CN117106149A - 一种聚合物夹心复合磁性微球及其制备方法 - Google Patents
一种聚合物夹心复合磁性微球及其制备方法 Download PDFInfo
- Publication number
- CN117106149A CN117106149A CN202310909657.9A CN202310909657A CN117106149A CN 117106149 A CN117106149 A CN 117106149A CN 202310909657 A CN202310909657 A CN 202310909657A CN 117106149 A CN117106149 A CN 117106149A
- Authority
- CN
- China
- Prior art keywords
- polymer
- microsphere
- pddbp
- magnetic microsphere
- composite magnetic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000004005 microsphere Substances 0.000 title claims abstract description 147
- 230000005291 magnetic effect Effects 0.000 title claims abstract description 106
- 229920000642 polymer Polymers 0.000 title claims abstract description 62
- 239000002131 composite material Substances 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims description 10
- -1 2-biphenyl thiazole Chemical compound 0.000 claims abstract description 12
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 12
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 10
- 239000000126 substance Substances 0.000 claims abstract description 7
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 claims abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 70
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 58
- 239000000243 solution Substances 0.000 claims description 54
- 239000008367 deionised water Substances 0.000 claims description 37
- 229910021641 deionized water Inorganic materials 0.000 claims description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 37
- 230000008961 swelling Effects 0.000 claims description 30
- 229910052757 nitrogen Inorganic materials 0.000 claims description 29
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 21
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 21
- 235000019441 ethanol Nutrition 0.000 claims description 21
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 21
- 239000007788 liquid Substances 0.000 claims description 19
- 239000011259 mixed solution Substances 0.000 claims description 19
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 17
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 13
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 12
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 12
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 12
- 239000005457 ice water Substances 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 12
- 238000006116 polymerization reaction Methods 0.000 claims description 12
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 11
- 238000005470 impregnation Methods 0.000 claims description 11
- 239000010410 layer Substances 0.000 claims description 11
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 10
- 125000003277 amino group Chemical group 0.000 claims description 10
- 150000008064 anhydrides Chemical class 0.000 claims description 10
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 9
