CN114433034B - Super-crosslinked polymer modified magnetic nanoparticle and preparation method and application thereof - Google Patents

Super-crosslinked polymer modified magnetic nanoparticle and preparation method and application thereof Download PDF

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CN114433034B
CN114433034B CN202011205312.8A CN202011205312A CN114433034B CN 114433034 B CN114433034 B CN 114433034B CN 202011205312 A CN202011205312 A CN 202011205312A CN 114433034 B CN114433034 B CN 114433034B
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imidazole
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CN114433034A (en
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王晓鹏
陈婧
王蔼廉
计文希
魏芸
张韬毅
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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China Petroleum and Chemical Corp
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    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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    • B01J20/28002—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 physical properties
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    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
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    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
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    • 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
    • B01J20/265—Synthetic macromolecular compounds modified or post-treated polymers
    • B01J20/267—Cross-linked polymers
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    • B01J20/28007—Sorbent size or size distribution, e.g. particle size with size in the range 1-100 nanometers, e.g. nanosized particles, nanofibers, nanotubes, nanowires or the like
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    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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Abstract

The invention discloses a super-crosslinked polymer modified magnetic nanoparticle and a preparation method and an application method thereof, wherein the super-crosslinked polymer modified magnetic nanoparticle comprises a magnetic nanoparticle and a super-crosslinked polymer connected with the magnetic nanoparticle, wherein the super-crosslinked polymer comprises a structural unit A derived from an imidazole monomer, a structural unit B derived from a modified material containing an unsaturated bond and optionally a structural unit C derived from an unsaturated olefin monomer. The super-crosslinked polymer modified magnetic nanoparticle can be used for efficiently and specifically adsorbing aromatic hydrocarbon and can be completely recycled.

Description

Super-crosslinked polymer modified magnetic nanoparticle and preparation method and application thereof
Technical Field
The invention belongs to the technical field of materials for adsorption and separation of aromatic hydrocarbons, and particularly relates to a super-crosslinked polymer modified magnetic nanoparticle, and a preparation method and application thereof.
Background
Naphtha and its separated components find very wide application in the petrochemical industry, for example: 1) The ethylene is used as a raw material for preparing ethylene, and the ethylene raw material obtained by a naphtha way accounts for more than 60 percent of the total ethylene raw material in China; 2) The catalyst is used as a raw material for preparing aromatic hydrocarbon; 3) It is used as a blending oil for vehicles.
The crude oil in China is generally heavy, so that the yield of naphtha is low, and obviously, in order to meet various requirements, how to maximally improve the utilization rate of naphtha in addition to the extraction yield of naphtha as much as possible is an important subject.
In one direction of improving the utilization rate of the naphtha, the components with different properties and effects in the naphtha are thoroughly separated as far as possible, so that the method is aromatic, olefine and olefine, and the utilization rate of the naphtha resource can be greatly optimized, so that the utilization of the naphtha is fully utilized.
The main way of separating naphtha industrially is light and heavy cutting, but it has the defect that component separation cannot be fully realized, especially the optimized utilization of naphtha on hydrocarbon group composition is limited, so new improvements are continuously proposed.
In the existing improved method, the directional separation of alkane molecules in naphtha is a main development direction, and common technical means comprise low-temperature rectification, solvent absorption, adsorption separation, extractive distillation, membrane separation and the like.
An application of ionic liquid as extraction, rectification and separation of benzene-cyclohexane is disclosed in Chinese patent CN101265152A, wherein one ionic liquid or two or more compound ionic liquids are used as separation solvents to separate specific components, so that the separation precision can be improved, the process flow can be simplified, the equipment investment can be reduced, and the separation energy consumption can be reduced.
Although the above technical means have a certain effect in separating saturated hydrocarbon and unsaturated hydrocarbon components in naphtha, they are nonspecific separation, and require multiple separation processes, which are complicated and costly; in addition, the separation media used by the technical means, such as ionic liquid and the like, have large recovery difficulty and high recycling cost, and are difficult to meet the production requirements.
Disclosure of Invention
In order to solve the problems of the prior art, a first aspect of the present invention provides a super-crosslinked polymer modified magnetic nanoparticle. The functionalized magnetic nano particles have the advantages of high structural stability, uniform morphology, high adsorption and separation effects of aromatic compounds with high selectivity and high adsorption capacity, easy recycling and simple and rapid application process.
The second aspect of the invention provides a method for preparing the super-crosslinked polymer modified magnetic nanoparticle. The preparation process is simple and stable, and the product quality is good.
In a third aspect the invention provides the use of any of the above described super cross-linked polymer modified magnetic nanoparticles.
According to a first aspect of the present invention there is provided a super-crosslinked polymer modified magnetic nanoparticle comprising a magnetic nanoparticle and a super-crosslinked polymer linked to the magnetic nanoparticle, wherein the super-crosslinked polymer comprises structural units a derived from an imidazole-based monomer, structural units B derived from an unsaturated bond-containing modified material and optionally structural units C derived from an unsaturated olefin-based monomer.
According to some embodiments of the invention, the super-crosslinked polymer is linked to the magnetic nanoparticle by its structural units derived from an unsaturated bond-containing modified material.
