CN115364824A - Tetrabromobisphenol A molecularly imprinted membrane and preparation method and application thereof - Google Patents
Tetrabromobisphenol A molecularly imprinted membrane and preparation method and application thereof Download PDFInfo
- Publication number
- CN115364824A CN115364824A CN202211061496.4A CN202211061496A CN115364824A CN 115364824 A CN115364824 A CN 115364824A CN 202211061496 A CN202211061496 A CN 202211061496A CN 115364824 A CN115364824 A CN 115364824A
- Authority
- CN
- China
- Prior art keywords
- tetrabromobisphenol
- molecularly imprinted
- membrane
- product system
- film
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- 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
- B01J20/261—Synthetic macromolecular compounds obtained by reactions only involving carbon to carbon unsaturated bonds
-
- 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
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/103—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate comprising silica
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28033—Membrane, sheet, cloth, pad, lamellar or mat
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
Abstract
The invention provides a tetrabromobisphenol A molecularly imprinted membrane, a preparation method and application thereof, and belongs to the technical field of environmental materials. The invention firstly provides a modified nano silicon dioxide ball, which is obtained by modifying a nano silicon dioxide ball by a silane coupling agent; mixing the modified nano-silica spheres with a functional monomer, tetrabromobisphenol A and an organic solvent, and pre-assembling to obtain a pre-assembled product system; mixing the pre-assembled product system with a cross-linking agent and an initiator to carry out polymerization reaction to obtain a polymerization product system; eluting the polymerization product system to obtain molecularly imprinted polymer feed liquid; and (3) forming the molecularly imprinted polymer feed liquid on the surface of the substrate membrane to obtain the tetrabromobisphenol A molecularly imprinted membrane. The tetrabromobisphenol A molecularly imprinted membrane can be prepared simply and efficiently by adopting the method provided by the invention, can specifically identify tetrabromobisphenol A, and has stronger selectivity and adsorption capacity to tetrabromobisphenol A.
Description
Technical Field
The invention relates to the technical field of environmental materials, in particular to a tetrabromobisphenol A molecularly imprinted membrane and a preparation method and application thereof.
Background
With the continuous innovation and improvement of environmental monitoring technology, people continuously and deeply know the environment and health harms of chemical substances, and more new pollutants are concerned, and mainly comprise environmental endocrine disruptors, persistent organic pollutants, micro plastics and antibiotics. The Endocrine Disruptors (EDCs) have the characteristics of large potential hazard, wide source range, low concentration, strong toxic effect and the like, and are a hot point of social attention. Of these, tetrabromobisphenol a (TBBPA), a persistent environmental endocrine disrupter, has been detected in sewage, sediment, wild animal and human serum, and has adverse effects on both natural and human health. Therefore, research on the specific adsorption of contaminants such as tetrabromobisphenol a is of great interest.
The molecular imprinting technology can selectively adsorb specific substances. The basic principle of the conventional molecular imprinting technology is that a template molecule (imprinting molecule) forms multiple action points when contacting a functional monomer, the action is memorized in the polymerization process, and after the template molecule is removed, a cavity with the multiple action points, which is matched with the spatial configuration of the template molecule, is formed in a polymer, and the cavity has selective recognition characteristics on the template molecule and analogues thereof.
The membrane separation technology is a technology for separating, purifying and concentrating different gas or liquid raw materials by using pressure difference, concentration difference or potential difference as driving force and depending on the selective osmosis action of a membrane. The technology has the advantages of high efficiency, energy conservation, convenient operation, environmental friendliness and the like, and is widely applied to the fields of biotechnology, medicine, food industry, environmental protection, petroleum detection and the like. However, there are some limiting factors, such as the current commercial membranes can only realize the separation of a certain class of substances but cannot realize the selective separation of single substances.
The molecular engram membrane prepared by combining the molecular engram technology and the membrane separation technology is a separation membrane with specificity. The molecular imprinting sites constructed based on the molecular imprinting technology are integrated on the surface of the membrane and the inner wall of the pore channel, and the specific adsorption of target molecules is realized by utilizing the specific action of formed imprinting cavities, so that the selective separation, removal, enrichment or purification of specific target molecules in a mixed system is realized. In the prior art, when a molecularly imprinted membrane is prepared, a separation membrane is usually prepared, then the separation membrane is modified, and the molecularly imprinted membrane is prepared through a molecularly imprinted polymerization reaction, so that the operation is complex, the efficiency is low, and the method is not beneficial to large-scale application.
Disclosure of Invention
The invention aims to provide a tetrabromobisphenol A molecularly imprinted membrane, and a preparation method and application thereof.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of a tetrabromobisphenol A molecularly imprinted membrane, which comprises the following steps:
providing modified nano-silica spheres, wherein the modified nano-silica spheres are obtained by modifying nano-silica spheres with a silane coupling agent;
mixing the modified nano-silica spheres with a functional monomer, tetrabromobisphenol A and an organic solvent, and pre-assembling to obtain a pre-assembled product system;
mixing the pre-assembled product system with a cross-linking agent and an initiator to carry out polymerization reaction to obtain a polymerization product system;
eluting the polymerization product system to obtain a molecularly imprinted polymer feed liquid;
and (3) forming the molecularly imprinted polymer feed liquid on the surface of the substrate membrane to obtain the tetrabromobisphenol A molecularly imprinted membrane.