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 230000009471 action Effects 0.000 claims description 9
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 8
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 8
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 7
- 150000003839 salts Chemical class 0.000 claims description 7
- 239000003431 cross linking reagent Substances 0.000 claims description 6
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 5
- 229960002089 ferrous chloride Drugs 0.000 claims description 5
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 5
- 239000001509 sodium citrate Substances 0.000 claims description 5
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical group O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 5
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 4
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 claims description 4
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 claims description 4
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 4
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 4
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- 238000007112 amidation reaction Methods 0.000 claims description 4
- 238000005576 amination reaction Methods 0.000 claims description 4
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 4
- 239000003153 chemical reaction reagent Substances 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 238000000975 co-precipitation Methods 0.000 claims description 4
- 238000000151 deposition Methods 0.000 claims description 4
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 claims description 4
- 239000011790 ferrous sulphate Substances 0.000 claims description 4
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 4
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 4
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 4
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 4
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- 229940014800 succinic anhydride Drugs 0.000 claims description 4
- 239000004094 surface-active agent Substances 0.000 claims description 4
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 3
- JPSKCQCQZUGWNM-UHFFFAOYSA-N 2,7-Oxepanedione Chemical compound O=C1CCCCC(=O)O1 JPSKCQCQZUGWNM-UHFFFAOYSA-N 0.000 claims description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 3
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 3
- VANNPISTIUFMLH-UHFFFAOYSA-N glutaric anhydride Chemical compound O=C1CCCC(=O)O1 VANNPISTIUFMLH-UHFFFAOYSA-N 0.000 claims description 3
- 239000003999 initiator Substances 0.000 claims description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 claims description 3
- 239000011247 coating layer Substances 0.000 claims description 2
- 125000003700 epoxy group Chemical group 0.000 claims description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 2
- 239000003505 polymerization initiator Substances 0.000 claims description 2
