CN100443508C - Process for preparing functional high molecule composite micro ball with quick magnetic field responsiveness - Google Patents
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Abstract
The present invention relates to composite material technology, and is especially preparation process of functional high molecular composite micro ball with quick magnetic field response. The preparation process includes the first coprecipitation to prepare superparamagnetic nanometer Fe3O4 particle with renselin and oleic acid modified surface and in-situ dispersing in n-octane to form oil base magnetic fluid; and the subsequent fine emulsion process to prepare composite superparamagnetic high molecular composite micro ball with carboxylated surface.The composite micro ball of the present invention has magnetic material content up to 78 wt %, average particle size of 41-185 nm and surface carboxy radical density of 0.0587-0.251 mmol/g, and may be applied in cell separation, target medicine and other biomedicine fields.
Description
Technical field
The present invention relates to a kind of method of technical field of composite materials, specifically is a kind of preparation method with functional high molecule composite micro ball of quick magnetic field responsiveness.
Background technology
In recent years, surface-functionalized magnetic composite microsphere is because of its special nature, purposes more and more is subjected to people's attention widely.The functionalization group that the magnetic composite microsphere surface existence of functionalization can be carried out chemically crosslinked with biologically active substance, simultaneously because it has stronger magnetic field responsiveness, can under extraneous the action of a magnetic field, separate easily and quickly, control and detect, thereby go out application prospects in biomedical fields such as immobilized enzyme, immunodetection, protein purification, target administration, cellular segregation.
At present, the method for the surface-functionalized magnetic composite microsphere of preparation mainly comprises: entrapping method, monomer copolymerization method and polymer microsphere swelling-take off swelling method.Entrapping method is meant magnetic particle is dispersed in the macromolecular solution, obtains magnetic composite microsphere by means such as atomizing, flocculation, deposition, evaporations.The required condition of magnetic composite microsphere of this method preparation is simple, be easy to carry out, but the thus obtained microsphere particle diameter is bigger, and shape is difficult to control.Polymer microsphere swelling-take off swelling method need at first prepare polymer microsphere, and oxide compound that carries out electroless plating iron then in porous microballoon inside etc. has the material of superparamagnetism, thereby finally obtains magnetic composite microsphere.This method for preparing magnetic composite microsphere need repeat multistep, and process is loaded down with trivial details, is difficult to control.The monomer copolymerization method is to prepare the most frequently used method of functional magnetic high molecular complex microsphere at present, it typically refers to the monomer (wherein a kind of is function monomer) that adopts two or more, carry out polyreaction under certain conditions, generate the magnetic composite microsphere that the surface has functional group, mainly comprise dispersion polymerization, letex polymerization, emulsifier-free emulsion polymerization, mini-emulsion polymerization etc.Wherein fine emulsion polymerization because of its unique monomer droplet mechanism of nucleation, is having significant advantage aspect the complex microsphere of the high magnetic substance content of preparation as a kind of novel method that is fit to preparation organic/inorganic complex microsphere that grew up in recent years.
Find through literature search prior art, Ramirez L P etc. were " Macromolecular Chemistryand Physics " (macromolecular chemistry and physics) (2003, the 204th phase, the 22nd page) on (MagneticPolystyrene Nanoparticles with a High Magnetite Content Obtained by MiniemulsionProcesses) (fine emulsion polymerization prepares the pipe/polyhenylethylene nano microballoon of high magnetic substance content) of delivering, propose in this article to adopt three step miniemulsion polymerizations, prepare the magnetic composite microsphere that the surface has carboxyl.Its concrete grammar is: at first prepare the surface that is dispersed in the octane by the Fe of oleic acid modified
3O
4Magnetic fluid, then with magnetic fluid in the ultrasonic thin emulsification of the aqueous phase that contains tensio-active agent, obtain the magnetic particle cluster aggressiveness of stable dispersion at aqueous phase.Then previously prepared vinylbenzene miniemulsion is mixed with the magnetic particle cluster aggressiveness of gained, and ultrasonic once more thin emulsification, thereby the compound drop of vinylbenzene that inside includes magnetic particle obtained.In the gained system, add a certain amount of initiator and Acrylic Acid Monomer at last, obtain the magnetic composite microsphere that the surface has carboxyl behind the initiated polymerization.The deficiency of this method is: reactions steps is various, length consuming time, and reaction process is wayward, Fe in the prepared in addition magnetic microsphere
3O
4Content is 34.7wt%, though than traditional method raising has to a certain degree been arranged, the amplitude that improves is not remarkable.
