CN102964539A - Preparation method of porous magnetic polystyrene microspheres - Google Patents
Preparation method of porous magnetic polystyrene microspheres Download PDFInfo
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- CN102964539A CN102964539A CN201210401093XA CN201210401093A CN102964539A CN 102964539 A CN102964539 A CN 102964539A CN 201210401093X A CN201210401093X A CN 201210401093XA CN 201210401093 A CN201210401093 A CN 201210401093A CN 102964539 A CN102964539 A CN 102964539A
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Abstract
The invention discloses a preparation method of porous magnetic polystyrene microspheres. The method comprises steps of: (1) adding dry Fe3O4 magnetic nanoparticles into an aqueous ethanol solution, treating with ultrasonic, adding vinyltriethoxysilane, transferring into a reactor together, stirring under a constant temperature and a nitrogen atmosphere for aging, and then washing, drying under vacuum and grinding the obtained product into powder; (2) mixing the powder obtained in the step (1) and benzoyl peroxide, and then adding into styrene containing a pore forming agent and a cross-linking agent for the ultrasonic treating; (3) dissolving polyvinylpyrrolidone and sodium dodecyl sulfate into water by using the ultrasonic; and (4) adding the liquid obtained in the step (2) into the liquid obtained in the step (3), treating with the ultrasonic, pouring the obtained mixture into a reactor, heating for condensation reflux to obtain a suspension liquid, separating with magnet, washing with ethanol, re-separating with the magnet, re-washing with pure water, drying under vacuum and grinding to obtain claybank powdery product, extracting with a soxhlet way, and drying under vacuum to obtain the finish product.
Description
Technical field
The present invention relates to a kind of preparation method of porous magnetic polymer microballoon, particularly the preparation method of porous magnetic polystyrene microsphere.
Background technology
Along with the development of life science, the compartment analysis that carries out fast and efficiently biomacromolecule more and more is subject to people's attention.The separation means that biological magnetic separation technique gets up as a kind of development in recent years has efficiently, quick, solvent consumption is few, realize easily the fashionable biology of advantage, biotechnology and the biomedical sector such as automatization.Biological magnetic separates and needs that ball-type is regular, uniform particle diameter, good dispersion, magnetic responsiveness are strong, the magnetic ball with superparamagnetism.For biological magnetic separation technique is applied even more extensively, should prepare the surface with the magnetic ball of the functional groups such as carboxyl, hydroxyl, epoxy group(ing), amido, easily be combined with different biological molecules with the magnetic ball of these functional groups.
Magnetic porous polymer microballoon is an important branch of magnetic polymer microsphere, it refers to a kind of magnetic polymer composite microspheres with vesicular structure by certain method preparation, it is a kind of novel functional materials, its character depends on the varied property of magnetic property that character and the recombination mechanism thereof of inorganic magnetic material, macromolecular compound, particularly different magnetic substances show.For magnetic porous polymer microballoon, on the one hand, monomer polymerization or surface modification etc. give its surperficial several functions group (as: OH ,-COOH ,-NH
2,-CHO etc.), make it have wetting ability, bioaffinity or other surface property; Secondly, it has stronger magnetic or magnetic responsiveness, therefore is convenient to magnetic and separates and magnetic steering; It also has the porous surface structure in addition, thus microballoon to have a larger surfaces externally and internally long-pending, and vesicular structure can also give microballoon special application performance, therefore in affinity chromatography, the fields such as the immobilization of enzyme and environmental engineering have broad application prospects.Therefore, design and the magnetic porous material that synthesizes different structure has significant scientific meaning and using value.
At present, the report of existing preparation porous magnetic polymer microballoon seldom, in order to obtain the less porous magnetic polymer microballoon of particle diameter, so that it fully represents the advantage that the small size microballoon has, enlarge its range of application, the invention provides a kind of preparation method of porous magnetic polymer microballoon.