- 238000007142 ring opening reaction Methods 0.000 claims description 2
- 239000012266 salt solution Substances 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims 4
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims 4
- 229910052681 coesite Inorganic materials 0.000 claims 3
- 229910052906 cristobalite Inorganic materials 0.000 claims 3
- 229910052682 stishovite Inorganic materials 0.000 claims 3
- 229910052905 tridymite Inorganic materials 0.000 claims 3
- 239000000377 silicon dioxide Substances 0.000 claims 1
- 235000012239 silicon dioxide Nutrition 0.000 claims 1
- 239000006185 dispersion Substances 0.000 abstract description 20
- 230000004044 response Effects 0.000 abstract description 9
- 125000000524 functional group Chemical group 0.000 abstract description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 75
- 239000002244 precipitate Substances 0.000 description 25
- 239000000047 product Substances 0.000 description 22
- 238000003756 stirring Methods 0.000 description 15
- 238000001291 vacuum drying Methods 0.000 description 15
- 238000001000 micrograph Methods 0.000 description 11
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 10
- 239000000696 magnetic material Substances 0.000 description 10
- 238000001556 precipitation Methods 0.000 description 10
- 239000011258 core-shell material Substances 0.000 description 9
- 238000005406 washing Methods 0.000 description 9
- UWNADWZGEHDQAB-UHFFFAOYSA-N 2,5-dimethylhexane Chemical group CC(C)CCC(C)C UWNADWZGEHDQAB-UHFFFAOYSA-N 0.000 description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- 230000005540 biological transmission Effects 0.000 description 6
- 230000004048 modification Effects 0.000 description 6
- 238000012986 modification Methods 0.000 description 6
- 239000000178 monomer Substances 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- 239000004115 Sodium Silicate Substances 0.000 description 5
- 102000039446 nucleic acids Human genes 0.000 description 5
- 108020004707 nucleic acids Proteins 0.000 description 5
- 150000007523 nucleic acids Chemical class 0.000 description 5
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 5
- 229910052911 sodium silicate Inorganic materials 0.000 description 5
- 150000001409 amidines Chemical class 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- 238000003018 immunoassay Methods 0.000 description 4
- 238000011065 in-situ storage Methods 0.000 description 4
- 239000002861 polymer material Substances 0.000 description 4
- 108090000623 proteins and genes Proteins 0.000 description 4
- 102000004169 proteins and genes Human genes 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 230000000379 polymerizing effect Effects 0.000 description 3
- BHXBZLPMVFUQBQ-UHFFFAOYSA-K samarium(iii) chloride Chemical compound Cl[Sm](Cl)Cl BHXBZLPMVFUQBQ-UHFFFAOYSA-K 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001493 electron microscopy Methods 0.000 description 2