Preferably, the diameter of the nano silica sphere is 300 to 500nm.
Preferably, the functional monomer comprises 4-vinylpyridine, methacrylic acid or methyl methacrylate; the crosslinking agent comprises ethylene glycol dimethacrylate, N' -methylenebisacrylamide or divinylbenzene.
Preferably, the mol ratio of the tetrabromobisphenol A, the functional monomer and the cross-linking agent is 1: (1-6): (5-25); the dosage ratio of the tetrabromobisphenol A to the modified nano silicon dioxide ball is (0.1-0.5) mmol:0.1g.
Preferably, the preassembly temperature is 25-35 ℃, and the time is 0.5-1.5 h; the temperature of the polymerization reaction is 50-80 ℃, and the time is 12-48 h.
Preferably, the elution is performed by Soxhlet extraction; and the eluent adopted by elution is a mixed solution of methanol and glacial acetic acid.
Preferably, the base film comprises a polyvinylidene fluoride film or a polytetrafluoroethylene film; the film forming mode is suction filtration film forming.
The invention provides a tetrabromobisphenol A molecularly imprinted membrane prepared by the preparation method in the technical scheme, which comprises a base membrane and a functional thin film arranged on the surface of the base membrane; the functional film is formed by modified nano silicon dioxide spheres loaded with molecularly imprinted polymers.
Preferably, the functional film has a thickness of 0.25 to 0.35mm.
The invention provides application of the tetrabromobisphenol A molecularly imprinted membrane in the technical scheme in selective adsorption or separation of tetrabromobisphenol A.
The invention provides a preparation method of a tetrabromobisphenol A molecularly imprinted membrane, which comprises the following steps: providing a modified nano-silica ball, wherein the modified nano-silica ball is obtained by modifying a nano-silica ball by using a silane coupling agent; mixing the modified nano-silica spheres with a functional monomer, tetrabromobisphenol A and an organic solvent, and pre-assembling to obtain a pre-assembled product system; mixing the pre-assembled product system with a cross-linking agent and an initiator to carry out polymerization reaction to obtain a polymerization product system; eluting the polymerization product system to obtain a molecularly imprinted polymer feed liquid; and (3) forming the molecularly imprinted polymer feed liquid on the surface of the substrate membrane to obtain the tetrabromobisphenol A molecularly imprinted membrane. According to the invention, the molecularly imprinted polymer is prepared and loaded on the modified nano silicon dioxide spheres, and then the membrane is directly formed on the surface of the basement membrane in the form of the dispersion liquid, so that the method is simple and efficient to operate and is beneficial to large-scale application. In the embodiment, the adsorption balance and the selective recognition performance of the tetrabromobisphenol A molecularly imprinted membrane provided by the invention are researched through a static adsorption experiment and a selective adsorption experiment, and the result shows that the tetrabromobisphenol A molecularly imprinted membrane provided by the invention has higher adsorption quantity and excellent tetrabromobisphenol A molecularly imprinted performance. In addition, repeated use experiments prove that the tetrabromobisphenol A molecularly imprinted membrane provided by the invention has good stability of the recognition sites, so that the tetrabromobisphenol A molecularly imprinted membrane has a good repeated use effect.
Drawings
FIG. 1 is a scanning electron micrograph of a polyvinylidene fluoride film of example 1;
FIG. 2 is a scanning electron micrograph of a tetrabromobisphenol A molecularly imprinted membrane in example 1;
FIG. 3 is a N1s fine spectrum of XPS before elution of tetrabromobisphenol A molecularly imprinted polymer in example 1;
FIG. 4 is a N1s fine spectrum of XPS after elution of tetrabromobisphenol A molecularly imprinted polymer in example 1;
FIG. 5 is a graph showing the static adsorption of tetrabromobisphenol A molecularly imprinted membrane of example 1 and the non-molecularly imprinted membrane of comparative example 1;
FIG. 6 is a graph showing selective adsorption of a tetrabromobisphenol A molecularly imprinted membrane in example 1 and a non-molecularly imprinted membrane in comparative example 1;
FIG. 7 is a graph showing the effect of the tetrabromobisphenol A molecularly imprinted membrane in example 1 in repeated use.
