CN103113515B - A kind of magnetic porous polymer beads and preparation method thereof - Google Patents
A kind of magnetic porous polymer beads and preparation method thereof Download PDFInfo
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- CN103113515B CN103113515B CN201310063672.2A CN201310063672A CN103113515B CN 103113515 B CN103113515 B CN 103113515B CN 201310063672 A CN201310063672 A CN 201310063672A CN 103113515 B CN103113515 B CN 103113515B
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Abstract
The invention provides a kind of preparation method of magnetic porous polymer beads, comprise the following steps: a) oil-soluble monomer, emulsifying agent and light trigger are mixed, obtain polymerization single polymerization monomer mixed solution; B) the polymerization single polymerization monomer mixed solution that described step a) obtains is mixed with iron salt solutions, obtain emulsion; C) emulsion adopting drop microfluidic technology described step b) to be obtained and basic solution are mixed to get water-in-oil-in-water double emulsion small droplets, carry out light initiating polymerizing reaction, obtain magnetic porous polymer beads.The present invention for external phase with polymerization single polymerization monomer mixed solution, is disperse phase with iron salt solutions, obtains water-in-oil High Internal Phase Emulsion; Drop microfluidic technology is adopted to take basic solution as carrier external phase, itself and described emulsion are mixed to get water-in-oil-in-water compositions small droplets, porous polymer particles is obtained after polyreaction, molysite generates magnetic nano-particle at polymer in situ simultaneously, obtain magnetic porous polymer beads, described aggregated particles is spherical, and porosity is larger.
Description
Technical field
The present invention relates to technical field of polymer, particularly relate to a kind of magnetic porous polymer beads and preparation method thereof.
Background technology
Magnetic porous polymkeric substance is obtained new function material by magnetic nano-particle and porous polymer compound.Magnetic porous polymer particle can give its surperficial several functions group by the method such as monomer polymerization or surface modification, makes it have wetting ability, bioaffinity or other surface propertys; It also has extremely strong magnetic or magnetic responsiveness simultaneously, is therefore convenient to Magneto separate and magnetic steering; It also has porous surface structure in addition, make magnetic porous polymer particle have larger surfaces externally and internally to amass, and vesicular structure can also give magnetic porous polymer particle special application performance, the internal space making it larger and good Surface Permeability.Magnetic porous polymer particle has excellent performance, and therefore, it is widely used in the fields such as bioseparation, pharmaceutical carrier, support of the catalyst.
The method preparing magnetic microsphere is at present a lot, Ugelstad etc. report a kind of method preparing porous magnetic complex microsphere, first the method utilizes the method for heteropolymerization to obtain monodispersed porous polymer microsphere, add divalence and the ferric salt solution of suitable proportion subsequently, make polymer microballoon swelling in iron salt solutions, infiltration, by raising pH value be warming up to suitable temperature, can in polymer microballoon deposited magnetic nanoparticle, obtained magnetic composite microsphere.The method has following advantage: (1), in magnetic history, particle diameter and the size distribution of monodisperse polymer micro-sphere are constant, and therefore the magnetic composite microsphere of final gained has good monodispersity; (2) densification or the porous magnetic complex microsphere (the best is 0.5 ~ 20 μm) of multiple particle diameter can be prepared; (3) the high magnetic content microballoon that magnetic compound content is greater than 30% can be prepared.But the method material aperture of preparing is less and porosity is little, limit its use as sharp separation medium.
The High Internal Phase Emulsion polymerization process of development in recent years prepares the poromeric novel method of high porosity, and the porous polymer of preparation has homogeneous open-celled structure, and have window to be communicated with between hole, porosity is more than 75%.Prior art by the method for the preparation of magnetic porous polymkeric substance, such as: the people such as Li combine High Internal Phase Emulsion polymerization process (J.Mater.Chem., 2011,21,12865-12872.), using the magnetic nano-particle of finishing as stablizer, with vinylbenzene and Vinylstyrene for polymerization single polymerization monomer, the method utilizing High Internal Phase Emulsion to be polymerized has prepared block macropore magnetic composite; The people such as Ghosh (Progress inColloid Polymer Science, 2011,138,161 – 164.) also utilize similar method, ferric oxide nano particles is mixed into oil-soluble monomer as oil phase, the aqueous solution containing emulsifying agent and light trigger is as aqueous phase, and prepare water-in-oil emulsion, initiated polymerization prepares block macropore Magnetic polymer composite materials.But the magnetic porous polymkeric substance that these two kinds of methods above-mentioned prepare is bulk material, limit its application at some specific area.
