5, 10, 25, 50, 75, 100, 150 and 200 mg/L for 3 hours are shown in table 3 (a).
TABLE 3(a) isothermal adsorption data for bisphenol A molecularly imprinted composite membrane with through hierarchical pore structure
Fig. 4 (b) is a kinetic adsorption curve of the prepared through hierarchical pore structure bisphenol a molecularly imprinted composite membrane, and the adsorption amounts of the prepared through hierarchical pore structure bisphenol a molecularly imprinted composite membrane to bisphenol a, 4' -dihydroxybiphenyl and hydroquinone in a mixed solution with a concentration of 75 mg/L at 5 min, 10 min, 15 min, 30 min, 60 min, 90 min, 120 min and 180min are shown in table 3 (b).
TABLE 3(b) dynamic adsorption data of bisphenol A molecularly imprinted composite membrane with through hierarchical pore structure
Fig. 4 (c) is a concentration curve of a permeate obtained by the prepared penetrating hierarchical pore structure bisphenol a molecularly imprinted composite membrane in a selective permeation experiment, a mixed solution with a concentration of 75 mg/L is used as a stock solution, the prepared penetrating hierarchical pore structure bisphenol a molecularly imprinted composite membrane is used as a permeation medium, and the concentrations of bisphenol a, 4' -dihydroxybiphenyl and hydroquinone in the permeate are shown in table 3(c) at 5 min, 10 min, 15 min, 30 min, 60 min, 90 min, 120 min, 180min, 360 min and 720 min.
TABLE 3(c) Permeability data of bisphenol A molecularly imprinted composite membrane with through hierarchical pore structure
As can be seen from the isothermal adsorption curve and the kinetic adsorption curve of the penetrated hierarchical pore structure bisphenol a molecularly imprinted composite membrane for bisphenol a in fig. 2 to 4, the penetrated hierarchical pore structure bisphenol a molecularly imprinted composite membrane prepared by the present invention has high adsorption selectivity for bisphenol a in the mixed solution of bisphenol a and structural analogues thereof, and can realize effective separation of bisphenol a from analogues in the permeation process.
Description of the drawings: the above embodiments are only used to illustrate the present invention and do not limit the technical solutions described in the present invention; thus, while the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted; all such modifications and variations are intended to be included herein within the scope of this disclosure and the present invention and protected by the following claims.
Claims (10)
1. A preparation method of a bisphenol A molecularly imprinted composite membrane with a through hierarchical pore structure is characterized by comprising the following steps:
s1, uniformly mixing polyvinylidene fluoride powder and sodium chloride crystal particles, placing the mixture in a film forming container, heating the mixture for a period of time to melt the mixture, cooling the mixture, taking out the shaped mixture from the container, placing the mixture in water at a certain temperature for soaking and cleaning, replacing the water solution for multiple times, taking out the shaped mixture, and drying the mixture to obtain a through multistage pore structure base film;
s2, preparing a mixed solution of ethanol and water, then immersing the mixed solution into the through hierarchical pore structure basement membrane prepared in S1, adding a certain amount of 3- (methacryloyloxy) propyl trimethoxy silane, then heating and refluxing, and then washing and drying the mixture by using ethanol to obtain the through hierarchical pore structure vinyl modified membrane;
s3, firstly dissolving bisphenol A and methacrylic acid in acetonitrile, stirring for a period of time to obtain a prepolymerization system, then adding dipentaerythritol penta-/hexa-acrylic acid, tetra (3-mercaptopropionic acid) pentaerythritol ester and 2, 2-dimethoxy-2-phenylacetophenone to obtain a mixed solution, finally immersing the through hierarchical pore structure vinyl modified membrane prepared in S2 in the mixed solution, discharging oxygen by using nitrogen, sealing, carrying out imprinting polymerization reaction under ultraviolet irradiation, eluting template molecules by using an eluent after alcohol washing and water washing, and drying to obtain the through hierarchical pore structure bisphenol A molecularly imprinted composite membrane.