According to some embodiments of the invention, the molar ratio of structural unit A to structural unit C is 1 (0-5), such as 1:0.15、1:0.20、1:0.25、1:0.30、1:0.35、1:0.40、1:0.45、1:0.50、1:0.55、1:0.60、1:0.65、1:0.70、1:0.75、1:0.80、1:0.85、1:0.90、1:0.95、1:1.2、1:1.5、1:2、1:2.5、1:3、1:3.5、1:4、1:4.5 and any values therebetween.
According to some embodiments of the invention, the molar ratio of structural unit A to structural unit C is 1 (0-2).
According to some embodiments of the invention, the molar ratio of structural unit A to structural unit C is 1 (0.1-1).
According to some embodiments of the invention, the magnetic nanoparticle is a silicon-based coated magnetic nanoparticle.
In some preferred embodiments of the invention, the magnetic nanoparticles are silicon-based coated magnetic nanoparticles.
According to some embodiments of the invention, the silicon-based layer refers to a material consisting of silicon and/or a compound of silicon, and is not limited to necessarily a layered structure.
It will be appreciated that the above scheme should include the following combinations:
magnetic iron-based nanoparticle-super cross-linked polymer;
magnetic iron-based nanoparticle-silicon-based-super cross-linked polymer.
According to some embodiments of the invention, the magnetic nanoparticle is selected from one or more of Fe 3O4 magnetic nanoparticle, γ -Fe 2O3 magnetic nanoparticle, nickel zinc ferrite magnetic nanoparticle, manganese zinc ferrite magnetic nanoparticle, and nickel copper zinc ferrite magnetic nanoparticle.
According to some embodiments of the invention, the imidazole-type monomer is selected from one or more of the monomers represented by formula I, formula II and formula III,
In the formula I, the formula II and the formula III, R 1-R3 are the same or different and are each independently selected from C2-C6 alkenyl; r 4-R15 are the same or different and are each independently selected from hydrogen, halogen, amino, hydroxyl, carboxyl, C1-C6 alkyl containing substituent and no substituent, C1-C6 alkoxy containing substituent and no substituent, and C6-C20 aryl containing substituent and no substituent, wherein the substituent is selected from halogen or cyano.
According to some embodiments of the invention, in formula i, formula ii and formula III, R 1-R3 are the same or different and are each independently selected from ethenyl, propenyl and butenyl.
According to some embodiments of the invention, R 4-R15 in formulas I, II, and III, which are the same or different, are selected from hydrogen, halogen, amino, hydroxyl, carboxyl, C1-C6 alkyl, CF 3、CH2Cl、OCH3, and OEt.
According to some embodiments of the invention, in formula ii, R 2 is vinyl and R 8-R10 are both the same hydrogen.
According to some embodiments of the invention, in formula ii, R 2 is vinyl, R 8 and R 9 are both hydrogen and R 10 is methyl.
According to some embodiments of the invention, in formula III, R 3 is vinyl and R 11-R15 are both the same hydrogen.
According to some embodiments of the invention, the unsaturated olefinic monomer is selected from one or more of the monomers of formula IV,
In formula IV, R 16-R21, which are the same or different, are each independently selected from hydrogen, halogen, C1-C6 alkyl, C2-C6 alkenyl, and C1-C6 alkoxy, wherein at least one of R 16-R21 is selected from C2-C6 alkenyl.
According to some embodiments of the invention, R 16-R21 are the same or different and are each independently selected from hydrogen, methyl, ethyl, propyl, methoxy, ethoxy, propoxy, ethenyl, propenyl, and butenyl, wherein at least one of R 16-R21 is selected from ethenyl, propenyl, and butenyl.
According to some embodiments of the invention, in formula IV, R 16 is vinyl and R 17-R21 are both the same hydrogen.
According to some embodiments of the invention, in formula IV, R 16 and R 17 are vinyl and R 18-R21 are both hydrogen.
According to some embodiments of the invention, the unsaturated bond-containing modified material is selected from one or more of unsaturated bond-containing silane coupling agents.
According to some embodiments of the invention, the unsaturated bond-containing modifying material is selected from one or more of double bond-containing silane coupling agents.
According to some embodiments of the invention, the unsaturated bond-containing modifying material is selected from one or more of the compounds represented by formulas 1 and 2,
In the formulas 1 and 2, R 1-R3 are the same or different and are each independently selected from halogen, C1-C6 alkoxy containing substituent or no substituent, wherein the substituent is selected from halogen, cyano or C1-C6 alkoxy and C1-C6 alkyl containing substituent or no substituent; r 4-R6 are the same or different and are each independently selected from hydrogen and C1-C6 alkyl; n is a positive integer from 1 to 6.
According to some embodiments of the invention, R 1-R3 are the same or different and are each independently selected from chlorine, bromine, iodine, methoxy, ethoxy, propoxy and methoxyethoxy.
According to some embodiments of the invention, R 4-R6 are the same or different and are each independently selected from hydrogen, methyl, ethyl, n-propyl and isopropyl.
According to some embodiments of the invention, the unsaturated bond-containing modifying material is selected from one or more of 3-methacryloxypropyl trimethoxysilane, vinyl trichlorosilane, vinyl triethoxysilane, vinyl tris (2-methoxyethoxy) silane, vinyl trimethoxysilane, and vinyl methyl dimethoxy silane.
