CN106622172A - Preparation method of surface-functionalized, micron-sized, porous, paramagnetic and spherical resin particle - Google Patents
Preparation method of surface-functionalized, micron-sized, porous, paramagnetic and spherical resin particle Download PDFInfo
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- CN106622172A CN106622172A CN201611244491.XA CN201611244491A CN106622172A CN 106622172 A CN106622172 A CN 106622172A CN 201611244491 A CN201611244491 A CN 201611244491A CN 106622172 A CN106622172 A CN 106622172A
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- 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
- B01J20/265—Synthetic macromolecular compounds modified or post-treated polymers
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- 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
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0225—Compounds of Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt
- B01J20/0229—Compounds of Fe
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28002—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
- B01J20/28009—Magnetic properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—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 surface properties or porosity
- B01J20/28057—Surface area, e.g. B.E.T specific surface area
- B01J20/28061—Surface area, e.g. B.E.T specific surface area being in the range 100-500 m2/g
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—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 surface properties or porosity
- B01J20/28078—Pore diameter
- B01J20/28083—Pore diameter being in the range 2-50 nm, i.e. mesopores
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/08—Epoxidation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/34—Introducing sulfur atoms or sulfur-containing groups
- C08F8/36—Sulfonation; Sulfation
Abstract
The invention provides a preparation method of a micron-sized, porous and spherical resin particle with paramagnetic performance and different surface functionalization. The preparation method comprises steps as follows: a polymer microsphere is taken as an initial raw material, a nitrification reagent is used for nitrifying the surface of the polymer microsphere, then, a magnetic material is generated on the surface of the microsphere through an oxidation-reduction reaction with water-soluble ferrite, and the polymer microsphere with the paramagnetic performance is obtained. On the basis, the surface of the microsphere is subjected to epoxy activation and functional derivatization, and the surface-functionalized magnetic polymer microsphere is obtained. By optimizing and controlling the ferric content of the microsphere, influences on microsphere pore diameter, specific surface area and other parameters in the magnetization process can be reduced as much as possible, follow-up surface functionalization of the magnetic microsphere is easier to realize, the adsorption effect is better, and the prepared surface-functionalized magnetic polymer microsphere, particularly, a surface-functionalized, magnetic, porous and spherical crosslinking polystyrene particle has a good effect when used for solid-phase extraction as an extraction agent.
Description
Technical field
The present invention relates to solid material technical field, and in particular to a kind of micrometer level porous paramagnetic of different surfaces functionalization
The preparation method of property spherical resin particle.
Background technology
Magnetic material, particularly magnetic Nano material, because its higher specific surface area and paramagnetic properties make its go out it is quick,
It is easy to carry out showing huge advantage during separation and concentration material.But nano material also has clearly disadvantageous and scarce when in use
Fall into, not easy enough, stable including preparation method, granule is easily reunited, the problems such as the easy blocking filtering device of the residual in solution.And it is micro-
The resin porous particle of the functionalization of meter level has the good characteristics such as high intensity, high-ratio surface, acid and alkali-resistance, medicine, it is biological and
The fields such as chemical are extensively used as separation, analysis and enrichment material.But relative magnetism material, simple resin particle cannot
Quickly separated and shifted by magnetic field.Prepare the material of the porous resin granule of the micron order functionalization with paramagnetic properties
Material can then be effectively combined the advantage of aforementioned bi-material so as to bring more when being combined in separation and concentration and its with self-reacting device
Big advantage.
The content of the invention
The invention provides a kind of preparation method of the polymer microballoon with paramagnetic performance；Methods described includes following step
Suddenly：
(1) nitration treatment is carried out to polymer microballoon surface by nitrating agent；
(2) combination of the salt of the microsphere for obtaining step (1) and ferrous salt or ferrous salt and other metals and alkali are carried out instead
Should；
Preferably, described polymer microballoon is obtained for polymerization of vinyl monomer, can be a kind of the equal of vinyl monomer
Polymers, it is also possible to the copolymer of two or more vinyl monomers；Described vinyl monomer preferably is selected from：Styrene, maleic acid
Acid anhydride, acrylate, vinyl esters and its derivant, more preferably certainly：Styrene, acrylic acid methyl ester., methyl methacrylate, third
One or more in olefin(e) acid ethyl ester, ethyl methacrylate, butyl acrylate, butyl methacrylate, vinyl acetate；
In a preferred embodiment of the invention, described vinyl monomer be styrene, described polymer microballoon
For cinnamic homopolymer；
In above-mentioned steps (1), polymer microballoon used can adopt the method disclosed in prior art to prepare, and also may be used
It is commercially available to adopt；
Preferably, described polymer microballoon is cross linked porous；Preferably, the degree of cross linking of polymer microballoon is 40-
80%；More preferably 60-80%；
Preferably, described polymer microballoon is spherical；
Preferably, the particle diameter of described microsphere is 100-400 mesh, more preferably 200-400 mesh；
Preferably, specific surface area 100-600m of described microsphere2/ g, more preferably 300-500m2/g；
Preferably, the aperture of described microsphere is 3-50nm, more preferably 3-10nm；
Preferably, described nitrating agent preferably is selected from：Concentrated nitric acid (65-70wt%), concentrated nitric acid (65-70wt%)-dense sulfur
Acid (>Mixed liquor 98wt%), the mixed liquor of concentrated nitric acid (65-70wt%)-glacial acetic acid；
Preferably, the mixed liquor of described concentrated nitric acid-concentrated sulphuric acid is concentrated nitric acid and concentrated sulphuric acid with volume ratio 1:1 mixing
Liquid；
Preferably, the mixed liquor of described concentrated nitric acid-glacial acetic acid is concentrated nitric acid and glacial acetic acid with volume ratio 1:1 mixing
Liquid；
Preferably, described ferrous salt is ferrous chloride or ferrous sulfate, such as Iron dichloride tetrahydrate or seven hydrated sulfuric acids
It is ferrous；
Preferably, other described metals are nickel (Ni), cobalt (Co), manganese (Mn).
In one embodiment of the invention, the microsphere for step (1) being obtained in step (2) and ferrous salt, alkali reaction, shape
Into magnetic particle Fe3O4；
Preferably, described alkali is ammonia；In a preferred embodiment of the invention, the ammonia is saturation ammonia；
Preferably, described polymer microballoon and the mass volume ratio of nitrating agent are 0.5-10g/ml；More preferably 1-
5g/ml；
Preferably, the described nitrification time is 1-24h, more preferably 1-10h；
Preferably, described nitrification temperature is room temperature；
Preferably, in step (2), the microsphere that step (1) is obtained is 1 with the mass ratio of ferrous salt:0.6-5；More preferably
For 1:0.8-1.5；
Preferably, in step (2), the microsphere that step (1) is obtained is 0.1-10g/ml with the mass volume ratio of alkali, more preferably
For 0.1-1.0g/ml；
Preferably, reaction temperature 50-70 DEG C of step (2), response time 2-3 hour.
In one embodiment of the invention, described step (1) includes：Under room temperature, polymer microballoon is suspended in molten
In agent, nitration treatment is carried out to its surface using nitrating agent so as to which nitro functions are contained on surface, the granule after process is washed
Wash, be dried.
Preferably, described suspension solvent is dichloromethane or tetrahydrofuran；
Preferably, described washing reagent is distilled water and/or methanol.
In a preferred embodiment of the invention, described step (2) includes：By step (1) obtain it is nitrifying granular activated
It is suspended in solvent, under nitrogen protection, adds saturation ammonia and water solublity ferrous salt, intensification to carry out redox reaction, react
Granule washing afterwards, flotation are dried.
Preferably, described suspension solvent is distilled water；
Preferably, described washing reagent is distilled water and/or methanol.
The present invention also provides a kind of polymer microballoon with paramagnetic performance prepared by said method；
Preferably, described microsphere is the porous crosslinked polystyrene granule with paramagnetic performance；
Preferably, the iron content of described microsphere be 1-20% (mass percent), preferably 1-10%, more preferably 5-
10%.
In a preferred embodiment of the invention, the iron content of described microsphere is 10%；
Preferably, described microsphere is spherical；
Preferably, the particle diameter of described microsphere is 100-400 mesh, more preferably 200-400 mesh；
Preferably, specific surface area 100-500m of described microsphere2/ g, more preferably 300-450m2/g；
Preferably, the aperture of described microsphere is 3-50nm, more preferably 3-10nm.
The present invention also provides a kind of preparation method of the magnetic polymer microsphere of surface epoxy-activated, methods described bag
Include：Epoxy-activated is carried out to the above-mentioned polymer microballoon surface with paramagnetic performance using epoxy based monomers；
Preferably, described epoxy based monomers are glycidyl acrylate, glycidyl methacrylate pi-allyl
One or more in ethylene oxidic ester, cyclobutenyl ethylene oxidic ester, and/or, one kind in diglycidyl ether, epoxy alcohol or
It is various；
Preferably, described diglycidyl ether is butanediol diglycidyl ether；
Preferably, described epoxy alcohol is epoxy prapanol.
