CN105199135B - A kind of preparation method of magnetic composite microsphere - Google Patents
A kind of preparation method of magnetic composite microsphere Download PDFInfo
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- CN105199135B CN105199135B CN201510690670.5A CN201510690670A CN105199135B CN 105199135 B CN105199135 B CN 105199135B CN 201510690670 A CN201510690670 A CN 201510690670A CN 105199135 B CN105199135 B CN 105199135B
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Abstract
The present invention discloses a kind of preparation method of magnetic composite microsphere, and this method comprises the following steps: the porous polymer microsphere of modifier modification height crosslinking；Modified microballoon is impregnated in metal cation solution；Microballoon after dipping under inert gas protection, carries out precipitation reaction in alkaline solution, obtains the magnetic composite microsphere with core-shell structure.The magnetic composite microsphere of the method for the present invention preparation has many advantages, such as porosity, magnetism, solvent resistance, therefore is used directly for adsorbing separation organic impurities, is also convenient for Magnetic Isolation recycling, has application prospect in fields such as water process, chromatographic isolations.
Description
Technical field
The invention belongs to technical field of polymer materials, in particular to a kind of preparation method of magnetic composite microsphere.
Background technique
Magnetic composite microsphere due to physics and steady chemical structure, chromatographic isolation, biological medicine, biological detection, coating,
The fields such as environmental project and catalysis engineering tool has been widely used.Magnetic composite microsphere in the application, on the one hand requires it to have
On the other hand higher magnetic content, i.e., high specific saturation magnetization also require magnetic-particle to be evenly distributed, and preparation process
It is simple and controllable.
From the point of view of preparation route, most of magnetic composite microsphere is all first to prepare magnetic metal oxide particle, then
It carries out certain surface processing to it, and then magnetic-particle and polymer is combined magnetic composite microsphere.Magnetic-particle and poly-
The complex method for closing object mainly has: investment, emulsion method, LBL self-assembly and seed swelling method.Investment is exactly will be magnetic
Even particulate dispersion in a polymer solution, then passes through the methods of atomization, evaporation solvent flashing, to prepare magnetic coupling
Microballoon.The method is easy to operate, but the performances such as particle size, pattern prepared not easy-regulating.Although emulsion method can overcome
The problem of investment is in terms of partial size, pattern, but generally require to hold by surfactant in this method preparation process
Product easy to pollute makes its performance be affected.Layer assembly method is to gather using polymer microballoon as template in its adsorption
Then electrolyte utilizes the sucking action of polyelectrolyte and magnetic-particle surface charge, carry out cladding group layer by layer in microsphere surface
Dress, prepares magnetic composite microsphere.The method principle is simple, but in order to obtain the magnetic composite microsphere of high magnetic content, needs repeatedly
Cladding assembling is carried out in microsphere surface, it is cumbersome.Seed swelling rule is the swelling action using solvent to polymer microballoon,
Microballoon is set to adsorb magnetic metal oxide particle during volume expansion to prepare magnetic composite microsphere.Seed swelling system
It is mainly made of seed microballoon (or seed drop), monomer (or monomer droplet), dispersed phase, initiator, stabilizer etc., sometimes
It needs to add swelling auxiliary agent.Magnetic composite microsphere magnetic content using the preparation of seed swelling method is high, and magnetic-particle distribution is equal
It is even, but the preparation process of this method is more complex, and cost is also higher.
In addition to the above method, the United States Patent (USP) of Patent No. US 4774265 is also disclosed that a kind of to prepare magnetic coupling micro-
The method of ball, this method are similar with seed swelling method.This method is first to prepare the macroporous type containing special groups or non-porous
Then polymer microballoon is placed in organic solvent by polymer microballoon.In the solvent contain specific metal cation, these from
Son is constantly inhaled into inside polymer microballoon with the swelling of microballoon.Microballoon after swelling is finally placed in certain solution again
In, inside or Surface Creation magnetic metal oxide particle by precipitation reaction, in microballoon.Although this method does not need individually
Synthesizing magnetic particle, but the polymer microballoon degree of cross linking used is low, and poor solvent resistance affects answering for the magnetic composite microsphere
With.