Summary of the invention
Technical problem to be solved by this invention provides a kind of preparation method of porous magnetic polystyrene microsphere, the method mainly is that the method by the finishing of magnetic particle and microsuspension prepares magnetic microsphere, and ultrasonic high speed shear has effectively promoted homogeneity and the stability of dispersion system.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows:
The preparation method of porous magnetic polystyrene microsphere, it comprises the steps:
(1) with the Fe of drying
3O
4Magnetic nano-particle joins in the aqueous solution of ethanol, behind ultrasonic cleaning machine supersound process 20 ~ 30min, to Fe
3O
4Dropwise add vinyltriethoxysilane (SG-151) in the suspension, change in the lump again in the reactor, under the nitrogen protection condition, stir ageing 12 ~ 24h, the Fe after the resulting modification at 35 ~ 50 ℃ of constant temperature
3O
4Magnetic nano-particle through washing, vacuum-drying, pulverize;
(2) get powder and benzoyl peroxide (BPO) mixing that step (1) obtains, add and contain in the styrene solvent of pore-creating agent and linking agent, supersound process 0.5 ~ 1h, described perforating agent are the mixture of toluene and normal heptane, and described linking agent is Vinylstyrene;
(3) polyvinylpyrrolidone (PVP) and sodium lauryl sulphate (SDS) supersound process are dissolved in the water;
(4) oily liquid that step (2) is obtained joins in the liquid that step (3) obtains, large power supersonic instrument supersound process 5 ~ 10min is to fully disperseing, the mixture that obtains is poured in the reactor, behind 70 ~ 80 ℃ of condensing reflux reaction 1.5 ~ 2h, be warming up to again 80 ~ 90 ℃ of condensing reflux reaction 6 ~ 8h, obtain little bluish voilet suspension, wash through magnet magnetic separating alcohol respectively, after magnetic separates the pure water washing, the brown color powdered product is ground to get in vacuum-drying, the brown color powdered product is carried out Soxhlet extracting 24h, last vacuum-drying, and get final product.
In the step (1), Fe
3O
4Magnetic nano-particle can be according to the preparation of existing routine techniques, and concrete preparation method can be with reference to as follows:
With FeCl
24H
2O, FeC1
36H
2O mixes with the mol ratio (mass ratio 1:2.7) of 1:2, is dissolved in the water of 10～12 times of quality, stirs lower dissolving, and logical nitrogen drives oxygen half an hour, then is warming up to 60 ℃, adds rapidly excessive NH under rapid stirring
3H
2O, system becomes black from transparent yellow-green colour immediately.Be warming up to subsequently 90 ℃, keep temperature 30min, then drop to room temperature, add 3mol.L
-1HCl regulates pH=4, leaves standstill, and product is collected with magnetic field separation.The product deionized water dispersed with stirring of collecting, magnetic field separation then, said process is repeated multiple times until without the Cl that dissociates
-, after the vacuum-drying, grind into powder.
In the step (1), in the aqueous solution of ethanol, the concentration expressed in percentage by volume of ethanol is 40% ~ 60%.
In the step (1), for the aqueous solution of 1L ethanol, dry Fe
3O
4It is 8 ~ 12g that magnetic nano-particle adds quality.
In the step (1), for 1gFe
3O
4Magnetic nano-particle, the add-on of vinyltriethoxysilane are 1 ~ 2ml.
In the step (1), mode of washing is first absolute ethanol washing 2 ~ 3 times, and the deionization washing is 2 ~ 3 times again.
In step (1) and (4), the vacuum-drying temperature is 40 ~ 60 ℃.
In the step (2), the powder that step (1) obtains and benzoyl peroxide in mass ratio 2 ~ 4:1 mix.
In the step (2), the volume ratio 10 ~ 16:4:2:1 of vinylbenzene, toluene, normal heptane and Vinylstyrene; For the powder that every 1g step (1) obtains, the use volume of Vinylstyrene is 1 ~ 1.5ml.
In the step (3), the mass ratio of polyvinylpyrrolidone, sodium lauryl sulphate and water is 5 ~ 8:1 ~ 3:1000; The mass ratio of the powder that polyvinylpyrrolidone and step (1) obtain is 1 ~ 2:1.
Step (1) is ultrasonic wave dispersing and dissolving in the conventional ultrasound cleaning apparatus to step (3).In the step (4), ultrasound condition is that 20KHz ultrasonic apparatus intermittent type is ultrasonic, and ultrasonic time is 5 ~ 10min, and the intermittent time is 2 ~ 5 seconds/time.
In the step (4), in the Soxhlet extracting, the solvent of use is for adding the ethanolic soln of hydrochloric acid, and the concentration of the hydrochloric acid of adding is 36 ~ 38wt%, and the volume ratio of hydrochloric acid and ethanol is 1:75 ~ 1:30.
The porous magnetic polystyrene microsphere for preparing according to the method described above is also within protection scope of the present invention.