Summary of the invention
The present invention is directed to the problems referred to above that exist in the background technology, a kind of preparation method with functional high molecule composite micro ball of quick magnetic field responsiveness is provided, make it adopt a simple step miniemulsion polymerization to prepare the high molecular composite microsphere of the carboxylated high magnetic substance content in surface, solve above deficiency, improved Fe in the complex microsphere greatly
3O
4The covering amount of nanoparticle, and further improved the combine fastness of magnetic particle with polymer segment.
The present invention is achieved by the following technical solutions: at first adopt coprecipitation method preparation surface by undecylenic acid and the common superparamagnetism Fe that modifies of oleic acid
3O
4Nanoparticle, and original position is scattered in formation oil base magnetic fluid in the octane.Be equipped with the carboxylated superparamagnetic polymer complex microsphere in surface with a step miniemulsion legal system then, being about to magnetic fluid mixes with vinylbenzene, Vinylstyrene and is made into oil phase, at the ultrasonic aqueous phase that contains tensio-active agent that progressively joins down, after gained suspension supersound process, add function monomer vinylformic acid again and carry out copolymerization, finally obtain the carboxylated high Fe in surface
3O
4The composite nano-microsphere of content.
Described employing coprecipitation method preparation surface is by undecylenic acid and the common superparamagnetism Fe that modifies of oleic acid
3O
4Nanoparticle is specially:
At first with FeSO
47H
2O and FeCl
36H
2O is dissolved in and is made into molysite aqueous solution in the deionized water, and then at 70 ℃, high-speed stirring is under the condition of nitrogen protection, to containing Fe
2+And Fe
3+Molysite aqueous solution in add basic solution successively, undecylenic acid and oleic mixed solution, react after one hour, be warming up to 85 ℃, be incubated 60 minutes, to evaporate excess of ammonia water, after the pH of system value is 7 ± 1, stop evaporation, be cooled to room temperature, finally obtain the superparamagnetism Fe of surface by undecylenic acid and the common modification of oleic acid
3O
4Nanoparticle.
Above-mentioned surface is by undecylenic acid and the common superparamagnetism Fe that modifies of oleic acid
3O
4Nanoparticle, preparation condition is: Fe in the molysite aqueous solution
2+And Fe
3+Mol ratio be 1.42 to 1, add the OH of alkali
-With Fe in the molysite water
2+Mol ratio be 13.44 to 1, described alkali is ammoniacal liquor, the undecylenic acid of adding and oleic mixed solution are FeSO
47H
2The 18.5wt% of O quality, the undecylenic acid mass percent is 20～80wt% in the mixed solution.
Described formation oil base magnetic fluid is specially:
At first with the superparamagnetism Fe of surface by undecylenic acid and the common modification of oleic acid
3O
4The nanoparticle dehydrated alcohol, the deionized water repetitive scrubbing placed 80 ℃ of baking ovens dry 15 minutes, then at last with Fe
3O
4The nanoparticle original position is dispersed in the octane, forms magnetic fluid, Fe in the magnetic fluid
3O
4The mass percent of nanoparticle is 45～55wt%.
Described usefulness one step miniemulsion legal system is equipped with the carboxylated superparamagnetic polymer complex microsphere in surface, and concrete steps are as follows:
(1) with above-mentioned oil base magnetic fluid, with polymerization single polymerization monomer vinylbenzene, the linking agent Vinylstyrene is made into oil phase after mixing, and wherein the mass percentage content of magnetic fluid is 21～46wt%.Sodium lauryl sulphate is dissolved in again and forms water in the deionized water, the consumption of sodium lauryl sulphate is 2.2～4.1wt% of oil phase quality, and the oil phase quality is 13～19wt% of water quality.Under the ultransonic condition of Ultrasonic Cleaners (USC202), oil phase progressively is added dropwise to aqueous phase then, whole ultrasonic time remaining 2 and a half hours obtains the homogeneous black suspension.