Detailed Description
The invention provides a preparation method of a tetrabromobisphenol A molecularly imprinted membrane, which comprises the following steps:
providing a modified nano-silica ball, wherein the modified nano-silica ball is obtained by modifying a nano-silica ball by using a silane coupling agent;
mixing the modified nano-silica spheres with a functional monomer, tetrabromobisphenol A and an organic solvent, and pre-assembling to obtain a pre-assembled product system;
mixing the pre-assembled product system with a cross-linking agent and an initiator to carry out polymerization reaction to obtain a polymerization product system;
eluting the polymerization product system to obtain a molecularly imprinted polymer feed liquid;
and (3) forming the molecularly imprinted polymer solution on the surface of the base membrane to obtain the tetrabromobisphenol A molecularly imprinted membrane.
In the present invention, the starting materials are all commercially available products well known to those skilled in the art unless otherwise specified.
The invention provides a modified nano-silica ball, which is obtained by modifying a nano-silica ball with a silane coupling agent. In the present invention, the diameter of the nano silica spheres is preferably 300 to 500nm. In the present invention, the method for preparing the nano silica spheres preferably comprises the following steps: and mixing a silicon source, ethanol, water and ammonia water, and carrying out hydrolysis reaction to obtain the nano silicon dioxide spheres. In the present invention, the silicon source, ethanol, and water are mixed with ammonia water, preferably, ethanol, water, and ammonia water are mixed, and then the silicon source is added to the resulting mixture. In the invention, the silicon source is preferably tetraethoxysilane; the concentration of the ammonia water is preferably 25-28 wt%; the water is preferably deionized water; the volume ratio of the silicon source, the ethanol, the water and the ammonia water is preferably 1: (10-15): (4-8): (1 to 4), more preferably 1:11:5:2. in the present invention, the hydrolysis reaction is preferably performed at room temperature, which is specifically 25 ℃ in the examples of the present invention; the time of the hydrolysis reaction is preferably 1 to 4 hours, and is further preferably 2 hours, and the time of the hydrolysis reaction is counted by the completion of the dropwise addition of the silicon source; the hydrolysis reaction is preferably carried out under stirring. After the hydrolysis reaction, the obtained suspension is preferably centrifuged, the supernatant is discarded, and the obtained solid material is washed and dried to obtain the nano silicon dioxide ball. In the present invention, the washing reagent is preferably ethanol, and more preferably absolute ethanol; the drying is preferably vacuum drying.
After the nano-silica spheres are obtained, the silane coupling agent is adopted to modify the nano-silica spheres to obtain the modified nano-silica spheres. In the present invention, the silane coupling agent preferably includes 3- (methacryloyloxy) propyltrimethoxysilane, γ - (2,3-glycidoxy) propyltrimethoxysilane, γ -aminopropyltriethoxysilane or 3-mercaptopropyltrimethoxysilane, and more preferably 3- (methacryloyloxy) propyltrimethoxysilane. In the present invention, the amount ratio of the silane coupling agent to the nano silica spheres is preferably (1 to 4) mL:0.1g, more preferably 2mL:0.1g. In the present invention, the modification is preferably carried out in the presence of an organic solvent, preferably ethanol; the dosage ratio of the organic solvent to the nano-silica spheres is preferably (10-40) mL:0.1g, more preferably 30mL:0.1g. According to the invention, the nano-silica spheres, the silane coupling agent and the organic solvent are preferably mixed and modified to obtain the modified nano-silica spheres. In the invention, the nano-silica spheres, the silane coupling agent and the organic solvent are mixed, preferably, the nano-silica spheres and the organic solvent are mixed, dispersed uniformly under the ultrasonic condition, and then the silane coupling agent is dripped into the obtained dispersion system; the dropping rate of the silane coupling agent is not particularly limited, and the silane coupling agent can be dropped dropwise. In the invention, the modification is preferably carried out under the condition of system reflux, taking ethanol as an organic solvent as an example, the temperature of the modification is preferably 40-70 ℃, and more preferably 50 ℃; the modification time is preferably 10-24 h, more preferably 12h, and specifically refers to the modification time after the silane coupling agent is added; the modification is preferably carried out under stirring. According to the invention, the silane coupling agent is adopted to modify the nano-silica spheres, so that the amount of silicon hydroxyl on the surfaces of the nano-silica spheres can be reduced, the hydrophilicity of the silicon hydroxyl is changed into hydrophobicity, the alkylation modified nano-silica spheres are obtained, the subsequent polymerization reaction is favorably promoted to be smoothly carried out, and the affinity of the alkylation modified nano-silica spheres with a polymer is improved. After the modification, the obtained system is preferably centrifuged, the obtained solid material is washed by ethanol, and then the solid material is dried to obtain the modified nano silicon dioxide ball.