In a preferred embodiment of the invention, described epoxy based monomers are epoxy prapanol, Glycidyl methacrylate
The combination of glyceride, butanediol diglycidyl ether；
In a preferred embodiment of the present invention, it is 1 that described epoxy based monomers are volume ratio：1：1 epoxy
Propanol, glycidyl methacrylate, the combination of butanediol diglycidyl ether；
Preferably, described epoxy based monomers and the part by weight of the polymer microballoon with paramagnetic performance are 1：3-2：1；
Preferably, described reaction temperature is 65-75 DEG C；
Preferably, the described response time is 16-24h.
In a preferred embodiment of the invention, said method includes：
The above-mentioned polymer microballoon with paramagnetic performance is suspended in solvent, epoxy prapanol, methacrylic acid contracting is added
Water glycerin ether, butanediol diglycidyl ether, the lower reacting by heating of stirring, reacted granule washing are dried.
Preferably, described suspension solvent is glycol dimethyl ether；
Preferably, described washing reagent is dehydrated alcohol and/or methanol.
The present invention also provides a kind of magnetic polymer microsphere of the surface epoxy-activated that said method is prepared.
The present invention also provides a kind of preparation method of surface-functionalized magnetic polymer microsphere, and methods described includes：Work(
React on the magnetic polymer microsphere surface that reactant can be changed with above-mentioned surface epoxy-activated；
In one embodiment of the invention, described reaction kinetic thing is the compound containing functionalization group, is passed through
It is connected or is polymerized with microsphere surface epoxy reaction, realizes surface-functionalized；
In a preferred embodiment of the invention, described reaction kinetic thing be functionalization polymerized monomer, the side
Method includes：Using radical polymerization technique, cause functionalization polymerized monomer in the magnetic polymer of above-mentioned surface epoxy-activated
Microsphere surface carries out polyreaction；
In step (2), the initiator for adopting can be azo-initiator, organic or inorganic peroxide initiator, preferably
From：Double (2- methyl-prop amidines) two hydrochloric acid of Ammonium persulfate., potassium peroxydisulfate, azodiisobutyronitrile, benzoyl peroxide, 2,2 '-azo
Salt；
Described functionalization group preferably is selected from：Hydroxyl, carboxyl, amino, sulfydryl, amide groups, quaternary ammonium group, sulfonic group, imidazoles,
One or more in pyridine, pyrrolidone-base；
Preferably, described functionalization polymerized monomer contains vinyl and functionalization group.
In a preferred embodiment of the invention, described functionalization polymerized monomer is selected from：Vinyl pyrrolidone, first
Base 2-(Acryloyloxy)ethanol, Sodium styrene sulfonate, vinyl imidazole, methyl-prop acyloxyethyl trimethyl ammonium chloride, acrylamide；
Preferably, described initiator and the weight ratio of functionalization polymerized monomer are 1：10-100, preferably 1:20-40；
Preferably, the weight ratio of the granule that described functionalization polymerized monomer is obtained with step (1) is 1：5-100, preferably
For 1:5-50, more preferably 1:5-10.
In a preferred embodiment of the invention, said method includes：
The magnetic polymer microsphere of above-mentioned surface epoxy-activated is suspended in solvent, initiator, functional poly is added
Monomer is closed, heat up polymerization, product is washed, is dried.
Preferably, described solvent is selected from：The ethanol (or methanol) of ethanol, methanol, water and various ratios-water mixing is molten
Liquid, described solvent and the envelope-bulk to weight ratio of granule are 5-20ml/g；
Preferably, described washing reagent is selected from：One or more in dehydrated alcohol, methanol, water.
Another aspect of the present invention also provides the surface-functionalized magnetic polymer microsphere that a kind of said method is prepared.
Preferably, described microsphere is the porous crosslinked polystyrene granule with paramagnetic performance；
Preferably, described microsphere iron content be 1-20% (mass percent), preferably 1-10%, more preferably 5-
10%.
In a preferred embodiment of the invention, the iron content of described microsphere is 10%；
Preferably, described microsphere is spherical；
Preferably, the particle diameter of described microsphere is 100-400 mesh, more preferably 200-400 mesh；
Preferably, specific surface area 100-500m of described microsphere2/ g, more preferably 300-450m2/g；
Preferably, the aperture of described microsphere is 3-50nm, more preferably 3-10nm；
Preferably, the functionalization group of described microsphere is selected from：Hydroxyl, carboxyl, amino, sulfydryl, amide groups, quaternary ammonium group,
One or more in sulfonic group, imidazoles, pyridine, pyrrolidone-base.
The present invention also provides a kind of above-mentioned preparation method with the microsphere for preparing in biological engineering (such as immobilized enzyme), life
Thing medical science (such as targeted drug, enzyme mark, clinical diagnosises), cytology's (such as cell separation, cell marking), Chemical Decomposition are (such as solid phase
Extraction) etc. application in field.
Preferably, described application is the application in Solid-Phase Extraction.
The present invention also provides a kind of Solid-Phase Extraction material, including the above-mentioned polymer microballoon with paramagnetic performance, surface loop
The magnetic polymer microsphere of epoxide activation, surface-functionalized magnetic polymer microsphere；
In a preferred embodiment of the invention, described Solid-Phase Extraction material includes above-mentioned surface-functionalized magnetic
Porous crosslinked polystyrene spheroidal particle, the group of the functionalization are selected from：Hydroxyl, pyrrolidone-base, sulfonic group, imidazole radicals,
One or more in quaternary ammonium group, amide groups；
Preferably, described microsphere iron content be 1-20%, preferably 1-10%, more preferably 5-10%.
In a preferred embodiment of the invention, the iron content of described microsphere is 10%.
The present invention also provides a kind of preparation method of above-mentioned solid phase fiber material, and the preparation method includes above-mentioned with suitable
The preparation process of the polymer microballoon of magnetic property；
Preferably, the preparation method is also included using epoxy based monomers to the above-mentioned polymer microballoon with paramagnetic performance
The step of surface carries out epoxy-activated；
Preferably, the preparation method also includes the magnetic polymer of reaction kinetic thing and above-mentioned surface epoxy-activated
The step of microsphere surface reacts.
The drying of heretofore described polymer microballoon granule preferably uses vacuum drying mode.
The preparation method of the polymer microballoon with paramagnetic performance that the present invention is provided, including with polymer microballoon as starting
Raw material, is nitrified to its surface using nitrating agent, then by with the redox reaction of water solublity ferrous salt in microsphere
Surface Creation magnetic material, obtains the polymer microballoon with paramagnetic performance, can also on this basis to above-mentioned microsphere surface
Carry out epoxy-activated, functionalization to derive, obtain surface-functionalized magnetic polymer microsphere.By optimizing and controlling microsphere ferrum
Content, can reduce magnetic history as far as possible on microsphere aperture, the isoparametric impact of specific surface area, and the surface of follow-up magnetization microsphere
Functionalization easily realizes that the adsorption effect of microsphere is more preferable.Above-mentioned preparation method process is simple, reaction condition are gentle, and technique can
Strong operability, selectivity are more, easy to operate, and preparation efficiency is higher.The polymer microballoon with paramagnetic performance for obtaining, particularly table
The crosslinked polystyrene spheroidal particle of face functionalization is capable of achieving rapidly and efficiently to separate using externally-applied magnetic field, can regenerate and repeat
Utilize, specific surface area is big, and surface-functionalized, can be widely used for immobilized enzyme, targeted drug prepare, enzyme or isotope marks,
Cell separation, cell surface marker, Solid-Phase Extraction, the effect particularly as Solid-Phase Extraction material are good.
Description of the drawings
Fig. 1 show the impact knot in the specific surface area of the iron content to magnetic microsphere of the offer of the embodiment of the present invention 3, aperture
Really.
Fig. 2 show impact of the iron content of the offer of the embodiment of the present invention 4 to the ketopyrrolidine substitution value of magnetic microsphere and ties
Really.
Fig. 3 show acetaminophen of the iron content of the offer of the embodiment of the present invention 5 to ketopyrrolidine paramagnetism microsphere
The impact result of adsorption rate.
Fig. 4 show the extraction experiments result that the magnetic microsphere of the offer of the embodiment of the present invention 11 is inhaled.
Specific embodiment
Below in conjunction with the accompanying drawing in the embodiment of the present invention, the technical scheme in the embodiment of the present invention is carried out clear, complete
Site preparation is described, it is clear that described embodiment is only a part of embodiment of the invention, rather than the embodiment of whole.Based on this
Embodiment in invention, the every other reality obtained under the premise of creative work is not made by those of ordinary skill in the art
Example is applied, the scope of protection of the invention is belonged to.
Embodiment 1
Preparation process is as follows：
(1) 10.0g porous crosslinked polystyrenes spheroidal particle (200-300 mesh, 80% crosslinking, 400m2/ g) it is suspended in
In 100ml dichloromethane, concentrated nitric acid (65-70wt%) 3ml is added, under room temperature, 12h is stirred.Product is filtered, successively with water, methanol
Washing, 60 DEG C are vacuum dried more than 6 hours.
(2) dry particle obtained in step (1) is suspended in 50ml distilled water, nitrogen protection is lower to add 40ml saturated ammonias
Water, 13.0g green vitriols, stir lower 60 DEG C and react 3 hours.Product is filtered, washing, flotation, and 60 DEG C of vacuum drying 6 are little
When more than.
(3) product obtained in 6.0g steps (2) is suspended in 40ml glycol dimethyl ethers, adds epoxy prapanol, methyl
Glycidyl acrylate, (volume ratio is 1 to the mixed solution of butanediol diglycidyl ether：1：1) 3.0g, 65 DEG C of stirring reactions
24 hours.Reacted granule is washed with dehydrated alcohol, methanol, is vacuum dried more than 6 hours.
(4) granule that 2.0g steps (3) are obtained is suspended in 20ml dehydrated alcohol, adds vinyl pyrrolidone
0.20g, 0.01g azodiisobutyronitrile, stirs lower 70 DEG C and reacts 24 hours.Product ethanol, methanol are washed, are vacuum dried 6 hours
More than, obtain the granule of ketopyrrolidine functionalization.Obtained product Jing tests, with paramagnetism, iron-holder 6%, 200-300
Mesh, spherical, specific surface 316m2/ g, aperture 4.6nm.
Embodiment 2
Preparation process is as follows：
(1) 10.0g porous crosslinked polystyrenes spheroidal particle (200-400 mesh, 60% crosslinking, 500m2/ g) it is suspended in
In 100ml dichloromethane, the mixed liquor (volume ratio 1 of concentrated nitric acid (65-70wt%) glacial acetic acid is added：1) 4ml, stirs under room temperature
12h.Product is filtered, and is washed with water, methanol successively, and 60 DEG C are vacuum dried more than 6 hours.
(2) dry particle obtained in step (1) is suspended in 50ml distilled water, nitrogen protection is lower to add 40ml saturated ammonias
Water, 9.2g Iron dichloride tetrahydrates, stir lower 75 DEG C and react 2 hours.Product is filtered, washing, flotation, and 60 DEG C of vacuum drying 6 are little
When more than.
(3) product obtained in 6.0g steps (2) is suspended in 40ml glycol dimethyl ethers, adds epoxy prapanol, methyl
Glycidyl acrylate, (volume ratio is 1 to the mixed solution of butanediol diglycidyl ether：1：1) 3.0g, 65 DEG C of stirring reactions
24 hours.Reacted granule is washed with dehydrated alcohol, methanol, is vacuum dried more than 6 hours.
(4) granule that 2.0g steps (3) are obtained is suspended in 20ml dehydrated alcohol, adds 0.2g hydroxyethyl methacrylate second
Ester, 0.01g azodiisobutyronitriles stir lower 70 DEG C and react 24 hours.Product ethanol, methanol washing, vacuum drying 6 hours with
On, obtain hydroxy functionalized granule.
Obtained product Jing tests, with paramagnetism, iron-holder 8%, 200-400 mesh are spherical, specific surface 401m2/ g, hole
Footpath 3.8nm.
Embodiment 3
Magnetic microsphere is prepared with reference to 1 step of embodiment (1) and (2), nitrating agent, ferrous salt addition is adjusted, is obtained not
With the magnetic microsphere of iron content, it is control for magnetized base polymer microsphere (iron content is 0), contrasts what magnetization was obtained
Specific surface area of the iron content to microsphere, the impact in aperture, as a result as shown in Figure 1.
From Fig. 1 results, magnetic history declines all can microsphere specific surface area, aperture shadow of the different iron contents to microsphere
Ring different, iron content is 1% and 15%, relatively small to the pore size influences of microsphere.
Embodiment 4
(1) magnetic microsphere is prepared with reference to 1 step of embodiment (1) and (2), adjust nitrating agent, ferrous salt addition, prepare
Obtain the magnetic microsphere that iron content is respectively 1%, 3%, 5%, 8%, 10%, 12%, 15%, 18%, 20%.
(2) product obtained in 6.0g steps (1) is suspended in 40ml glycol dimethyl ethers, adds epoxy prapanol, methyl
Glycidyl acrylate, (volume ratio is 1 to the mixed solution of butanediol diglycidyl ether：1：1) 3.0g, 65 DEG C of stirring reactions
24 hours.Reacted granule is washed with dehydrated alcohol, methanol, is vacuum dried more than 6 hours.
(3) granule that 2.0g steps (2) are obtained is suspended in 20ml dehydrated alcohol, adds vinyl pyrrolidone
0.20g, 0.01g azodiisobutyronitrile, stirs lower 70 DEG C and reacts 24 hours.Product Jing ethanol, methanol washing, vacuum drying 6 are little
When more than, obtain the granule of ketopyrrolidine functionalization.Jing elementary analysiss test nitrogen content, pyrrolidine in every gram of magnetic microsphere of conversion
MM number (mmol/g) of ketone, as a result as shown in Figure 2.
As shown in Figure 2, iron content is higher, and the ketopyrrolidine substitution value of the magnetic microsphere for preparing is lower, Solid-Phase Extraction
Preferred corresponding substitution value scope 0.5-0.8mmol/g of process.I.e. preferably iron content scope is 1-10%, the higher paramagnetic of iron content
Property it is stronger, therefore preferably iron content is 5-10%.
Embodiment 5
(1) iron content that Example 4 is prepared be respectively 1%, 3%, 5%, 8%, 10%, 12%, 15%,
18%th, the 20% each 10mg of ketopyrrolidine paramagnetism microsphere.
(2) 0.30mg acetaminophen is dissolved in 30ml deionized waters to be placed in 50ml centrifuge tubes, then will step
Magnetic microsphere in rapid 1, vortex oscillation 3min use magnet adsorption magnetic microsphere, take the HPLC analyses of centrifugation liquid in pipe, calculate
After HPLC analytical data, acetaminophen adsorption rate is as shown in Figure 3 with iron content relation curve.
From the figure 3, it may be seen that iron content is preferable for the microsphere adsorption effect of 1-10%.
Embodiment 6
Preparation process is as follows：
Using the porous crosslinked polystyrene spheroidal particle of 200-400 mesh, Jing is obtained using the method in similar embodiment 1
The dry particle that epoxy prapanol, glycidyl methacrylate, the mixed solution of butanediol diglycidyl ether reacted.Take
10.0g is suspended in 90ml methanol-waters (4：1, volume ratio) in, addition 2.0g Sodium styrene sulfonate, 0.10g Ammonium persulfate .s, 60 DEG C
Reaction 24 hours, obtains the granule of sulfonic functional.
After the scrubbed drying of product, test is with paramagnetism, specific surface 384m2/ g, aperture 4.5nm.
Embodiment 7
Using the porous crosslinked polystyrene spheroidal particle of 200-400 mesh, Jing is obtained using the method in similar embodiment 1
The dry particle that epoxy prapanol, glycidyl methacrylate, the mixed solution of butanediol diglycidyl ether reacted.Take
15.0g is suspended in 120ml ethanol, adds 1.5g vinyl imidazoles, 0.075g benzoyl peroxides, and 75 DEG C are reacted 18 hours,
Obtain the granule of imidazoles functionalization.
After the scrubbed drying of product, test is with paramagnetism, specific surface 384m2/ g, aperture 4.5nm.
Embodiment 8
Using the porous crosslinked polystyrene spheroidal particle of 200-400 mesh, Jing is obtained using the method in similar embodiment 1
The dry particle that epoxy prapanol, glycidyl methacrylate, the mixed solution of butanediol diglycidyl ether reacted.Take
10.0g is suspended in 100ml alcohol-waters (9：1, volume ratio) in, 1.5g methyl-prop acyloxyethyl trimethyl ammonium chlorides are added,
0.05g2, double (the 2- methyl-prop amidines) dihydrochlorides of 2 '-azo, 70 DEG C are reacted 20 hours, obtain 0.5-0.7mmol/g quaternary ammonium group work(
The granule of energyization.
After the scrubbed drying of product, test is with paramagnetism, specific surface 413m2/ g, aperture 4.5nm.
Embodiment 9
Using the porous crosslinked polystyrene spheroidal particle of 200-400 mesh, Jing is obtained using the method in similar embodiment 1
The dry particle that epoxy prapanol, glycidyl methacrylate, the mixed solution of butanediol diglycidyl ether reacted.Take
10.0g is suspended in 100ml alcohol-waters (3：1, volume ratio) in, addition 2.0g acrylamides, 0.075g benzoyl peroxides, 75
DEG C reaction 24 hours, obtain amine functionalized granule.
After the scrubbed drying of product, test is with paramagnetism, specific surface 384m2/ g, aperture 4.5nm.
Embodiment 10
Preparation process is as follows：
(1)Fe3O4It is prepared by nanoparticle：In N2Under environment, by a certain amount of, ion number ratio n (Fe3+)：n(Fe2+) for 2: 1
Mixing salt solution is placed in there-necked flask, dilute, is heated to 55 DEG C, is slowly added to excess of ammonia water reaction 0.5h, is heated up
To 70 DEG C of ripening 0.5h, black product is obtained, it is standby that washing is made into finite concentration after being dried.
(2)Fe3O4Nanoparticle surface：It is modified to take 3mL Silane coupling reagent KH-570s in round-bottomed flask, sequentially add water,
Stir uniform to system under glacial acetic acid, room temperature.70℃、N2Under atmosphere, a certain amount of nanometer Fe is added in above-mentioned system3O4It is water-soluble
Liquid, reacts to shiny black grease and separates out.
(3) prepared by Magnetic Polystyrene Microsphere：Take the Fe of a certain amount of silylating reagent3O4, St, MMA, deionized water is in three
Mouth flask, ultrasonic disperse pretreatment 10min form stabilising system, and nitrogen is protected, 70 DEG C of waters bath with thermostatic control, stirring, condensing reflux,
It is added dropwise over K2S2O8Solution, reaction 4h, separating, washing, with neutrality is washed to after 1mol/L soak with hydrochloric acid 24h, Magneto separate is obtained
Magnetic Polystyrene Microsphere.
(4) using the porous crosslinked polystyrene spheroidal particle of above-mentioned preparation, obtained using the method in similar embodiment 1
The dry particle that Jing epoxy prapanols, glycidyl methacrylate, the mixed solution of butanediol diglycidyl ether reacted.
Take 10.0g and be suspended in 100ml alcohol-waters (9：1, volume ratio) in, 1.5g methyl-prop acyloxyethyl trimethyl ammonium chlorides are added,
0.05g2, double (the 2- methyl-prop amidines) dihydrochlorides of 2 '-azo, 70 DEG C are reacted 20 hours, obtain 0.3mmol/g quaternary ammonium group functionalization
Granule.
After the scrubbed drying of product, test is with paramagnetism, specific surface 430m2/ g, aperture 4.6nm.
Comparative example 8 and 10 is understood, is easily realized using the magnetic microsphere that the present processes are prepared follow-up
It is surface-functionalized.
11 effect of extracting of embodiment is tested
Extraction experiments, the porous quaternary ammonium group functional polystyrene magnetic of 10mg are done with the magnetic microsphere obtained in embodiment 8
Property microsphere as adsorbent, the methyl orange solution of the 10mg/L of 100mL, take 8 parts of 10mL methyl orange solutions (10mg/L), use
The HNO of 0.1mol/L3PH=3,4,5,6,7,8,9,10 are adjusted with 0.1mol/L NaOH, 10mg porous quaternary ammonium groups are separately added into
Then functional polystyrene magnetic microsphere adsorbent, Jing vortex oscillations is separated with Magnet, is entered with ultraviolet spectrophotometer
Row mensuration absorbance value.Experimental result is as shown in Figure 4.
Presently preferred embodiments of the present invention is the foregoing is only, not to limit the present invention, all essences in the present invention
Within god and principle, any modification for being made, equivalent etc. should be included within the scope of the present invention.
Claims (16)
1. a kind of preparation method of the polymer microballoon with paramagnetic performance；Methods described comprises the steps：
(1) nitration treatment is carried out to polymer microballoon surface；
(2) combination of the microsphere for obtaining step (1) and ferrous salt or ferrous salt and the salt of other metals and alkali are reacted.
2. preparation method as claimed in claim 1, it is characterised in that described polymer microballoon is obtained for polymerization of vinyl monomer
Arrive；
Preferably, described vinyl monomer preferably is selected from：Styrene, maleic anhydride, acrylate, vinyl esters and its derivative
Thing, more preferably certainly：Styrene, acrylic acid methyl ester., methyl methacrylate, ethyl acrylate, ethyl methacrylate, acrylic acid
One or more in butyl ester, butyl methacrylate, vinyl acetate；Most preferably styrene；
Preferably, described polymer microballoon is cross linked porous.
3. preparation method as claimed in claim 1 or 2, it is characterised in that the reagent of described nitrification is selected from：It is concentrated nitric acid, dense
The mixed liquor of nitric acid-concentrated sulphuric acid, the mixed liquor of concentrated nitric acid-glacial acetic acid；And/or,
Described ferrous salt is ferrous chloride or ferrous sulfate；And/or,
Other described metals are nickel, cobalt, manganese；And/or,
Described alkali is ammonia.
4. preparation method as claimed in claim 3, it is characterised in that the mass body of described polymer microballoon and nitrating agent
Product is than being 0.5-10g/ml；And/or,
In step (2), the microsphere that step (1) is obtained is 1 with the mass ratio of ferrous salt:0.6-5；And/or,
In step (2), the microsphere that step (1) is obtained is 0.1-10g/ml with the mass volume ratio of alkali.
5. the polymer microballoon with paramagnetic performance that a kind of method by described in any one of claim 1-4 is prepared.
6. polymer microballoon as claimed in claim 5, it is characterised in that described microsphere is that the porous with paramagnetic performance is handed over
Polystyrene granule；And/or,
Described microsphere iron-holder is 1-20%；And/or,
The particle diameter of described microsphere is 100-400 mesh；And/or,
Specific surface area 100-500m of described microsphere2/g；And/or,
The aperture of described microsphere is 3-50nm.
7. a kind of preparation method of the magnetic polymer microsphere of surface epoxy-activated, methods described include：Using epoxy radicals list
Body carries out epoxy-activated to the above-mentioned polymer microballoon surface with paramagnetic performance.
8. preparation method as claimed in claim 7, it is characterised in that described epoxy based monomers are glycidyl
One or more in ester, glycidyl methacrylate allyl glycidyl, cyclobutenyl ethylene oxidic ester, and/or,
One or more in diglycidyl ether, epoxy alcohol；And/or,
Described epoxy based monomers are 1 with the part by weight of the polymer microballoon with paramagnetic performance：3-2：1.
9. the magnetic polymer microsphere of the surface epoxy-activated that a kind of method by described in claim 7 or 8 is prepared.
10. a kind of preparation method of surface-functionalized magnetic polymer microsphere, methods described include：Reaction kinetic thing and power
Profit requires the magnetic polymer microsphere surface reaction of the surface epoxy-activated described in 9, and described reaction kinetic thing is containing work(
The compound of group can be changed.
11. preparation methoies as claimed in claim 10, it is characterised in that described functionalization group is selected from：Hydroxyl, carboxyl,
One or more in amino, sulfydryl, amide groups, quaternary ammonium group, sulfonic group, imidazoles, pyridine, pyrrolidone-base.
12. preparation methoies as described in claim 10 or 11, it is characterised in that described reaction kinetic thing is functional poly
Monomer is closed, methods described includes：Using radical polymerization technique, cause functionalization polymerized monomer in above-mentioned surface epoxy-activated
Magnetic polymer microsphere surface carry out polyreaction.
13. preparation methoies as claimed in claim 12, it is characterised in that described functionalization polymerized monomer is selected from：Vinyl
Ketopyrrolidine, hydroxyethyl methylacrylate, Sodium styrene sulfonate, vinyl imidazole, methyl-prop acyloxyethyl trimethyl ammonium chloride,
Acrylamide；And/or,
The weight of the magnetic polymer microsphere of described functionalization polymerized monomer and the surface epoxy-activated described in claim 9
Than for 1：5-100.
The surface-functionalized magnetic polymer microsphere that method described in a kind of 14. any one of claim 10-13 is prepared.
A kind of 15. methods as described in any one of claim 1-4, the polymer microballoon as described in claim 5 or 6, right will
Ask method described in the method described in 7 or 8, the polymer microballoon described in claim 9, any one of claim 10-13, right
Require application of the polymer microballoon described in 14 in biological engineering, biomedicine, cytology, Chemical Decomposition field.
A kind of 16. Solid-Phase Extraction materials, including the polymerization described in the polymer microballoon described in claim 5 or 6, claim 9
Polymer microballoon described in thing microsphere, claim 14.
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| CN112807744A (en) * | 2021-01-18 | 2021-05-18 | 南京工业大学 | Magnetic dispersion solid phase extraction material for enriching pesticide and veterinary drug residues and preparation method thereof |
| CN113278194A (en) * | 2021-05-17 | 2021-08-20 | 苏州英芮诚生化科技有限公司 | Preparation method of monodisperse magnetic polystyrene microsphere, microsphere and application thereof |
| CN115651264A (en) * | 2022-11-28 | 2023-01-31 | 南京伯仪生物科技有限公司 | Preparation method of silicon dioxide coated magnetic porous polystyrene microspheres |
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