(2) suspension in the step (1) is placed ice bath, use ultrasonic cell disruptor (JY92-11D) ultrasonic thin emulsification under 200 watts of power to obtain stable miniemulsion in 10 minutes then, then miniemulsion is poured in the there-necked flask, under 300rpm stirs, logical in advance nitrogen half an hour.
(3) in the miniemulsion behind pre-logical nitrogen, add vinylformic acid, Potassium Persulphate, wherein acrylic acid consumption are 2.1～21wt% of oil phase quality, and the Potassium Persulphate consumption is the 0.4wt% of oil phase quality.Polyreaction in 70 ℃ of waters bath with thermostatic control then, the control stirring velocity is 300rpm, sustained reaction is 18 hours under the nitrogen protection, finally obtains the carboxylated magnetic Nano complex microsphere in surface.
Compared with prior art, what the present invention adopted is a step miniemulsion polymerization, directly will contain magnetic fluid, the oil phase of monomer and linking agent, mix with the water that contains tensio-active agent, can form the compound monomer drop that inside includes a large amount of magnetic particles after the one step supersound process, after polymerization begins, the oligopolymer free radical that monomer droplet is caught aqueous phase causes nucleating growth, each monomer droplet can be regarded an independently reactor as, the complex microsphere that reaction generates and monomer droplet are 1 to 1 replication relations, this just special monomer droplet nucleation mechanism and simple process make it to become a kind of easy, the method for preparing the high molecular composite microsphere of surface-functionalized high magnetic substance content efficiently.The complex microsphere Fe of the present invention's preparation
3O
4Nanoparticle content can be up to 78wt%, and microsphere average grain diameter is 41～185nm, and surperficial carboxyl density is 0.0587～0.251mmol/g, the complex microsphere that this is prepared far above prior art, and the present invention has selected oleic acid and the common Fe that modifies of undecylenic acid for use
3O
4Nanoparticle is as magneticsubstance, because the Fe behind the oleic acid modified
3O
4Nanoparticle can stably be dispersed in the monomer droplet, and undecylenic acid has the easy and monomer reaction of terminal double bond, like this through oleic acid and the common Fe that modifies of undecylenic acid
3O
4Nanoparticle can be a large amount of stably be dispersed in the monomer, can participate in polyreaction again, thereby further improved the covering amount of magnetic particle, and the fastness that combines of magnetic particle and polymer segment, realized the uniform distribution of magnetic particle in microballoon, therefore the application in the biomedicine fields such as targeted drug can fully be satisfied in cellular segregation.
Embodiment
Embodiment 1
Get 26.9g FeSO
47H
2O and 18.4g FeCl
36H
2O; be dissolved in the 50ml deionized water; treat that molysite all joins in the 250ml there-necked flask after the dissolving, in nitrogen protection, 300rpm stirs down; be warming up to 70 ℃; add 50ml ammoniacal liquor then fast, add the mixture of 2g oleic acid and 3g gram undecylenic acid after five minutes, keep 70 ℃ of sustained reactions after 1 hour; open wide bottleneck; be warming up to 85 ℃, be incubated 60 minutes, to evaporate excess of ammonia water; after the pH of system value is 7 ± 1; stop evaporation, be cooled to room temperature, dehydrated alcohol is used in the outside magnetic field effect down then; deionized water repetitive scrubbing three times is removed excess of ammonia salt; oleic acid and undecylenic acid.With the Fe after the washing
3O
4Particle placed 80 ℃ of oven dryings 15 minutes, at last with Fe
3O
4The particle original position is dispersed in the octane, forms magnetic fluid, and with Fe
3O
4The mass percent of nanoparticle is adjusted to about 50wt%, and sealed storage is put in the refrigerator standby.