Summary of the invention
The object of the present invention is to provide a kind of magnetic porous polymer beads and preparation method thereof, magnetic porous polymer beads provided by the invention has larger porosity, and magnetic porous polymer beads is spherical, is conducive to its application.
The invention provides a kind of preparation method of magnetic porous polymer beads, comprise the following steps:
A) oil-soluble monomer, emulsifying agent and light trigger are mixed, obtain polymerization single polymerization monomer mixed solution;
B) the polymerization single polymerization monomer mixed solution that described step a) obtains is mixed with iron salt solutions, obtain emulsion;
C) emulsion adopting drop microfluidic technology described step b) to be obtained and basic solution are mixed to get water-in-oil-in-water double emulsion small droplets, carry out light initiating polymerizing reaction, obtain magnetic porous polymer beads.
Preferably, described step a) is:
Under lucifuge condition, oil-soluble monomer, emulsifying agent and light trigger are mixed, obtains polymerization single polymerization monomer mixed solution.
Preferably, the oil-soluble monomer in described step a) is one or more in glycidyl methacrylate, ethylene glycol dimethacrylate, vinylbenzene, Vinylstyrene and methyl methacrylate;
Emulsifying agent in described step a) is one or both in class 80 of department and poly-(the propylene glycol)-block-PEG of PEG-block-;
Light trigger in described step a) is dimethoxybenzoin, 2-hydroxy-2-methyl-1-phenyl-acetone or 1-hydroxy-cyclohexyl ketone.
Preferably, the mass ratio of oil-soluble monomer, emulsifying agent and light trigger in described step a) is (1 ~ 5): (0.1 ~ 3): (0.01 ~ 0.15).
Preferably, the iron ion in the iron salt solutions in described step b) comprises ferric ion and ferrous ion;
The mol ratio of described ferric ion and described ferrous ion is 10:(5 ~ 10).
Preferably, the volume ratio of described oil-soluble monomer and described iron salt solutions is 1:(3 ~ 4).
Preferably, in described iron salt solutions, the volumetric molar concentration of iron ion is 0.01mol/L ~ 0.5mol/L.
Preferably, described step b) is specially:
Under the condition stirred, in the polymerization single polymerization monomer mixed solution that described step a) obtains, drip iron salt solutions, be added dropwise to complete rear continuation and stir, obtain emulsion.
Preferably, described step c) is specially:
C1) emulsion that described step b) obtains is mixed with basic solution in microchannel, obtain water-in-oil-in-water double emulsion small droplets;
C2) described small droplets is carried out light initiating polymerizing reaction, obtain magnetic porous polymer beads.
The invention provides the magnetic porous polymer beads that preparation method described in a kind of technique scheme obtains.
The invention provides a kind of preparation method of magnetic porous polymer beads, comprise the following steps: a) oil-soluble monomer, emulsifying agent and light trigger are mixed, obtain polymerization single polymerization monomer mixed solution; B) the polymerization single polymerization monomer mixed solution that described step a) obtains is mixed with iron salt solutions, obtain emulsion; C) emulsion adopting drop microfluidic technology described step b) to be obtained and basic solution are mixed to get water-in-oil-in-water double emulsion small droplets, carry out light initiating polymerizing reaction, obtain magnetic porous polymer beads.Preparation method provided by the invention take iron salt solutions as disperse phase, and oil-soluble monomer is that external phase prepares water-in-oil High Internal Phase Emulsion; Then, adopt drop microfluidic technology to take basic solution as carrier external phase, described basic solution and described water-in-oil High Internal Phase Emulsion are mixed with and obtain water-in-oil-in-water compositions small droplets; In microchannel, light-initiated small droplets is polymerized to porous polymer particles, and molysite and alkaline aqueous solution react in-situ preparation magnetic nano-particle simultaneously, obtain magnetic porous polymer beads.Method provided by the invention obtains High Internal Phase Emulsion, adopts drop microfluidic technology to carry out light initiation polymerization, the aggregated particles obtained is presented spherical, and have larger porosity and higher room temperature saturation magnetization.Experimental result shows, the porosity of magnetic porous polymer beads provided by the invention is more than 70%, and room temperature saturation magnetization can up to 3.07emu/g.
Accompanying drawing explanation
The magnetic porous polymer beads preparation flow schematic diagram that Fig. 1 provides for the embodiment of the present invention.
