CN110511309A - A kind of preparation method of magnetic macromolecular microsphere - Google Patents
A kind of preparation method of magnetic macromolecular microsphere Download PDFInfo
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- CN110511309A CN110511309A CN201910844197.XA CN201910844197A CN110511309A CN 110511309 A CN110511309 A CN 110511309A CN 201910844197 A CN201910844197 A CN 201910844197A CN 110511309 A CN110511309 A CN 110511309A
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- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
- B01J13/06—Making microcapsules or microballoons by phase separation
- B01J13/14—Polymerisation; cross-linking
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- C08F112/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F112/02—Monomers containing only one unsaturated aliphatic radical
- C08F112/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F112/06—Hydrocarbons
- C08F112/08—Styrene
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- C08F112/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F112/02—Monomers containing only one unsaturated aliphatic radical
- C08F112/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F112/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by hetero atoms or groups containing heteroatoms
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- C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F120/04—Acids; Metal salts or ammonium salts thereof
- C08F120/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
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- C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F120/10—Esters
- C08F120/12—Esters of monohydric alcohols or phenols
- C08F120/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F120/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
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- C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F120/10—Esters
- C08F120/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F120/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
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- C08F2/00—Processes of polymerisation
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- C08K5/00—Use of organic ingredients
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- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
- H01F1/42—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of organic or organo-metallic materials, e.g. graphene
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- C08K2201/00—Specific properties of additives
- C08K2201/01—Magnetic additives
Abstract
The invention discloses a kind of preparation methods of magnetic macromolecular microsphere, and the preparation method comprises the following steps: polymer seeds being added in the aqueous solution containing stabilizer and initiator, stirs evenly, forms evenly dispersed seed suspension liquid；Iron oleate and monomer are uniformly mixed, iron oleate monomer solution is formed；The iron oleate monomer solution is formed uniform drop by nozzle to enter in the seed suspension liquid, neutron absorption droplet growth and one-step polymerization obtain iron oleate polymer microsphere；Heating decomposes the iron oleate, obtains magnetic macromolecular microsphere.Magnetic macromolecular microsphere prepared by the present invention not only can control the magnetic property of microballoon, can also further promote the uniform particle diameter of microballoon.Moreover, improving the yield of magnetic macromolecular microsphere, efficiency and stability, it is suitable for large-scale production.
Description
Technical field
The present invention relates to polymeric material field, in particular to a kind of preparation method of magnetic macromolecular microsphere.
Background technique
In recent years, magnetic macromolecular microsphere nucleic acid extraction, cell separation, immobilised enzymes, immune detection, targeted drug,
The equal fields that isolate and purify of protein and enzyme are widely used.But it is controllable how to synthesize uniform particle diameter, magnetic property
Magnetic macromolecular microsphere is the hot and difficult issue of presently relevant area research.
The conventional method of prior art synthesizing magnetic polymer microsphere mainly has investment, monomer polymerization method and interface deposition
Method etc..
Not only magnetic macromolecular microsphere partial size is uncontrollable for current this synthetic method, and homogeneity is poor.And preparation process is not
The phenomenon that controllable factor is more, and many little particle impurity are had in magnetic polymer microsphere obtained, yield is lower.And it reacts
Period is long, and production efficiency is lower, is unfavorable for being mass produced, and production stability etc. is also to be improved.
Summary of the invention
In order to solve the above technical problems, the present invention provides a kind of preparation methods of magnetic macromolecular microsphere.
In order to achieve the above objectives, the technical scheme of the present invention is realized as follows:
The embodiment of the invention provides a kind of preparation method of magnetic macromolecular microsphere, the preparation method includes:
Polymer seeds are added in the aqueous solution containing stabilizer and initiator, stirs evenly, is formed evenly dispersed
Seed suspension liquid；
Iron oleate and monomer are uniformly mixed, iron oleate monomer solution is formed；
The iron oleate monomer solution is formed uniform drop by nozzle to enter in the seed suspension liquid, neutron absorption
Droplet growth and one-step polymerization, obtain iron oleate polymer microballoon；
Heating decomposes the iron oleate, obtains magnetic macromolecular microsphere.
Further, the polymer seeds are as follows: by the poly- of emulsion polymerization, dispersion copolymerization method or suspension polymerization preparation
Styrene seed or styrene-divinylbenzene seed.
Further, the stabilizer is surfactant.