- 125000004185 ester group Chemical group 0.000 description 2
- 238000007885 magnetic separation Methods 0.000 description 2
- 230000005415 magnetization Effects 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- ATINCSYRHURBSP-UHFFFAOYSA-K neodymium(iii) chloride Chemical compound Cl[Nd](Cl)Cl ATINCSYRHURBSP-UHFFFAOYSA-K 0.000 description 2
- 229920002189 poly(glycerol 1-O-monomethacrylate) polymer Polymers 0.000 description 2
- 238000012673 precipitation polymerization Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000006277 sulfonation reaction Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229910001428 transition metal ion Inorganic materials 0.000 description 2
- 229960001124 trientine Drugs 0.000 description 2
- CHRJZRDFSQHIFI-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;styrene Chemical compound C=CC1=CC=CC=C1.C=CC1=CC=CC=C1C=C CHRJZRDFSQHIFI-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 108010093096 Immobilized Enzymes Proteins 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000021523 carboxylation Effects 0.000 description 1
- 238000006473 carboxylation reaction Methods 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000012674 dispersion polymerization Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 150000004870 dithiazoles Chemical group 0.000 description 1
- 230000005294 ferromagnetic effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920001184 polypeptide Polymers 0.000 description 1
- 102000004196 processed proteins & peptides Human genes 0.000 description 1
- 108090000765 processed proteins & peptides Proteins 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000004621 scanning probe microscopy Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
Classifications
-
- 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
- H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
- H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
- H01F1/0302—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity characterised by unspecified or heterogeneous hardness or specially adapted for magnetic hardness transitions
- H01F1/0311—Compounds
- H01F1/0313—Oxidic compounds
- H01F1/0315—Ferrites
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
- C08G12/26—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
- C08G12/40—Chemically modified polycondensates
- C08G12/42—Chemically modified polycondensates by etherifying
- C08G12/424—Chemically modified polycondensates by etherifying of polycondensates based on heterocyclic compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/12—Powdering or granulating
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
- G01N1/34—Purifying; Cleaning
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
- G01N1/40—Concentrating samples
- G01N1/405—Concentrating samples by adsorption or absorption
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2361/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