Accordingly, it is desirable to provide a kind of preparation method of magnetic composite microsphere, this method have it is easy to operate, without individually closing
The method that magnetic composite microsphere can be prepared at magnetic-particle.
Summary of the invention
The invention solves first technical problem be to provide with the preparation method of middle magnetic composite microsphere, the preparation side
Method is easy to operate, the method that can prepare magnetic composite microsphere without separately synthesized magnetic-particle.
The invention solves second technical problem be to provide a kind of magnetic composite microsphere.
In order to achieve the above objectives, the present invention adopts the following technical solutions:
A kind of preparation method of magnetic composite microsphere comprising following steps:
The porous polymer microsphere of modifier modification height crosslinking；Modified microballoon is impregnated in metal cation solution；
Microballoon after dipping under inert gas protection, carries out precipitation reaction in alkaline solution, obtains the magnetism with core-shell structure
Complex microsphere.
The porous polymer microsphere of the crosslinking includes that polydivinylbenezene microballoon or polydivinylbenezene and styrene are total
Poly- microballoon, it is preferable that the insolubles content of the porous polymer microsphere of the crosslinking is 80-98%, BET specific surface area 200-
1000m2/ g, aperture is between 2-10nm, it is highly preferred that the insolubles content of the porous polymer microsphere of the crosslinking is 90-
98%, BET specific surface area 400-800m2/ g, aperture is in 2-6nm.
The modifying agent is Strong oxdiative dosage form solutions, it is therefore preferable to the concentrated sulfuric acid or concentrated nitric acid.Preferably, amount of modifier with
The mass ratio of porous polymer microsphere is 2-40:1, it is highly preferred that the mass ratio of amount of modifier and porous polymer microsphere is
10-20:1；The temperature of modifier modification is 40-60 DEG C, and the time of modifier modification is 10-60min.
The metal cation solution is to include Fe2+And Fe3+The aqueous solution of ion；Described includes Fe2+And Fe3+Ion
Metal cation solution concentration is 0.5-5mol/L；Described includes Fe2+And Fe3+Fe in the metal cation aqueous solution of ion2+With
Fe3+Molar ratio be 1:1-4；The temperature that the porous polymer microsphere of the high crosslinking impregnates in aqueous solution containing metal cation
It is 40-70 DEG C；Dip time of the porous polymer microsphere of the high crosslinking in aqueous solution containing metal cation is that 2-24 is small
When.
Alkaline matter in the alkaline solution is NaOH, ammonium hydroxide, KOH or LiOH；Reaction temperature in the precipitation reaction
Degree is 40-90 DEG C, it is preferable that the reaction temperature in the precipitation reaction is 60-90 DEG C；The pH that the precipitation reaction reacts
Value is 8-14；The reaction time of the precipitation reaction is 10-600min, it is preferable that the reaction time of the precipitation reaction is 30-
120min。
The protection gas is inert gas, is selected from one of nitrogen, argon gas and neon or a variety of, it is therefore preferable to nitrogen.
The preparation method further comprises separation magnetic composite microsphere, preferably separates magnetic coupling using externally-applied magnetic field
Microballoon.
The preparation method further comprises washing modified microballoon, preferably modified micro- by being centrifugated
Ball, and be washed with deionized to neutrality, the microballoon after washing is collected by centrifugation；The porous polymer of modified high crosslinking is micro-
Ball, which is added in the aqueous solution containing metal cation, carries out impregnation, it is preferable that condition of the impregnation in sealing
Lower progress.
A kind of magnetic composite microsphere, the magnetic composite microsphere have many advantages, such as porosity, magnetism, solvent resistance.