Beneficial effect: the preparation method of porous magnetic polystyrene microsphere microballoon of the present invention, adopt single stage method to prepare porous microsphere, the finishing process is so that magnetic particle and polymer bonding are more abundant, ultrasonic technique is so that magnetic particle distributes more even, SEM, TEM(sees accompanying drawing) the preparation balling-up that intuitively characterizes magnetic porous microspheres is good, and size reaches below the 20um, size distribution is narrower, and magnetic responsiveness is good.In present method, add in the time of stablizer and emulsifying agent and improved stability of system, the microspherulite diameter narrow distribution of the preparation of ultrasonic apparatus, the porous microsphere form is better, and micropore is evenly distributed, at immunoassay, the immobilization of enzyme, target administration, the fields such as cellular segregation have wide practical use.
Description of drawings
Fig. 1 is the homemade magnetic Nano Fe that arrives involved in the present invention
3O
4The TEM photo of particle.
Fig. 2 is the SEM photo of porous magnetic polystyrene microsphere of the present invention.
Fig. 3 is the TEM photo of porous magnetic polystyrene microsphere of the present invention.
Embodiment
According to following embodiment, the present invention may be better understood.Yet, those skilled in the art will readily understand that the described content of embodiment only is used for explanation the present invention, and should also can not limit the present invention described in detail in claims.
Embodiment 1: the preparation of material.
Cinnamic refining: the NaOH aqueous solution repetitive scrubbing with 200ml 5wt% is extremely colourless, and to remove stopper, distilled water wash three times adds anhydrous CaCl afterwards
2Drying, the brown bottle of packing into saves backup.
Making with extra care of benzoyl peroxide (BPO): 10gBPO is dissolved in stirring and dissolving in the 50ml chloroform, filters, and filtrate splashes in the 100ml methyl alcohol, put into refrigerator and leave standstill, obtain white, needle-shaped crystals, with a small amount of cold methanol washing three times, room temperature vacuum-drying 10h, the brown wide-necked bottle of packing into, refrigerator cold-storage is for subsequent use.
Fe
3O
4The preparation of magnetic nano-particle: with 4.28g FeCl
24H
2O, 11.70gFeCl
36H
2O is dissolved in the 180ml water, stirring and dissolving, and logical nitrogen is warming up to 60 ℃ after driving oxygen 0.5h, the 20.0mlNH that adds rapidly under rapid stirring
3H
2O, system becomes black from transparent yellow-green colour.Be warming up to subsequently 90 ℃, keep 30min, then leave standstill cool to room temperature, add 3mol.l
-1HCl regulates pH=4, leaves standstill, after washing magnetic separates several final vacuum drying, and grind into powder.
Embodiment 2: the preparation of porous magnetic polystyrene microsphere.
Specifically comprise the steps:
(1) gets the Fe of the drying of 0.8g embodiment 1 preparation
3O
4Magnetic nano-particle joins in 100ml 50 (v/v) the % aqueous ethanolic solution, then with mixed solution supersound process 30min, drips gradually the 1ml vinyltriethoxysilane to being dissolved with Fe
3O
4Suspension in.Afterwards, change in the 250m1 three-necked flask, at N
2Protection is lower, the ageing of 40 ℃ of rapid stirring 12h constant temperature.Absolute ethanol washing three times of resulting product, deionized water wash twice, afterwards 40 ℃ of vacuum-dryings, grind into powder.
(2) get powder 0.5g that step (1) obtains and the BPO 0.2g behind the purifying, it is joined in the test tube of the vinylbenzene, 2ml toluene, 1ml normal heptane and the 0.5mlDVB linking agent that contain 6ml, place the ultrasonic mixing of ultrasonic wave 1h.
(3) measure deionized water 100ml in the beaker of 150ml, take by weighing respectively 0.6gPVP, 0.2gSDS adds wherein, stirs with glass stick, dissolves in ultrasonic wave.
(4) the resulting oily liquid of step (2) is joined in the aqueous solution of step (3), place processor for ultrasonic wave 20KHz intermittent type supersound process 5min, fully disperse, pour the system that obtains into the 100ml there-necked flask, 80 ℃ of heating in water bath, behind the condensing reflux 2h, be warming up to 90 ℃ of reaction 6h, obtain at last little bluish voilet suspension, wash through magnet magnetic separating alcohol respectively, after magnetic separated the pure water washing, the brown color powdered product was ground to get in 40 ℃ of vacuum-dryings.Dry sample is carried out Soxhlet extracting 24h, and the solvent that the Soxhlet extracting is used is for adding the ethanolic soln of hydrochloric acid, and the concentration of the hydrochloric acid of adding is 36 ~ 38wt%, and the volume ratio of hydrochloric acid and ethanol is 1:75, and last vacuum-drying can obtain product.
Embodiment 3:
Specifically comprise the steps:
(1) gets the Fe of the drying of 1g embodiment 1 preparation
3O
4Magnetic nano-particle joins in 100ml 40 (v/v) the % aqueous ethanolic solution, then with mixed solution supersound process 20min, drips gradually the 2ml vinyltriethoxysilane to being dissolved with Fe
3O
4Suspension in.Afterwards, change in the 250m1 three-necked flask, at N
2Protection is lower, the ageing of 50 ℃ of rapid stirring 24h constant temperature.Absolute ethanol washing three times of resulting product, deionized water wash three times, afterwards 60 ℃ of vacuum-dryings, grind into powder.
(2) get powder 0.34g that step (1) obtains and the BPO 0.17g behind the purifying, it is joined in the test tube of the vinylbenzene, 2ml toluene, 1ml normal heptane and the 0.5mlDVB linking agent that contain 8ml, place the ultrasonic mixing of ultrasonic wave 0.5h.
(3) measure deionized water 100ml in the beaker of 150ml, take by weighing respectively 0.8gPVP, 0.3gSDS adds wherein, stirs with glass stick, dissolves in ultrasonic wave.
(4) the resulting oily liquid of step (2) is joined in the aqueous solution of step (3), place processor for ultrasonic wave 20KHz intermittent type supersound process 10min, fully disperse, pour the system that obtains into the 100ml there-necked flask, 70 ℃ of heating in water bath, behind the condensing reflux 1.5h, be warming up to 80 ℃ of reaction 8h, obtain at last little bluish voilet suspension, wash through magnet magnetic separating alcohol respectively, after magnetic separated the pure water washing, the brown color powdered product was ground to get in 40 ℃ of vacuum-dryings.Dry sample is carried out Soxhlet extracting 24h, and the solvent that the Soxhlet extracting is used is for adding the ethanolic soln of hydrochloric acid, and the concentration of the hydrochloric acid of adding is 36 ~ 38wt%, and the volume ratio of hydrochloric acid and ethanol is 1:30, and last vacuum-drying can obtain product.
Embodiment 4:
Specifically comprise the steps:
(1) gets the Fe of the drying of 1.2g embodiment 1 preparation
3O
4Magnetic nano-particle joins in 100ml 60 (v/v) the % aqueous ethanolic solution, then with mixed solution supersound process 20min, drips gradually the 2ml vinyltriethoxysilane to being dissolved with Fe
3O
4Suspension in.Afterwards, change in the 250m1 three-necked flask, at N
2Protection is lower, the ageing of 50 ℃ of rapid stirring 24h constant temperature.Absolute ethanol washing 2 times of resulting product, deionized water wash 3 times, afterwards 60 ℃ of vacuum-dryings, grind into powder.
(2) get powder 0.5g that step (1) obtains and the BPO 0.15g behind the purifying, it is joined in the test tube of the vinylbenzene, 2ml toluene, 1ml normal heptane and the 0.5mlDVB linking agent that contain 8ml, place the ultrasonic mixing of ultrasonic wave 0.5h.
(3) measure deionized water 200ml in the beaker of 500ml, take by weighing respectively 1gPVP, 0.3gSDS adds wherein, stirs with glass stick, dissolves in ultrasonic wave.
(4) the resulting oily liquid of step (2) is joined in the aqueous solution of step (3), place processor for ultrasonic wave 20KHz intermittent type supersound process 10min, fully disperse, pour the system that obtains into the 100ml there-necked flask, 70 ℃ of heating in water bath, behind the condensing reflux 1.5h, be warming up to 80 ℃ of reaction 8h, obtain at last little bluish voilet suspension, wash through magnet magnetic separating alcohol respectively, after magnetic separated the pure water washing, the brown color powdered product was ground to get in 40 ℃ of vacuum-dryings.Dry sample is carried out Soxhlet extracting 24h, and the solvent that the Soxhlet extracting is used is for adding the ethanolic soln of hydrochloric acid, and the concentration of the hydrochloric acid of adding is 36 ~ 38wt%, and the volume ratio of hydrochloric acid and ethanol is 1:30, and last vacuum-drying can obtain product.