- C08J2361/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C08J2361/32—Modified amine-aldehyde condensateS
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2265—Oxides; Hydroxides of metals of iron
- C08K2003/2275—Ferroso-ferric oxide (Fe3O4)
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Physics & Mathematics (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- Engineering & Computer Science (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- General Chemical & Material Sciences (AREA)
- Power Engineering (AREA)
- Biomedical Technology (AREA)
- Molecular Biology (AREA)
- Soft Magnetic Materials (AREA)
Abstract
本发明公开了一种聚合物夹心复合磁性微球,夹心复合微球的平均粒径为0.3~5.0μm,由SiO2层、Fe3O4层以及磁性高分子聚合物层三部分构成,其中磁性高分子为聚1,3‑二(4,4‑二亚氨基‑2,2‑联苯并噻唑)亚苯基(PDDBP),平均分子量为15000~30000。本发明合成出的磁性高分子夹心复合微球具有磁响应时间短、单分散性好、化学稳定性强、表面羧基官能团密度高、在介质中稳定分散等优点。
Description
技术领域
本发明涉及高分子材料和磁性材料技术领域,具体涉及一种聚合物夹心复合磁性微球及其制备方法。
背景技术
磁性高分子微球是指磁性材料与高分子聚合物材料复合而形成的、表面带有功能性官能团的球形复合材料,粒径范围通常在100-100000nm之间。其中,磁性材料通常为Fe3O4,也有使用γ-Fe2O3或铁氧体的类型;高分子聚合物材料的种类则较多,可以是一种单体聚合而成,也可是多种聚合物单体共聚而成。
磁性高分子微球通常有四种类型:核壳型,反核壳型,夹心型和弥散型。其中核壳型磁性微球通常是先合成磁性材料,再通过表面改性和聚合的方式在其表面形成高分子聚合物层;反核壳型和夹心型都是先合成聚合物微球,再使用原位浸渍的方法使磁性材料分布于聚合物微球表面,只是夹心型微球会在反核壳结构的基础上再包覆一层聚合物或无机材料层;弥散型磁性微球的合成则通常是先将磁性材料表面改性后稳定分散于聚合物单体中,再通过聚合形成。
磁性高分子微球通常在外界磁场作用下发生聚集,撤去磁场后能稳定分散于介质中,而其表面丰富的官能团又能与特定的有机或无机物质结合,因此磁性高分子微球广泛应用于物质的吸附与分离中。尤其是在生物医学领域,磁性高分子微球经表面改性后能与蛋白质、多肽、核酸等特异性结合,在免疫分析、固定化酶、核酸提取等需要借助磁分离的操作中起到重要作用。
磁性高分子微球的研究与应用在国内外均较为成熟,且有较多产品上市。然而,目前应用于生物磁分离的磁性高分子微球仍存在一些不足之处:市面上大部分磁性微球为核壳型或弥散型结构,其中核壳型微球磁含量较高,磁响应时间短;弥散型微球根据聚合方式不同可实现较为广泛的粒径调控范围,但磁性材料经亲油物质表面改性后,在聚合物单体中的分散能力仍然有限,因此该种微球磁含量通常不高。相比较而言,反核壳型或夹心型磁性微球中的高分子内核起到模板的作用,能保证复合微球的单分散性;内核经氨基或磺化处理后能对金属离子捕获与吸附,确保复合微球的磁含量较高;夹心型磁性微球的外层结构又能防止磁性组分溢出。
专利CN108467461A中,在一步种子溶胀聚合法制备多孔结构的PGMA微球和原位共沉淀合成磁性微球的基础上,使用含羧基的可聚合单体(丙烯酸或甲基丙烯酸)和交联剂(N,N’-亚甲基双丙烯酰胺),以蒸馏沉淀聚合的方式在微球表面引入羧基而形成复合微球,该方法所制备的微球饱和磁化强度高,单分散性好,但蒸馏沉淀聚合需要用到毒性较大的溶剂乙腈,且反应的高温可能导致微球中的Fe3O4组分氧化。
专利CN111205581A中,聚合物微球模板为PGMA,采用分散聚合法合成,磁性微球仍然通过原位共沉淀合成,羧基改性则是先在磁性微球表面引入酯基,然后加入多元醇产生大量羟基,再使用酸酐引入羧基,该方法合成出的微球具有表面亲水性高、特异性吸附强的特点,但流程复杂且反应过程仍需在高温下进行。
专利CN114093586A中,多孔聚合物微球模板为种子溶胀法制备的聚(苯乙烯-二乙烯基苯)微球,经磺化改性后浸渍铁盐,再使用蒸馏沉淀聚合法引入酯基,然后经氨基和羧基改性制得产品。该微球的制备流程仍然复杂,且会使用到有毒的乙腈和强腐蚀性的硫酸。
综上所述,有必要从反核壳或夹心型磁性微球的合成原理出发,通过更加简单、高效、环保的方法,研制磁含量较高、单分散性好、粒径可调范围大、磁响应时间短、介质中稳定性强的生物磁分离用的复合磁性微球。
发明内容
针对现有技术的不足,本发明提供一个新的磁性高分子聚合物PDDBP,再通过原位浸渍法合成磁性高分子夹心复合微球以避免Fe3O4在合成过程中被氧化以及Fe3O4分布不均的问题,并在磁性高分子微球表面修饰SiO2和羧基使合成出的聚合物夹心复合磁性微球具有磁响应时间短、单分散性好、化学稳定性强、表面羧基官能团密度高、在介质中稳定分散等特点。
为实现本发明的第一个目的,本发明公开了一种聚合物夹心复合磁性微球,内层为磁性高分子聚合物,夹心层为Fe3O4,外包覆层为SiO2;其中,磁性高分子聚合物为聚1,3-二(4,4-二亚氨基-2,2-联苯并噻唑)亚苯基(PDDBP),其结构式为:
其中,M为稀土元素。
进一步的技术方案是:M为Sm3+、Nd3+。
进一步的技术方案是:聚合物夹心复合磁性微球的粒径通过调控在300-500nm之间;其中,磁性高分子聚合物厚度250~350nm,Fe3O4厚度20~50nm,SiO2厚度10~20nm。
进一步的技术方案是:聚合物夹心复合磁性微球中Fe3O含量为1.5~54.5wt%,PDDBP含量为38~66.5wt%,SiO2含量为7.5~32wt%。
进一步的技术方案是:PDDBP平均分子量为15000~30000。
为实现本发明的第二个目的,本发明公开了聚合物夹心复合磁性微球的制备方法整个反应过程简单环保,产品可应用于免疫分析、核酸提取、蛋白质分离等生物医学分析检测中。本发明的一种聚合物夹心复合磁性微球的制备方法,包括以下制备步骤:
(1)在冰水浴中将4,4-二胺基-2,2-联苯并噻唑与乙二胺进行聚合反应,再与甲醛进行反应后加入稀土氯化物得到磁性高分子聚合物PDDBP微球;其中,4,4-二胺基-2,2-联苯并噻唑、乙二胺、甲醛与稀土氯化物的摩尔质量比为1:2:1.01:2;
(2)PDDBP微球在引发剂、交联剂、致孔剂的作用下于聚乙烯醇和十二烷基硫酸钠的混合溶液中形成分散液滴,再加入到以PDDBP微球为种子的聚乙烯醇溶液中进行溶胀聚合反应,得到溶胀微球;
(3)通过环氧基团的开环反应在溶胀微球表面修饰氨基,将其与二价和三价铁盐溶液混合,于真空条件下进行表面浸渍,之后在氮气保护下升高温度并加入表面活性剂和碱性沉淀剂,通过化学共沉淀法制备单分散、超顺磁性的PDDBP@Fe3O4微球;
(4)将PDDBP@Fe3O4微球分散于无水乙醇和去离子水的混合溶液中,加入催化剂氨水,然后逐滴加入正硅酸四乙酯的乙醇溶液,通过基于溶胶-凝胶的法沉积SiO2层,一段时间后逐滴加入氨基化硅烷偶联剂的乙醇溶液,形成表面带氨基的PDDBP@Fe3O4@SiO2微球;
(5)在氮气保护下将氨基化的PDDBP@Fe3O4@SiO2微球溶于DMF中,逐滴加入到酸酐的DMF溶液中,通过酸酐与微球表面氨基的酰胺化反应将氨基改性为羧基,得到聚合物夹心复合磁性微球。
进一步的技术方案是:步骤(2)中所述溶胀聚合引发剂为过氧化苯甲酰、偶氮二异丁腈、偶氮二异丁基脒盐酸盐中至少一种,使用浓度为0.1~0.3wt%;所述交联剂为二乙烯苯、乙二醇二甲基丙烯酸酯中至少一种,使用浓度为1~4wt%;所述致孔剂为甲苯、环己烷、正己烷、正庚烷中至少一种,使用浓度为1~2wt%;所述聚乙烯醇溶液浓度为0.5~1.0wt%;所述十二烷基硫酸钠溶液浓度为0.2~0.3wt%;所述溶胀聚合反应时间12~24h。
进一步的技术方案是:步骤(3)中所述修饰氨基所用的试剂为乙二胺、二乙烯三胺、三乙烯四胺、四乙烯五胺中至少一种,与溶胀微球的摩尔质量比为1:4;所述二价铁盐为氯化亚铁、硫酸亚铁中至少一种,三价铁盐为氯化铁、硫酸铁、硝酸铁中至少一种,二价和三价铁盐摩尔比为1:1.5~2.0,磁性微球与铁盐总质量的比例为1:1~3;所述表面浸渍温度为0~10℃;所述表面活性剂为柠檬酸钠或聚乙二醇,使用浓度为1~5wt%;所述碱性沉淀剂为浓氨水或NaOH溶液并调整反应体系pH为10~12;所述反应温度为70~80℃,加入沉淀剂后继续熟化1~1.5h。
进一步的技术方案是:步骤(4)中所述氨基化硅烷偶联剂为3-氨丙基三甲氧基硅烷、3-氨丙基三乙氧基硅烷中至少一种;所述法沉积SiO2层的反应时间为12~24h;所述正硅酸四乙酯的乙醇溶液滴加时间为45~60min,磁性微球、正硅酸四乙酯与氨基化硅烷偶联剂的质量比为1:0.5~1.5:0.25~0.5,加入硅烷偶联剂后继续保持反应6~12h。
进一步的技术方案是:步骤(5)中所述酸酐为丁二酸酐、顺丁烯二酸酐、戊二酸酐、己二酸酐中至少一种;所述反应前酸酐的DMF溶液需磁力搅拌4~6h;所述磁性微球与酸酐的质量比为1:0.5~1.5,磁性微球的DMF溶液滴加时间为5~10min,酰胺化反应时间为10~15h。
本发明的有益效果:
1、聚双噻唑本身是抗磁体,但是双噻唑结构是一个良好的配体,能和众多的过渡金属离子配位生成螯合物。本发明在聚双噻唑分子链中引入过渡金属离子,在外加磁场的作用下,使螯合物中金属离子的未成对电子通过超交换作用和极化作用实现磁有序以具备良好的铁磁性能。
2、本发明通过调节反应参数:如单体体积、引发剂用量、分散剂用量、交联剂用量、反应介质类型等,控制微球的平均粒径为300-500nm,因此所制备的聚合物夹心复合磁性微球具有单分散性好、磁含量高、磁响应时间短、表面羧基密度高、在介质中分散稳定性强等特点。
3、本发明在磁性高分子微球表面包覆无机壳层SiO2,可防止微球的磁性组分外漏并丰富其表面官能团类型,并且对磁性微球的表面包覆及后续改性均在室温条件下进行,羧基化步骤所用的溶剂DMF毒性要小于乙腈,整个反应过程简单环保,制备的聚合物夹心复合磁性微球可应用于免疫分析、核酸提取、蛋白质分离等生物医学分析检测中。
附图说明
图1为聚1,3-二(4,4-二亚氨基-2,2-联苯并噻唑)亚苯基(PDDBP)的合成路线图。
图2为本发明实施例制备的聚合物夹心复合磁性微球的扫描电镜图;其中,(a)为实施例1的聚合物夹心复合磁性微球的扫描电镜图,(b)为实施例2的聚合物夹心复合磁性微球的扫描电镜图。
图3为本发明实施例制备的聚合物夹心复合磁性微球的透射电镜图;其中,(a)、(b)为本发明实施例3制备的聚合物夹心复合磁性微球的透射电镜图,(c)、(d)为本发明实施例4制备的聚合物夹心复合磁性微球的透射电镜图。
图4为本发明实施例1-2制备的聚合物夹心复合磁性微球的磁滞回线。
图5为本发明实施例1制备的聚合物夹心复合磁性微球的分散稳定性和磁响应性能测试图。
具体实施方式
为使本发明实施例的目的、技术方案和优点更加清楚,对本发明实施例中的技术方案进行清楚、完整地描述,显然,所描述的实施例是本发明一部分实施例,而不是全部的实施例。基于本发明中的实施例,本领域普通技术人员在没有作出创造性劳动前提下所获得的所有其他实施例,都属于本发明保护的范围。
本申请实施例提供的聚合物夹心复合磁性微球具有单分散性好、磁含量高、磁响应时间短、表面羧基密度高、在介质中分散稳定性强等特点;其制备过程简单环保,制备的功能化磁性复合微球可应用于免疫分析、核酸提取、蛋白质分离等生物医学分析检测中。
为了更好的理解上述技术方案,下面将结合说明书附图以及具体的实施方式对上述技术方案进行详细的说明。
实施例1
(1)将1.49g的4,4-二胺基-2,2-联苯并噻唑加入到20ml DMF中并搅拌均匀,在氮气保护下加入0.6g乙二胺,并用冰水浴冷却。通过恒压液滴漏斗慢慢加入0.19ml甲醛与10mlDMF的混合液,在冰水浴中反应6h后倒入100ml甲醇中沉淀,用去离子水和甲醇反复洗涤沉淀物,置于80℃真空干燥箱中烘干。将10g得到的产物加入到50ml二甲基亚砜中,在氮气保护下加入0.17g氯化钐,80℃反应24h后倒入去离子水中沉淀,用去离子水和甲醇反复洗涤沉淀物,置于80℃真空干燥箱中烘干得到PDDBP,如图1所示为PDDBP的合成路线图。
(2)以0.2g PDDBP为种子微球,分散于20ml浓度为0.5wt%的聚乙烯醇溶液中,另取0.1g十二烷基硫酸钠和0.2g聚乙烯醇溶于50ml去离子水中形成混合溶液,再加入10gPDDBP、0.08g过氧化苯甲酰、0.8g二乙烯苯、0.8g甲苯,在高压均质机作用下形成粒径小于1μm的稳定分散液滴,将该液滴分散液加入到含有种子微球的聚乙烯醇溶液中,在氮气保护下室温溶胀12h,溶胀结束后聚合反应12h即得溶胀微球。
(3)将10g溶胀微球、0.08g过氧化苯甲酰、0.12g乙二胺加入到50ml甲醇中,于90℃下反应3h后反复离心洗涤得到沉淀物,将其与4.4g氯化亚铁、6.6g氯化铁一同加入50ml去离子水中混合,降温至0℃,于真空条件下进行表面浸渍,之后在氮气保护下升温至70℃并加入0.21g柠檬酸钠,加入浓氨水调节溶液pH为10,熟化1h。