Beneficial effects of the present invention are as follows:
There is preparation method of the invention magnetic nanoparticle to be oriented in microsphere surface deposition, Magnetic Granular Films composition, thickness
The advantages of easy regulations such as degree, performance.And the preparation method is easy to operate, can prepare magnetism without separately synthesized magnetic-particle
Complex microsphere.
Magnetic composite microsphere prepared by the present invention has many advantages, such as porosity, magnetism, solvent resistance, therefore can directly use
In adsorbing separation organic impurities, it is also convenient for Magnetic Isolation recycling, there is application prospect in fields such as water process, chromatographic isolations.
Detailed description of the invention
Specific embodiments of the present invention will be described in further detail with reference to the accompanying drawing.
Fig. 1 shows the scanning electron microscope (SEM) photograph of the magnetic composite microsphere of embodiment 1.
Fig. 2 shows the scanning electron microscope (SEM) photographs of the magnetic composite microsphere of embodiment 1 amplification.
Fig. 3 shows response of the magnetic composite microsphere of embodiment 1 under externally-applied magnetic field.
Fig. 4 shows the magnetism testing curve of the magnetic composite microsphere of embodiment 1.
Fig. 5 shows the scanning electron microscope (SEM) photograph of the magnetic composite microsphere of embodiment 2.
Fig. 6 shows the scanning electron microscope (SEM) photograph of the magnetic composite microsphere of embodiment 3.
Fig. 7 shows the scanning electron microscope (SEM) photograph of the magnetic composite microsphere of embodiment 4.
Fig. 8 shows the scanning electron microscope (SEM) photograph of the magnetic composite microsphere of embodiment 5.
Fig. 9 shows the scanning electron microscope (SEM) photograph of the magnetic composite microsphere of embodiment 6.
Specific embodiment
In order to illustrate more clearly of the present invention, the present invention is done further below with reference to preferred embodiments and drawings
It is bright.Similar component is indicated in attached drawing with identical appended drawing reference.It will be appreciated by those skilled in the art that institute is specific below
The content of description is illustrative and be not restrictive, and should not be limited the scope of the invention with this.
Polydivinylbenezene microballoon or polystyrene used in embodiment and polydivinylbenezene copolymerization microsphere, no
Molten object is 80%-98%, BET specific surface area 200-1000m2/ g, aperture is in 2-10nm.
Embodiment 1
The porous polydivinylbenezene microballoon being crosslinked using height is substrate, insoluble matter 95%, and BET specific surface area is
325m2/ g, aperture 4nm.Round-bottomed flask is added in the 0.5g microballoon, stirring is warming up to 40 DEG C.10g concentrated nitric acid is added dropwise dropwise,
After handling 30min, slow dilute solution, centrifugation is washed with deionized to neutrality.By treated, microballoon addition concentration is
2mol/L's contains Fe2+And Fe3+Aqueous solution in, Fe2+With Fe3+Ratio be 1:2, mix, sealing, be placed in baking oven.Baking oven is set
Temperature is 70 DEG C.It after 6h, takes out, centrifugation.The round-bottomed flask that deionized water is housed is added in the microballoon that centrifugation is obtained, and is passed through nitrogen
Protective atmosphere is warming up to 70 DEG C, and NaOH solution is added dropwise dropwise to pH=12.After reacting 30min, externally-applied magnetic field separation be can be obtained
Magnetic composite microsphere.The magnetic content of the magnetic composite microsphere is 35.7%, and saturation magnetic content is 23.888emu/g, BET specific surface
Product is 207m2/g.The scanning electron microscope of magnetic composite microsphere such as Fig. 1.The clad section of magnetic composite microsphere is as shown in Figure 2.Magnetic
Property complex microsphere is as shown in Figure 3 in the response performance of externally-applied magnetic field.The magnetic property curve of magnetic composite microsphere is as shown in Figure 4.