Embodiment
The invention provides a kind of preparation method of magnetic porous polymer beads, comprise the following steps:
A) oil-soluble monomer, emulsifying agent and light trigger are mixed, obtain polymerization single polymerization monomer mixed solution;
B) the polymerization single polymerization monomer mixed solution that described step a) obtains is mixed with iron salt solutions, obtain emulsion;
C) emulsion adopting drop microfluidic technology described step b) to be obtained and basic solution are mixed to get water-in-oil-in-water double emulsion small droplets, carry out light initiating polymerizing reaction, obtain magnetic porous polymer beads.
Preparation method provided by the invention take iron salt solutions as disperse phase, and oil-soluble monomer is that external phase prepares water-in-oil High Internal Phase Emulsion; Then, adopt drop microfluidic technology to take basic solution as carrier external phase, described basic solution and described water-in-oil High Internal Phase Emulsion are mixed with and obtain water-in-oil-in-water compositions small droplets; In microchannel, light-initiated small droplets is polymerized to porous polymer particles, and molysite and alkaline aqueous solution react in-situ preparation magnetic nano-particle simultaneously, obtain porous polymer particles.Method provided by the invention obtains High Internal Phase Emulsion, adopts drop microfluidic technology to carry out light initiation polymerization, the aggregated particles obtained is presented spherical, and have larger porosity and higher room temperature saturation magnetization.
Drop microfluidic technology is a kind of method of emerging, micron-scale drop that simple effective method preparation size is homogeneous, its principle be mutual immiscible continuous fluid in interface because capillary effect can generate stable, orderly discontinuous flow, i.e. small droplets.
Oil-soluble monomer, emulsifying agent and light trigger mix by the present invention, obtain polymerization single polymerization monomer mixed solution.Mix in order to oil-soluble monomer, emulsifying agent and light trigger can be made, oil-soluble monomer, emulsifying agent and light trigger preferably mix by the present invention under the condition stirred, and more preferably oil-soluble monomer, emulsifying agent and light trigger are placed in the there-necked flask that whipping appts is housed; The method of the present invention to described stirring does not have special restriction, adopt the technical scheme of stirring well known to those skilled in the art, in the present invention, the speed of described stirring is preferably 300 turns/min ~ 500 turn/min, be more preferably 350 turns/min ~ 450 turn/min, most preferably be 400 turns/min.The present invention reacts before mixing with disperse phase to avoid polymerization single polymerization monomer, preferably under lucifuge condition, oil-soluble monomer, emulsifying agent and light trigger are mixed, the acquisition of the present invention to described lucifuge condition does not have special restriction, adopt the technical scheme of acquisition lucifuge well known to those skilled in the art, tinfoil can be adopted to carry out coated to reaction unit, preferably oil-soluble monomer, emulsifying agent and light trigger are placed in and whipping appts are housed and the there-necked flask using tinfoil lucifuge coated.
In the present invention, described oil-soluble monomer be preferably in glycidyl methacrylate, ethylene glycol dimethacrylate, vinylbenzene, Vinylstyrene and methyl methacrylate one or more, be more preferably in glycidyl methacrylate, ethylene glycol dimethacrylate and methyl methacrylate one or more, most preferably be glycidyl methacrylate and ethylene glycol dimethacrylate.The kind of the present invention to described emulsifying agent does not have special restriction, adopt emulsifying agent well known to those skilled in the art, in the present invention, described emulsifying agent be preferably in class 80 of department and poly-(the propylene glycol)-block-PEG of PEG-block-one or both, be more preferably class 80 of department, class 80 of department has another name called Span-80 or S-80 emulsifying agent, chemical name sorbitan monooleate.The kind of the present invention to described light trigger does not have special restriction, adopt light trigger well known to those skilled in the art, in the present invention, described light trigger is preferably dimethoxybenzoin, 2-hydroxy-2-methyl-1-phenyl-acetone or 1-hydroxy-cyclohexyl ketone, be more preferably dimethoxybenzoin or 2-hydroxy-2-methyl-1-phenyl-acetone, most preferably be dimethoxybenzoin.In the present invention, the mass ratio of described oil-soluble monomer, emulsifying agent and light trigger is (1 ~ 5): (0.1 ~ 3): (0.01 ~ 0.15), is more preferably (2 ~ 4): (0.5 ~ 2): (0.01 ~ 0.15).The add-on of described emulsifying agent preferably accounts for 15 ~ 30% of described oil-soluble monomer quality, is more preferably 20% ~ 25%; The add-on of described light trigger preferably accounts for 1 ~ 2% of described oil-soluble monomer quality.
After obtaining polymerization single polymerization monomer mixed solution, described polymerization single polymerization monomer mixed solution mixes with iron salt solutions by the present invention, obtains emulsion.The present invention is disperse phase with iron salt solutions, and the oil-soluble monomer described in technique scheme is external phase, prepares water-in-oil High Internal Phase Emulsion.The present invention preferably, under the condition stirred, drips iron salt solutions, is more preferably and dropwise adds in described polymerization single polymerization monomer mixed solution, proceeds to stir after being added dropwise to complete, and obtains homogeneous water-in-oil High Internal Phase Emulsion.The method of the present invention to described stirring does not have special restriction, adopts the technical scheme of stirring well known to those skilled in the art.In the present invention, the iron ion in described iron salt solutions is preferably ferric ion and ferrous ion, and the mol ratio of described ferric ion and described ferrous ion is preferably 10:(5 ~ 10), be more preferably 10:(6.5 ~ 9.5), most preferably be 10:9.In described iron salt solutions, the volumetric molar concentration of salt ion is preferably 0.01mol/L ~ 0.5mol/L, is more preferably 0.02mol/L ~ 0.3mol/L; The volume of described iron salt solutions preferably accounts for 70% ~ 85% of the total emulsion volume obtained, is more preferably 75% ~ 80%.In the present invention, described in be added dropwise to complete rear stirring time be preferably 5min ~ 10min, be more preferably 5min ~ 8min.
After obtaining emulsion, the present invention adopts drop microfluidic technology that described emulsion and basic solution are mixed to get water-in-oil-in-water double emulsion small droplets, after carrying out light initiating polymerizing reaction, obtains magnetic porous polymer beads.In the present invention, after the emulsion that technique scheme obtains mixes with basic solution, obtain water-in-oil-in-water double emulsion small droplets, under light-initiated effect, described water-in-oil-in-water double emulsion small droplets polymerization obtains porous polymer particles, molysite and alkaline aqueous solution react at porous polymer particles in-situ preparation magnetic nano-particle simultaneously, thus make the porous polymer particles obtained have magnetic, obtain magnetic porous polymer particle.
In the present invention, described basic solution is preferably hydroxide solution, is more preferably sodium hydroxide solution or solution of ammonium hydroxide, most preferably is sodium hydroxide solution.The massfraction of described basic solution is preferably 1% ~ 5%, is more preferably 1% ~ 2%.
Described emulsion, in order to prepare granular porous polymkeric substance, preferably mixes in microchannel with basic solution by the present invention, obtains water-in-oil-in-water double emulsion small droplets; Again described small droplets is carried out light initiating polymerizing reaction, obtain magnetic porous polymer beads.In the present invention, the cross sectional inner diameter of described microchannel is preferably 1mm ~ 5mm, is more preferably 1mm ~ 3mm, most preferably is 1mm ~ 2mm; In the present invention, described microchannel is preferably provided by silicone tube, and the present invention does not have special restriction to described silicone tube, adopts silicone tube well known to those skilled in the art; Described emulsion is preferably placed in injector syringe by the present invention, the syringe needle of described syringe is inserted in silicone tube, emulsion in described syringe is pushed in described silicone tube, there is basic solution to pass through in described silicone tube, after described emulsion mixes with the basic solution in described silicone tube, form water-in-oil-in-water double emulsion small droplets; Described small droplets is carried out light initiating polymerizing reaction, obtains porous polymer particles, molysite and basic solution react simultaneously, at porous polymer particles in-situ preparation magnetic nano-particle, thus the magnetic porous polymer beads obtained.
Referring to Fig. 1, Fig. 1 for the embodiment of the present invention provides magnetic porous polymer beads preparation flow schematic diagram, according to Fig. 1, described emulsion is placed in syringe, and described emulsion comprises external phase and disperse phase; And the syringe needle of described syringe is inserted in silicone tube, in silicone tube, pass into carrier phase, the basic solution namely described in technique scheme of the present invention simultaneously; The present invention is by controlling the speed that pushes of syringe and the flow velocity of carrier phase, control the mass ratio between emulsion and basic solution, in the present invention, the speed that described syringe pushes emulsion is preferably 0.1mL/h ~ 0.5mL/h, is more preferably 0.2mL/h ~ 0.4mL/h; The flow velocity of described carrier phase is preferably 0.5mL/min ~ 5mL/min, is more preferably 1mL/min ~ 3mL/min, most preferably is 1.2mL/min ~ 2.0mL/min;
The specification of the present invention to described syringe does not have special restriction, adopt syringe well known to those skilled in the art, in the present invention, the internal diameter of described syringe needle is preferably 200 μm ~ 500 μm, be more preferably 230 μm ~ 450 μm, most preferably be 300 μm ~ 400 μm; The source of the present invention to described syringe does not have special restriction, adopts the commercial goods of syringe well known to those skilled in the art.The present invention preferably adopts the syringe of syringe pump to syringe to drive, thus makes syringe can be pushed in microchannel by emulsion with above-mentioned speed; Described carrier drives preferably by peristaltic pump, makes it keep above-mentioned velocity of flow, fully can mix with described emulsion, forms water-in-oil-in-water double emulsion small droplets.
In described microchannel, described emulsion mixes with basic solution, and obtain water-in-oil-in-water double emulsion small droplets, described small droplets is carried out light initiating polymerizing reaction by the present invention, obtains magnetic porous polymer beads.The present invention preferably carries out UV-irradiation to described microchannel, while initiated polymerization, molysite in small droplets can react with basic solution, generates ferroferric oxide magnetic nano-particles, thus obtain magnetic porous polymer beads at polymer in situ.The present invention controls the time of light initiating polymerizing reaction by the flow velocity controlling small droplets in microchannel, in the present invention, the flow velocity of described small droplets is preferably 0.5mL/min ~ 5mL/min, is more preferably 1mL/min ~ 3mL/min, most preferably is 1.2mL/min ~ 2.0mL/min.
The pattern of the present invention to the magnetic porous polymer beads obtained detects, by the surface of the magnetic porous polymer beads obtained and the inner analysis carrying out scanning electron microscope and transmission electron microscope, result shows, magnetic porous polymer beads provided by the invention presents spherical or class is spherical, the surface of magnetic porous polymer beads and inside are all distributed with multiple duct, and described duct is interconnected; And the present invention have detected aperture and the porosity of the magnetic porous polymer beads obtained, result shows, magnetic porous polymer beads provided by the invention has larger porosity, is more than or equal to 70%, can separating medium fast, is beneficial to its application;
The present invention also have detected the magnetic of the magnetic porous polymer beads obtained, and result shows, magnetic porous polymer beads provided by the invention has the higher specific magnetising moment, and its room temperature saturation magnetization can up to 3.07emu/g.
The invention provides a kind of preparation method of magnetic porous polymer beads, comprise the following steps: a) oil-soluble monomer, emulsifying agent and light trigger are mixed, obtain polymerization single polymerization monomer mixed solution; B) the polymerization single polymerization monomer mixed solution that described step a) obtains is mixed with iron salt solutions, obtain emulsion; C) emulsion adopting drop microfluidic technology described step b) to be obtained and basic solution are mixed to get water-in-oil-in-water double emulsion small droplets, carry out light initiating polymerizing reaction, obtain magnetic porous polymer beads.Preparation method provided by the invention take iron salt solutions as disperse phase, and oil-soluble monomer is that external phase prepares water-in-oil High Internal Phase Emulsion; Then, adopt drop microfluidic technology to take basic solution as carrier external phase, described basic solution and described water-in-oil High Internal Phase Emulsion are mixed with and obtain water-in-oil-in-water compositions small droplets; In microchannel, light-initiated emulsion droplets is polymerized to porous polymer particles, and molysite and alkaline aqueous solution react in-situ preparation magnetic nano-particle simultaneously, obtain magnetic porous polymer beads.Method provided by the invention obtains High Internal Phase Emulsion, adopts drop microfluidic technology to carry out light initiation polymerization, the aggregated particles obtained is presented spherical, and have larger porosity and higher room temperature saturation magnetization.Experimental result shows, the porosity of magnetic porous polymer beads provided by the invention is more than 70%, and room temperature saturation magnetization can up to 3.07emu/g.
In order to further illustrate the present invention, below in conjunction with embodiment, magnetic porous polymkeric substance provided by the invention and preparation method thereof being described in detail, but they can not being interpreted as limiting the scope of the present invention.