(4)将11g步骤(3)的产物分散于10ml无水乙醇和15ml去离子水的混合溶液中,加入催化剂氨水,然后逐滴加入5.5g正硅酸四乙酯与10ml乙醇的混合溶液,并逐滴加入含有4.3g硅酸钠的乙醇溶液,室温下搅拌12h后在45min内逐滴加入含有2.75g 3-氨丙基三甲氧基硅烷的乙醇溶液,形成表面带氨基的PDDBP@Fe3O4@SiO2微球。
(5)将16.5g丁二酸酐溶解于20ml DMF中,搅拌4h后在氮气保护下逐滴加入含有10g步骤(4)产物的DMF混合液,室温下继续搅拌10h后用甲醇与去离子水反复洗涤,60℃真空烘干后得到产物。
实施例2
(1)将1.49g的4,4-二胺基-2,2-联苯并噻唑加入到20ml DMF中并搅拌均匀,在氮气保护下加入0.6g乙二胺,并用冰水浴冷却。通过恒压液滴漏斗慢慢加入0.19ml甲醛与10mlDMF的混合液,在冰水浴中反应6h后倒入100ml甲醇中沉淀,用去离子水和甲醇反复洗涤沉淀物,置于80℃真空干燥箱中烘干。将10g得到的产物加入到50ml二甲基亚砜中,在氮气保护下加入0.13g氯化钐,80℃反应24h后倒入去离子水中沉淀,用去离子水和甲醇反复洗涤沉淀物,置于80℃真空干燥箱中烘干得到PDDBP。
(2)以0.2g PDDBP为种子微球,分散于20ml浓度为0.6wt%的聚乙烯醇溶液中,另取0.11g十二烷基硫酸钠和0.24g聚乙烯醇溶于50ml去离子水中形成混合溶液,再加入10gPDDBP、0.16g偶氮二异丁腈、1.6g二乙烯苯、0.96g环己烷,在高压均质机作用下形成粒径小于1μm的稳定分散液滴,将该液滴分散液加入到含有种子微球的聚乙烯醇溶液中,在氮气保护下室温溶胀14h,溶胀结束后聚合反应15h即得溶胀微球。
(3)将10g溶胀微球、0.16g偶氮二异丁腈、0.21g二乙烯三胺加入到50ml甲醇中,于90℃下反应3h后反复离心洗涤得到沉淀物,将其与8.5g氯化亚铁、13.5g硫酸铁一同加入50ml去离子水中混合,降温至3℃,于真空条件下进行表面浸渍,之后在氮气保护下升温至75℃并加入0.66g柠檬酸钠,加入浓氨水调节溶液pH为11,熟化1.5h。
(4)将11g步骤(3)的产物分散于10ml无水乙醇和15ml去离子水的混合溶液中,加入催化剂氨水,然后逐滴加入7.7g正硅酸四乙酯与10ml乙醇的混合溶液,并逐滴加入含有4.3g硅酸钠的乙醇溶液,室温下搅拌16h后在50min内逐滴加入含有3.3g 3-氨丙基三甲氧基硅烷的乙醇溶液,形成表面带氨基的PDDBP@Fe3O4@SiO2微球。
(5)将12.1g丁二酸酐溶解于20ml DMF中,搅拌5h后在氮气保护下逐滴加入含有10g步骤(4)产物的DMF混合液,室温下继续搅拌11h后用甲醇与去离子水反复洗涤,60℃真空烘干后得到产物。
实施例3
(1)将1.49g的4,4-二胺基-2,2-联苯并噻唑加入到20ml DMF中并搅拌均匀,在氮气保护下加入0.6g乙二胺,并用冰水浴冷却。通过恒压液滴漏斗慢慢加入0.19ml甲醛与10mlDMF的混合液,在冰水浴中反应6h后倒入100ml甲醇中沉淀,用去离子水和甲醇反复洗涤沉淀物,置于80℃真空干燥箱中烘干。将10g得到的产物加入到50ml二甲基亚砜中,在氮气保护下加入0.09g氯化钐,80℃反应24h后倒入去离子水中沉淀,用去离子水和甲醇反复洗涤沉淀物,置于80℃真空干燥箱中烘干得到PDDBP。
(2)以0.2g PDDBP为种子微球,分散于20ml浓度为0.7wt%的聚乙烯醇溶液中,另取0.13g十二烷基硫酸钠和0.28g聚乙烯醇溶于50ml去离子水中形成混合溶液,再加入10gPDDBP、0.24g偶氮二异丁基脒盐酸盐、2.4g二乙烯苯、1.12g正己烷,在高压均质机作用下形成粒径小于1μm的稳定分散液滴,将该液滴分散液加入到含有种子微球的聚乙烯醇溶液中,在氮气保护下室温溶胀16h,溶胀结束后聚合反应17h即得溶胀微球。
(3)将10g溶胀微球、0.24g偶氮二异丁腈脒盐酸盐、0.3g三乙烯四胺加入到50ml甲醇中,于90℃下反应3h后反复离心洗涤得到沉淀物,将其与12g氯化亚铁、21g硝酸铁一同加入50ml去离子水中混合,降温至5℃,于真空条件下进行表面浸渍,之后在氮气保护下升温至80℃并加入1.32g柠檬酸钠,加入浓氨水调节溶液pH为12,熟化1h。
(4)将11g步骤(3)的产物分散于10ml无水乙醇和15ml去离子水的混合溶液中,加入催化剂氨水,然后逐滴加入9.9g正硅酸四乙酯与10ml乙醇的混合溶液,并逐滴加入含有4.3g硅酸钠的乙醇溶液,室温下搅拌18h后在55min内逐滴加入含有3.8g 3-氨丙基三甲氧基硅烷的乙醇溶液,形成表面带氨基的PDDBP@Fe3O4@SiO2微球。
(5)将7.7g顺丁烯二酸酐溶解于20ml DMF中,搅拌6h后在氮气保护下逐滴加入含有10g步骤(4)产物的DMF混合液,室温下继续搅拌14h后用甲醇与去离子水反复洗涤,60℃真空烘干后得到产物。
实施例4
(1)将1.49g的4,4-二胺基-2,2-联苯并噻唑加入到20ml DMF中并搅拌均匀,在氮气保护下加入0.6g乙二胺,并用冰水浴冷却。通过恒压液滴漏斗慢慢加入0.19ml甲醛与10mlDMF的混合液,在冰水浴中反应6h后倒入100ml甲醇中沉淀,用去离子水和甲醇反复洗涤沉淀物,置于80℃真空干燥箱中烘干。将10g得到的产物加入到50ml二甲基亚砜中,在氮气保护下加入0.24g氯化钕,80℃反应24h后倒入去离子水中沉淀,用去离子水和甲醇反复洗涤沉淀物,置于80℃真空干燥箱中烘干得到PDDBP。
(2)以0.2g PDDBP为种子微球,分散于20ml浓度为0.8wt%的聚乙烯醇溶液中,另取0.14g十二烷基硫酸钠和0.32g聚乙烯醇溶于50ml去离子水中形成混合溶液,再加入10gPDDBP、0.12g偶氮二异丁腈、3.2g乙二醇二甲基丙烯酸酯、1.28g正庚烷,在高压均质机作用下形成粒径小于1μm的稳定分散液滴,将该液滴分散液加入到含有种子微球的聚乙烯醇溶液中,在氮气保护下室温溶胀20h,溶胀结束后聚合反应22h即得溶胀微球。
(3)将10g溶胀微球、0.12g偶氮二异丁腈、0.38g四乙烯五胺加入到50ml甲醇中,于90℃下反应3h后反复离心洗涤得到沉淀物,将其与5.7g硫酸亚铁、11.3g氯化铁一同加入50ml去离子水中混合,降温至7℃,于真空条件下进行表面浸渍,之后在氮气保护下升温至70℃并加入1.12g聚乙二醇,加入NaOH调节溶液pH为10,熟化1h。
(4)将11g步骤(3)的产物分散于10ml无水乙醇和15ml去离子水的混合溶液中,加入催化剂氨水,然后逐滴加入13.2g正硅酸四乙酯与10ml乙醇的混合溶液,并逐滴加入含有4.3g硅酸钠的乙醇溶液,室温下搅拌22h后在60min内逐滴加入含有4.9g 3-氨丙基三乙氧基硅烷的乙醇溶液,形成表面带氨基的PDDBP@Fe3O4@SiO2微球。