The magnetic nanoparticles are compounded with the super-crosslinked polymer, wherein the magnetic nanoparticles have magnetic responsiveness, are easy to orient under the action of an external magnetic field, realize quick recycling, are easy to surface functionalize, and can be combined with various polymers in a physical or chemical way in an efficient and stable manner; the super-crosslinked polymer has an imidazole structure, can generate pi-pi complexation with unsaturated double bonds in aromatic hydrocarbon compound molecules, has a simple structure and low steric hindrance, can realize high crosslinking, and forms a selective separation layer with a super-crosslinked network structure so as to realize specific adsorption separation of the aromatic hydrocarbon compound. Meanwhile, the cross-linked polymer with a net structure can be formed through cross-linking of double bonds, which is beneficial to further increasing the selective absorption performance of the material.
In addition, the inventor discovers that the magnetic nano particles can effectively strengthen the complexing effect of the hypercrosslinked polymer containing imidazole structure on aromatic hydrocarbon compounds under the action of an external magnetic field, so that the effect of specific adsorption separation is further improved.
In some preferred embodiments of the invention, the surface of the magnetic nanoparticle is coated with the silicon-based layer, which can prevent the oxidative denaturation of the magnetic particle, effectively improve the structural stability of the functionalized magnetic nanoparticle, and enhance the bonding capability between the core and the shell material.
In some preferred embodiments of the present invention, the silicon-based layer is selected to be a SiO 2 film, which may further enhance the adsorption capacity of the product.
According to a second aspect of the present invention, there is provided a method for preparing a super-crosslinked polymer modified magnetic nanoparticle, comprising the steps of:
s1: modifying the magnetic nano particles by adopting a modified material containing unsaturated bonds to obtain modified magnetic nano particles;
S2: dispersing the modified magnetic nano particles obtained in the step S1 in a first solvent to obtain a dispersion liquid;
S3: and (3) adding imidazole monomer, initiator, cross-linking agent and optionally unsaturated olefin monomer into the dispersion liquid obtained in the step (S2) to carry out polymerization reaction, thus obtaining the super-crosslinked polymer modified magnetic nanoparticle.
According to some embodiments of the invention, the method further comprises coating the magnetic nanoparticles with a silicon-based layer, preferably at the surface, before performing step S1.
According to some embodiments of the present invention, the magnetic nanoparticle surface is coated with a silicon-based layer using methods conventional in the art, preferably using the following methods: the magnetic nanoparticles are dispersed in a solvent such as a mixed solution of H 2 O and ethanol, and reacted by adding a silicon source such as ethyl orthosilicate at pH 9-10.
According to some embodiments of the invention, the unsaturated bond-containing modified material is selected from one or more of unsaturated bond-containing silane coupling agents.
According to some embodiments of the invention, the unsaturated bond-containing modifying material is selected from one or more of double bond-containing silane coupling agents.
According to some embodiments of the invention, the unsaturated bond-containing modifying material is selected from one or more of the compounds represented by formulas 1 and 2,
In the formulas 1 and 2, R 1-R3 are the same or different and are each independently selected from halogen, C1-C6 alkoxy containing substituent or no substituent, wherein the substituent is selected from halogen, cyano or C1-C6 alkoxy and C1-C6 alkyl containing substituent or no substituent; r 4-R6 are the same or different and are each independently selected from hydrogen and C1-C6 alkyl; n is a positive integer from 1 to 6.
According to some embodiments of the invention, R 1-R3 are the same or different and are each independently selected from chlorine, bromine, iodine, methoxy, ethoxy, propoxy and methoxyethoxy.
According to some embodiments of the invention, R 4-R6 are the same or different and are each independently selected from hydrogen, methyl, ethyl, n-propyl and isopropyl.
According to some embodiments of the invention, the unsaturated bond-containing modifying material is selected from one or more of 3-methacryloxypropyl trimethoxysilane, vinyl trichlorosilane, vinyl triethoxysilane, vinyl tris (2-methoxyethoxy) silane, vinyl trimethoxysilane, and vinyl methyl dimethoxy silane.
According to some embodiments of the invention, the modifying treatment comprises: dispersing the magnetic nano particles or the magnetic nano particles coated with the silicon base layer in a second solvent, and adding the modified material containing unsaturated bonds under the condition that the pH is 9-10.
The modification treatment in the present invention refers to a process of changing physical and/or chemical properties of the target (e.g., the magnetic nanoparticle or/and the further encapsulated silicon substrate in the present invention) by physical and/or chemical means, such as introducing new functional groups on the surface of the target, changing the surface morphology of the target, removing part of the surface of the target, etc.
According to some embodiments of the invention, functional groups such as silica groups are introduced into the magnetic nano particles or/and the further coated silicon base layer through modification treatment, so that the magnetic matrix and the super-crosslinked polymer are connected, and the composite performance of the magnetic nano particles and the super-crosslinked polymer is further improved.
According to some embodiments of the invention, the second solvent is selected from one or more of water and a C1-C6 alcohol.
According to some embodiments of the invention, the second solvent is a mixed solution of water and ethanol.
According to some embodiments of the invention, the magnetic nanoparticle is selected from one or more of Fe 3O4 magnetic nanoparticle, γ -Fe 2O3 magnetic nanoparticle, nickel zinc ferrite magnetic nanoparticle, manganese zinc ferrite magnetic nanoparticle, and nickel copper zinc ferrite magnetic nanoparticle.
According to some embodiments of the invention, the magnetic nanoparticles may be commercially available finished products or laboratory self-manufactured products.
