CN103627022A - Method for preparing magnetic porous polystyrene microspheres on basis of suspension polymerization - Google Patents
Method for preparing magnetic porous polystyrene microspheres on basis of suspension polymerization Download PDFInfo
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- CN103627022A CN103627022A CN201310545988.5A CN201310545988A CN103627022A CN 103627022 A CN103627022 A CN 103627022A CN 201310545988 A CN201310545988 A CN 201310545988A CN 103627022 A CN103627022 A CN 103627022A
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Abstract
The invention relates to a method for preparing magnetic porous polystyrene microspheres on the basis of suspension polymerization, belonging to the technical field of preparation of environmental functional materials. The method comprises the following steps: synthesizing Fe3O4 magnetic particles by a solvothermal process; and preparing magnetic porous polystyrene microspheres by suspension polymerization by using styrene and divinylbenzene as functional monomers, azodiisobutyronitrile as an initiator and toluene and cyclohexanol as pore-forming agents. The obtained microspheres have abundant pores on the surface, thereby being beneficial to enhancing adsorbability; and the Fe3O4 magnetic particles inside the microspheres have magnetic stability, and can be quickly separated under the action of an external magnetic field. The adsorbent is used in a water environment for selectively adsorbing 2,4-dichlorophenol and 2,6-dichlorophenol. The static adsorption experiment result indicates that the magnetic porous microspheres prepared by the method have the advantages of favorable adsorption capacity, quick adsorption kinetic property and favorable regenerability.
Description
Technical field
A kind of method that the present invention relates to magnetic porous polystyrene microsphere of preparation based on suspension polymerization, belongs to environment functional material preparing technical field.
Background technology
Chlorophenol is classified toxic pollutant as third generation environmental pollutant ，Yi Bei EPA (EPA), and according to the regulation of EPA tissue, in water surrounding, the concentration of chlorophenol pollutant must not be higher than 0.1mg/L.Chlorophenol, as multiduty starting material in a kind of chemical industry production, mainly comes from various industrial production, as petrochemical complex, and Coal Industrial, timber, pharmacy, fibre paper, dyestuff, agricultural chemicals, rubber and Plastics Industry.Chlorophenol has higher toxicity to the mankind and other biology, the water that long-term drinking contains chlorophenol pollutants, can cause pain in various degree, vomiting, the disease of neurological disorder and reproductive system, most phenolic comp ' ds pollution or the mankind's carcinogens, therefore, stable, efficient, economical and practical treatment technology is urgently set up and is perfect.
At present, the conventional treatment technology of phenolic comp ' ds pollution has biological degradation, photochemical catalytic oxidation, ozone oxidation, membrane sepn, absorption and Solid-Phase Extraction etc.In these methods, absorption is a kind of not only economy but also efficient method.Recently, porous polymeric sorbent material is produced production, and these materials generally have porous, and density is low, the easy characteristic of functionalization, and be widely used in the removal of chlorophenol in the aqueous solution.In preparing the method for porous polymer material, suspension polymerization is proved to be the most simple and efficient method.Suspension polymerization technique is to prepare the traditional method of porous polymer sorbent material, and it is to make the mixture of water-fast monomer or various of monomer become droplet-like by strong mechanical agitation, is scattered in a kind of method of carrying out polyreaction in suspension medium.Suspension polymerization not only product purity is very high, and simple to operate.In addition, the porous polymer microsphere of preparing by suspension polymerization, as a kind of functionalization high polymer material with special surface morphology, has advantages of that loading capacity is large, adsorption rate is fast, regenerability is good.