Embodiment 1
1.02 milliliters of glycidyl methacrylate, 0.68 milliliter of ethylene glycol dimethacrylate, 0.3 milliliter of class 80 of department and 0.033 gram of dimethoxybenzoin being added is equipped with in the there-necked flask of whipping appts, and dropwise adding containing volumetric molar concentration under the constant agitation speed of 400 revs/min is wherein the Fe of 0.1mol/L
3+with the Fe of 0.09mol/L
2+iron salt solutions 7.2 milliliters, drip off rear continuation and stir 5 minutes at those speeds, obtain homogeneous emulsion;
Above-mentioned emulsion is poured into 22G(internal diameter 390 microns) in the injector syringe of syringe needle, injector syringe is installed on syringe pump, controlling injection speed is 0.2 ml/hour, and the syringe needle of syringe is inserted in silicone tube, containing massfraction in described silicone tube is 1% sodium hydroxide solution, described sodium hydroxide solution is run with 1.2 ml/min speed by the driving of peristaltic pump in silicone tube, thus the emulsion in syringe is pushed after in silicone tube, the sodium hydroxide solution in itself and silicone tube forms water-in-oil-in-water compositions small droplets;
Small droplets is carried out UV-irradiation initiated polymerization, and molysite and sodium hydroxide solution react and generate ferriferrous oxide nano-particle simultaneously, obtain magnetic porous polymer beads after having reacted.
The magnetic porous polymer beads obtained is carried out scanning electron microscope scanning analysis by the present invention, and result shows, magnetic porous polymer beads provided by the invention is spherical, and surface arrangement is porose, and the magnetic porous polymer beads particle diameter obtained is about 740 microns;
The present invention also have detected the structure of the magnetic porous polymer beads inside obtained, magnetic porous polymer beads is cut open rear its internal structure of employing scanning of scanning electron microscope, result shows, the pore structure of magnetic porous material provided by the invention runs through whole particle, its inside is also distributed with more hole, has larger aperture and porosity; The present invention detects the mean pore size obtaining magnetic porous polymer beads and is about 15 microns;
The magnetic porous polymer beads obtained is carried out magnetic measurement by the present invention, and result shows, the room temperature saturation magnetization of magnetic porous polymer beads provided by the invention is 3.07emu/g.
Embodiment 2
1.02 milliliters of glycidyl methacrylate, 0.68 milliliter of ethylene glycol dimethacrylate, 0.3 milliliter of class 80 of department and 0.033 gram of dimethoxybenzoin being added is equipped with in the there-necked flask of whipping appts, and dropwise adding containing volumetric molar concentration under the constant speed of 400 revs/min is wherein the Fe of 0.05mol/L
3+with the Fe of 0.045mol/L
2+iron salt solutions 7.2 milliliters, drip off rear continuation and stir 5 minutes at those speeds, obtain homogeneous emulsion;
Above-mentioned emulsion is poured into 22G(internal diameter 390 microns) in the injector syringe of syringe needle, injector syringe is installed on syringe pump, controlling injection speed is 0.2 ml/hour, and the syringe needle of syringe is inserted in silicone tube, containing massfraction in described silicone tube is 1% sodium hydroxide solution, described sodium hydroxide solution is run with the speed of 1.2 ml/min by the driving of peristaltic pump in silicone tube, thus the emulsion in syringe is pushed after in silicone tube, the sodium hydroxide solution in itself and silicone tube forms water-in-oil-in-water compositions small droplets;
Small droplets is carried out UV-irradiation initiated polymerization, and molysite and sodium hydroxide solution react and generate ferriferrous oxide nano-particle simultaneously, obtain magnetic porous polymer beads after having reacted.
The magnetic porous polymer beads obtained is carried out scanning electron microscope scanning analysis by the present invention, and result shows, magnetic porous polymer beads provided by the invention is spherical, and surface arrangement is porose, and the magnetic porous polymer beads particle diameter obtained is about 740 microns;
The present invention also have detected the structure of the magnetic porous polymer beads inside obtained, magnetic porous polymer beads is cut open rear its internal structure of employing scanning of scanning electron microscope, result shows, the pore structure of magnetic porous material provided by the invention runs through whole particle, its inside is also distributed with more hole, has larger aperture and porosity; The present invention detects the mean pore size obtaining magnetic porous polymer beads and is about 16 microns;
The magnetic porous polymer beads obtained is carried out magnetic measurement by the present invention, and result shows, the room temperature saturation magnetization of magnetic porous polymer beads provided by the invention is 2.09emu/g.
