CN1105741C - 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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- CN1105741C CN1105741C CN98124516A CN98124516A CN1105741C CN 1105741 C CN1105741 C CN 1105741C CN 98124516 A CN98124516 A CN 98124516A CN 98124516 A CN98124516 A CN 98124516A CN 1105741 C CN1105741 C CN 1105741C
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- 229920000642 polymer Polymers 0.000 title claims abstract description 56
- 238000000034 method Methods 0.000 title claims abstract description 32
- 239000011806 microball Substances 0.000 title claims description 24
- 239000002245 particle Substances 0.000 claims abstract description 65
- 239000000178 monomer Substances 0.000 claims abstract description 36
- 239000004005 microsphere Substances 0.000 claims abstract description 27
- 238000004519 manufacturing process Methods 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000000126 substance Substances 0.000 claims abstract description 12
- 239000004094 surface-active agent Substances 0.000 claims abstract description 10
- 239000000725 suspension Substances 0.000 claims abstract description 10
- 239000002253 acid Substances 0.000 claims abstract description 9
- 150000001336 alkenes Chemical class 0.000 claims abstract description 7
- 239000007900 aqueous suspension Substances 0.000 claims abstract description 6
- 238000001556 precipitation Methods 0.000 claims abstract description 4
- 239000007788 liquid Substances 0.000 claims abstract description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 76
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 27
- 229920002554 vinyl polymer Polymers 0.000 claims description 26
- 239000012071 phase Substances 0.000 claims description 20
- 230000002776 aggregation Effects 0.000 claims description 18
- 238000004220 aggregation Methods 0.000 claims description 17
- 238000006116 polymerization reaction Methods 0.000 claims description 17
- 239000007864 aqueous solution Substances 0.000 claims description 16
- 239000006185 dispersion Substances 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 15
- 239000011805 ball Substances 0.000 claims description 13
- 239000000243 solution Substances 0.000 claims description 11
- 239000006249 magnetic particle Substances 0.000 claims description 10
- 239000013543 active substance Substances 0.000 claims description 7
- -1 iron ion Chemical class 0.000 claims description 6
- 238000010557 suspension polymerization reaction Methods 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 5
- 239000002131 composite material Substances 0.000 claims description 5
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 5
- 239000000194 fatty acid Substances 0.000 claims description 5
- 229930195729 fatty acid Natural products 0.000 claims description 5
- 150000004665 fatty acids Chemical class 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 239000008346 aqueous phase Substances 0.000 claims description 4
- 229920006037 cross link polymer Polymers 0.000 claims description 4
- 229920001519 homopolymer Polymers 0.000 claims description 4
- 125000001931 aliphatic group Chemical group 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 239000010954 inorganic particle Substances 0.000 claims description 3
- 229920000620 organic polymer Polymers 0.000 claims description 3
- 238000009736 wetting Methods 0.000 claims description 3
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 2
- 150000001298 alcohols Chemical class 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 229920001577 copolymer Polymers 0.000 claims description 2
- 239000004064 cosurfactant Substances 0.000 claims description 2
- 229910001448 ferrous ion Inorganic materials 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 125000005480 straight-chain fatty acid group Chemical group 0.000 claims description 2
- 239000000084 colloidal system Substances 0.000 abstract description 15
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 abstract 8
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 14
- 239000012153 distilled water Substances 0.000 description 8
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical class C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000009826 distribution Methods 0.000 description 6
- 239000006228 supernatant Substances 0.000 description 6
- 239000004342 Benzoyl peroxide Substances 0.000 description 5
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 5
- 235000019400 benzoyl peroxide Nutrition 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 238000002955 isolation Methods 0.000 description 5
- 239000012074 organic phase Substances 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 239000004793 Polystyrene Substances 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 239000008187 granular material Substances 0.000 description 4
- 229920002223 polystyrene Polymers 0.000 description 4
- 238000010792 warming Methods 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000005389 magnetism Effects 0.000 description 3
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 description 3
- 229960000907 methylthioninium chloride Drugs 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000003495 polar organic solvent Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000004062 sedimentation Methods 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 108010010803 Gelatin Proteins 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- DTOSIQBPPRVQHS-PDBXOOCHSA-N alpha-linolenic acid Chemical compound CC\C=C/C\C=C/C\C=C/CCCCCCCC(O)=O DTOSIQBPPRVQHS-PDBXOOCHSA-N 0.000 description 2
- 235000020661 alpha-linolenic acid Nutrition 0.000 description 2
- 238000010364 biochemical engineering Methods 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
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- 235000011852 gelatine desserts Nutrition 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 229960004488 linolenic acid Drugs 0.000 description 2
- KQQKGWQCNNTQJW-UHFFFAOYSA-N linolenic acid Natural products CC=CCCC=CCC=CCCCCCCCC(O)=O KQQKGWQCNNTQJW-UHFFFAOYSA-N 0.000 description 2
- 150000002632 lipids Chemical class 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 239000004926 polymethyl methacrylate Substances 0.000 description 2