Traditional sorbing material is difficult to from the aqueous solution separated, and in order to solve better this difficulty, people combine porous adsorbent with magnetic Nano material.By the hole binding pollutent of polymer layer, by the magneticsubstance of polymkeric substance inside, realize separated fast.The a series of sorbent material being comprised of magnetic-particle and inorganic materials is produced and applies, for example, and Mierocrystalline cellulose and Fe
3o
4form magnetic Nano material, γ-Fe
2o
3nano particle is applied to multilayer carbon nanotube synthesizing magnetic sorbing material.Magnetic particle no longer needs extra centrifugal or filtration, under the effect of externally-applied magnetic field, can realize sharp separation.The magnetic porous polymer microballoon of preparing by suspension polymerization not only has higher specific surface area, remarkable absorption property, and can under the effect of external magnetic field, realize simple separated.The magnetic porous sorbent material of preparing by suspension polymerization pollutes process field at water and has broad application prospects.
Summary of the invention
Technical scheme of the present invention refers to the synthetic Fe of solvent-thermal method
3o
4magnetic particle, and to take vinylbenzene and Vinylstyrene be function monomer, take Diisopropyl azodicarboxylate as initiator, take toluene and hexalin as pore-creating agent, adopt the method preparation of suspension polymerization to generate magnetic porous polystyrene microsphere (MSt), and be applied to selective adsorption 2,4 dichloro phenol and 2,6-chlorophenesic acid in water surrounding.
technical scheme
The method of the magnetic porous polystyrene microsphere of preparation based on suspension polymerization, carry out according to the following steps:
(1) the synthetic ferroferric oxide magnetic nano-particles of solvent-thermal method:
Ferric chloride (FeCl36H2O) (FeCl
36H
2o) and sodium acetate, anhydrous (NaAc) be dissolved in ethylene glycol solution, wherein control FeCl
36H
2o:NaAc: the mol ratio of ethylene glycol is (5-7): (87-90): (718-810).Mixing solutions speed with 800rpm/min under the protection of nitrogen stirs 1-2h in the water bath with thermostatic control of 160 ℃; then mixing solutions is transferred in the reactor of 50ml; under 200 ℃ of temperature condition, react 10-12h; cool to room temperature; suspension is cleaned to 3-5 time with ethanolic soln; the product of acquisition is dried under the vacuum environment of 60 ℃, finally in mortar, pulverize and grind, obtain Fe
3o
4nanoparticle.
(2) oleic acid is to Fe
3o
4magnetic nano-particle carries out finishing
Oleic acid joins Fe
3o
4in nanoparticle, control oleic acid and Fe
3o
4the ratio of nanoparticle is 4:0.1 ml/g, continues to stir 1-2h form dark-brown magnetic fluid with the speed of 200rpm/min.
(3) magnetic porous polystyrene microsphere is prepared in suspension polymerization
By vinylbenzene (St), Vinylstyrene (DVB), hexalin, the magnetic fluid in Diisopropyl azodicarboxylate (AIBN) and step (2) is dissolved in toluene solution and forms oil phase, controls vinylbenzene: in step (2), the ratio of magnetic fluid is (43-46): 4 mmol/ml; Natvosol (HEC) and sodium-chlor (NaCl) are dissolved in and in deionized water, form water.Wherein control St:DVB:AIBN: hexalin: the mol ratio of toluene is (43-46): (52-55): (1.2-1.6): (60-80): (39-41); The mass ratio of controlling NaCl and HEC and deionized water is (1.0-1.5): (0.6-0.9): (70-75).Oil phase and water after abundant stirring, mix two-phase 15-30 min and form emulsion respectively under ultrasonic condition, control oil phase: water volume ratio is (27-30): (70-75).This emulsion is transferred to 70 ℃ of constant water bath box, under the protection of nitrogen, with 400 rpm/min, stir 1-2 h, then temperature is remained on to 70 ℃.Reactant is sustained reaction 24 h under the high-speed stirring condition of 800 rpm/min.Finally, obtain MSt microballoon, the microballoon of acquisition is successively used to distilled water, acetone and ethanolic soln clean 2-3 time, with methylene dichloride extracting 8-24h in apparatus,Soxhlet's, finally use again methyl alcohol and washed with de-ionized water 2-3 time, in 80 ℃ of vacuum drying ovens, dry 24h.
The polymerization process adopting in above-mentioned technical scheme is suspension polymerization.
Vinylbenzene described in above-mentioned technical scheme and Vinylstyrene, it act as function monomer.
Diisopropyl azodicarboxylate described in above-mentioned technical scheme, it act as initiator.
Toluene described in above-mentioned technical scheme and hexalin, it act as pore-creating agent.
Natvosol described in above-mentioned technical scheme, it act as tensio-active agent.
Oleic acid described in above-mentioned technical scheme, it act as coating materials.
Technological merit of the present invention: the magnetic porous polystyrene microsphere output of preparing by suspension polymerization is high, and physical strength is high, and recognition site is survivable; Microsphere surface a large amount of hole that distributing, specific surface area is large, has guaranteed that microballoon has good absorption property; Be embedded in the magnetic Fe of microballoon inside
3o
4nanoparticle has good magnetic response character, is difficult for magnetic leakage occurs, and under the effect of externally-applied magnetic field, can realize sharp separation.
Accompanying drawing explanation
Fig. 1 is the optical microscope photograph of magnetic porous polystyrene microsphere in embodiment 1.From figure a, can see, the well-regulated spherical morphology of microballoon tool, particle diameter is approximately 20 um.From figure b, can find out, on magnetic microsphere surface, have a large amount of holes, the power spectrum of figure c has proved the existence of magnetic substance in microballoon.The configuration of surface that has shown the microballoon after four times are reused in figure d, figure e shows that the surface of regeneration microballoon still exists a large amount of holes.
Fig. 2 is the stereoscan photograph of magnetic porous polystyrene microsphere in embodiment 2, from figure a, can find out, and microballoon pattern size heterogeneity, but present spherical; Figure b shows that microsphere surface exists hole.
Fig. 3 is the Fourier transform infrared spectrum figure of expanded polystyrene microballoon (a) and magnetic porous polystyrene microsphere (b) in embodiment 1, in Fig. 3 b, at 599cm
-1the absorption peak that place shows is corresponding to Fe-O; Appear at 3090,3065 and 3029 cm
-1absorption peak corresponding to the stretching vibration of the C-H combination on polymkeric substance phenyl ring; Appear at 1453,1489 cm
-1the absorption peak at place is also the stretching vibration due to phenyl ring; Appear at 694 and 755 cm
-1the strong peak value at place has proved the existence of polystyrene in polymkeric substance; In addition, 1610 cm
-1the peak value at place has proved the existence of the C=C in Vinylstyrene in polymkeric substance.
Fig. 4 is Fe in embodiment 1
3o
4the X-ray diffraction curve of nanoparticle (a) and magnetic porous polystyrene microsphere (b), in 2 θ scopes are the scope of 25-65 °, six characteristic peak (2 θ=30.00
°, 35.45
°, 42.98
°, 53.41
°, 57.03
°, 62.55
°) appear at Fe
3o
4collection of illustrative plates in, these peak positions can be (2 2 0) by index, (3 1 1), (4 0 0), (4 2 2), (5 1 1) and (4 4 0), meanwhile, these peaks also appear in corresponding MSt microballoon, but than at Fe
3o
4in intensity slightly reduce.
Embodiment
Absorption property analysis test method described in technique scheme is specially:
(1) Static Adsorption test
By 2 of 10 ml different concns, 4-DCP and 2,6-DCP solution joins in colorimetric cylinder, the MSt microballoon that adds respectively 10mg, be placed on the standing different time in the water bath with thermostatic control of differing temps, investigate in test soln 2,4-DCP and 2, the starting point concentration of 6-DCP, the impact on sorbent material absorption property of temperature of reaction and time of repose; After saturated adsorption, sorbent material is collected with additional magnet, not absorption 2, the concentration ultraviolet spectral analysis of 4-DCP and 2,6-DCP, and according to result calculate loading capacity (
q e, mg/g):
Wherein
c 0(mg/L) and
c e(mg/L) be respectively absorption front and back 2, the concentration of 4-DCP and 2,6-DCP,
w(g) be sorbent material consumption,
v(mL) be test fluid volume.
(2) regeneration adsorption test
Desorption process uses acetic acid and methanol solution (9:1, v/v) as eluent, and the MSt microballoon that has adsorbed 2,4-DCP and 2,6-DCP is placed on wash-out in elutriant, utilizes 2 under ultraviolet spectral analysis wash-out, the concentration of 4-DCP and 2,6-DCP.Microballoon after wash-out is dry 12h under 60 ℃ of vacuum environments, again joins 2 of 100mg/L, 4-DCP and 2, in the solution of 6-DCP, adsorb, adsorption process continues 12h equally, and above adsorption and desorption additive process carries out repeatedly repeatedly, to verify the regenerability of MSt microballoon.
Below in conjunction with concrete embodiment, the present invention will be further described.
embodiment 1:
1, a method for magnetic porous polystyrene microsphere is prepared in suspension polymerization, and its preparation method carries out according to following step:
(1) the synthetic Z 250 (Fe of solvent-thermal method
3o
4) magnetic nano-particle:
1.35 g ferric chloride (FeCl36H2O) (FeCl
36H
2o) and 7.2 g sodium-acetates (NaAc) are dissolved in 40 ml ethylene glycol solutions; mixing solutions speed with 800rpm/min under the protection of nitrogen stirs 1h in the water bath with thermostatic control of 160 ℃; then mixing solutions is transferred in the reactor of 50ml; under 200 ℃ of temperature condition, react 10h; cool to room temperature, cleans suspension 3 times with ethanolic soln, and the product of acquisition is dried under the vacuum environment of 60 ℃; finally in mortar, pulverize and grind, obtain Fe
3o
4nanoparticle.
(2) oleic acid is to Fe
3o
4magnetic nano-particle carries out finishing
4 ml oleic acid join the Fe of 0.1g
3o
4in nanoparticle, with the speed of 200rpm/min, continue to stir 1h and form dark-brown magnetic fluid.
(3) magnetic porous polystyrene microsphere is prepared in suspension polymerization
By 5 ml vinylbenzene (St), 7.5 ml Vinylstyrenes (DVB), 6.25 ml hexalin, magnetic fluid in 0.25 g Diisopropyl azodicarboxylate (AIBN) and 4 ml steps (2) is dissolved in 4.2 ml toluene solutions and forms oil phase, and 0.9 g Natvosol (HEC) and 1.5 g sodium-chlor (NaCl) are dissolved in 70 ml deionized waters and form water.27 ml oil phases and 70 ml waters after abundant stirring, mix two-phase 15 min and form emulsion respectively under ultrasonic condition.This emulsion is transferred to 70 ℃ of constant water bath box, under the protection of nitrogen, with 400 rpm/min, stir 1 h, then temperature is remained on to 70 ℃.Reactant is sustained reaction 24 h under the high-speed stirring condition of 800 rpm/min.Finally, obtain MSt microballoon, the microballoon of acquisition is successively used to distilled water, acetone and ethanolic soln clean 3 times, with methylene dichloride extracting 24h in apparatus,Soxhlet's, finally use methyl alcohol and washed with de-ionized water 2 times again, in 80 ℃ of vacuum drying ovens, dry 24h.Prepare gained microballoon scanning electron microscope (SEM) photograph and can spectrogram as shown in Figure 1, microballoon is the spherical of rule as seen from the figure, and is distributed with a large amount of holes; The infrared spectrogram of microballoon as shown in Figure 3; The X-ray diffractogram of microballoon as shown in Figure 4.
2, absorption property analytical test:
(1) Static Adsorption test 1
10 ml concentration are respectively to 10,30,50,80,100,150,2 of 200,300 mg/L, 4-DCP and 2,6-DCP solution joins in colorimetric cylinder, the MSt microballoon that adds respectively 10mg, is placed on standing 12h in 25 ℃ of waters bath with thermostatic control, investigates in test soln 2, the impact of the starting point concentration of 4-DCP and 2,6-DCP on sorbent material absorption property; After saturated adsorption, microballoon is separated with externally-applied magnetic field, and not 2 of absorption, the concentration ultraviolet spectral analysis of 4-DCP and 2,6-DCP, according to formula calculation result.
Result shows: MSt microballoon is 131 mg/g to the saturated adsorption capacity of 2,4-DCP in the time of 25 ℃, and MSt microballoon is 124 mg/g to the saturated adsorption capacity of 2,6-DCP in the time of 25 ℃, MSt microballoon to the saturated adsorption capacity of 2,4-DCP a little more than 2,6-DCP.
(2) Static Adsorption test 2
By 10 ml concentration, be 2 of 100 mg/L, 4-DCP and 2,6-DCP solution join in colorimetric cylinder, add respectively the MSt microballoon of 10 mg, standing 10 min of difference in 25 ℃ of waters bath with thermostatic control, 30 min, 1 h, 2 h, 4 h, 6 h, 8 h and 12 h, investigate the impact of reaction times on sorbent material absorption property; After saturated adsorption, microballoon is separated with externally-applied magnetic field, and not 2 of absorption, the concentration ultraviolet spectral analysis of 4-DCP and 2,6-DCP, according to formula calculation result.
Result shows: MSt microballoon is 100 min to the adsorption saturation time of 2,4-DCP, and MSt microballoon is 70 min to the adsorption saturation time of 2,6-DCP, and MSt microballoon can reach quickly balance when absorption 2,6-DCP.
(3) Static Adsorption test 3
By 10 ml concentration, be 2 of 50 mg/L, 4-DCP solution joins in colorimetric cylinder, adds respectively the MSt microballoon of 10 mg, and respectively at 25 ℃, standing 12h in the water bath with thermostatic control of 35 ℃ and 45 ℃, investigates the impact of differential responses temperature on sorbent material absorption property; After saturated adsorption, sorbent material is separated with externally-applied magnetic field, and not 2 of absorption, the concentration ultraviolet spectral analysis of 4-DCP, according to formula calculation result.Result substitution Gibbs free energy (Gibbs free energy) formula calculates.
Result shows: by Gibbs free energy formula, the value of trying to achieve Δ Ho is 23.28, and the value of Δ So is that Δ G corresponding under 65.68, three differing tempss is respectively-19.55 ,-20.21 and-20.93.Δ Ho>0 explanation adsorption process is absorbed heat, and Δ G<0 shows that sorbent material is spontaneous to the absorption of 2,4-DCP.
embodiment 2:
1, a method for magnetic porous sorbent material is prepared in suspension polymerization, and its preparation method carries out according to following step:
(1) the synthetic ferroferric oxide magnetic nano-particles of solvent-thermal method:
1.85 g ferric chloride (FeCl36H2O) (FeCl
36H
2o) and 7.3 g sodium-acetates (NaAc) are dissolved in 45 ml ethylene glycol solutions; mixing solutions speed with 800rpm/min under the protection of nitrogen stirs 2h in the water bath with thermostatic control of 160 ℃; then mixing solutions is transferred in the reactor of 50ml; under 200 ℃ of temperature condition, react 12h; cool to room temperature, cleans suspension 5 times with ethanolic soln, and the product obtaining is dry under the vacuum environment of 60 ℃; finally in mortar, pulverize and grind, obtain Fe
3o
4nanoparticle.
(2) oleic acid is to Fe
3o
4magnetic nano-particle carries out finishing
4 ml oleic acid join the Fe of 0.1g
3o
4in nanoparticle, with the speed of 200rpm/min, continue to stir 2h and form dark-brown magnetic fluid.
(3) magnetic porous polystyrene microsphere is prepared in suspension polymerization
By 5.3ml vinylbenzene (St), 7.8 ml Vinylstyrenes (DVB), 8 ml hexalin, magnetic fluid in 0.2 g Diisopropyl azodicarboxylate (AIBN) and 4 ml steps (2) is dissolved in 4.3 ml toluene solutions and forms oil phase, and 0.6 g Natvosol (HEC) and 1.0 g sodium-chlor (NaCl) are dissolved in 75 ml deionized waters and form water.30 ml oil phases and 75 ml waters after abundant stirring, mix two-phase 30 min and form emulsion respectively under ultrasonic condition.This emulsion is transferred to 70 ℃ of constant water bath box, under the protection of nitrogen, with 400 rpm/min, stir 2 h, then temperature is remained on to 70 ℃.Reactant is sustained reaction 24 h under the high-speed stirring condition of 800 rpm/min.Finally, obtain MSt microballoon, the microballoon of acquisition is successively used to distilled water, acetone and ethanolic soln clean 2 times, with methylene dichloride extracting 8h in apparatus,Soxhlet's, finally use methyl alcohol and washed with de-ionized water 3 times again, in 80 ℃ of vacuum drying ovens, dry 24h.Prepare the scanning electron microscope (SEM) photograph of thus obtained microsphere as shown in Figure 2, as can be seen from the figure, microballoon pattern is heterogeneity very much not, but presents spherically, and surface exists hole.
2, absorption property analytical test:
(1) regeneration adsorption test 1
Desorption process is with 100 ml acetic acid and methanol solution (9:1, v/v) as eluent, and the MSt microballoon that has adsorbed 2,4-DCP is placed in elutriant and soaks, and utilizes 2 under ultraviolet spectral analysis wash-out, the concentration of 4-DCP.Microballoon after wash-out is dry 12h under 60 ℃ of vacuum environments, again join 2 of 100mg/L, in the solution of 4-DCP, adsorb, adsorption process continues 12h equally, above adsorption and desorption additive process carries out 4 times repeatedly, utilizes formula to calculate each loading capacity.
Result shows: after through 4 regeneration tests, MSt microballoon has only reduced by 15.6 % to the adsorptive power of 2,4-DCP, and result shows that MSt microballoon has still kept good absorption property after reusing for 4 times.
(2) regeneration adsorption test 2
Desorption process is with 100 ml acetic acid and methanol solution (9:1, v/v) as eluent, and the MSt microballoon that has adsorbed 2,6-DCP is placed in elutriant and soaks, and utilizes 2 under ultraviolet spectral analysis wash-out, the concentration of 6-DCP.Microballoon after wash-out is dry 12h under 60 ℃ of vacuum environments, again join 2 of 100mg/L, in the solution of 6-DCP, adsorb, adsorption process continues 12h equally, above adsorption and desorption additive process carries out 4 times repeatedly, utilizes formula to calculate each loading capacity.
Result shows: after through 4 regeneration tests, MSt microballoon has only reduced by 20.06 % to the adsorptive power of 2,6-DCP, and result shows that MSt microballoon has still kept good absorption property after reusing for 4 times.
Claims (4)
1. a method for the magnetic porous polystyrene microsphere of preparation based on suspension polymerization, refers to the synthetic Fe of solvent-thermal method
3o
4magnetic particle, and to take vinylbenzene and Vinylstyrene be function monomer, take Diisopropyl azodicarboxylate as initiator, take toluene and hexalin as pore-creating agent, adopt the method preparation of suspension polymerization to generate magnetic porous polystyrene microsphere, and be applied to selective adsorption 2,4 dichloro phenol and 2,6-chlorophenesic acid in water surrounding.
2. the method for the magnetic porous polystyrene microsphere of preparation based on suspension polymerization according to claim 1, is characterized in that, the preparation process of described synthesizing magnetic expanded polystyrene microballoon is as follows:
(1) the synthetic ferroferric oxide magnetic nano-particles of solvent-thermal method:
Ferric chloride (FeCl36H2O) and sodium acetate, anhydrous are dissolved in ethylene glycol solution; mixing solutions speed with 800rpm/min under the protection of nitrogen stirs 1-2h in the water bath with thermostatic control of 160 ℃; then mixing solutions is transferred in the reactor of 50ml; under 200 ℃ of temperature condition, react 10-12h; cool to room temperature, cleans 3-5 time suspension with ethanolic soln, and the product of acquisition is dried under the vacuum environment of 60 ℃; finally in mortar, pulverize and grind, obtain Fe
3o
4nanoparticle;
(2) oleic acid is to Fe
3o
4magnetic nano-particle carries out finishing
Oleic acid joins Fe
3o
4in nanoparticle, control oleic acid and Fe
3o
4the ratio of nanoparticle is 4:0.1 ml/g, continues to stir 1-2h form dark-brown magnetic fluid with the speed of 200rpm/min;
(3) magnetic porous polystyrene microsphere is prepared in suspension polymerization
By vinylbenzene, Vinylstyrene, hexalin, the magnetic fluid in Diisopropyl azodicarboxylate and step (2) is dissolved in and in toluene solution, forms oil phase, and Natvosol and sodium-chlor are dissolved in and in deionized water, form water; Oil phase and water after abundant stirring, mix two-phase 15-30 min and form emulsion respectively under ultrasonic condition, control oil phase: water volume ratio is (27-30): (70-75); This emulsion is transferred to 70 ℃ of constant water bath box, under the protection of nitrogen, with 400 rpm/min, stir 1-2 h, then temperature is remained on to 70 ℃; Reactant is sustained reaction 24 h under the high-speed stirring condition of 800 rpm/min; Finally, obtain magnetic porous polystyrene microsphere, the microballoon of acquisition is successively used to distilled water, acetone and ethanolic soln clean 2-3 time, with methylene dichloride extracting 8-24h in apparatus,Soxhlet's, finally use again methyl alcohol and washed with de-ionized water 2-3 time, in 80 ℃ of vacuum drying ovens, dry 24h.
3. the method for preparing magnetic porous polystyrene microsphere based on suspension polymerization according to claim 2, is characterized in that the wherein middle ferric chloride (FeCl36H2O) of controlling of step (1): sodium acetate, anhydrous: the mol ratio of ethylene glycol is (5-7): (87-90): (718-810).
4. the method for preparing magnetic porous polystyrene microsphere based on suspension polymerization according to claim 2, is characterized in that wherein the add-on of the middle magnetic fluid of step (3) is control vinylbenzene: in step (2), the ratio of magnetic fluid is (43-46): 4 mmol/ml; Control vinylbenzene: Vinylstyrene: Diisopropyl azodicarboxylate: hexalin: the mol ratio of toluene is (43-46): (52-55): (1.2-1.6): (60-80): (39-41); The mass ratio of control sodium-chlor and Natvosol and deionized water is (1.0-1.5): (0.6-0.9): (70-75).
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1375507A (en) * | 2001-03-20 | 2002-10-23 | 清华大学 | Surface cladding and radical functino modification method of magnetic microsphere, thus obtained microsphere and its application |
-
2013
- 2013-11-06 CN CN201310545988.5A patent/CN103627022A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1375507A (en) * | 2001-03-20 | 2002-10-23 | 清华大学 | Surface cladding and radical functino modification method of magnetic microsphere, thus obtained microsphere and its application |
Non-Patent Citations (1)
| Title |
|---|
| PING YU ET AL.: "Performance of Poly(Styrene–Divinylbenzene) Magnetic Porous Microspheres Prepared by Suspension Polymerization for the Adsorption of 2, 4-Dichlorophenol and 2, 6-Dichlorophenol from Aqueous Solutions", 《ADSORPTION SCIENCE & TECHNOLOGY》, vol. 31, no. 7, 1 October 2013 (2013-10-01), pages 641 - 656 * |
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