Take by weighing 7.2g vinylbenzene, 0.1g Vinylstyrene and the above-mentioned 4gFe that handles through modification
3O
4Magnetic fluid, mix and be made into oil phase, sodium lauryl sulphate with 0.36g is dissolved in the 70g deionized water in addition, place the 125ml beaker to constitute water, under the ultransonic condition of Ultrasonic Cleaners (USC202), lentamente oil phase is splashed into aqueous phase and carry out pre-emulsification, whole pre-emulsion process continues 2 and a half hours, obtains the homogeneous black suspension.Again with suspension (JY92-11D) ultrasonic thin emulsification 10 minutes in ultrasonic cell disruptor under 200 watts of power; obtain stable miniemulsion; miniemulsion is poured in the 250ml there-necked flask that agitator, reflux condensing tube and nitrogen conduit are housed; and logical in advance nitrogen half an hour; add 0.72g vinylformic acid then; 0.05gKPS; polyreaction in 70 ℃ of waters bath with thermostatic control; the control stirring velocity is 300rpm; sustained reaction is 18 hours under the nitrogen protection, finally obtains the super-paramagnetism nano complex microsphere that the surface has carboxyl.The surperficial carboxyl density 0.246mmol/g of microballoon, median size is 60.8 nanometers, after removing supernatant liquor four times with deionized water wash under the externally-applied magnetic field, lyophilize 8 hours finally records Fe in the microballoon with microballoon
3O
4Nanoparticle content can be up to 67wt%, and has superparamagnetism.
Embodiment 2
According to embodiment 1 described method, different is that acrylic acid add-on is 0.24g, and other processing modes are all identical with temperature of reaction, time.
The surperficial carboxylated magnetic composite microsphere Fe that present embodiment prepares
3O
4Nanoparticle content can reach 69wt%, surperficial carboxyl density 0.0587mmol/g, and median size is 64 nanometers, has superparamagnetism.
Embodiment 3
According to embodiment 1 described method, different is that acrylic acid add-on is 2.4g, and other processing modes are all identical with temperature of reaction, time.
The surperficial carboxylated magnetic composite microsphere Fe that present embodiment prepares
3O
4Nanoparticle content can reach 69.4wt%, surperficial carboxyl density 0.251mmol/g, and median size is 41 nanometers, has superparamagnetism.
Embodiment 4
According to embodiment 1 described method, the add-on of different is magnetic fluid is 2g, and the add-on of sodium lauryl sulphate is 0.3g, and other processing modes are all identical with temperature of reaction, time.
The surperficial carboxylated magnetic composite microsphere Fe that present embodiment prepares
3O
4Nanoparticle content is 49wt%, and median size is 52 nanometers, has superparamagnetism.
Embodiment 5
According to embodiment 1 described method, the adding consumption of different is magnetic fluid in the oil phase is 6g, and the add-on of aqueous phase sodium lauryl sulphate is 0.42g.And before ultrasonic thin emulsification, at first water is placed the 250ml there-necked flask, and stir with stirring rake, rotating speed is 450rpm, under the ultransonic condition of Ultrasonic Cleaners (USC202), oil phase is added aqueous phase in three batches carry out pre-emulsification then, whole pre-emulsion process continues 1 hour.In this external ultrasonic thin emulsion process, the power of ultrasonic cell disruptor (JY92-11D) is increased to 350 watts.Other processing modes are all identical with temperature of reaction, time.
Concrete implementation step is as follows: take by weighing 7.2g vinylbenzene, 0.1g Vinylstyrene and the above-mentioned 6g Fe that handles through modification
3O
4Magnetic fluid, mix and be made into oil phase, sodium lauryl sulphate with 0.42g is dissolved in the 70g deionized water in addition, place the 250ml there-necked flask to constitute water, water is stirred with stirring rake, rotating speed is 450rpm, place Ultrasonic Cleaners ultrasonic simultaneously, then oil phase is added aqueous phase in three batches and carry out pre-emulsification, whole pre-emulsion process continues 1 hour, obtains the homogeneous black suspension.Be 350 watts then with suspension 10 minutes ultrasonic powers of ultrasonic thin emulsification in ultrasonic cell disruptor, obtain stable miniemulsion after, logical in advance nitrogen half an hour.Add 0.72g vinylformic acid then, 0.05gKPS begins polyreaction in 70 ℃ of waters bath with thermostatic control, and stirring velocity is controlled at 300rpm, and entire reaction is carried out in nitrogen atmosphere, continues 18 hours, finally obtains the super-paramagnetism nano complex microsphere that the surface has carboxyl.The surperficial carboxyl density 0.08mmol/g of microballoon, median size is 138 nanometers, after removing supernatant liquor four times with deionized water wash under the externally-applied magnetic field, lyophilize 8 hours finally records Fe in the microballoon with microballoon
3O
4Nanoparticle content can be up to 78wt%, and has superparamagnetism.
Embodiment 6
According to embodiment 5 described methods, the add-on of sodium lauryl sulphate that different is is 0.30g, and other processing modes are all identical with temperature of reaction, time.
The surperficial carboxylated magnetic composite microsphere Fe that present embodiment prepares
3O
4Nanoparticle content is 70wt%, and median size is 185 nanometers, has superparamagnetism.
Embodiment 7
According to embodiment 5 described methods, the add-on of sodium lauryl sulphate that different is is 0.54g, and other processing modes are all identical with temperature of reaction, time.
The surperficial carboxylated magnetic composite microsphere Fe that present embodiment prepares
3O
4Nanoparticle content is 75wt%, and median size is 111 nanometers, has superparamagnetism.
Embodiment 8
According to embodiment 5 described methods, when different was the magnetic fluid of being modified jointly by undecylenic acid, oleic acid on the preparation surface, the add-on of undecylenic acid was 1 gram, and oleic add-on is 4 grams, and other processing modes are all identical with temperature of reaction, time.
The surperficial carboxylated magnetic composite microsphere Fe that present embodiment prepares
3O
4Nanoparticle content is 52wt%, and median size is 235 nanometers, has superparamagnetism.
Embodiment 9
According to embodiment 5 described methods, when different was the magnetic fluid of being modified jointly by undecylenic acid, oleic acid on the preparation surface, the add-on of undecylenic acid was 4 grams, and oleic add-on is 1 gram, and other processing modes are all identical with temperature of reaction, time.
The surperficial carboxylated magnetic composite microsphere Fe that present embodiment prepares
3O
4Nanoparticle content is 76wt%, and median size is 125 nanometers, has superparamagnetism.
Claims (7)
1. the preparation method with functional high molecule composite micro ball of quick magnetic field responsiveness is characterized in that: at first adopt coprecipitation method preparation surface by undecylenic acid and the common superparamagnetism Fe that modifies of oleic acid
3O
4Nanoparticle, and original position is scattered in formation oil base magnetic fluid in the octane, be equipped with the carboxylated superparamagnetic polymer complex microsphere in surface with a step miniemulsion legal system then, being about to magnetic fluid mixes with vinylbenzene, Vinylstyrene and is made into oil phase, at the ultrasonic aqueous phase that contains tensio-active agent that progressively joins down, after gained suspension supersound process, add function monomer vinylformic acid again and carry out copolymerization, finally obtain the carboxylated high Fe in surface
3O
4The composite nano-microsphere of content;
Described employing coprecipitation method preparation surface is by undecylenic acid and the common superparamagnetism Fe that modifies of oleic acid
3O
4Nanoparticle is specially:
At first with FeSO
47H
2O and FeCl
36H
2O is dissolved in and is made into molysite aqueous solution in the deionized water, then at 70 ℃, stirs, under the condition of nitrogen protection, to containing Fe
2+And Fe
3+Molysite aqueous solution in add basic solution successively, undecylenic acid and oleic mixed solution react after one hour, be warming up to 85 ℃, be incubated 60 minutes, after the pH of system value is 7 ± 1, stop evaporation, be cooled to room temperature, finally obtain the surface by undecylenic acid and the common superparamagnetism Fe that modifies of oleic acid
3O
4Nanoparticle.