After the modified nano-silica ball is obtained, the modified nano-silica ball is mixed with a functional monomer, tetrabromobisphenol A and an organic solvent, and is pre-assembled to obtain a pre-assembled product system. In the invention, the dosage ratio of the tetrabromobisphenol A to the modified nano-silica spheres is preferably (0.1-0.5) mmol:0.1g, more preferably 0.1mmol:0.1g. In the present invention, the functional monomer preferably includes 4-vinylpyridine, methacrylic acid or methyl methacrylate, and more preferably 4-vinylpyridine; the mol ratio of the tetrabromobisphenol A to the functional monomer is preferably 1: (1 to 6), more preferably 1:4. in the present invention, the organic solvent is preferably toluene, and the amount ratio of the tetrabromobisphenol a to the organic solvent is preferably 0.1mmol: (10 to 40) mL, more preferably 0.1mmol:20mL. In the invention, the modified nano-silica spheres are mixed with the functional monomer, the tetrabromobisphenol A and the organic solvent, preferably, the modified nano-silica spheres are mixed with the organic solvent, the mixture is uniformly dispersed under the ultrasonic condition, and then the functional monomer and the tetrabromobisphenol A are added into the obtained dispersion system for preassembly. In the present invention, the temperature of the preassembly is preferably 25 to 35 ℃, more preferably 30 ℃; the time is preferably 0.5 to 1.5 hours, and more preferably 1 hour; the preassembly is preferably carried out under oscillating conditions. In the invention, tetrabromobisphenol A and a functional monomer form a prepolymer through non-covalent bond hydrogen bonds in the preassembling process, and the prepolymer is loaded on the surface of the modified nano silicon dioxide sphere.
After the pre-assembled product system is obtained, the pre-assembled product system, the cross-linking agent and the initiator are directly mixed for polymerization reaction without any post-treatment, so that the polymerization product system is obtained. In the present invention, the crosslinking agent preferably includes ethylene glycol dimethacrylate, N' -methylenebisacrylamide or divinylbenzene, and more preferably ethylene glycol dimethacrylate; the molar ratio of the tetrabromobisphenol a to the crosslinking agent is preferably 1: (5 to 25), more preferably 1:20. in the present invention, the initiator preferably includes azobisisobutyronitrile or dibenzoyl peroxide, more preferably azobisisobutyronitrile; the molar ratio of tetrabromobisphenol a to the initiator is preferably 1: (1 to 3), more preferably 1:1.2. in the invention, the preassembly product system is mixed with a cross-linking agent and an initiator, preferably, the cross-linking agent and the initiator are added into the preassembly product system, the mixture is uniformly dispersed under ultrasonic conditions, and then the polymerization reaction is carried out. In the present invention, the polymerization reaction is preferably carried out in a protective atmosphere, the protective gas providing the protective atmosphere preferably being nitrogen; in the embodiment of the present invention, specifically, after mixing the raw materials, the obtained system is purged with nitrogen to remove oxygen, and the polymerization reaction is performed under a sealed condition. In the present invention, the temperature of the polymerization reaction is preferably 50 to 80 ℃, and more preferably 60 ℃; the time is preferably 12 to 48 hours, and more preferably 24 hours; the polymerization reaction is preferably carried out under stirring conditions. In the present invention, during the polymerization reaction, under the action of the initiator, the cross-linking agent further links and crosslinks the prepolymer formed by tetrabromobisphenol a and the functional monomer, and finally forms the high molecular polymer.
After a polymerization product system is obtained, the invention elutes the polymerization product system to obtain the molecularly imprinted polymer feed liquid. In the present invention, the elution mode is preferably soxhlet extraction; the eluent used for elution is preferably a mixed solution of methanol and glacial acetic acid, and the volume ratio of the methanol to the glacial acetic acid in the eluent is preferably (8-10): 1, more preferably 9:1. the tetrabromobisphenol A is removed by elution, in particular until the obtained eluent has no tetrabromobisphenol A.
In the invention, the molecularly imprinted polymer feed liquid contains modified nano-silica spheres loaded with the molecularly imprinted polymer, the molecularly imprinted polymer is loaded on the modified nano-silica spheres, the nano-silica spheres are modified by a silane coupling agent, the tendency of silicon hydroxyl (Si-OH) on the surfaces of the nano-silica spheres to aggregate can be effectively reduced, the dispersibility of the nano-silica spheres in an organic phase can be increased, specifically, macromolecular substances with hydroxyl in hydrolysate of the silane coupling agent can be chemically bonded with the silicon hydroxyl on the surfaces of the nano-silica spheres and are linked to the surfaces of the nano-silica spheres, the number of the silicon hydroxyl on the surfaces of the nano-silica spheres can be reduced, and the aggregation condition of the nano-silica spheres is reduced; and the hydrophobic long chain of the silane coupling agent is introduced to change the hydrophilic type of the nano silicon dioxide spheres into the hydrophobic type, so that the molecular polarity is weakened, the surface energy is reduced, and the hydrophobic long chain plays a certain role in blocking, thereby further reducing the agglomeration of the nano silicon dioxide spheres. The modified nano-silica spheres are used as carriers of the molecularly imprinted polymer, and the surface area of the molecularly imprinted polymer is increased by reducing the agglomeration of the carriers, so that the possibility of forming molecularly imprinted binding sites is improved.