In some preferred embodiments of the present invention, the preparation method of the magnetic nanoparticle comprises dissolving iron-based raw materials, succinic acid and urea, and reacting at 150-250 ℃ to obtain the magnetic nanoparticle.
According to some embodiments of the invention, the imidazole-type monomer is selected from one or more of the monomers represented by formula I, formula II and formula III,
In the formula I, the formula II and the formula III, R 1-R3 are the same or different and are each independently selected from C2-C6 alkenyl; r 4-R15 are the same or different and are each independently selected from hydrogen, halogen, amino, hydroxyl, carboxyl, C1-C6 alkyl containing substituent and no substituent, C1-C6 alkoxy containing substituent and no substituent, and C6-C20 aryl containing substituent and no substituent, wherein the substituent is selected from halogen or cyano.
According to some embodiments of the invention, in formula i, formula ii and formula III, R 1-R3 are the same or different and are each independently selected from ethenyl, propenyl and butenyl.
According to some embodiments of the invention, R 4-R15 in formulas I, II, and III, which are the same or different, are selected from hydrogen, halogen, amino, hydroxyl, carboxyl, C1-C6 alkyl, CF 3、CH2Cl、OCH3, and OEt.
According to some embodiments of the invention, in formula ii, R 2 is vinyl and R 8-R10 are both the same hydrogen.
According to some embodiments of the invention, in formula ii, R 2 is vinyl, R 8 and R 9 are both hydrogen and R 10 is methyl.
According to some embodiments of the invention, in formula III, R 3 is vinyl and R 11-R15 are both the same hydrogen.
According to some embodiments of the invention, the unsaturated olefinic monomer is selected from one or more of the monomers of formula IV,
In formula IV, R 16-R21, which are the same or different, are each independently selected from hydrogen, halogen, C1-C6 alkyl, C2-C6 alkenyl, and C1-C6 alkoxy, wherein at least one of R 16-R21 is selected from C2-C6 alkenyl.
According to some embodiments of the invention, R 16-R21 are the same or different and are each independently selected from hydrogen, methyl, ethyl, propyl, methoxy, ethoxy, propoxy, ethenyl, propenyl, and butenyl, wherein at least one of R 16-R21 is selected from ethenyl, propenyl, and butenyl.
According to some embodiments of the invention, in formula IV, R 16 is vinyl and R 17-R21 are both the same hydrogen.
According to some embodiments of the invention, in formula IV, R 16 and R 17 are vinyl and R 18-R21 are both hydrogen.
According to some embodiments of the invention, the initiator is selected from one or more of azobisisobutyronitrile, azobisisoheptonitrile, dimethyl azobisisobutyrate, benzoyl peroxide, diacyl peroxide, potassium persulfate and sodium bisulfite.
According to some embodiments of the invention, the cross-linking agent is selected from at least one of ethylene glycol dimethacrylate, divinylbenzene, trimethylpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, tetraethyloxysilane, and N, N-methylenebisacrylamide.
According to some embodiments of the invention, the first solvent is selected from one or more of toluene, acetonitrile, N-dimethylformamide, dimethylacetamide and dimethylsulfoxide.
According to some embodiments of the invention, the mass ratio of the unsaturated bond-containing modifying material to the magnetic nanoparticle is 1 (1-50), such as 1:3、1:6、1:7、1:8、1:9、1:10、1:11、1:12、1:13、1:14、1:15、1:16、1:17、1:18、1:19、1:22、1:25、1:30、1:33、1:35、1:37、1:40、1:43、1:45、1:48 and any values therebetween.
According to some embodiments of the invention, the mass ratio of the unsaturated bond-containing modified material to the magnetic nanoparticle is 1 (5-20).
According to some embodiments of the invention, the mass ratio of the imidazole-based monomer to the modified magnetic nanoparticle is 1 (0.1-0.3), such as 1:0.11、1:0.12、1:0.13、1:0.14、1:0.15、1:0.16、1:0.17、1:0.18、1:0.19、1:0.20、1:0.21、1:0.22、1:0.23、1:0.24、1:0.25、1:0.26、1:0.27、1:0.28、1:0.29 and any values therebetween.
According to some embodiments of the invention, the mass ratio of the imidazole-based monomer to the modified magnetic nanoparticle is 1 (0.1-0.2).
According to some embodiments of the invention, the mass ratio of the imidazole-based monomer to the unsaturated olefin-based monomer is 1 (0-10), such as 1:0.15、1:0.20、1:0.25、1:0.30、1:0.35、1:0.40、1:0.45、1:0.50、1:0.55、1:0.60、1:0.65、1:0.70、1:0.75、1:0.80、1:0.85、1:0.90、1:0.95、1:1.2、1:1.5、1:2、1:2.5、1:3、1:3.5、1:4、1:4.5、1:4.5、1:4.5、1:5.5、1:6、1:7、1:8、1:9 and any value therebetween.
According to some embodiments of the invention, the mass ratio of the imidazole-based monomer to the unsaturated olefin-based monomer is 1 (0-5).
According to some embodiments of the invention, the mass ratio of the imidazole-based monomer to the unsaturated olefin-based monomer is 1 (0.1-2).
According to some embodiments of the invention, the mass ratio of the imidazole-based monomer to the first solvent is 1 (1-30), such as 1:2, 1:4, 1:6, 1:8, 1:12, 1:14, 1:16, 1:18, 1:22, 1:25, 1:27, and any value therebetween.