Further, the surfactant is polyvinyl alcohol, polyvinylpyrrolidone, hydroxymethyl cellulose, oleic acid, oil
At least one of alcohol, hydroxypropyl cellulose or octadecyl alcolol.
Further, the initiator be benzoyl peroxide, lauroyl peroxide, in peroxidating t-butyl formate extremely
Few one kind.
Further, the monomer is styrene, divinylbenzene, 2,4- dichlorostyrene, acrylic acid, metering system amino acid
At least one of methyl esters, ethyl acrylate, vinylacetate, glycidyl methacrylate.
Further, the average grain diameter of the magnetic polymer microsphere is 100nm~1000 μm.
Further, the iron oleate monomer solution is dispersed into the seed suspension liquid by nozzle with drop form
Include:
The seed suspension liquid is put into the first container；
The iron oleate monomer solution is put into second container, the nozzle is mounted on the second container；；
Preset pressure is applied to the second container, under the preset pressure, described in the iron oleate monomer solution warp
Nozzle is dispersed into the seed suspension liquid with drop form.
Further, the preset pressure is 0.1~10MPa.
The embodiment of the invention provides a kind of preparation method of magnetic macromolecular microsphere, using eruption mode by iron oleate list
Liquid solution forms uniform drop, and is dispersed in seed suspension liquid, and seed rapidly absorbs iron oleate monomer droplet and grows,
It polymerize and obtains the iron oleate polymer microsphere of uniform particle diameter, after heat resolve, obtains magnetic macromolecular microsphere.Because of oil of the invention
Sour iron monomer solution size droplet diameter is uniform, it is easier to be fully absorbed by polymer seeds, the entire system of iron oleate polymer microsphere
Standby process is completed in 2 hours, and the time greatly shortens.In addition, uniform iron oleate monomer solution drop is easier by polymer
Seed fully absorbs, is magnetic strong, and little particle impurity is free of in the magnetic macromolecular microsphere of preparation.Therefore, magnetic prepared by the present invention
Property polymer microsphere not only can control the magnetic property of microballoon, can also further promote the uniform particle diameter of microballoon.Moreover, mentioning
The high yield of magnetic macromolecular microsphere, efficiency and stability, are suitable for large-scale production.
Detailed description of the invention
Fig. 1 is the electron microscope of magnetic macromolecular microsphere in the embodiment of the present invention one；
Fig. 2 is the grading curve of magnetic macromolecular microsphere in the embodiment of the present invention one.
Specific embodiment
In order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below in conjunction with the embodiment of the present invention
Attached drawing, the technical solution of the embodiment of the present invention is clearly and completely described.Obviously, described embodiment is this hair
Bright a part of the embodiment, rather than whole embodiments.Based on described the embodiment of the present invention, those skilled in the art institute
The every other embodiment obtained, belongs to the scope of the present invention.
The embodiment of the invention provides a kind of preparation method of magnetic macromolecular microsphere, preparation method includes:
Polymer seeds are added in the aqueous solution containing stabilizer and initiator, stirs evenly, is formed evenly dispersed
Seed suspension liquid；
Iron oleate and monomer are uniformly mixed, iron oleate monomer solution is formed；
The iron oleate monomer solution is formed uniform drop by nozzle to enter in the seed suspension liquid, neutron absorption
Droplet growth and one-step polymerization, obtain iron oleate polymer microballoon；
Heating decomposes the iron oleate, obtains magnetic macromolecular microsphere.
Iron oleate can current existing system, the preparation method of specific iron oleate is well known to those skilled in the art.Preferably,
Following methods preparation can be used in iron oleate: by Dissolvable Fe3+Salt and enuatrol are added in the mixed liquor of alcoholic solution and n-hexane, add
Thermal agitation obtains iron oleate after filtering, vacuum drying.Alcoholic solution is the aqueous solution of methanol, ethyl alcohol or isopropanol etc..Dissolvable Fe3+
Salt includes but is not limited to iron chloride, ferric sulfate etc..
The preparation method of the embodiment of the present invention is constantly grown using seed, by adjusting the size and use of polymer seeds
The purpose to size tunable can be realized in the conditions such as amount, iron oleate and monomer dosage.Specifically, oleic acid in iron oleate monomer solution
Iron and monomer grow polymer seeds, after reaching default microspherulite diameter, stop that iron oleate monomer solution is added, in polymerization temperature
Reaction obtains iron oleate macromolecule under (preferably 70~100 DEG C, such as: 70 DEG C, 75 DEG C, 80 DEG C, 85 DEG C, 90 DEG C, 100 DEG C etc.)
Microballoon, heating (temperature after heating is preferably 250~300 DEG C, such as: 250 DEG C, 260 DEG C, 290 DEG C, 300 DEG C etc.) continue instead
It answers, obtains magnetic macromolecular microsphere.
Iron oleate monomer solution is added with uniform drops into seed suspension liquid using nozzle, is guaranteeing stronger magnetic
Under the premise of property performance, polymer seeds are improved to the adsorption efficiency of monomer and iron oleate, reduce the generation of little particle impurity,
Reaction condition is easier to control, and not only preparation process is simple, further improves size tunable and uniform particle diameter, product
Quality stability is more preferable.It is suitable for mass production.
Further, iron oleate monomer solution is dispersed into seed suspension liquid packet by nozzle with uniform drop form
It includes:
Seed suspension liquid is put into the first container；
Iron oleate monomer solution is put into second container, nozzle is mounted on second container；
Preset pressure is applied to second container, under preset pressure, iron oleate monomer solution is through nozzle with uniform drop side
Formula is dispersed into seed suspension liquid.
Preferably, preset pressure is 0.1~10MPa.The pressure for improving second container advantageously forms drop, accelerates oleic acid
The jet velocity of iron monomer solution improves reaction speed.
Preferably, the aperture of nozzle can be 50nm~5000 μm, it is further preferred that the aperture of nozzle be 10 μm~
200μm。
Unrestrictedly, polymer seeds are as follows: the polyphenyl second prepared by emulsion polymerization, dispersion copolymerization method or suspension polymerization
Alkene seed or styrene-divinylbenzene seed.
In some embodiments of the invention, stabilizer is surfactant.It is further preferred that surfactant is poly-
At least one in vinyl alcohol, polyvinylpyrrolidone, hydroxymethyl cellulose, oleic acid, oleyl alcohol, hydroxypropyl cellulose or octadecyl alcolol
Kind.
According to some embodiments of the present invention, initiator is benzoyl peroxide, lauroyl peroxide, peroxidating formic acid uncle
At least one of butyl ester.
Further, monomer is styrene, divinylbenzene, 2,4- dichlorostyrene, acrylic acid, metering system amino acid first
At least one of ester, ethyl acrylate, vinylacetate, glycidyl methacrylate.
In some embodiments of the invention, the average grain diameter of magnetic macromolecular microsphere is 100nm~1000 μm.The present invention
The preparation method further expansion particle size range of magnetic macromolecular microsphere.
Preparation method of the invention is described further combined with specific embodiments below, it is to be understood that the present invention
It is not limited to following embodiment:
Embodiment one
It prepares iron oleate: soluble iron chloride and enuatrol is added in the mixed liquor of 75% ethanol solution and n-hexane,
Heating stirring obtains iron oleate after filtering, vacuum drying.
It is put into 2g polyvinylpyrrolidone and 0.5g benzoyl peroxide in the first container equipped with 600g deionized water,
It stirs evenly, 56g polystyrene seed (its granularity is 0.8 micron, CV=3%) is added, stirs evenly, is formed evenly dispersed
Seed suspension liquid, it is spare.
290g iron oleate and 206g ethyl acrylate are added in second container, stirs evenly, it is molten to form iron oleate monomer
Liquid, it is spare.Nozzle is installed, the aperture of nozzle is 10 μm on second container.2.15MPa preset pressure is applied to second container,
The temperature environment for being kept for 97 DEG C, is dispersed into seed suspension through nozzle by iron oleate monomer solution with drop form in 10min
In liquid, 110min is reacted after the completion of injection, obtains iron oleate polymer microballoon.Temperature is then warming up to 280 DEG C, makes iron oleate point
Solution, obtains magnetic macromolecular microsphere.
Its partial size and particle diameter distribution are measured using Beckman Coulter Counter, partial size is 3 microns, CV
(Coefficient of Variation)=2.8%.Magnetic ferroferric oxide accounts for entire magnetic macromolecular microsphere weight
55%.The yield of magnetic macromolecular microsphere is 99.6%.