After the molecularly imprinted polymer feed liquid is obtained, the invention forms a film on the surface of the basement membrane by the molecularly imprinted polymer feed liquid to obtain the tetrabromobisphenol A molecularly imprinted membrane. In the present invention, the base film preferably includes a polyvinylidene fluoride (PVDF) film or a Polytetrafluoroethylene (PTFE) film, and more preferably a polyvinylidene fluoride (PVDF) film. In the present invention, the thickness of the base film is preferably 0.25 to 0.35mm, and more preferably 0.28mm. In the invention, the film forming mode is preferably suction filtration film forming, specifically, the molecularly imprinted polymer feed liquid is placed on one side of a base film for suction filtration, the molecularly imprinted polymer feed liquid forms a wet film on the one side of the base film, and then the wet film is dried, and a functional film is formed on the one side of the base film to obtain the tetrabromobisphenol A molecularly imprinted film. In the present invention, the suction filtration is preferably vacuum filtration; the drying is preferably vacuum drying, the temperature of the drying is preferably 50-80 ℃, more preferably 60 ℃, and the time is preferably 10-24 h, more preferably 12h. In the present invention, the thickness of the functional film is preferably 0.25 to 0.35mm, and more preferably 0.29mm.
The invention provides a tetrabromobisphenol A molecularly imprinted membrane prepared by the preparation method in the technical scheme, which comprises a base membrane and a functional thin film arranged on the surface of the base membrane; the functional film is formed by modified nano silicon dioxide spheres loaded with molecularly imprinted polymers. In the invention, a prepolymer is formed by a functional monomer and tetrabromobisphenol A, and then the molecularly imprinted polymer is obtained by the polymerization reaction of the prepolymer and a cross-linking agent under the action of an initiator. The functional film in the tetrabromobisphenol A molecularly imprinted membrane provided by the invention is firmly present on the surface of the basement membrane, and the functional film does not obviously fall off in the recycling process.
According to the invention, a molecular imprinting technology is introduced into a membrane separation technology, and the obtained tetrabromobisphenol A molecular imprinting membrane has the advantages of both the molecular imprinting membrane and the membrane separation technology, and has the advantages of low energy consumption of green chemistry, high energy utilization rate, convenience for continuous amplification operation and the like; on the other hand, the method has high selectivity and strong specificity which are not possessed by other methods, and overcomes the defect that the current commercial membrane material is difficult to realize selective adsorption or separation of single substances.
The invention provides application of the tetrabromobisphenol A molecularly imprinted membrane in the technical scheme in selective adsorption or separation of tetrabromobisphenol A. In the invention, the tetrabromobisphenol A molecularly imprinted membrane can be preferably used as an adsorbent in the field of sewage treatment, is convenient to recycle (can be reused after being recycled and subjected to Soxhlet elution to remove tetrabromobisphenol A), is more environment-friendly, stable, efficient and energy-saving in the using process, can realize continuous operation, and solves the problem that the traditional granular molecularly imprinted polymer cannot be recycled after being used.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Adding 110mL of ethanol, 50mL of deionized water and 20mL of ammonia water (28 wt%) into a conical flask, stirring for 10min by strong magnetic force, adding 10mL of ethyl orthosilicate, and stirring and reacting for 2h at room temperature (25 ℃); after the reaction is finished, centrifuging the obtained white suspension in a centrifugal tube, removing supernatant, cleaning solid materials attached to the tube wall with absolute ethyl alcohol, and then carrying out vacuum drying to obtain nano silicon dioxide spheres with the diameter of 300-500 nm;
adding 0.1g of the nano silicon dioxide ball into 30mL of ethanol, performing uniform ultrasonic dispersion, then dropwise adding 2mL of 3- (methacryloyloxy) propyl trimethoxy silane into the obtained dispersion system, performing oil bath heating under the stirring condition until the system is refluxed (50 ℃), and performing modification for 12h; after the modification is finished, centrifuging the obtained system, washing the obtained solid material by adopting ethanol, and drying to obtain modified nano silicon dioxide spheres;
adding 0.1g of the modified nano-silica spheres into 20mL of toluene, performing ultrasonic dispersion uniformly, then adding 0.4mmol of 4-vinylpyridine and 0.1mmol of tetrabromobisphenol A into the obtained dispersion system, performing pre-assembly for 1h at 30 ℃ in a constant temperature oscillator, then adding 1mmol of ethylene glycol dimethacrylate and 0.12mmol of azobisisobutyronitrile into the obtained pre-assembly system, performing ultrasonic dispersion uniformly, introducing nitrogen to remove oxygen, and reacting for 24h at 60 ℃ under the conditions of sealing and stirring to obtain a polymerization product system;
and (3) eluting the polymerization product system (specifically, by adopting a Soxhlet extraction method), wherein the used eluent is a mixed solution of methanol and glacial acetic acid, and the volume ratio of the methanol to the glacial acetic acid is 9:1, until tetrabromobisphenol A can not be detected in the obtained eluent, obtaining molecularly imprinted polymer feed liquid;
and placing the molecularly imprinted polymer feed liquid on a single surface of a polyvinylidene fluoride membrane (with the thickness of 0.28 mm) for vacuum filtration, forming a wet membrane on the single surface of the polyvinylidene fluoride membrane by the molecularly imprinted polymer feed liquid, then performing vacuum drying for 12 hours at 60 ℃ to remove a solvent, and forming a functional thin film (with the thickness of 0.29 mm) on the single surface of the polyvinylidene fluoride membrane to obtain the tetrabromobisphenol A molecularly imprinted membrane.