According to some embodiments of the invention, the mass ratio of the imidazole monomer to the first solvent is 1 (10-20).
According to some embodiments of the invention, the mass ratio of the imidazole-based monomer to the crosslinker is 1 (0.1-1.5), such as 1:0.15, 1:0.2, 1:0.3, 1:0.4, 1:0.5, 1:0.6, 1:0.7, 1:0.8, 1:0.9, 1:1.0, 1:1.1, 1:1.2, 1:1.3, 1:1.4, and any value therebetween.
According to some embodiments of the invention, the mass ratio of the imidazole monomer to the initiator is 1 (0.0001-0.05).
In one embodiment of the present invention, the preparation method of the functionalized magnetic nanoparticle comprises the following specific steps:
(1) Preparation of Fe 3O4 magnetic nanoparticles: feCl 3·6H2 O3-6 mmol, succinic acid 1-2mmol and urea 30-60mmol are dissolved in 40mL propylene glycol, stirred at 60 ℃ for 30min, then placed into a 50mL reaction kettle and reacted at 200 ℃ for 8-16h. Cooling, transferring the reaction mixture to a centrifuge tube for centrifugal separation (5000-10000 r/min,5-8 min), washing with deionized water and ethanol for 3 times, and vacuum drying at 60deg.C to obtain Fe3O4 magnetic nanoparticles;
(2) Preparation of Fe 3O4/SiO2 shell-core magnetic nanoparticles: weighing 0.1-1g of Fe 3O4 magnetic nano particles of the product (1), dispersing in a mixed solution of H 2 O and ethanol (volume ratio is 1:4), performing ultrasonic dispersion for 10-30min, and adding NH 3·H2 O under stirring to adjust the pH to be 9-10. Adding 0.1-4mL of ethyl orthosilicate, mechanically stirring and reacting for 1-12h, transferring the reaction mixture to a centrifuge tube for centrifugal separation (5000-10000 r/min,5-8 min), washing with deionized water and ethanol, and vacuum drying at 60 ℃ to obtain Fe 3O4/SiO2 nano particles;
(3) Synthesizing the ionic liquid functionalized magnetic nano particles: ① Weighing 0.1-0.8g of the core-shell magnetic nano particles prepared in the step (2), dispersing in a mixed solution of H 2 O and ethanol (volume ratio is 1:4), performing ultrasonic dispersion for 10-30min, and adding NH 3.H2O to adjust the pH to be 9-10. 1-4ml of 3-methacryloxypropyl trimethoxysilane (KH 570) was then added and stirred at 60℃for 24-48h. Cooling to room temperature, washing with toluene, ethanol and deionized water in sequence, and vacuum drying at 60 ℃ to obtain double bond modified magnetic nano particles;
(4) And (3) weighing double-bond modified magnetic nano particles, dispersing the magnetic nano particles in anhydrous toluene, sequentially adding an initiator, a cross-linking agent, an imidazole monomer and an unsaturated olefin monomer, carrying out reflux reaction for 24-48h in an N 2 atmosphere, cooling to room temperature, sequentially washing with toluene, ethanol and water, and then carrying out vacuum drying to obtain the polymerization modified functionalized magnetic nano particles.
According to a third aspect of the present invention, there is provided the use of the super-crosslinked polymer modified magnetic nanoparticle according to the first aspect or the super-crosslinked polymer modified magnetic nanoparticle prepared by the method according to the second aspect in aromatic hydrocarbon adsorption separation.
According to some embodiments of the invention, the super-crosslinked polymer modified magnetic nanoparticles are separated from adsorption of aromatic hydrocarbons and naphthenes in naphtha, such as separation of toluene and cyclohexane.
The invention has the following beneficial effects:
(1) The invention obtains a functional magnetic nano particle by compounding the magnetic nano particle and the super cross-linked polymer containing imidazole structure, which can realize the high-efficiency specific adsorption separation of aromatic hydrocarbon;
(2) The functionalized magnetic nano particles can be completely recycled, and the recycling process is convenient and quick;
(3) The cross-linked polymer with a reticular structure can be formed through cross-linking of double bonds, so that the product has a stable and porous structure and uniform morphology, and the selective absorption performance of the material is further improved.
Drawings
FIG. 1 is a schematic structural diagram of a functionalized magnetic nanoparticle according to an embodiment of the present invention.
Detailed Description
The present invention will be further illustrated by the following specific examples, but it should be understood that the scope of the present invention is not limited thereto.
The starting materials used in the examples were all commercially available and analytically pure unless specified.
The evaluation method of the adsorption and separation performance of the functionalized magnetic nano particles on aromatic hydrocarbon comprises the following steps:
(1) The specific surface area of the functionalized magnetic nano particles is measured by adopting an N 2 adsorption method;
(2) Characterization of adsorption separation performance: 200mg of functionalized magnetic nano particles are weighed, dispersed in 2mL of methanol, filled in a pipeline, fixed by an external magnetic field, slowly heated to 120 ℃, kept for 1h, and the methanol and redundant water vapor are removed completely. After the pipeline was cooled to room temperature, the simulated liquid (cyclohexane, toluene) was purged into the pipeline with N 2, the toluene concentration was controlled to 3.64%, the cyclohexane concentration was controlled to 3.64%, the N2 concentration was 92.72%, the flow rate of N 2 was 60mL/min, and the gas composition and content of the outlet were detected by GC-MS.