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- 239000011118 polyvinyl acetate Substances 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- CUXYLFPMQMFGPL-UHFFFAOYSA-N (9Z,11E,13E)-9,11,13-Octadecatrienoic acid Natural products CCCCC=CC=CC=CCCCCCCCC(O)=O CUXYLFPMQMFGPL-UHFFFAOYSA-N 0.000 description 1
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- PXFBZOLANLWPMH-UHFFFAOYSA-N 16-Epiaffinine Natural products C1C(C2=CC=CC=C2N2)=C2C(=O)CC2C(=CC)CN(C)C1C2CO PXFBZOLANLWPMH-UHFFFAOYSA-N 0.000 description 1
- TWJNQYPJQDRXPH-UHFFFAOYSA-N 2-cyanobenzohydrazide Chemical compound NNC(=O)C1=CC=CC=C1C#N TWJNQYPJQDRXPH-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- 108010093096 Immobilized Enzymes Proteins 0.000 description 1
- OYHQOLUKZRVURQ-HZJYTTRNSA-N Linoleic acid Chemical compound CCCCC\C=C/C\C=C/CCCCCCCC(O)=O OYHQOLUKZRVURQ-HZJYTTRNSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 235000021360 Myristic acid Nutrition 0.000 description 1
- TUNFSRHWOTWDNC-UHFFFAOYSA-N Myristic acid Natural products CCCCCCCCCCCCCC(O)=O TUNFSRHWOTWDNC-UHFFFAOYSA-N 0.000 description 1
- RCEAADKTGXTDOA-UHFFFAOYSA-N OS(O)(=O)=O.CCCCCCCCCCCC[Na] Chemical compound OS(O)(=O)=O.CCCCCCCCCCCC[Na] RCEAADKTGXTDOA-UHFFFAOYSA-N 0.000 description 1
- 235000021314 Palmitic acid Nutrition 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
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- 238000005054 agglomeration Methods 0.000 description 1
- CUXYLFPMQMFGPL-SUTYWZMXSA-N all-trans-octadeca-9,11,13-trienoic acid Chemical compound CCCC\C=C\C=C\C=C\CCCCCCCC(O)=O CUXYLFPMQMFGPL-SUTYWZMXSA-N 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
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- 238000010276 construction Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000012674 dispersion polymerization Methods 0.000 description 1
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 1
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical class CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229920001002 functional polymer Polymers 0.000 description 1
- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 description 1
- 150000002617 leukotrienes Chemical class 0.000 description 1
- 229960004232 linoleic acid Drugs 0.000 description 1
- 239000011553 magnetic fluid Substances 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- 150000002888 oleic acid derivatives Chemical class 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
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- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
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Abstract
The present invention particularly relates to a super-paramagnetic polymer microsphere and a manufacturing method thereof. The surfaces of nanometer Fe3O4 particles prepared by a precipitation method are packed with lipophilic layers so as to dissolve the nanometer Fe3O4 particles into lipophilicity olefin monomers and become oil phase magnetic colloid which is dispersed in a water phase containing a surfactant to form oil-in-water suspension or fine suspension liquid which is initiated to polymerize and manufacture the super-paramagnetic polymer microsphere, wherein the Fe3O4 is highly dispersed in a cross-linked network structure of polymers. The particle diameter of the super-paramagnetic microsphere is from 0.1 mum to 800 mum, and the magnetic Fe3O4 accounts for 0.5 to 50 wt% of the whole microsphere. The super-paramagnetic microsphere has uniform magnetic content among different microspheres, stable chemical property and acid base resistance.
Description
Technical field
The present invention relates to magnetic polymer microsphere, particularly microballs of super-paramagnetic polymer and manufacture method thereof.
Background technology
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, differs for lipophile vinyl monomer polymerisation on the other hand and establishes 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.
Summary of the invention
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 and the mol ratio of duple ferrous ion and triple iron ion sum are 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.
Description of drawings
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.
Embodiment
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, 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 0.Introduce above-mentioned oil phase magnetic colloid after 5 hours, 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
3+Mol ratio be 1: 2 to 1: 0; The alkali OH that adds and the mol ratio of duple ferrous ion and triple iron ion sum are 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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| CN100442052C (en) * | 2002-08-15 | 2008-12-10 | 陕西西大北美基因股份有限公司 | Magnetic fluorescent microspheres, preparation method thereof, and method for detecting biomolecules using the magnetic fluorescent microspheres |
| CN100334105C (en) * | 2003-12-12 | 2007-08-29 | 上海交通大学 | Method for separation and purification of streptavidin by means of nano magnetic particles |
| CN100412093C (en) * | 2005-03-17 | 2008-08-20 | 中国科学院过程工程研究所 | Preparation of Magnetic Polymer Microspheres by Double Emulsion Method (W1/O/W2 Type) |
| CN100392025C (en) * | 2005-05-30 | 2008-06-04 | 河南大学 | Method for in-situ preparation of modified hydroxide, hydroxyl salt and oxide nanopowder |
| 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 | Preparation method of superparamagnetic mesoporous ferric oxide nanoparticles |
| CN101838426B (en) * | 2010-05-05 | 2011-12-28 | 北京科技大学 | Synthesis method of superparamagnetic polymer microspheres |
| 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 |
| CN107419288B (en) * | 2017-07-04 | 2019-02-05 | 徐州工程学院 | A kind of method for preparing magnetic iron tetroxide by anodic oxidation-co-precipitation |
| CN115463250A (en) * | 2022-08-31 | 2022-12-13 | 武汉理工大学 | A kind of gelatin-coated ferric iron tetroxide magnetic microspheres promoting osteogenesis and its preparation method and application |
| CN117563564A (en) * | 2023-11-02 | 2024-02-20 | 北京科技大学 | Magnetic oil gel microsphere containing extractant and manufacturing method thereof |
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| US4358388A (en) * | 1980-04-18 | 1982-11-09 | Rhone Poulenc Industries | Magnetic polymer latex and preparation process |
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