Claims (9)
1. the preparation method of porous magnetic polystyrene microsphere is characterized in that, it comprises the steps:
(1) with the Fe of drying
3O
4Magnetic nano-particle joins in the aqueous solution of ethanol, behind ultrasonic cleaner supersound process 20 ~ 30min, to Fe
3O
4Dropwise add vinyltriethoxysilane in the suspension, change in the lump again in the reactor, under the nitrogen protection condition, stir ageing 12 ~ 24h, the Fe after the resulting modification at 35 ~ 50 ℃ of constant temperature
3O
4Magnetic nano-particle through washing, vacuum-drying, pulverize;
(2) get powder and the benzoyl peroxide mixing that step (1) obtains, add and contain in the styrene solvent of pore-creating agent and linking agent, supersound process 0.5 ~ 1h, described pore-creating agent are the mixture of toluene and normal heptane, and described linking agent is Vinylstyrene;
(3) with polyvinylpyrrolidone and sodium lauryl sulphate ultrasonic dissolution in water;
(4) liquid that step (2) is obtained joins in the liquid that step (3) obtains, large power supersonic instrument supersound process 5 ~ 10min is to fully disperseing, the mixture that obtains is poured in the reactor, behind 70 ~ 80 ℃ of condensing reflux reaction 1.5 ~ 2h, be warming up to again 80 ~ 90 ℃ of condensing reflux reaction 6 ~ 8h, obtain suspension, wash through magnet magnetic separating alcohol, magnetic separates the pure water washing again, the brown color powdered product is ground to get in vacuum-drying, the brown color powdered product is carried out Soxhlet extracting 24h, last vacuum-drying, and get final product.
2. the preparation method of porous magnetic polystyrene microsphere according to claim 1 is characterized in that, in the step (1), in the aqueous solution of ethanol, the concentration expressed in percentage by volume of ethanol is 40 ~ 60%.
3. the preparation method of porous magnetic polystyrene microsphere according to claim 1 is characterized in that, in the step (1), and for the aqueous solution of 1L ethanol, dry Fe
3O
4It is 8 ~ 12g that magnetic nano-particle adds quality.
4. the preparation method of porous magnetic polystyrene microsphere according to claim 1 is characterized in that, in the step (1), for 1g Fe
3O
4Magnetic nano-particle, the add-on of vinyltriethoxysilane are 1ml ~ 2ml.
5. the preparation method of porous magnetic polystyrene microsphere according to claim 1 is characterized in that, in the step (2), the powder that step (1) obtains and benzoyl peroxide in mass ratio 2 ~ 4:1 mix.
6. the preparation method of porous magnetic polystyrene microsphere according to claim 1 is characterized in that, in the step (2), and the volume ratio 10 ~ 16:4:2:1 of vinylbenzene, toluene, normal heptane and Vinylstyrene; For the powder that every 1g step (1) obtains, the use volume of Vinylstyrene is 1 ~ 1.5ml.
7. the preparation method of porous magnetic polystyrene microsphere according to claim 1 is characterized in that, in the step (3), the mass ratio of polyvinylpyrrolidone, sodium lauryl sulphate and water is 5 ~ 8:1 ~ 3:1000; The mass ratio of the powder that polyvinylpyrrolidone and step (1) obtain is 1 ~ 2:1.
8. the preparation method of porous magnetic polystyrene microsphere according to claim 1 is characterized in that, in the step (4), in the Soxhlet extracting, the solvent that uses is for adding the ethanolic soln of hydrochloric acid, and the concentration of the hydrochloric acid of adding is 36 ~ 38wt%, and the volume ratio of hydrochloric acid and ethanol is 1:75 ~ 1:30.
9. the porous magnetic polystyrene microsphere that any one prepares in the claim 1 ~ 8.
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| CN103212352A (en) * | 2013-05-02 | 2013-07-24 | 黑龙江大学 | Preparation method of magnetic microspheres |
| CN103588919A (en) * | 2013-10-31 | 2014-02-19 | 江苏大学 | Preparation method of magnetic porous adsorbent by suspension polymerization |
| CN104829768A (en) * | 2015-05-12 | 2015-08-12 | 南京理工大学 | Preparation method of low-density bulk magnetic polystyrene oil absorption material |
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Application publication date: 20130313 Assignee: Suzhou Anhongtai New Material Co., Ltd. Assignor: Nanjing Forestry University Contract record no.: 2018320000361 Denomination of invention: Preparation method of porous magnetic polystyrene microspheres Granted publication date: 20160525 License type: Common License Record date: 20181129 |
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