Example 1
The functionalized magnetic nanoparticles were prepared by the following procedure:
(1) Weighing 1.62g of FeCl 3·6H2 O, 0.12g of succinic acid and 1.8g of urea, dissolving in 40mL of propylene glycol, stirring at 60 ℃ for 30min, putting into a 50mL reaction kettle, reacting at 200 ℃ for 8-16h, cooling, transferring the reaction mixture to a centrifuge tube for centrifugal separation (5000-10000 r/min,5-8 min), washing the separated solid with deionized water and ethanol for 3 times, and then vacuum drying at 60 ℃ to obtain Fe 3O4 magnetic nanoparticles;
(2) Weighing 0.4g of Fe 3O4 magnetic nano particles in the product (1), dispersing in a mixed solution of H 2 O and ethanol (volume ratio is 1:4), performing ultrasonic dispersion for 30min, adding NH 3·H2 O under stirring to adjust pH=9-10, adding 0.6mL of ethyl orthosilicate, performing mechanical stirring reaction for 6H, transferring the reaction mixture to a centrifuge tube for centrifugal separation (5000-10000 r/min,5-8 min), washing the solid with deionized water and ethanol, and performing vacuum drying at 60 ℃ to obtain Fe 3O4/SiO2 nano particles with a core-shell structure;
(3) Weighing 0.2g of the magnetic nano particles with the shell-core structure prepared in the step (2), dispersing in a mixed solution of H 2 O and ethanol (volume ratio is 1:4), performing ultrasonic dispersion for 30min, adding NH 3·H2 O under stirring to adjust the pH to be 9-10, adding 2mL (2.1 g) of 3-methacryloxypropyl trimethoxysilane, stirring for 24H at 60 ℃, cooling to room temperature, washing with toluene, ethanol and deionized water in sequence, and performing vacuum drying to obtain a solid, thus obtaining modified magnetic nano particles;
(4) And (3) weighing 0.4g of the modified magnetic nano particles obtained in the step (3), dispersing the modified magnetic nano particles in 40mL (34.6 g) of anhydrous toluene, sequentially adding 20mg of dibenzoyl peroxide (BPO), 3mL (3.2 g) of Ethylene Glycol Dimethacrylate (EGDMA) and 3.2g of 1-vinylimidazole, carrying out reflux reaction for 24 hours, cooling to room temperature, sequentially washing with toluene, ethanol and deionized water, and vacuum drying the obtained solid to obtain the polyethylene imidazole functionalized magnetic nano particles.
The specific surface area test of the functionalized magnetic nanoparticle and the evaluation method for the adsorption and separation performance of aromatic hydrocarbon were used to evaluate the application capacity of the functionalized magnetic nanoparticle, and the results are shown in table 1.
Example 2
The modified magnetic nanoparticles were prepared by using the same steps (1) - (3) as in example 1, 0.4g of the modified magnetic nanoparticles were weighed and dispersed in 40mL (34.6 g) of anhydrous toluene, then 10mg of dibenzoyl peroxide (BPO), 3mL (3.2 g) of Ethylene Glycol Dimethacrylate (EGDMA) and 4g of 2-vinylbenzimidazole (CAS number: 14984-26-0) were sequentially added to carry out reflux reaction for 24 hours, and then cooled to room temperature, washed sequentially with toluene, ethanol and deionized water, and then the obtained solid was dried in vacuo, thereby obtaining the polybenzimidazole functionalized magnetic nanoparticles.
The specific surface area test of the functionalized magnetic nanoparticle and the evaluation method for the adsorption and separation performance of aromatic hydrocarbon were used to evaluate the application capacity of the functionalized magnetic nanoparticle, and the results are shown in table 1.
Example 3
The modified magnetic nanoparticles were prepared by using the same steps (1) - (3) as in example 1, 0.4g of the modified magnetic nanoparticles were weighed and dispersed in 40mL (34.6 g) of anhydrous toluene, then 20mg of dibenzoyl peroxide (BPO), 3mL (3.2 g) of Ethylene Glycol Dimethacrylate (EGDMA) and 3mL (2.8 g) of 2-methyl-1-vinylimidazole were sequentially added, reflux reaction was performed for 24 hours, after which the temperature was lowered to room temperature, washing was performed sequentially with toluene, ethanol and deionized water, and then the obtained solid was dried in vacuo, thereby obtaining the polyimidazole functionalized magnetic nanoparticles.
The specific surface area test of the functionalized magnetic nanoparticle and the evaluation method for the adsorption and separation performance of aromatic hydrocarbon were used to evaluate the application capacity of the functionalized magnetic nanoparticle, and the results are shown in table 1.
Example 4
The modified magnetic nanoparticles were prepared by using the same steps (1) - (3) as in example 1, 0.4g of the modified magnetic nanoparticles were weighed and dispersed in 40mL (34.6 g) of anhydrous toluene, then 20mg of dibenzoyl peroxide (BPO), 3mL (3.2 g) of Ethylene Glycol Dimethacrylate (EGDMA), 3.2g of 1-vinylimidazole and 1mL (0.9 g) of styrene were sequentially added, and a reflux reaction was performed for 24 hours, after which the temperature was lowered to room temperature, and then washed with toluene, ethanol and deionized water in sequence, and then the obtained solid was dried in vacuo, thereby obtaining the monomer-functionalized magnetic nanoparticles of imidazole copolymer.