Illustrate: above-mentioned material amounts being expanded into 2 times, 10 times, 50 times, 100 times, 500 times of productions respectively in proportion, per secondary
Cheng Jun is repeated 3 times, and having obtained partial size is 3 microns, the magnetic of CV (Coefficient of Variation)=2.5~2.6%
Property macromolecule is micro-.And magnetic high-molecular it is micro- in, magnetic ferroferric oxide accounts for the 54~56% of entire magnetic macromolecular microsphere weight,
It is 99.5~99.8% that magnetic macromolecular microsphere, which obtains yield,.No little particle generates, and particle size is uniform, as depicted in figs. 1 and 2,
The quality of production is stablized.
Embodiment two
3.5g polyvinylpyrrolidone and 2.5g benzoyl peroxide first are put into the first container equipped with 1200g deionized water
Acyl stirs evenly, and 132g polystyrene seed (its granularity is 100nm, CV=2.8%) is added, stirs evenly, is formed and uniformly divided
Scattered seed suspension liquid, it is spare.
392g iron oleate and 398g styrene monomer are added in second container, stirs evenly, it is molten to form iron oleate monomer
Liquid, it is spare.Nozzle is installed, the aperture of nozzle is 30 μm on second container.2.15MPa preset pressure is applied to second container,
The temperature environment for being kept for 90 DEG C, is dispersed into seed suspension through nozzle by iron oleate monomer solution with drop form in 20min
In liquid, 100min is reacted after the completion of injection, obtains iron oleate polymer microsphere.Temperature is then warming up to 290 DEG C, makes iron oleate point
Solution, obtains magnetic macromolecular microsphere.
Its partial size and particle diameter distribution, partial size 500nm, CV are measured using Beckman Coulter Counter
(Coefficient of Variation)=2.7%.Magnetic ferroferric oxide accounts for entire magnetic polymer microsphere weight
52%.The yield of magnetic macromolecular microsphere is 99.5%.
Embodiment three
1.8g polyvinylpyrrolidone and 0.8g benzoyl peroxide first are put into the first container equipped with 650g deionized water
Acyl stirs evenly, and 63g polystyrene seed (its granularity is 500 nanometers, CV=2.8%) is added, stirs evenly, is formed uniform
The seed suspension liquid of dispersion, it is spare.
205g iron oleate and 201g 2,4- dichlorostyrene monomer are added in second container, stirs evenly, forms oleic acid
Iron monomer solution, it is spare.Nozzle is installed, the aperture of nozzle is 100 μm on second container.It is pre- that 1.5MPa is applied to second container
If pressure, 95 DEG C of temperature environment is kept, iron oleate monomer solution is dispersed into 10min through nozzle with drop form
In seed suspension liquid, 110min is reacted after the completion of injection, obtains iron oleate polymer microsphere.Temperature is then warming up to 300 DEG C, is made
Iron oleate decomposes, and obtains magnetic macromolecular microsphere.
Its partial size and particle diameter distribution are measured using Beckman Coulter Counter, partial size is 1 micron, CV
(Coefficient of Variation)=2.8%.Magnetic ferroferric oxide accounts for entire magnetic polymer microsphere weight
55%.The yield of magnetic macromolecular microsphere is 99.6%.
Example IV
1.8g polyvinylpyrrolidone and 0.8g benzoyl peroxide first are put into the first container equipped with 650g deionized water
Acyl stirs evenly, and 63g polystyrene seed (its granularity is 500 nanometers, CV=2.8%) is added, stirs evenly, is formed uniform
The seed suspension liquid of dispersion, it is spare.
420g iron oleate and 430g styrene monomer are added in second container, stirs evenly, it is molten to form iron oleate monomer
Liquid, it is spare.Nozzle is installed, the aperture of nozzle is 100 μm on second container.1.5MPa preset pressure is applied to second container,
The temperature environment for being kept for 95 DEG C, is dispersed into seed suspension through nozzle by iron oleate monomer solution with drop form in 5min
In liquid, 115min is reacted after the completion of injection, obtains iron oleate polymer microsphere.Temperature is then warming up to 300 DEG C, makes iron oleate point
Solution, obtains magnetic macromolecular microsphere.
Its partial size and particle diameter distribution are measured using Beckman Coulter Counter, partial size is 2 microns, CV
(Coefficient of Variation)=2.8%.Magnetic ferroferric oxide accounts for entire magnetic macromolecular microsphere weight
55%.The yield of magnetic macromolecular microsphere is 99.8%.