Fig. 1 is a scanning electron micrograph of a polyvinylidene fluoride film, and it can be seen from fig. 1 that the polyvinylidene fluoride film has a porous structure.
FIG. 2 is a scanning electron microscope image of a tetrabromobisphenol A molecularly imprinted membrane, and it can be seen from FIG. 2 that a large number of spherical particles are aggregated on the surface of the base membrane, indicating that the molecularly imprinted polymer prepared in example 1 is successfully loaded on the base membrane.
FIG. 3 is a N1s fine spectrum of XPS before elution of tetrabromobisphenol A molecularly imprinted polymer, FIG. 4 is a N1s fine spectrum of XPS after elution of tetrabromobisphenol A molecularly imprinted polymer, and it can be seen from FIGS. 3 and 4 that the tetrabromobisphenol A molecularly imprinted polymer before elution shows three characteristic peaks, which are N-C, N-H, N = C bond, mainly from functional monomer and non-covalent bond N-H connecting functional monomer and tetrabromobisphenol A, and the non-covalent bond N-H connecting functional monomer and tetrabromobisphenol A after elution is broken, which shows that tetrabromobisphenol A is removed from the structure to form imprinted cavity.
Comparative example 1
A non-molecularly imprinted membrane was prepared according to the method of example 1 except that the steps of adding tetrabromobisphenol A and eluting were omitted.
The film materials prepared in example 1 and comparative example 1 were subjected to performance tests, specifically as follows:
(1) Static adsorption experiment
Respectively weighing the same amount of membrane materials, placing the membrane materials in 20mL of tetrabromobisphenol A methanol solutions with the concentrations of 10mg/L, 20mg/L, 40mg/L, 60mg/L, 80mg/L and 100mg/L, oscillating in a constant temperature water bath for 4h at the temperature of 25 ℃, measuring the concentration of tetrabromobisphenol A by using an ultraviolet absorption spectrophotometer after adsorption is finished, and calculating the adsorption amount according to the result.
(2) Selective adsorption experiment
Selecting tetrabromobisphenol A (TBBPA), bisphenol A (BPA), p-tert-Butylphenol (BP) and 4,4' -dihydroxybiphenyl (DDBP) as substrates, namely BPA, BP and DDBP as competitive adsorbates of TBBPA, respectively preparing 20mL of four substrate solutions with the concentration of 40mg/L, weighing the same amount of film materials in the substrate solutions, oscillating in a constant-temperature water bath at 25 ℃ for 4h, respectively measuring the concentrations of the four substrates by using an ultraviolet absorption spectrophotometer after adsorption is finished, and calculating the adsorption quantity according to the result.
FIG. 5 is a graph showing the static adsorption of tetrabromobisphenol A molecularly imprinted membrane of example 1 and the non-molecularly imprinted membrane of comparative example 1. As can be seen from fig. 5, the adsorption amount of the film material to tetrabromobisphenol a gradually increased with the increase of the concentration of tetrabromobisphenol a, and the maximum adsorption amount was gradually reached at a concentration of tetrabromobisphenol a of about 100mg/L, but the adsorption of the tetrabromobisphenol a molecularly imprinted film in example 1 was stronger than that of the non-molecularly imprinted film in comparative example 1 because there was no characteristic imprinted hole compared to the non-molecularly imprinted film in comparative example 1, and the adsorption performance was poor; wherein, when the concentration of tetrabromobisphenol A is 100mg/L, the adsorption quantity of the tetrabromobisphenol A molecularly imprinted membrane in example 1 is 14.5mg/g, and the adsorption quantity of the non-molecularly imprinted membrane in comparative example 1 is 5.6mg/g.
FIG. 6 is a selective adsorption curve of tetrabromobisphenol A molecularly imprinted membrane in example 1 and a non-molecularly imprinted membrane in comparative example 1. As can be seen from FIG. 6, the tetrabromobisphenol A molecularly imprinted membrane in example 1 can specifically adsorb TBBPA, and the adsorption amount of the tetrabromobisphenol A molecularly imprinted membrane to any one substrate is higher than that of the non-molecularly imprinted membrane in comparative example 1; in contrast, in the non-molecularly imprinted membrane in comparative example 1, although the adsorption amounts of different substrates are different, the difference is small, and the membrane does not have a characteristic adsorption site for TBBPA.