The specific surface area test of the functionalized magnetic nanoparticle and the evaluation method for the adsorption and separation performance of aromatic hydrocarbon were used to evaluate the application capacity of the functionalized magnetic nanoparticle, and the results are shown in table 1.
Example 5
The modified magnetic nanoparticles were prepared by using the same steps (1) - (3) as in example 1, 0.4g of the modified magnetic nanoparticles were weighed and dispersed in 40mL (37.9 g) of DMF, then 50mg of Azobisisobutyronitrile (AIBN), 3.2g of 1-vinylimidazole and 3mL (2.8 g) of divinylbenzene were sequentially added, the reflux reaction was performed for 24 hours, then cooled to room temperature, washed sequentially with toluene, ethanol and deionized water, and then the obtained solid was dried in vacuo, thus obtaining the monomer-functionalized magnetic nanoparticles of imidazole copolymer.
The specific surface area test of the functionalized magnetic nanoparticle and the evaluation method for the adsorption and separation performance of aromatic hydrocarbon were used to evaluate the application capacity of the functionalized magnetic nanoparticle, and the results are shown in table 1.
Example 6
The modified magnetic nanoparticles were prepared by using the same steps (1) - (3) as in example 1, 0.4g of the modified magnetic nanoparticles were weighed and dispersed in 40mL (34.6 g) of anhydrous toluene, then 20mg of dibenzoyl peroxide (BPO), 5mL (5.3 g) of Ethylene Glycol Dimethacrylate (EGDMA) and 3.2g of 1-vinylimidazole were sequentially added, the mixture was subjected to reflux reaction for 24 hours, and then cooled to room temperature, and then washed with toluene, ethanol and deionized water in sequence, and then the obtained solid was dried in vacuo to obtain the monomer-functionalized magnetic nanoparticles of imidazole copolymer.
The specific surface area test of the functionalized magnetic nanoparticle and the evaluation method for the adsorption and separation performance of aromatic hydrocarbon were used to evaluate the application capacity of the functionalized magnetic nanoparticle, and the results are shown in table 1.
Example 7
The modified magnetic nanoparticles were prepared by using the same steps (1) - (3) as in example 1, 0.4g of the modified magnetic nanoparticles were weighed and dispersed in 40mL (34.6 g) of anhydrous toluene, then 20mg of dibenzoyl peroxide (BPO), 3mL (3.2 g) of Ethylene Glycol Dimethacrylate (EGDMA) and 1.07g of 1-vinylimidazole were sequentially added, the mixture was subjected to reflux reaction for 24 hours, and then cooled to room temperature, and then washed with toluene, ethanol and deionized water in sequence, and then the obtained solid was dried in vacuo to obtain the monomer-functionalized magnetic nanoparticles of imidazole copolymer.
The specific surface area test of the functionalized magnetic nanoparticle and the evaluation method for the adsorption and separation performance of aromatic hydrocarbon were used to evaluate the application capacity of the functionalized magnetic nanoparticle, and the results are shown in table 1.
TABLE 1
Specific surface area/m 2·g-1 Toluene adsorption amount/mg.g -1
Example 1 323 120.4
Example 2 329 121.2
Example 3 276 112.2
Example 4 288 115.8
Example 5 275 113.1
Example 6 156 65.8
Example 7 133 56.3
It should be noted that the above-described embodiments are only for explaining the present invention and do not limit the present invention in any way. The invention has been described with reference to exemplary embodiments, but it is understood that the words which have been used are words of description and illustration, rather than words of limitation. Modifications may be made to the invention as defined in the appended claims, and the invention may be modified without departing from the scope and spirit of the invention. Although the invention is described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, as the invention extends to all other means and applications which perform the same function.

Claims (19)

1. Use of a super-crosslinked polymer-modified magnetic nanoparticle comprising a magnetic nanoparticle and a super-crosslinked polymer linked to the magnetic nanoparticle, wherein the super-crosslinked polymer comprises a structural unit a derived from an imidazole-based monomer, a structural unit B derived from an unsaturated bond-containing modified material, for adsorbing aromatic hydrocarbons in naphtha;
the preparation method of the super-crosslinked polymer modified magnetic nanoparticle comprises the following steps:
s1: modifying the magnetic nano particles by adopting a modified material containing unsaturated bonds to obtain modified magnetic nano particles;
S2: dispersing the modified magnetic nano particles obtained in the step S1 in a first solvent to obtain a dispersion liquid;
S3: adding imidazole monomer, initiator and cross-linking agent into the dispersion liquid obtained in the step S2 to carry out polymerization reaction, thus obtaining the super-crosslinked polymer modified magnetic nano-particles;
The cross-linking agent is at least one selected from ethylene glycol dimethacrylate, divinylbenzene, trimethylpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, tetraethyloxysilane and N, N-methylene bisacrylamide;
the mass ratio of the imidazole monomer to the cross-linking agent is 1 (0.1-1.5);
the imidazole monomer is selected from monomers shown in a formula III,
In formula III, R 3 is selected from C2-C6 alkenyl; r 11-R15 are the same or different and are each independently selected from hydrogen, halogen, amino, hydroxyl, carboxyl, substituted and unsubstituted C1-C6 alkyl, substituted and unsubstituted C1-C6 alkoxy and substituted and unsubstituted C6-C20 aryl, wherein the substituents are selected from halogen or cyano;
the unsaturated bond-containing modified material is selected from one or more of compounds shown in formula 1 and formula 2,
In the formulas 1 and 2, R 1-R3 are the same or different and are each independently selected from halogen, C1-C6 alkoxy containing substituent or no substituent, wherein the substituent is selected from halogen, cyano or C1-C6 alkoxy; r 4-R6 are identical or different and are each independently selected from hydrogen and C1-C6 alkyl, n is a positive integer from 1 to 6.