Embodiment 3
1.02 milliliters of glycidyl methacrylate, 0.68 milliliter of ethylene glycol dimethacrylate, 0.3 milliliter of class 80 of department and 0.033 gram of dimethoxybenzoin being added is equipped with in the there-necked flask of whipping appts, and dropwise adding containing volumetric molar concentration under the constant agitation speed of 400 revs/min is wherein the Fe of 0.02mol/L
3+with the Fe of 0.018mol/L
2+iron salt solutions 7.2 milliliters, drip off rear continuation and stir 5 minutes at those speeds, obtain homogeneous emulsion;
Above-mentioned emulsion is poured into 23G(internal diameter 320 microns) in the injector syringe of syringe needle, injector syringe is installed on syringe pump, controlling injection speed is 0.2 ml/hour, and the syringe needle of syringe is inserted in silicone tube, containing massfraction in described silicone tube is 1% sodium hydroxide solution, described sodium hydroxide solution is run with the speed of 1.2 ml/min by the driving of peristaltic pump in silicone tube, thus the emulsion in syringe is pushed after in silicone tube, the sodium hydroxide solution in itself and silicone tube forms oil in water in oil emulsion small droplets;
Small droplets is carried out UV-irradiation initiated polymerization, and molysite and sodium hydroxide solution react and generate ferriferrous oxide nano-particle simultaneously, obtain magnetic porous polymer beads after having reacted.
The magnetic porous polymer beads obtained is carried out scanning electron microscope scanning analysis by the present invention, and result shows, magnetic porous polymer beads provided by the invention is spherical, and surface arrangement is porose, and the magnetic porous polymer beads particle diameter obtained is about 620 microns;
The present invention also have detected the structure of the magnetic porous polymer beads inside obtained, magnetic porous polymer beads is cut open rear its internal structure of employing scanning of scanning electron microscope, result shows, the pore structure of magnetic porous material provided by the invention runs through whole particle, its inside is also distributed with more hole, has larger aperture and porosity; It is 20 microns that the present invention detects the mean pore size obtaining magnetic porous polymer beads;
The magnetic porous polymer beads obtained is carried out magnetic measurement by the present invention, and result shows, the room temperature saturation magnetization of magnetic porous polymer beads provided by the invention is 0.74emu/g.
Embodiment 4
1.02 milliliters of glycidyl methacrylate, 0.68 milliliter of ethylene glycol dimethacrylate, 0.3 milliliter of class 80 of department and 0.033 gram of dimethoxybenzoin being added is equipped with in the there-necked flask of whipping appts, and dropwise adding containing volumetric molar concentration under the constant agitation speed of 400 revs/min is wherein the Fe of 0.01mol/L
3+with the Fe of 0.009mol/L
2+iron salt solutions 7.2 milliliters, be added dropwise to complete rear continuation and stir 5 minutes at those speeds, obtain homogeneous emulsion;
Above-mentioned emulsion is poured into 25G(internal diameter 230 microns) in the injector syringe of syringe needle, injector syringe is installed on syringe pump, controlling injection speed is 0.2 ml/hour, and the syringe needle of syringe is inserted in silicone tube, containing massfraction in described silicone tube is 1% sodium hydroxide solution, described sodium hydroxide solution is run with the speed of 1.2 ml/min by the driving of peristaltic pump in silicone tube, thus the emulsion in syringe is pushed in silicone tube, the sodium hydroxide solution in itself and silicone tube forms water-in-oil-in-water compositions small droplets;
Small droplets is carried out UV-irradiation initiated polymerization, and molysite and sodium hydroxide solution react and generate ferriferrous oxide nano-particle simultaneously, obtain magnetic porous polymer beads after having reacted.
The magnetic porous polymer beads obtained is carried out scanning electron microscope scanning analysis by the present invention, and result shows, magnetic porous polymer beads provided by the invention is spherical, and surface arrangement is porose, and the magnetic porous polymer beads particle diameter obtained is about 420 microns;
The present invention also have detected the structure of the magnetic porous polymer beads inside obtained, magnetic porous polymer beads is cut open rear its internal structure of employing scanning of scanning electron microscope, result shows, the pore structure of magnetic porous material provided by the invention runs through whole particle, its inside is also distributed with more hole, has larger aperture and porosity; The present invention detects the mean pore size obtaining magnetic porous polymer beads and is about 18 microns;
The magnetic porous polymer beads obtained is carried out magnetic measurement by the present invention, and result shows, the room temperature saturation magnetization of magnetic porous polymer beads provided by the invention is 0.28emu/g.