(3) Repeated use experiment
Placing the tetrabromobisphenol A molecularly imprinted membrane prepared in example 1 in 20mL of tetrabromobisphenol A methanol solution with the concentration of 40mg/L, and oscillating in a constant temperature water bath at 25 ℃ for 4h to complete adsorption (marked as first adsorption);
mixing methanol and glacial acetic acid according to a volume ratio of 9:1 as an eluent, eluting the used tetrabromobisphenol A molecularly imprinted membrane (specifically, adopting a Soxhlet extraction method) until tetrabromobisphenol A is not detected in the obtained eluent, then drying the tetrabromobisphenol A molecularly imprinted membrane in vacuum at 60 ℃ for 12h, repeating the adsorption experiment (recorded as repeated adsorption) on the regenerated tetrabromobisphenol A molecularly imprinted membrane for 4 times according to the method, measuring the concentration of tetrabromobisphenol A by using an ultraviolet absorption spectrophotometer after each adsorption is completed, and calculating the adsorption quantity according to the result.
Fig. 7 is a graph showing the effect of the tetrabromobisphenol a molecularly imprinted membrane in example 1 in repeated use, and it can be seen from fig. 7 that the tetrabromobisphenol a molecularly imprinted membrane after the initial adsorption is eluted and repeatedly adsorbed, and the adsorption capacity of the tetrabromobisphenol a molecularly imprinted membrane repeatedly adsorbed 1 to 4 times is still maintained around the original adsorption capacity, which indicates that the functional thin film is stably present on the surface of the base film in the tetrabromobisphenol a molecularly imprinted membrane prepared by the method of the present invention, wherein the recognition site on the functional thin film can be stably present after being eluted and regenerated, and the tetrabromobisphenol a molecularly imprinted membrane has excellent recombination selectivity.
In conclusion, the tetrabromobisphenol A molecularly imprinted membrane provided by the invention can specifically identify tetrabromobisphenol A, and has stronger selectivity and adsorption capacity to tetrabromobisphenol A; but also is convenient for recycling and has better repeated use effect.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A preparation method of a tetrabromobisphenol A molecularly imprinted membrane comprises the following steps:
providing modified nano-silica spheres, wherein the modified nano-silica spheres are obtained by modifying nano-silica spheres with a silane coupling agent;
mixing the modified nano-silica spheres with a functional monomer, tetrabromobisphenol A and an organic solvent, and pre-assembling to obtain a pre-assembled product system;
mixing the pre-assembled product system with a cross-linking agent and an initiator to carry out polymerization reaction to obtain a polymerization product system;
eluting the polymerization product system to obtain a molecularly imprinted polymer feed liquid;
and (3) forming the molecularly imprinted polymer feed liquid on the surface of the substrate membrane to obtain the tetrabromobisphenol A molecularly imprinted membrane.
2. The method according to claim 1, wherein the diameter of the nano silica spheres is 300 to 500nm.
3. The method of claim 1, wherein the functional monomer comprises 4-vinylpyridine, methacrylic acid or methyl methacrylate; the crosslinking agent comprises ethylene glycol dimethacrylate, N' -methylenebisacrylamide or divinylbenzene.
4. The method according to any one of claims 1 to 3, wherein the molar ratio of tetrabromobisphenol A, functional monomer and crosslinking agent is 1: (1-6): (5-25); the dosage ratio of the tetrabromobisphenol A to the modified nano silicon dioxide ball is (0.1-0.5) mmol:0.1g.
5. The method for preparing a composite material according to claim 1, wherein the preassembly temperature is 25-35 ℃ and the time is 0.5-1.5 h; the temperature of the polymerization reaction is 50-80 ℃, and the time is 12-48 h.
6. The method according to claim 1, wherein the elution is performed by Soxhlet extraction; and the eluent adopted by elution is a mixed solution of methanol and glacial acetic acid.
7. The production method according to claim 1, wherein the base film comprises a polyvinylidene fluoride film or a polytetrafluoroethylene film; the film forming mode is suction filtration film forming.
8. Tetrabromobisphenol A molecularly imprinted membrane prepared by the preparation method of any one of claims 1 to 7, comprising a base membrane and a functional thin film arranged on the surface of the base membrane; the functional film is formed by modified nano silicon dioxide spheres loaded with molecularly imprinted polymers.
9. The tetrabromobisphenol a molecularly imprinted membrane of claim 8, wherein the functional thin film has a thickness of 0.25 to 0.35mm.
