CN1253147A - Microballs of super-paramagnetic polymer and preparing process thereof - Google Patents
Microballs of super-paramagnetic polymer and preparing process thereof Download PDFInfo
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Abstract
A microball of super-paramagnetic polymer is prepared through such technological steps as preparing nm-class Fe3O4 particles by the sedimentation method, lipophilic coating of particles, dissolving in lipophilic vinyl monomers to become oil-phase magnetic colloid, dispersing in water phase containing surfactant to obtain oil-in-water suspension or microsuspension, and polymerization. Its advantages are high dispersion of Fe3O4 in cross-linking network structure of polymer, small granularity of super-paramagnetic microsphere (0.1-800 microns), the wt% of magnetic Fe3O4 occupying 0.5-50% of the total wt. of microspheres, magnetic uniformity, stable chemical properties and high resistance to acid and alkali.
Description
The present invention relates to magnetic polymer microsphere, particularly microballs of super-paramagnetic polymer and manufacture method thereof.
Magnetic polymer microsphere is as a kind of carrier of separating, having tempting application prospect in biomedicines such as immobilized enzyme, cell divide, immunodetection, targeted drug and affine separation and biochemical engineering field, is current one of the prospective research topic that has.
The method of prior art synthesizing magnetic polymer microballoon mainly contains polymer entrapping method, chemical transformation and monomer polymerization method, wherein monomer polymerization method is compared with the polymer entrapping method, synthetic magnetic polymer microsphere better performances, though chemical transformation synthetic magnetic polymer microsphere performance is good, synthesis technique is very loaded down with trivial details.
The monomer polymerization method of synthesizing magnetic polymer microballoon comprises letex polymerization, dispersion polymerization, seeding polymerization and the methods such as suspension polymerization, microsuspension under the magnetic-particle existence, and adopting the key of this class methods synthetic magnetic polymer microsphere performance quality is the uncompatibility problem that how to solve inorganic hydrophilic magnetic-particle and organic lipophilicity vinyl monomer.
Emulsion polymerization related to the present invention is (referring to J.Appl.Polym.Sci., Vol.50,765-776,1993), dispersion copolymerization method is (referring to " Journal of Functional Polymers " .Vol.6, No.2,123--130,1993) and the seeding polymerization method (referring to Colloid.Polym.Sci., Vol.273,76-82,1995) be that heat causes the polymerization of lipophile vinyl monomer and carries out in the presence of the stable water magnetic fluid of surfactant, these class methods are difficult synthetic large grain size magnetic polymer microballoon on the one hand, on the other hand since lipophile vinyl monomer polymerisation differ and establish a capital in magnetic Fe
3O
4Take place around the particle, cause synthetic magnetic polymer microsphere to exist magnetic Fe
3O
4Granule content is wayward, magnetic Fe in the ball
3O
4It is block that particle agglomeration becomes, and is heterogeneous structure, and how much magnetic content differs between ball and the ball, even the shortcoming such as some microballoon is nonmagnetic, and the finished product output capacity is low.
The suspension polymerization close with the present invention (referring to US 4,339,337) and microsuspension polymerization method (referring to US 4,358,388) are earlier the magnetic Fe of hydrocarbon ils oleophylic processing
3O
4Particle adds and contains in the thickness lipophile vinyl monomer solution of partial polymer, or directly add in the lipophile vinyl monomer solution, it is scattered in the aqueous solution that contains surfactant again, forms oil-in-water suspensions or fine suspension, thermal-initiated polymerization forms magnetic polymer microsphere.Experiment shows, hydrocarbon ils and hydrophilic magnetic Fe
3O
4The particle associativity is poor, and the oleophylic treatment effect is bad, is difficult to effectively disperse in lipophile vinyl monomer solution, especially nano-scale magnetic Fe
3O
4Particle takes place with being separated of vinyl monomer unavoidable in polymerization process owing to reuniting, there are some defectives in synthetic magnetic polymer microsphere in performance, such as magnetic Fe
3O
4A little less than granule content low (0.8-2.7%), the magnetic, magnetic Fe
3O
4Particle aggregation is bad at ball periphery, composite effect, and different ball magnetic changes of contents are big, homogeneity is poor, and instability etc. under the acid condition is difficult to satisfy the practical application needs.