2. The use according to claim 1, characterized in that the super-crosslinked polymer further comprises structural units C derived from unsaturated olefinic monomers.
3. Use according to claim 2, characterized in that the molar ratio of structural unit a to structural unit C is 1 (0-5).
4. Use according to claim 2, characterized in that the molar ratio of structural unit a to structural unit C is 1 (0-2).
5. The use according to claim 2, wherein the molar ratio of structural unit A to structural unit C is 1 (0.1-1).
6. The use according to claim 1, wherein the magnetic nanoparticles are silicon-based coated magnetic nanoparticles.
7. The use according to any one of claims 1 to 6, wherein the magnetic nanoparticles are selected from one or more of Fe 3O4 magnetic nanoparticles, γ -Fe 2O3 magnetic nanoparticles, magnetic iron nanoparticles, nickel zinc ferrite magnetic nanoparticles, manganese zinc ferrite magnetic nanoparticles and nickel copper zinc ferrite magnetic nanoparticles.
8. The use according to claim 2, wherein the unsaturated olefin monomer is selected from one or more of the monomers of formula IV,
In formula IV, R 16-R21, which are the same or different, are each independently selected from hydrogen, halogen, C1-C6 alkyl, C2-C6 alkenyl, and C1-C6 alkoxy, wherein at least one of R 16-R21 is selected from C2-C6 alkenyl.
9. The use according to claim 8, wherein in the imidazole-based monomer of formula III, R 3 is selected from ethenyl, propenyl and butenyl; r 11-R15, which are identical or different, are each independently selected from the group consisting of hydrogen, halogen, amino, hydroxyl, carboxyl, C1-C6 alkyl, CF 3、CH2Cl、OCH3 and OEt;
In the unsaturated olefin monomer of the formula IV, R 16-R21 is the same or different and is independently selected from hydrogen, methyl, ethyl, propyl, methoxy, ethoxy, propoxy, ethenyl, propenyl and butenyl, wherein at least one of R 16-R21 is selected from ethenyl, propenyl and butenyl.
10. Use according to claim 1, wherein in formulae 1 and 2, R 1-R3, identical or different, are selected from chlorine, bromine, iodine, methoxy, ethoxy, propoxy and methoxyethoxy; r 4-R6, which are identical or different, are selected from hydrogen, methyl, ethyl, n-propyl and isopropyl.
11. The use according to claim 1, wherein the unsaturated bond-containing modifying material is selected from one or more of 3-methacryloxypropyl trimethoxysilane, vinyl trichlorosilane, vinyl triethoxysilane, vinyl tris (2-methoxyethoxy) silane, vinyl trimethoxysilane and vinyl methyl dimethoxy silane.
12. The use according to claim 2, characterized in that in step S3, it further comprises the step of adding an unsaturated olefin monomer to the dispersion.
13. The use according to claim 1, further comprising coating the magnetic nanoparticles with a silicon-based layer prior to step S1.
14. The use according to claim 1, wherein the modification treatment comprises: dispersing the magnetic nano particles or the magnetic nano particles coated with the silicon base layer in a second solvent, and adding the modified material containing unsaturated bonds under the condition that the pH is 9-10.
15. The use according to claim 14, wherein in the modification treatment the second solvent is selected from one or more of water and a C1-C6 alcohol.
16. The use according to claim 1, wherein the initiator is selected from one or more of azobisisobutyronitrile, azobisisoheptonitrile, dimethyl azobisisobutyrate, benzoyl peroxide, diacyl peroxide, potassium persulfate and sodium bisulfite;
the first solvent is selected from one or more of toluene, acetonitrile, N-dimethylformamide, dimethylacetamide and dimethyl sulfoxide.
17. The use according to claim 2, wherein the mass ratio of the unsaturated bond-containing modified material to the magnetic nanoparticles is 1 (1-50);
The mass ratio of the imidazole monomer to the modified magnetic nano-particles is 1 (0.1-0.3);
The mass ratio of the imidazole monomer to the unsaturated olefin monomer is 1 (0-10);
The mass ratio of the imidazole monomer to the first solvent is 1 (1-30);
the mass ratio of the imidazole monomer to the initiator is 1 (0.0001-0.05).
18. The use according to claim 17, wherein the mass ratio of the unsaturated bond-containing modified material to the magnetic nanoparticles is 1 (5-20);
the mass ratio of the imidazole monomer to the modified magnetic nano-particles is 1 (0.1-0.2);
the mass ratio of the imidazole monomer to the unsaturated olefin monomer is 1 (0-5);
the mass ratio of the imidazole monomer to the first solvent is 1 (10-20).
19. The use according to claim 17, wherein the mass ratio of the imidazole-based monomer to the unsaturated olefin-based monomer is 1 (0.1-2).
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