Embodiment five
It is put into 2g polyvinylpyrrolidone and 0.5g benzoyl peroxide in the first container equipped with 600g deionized water,
It stirs evenly, 61g polystyrene seed (its granularity is 4.6 microns, CV=3%) is added, stirs evenly, is formed evenly dispersed
Seed suspension liquid, it is spare.
180g iron oleate and 192g styrene monomer are added in second container, stirs evenly, it is molten to form iron oleate monomer
Liquid, it is spare.Nozzle is installed, the aperture of nozzle is 10 μm on second container.0.15MPa preset pressure is applied to second container,
The temperature environment for being kept for 75 DEG C, is dispersed into seed suspension through nozzle by iron oleate monomer solution with drop form in 10min
In liquid, 110min is reacted after the completion of injection, obtains iron oleate polymer microsphere.Temperature is then warming up to 260 DEG C, makes iron oleate point
Solution, obtains magnetic macromolecular microsphere.
Its partial size and particle diameter distribution are measured using Beckman Coulter Counter, partial size is 10 microns, CV
(Coefficient of Variation)=2.5%.Magnetic ferroferric oxide accounts for entire magnetic polymer microsphere weight
60%.The yield of magnetic macromolecular microsphere is 99.7%.
Embodiment six
It is put into 2g polyvinylpyrrolidone and 0.5g benzoyl peroxide in the first container equipped with 600g deionized water,
It stirs evenly, 56g polystyrene seed (its granularity is 1.5 microns, CV=3%) is added, stirs evenly, is formed evenly dispersed
Seed suspension liquid, it is spare.
405g iron oleate and 411g styrene monomer are added in second container, stirs evenly, it is molten to form iron oleate monomer
Liquid, it is spare.Nozzle is installed, the aperture of nozzle is 10 μm on second container.1.15MPa preset pressure is applied to second container,
The temperature environment for being kept for 95 DEG C, is dispersed into seed suspension through nozzle by iron oleate monomer solution with drop form in 8min
In liquid, 112min is reacted after the completion of injection, obtains iron oleate polymer microsphere.Temperature is then warming up to 280 DEG C, makes iron oleate point
Solution, obtains magnetic macromolecular microsphere.
Its partial size and particle diameter distribution are measured using Beckman Coulter Counter, partial size is 4.5 microns, CV
(Coefficient of Variation)=2.7%.Magnetic ferroferric oxide accounts for entire magnetic macromolecular microsphere weight
54%.The yield of magnetic macromolecular microsphere is 99.6%.
Embodiment seven
It is put into 2g polyvinylpyrrolidone and 0.5g benzoyl peroxide in the first container equipped with 600g deionized water,
It stirs evenly, 56g polystyrene seed (its granularity is 2 microns, CV=3%) is added, stirs evenly, forms evenly dispersed kind
Sub- suspension, it is spare.
475g iron oleate and 451g glycidyl methacrylate are added in second container, stirs evenly, forms oil
Sour iron monomer solution, it is spare.Nozzle is installed, the aperture of nozzle is 10 μm on second container.1.15MPa is applied to second container
Preset pressure keeps 95 DEG C of temperature environment, iron oleate monomer solution is dispersed into 10min through nozzle with drop form
Enter in seed suspension liquid, 110min is reacted after the completion of injection, obtains iron oleate polymer microsphere.Temperature is then warming up to 280 DEG C,
Iron oleate is decomposed, magnetic macromolecular microsphere is obtained.
Its partial size and particle diameter distribution are measured using Beckman Coulter Counter, partial size is 5.3 microns, CV
(Coefficient of Variation)=2.6%.Magnetic ferroferric oxide accounts for entire magnetic macromolecular microsphere weight
51%.The yield of magnetic macromolecular microsphere is 99.5%.
Embodiment eight
It is put into 2g polyvinylpyrrolidone and 0.5g benzoyl peroxide in the first container equipped with 610g deionized water,
It stirs evenly, 61g polystyrene seed (its granularity is 550 microns, CV=3%) is added, stirs evenly, is formed evenly dispersed
Seed suspension liquid, it is spare.
184g iron oleate and 196g styrene monomer are added in second container, stirs evenly, it is molten to form iron oleate monomer
Liquid, it is spare.Nozzle is installed, the aperture of nozzle is 10 μm on second container.2.5MPa preset pressure is applied to second container, is protected
It is outstanding to be dispersed into seed by iron oleate monomer suspension through nozzle with drop form in 10min for the temperature environment for holding 100 DEG C
In supernatant liquid, 110min is reacted after the completion of injection, obtains iron oleate polymer microsphere.Temperature is then warming up to 270 DEG C, makes iron oleate
It decomposes, obtains magnetic macromolecular microsphere.
Its partial size and particle diameter distribution are measured using Beckman Coulter Counter, partial size is 1000 microns, CV
(Coefficient of Variation)=2.6%.Magnetic ferroferric oxide accounts for entire magnetic macromolecular microsphere weight
53%.The yield of magnetic macromolecular microsphere is 99.7%.
Embodiment nine
4.9g polyvinylpyrrolidone and 3.5g benzoyl peroxide first are put into the first container equipped with 1810g deionized water
Acyl stirs evenly, and 253g polystyrene seed (its granularity is 100 microns, CV=3%) is added, stirs evenly, is formed and uniformly divided
Scattered seed suspension liquid, it is spare.
481g iron oleate and 490g acrylic monomers are added in second container, stirs evenly, it is molten to form iron oleate monomer
Liquid, it is spare.Nozzle is installed, the aperture of nozzle is 150 μm on second container.1.5MPa preset pressure is applied to second container,
The temperature environment for being kept for 90 DEG C, is dispersed into seed suspension through nozzle by iron oleate monomer solution with drop form in 10min
In liquid, 110min is reacted after the completion of injection, obtains iron oleate polymer microsphere.Temperature is then warming up to 270 DEG C, makes iron oleate point
Solution, obtains magnetic macromolecular microsphere.
Its partial size and particle diameter distribution are measured using Beckman Coulter Counter, partial size is 300 microns, CV
(Coefficient of Variation)=2.6%.Magnetic ferroferric oxide accounts for entire magnetic macromolecular microsphere weight
55%.The yield of magnetic macromolecular microsphere is 99.6%.
Jet flow suspension polymerization device and method for preparing magnetic high molecular micro ball according to an embodiment of the present invention other
All it is structurally and operationally to be understood that and easy to accomplish to those skilled in the art, therefore is not described in detail.
The foregoing is only a preferred embodiment of the present invention, is not intended to limit the scope of the present invention.
Claims (9)
1. a kind of preparation method of magnetic macromolecular microsphere, which is characterized in that the preparation method includes:
Polymer seeds are added in the aqueous solution containing stabilizer and initiator, stirs evenly, forms evenly dispersed seed
Suspension；
Iron oleate and monomer are uniformly mixed, iron oleate monomer solution is formed；
The iron oleate monomer solution is formed uniform drop by nozzle to enter in the seed suspension liquid, neutron absorption drop
Simultaneously one-step polymerization is grown, iron oleate polymer microsphere is obtained；
Heating decomposes the iron oleate, obtains magnetic macromolecular microsphere.
2. preparation method according to claim 1, which is characterized in that the polymer seeds are as follows: by emulsion polymerization, divide
Dissipate the polystyrene seed or styrene-divinylbenzene seed of polymerization or suspension polymerization preparation.
3. preparation method according to claim 1, which is characterized in that the stabilizer is surfactant.
4. preparation method according to claim 3, which is characterized in that the surfactant is polyvinyl alcohol, polyethylene
At least one of pyrrolidones, hydroxymethyl cellulose, oleic acid, oleyl alcohol, hydroxypropyl cellulose or octadecyl alcolol.
5. preparation method according to claim 1, which is characterized in that the initiator is benzoyl peroxide, peroxidating
At least one of lauroyl, peroxidating t-butyl formate.
6. preparation method according to claim 1, which is characterized in that the monomer is styrene, divinylbenzene, 2,4- bis-
Chlorostyrene, acrylic acid, metering system amino acid methyl esters, ethyl acrylate, vinylacetate, in glycidyl methacrylate
At least one.
7. preparation method according to claim 1, which is characterized in that the average grain diameter of the magnetic macromolecular microsphere is
100nm~1000 μm.
8. preparation method according to claim 1, which is characterized in that by the iron oleate monomer solution by nozzle with liquid
Drop mode is dispersed into the seed suspension liquid
The seed suspension liquid is put into the first container；
The iron oleate monomer solution is put into second container, the nozzle is mounted on the second container；
Preset pressure is applied to the second container, under the preset pressure, the iron oleate monomer solution is through the nozzle
It is dispersed into the seed suspension liquid with drop form.
9. preparation method according to claim 8, which is characterized in that the preset pressure is 0.1~10MPa.
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