As seen from the above embodiment, the invention provides a kind of preparation method of magnetic porous polymer beads, comprise the following steps: a) oil-soluble monomer, emulsifying agent and light trigger are mixed, obtain polymerization single polymerization monomer mixed solution; B) the polymerization single polymerization monomer mixed solution that described step a) obtains is mixed with iron salt solutions, obtain emulsion; C) emulsion adopting drop microfluidic technology described step b) to be obtained and basic solution are mixed to get water-in-oil-in-water double emulsion small droplets, carry out light initiating polymerizing reaction, obtain magnetic porous polymer beads.Preparation method provided by the invention take iron salt solutions as disperse phase, and oil-soluble monomer is that external phase prepares water-in-oil High Internal Phase Emulsion; Then, adopt drop microfluidic technology to take basic solution as carrier external phase, described basic solution and described water-in-oil High Internal Phase Emulsion are mixed with and obtain water-in-oil-in-water compositions small droplets; In microchannel, light-initiated emulsion droplets is polymerized to porous polymer particles, and molysite and alkaline aqueous solution react in-situ preparation magnetic nano-particle simultaneously, obtain magnetic porous polymer beads.Method provided by the invention obtains High Internal Phase Emulsion, adopts drop microfluidic technology to carry out light initiation polymerization, the aggregated particles obtained is presented spherical, and have larger porosity and higher room temperature saturation magnetization.Experimental result shows, the porosity of magnetic porous polymer beads provided by the invention is more than 70%, and room temperature saturation magnetization can up to 3.07emu/g.
The above is only the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (9)
1. a preparation method for magnetic porous polymer beads, comprises the following steps:
A) oil-soluble monomer, emulsifying agent and light trigger are mixed, obtain polymerization single polymerization monomer mixed solution;
B) the polymerization single polymerization monomer mixed solution that described step a) obtains is mixed with iron salt solutions, obtain emulsion;
C) drop microfluidic technology is adopted by described step b) emulsion that obtains and basic solution be mixed to get water-in-oil-in-water double emulsion small droplets, and carry out light initiating polymerizing reaction, obtain magnetic porous polymer beads;
Described iron salt solutions is disperse phase, and described polymerization single polymerization monomer mixed solution is external phase, and described basic solution is carrier external phase.
2. preparation method according to claim 1, is characterized in that, described step a) is:
Under lucifuge condition, oil-soluble monomer, emulsifying agent and light trigger are mixed, obtains polymerization single polymerization monomer mixed solution.
3. the preparation method according to claim 1 ~ 2 any one, it is characterized in that, described step a) in oil-soluble monomer be one or more in glycidyl methacrylate, ethylene glycol dimethacrylate, vinylbenzene, Vinylstyrene and methyl methacrylate;
Described step a) in emulsifying agent be one or both in class 80 of department and poly-(the propylene glycol)-block-PEG of PEG-block-;
Described step a) in light trigger be dimethoxybenzoin, 2-hydroxy-2-methyl-1-phenyl-acetone or 1-hydroxy-cyclohexyl ketone.
4. the preparation method according to claim 1 ~ 2 any one, it is characterized in that, described step a) in the mass ratio of oil-soluble monomer, emulsifying agent and light trigger be (1 ~ 5): (0.1 ~ 3): (0.01 ~ 0.15).
5. preparation method according to claim 1, is characterized in that, described step b) in iron salt solutions in iron ion comprise ferric ion and ferrous ion;
The mol ratio of described ferric ion and described ferrous ion is 10:(5 ~ 10).
6. preparation method according to claim 1, is characterized in that, the volume ratio of described oil-soluble monomer and described iron salt solutions is 1:(3 ~ 4).
7. the preparation method according to claim 1,5 ~ 6 any one, is characterized in that, in described iron salt solutions, the volumetric molar concentration of iron ion is 0.01mol/L ~ 0.5mol/L.
8. preparation method according to claim 1, is characterized in that, described step b) be specially:
Under the condition stirred, in the polymerization single polymerization monomer mixed solution that described step a) obtains, drip iron salt solutions, be added dropwise to complete rear continuation and stir, obtain emulsion.
9. preparation method according to claim 1, is characterized in that, described step c) be specially:
C1) by described step b) emulsion that obtains mixes in microchannel with basic solution, obtains water-in-oil-in-water double emulsion small droplets;
C2) described small droplets is carried out light initiating polymerizing reaction, obtain magnetic porous polymer beads.
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