2. the preparation method with functional high molecule composite micro ball of quick magnetic field responsiveness according to claim 1 is characterized in that, described surface is by undecylenic acid and the common superparamagnetism Fe that modifies of oleic acid
3O
4Nanoparticle, preparation condition is: Fe in the molysite aqueous solution
2+And Fe
3+Mol ratio be 1.42 to 1, add the OH of alkali
-With Fe in the molysite water
2+Mol ratio be 13.44 to 1, described alkali is ammoniacal liquor, the undecylenic acid of adding and oleic mixed solution are FeSO
47H
2The 18.5wt% of O quality, the undecylenic acid mass percent is 20～80wt% in the mixed solution.
3. the preparation method with functional high molecule composite micro ball of quick magnetic field responsiveness according to claim 1 is characterized in that, described formation oil base magnetic fluid is specially:
At first with the superparamagnetism Fe of surface by undecylenic acid and the common modification of oleic acid
3O
4The nanoparticle dehydrated alcohol, the deionized water repetitive scrubbing placed 80 ℃ of baking ovens dry 15 minutes, then at last with Fe
3O
4The nanoparticle original position is dispersed in the octane, forms magnetic fluid, Fe in the magnetic fluid
3O
4The mass percent of nanoparticle is 45～55wt%.
4. the preparation method with functional high molecule composite micro ball of quick magnetic field responsiveness according to claim 1 is characterized in that, described usefulness one step miniemulsion legal system is equipped with the carboxylated superparamagnetic polymer complex microsphere in surface,
Concrete steps are as follows:
(1) with the oil base magnetic fluid, with polymerization single polymerization monomer vinylbenzene, the linking agent Vinylstyrene is made into oil phase after mixing, wherein the mass percentage content of magnetic fluid is 21～46wt%, sodium lauryl sulphate is dissolved in forms water in the deionized water again, and the consumption of sodium lauryl sulphate is 2.2～4.1wt% of oil phase quality, the oil phase quality is 13～19wt% of water quality, under the ultransonic condition of Ultrasonic Cleaners, oil phase is progressively splashed into aqueous phase then, obtain the homogeneous black suspension;
(2) suspension in the step (1) is placed ice bath, obtain stable miniemulsion with the ultrasonic thin emulsification of ultrasonic cell disruptor then, then miniemulsion is poured in the there-necked flask, stir, logical in advance nitrogen;
(3) in the miniemulsion behind pre-logical nitrogen, add vinylformic acid, Potassium Persulphate, wherein acrylic acid consumption is 2.1～21wt% of oil phase quality, the Potassium Persulphate consumption is the 0.4wt% of oil phase quality, polyreaction in water bath with thermostatic control finally obtains the carboxylated magnetic Nano complex microsphere in surface then.
5. the preparation method with functional high molecule composite micro ball of quick magnetic field responsiveness according to claim 4 is characterized in that, in the described step (1), ultrasonic time continues 2 and a half hours.
6. the preparation method with functional high molecule composite micro ball of quick magnetic field responsiveness according to claim 4, it is characterized in that, in the described step (2), ultrasonic cell disruptor ultrasonic thin emulsification under 200 watts of power obtained stable miniemulsion in 10 minutes, stirring velocity is 300rpm, logical in advance nitrogen half an hour.
7. the preparation method with functional high molecule composite micro ball of quick magnetic field responsiveness according to claim 4; it is characterized in that; in the described step (3); polyreaction in water bath with thermostatic control; be meant: polyreaction in 70 ℃ of waters bath with thermostatic control; the control stirring velocity is 300rpm, and sustained reaction is 18 hours under the nitrogen protection.
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| CN101604569B (en) * | 2009-04-28 | 2011-04-06 | 西安交通大学 | Method for preparing nuclear shell type high magnetic content super paramagnetic microsphere |
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