Embodiment 2
Using the porous polydivinylbenezene of height crosslinking and styrene copolymerized microballoon as substrate, insoluble matter 98%, BET ratio
Surface area is 730m2/ g, aperture 2.8nm.Round-bottomed flask is added in the 0.5g microballoon, stirring is warming up to 60 DEG C.It is added dropwise dropwise
The 10g concentrated sulfuric acid, after handling 10min, slow dilute solution, centrifugation is washed with deionized to neutrality.By treated, microballoon adds
Entering concentration is 0.5mol/L containing Fe2+And Fe3+Aqueous solution in, Fe2+With Fe3+Ratio be 1:1, mix, sealing, be placed in baking
Case.It is 40 DEG C that oven temperature, which is arranged,.After 12h, centrifugation is taken out, round-bottomed flask is added in the microballoon that centrifugation is obtained, and is passed through nitrogen guarantor
Atmosphere is protected, is warming up to 90 DEG C, KOH solution is added dropwise dropwise to pH=14.Externally-applied magnetic field separation can be obtained magnetic multiple after reaction 2h
Close microballoon.The magnetic content of the magnetic composite microsphere is 55.3%, and saturation magnetic content is 35.187emu/g, and BET specific surface area is
458m2/g.The scanning electron microscope of the magnetic composite microsphere such as Fig. 5.
Embodiment 3
Using the porous polydivinylbenezene of height crosslinking and styrene copolymerized microballoon as substrate, insoluble matter 90%, BET ratio
Surface area is 242m2/ g, aperture 10nm.Round-bottomed flask is added in the 0.5g microballoon, stirring is warming up to 50 DEG C.It is added dropwise dropwise
The 20g concentrated sulfuric acid, after handling 60min, slow dilute solution, centrifugation is washed with deionized to neutrality.By treated, microballoon adds
Entering concentration is 5mol/L containing Fe2+And Fe3+Aqueous solution in, Fe2+With Fe3+Ratio be 1:4, mix, sealing, be placed in baking oven.
It is 50 DEG C that oven temperature, which is arranged,.After for 24 hours, centrifugation is taken out, round-bottomed flask is added in the microballoon that centrifugation is obtained, and is passed through nitrogen protection gas
Atmosphere is warming up to 40 DEG C, and ammonia spirit is added dropwise dropwise to pH=8.It is micro- that magnetic coupling can be obtained in externally-applied magnetic field separation after reaction 10h
Ball.The magnetic content of the magnetic composite microsphere is 13.6%, and saturation magnetic content is 12.443emu/g, BET specific surface area 178m2/
g.The scanning electron microscope of magnetic composite microsphere such as Fig. 6.
Embodiment 4
Using the porous polydivinylbenezene of height crosslinking and styrene copolymerized microballoon as substrate, insoluble matter 80%, BET ratio
Surface area is 452m2/ g, aperture 6.1nm.Round-bottomed flask is added in the 0.5g microballoon, stirring is warming up to 40 DEG C.It is added dropwise dropwise
10g concentrated nitric acid, after handling 30min, slow dilute solution, centrifugation is washed with deionized to neutrality.By treated, microballoon adds
Entering concentration is 3mol/L containing Fe2+And Fe3+Aqueous solution in, Fe2+With Fe3+Ratio be 1:3, mix, sealing, be placed in baking oven.
It is 60 DEG C that oven temperature, which is arranged,.After 8h, centrifugation is taken out, round-bottomed flask is added in the microballoon that centrifugation is obtained, and is passed through nitrogen protection gas
Atmosphere is warming up to 60 DEG C, and LiOH solution is added dropwise dropwise to pH=10.It is micro- that magnetic coupling can be obtained in externally-applied magnetic field separation after reaction 4h
Ball.The magnetic content of the magnetic composite microsphere is 40.5%, and saturation magnetic content is 27.585emu/g, BET specific surface area 345m2/
g.The scanning electron microscope of magnetic composite microsphere such as Fig. 7.
Embodiment 5
The porous polydivinylbenezene microballoon being crosslinked using height is substrate, insoluble matter 85%, and BET specific surface area is
200m2/G, aperture 8.4nm.Round-bottomed flask is added in the 0.5g microballoon, stirring is warming up to 40 DEG C.The dense nitre of 15g is added dropwise dropwise
Acid, after handling 30min, slow dilute solution, centrifugation is washed with deionized to neutrality.By treated, concentration is added in microballoon
Contain Fe for 1mol/L2+And Fe3+Aqueous solution in, Fe2+With Fe3+Ratio be 1:1, mix, sealing, be placed in baking oven.Setting is dried
Box temperature degree is 40 DEG C.After 16h, centrifugation is taken out, round-bottomed flask is added in the microballoon that centrifugation is obtained, and is passed through nitrogen protection atmosphere, rises
NaOH solution is added dropwise to pH=14 to 80 DEG C in temperature dropwise.Magnetic composite microsphere can be obtained in externally-applied magnetic field separation after reaction 6h.It should
The magnetic content of magnetic composite microsphere is 22.3%, and saturation magnetic content is 21.058emu/g, BET specific surface area 148m2/g.Magnetic
Scanning electron microscope such as Fig. 8 of property complex microsphere.
Embodiment 6
The porous polydivinylbenezene microballoon being crosslinked using height is substrate, insoluble matter 97%, and BET specific surface area is
1000m2/ g, aperture 2nm.Round-bottomed flask is added in the 0.5g microballoon, stirring is warming up to 50 DEG C.5g concentrated nitric acid is added dropwise dropwise,
After handling 60min, slow dilute solution, centrifugation is washed with deionized to neutrality.By treated, microballoon addition concentration is
5mol/L's contains Fe2+And Fe3+Aqueous solution in, Fe2+With Fe3+Ratio be 1:3, mix, sealing, be placed in baking oven.Baking oven is set
Temperature is 70 DEG C.After 16h, centrifugation is taken out, round-bottomed flask is added in the microballoon that centrifugation is obtained, and is passed through nitrogen protection atmosphere, heats up
To 80 DEG C, NaOH solution is added dropwise dropwise to pH=13.Magnetic composite microsphere can be obtained in externally-applied magnetic field separation after reaction 2h.The magnetic
Property complex microsphere magnetic content be 50.5%, saturation magnetic content be 42.144emu/g, BET specific surface area 513m2/g.It is magnetic
The scanning electron microscope of complex microsphere such as Fig. 9.
Embodiment 7
The porous polydivinylbenezene microballoon being crosslinked using height is substrate, insoluble matter 92%, and BET specific surface area is
557m2/ g, aperture 3.4nm.Round-bottomed flask is added in the 0.5g microballoon, stirring is warming up to 40 DEG C.The dense sulphur of 1g is added dropwise dropwise
Acid, after handling 30min, slow dilute solution, centrifugation is washed with deionized to neutrality.By treated, concentration is added in microballoon
Contain Fe for 1mol/L2+And Fe3+Aqueous solution in, Fe2+With Fe3+Ratio be 1:1, mix, sealing, be placed in baking oven.Setting is dried
Box temperature degree is 70 DEG C.After 2h, centrifugation is taken out, round-bottomed flask is added in the microballoon that centrifugation is obtained, and is passed through nitrogen protection atmosphere, heats up
To 80 DEG C, NaOH solution is added dropwise dropwise to pH=14.Magnetic composite microsphere can be obtained in externally-applied magnetic field separation after reaction 6h.The magnetic
Property complex microsphere magnetic content be 34.3%, saturation magnetic content be 27.058emu/g, BET specific surface area 321m2/g。
Embodiment 8
Using the porous polydivinylbenezene of height crosslinking and styrene copolymerized microballoon as substrate, insoluble matter 88%, BET ratio
Surface area is 342m2/ g, aperture 5.6nm.Round-bottomed flask is added in the 0.5g microballoon, stirring is warming up to 50 DEG C.It is added dropwise dropwise
The 5g concentrated sulfuric acid, after handling 60min, slow dilute solution, centrifugation is washed with deionized to neutrality.By treated, microballoon adds
Entering concentration is 5mol/L containing Fe2+And Fe3+Aqueous solution in, Fe2+With Fe3+Ratio be 1:2, mix, sealing, be placed in baking oven.