2. The preparation method of the bisphenol A molecularly imprinted composite membrane with the through hierarchical pore structure according to claim 1, wherein the mass ratio of the polyvinylidene fluoride powder to the sodium chloride crystal particles in step S1 is 1-4: 8.
3. the method for preparing the bisphenol A molecularly imprinted composite membrane with the through hierarchical pore structure according to claim 1, wherein the heating time in the step S1 is 0.5-2h, and the heating temperature is 200 ℃.
4. The method for preparing the bisphenol A molecularly imprinted composite membrane with the through hierarchical pore structure according to claim 1, wherein the water temperature in step S1 is 90 ℃.
5. The method for preparing the bisphenol A molecularly imprinted composite membrane with the through hierarchical pore structure according to claim 1, wherein the volume ratio of the ethanol to the water to the 3- (methacryloyloxy) propyl trimethoxysilane in step S2 is 80: 20: 3.
6. the method for preparing the bisphenol A molecularly imprinted composite membrane with the through hierarchical pore structure according to claim 1, wherein the heating reflux temperature in the step S2 is 80 ℃; the heating reflux time is 9-27 h.
7. The method for preparing the bisphenol A molecularly imprinted composite membrane with the through hierarchical pore structure according to claim 1, wherein the dosage ratio of the bisphenol A, the methacrylic acid and the acetonitrile in the step S3 is 0.5-1.5 mmol: 2 mmol: 60m L.
8. The method for preparing the bisphenol A molecularly imprinted composite membrane with the through hierarchical pore structure according to claim 1, wherein the ratio of the methacrylic acid, the dipentaerythritol penta-/hexa-acrylic acid, the pentaerythritol tetrakis (3-mercaptopropionate), and the 2, 2-dimethoxy-2-phenylacetophenone in step S3 is 2 mmol: 1 mmol: 2 mmol: 10-30 mg.
9. The method for preparing the bisphenol A molecularly imprinted composite membrane with the through hierarchical pore structure according to claim 1, wherein in step S3, the wavelength of the ultraviolet light is 365 nm; the time of the imprinting polymerization reaction is 1-4 h.
10. The molecularly imprinted composite membrane prepared by the preparation method of the bisphenol A molecularly imprinted composite membrane with the through hierarchical pore structure according to any one of claims 1 to 9 is applied to selective recognition and separation of bisphenol A in a mixed solution of bisphenol A, 4' -dihydroxybiphenyl and hydroquinone.
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| CN113398887A (en) * | 2021-06-29 | 2021-09-17 | 江苏大学 | Three-dimensional towel gourd-shaped flexible tandem type selective adsorption filler and preparation method and application thereof |
| CN115282640A (en) * | 2022-07-05 | 2022-11-04 | 河北大学 | Molecularly imprinted solid-phase microextraction fiber coating and preparation method and application thereof |
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| CN110193290A (en) * | 2019-05-30 | 2019-09-03 | 江苏大学 | A kind of preparation method and application based on click chemistry trace lincomycin molecular compound film |
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| CN109772178A (en) * | 2018-12-17 | 2019-05-21 | 江苏大学 | A kind of preparation method and application of the pyrimethamine molecularly imprinted composite membrane based on the two-sided load of click chemistry |
| CN110193290A (en) * | 2019-05-30 | 2019-09-03 | 江苏大学 | A kind of preparation method and application based on click chemistry trace lincomycin molecular compound film |
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| CN113398887B (en) * | 2021-06-29 | 2023-05-09 | 江苏大学 | Three-dimensional towel gourd-like flexible serial selective adsorption filler and preparation method and application thereof |
| CN115282640A (en) * | 2022-07-05 | 2022-11-04 | 河北大学 | Molecularly imprinted solid-phase microextraction fiber coating and preparation method and application thereof |
| CN115282640B (en) * | 2022-07-05 | 2023-07-04 | 河北大学 | Molecularly imprinted solid-phase microextraction fiber coating and preparation method and application thereof |
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