In addition, the above-mentioned polymer microballoon that comprises multidomain or coacervate magnetic-particle does not have superparamagnetism, and exist remanent magnetism (Hc ≠ 0, Br ≠ 0), magnetic to attract each other causing the difficulties in dispersion in the use during no foreign field also is a urgent problem.
Purpose of the present invention is exactly the defective that exists on above-mentioned magnetic polymer microsphere and the manufacture method thereof, provides the controlled and narrow distribution of a kind of particle diameter, magnetic is strong and the microballs of super-paramagnetic polymer of distribution homogeneous, stable chemical nature and can make inorganic magnetic Fe
3O
4Particle and organic lipophile monomer-polymer form the high yield microballs of super-paramagnetic polymer manufacture method of nanoscale composite construction.
Main technical schemes of the present invention is: a kind ofly tie up magnetic Fe at bag
3O
4The particle existence is lower to the microballs of super-paramagnetic polymer that suspends or the microsuspension polymerization method is made, and ties up magnetic Fe by lipophile alkene monomer polymer and the bag that comprises within it
3O
4Particle forms, wherein the lipophile alkene monomer polymer mainly is homopolymers or the copolymer that is polymerized by the lipophile vinyl monomer, and magnetic-particle is the single domain nano-magnetic Fe that the surface bag is tied up aliphatic acid oleophilic layer that can be effectively compatible with the lipophile alkene monomer polymer
3O
4Particle; In microballs of super-paramagnetic polymer inside, the single domain nano-magnetic Fe that bag is tied up
3O
4The particle high degree of dispersion has inorganic particle and organic polymer uniform composite structure on the nanoscale in the crosslinked polymer network, superparamagnetism is arranged, and does not have remanent magnetism (Hc=0, Br=0) during no external magnetic field; The microballs of super-paramagnetic polymer particle diameter between 0.1--800 μ m, size distribution relative narrower, magnetic Fe
3O
4The weight ratio that accounts for whole microballoon is 0.5-50%, magnetic uniform content between the different balls, stable chemical nature, acid and alkali-resistance.
The single domain nano-magnetic Fe that above-mentioned bag is tied up
3O
4Particle has by the carboxyl of lipid acid and magnetic Fe
3O
4The nuclear of the chemical bond combination between the hydroxyl of particle surface/shell-type structure is examined and is the single domain superparamagnetism Fe of particle diameter between 4-30nm
3O
4Particle, shell are C
8-22The oleophilic layer that straight chain fatty acid forms; Here C
8-22Straight chain fatty acid is saturated lauric acid, myristic acid, Palmiticacid, stearic acid and undersaturated oleic acid, linolic acid, linolenic acid, eleostearic acid.
Above-mentioned lipophilicity vinyl monomer homopolymer is the polymkeric substance that is formed by a kind of lipophilicity vinyl monomer; Lipophilicity vinyl monomer multipolymer is the polymkeric substance that is formed by one or more lipophilicity vinyl monomers and one or more wetting ability vinyl monomers, and both gross weights are than between 8: 2 to 10: 0; The lipophilicity vinyl monomer here is styrenic, divinylbenzene class, (methyl) esters of acrylic acid, vinyl esters and derivative thereof, and the wetting ability vinyl monomer is allyl alcohol-like, propylene aldehydes, acrylic acid or the like, vinyl cyanide and derivative thereof.
The manufacture method of microballs of super-paramagnetic polymer, the magnetic-particle that comprises the oleophylic processing of magnetic-particle surface, the processing of blending surface oleophylic and lipophilicity vinyl monomer solution form water to form oil phase, at least a tensio-active agent of dissolving in the aqueous solution, disperse oil phase to form oil-in-water suspensions or fine suspension, thermal-initiated polymerization reaction with operations such as formation magnetic polymer microspheres in aqueous phase; The manufacture method that it is characterized in that microballs of super-paramagnetic polymer comprises following step:
A. the precipitation method prepare the soluble bag of oil phase and tie up magnetic Fe
3O
4The particle aggregation body:
Under 50-100 °, to containing Fe
2+And Fe
3+Impouring alkali lye in the aqueous solution of salt drips C at once
8-22Straight chain fatty acid can obtain the lumps magnetic Fe till the aqueous solution becomes clearly
3O
4The particle aggregation body.
B. suspension polymerization or microsuspension legal system are equipped with microballs of super-paramagnetic polymer:
1. with magnetic Fe
3O
4The particle aggregation body is dissolved in the superparamagnetism colloidal solution that forms the oil phase stable dispersion in the lipophile vinyl monomer;
2. add surfactant and in the aqueous solution, form water;
3. in stirring reactor, oil phase is scattered in aqueous phase and forms oil-in-water suspensions or fine suspension;
4. thermal-initiated polymerization reaction can obtain microballs of super-paramagnetic polymer.
Above-mentioned magnetic Fe
3O
4The preparation condition of particle aggregation body is Fe in the molysite aqueous solution
2+With Fe
3+Mol ratio be 1: 2 to 1: 0; The alkali OH that adds
-With 2Fe
2++ 3Fe
3+The mol ratio of sum is 1: 0.1 to 1: 1.5, and the alkali here is KOH, NaOH, NH
4OH, Na
2CO
3, NaHCO
3The C that adds
8-22Straight chain fatty acid and the magnetic Fe that is settled out
3O
4The weight ratio of particle is between 1: 3 to 1: 0.5.
The tensio-active agent of above-mentioned dispersion suspension liquid is one or more polymeric surface active agent, weight ratio content in water is 0.5-8%, and the polymeric surface active agent here is gelatin, Mierocrystalline cellulose, polyvinyl alcohol, polyvinylpyrrolidone, polyacrylamide, poly styrene sulfonate; The tensio-active agent that disperses fine suspension is the compound that ionic low-molecular-weight surfactant and a kind of alcohols cosurfactant by a kind of HLB＞8 forms, both weight ratios are 1: 0.5 to 1: 5, and the low-molecular-weight surfactant here is soap, alkyl-sulphate, fatty sulfonate, alkylbenzene sulfonate, alkyl quaternary ammonium salts.
Compare with existing magnetic polymer microsphere and manufacturing technology thereof, the present invention on manufacturing process to nano-magnetic Fe
3O
4Particle surface carried out simple and effectively the oleophilic layer bag tie up, make inorganic hydrophilic Fe
3O
4Change organic lipophile Fe into
3O
4, solved well single domain nano-magnetic Fe
3O
4Dispersiveness and the consistency problem of particle in lipophile vinyl monomer solution avoided nano-magnetic Fe
3O
4Particle incidental reunion, sedimentation and be separated in polymerization process, improved good effect is the optimization of magnetic polymer microsphere performance on this manufacturing process, be in particular in the following aspects: 1. have superparamagnetism, there is not remanent magnetism (Hc=0 during no external magnetic field, Br=0), easily disperse in the use procedure and magnetic can not take place reunite; 2. magnetic Fe
3O
4Granule content is adjustable, reaches as high as 50%, and magnetic is strong, is easy to Magnetic Isolation; 3. magnetic polymer microballoon output capacity＞90%, the Fe between the different balls
3O
4Content is even, the Magnetic Isolation term harmonization; 4. granule size can be controlled between 0.1-800 μ m as required; Wherein the microsuspension polymerization method can produce the uniform microsphere of 0.1-5 μ m; Suspension polymerization can produce the microballoon of 3-800 μ m, can make the size distribution relative narrower by improving reactor; 5. stable chemical nature, microballoon soak respectively all magnetic in 1M HCl and the 1M NaOH aqueous solution substantially unchanged, and Fe is described
3O
4Wrapped fully and tied up; As a kind of carrier of separating, above-mentioned performance meets the application needs in biomedical and Biochemical Engineering field.
Accompanying drawing 1: microballs of super-paramagnetic polymer section structure synoptic diagram of the present invention.
1. superparamagnetism Fe
3O
4Particle;
2. lipid acid oleophilic layer;
3. crosslinked polymer network.
Below by embodiment technical scheme of the present invention is further described:
1. precipitation method preparation bag is tied up magnetic Fe
3O
4The particle aggregation body:
In the 1 liter of stirring reactor that fills 500ml distilled water, add 0.086 mole of FeCl
24H
2O and 0.173 mole of FeCl
36H
2O is warming up to 90 ℃, and impouring contains 0.956 mole of NH
3H
2The O aqueous solution gets started by the speed of 0.5ml/min and drips the about 15ml of linolenic acid, until seeing one clearly till the supernatant liquor, and continuation constant temperature 1 hour, the supernatant liquor that inclines can obtain black lumps bag and tie up magnetic Fe
3O
4The particle aggregation body.
Above-mentioned magnetic agglomerate gross weight 35 gram, wherein Fe
3O
4About 20 grams, transmission electron microscope observing Fe
3O
4Particle is bordering on sphere, has superparamagnetism, and average grain diameter is 8nm, relative standard deviation 28%; The solidifying body solubilized in non-polar organic solvent of magnetic becomes magnetic colloid.
Embodiment 2.
In filling 1 liter of stirring reactor of 700ml distilled water, add 0.21 mole of FeCl
24H
2O and 0.31 mole of FeCl
36H
2O is warming up to 70 ℃, and impouring 100ml contains 1 mole NaHCO
3The aqueous solution gets started by the speed of 0.5ml/min and drips the about 20ml of stearic acid, until see one clearly till the supernatant, continuation constant temperature 1 hour, the supernatant that inclines can obtain black lumps bag and tie up magnetic Fe
3O
4The particle aggregation body.
Above-mentioned magnetic agglomerate gross weight 65 gram, wherein Fe
3O
4About 40 grams, transmission electron microscope observing Fe
3O
4Particle is bordering on sphere, and it has superparamagnetism, and average grain diameter is 15nm, relative standard deviation 34%; The solidifying body solubilized in non-polar organic solvent of magnetic becomes magnetic colloid.
Embodiment 3.
In the 1 liter of stirring reactor that fills 300ml distilled water, add 0.130 mole of FeSO
47H
2O is warming up to 50 ℃, and impouring contains 0.26 mole NaOH aqueous solution 50ml, dropwise adds H in 1 hour simultaneously
2O
2About 5ml and myristic acid 10ml, supernatant are warming up to 80 ℃ of constant temperature 1 hour after becoming clearly, and the supernatant that inclines can obtain black lumps bag and tie up magnetic Fe
3O
4The particle aggregation body.
Above-mentioned magnetic agglomerate contains magnetic Fe
3O
4About 10 grams, transmission electron microscope observing Fe
3O
4Particle is bordering on cube, and average grain diameter is 27nm; The solidifying body solubilized in non-polar organic solvent of magnetic becomes magnetic colloid.
2. suspension polymerization prepares microballs of super-paramagnetic polymer:
Embodiment 4.
35 gram bags of embodiment 1 preparation are tied up magnetic Fe
3O
4The particle aggregation body adds in the organic phase that styrene 50 restrains, hydroxyethyl methacrylate 5 restrains, divinylbenzene 10 restrains, benzoyl peroxide 5 grams form, and omits the oil phase magnetic colloid solution that can form stable dispersion through stirring; Add 500ml distilled water and 10 gram polyvinyl alcohol at one in 1 liter of cylindrical stirring reactor of vertical baffle plate, 50 ℃ of constant temperature stir introduces above-mentioned oil phase magnetic colloid after 0.5 hour, regulate mixing speed to 800rpm, be warmed up to 80 ℃ of reactions 6 hours, be warmed up to again 95 ℃ of slakings 4 hours; After the cooling, through Magnetic Isolation, washing, oven dry, etc. operation, can obtain output capacity and be bordering on 100% superparamagnetism polystyrene microsphere.
The section structure of above-mentioned superparamagnetism polystyrene microsphere wraps and ties up magnetic Fe as shown in drawings
3O
4Particle has nuclear/shell type structure, examines to be nanoscale single domain superparamagnetism Fe
3O
4Particle [1], the leukotrienes oleophilic layer [2] that shell is tied up for bag, bag is tied up nano-magnetic Fe
3O
4The particle high degree of dispersion is [3] in the crosslinked polymer network, have inorganic particle and organic polymer uniform composite structure on the nanoscale; Microballoon has superparamagnetism, Hc=0, Br=0; Laser particle analyzer is measured the microballoon of particle diameter between 5-15 μ m and is accounted for more than 80%; Magnetic Fe
3O
4The weight ratio that accounts for whole microballoon is 20%, magnetic uniform content between the different balls; Microballoon soaks respectively all magnetic in 1M HCl and the 1M NaOH aqueous solution substantially unchanged, stable chemical nature.
Embodiment 5.
The bag that takes by weighing among the embodiment 1 is tied up magnetic Fe
3O
4Particle aggregation body 28 grams dissolve in the organic phase of methyl methacrylate 80 grams, benzoyl peroxide 5 gram compositions, form the oil phase magnetic colloid solution of stable dispersion; Add 500ml distilled water, 2.5 gram polyvinylpyrrolidones and 0.1 gram methylene blue at one in 1 liter of cylindrical stirring reactor of vertical baffle plate, 50 ℃ of constant temperature stir introduces above-mentioned oil phase magnetic colloid after 0.5 hour, regulate mixing speed to 500rpm, be warmed up to 80 ℃ of reactions 8 hours, after the cooling, through Magnetic Isolation, washing, oven dry, etc. operation, can obtain output capacity and be bordering on 100% superparamagnetism polymethyl methacrylate microballoon.
Above-mentioned magnetic polymethyl methacrylate microsphere has superparamagnetism, and laser particle analyzer is measured the microballoon of particle diameter between 30-70 μ m and accounted for more than 90%; Magnetic Fe
3O
4The weight ratio that accounts for whole microballoon is 16%, magnetic uniform content between the different balls.
Embodiment 6.
The bag that takes by weighing among the embodiment 2 is tied up magnetic Fe
3O
4Particle aggregation body 65 grams dissolve in the organic phase of methyl acrylate 40 grams, propenyl 10 grams, benzoyl peroxide 5 gram compositions, form the oil phase magnetic colloid solution of stable dispersion; Add 500ml distilled water, 25 gram gelatin and 0.1 gram methylene blue at one in 1 liter of cylindrical stirring reactor of vertical baffle plate, 50 ℃ of constant temperature stir introduces above-mentioned oil phase magnetic colloid after 0.5 hour, regulate mixing speed to 300rpm, be warmed up to 80 ℃ of reactions 10 hours, after the cooling, through Magnetic Isolation, washing, oven dry, etc. operation, can obtain output capacity and be bordering on 100% superparamagnetism PMA microballoon.
Above-mentioned magnetic polyacrylic acid methyl esters microballoon has superparamagnetism, and laser particle analyzer is measured the microballoon of particle diameter between 400-700 μ m and accounted for more than 90%; Magnetic Fe
3O
4The weight ratio that accounts for whole microballoon is 40%, magnetic uniform content between the different balls.
3. the microsuspension legal system is equipped with microballs of super-paramagnetic polymer:
Embodiment 7.
Containing 10 gram Fe among the embodiment 3
3O
4Bag tie up magnetic Fe
3O
4The particle aggregation body all dissolves in the organic phase that is made up of styrene 65 grams, methacrylic acid 5 grams, divinylbenzene 10 grams and benzoyl peroxide 5 grams, forms the oil phase magnetic colloid of stable dispersion; In filling 1 liter of stirring reactor of 500ml distilled water, add neopelex 2 grams, lauryl alcohol 4 grams, 50 ℃ of constant temperature stirred 1 hour, introduced above-mentioned oil phase magnetic colloid, continuation was stirred under 600rpm after 1 hour, was warmed up to 80 ℃ of reactions 8 hours by the speed of 0.5 ℃/min; After the cooling, with magnet sedimentation washing for several times, the yield of superparamagnetism polystyrene microsphere about 90%.
Above-mentioned magnetic polystyrene microsphere has superparamagnetism, does not have and reunites, and redispersibility is good; Laser particle analyzer is measured the about 0.6 μ m of average grain diameter, narrower particle size distribution; Magnetic Fe
3O
4The weight ratio that accounts for whole microballoon is 10%, magnetic uniform content between the different balls.
Embodiment 8.
Get and contain 10 gram Fe among the embodiment 3
3O
4Bag tie up magnetic Fe
3O
4The particle aggregation body all is dissolved in the organic phase of vinylacetate 70 grams, divinylbenzene 10 grams, benzoyl peroxide 5 gram compositions, forms the oil phase magnetic colloid of stable dispersion; In 1 liter of stirring reactor, add 500ml distilled water, 1 gram lauryl sodium sulfate, 1 gram hexadecanol and 0.1 gram methylene blue, 60 ℃ of constant temperature stirred 1 hour, introduce above-mentioned oil phase magnetic colloid, under 400rpm stirs speed, keep this thermotonus 4 hours, and slowly be warmed up to again 70 ℃ of reactions 4 hours; After the cooling, with magnet sedimentation washing for several times, the yield about 90% of gained superparamagnetism polyvinyl acetate microballoon.
Above-mentioned magnetic polyvinyl acetate ester microsphere has superparamagnetism, does not have and reunites, and redispersibility is good; Laser particle analyzer is measured the about 1.5 μ m of average grain diameter, narrower particle size distribution; Magnetic Fe
3O
4The weight ratio that accounts for whole microballoon is 10%, magnetic uniform content between the different balls.
Claims (8)
1. microballs of super-paramagnetic polymer, formed by alkene monomer polymer and the magnetic-particle that comprises within it, it is characterized in that alkene monomer polymer is homopolymers or the copolymer that is polymerized by the lipophile vinyl monomer, magnetic-particle is the single domain nano-magnetic Fe that the surface bag is tied up aliphatic acid oleophilic layer that can be effectively compatible with the lipophile alkene monomer polymer
3O
4Particle; In microballs of super-paramagnetic polymer inside, the single domain nano-magnetic Fe that bag is tied up
3O
4The particle high degree of dispersion has inorganic particle and organic polymer uniform composite structure on the nanoscale in the crosslinked polymer network, superparamagnetism is arranged; The magnetic polymer microsphere particle diameter between 0.1--800 μ m, magnetic Fe
3O
4The weight ratio that accounts for whole microballoon is 0.5-50%, magnetic uniform content between the different balls, stable chemical nature, acid and alkali-resistance.
2. by the described microballs of super-paramagnetic polymer of claim 1, it is characterized in that the single domain nano-magnetic Fe that described bag is tied up
3O
4Particle has by the carboxyl of aliphatic acid and magnetic Fe
3O
4Nuclear/the shell type structure of the chemical bonds between the hydroxyl of particle surface is examined and is the single domain superparamagnetism Fe of particle diameter between 4--30nm
3O
4Particle, shell are C
8-22The oleophilic layer that straight chain fatty acid forms.
3. by the described microballs of super-paramagnetic polymer of claim 1, it is characterized in that described vinyl monomer homopolymer is the polymkeric substance that a kind of lipophilicity vinyl monomer forms.
4. by the described microballs of super-paramagnetic polymer of claim 1, it is characterized in that described vinyl monomer multipolymer is the polymkeric substance that one or more lipophilicity vinyl monomers and one or more wetting ability vinyl monomers form, both gross weights are than between 8: 2 to 10: 0.
5. the manufacture method of a microballs of super-paramagnetic polymer as claimed in claim 1, the magnetic-particle that comprises the oleophylic processing of magnetic-particle surface, the processing of blending surface oleophylic and lipophilicity vinyl monomer solution form water to form oil phase, at least a tensio-active agent of dissolving in the aqueous solution, disperse oil phase to form oil-in-water suspensions or fine suspension, thermal-initiated polymerization reaction with operations such as formation magnetic polymer microspheres in aqueous phase; The manufacture method that it is characterized in that microballs of super-paramagnetic polymer comprises following step:
A. the precipitation method prepare the soluble bag of oil phase and tie up magnetic Fe
3O
4The particle aggregation body:
Under 50-100 °, to containing Fe
2+And Fe
3+Impouring alkali lye in the aqueous solution of salt drips C at once
8-22Straight chain fatty acid can obtain the lumps magnetic Fe till the aqueous solution becomes clearly
3O
4The particle aggregation body;
B. suspension polymerization or microsuspension legal system are equipped with microballs of super-paramagnetic polymer:
(1). with magnetic Fe
3O
4The particle aggregation body is dissolved in the superparamagnetism colloidal solution that forms the oil phase stable dispersion in the lipophile vinyl monomer;
(2). add tensio-active agent and in the aqueous solution, form water;
(3). in stirring reactor, oil phase is scattered in aqueous phase and forms oil-in-water suspensions or fine suspension;
(4). the thermal-initiated polymerization reaction can obtain microballs of super-paramagnetic polymer.
6. by the described manufacture method of claim 5, it is characterized in that the Fe in the described molysite aqueous solution
2+And Fe
2-Mol ratio be 1: 2 to 1: 0; The alkali OH and the 2Fe that add
2++ 3Fe
3+The mol ratio of sum is 1: 0.1 to 1: 1.5; The C that adds
8-22Straight chain fatty acid and the magnetic Fe that is settled out
3O
4The weight ratio of particle is between 1: 3 to 1: 0.5.
7. by the described manufacture method of claim 5, the tensio-active agent that it is characterized in that described dispersion suspension liquid is one or more polymeric surface active agent, and the weight ratio content in water is 0.5-8%.
8. by the described manufacture method of claim 5, the tensio-active agent that it is characterized in that described dispersion fine suspension is the compound that is formed by the ionic low-molecular-weight surfactant of a kind of HLB＞8 and a kind of alcohols cosurfactant, and both weight ratios are 1: 0.5 to 1: 5.
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Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2480764B1 (en) * | 1980-04-18 | 1985-10-04 | Rhone Poulenc Spec Chim | LATEX OF MAGNETIC POLYMERS AND PREPARATION METHOD |
| US4554088A (en) * | 1983-05-12 | 1985-11-19 | Advanced Magnetics Inc. | Magnetic particles for use in separations |
| FR2645160B1 (en) * | 1989-03-31 | 1992-10-02 | Rhone Poulenc Chimie |
-
1998
- 1998-11-10 CN CN98124516A patent/CN1105741C/en not_active Expired - Fee Related
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| CN100412093C (en) * | 2005-03-17 | 2008-08-20 | 中国科学院过程工程研究所 | Prepn. of magnetic molecular pellets by complex emulsion process (W1/0/W2 type) |
| CN100392025C (en) * | 2005-05-30 | 2008-06-04 | 河南大学 | In situ method for preparing modified Nano powder of hydrate, hydroxy salt, and oxide |
| CN1298791C (en) * | 2005-07-19 | 2007-02-07 | 吉林大学 | Superparamagnetic Fe3O4 nanometer particle with synthetic polymer modification from one-step method |
| CN101417822B (en) * | 2008-11-24 | 2010-12-08 | 中国科学院长春应用化学研究所 | Method for preparing super paramagnetic mesoporous ferriferrous oxide nano particle |
| CN101838426A (en) * | 2010-05-05 | 2010-09-22 | 北京科技大学 | Synthesis method of superparamagnetic polymer microspheres |
| CN101838426B (en) * | 2010-05-05 | 2011-12-28 | 北京科技大学 | Synthesis method of superparamagnetic polymer microspheres |
| CN102070864A (en) * | 2010-12-18 | 2011-05-25 | 四川大学 | Nanoscale polymethylmethacrylate magnetic composite microsphere and preparation method thereof |
| CN102070864B (en) * | 2010-12-18 | 2012-07-04 | 四川大学 | Nanoscale polymethylmethacrylate magnetic composite microsphere and preparation method thereof |
| CN102331492A (en) * | 2011-06-14 | 2012-01-25 | 浙江大学 | Method for detecting mite allergen specific antibody in blood serum |
| CN107419288A (en) * | 2017-07-04 | 2017-12-01 | 徐州工程学院 | A kind of method that anodic oxidation co-precipitation prepares magnetic ferroferric oxide |
| CN107419288B (en) * | 2017-07-04 | 2019-02-05 | 徐州工程学院 | A kind of method that anodic oxidation-co-precipitation prepares magnetic ferroferric oxide |
| CN115463250A (en) * | 2022-08-31 | 2022-12-13 | 武汉理工大学 | Gelatin-coated ferroferric oxide magnetic microsphere for promoting osteogenesis and preparation method and application thereof |
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