It is 60 DEG C that oven temperature, which is arranged,.After for 24 hours, centrifugation is taken out, round-bottomed flask is added in the microballoon that centrifugation is obtained, and is passed through nitrogen protection gas
Atmosphere is warming up to 50 DEG C, and ammonia spirit is added dropwise dropwise to pH=10.It is micro- that magnetic coupling can be obtained in externally-applied magnetic field separation after reaction 2h
Ball.The magnetic content of the magnetic composite microsphere is 36.5%, and saturation magnetic content is 36.745emu/g, BET specific surface area 255m2/
g。
Embodiment 9
Using the porous polydivinylbenezene of height crosslinking and styrene copolymerized microballoon as substrate, insoluble matter 98%, BET ratio
Surface area is 953m2/ g, aperture 2.1nm.Round-bottomed flask is added in the 0.5g microballoon, stirring is warming up to 60 DEG C.It is added dropwise dropwise
The 20g concentrated sulfuric acid, after handling 60min, slow dilute solution, centrifugation is washed with deionized to neutrality.By treated, microballoon adds
Entering concentration is 3mol/L containing Fe2+And Fe3+Aqueous solution in, Fe2+With Fe3+Ratio be 1:2.5, mix, sealing, be placed in baking
Case.It is 50 DEG C that oven temperature, which is arranged,.After for 24 hours, centrifugation is taken out, round-bottomed flask is added in the microballoon that centrifugation is obtained, and is passed through nitrogen guarantor
Atmosphere is protected, is warming up to 70 DEG C, KOH solution is added dropwise dropwise to pH=14.Externally-applied magnetic field separation can be obtained magnetic multiple after reaction 6h
Close microballoon.The magnetic content of the magnetic composite microsphere is 43.5%, and saturation magnetic content is 36.285emu/g, and BET specific surface area is
545m2/g。
Embodiment 10
The porous polydivinylbenezene microballoon being crosslinked using height is substrate, insoluble matter 91%, and BET specific surface area is
625m2/ g, aperture 3.6nm.Round-bottomed flask is added in the 0.5g microballoon, stirring is warming up to 40 DEG C.The dense nitre of 10g is added dropwise dropwise
Acid, after handling 20min, slow dilute solution, centrifugation is washed with deionized to neutrality.By treated, concentration is added in microballoon
Contain Fe for 5mol/L2+And Fe3+Aqueous solution in, Fe2+With Fe3+Ratio be 1:3, mix, sealing, be placed in baking oven.Setting is dried
Box temperature degree is 70 DEG C.It after 6h, takes out, centrifugation.The round-bottomed flask that deionized water is housed is added in the microballoon that centrifugation is obtained, and is passed through nitrogen
Gas shielded atmosphere is warming up to 70 DEG C, and NaOH solution is added dropwise dropwise to pH=13.After reacting 8h, externally-applied magnetic field separation be can be obtained
Magnetic composite microsphere.The magnetic content of the magnetic composite microsphere is 28.7%, and saturation magnetic content is 27.556emu/g, BET specific surface
Product is 358m2/g。
Embodiment 11
Using the porous polydivinylbenezene of height crosslinking and styrene copolymerized microballoon as substrate, insoluble matter 87%, BET ratio
Surface area is 342m2/ g, aperture 4.8nm.Round-bottomed flask is added in the 0.5g microballoon, stirring is warming up to 40 DEG C.It is added dropwise dropwise
4g concentrated nitric acid, after handling 10min, slow dilute solution, centrifugation is washed with deionized to neutrality.By treated, microballoon adds
Entering concentration is 5mol/L containing Fe2+And Fe3+Aqueous solution in, Fe2+With Fe3+Ratio be 1:4, mix, sealing, be placed in baking oven.