10. Use of a tetrabromobisphenol a molecularly imprinted membrane according to claim 8 or 9 for selective adsorption or separation of tetrabromobisphenol a.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211061496.4A CN115364824A (en) | 2022-09-01 | 2022-09-01 | Tetrabromobisphenol A molecularly imprinted membrane and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211061496.4A CN115364824A (en) | 2022-09-01 | 2022-09-01 | Tetrabromobisphenol A molecularly imprinted membrane and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115364824A true CN115364824A (en) | 2022-11-22 |
Family
ID=84069578
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211061496.4A Pending CN115364824A (en) | 2022-09-01 | 2022-09-01 | Tetrabromobisphenol A molecularly imprinted membrane and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115364824A (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101524636A (en) * | 2009-04-10 | 2009-09-09 | 南京医科大学 | Method for preparing bisphenol A nanometer silicon gel carrier surface molecule print solid phase extraction filling |
| CN113145083A (en) * | 2021-04-16 | 2021-07-23 | 江苏大学 | Janus bifunctional blotting membrane and preparation method and application thereof |
| CN113368706A (en) * | 2021-06-02 | 2021-09-10 | 江苏大学 | Preparation method and application of bionic suction filtration type double-layer molecularly imprinted nanofiber composite membrane based on poly-dopamine imprinting strategy |
| CN114057965A (en) * | 2021-12-17 | 2022-02-18 | 中国地质大学（武汉） | Magnetic molecularly imprinted polymer material for targeted extraction of bisphenol A in sewage |
-
2022
- 2022-09-01 CN CN202211061496.4A patent/CN115364824A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101524636A (en) * | 2009-04-10 | 2009-09-09 | 南京医科大学 | Method for preparing bisphenol A nanometer silicon gel carrier surface molecule print solid phase extraction filling |
| CN113145083A (en) * | 2021-04-16 | 2021-07-23 | 江苏大学 | Janus bifunctional blotting membrane and preparation method and application thereof |
| CN113368706A (en) * | 2021-06-02 | 2021-09-10 | 江苏大学 | Preparation method and application of bionic suction filtration type double-layer molecularly imprinted nanofiber composite membrane based on poly-dopamine imprinting strategy |
| CN114057965A (en) * | 2021-12-17 | 2022-02-18 | 中国地质大学（武汉） | Magnetic molecularly imprinted polymer material for targeted extraction of bisphenol A in sewage |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101347721B (en) | Method for preparing protein magnetic blotting nanospheres | |
| Lu et al. | Irregular dot array nanocomposite molecularly imprinted membranes with enhanced antibacterial property: Synergistic promotion of selectivity, rebinding capacity and flux | |
| CN102794116B (en) | Mesoporous silicon dioxide sphere-polymer nano composite nano-filtration membrane and preparation method thereof | |
| CN109970912B (en) | Preparation method of flavonoid magnetic molecularly imprinted polymer | |
| CN109174023A (en) | A kind of nano-cellulose cross-linked graphene/chitosan aeroge and preparation method thereof, application | |
| CN108816058B (en) | Emodin molecular imprinting titanium dioxide nano particle composite membrane and preparation method and application thereof | |
| CN109772178B (en) | Preparation method and application of pyrimethamine molecularly imprinted composite membrane based on click chemistry double-sided loading | |
| CN101623623A (en) | Method for preparing chitosan-ferric oxide composite absorption arsenic removal material | |
| CN109078614B (en) | Preparation method and application of branched boric acid-based glycoprotein molecular surface imprinted polymer | |
| CN107952375A (en) | A kind of preparation method of antipollution polysulfones/graphene oxide blended ultrafiltration membrane based on ATRP method | |
| CN105080367A (en) | Composite nano-filtration membrane containing composite nanoparticles, and preparation method thereof | |
| CN109499393A (en) | A kind of super hydrophilic PVDF water-oil separationg film and the preparation method and application thereof separating oily wastewater | |
| CN107999019B (en) | Amphiphilic magnetic nanosphere and preparation method and adsorption application thereof | |
| CN109821511A (en) | A kind of preparation and application of polyvinylamine functional magnetic carbon-based nano adsorbent | |
| CN110327792B (en) | Tree-structure mixed matrix membrane constructed by bi-component nano additive and preparation method and application thereof | |
| CN111440354B (en) | Preparation method and application of bisphenol A molecularly imprinted composite membrane with through hierarchical pore structure | |
| CN115364824A (en) | Tetrabromobisphenol A molecularly imprinted membrane and preparation method and application thereof | |
| CN108178810B (en) | Preparation and application of reversed phase/anion exchange mixed mode polymer | |
| CN105618012B (en) | A kind of preparation method of organic inorganic hybridization whole separating material | |
| CN109535393B (en) | Preparation method of microporous organic polymer nano-microspheres and product thereof | |
| CN114100372B (en) | Preparation method of nano particle mixed matrix nanofiltration membrane for drug separation | |
| JPH11313670A (en) | Magnetic carrier, its production and extraction of nucleic acid by using the same | |
| CN110903509B (en) | Preparation method of molecularly imprinted nanocomposite membrane for selectively separating atrazine | |
| CN113368708B (en) | Preparation method and application of suction filtration type double-layer molecular imprinting nano composite membrane based on multiple nano composite imprinting system | |
| Zhang et al. | Preparation and application of magnetic microsphere carriers |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |