CN115368511B - Aqueous phase preparation method and application of eutectic solvent type imprinted polymer - Google Patents
Aqueous phase preparation method and application of eutectic solvent type imprinted polymer Download PDFInfo
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- CN115368511B CN115368511B CN202211076420.9A CN202211076420A CN115368511B CN 115368511 B CN115368511 B CN 115368511B CN 202211076420 A CN202211076420 A CN 202211076420A CN 115368511 B CN115368511 B CN 115368511B
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- 229920000642 polymer Polymers 0.000 title claims abstract description 48
- 239000002904 solvent Substances 0.000 title claims abstract description 46
- 230000005496 eutectics Effects 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 239000008346 aqueous phase Substances 0.000 title claims description 4
- 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 claims abstract description 40
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 11
- 239000003999 initiator Substances 0.000 claims abstract description 11
- CHRJZRDFSQHIFI-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;styrene Chemical compound C=CC1=CC=CC=C1.C=CC1=CC=CC=C1C=C CHRJZRDFSQHIFI-UHFFFAOYSA-N 0.000 claims abstract description 10
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims abstract description 10
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 claims abstract description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 30
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 27
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 13
- 238000000944 Soxhlet extraction Methods 0.000 claims description 9
- 238000011049 filling Methods 0.000 claims description 9
- 239000011259 mixed solution Substances 0.000 claims description 9
- 230000000379 polymerizing effect Effects 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 230000000977 initiatory effect Effects 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- 238000006116 polymerization reaction Methods 0.000 claims description 8
- 238000009210 therapy by ultrasound Methods 0.000 claims description 8
- 238000001291 vacuum drying Methods 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 6
- KXHPPCXNWTUNSB-UHFFFAOYSA-M benzyl(trimethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CC1=CC=CC=C1 KXHPPCXNWTUNSB-UHFFFAOYSA-M 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims 1
- 238000001179 sorption measurement Methods 0.000 abstract description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 4
- 239000007864 aqueous solution Substances 0.000 abstract description 4
- 238000001035 drying Methods 0.000 abstract description 2
- 238000010828 elution Methods 0.000 abstract description 2
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 2
- 238000012719 thermal polymerization Methods 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 12
- 239000000178 monomer Substances 0.000 description 11
- 229920000344 molecularly imprinted polymer Polymers 0.000 description 7
- 239000012046 mixed solvent Substances 0.000 description 5
- HTZCNXWZYVXIMZ-UHFFFAOYSA-M benzyl(triethyl)azanium;chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC1=CC=CC=C1 HTZCNXWZYVXIMZ-UHFFFAOYSA-M 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- UMESNHVJZFCGBV-UHFFFAOYSA-N 2-methyl-4-[(2-methylphenyl)methylidene]-1,3-oxazol-5-one Chemical compound O=C1OC(C)=NC1=CC1=CC=CC=C1C UMESNHVJZFCGBV-UHFFFAOYSA-N 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- VJGNLOIQCWLBJR-UHFFFAOYSA-M benzyl(tributyl)azanium;chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CC1=CC=CC=C1 VJGNLOIQCWLBJR-UHFFFAOYSA-M 0.000 description 2
- UUZYBYIOAZTMGC-UHFFFAOYSA-M benzyl(trimethyl)azanium;bromide Chemical compound [Br-].C[N+](C)(C)CC1=CC=CC=C1 UUZYBYIOAZTMGC-UHFFFAOYSA-M 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000000374 eutectic mixture Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000000370 acceptor Substances 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 238000002372 labelling Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012454 non-polar solvent Substances 0.000 description 1
- 238000002414 normal-phase solid-phase extraction Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- -1 polypropylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000007781 pre-processing Methods 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
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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
- C08F257/00—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00
- C08F257/02—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00 on to polymers of styrene or alkyl-substituted styrenes
-
- 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
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Analytical Chemistry (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention discloses a water phase preparation method of a eutectic solvent type imprinted polymer and application thereof, wherein a eutectic solvent and a template molecule bisphenol A are dissolved in a pure water solvent containing a carrier styrene-divinylbenzene, prepolymerization is carried out for 2-8 hours at 20-40 ℃, then a cross-linking agent N, N' -methylene bisacrylamide and an initiator azodiisobutyronitrile are added, after ultrasonic and nitrogen protection, thermal polymerization is carried out for 20-30 hours at 50-70 ℃, and elution and drying are carried out, thus obtaining the eutectic solvent type imprinted polymer. The imprinted polymer prepared by the invention has strong capability of selectively adsorbing bisphenol A as a target object in aqueous solution and high adsorption quantity, and can be used for separating and enriching bisphenol A in an actual water sample.
Description
Technical Field
The invention belongs to the technical field of preparation of functional high molecular polymers, and particularly relates to a water phase preparation method and application of a eutectic solvent type imprinted polymer.
Background
Molecularly Imprinted Polymers (MIPs) are highly crosslinked complexes formed by template molecules and functional monomers, and after template removal, specific recognition sites such as spatial structures, sizes, functional groups and the like in MIPs are highly matched with template molecules, and this "memory" ability can selectively adsorb and recognize template molecules coexisting with other compounds. In the preparation process, the pore-forming agent is used as a dispersion medium to influence the non-covalent bond strength of the functional monomer and the template molecule and the space structure of the formed MIPs. However, most of the current molecularly imprinted polymers are prepared in organic solvents, and secondary pollution to the environment is likely to occur. Moreover, the adsorption capacity of these MIPs in aqueous solutions is greatly affected by the presence of "solvent memory".
The eutectic solvent (DES) is a eutectic mixture of hydrogen bond donors (such as quaternary ammonium salts, etc.) and hydrogen bond acceptors (such as carboxylic acids, amides, etc.) in a certain molar ratio, and the solidifying point of the eutectic mixture is lower than the melting point of the pure substances of the components. DES is also known as a novel ionic liquid, so that it has the advantages of low melting point, no vapor pressure, strong solubility, low cost, simple preparation process, and the like. With the continuous and intensive research on DES, the DES has increasingly wide application in the fields of separation, extraction, polymer preparation and the like. However, MIPs currently using DES as a functional monomer have been studied for recognizing biomolecules, and there is a lack of studies for recognizing and adsorbing pollutants in the environment.
Disclosure of Invention
The invention solves the technical problem of providing a water phase preparation method of a eutectic solvent type imprinted polymer, wherein the imprinted polymer has strong capability of selectively adsorbing bisphenol A as a target in an aqueous solution and high adsorption capacity, and can be used for separating and enriching bisphenol A in an actual water sample.
The invention adopts the following technical scheme to solve the technical problems, and is characterized in that the aqueous phase preparation method of the eutectic solvent type imprinted polymer is adopted: dissolving a eutectic solvent and a template molecule bisphenol A into a pure water solvent containing a carrier styrene-divinylbenzene, pre-polymerizing for 2-8 hours at 20-40 ℃, adding a cross-linking agent N, N' -methylene bisacrylamide and an initiator azodiisobutyronitrile, performing ultrasonic and nitrogen filling protection, performing thermal polymerization for 20-30 hours at 50-70 ℃, eluting, and drying to obtain the eutectic solvent type imprinted polymer;
the eutectic solvent is a mixed solvent of methacrylic acid and benzyl trimethyl ammonium chloride with a molar ratio of 0.5-2:1, a mixed solvent of methacrylic acid and benzyl triethyl ammonium chloride with a molar ratio of 0.5-2:1, a mixed solvent of methacrylic acid and benzyl tributyl ammonium chloride with a molar ratio of 0.5-2:1, a mixed solvent of methacrylic acid and n-octyl trimethyl ammonium chloride with a molar ratio of 0.5-2:1 or a mixed solvent of methacrylic acid and benzyl trimethyl ammonium bromide with a molar ratio of 0.5-2:1.
Further defined, the mass ratio of the eutectic solvent to the template molecule to the cross-linking agent to the initiator is 0.05-0.3:0.03:0.05-0.2:0.05.
Further defined, the elution process is specifically Soxhlet extraction with a mixed solution of methanol and acetic acid in a volume ratio of 9:1 for 48 hours.
The eutectic solvent type imprinted polymer is used for separating and enriching bisphenol A in an actual water sample.
Compared with the prior art, the invention has the following advantages and beneficial effects:
1. the invention provides a method for preparing bisphenol A surface imprinted polymer by using various eutectic solvents as functional monomers, wherein the imprinted polymer has the properties of uniform particle size, large adsorption capacity, strong affinity in water and the like.
2. According to the invention, pure water is used as a preparation solvent, so that on one hand, the secondary damage of non-polar solvents such as acetonitrile, methanol and the like to the environment is reduced, and on the other hand, the adsorption capacity of the imprinted polymer in an aqueous medium is improved.
Drawings
FIG. 1 is a schematic diagram of the synthetic route of the eutectic solvent in the present invention.
FIG. 2 is a synthetic route diagram of the imprinted polymer in the invention.
FIG. 3 is an electron micrograph of a support, imprinted polymer and non-imprinted polymer according to the invention.
FIG. 4 is a graph of adsorption kinetics of the imprinted and non-imprinted polymers of the invention.
FIG. 5 is an adsorption isotherm plot of the imprinted polymer and non-imprinted polymer of the invention.
Detailed Description
The above-described matters of the present invention will be described in further detail by way of examples, but it should not be construed that the scope of the above-described subject matter of the present invention is limited to the following examples, and all techniques realized based on the above-described matters of the present invention are within the scope of the present invention.
Example 1
Preparation of the eutectic solvent: methacrylic acid and benzyl trimethyl ammonium chloride are mixed according to a molar ratio of 2:1 and then stirred at 80 ℃ for reaction to obtain clear and uniform liquid.
Preparation of the imprinted polymer: using 30mL of water as solvent, pre-polymerizing 0.10g of styrene-divinylbenzene (carrier), 0.10g of self-made eutectic solvent (functional monomer) and 0.03g of bisphenol A (template molecule) for 4 hours at 30 ℃, then adding 0.10g of cross-linking agent N, N' -methylene bisacrylamide and 0.05g of initiator azodiisobutyronitrile, and carrying out ultrasonic treatment and N filling 2 And performing thermal initiation polymerization at 60 ℃ for 24 hours to obtain a product, performing Soxhlet extraction on the product by using a methanol/acetic acid mixed solution with a volume ratio of 9:1 for 48 hours, and performing vacuum drying to obtain the imprinted polymer.
Example 2
Preparation of the eutectic solvent: methacrylic acid and benzyl triethyl ammonium chloride are mixed according to a molar ratio of 2:1 and then stirred at 80 ℃ for reaction to obtain clear and uniform liquid.
Preparation of the imprinted polymer: using 30mL of water as solvent, pre-polymerizing 0.10g of styrene-divinylbenzene (carrier), 0.10g of self-made eutectic solvent (functional monomer) and 0.03g of bisphenol A (template molecule) for 4 hours at 30 ℃, then adding 0.10g of cross-linking agent N, N' -methylene bisacrylamide and 0.05g of initiator azodiisobutyronitrile, and carrying out ultrasonic treatment and N filling 2 And performing thermal initiation polymerization at 60 ℃ for 24 hours to obtain a product, performing Soxhlet extraction on the product by using a methanol/acetic acid mixed solution with a volume ratio of 9:1 for 48 hours, and performing vacuum drying to obtain the imprinted polymer.
Example 3
Preparation of the eutectic solvent: methacrylic acid and benzyl tributyl ammonium chloride are mixed according to a molar ratio of 2:1 and then stirred at 80 ℃ for reaction to obtain clear and uniform liquid.
Preparation of the imprinted polymer: using 30mL of water as solvent, pre-polymerizing 0.10g of styrene-divinylbenzene (carrier), 0.10g of self-made eutectic solvent (functional monomer) and 0.03g of bisphenol A (template molecule) for 4 hours at 30 ℃, then adding 0.10g of cross-linking agent N, N' -methylene bisacrylamide and 0.05g of initiator azodiisobutyronitrile, and carrying out ultrasonic treatment and N filling 2 And performing thermal initiation polymerization at 60 ℃ for 24 hours to obtain a product, performing Soxhlet extraction on the product by using a methanol/acetic acid mixed solution with a volume ratio of 9:1 for 48 hours, and performing vacuum drying to obtain the imprinted polymer.
Example 4
Preparation of the eutectic solvent: methacrylic acid and n-octyl trimethyl ammonium chloride are mixed according to a molar ratio of 2:1 and then stirred at 80 ℃ for reaction to obtain clear and uniform liquid.
Preparation of the imprinted polymer: using 30mL of water as solvent, pre-polymerizing 0.10g of styrene-divinylbenzene (carrier), 0.10g of self-made eutectic solvent (functional monomer) and 0.03g of bisphenol A (template molecule) for 4 hours at 30 ℃, then adding 0.10g of cross-linking agent N, N' -methylene bisacrylamide and 0.05g of initiator azodiisobutyronitrile, and carrying out ultrasonic treatment and N filling 2 And performing thermal initiation polymerization at 60 ℃ for 24 hours to obtain a product, performing Soxhlet extraction on the product by using a methanol/acetic acid mixed solution with a volume ratio of 9:1 for 48 hours, and performing vacuum drying to obtain the imprinted polymer.
Example 5
Preparation of the eutectic solvent: methacrylic acid and benzyl trimethyl ammonium bromide are mixed according to a molar ratio of 2:1 and then stirred at 80 ℃ for reaction to obtain clear and uniform liquid.
Preparation of the imprinted polymer: using 30mL of water as solvent, pre-polymerizing 0.10g of styrene-divinylbenzene (carrier), 0.10g of self-made eutectic solvent (functional monomer) and 0.03g of bisphenol A (template molecule) for 4 hours at 30 ℃, then adding 0.10g of cross-linking agent N, N' -methylene bisacrylamide and 0.05g of initiator azodiisobutyronitrile, and carrying out ultrasonic treatment and N filling 2 And performing thermal initiation polymerization at 60 ℃ for 24 hours to obtain a product, performing Soxhlet extraction on the product by using a methanol/acetic acid mixed solution with a volume ratio of 9:1 for 48 hours, and performing vacuum drying to obtain the imprinted polymer.
Example 6
Preparation of the eutectic solvent: methacrylic acid and benzyl trimethyl ammonium chloride are mixed according to a molar ratio of 1:1 and then stirred at 80 ℃ for reaction to obtain clear and uniform liquid.
Preparation of the imprinted polymer: using 30mL of water as solvent, pre-polymerizing 0.10g of styrene-divinylbenzene (carrier), 0.10g of self-made eutectic solvent (functional monomer) and 0.03g of bisphenol A (template molecule) for 4 hours at 30 ℃, then adding 0.10g of cross-linking agent N, N' -methylene bisacrylamide and 0.05g of initiator azodiisobutyronitrile, and carrying out ultrasonic treatment and N filling 2 Then carrying out thermal initiation polymerization for 24 hours at 60 ℃ to obtain the productAnd performing Soxhlet extraction for 48 hours by using a methanol/acetic acid mixed solution with the volume ratio of 9:1, and then performing vacuum drying to obtain the imprinted polymer.
Example 7
Preparation of the eutectic solvent: methacrylic acid and benzyl trimethyl ammonium chloride are mixed according to the mol ratio of 0.5:1 and then stirred at 80 ℃ for reaction to obtain clear and uniform liquid.
Preparation of the imprinted polymer: using 30mL of water as solvent, pre-polymerizing 0.10g of styrene-divinylbenzene (carrier), 0.10g of self-made eutectic solvent (functional monomer) and 0.03g of bisphenol A (template molecule) for 4 hours at 30 ℃, then adding 0.10g of cross-linking agent N, N' -methylene bisacrylamide and 0.05g of initiator azodiisobutyronitrile, and carrying out ultrasonic treatment and N filling 2 And performing thermal initiation polymerization at 60 ℃ for 24 hours to obtain a product, performing Soxhlet extraction on the product by using a methanol/acetic acid mixed solution with a volume ratio of 9:1 for 48 hours, and performing vacuum drying to obtain the imprinted polymer.
Example 8
10mg of the imprinted polymer (MIP) and the non-imprinted polymer (NIP) prepared in example 1 were mixed with 10mL of 50mg L, respectively -1 Mixing bisphenol A aqueous solution, oscillating at room temperature for adsorption for a certain time (0-180 min), taking supernatant, and detecting absorbance value at 277nm by an ultraviolet spectrophotometer. The results are shown in FIG. 4.
Example 9
10mg of the imprinted polymer (MIP) and the non-imprinted polymer (NIP) obtained in example 1 were mixed with 10mL of an aqueous bisphenol A solution (0-1000 mg L) -1 ) After 3h of oscillation adsorption at room temperature, the supernatant was taken and absorbance at 277nm was detected with an ultraviolet spectrophotometer. The results are shown in FIG. 5.
Example 10
The imprinted polymer prepared in the example 1 is filled in a polypropylene small column provided with a sieve plate and used for preprocessing bisphenol A in actual wastewater, and the detection result of a labeling experiment shows that the recovery rate reaches more than 90%, which shows that the obtained imprinted polymer has good practicability for separating and enriching bisphenol A; after more than 10 times of recycling, the adsorption performance of the solid phase extraction column is not obviously reduced, which indicates that the obtained imprinted polymer has excellent regenerated adsorption performance.
While the basic principles, principal features and advantages of the present invention have been described in the foregoing examples, it will be appreciated by those skilled in the art that the present invention is not limited by the foregoing examples, but is merely illustrative of the principles of the invention, and various changes and modifications can be made without departing from the scope of the invention, which is defined by the appended claims.
Claims (3)
1. A method for preparing an aqueous phase of a eutectic solvent-borne imprinted polymer, which is characterized in that:
preparation of the eutectic solvent: mixing methacrylic acid and benzyl trimethyl ammonium chloride according to a molar ratio of 2:1, and stirring at 80 ℃ for reaction to obtain clear and uniform liquid;
preparation of the imprinted polymer: using 30mL of water as solvent, pre-polymerizing 0.10g of styrene-divinylbenzene, 0.10g of eutectic solvent prepared by the method and 0.03g of bisphenol A for 4 hours at 30 ℃, then adding 0.10g of cross-linking agent N, N' -methylene bisacrylamide and 0.05g of initiator azodiisobutyronitrile, and carrying out ultrasonic treatment and N filling 2 And performing thermal initiation polymerization at 60 ℃ for 24 hours to obtain a product, performing Soxhlet extraction on the product by using a methanol/acetic acid mixed solution with a volume ratio of 9:1 for 48 hours, and performing vacuum drying to obtain the imprinted polymer.
2. The eutectic solvent type imprinted polymer prepared by the method of claim 1.
3. A eutectic solvent type imprinted polymer according to claim 2, for separation and enrichment of bisphenol a in an actual water sample.
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| CN113171763A (en) * | 2021-05-24 | 2021-07-27 | 河南师范大学 | Method for preparing bisphenol A surface molecularly imprinted polymer in aqueous phase by taking MIL-100(Fe) as carrier |
| CN113248650A (en) * | 2021-06-18 | 2021-08-13 | 许昌学院 | Eutectic solvent type molecularly imprinted polymer with hydroxyapatite as carrier and preparation method and application thereof |
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| FR2935705B1 (en) * | 2008-09-05 | 2010-10-29 | Univ De Technologie De Compiegne | PROCESS FOR THE PREPARATION OF MOLECULAR IMPRESSION POLYMERS (PEM) BY RADICAL POLYMERIZATION |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101177500A (en) * | 2007-10-30 | 2008-05-14 | 湖北出入境检验检疫局检验检疫技术中心 | Method for preparing bisphenol A molecular engram polymer |
| CN107759736A (en) * | 2017-09-22 | 2018-03-06 | 河南师范大学 | A kind of preparation method of styrene divinylbenzene molecular imprinted polymer on surface for selective absorption Ciprofloxacin Hydrochloride |
| CN113171763A (en) * | 2021-05-24 | 2021-07-27 | 河南师范大学 | Method for preparing bisphenol A surface molecularly imprinted polymer in aqueous phase by taking MIL-100(Fe) as carrier |
| CN113248650A (en) * | 2021-06-18 | 2021-08-13 | 许昌学院 | Eutectic solvent type molecularly imprinted polymer with hydroxyapatite as carrier and preparation method and application thereof |
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