It is 40 DEG C that oven temperature, which is arranged,.After 18h, centrifugation is taken out, round-bottomed flask is added in the microballoon that centrifugation is obtained, and is passed through nitrogen protection gas
Atmosphere is warming up to 90 DEG C, and NaOH solution is added dropwise dropwise to pH=12.It is micro- that magnetic coupling can be obtained in externally-applied magnetic field separation after reaction 2h
Ball.The magnetic content of the magnetic composite microsphere is 19.5%, and saturation magnetic content is 18.344emu/g, BET specific surface area 266m2/
g。
Obviously, the above embodiment of the present invention be only to clearly illustrate example of the present invention, and not be pair
The restriction of embodiments of the present invention may be used also on the basis of the above description for those of ordinary skill in the art
To make other variations or changes in different ways, all embodiments can not be exhaustive here, it is all to belong to this hair
The obvious changes or variations that bright technical solution is extended out are still in the scope of protection of the present invention.
Claims (14)
1. a kind of preparation method of magnetic composite microsphere, which comprises the steps of:
The porous polymer microsphere of modifier modification height crosslinking；Modified microballoon is impregnated in metal cation solution；Dipping
Microballoon afterwards under inert gas protection, carries out precipitation reaction in alkaline solution, obtains the magnetic coupling with core-shell structure
Microballoon；Wherein, the insolubles content of the porous polymer microsphere of the high crosslinking is 80-98%, BET specific surface area 200-
1000m2/ g, aperture is between 2-10nm；The modifying agent is the concentrated sulfuric acid or concentrated nitric acid.
2. preparation method according to claim 1, which is characterized in that the preparation method further comprises that washing is modified
Microballoon.
3. preparation method according to claim 1, which is characterized in that the preparation method further comprises that separation is magnetic multiple
Close microballoon.
4. preparation method according to claim 3, which is characterized in that separate magnetic composite microsphere using externally-applied magnetic field.
5. preparation method according to claim 1, which is characterized in that the porous polymer microsphere of the high crosslinking includes poly-
Divinylbenzene microspheres or polydivinylbenezene and styrene copolymerized microballoon.
6. preparation method according to claim 1, which is characterized in that the porous polymer microsphere of the high crosslinking it is insoluble
Object content is 90-98%, BET specific surface area 400-800m2/ g, aperture is in 2-6nm.
7. preparation method according to claim 1, which is characterized in that the amount of modifier and porous polymer microsphere
Mass ratio is 2-40:1.
8. preparation method according to claim 7, which is characterized in that the amount of modifier and porous polymer microsphere
Mass ratio is 10-20:1.
9. preparation method according to claim 1, which is characterized in that the temperature of the modifier modification is 40-60 DEG C, is changed
Property the agent modified time be 10-60min.
10. preparation method according to claim 1, which is characterized in that the metal cation solution is to include Fe2+With
Fe3+The aqueous solution of ion.
11. preparation method according to claim 10, which is characterized in that described includes Fe2+And Fe3+The metal sun of ion from
Sub- solution concentration is 0.5-5mol/L, and described includes Fe2+And Fe3+Fe in the metal cation aqueous solution of ion2+And Fe3+Rub
You are than being 1:1-4；The temperature that the porous polymer microsphere of the high crosslinking impregnates in aqueous solution containing metal cation is 40-70
℃；Dip time of the porous polymer microsphere of the high crosslinking in aqueous solution containing metal cation is 2-24 hours.
12. preparation method according to claim 1, which is characterized in that alkaline matter in the alkaline solution be NaOH,
Ammonium hydroxide, KOH or LiOH.
13. preparation method according to claim 1, which is characterized in that the reaction temperature in the precipitation reaction is 40-90
℃；The pH value that the precipitation reaction reacts is 8-14；The reaction time of the precipitation reaction is 10-600min.
14. preparation method according to claim 13, which is characterized in that the reaction temperature of the precipitation reaction is 60-90
℃；The reaction time of the precipitation reaction is 30-120min.
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