(5)将5.5g戊二酸酐溶解于20ml DMF中,搅拌4.5h后在氮气保护下逐滴加入含有10g步骤(4)产物的DMF混合液,室温下继续搅拌13h后用甲醇与去离子水反复洗涤,60℃真空烘干后得到产物。
实施例5
(1)将1.49g的4,4-二胺基-2,2-联苯并噻唑加入到20ml DMF中并搅拌均匀,在氮气保护下加入0.6g乙二胺,并用冰水浴冷却。通过恒压液滴漏斗慢慢加入0.19ml甲醛与10mlDMF的混合液,在冰水浴中反应6h后倒入100ml甲醇中沉淀,用去离子水和甲醇反复洗涤沉淀物,置于80℃真空干燥箱中烘干。将10g得到的产物加入到50ml二甲基亚砜中,在氮气保护下加入0.18g氯化钕,80℃反应24h后倒入去离子水中沉淀,用去离子水和甲醇反复洗涤沉淀物,置于80℃真空干燥箱中烘干得到PDDBP。
(2)以0.2g PDDBP为种子微球,分散于20ml浓度为1.0wt%的聚乙烯醇溶液中,另取0.15g十二烷基硫酸钠和0.36g聚乙烯醇溶于50ml去离子水中形成混合溶液,再加入10gPDDBP、0.2g偶氮二异丁基脒盐酸盐、2g乙二醇二甲基丙烯酸酯、1.6g正庚烷,在高压均质机作用下形成粒径小于1μm的稳定分散液滴,将该液滴分散液加入到含有种子微球的聚乙烯醇溶液中,在氮气保护下室温溶胀24h,溶胀结束后聚合反应24h即得溶胀微球。
(3)将10g溶胀微球、0.2g偶氮二异丁基脒盐酸盐、0.24g乙二胺加入到50ml甲醇中,于90℃下反应3h后反复离心洗涤得到沉淀物,将其与10g硫酸亚铁、18g硫酸铁一同加入50ml去离子水中混合,降温至10℃,于真空条件下进行表面浸渍,之后在氮气保护下升温至80℃并加入1.95g聚乙二醇,加入NaOH调节溶液pH为12,熟化1.5h。
(4)将11g步骤(3)的产物分散于10ml无水乙醇和15ml去离子水的混合溶液中,加入催化剂氨水,然后逐滴加入16.5g正硅酸四乙酯与10ml乙醇的混合溶液,并逐滴加入含有4.3g硅酸钠的乙醇溶液,室温下搅拌24h后在55min内逐滴加入含有5.5g 3-氨丙基三乙氧基硅烷的乙醇溶液,形成表面带氨基的PDDBP@Fe3O4@SiO2微球。
(5)将9.9g己二酸酐溶解于20ml DMF中,搅拌5.5h后在氮气保护下逐滴加入含有10g步骤(4)产物的DMF混合液,室温下继续搅拌15h后用甲醇与去离子水反复洗涤,60℃真空烘干后得到产物。
实施例6
将实施例1-6所得的聚合物夹心复合磁性微球,分别进行电镜扫描和电镜透视,以及进行性能验证。
其中,图2中(a)为实施例1的聚合物夹心复合磁性微球的扫描电镜图,(b)为实施例2的聚合物夹心复合磁性微球的扫描电镜图,可以得到微球粒径在300-500nm之间且单分散性好。
图3中(a)、(b)为本发明实施例3制备的聚合物夹心复合磁性微球的透射电镜图,(c)、(d)为本发明实施例4制备的聚合物夹心复合磁性微球的透射电镜图,从透射电镜图中可以明显地观察到微球有三层,证实合成的为夹心复合微球。
图4为本发明实施例1-2制备的聚合物夹心复合磁性微球的磁滞回线,由图片可看出本发明的合物夹心复合磁性微球呈超顺磁性,剩余磁化强度和矫顽力几乎为零,且具有较高的饱和磁化强度。
图5为本发明实施例1制备的聚合物夹心复合磁性微球的分散稳定性和磁响应性能测试图,反映了本发明的聚合物夹心复合磁性微球磁响应时间短、在介质中分散稳定性强。
Claims (10)
1.一种聚合物夹心复合磁性微球,其特征在于,内层为磁性高分子聚合物,夹心层为Fe3O4,外包覆层为SiO2;其中,磁性高分子聚合物为聚1,3-二(4,4-二亚氨基-2,2-联苯并噻唑)亚苯基(PDDBP),其结构式为:
其中,M为稀土元素。
2.根据权利要求1所述的一种聚合物夹心复合磁性微球,其特征在于,M为Sm3+、Nd3+。
3.根据权利要求1所述的一种聚合物夹心复合磁性微球,其特征在于,聚合物夹心复合磁性微球的粒径在300~500nm之间;其中,磁性高分子聚合物厚度250~350nm,Fe3O4厚度20~50nm,SiO2厚度10~20nm。
4.根据权利要求1所述的一种聚合物夹心复合磁性微球,其特征在于,聚合物夹心复合磁性微球中Fe3O含量为1.5~54.5wt%,PDDBP含量为38~66.5wt%,SiO2含量为7.5~32wt%。
5.根据权利要求1所述的一种聚合物夹心复合磁性微球,其特征在于,PDDBP平均分子量为15000~30000。
6.一种聚合物夹心复合磁性微球的制备方法,其特征在于,包括以下制备步骤:
(1)在冰水浴中将4,4-二胺基-2,2-联苯并噻唑与乙二胺进行聚合反应,再与甲醛进行反应后加入稀土氯化物得到磁性高分子聚合物PDDBP微球;其中,4,4-二胺基-2,2-联苯并噻唑、乙二胺、甲醛与稀土氯化物的摩尔质量比为1:2:1.01:2;
(2)PDDBP微球在引发剂、交联剂、致孔剂的作用下于聚乙烯醇和十二烷基硫酸钠的混合溶液中形成分散液滴,再加入到以PDDBP微球为种子的聚乙烯醇溶液中进行溶胀聚合反应,得到溶胀微球;
(3)通过环氧基团的开环反应在溶胀微球表面修饰氨基,将其与二价和三价铁盐溶液混合,于真空条件下进行表面浸渍,之后在氮气保护下升高温度并加入表面活性剂和碱性沉淀剂,通过化学共沉淀法制备单分散、超顺磁性的PDDBP@Fe3O4微球;
(4)将PDDBP@Fe3O4微球分散于无水乙醇和去离子水的混合溶液中,加入催化剂氨水,然后逐滴加入正硅酸四乙酯的乙醇溶液,通过基于溶胶-凝胶的法沉积SiO2层,一段时间后逐滴加入氨基化硅烷偶联剂的乙醇溶液,形成表面带氨基的PDDBP@Fe3O4@SiO2微球;
(5)在氮气保护下将氨基化的PDDBP@Fe3O4@SiO2微球溶于DMF中,逐滴加入到酸酐的DMF溶液中,通过酸酐与微球表面氨基的酰胺化反应将氨基改性为羧基,得到聚合物夹心复合磁性微球。
7.根据权利要求6所述的聚合物夹心复合磁性微球的制备方法,其特征在于,步骤(2)中:所述溶胀聚合引发剂为过氧化苯甲酰、偶氮二异丁腈、偶氮二异丁基脒盐酸盐中至少一种,使用浓度为0.1~0.3wt%;所述交联剂为二乙烯苯、乙二醇二甲基丙烯酸酯中至少一种,使用浓度为1~4wt%;所述致孔剂为甲苯、环己烷、正己烷、正庚烷中至少一种,使用浓度为1~2wt%;所述聚乙烯醇溶液浓度为0.5~1.0wt%;所述十二烷基硫酸钠溶液浓度为0.2~0.3wt%;所述溶胀聚合反应时间12~24h。
8.根据权利要求6所述的聚合物夹心复合磁性微球的制备方法,其特征在于,步骤(3)中:所述修饰氨基所用的试剂为乙二胺、二乙烯三胺、三乙烯四胺、四乙烯五胺中至少一种,与溶胀微球的摩尔质量比为1:4;所述二价铁盐为氯化亚铁、硫酸亚铁中至少一种,三价铁盐为氯化铁、硫酸铁、硝酸铁中至少一种,二价和三价铁盐摩尔比为1:1.5~2.0,磁性微球与铁盐总质量的比例为1:1~3;所述表面浸渍温度为0~10℃;所述表面活性剂为柠檬酸钠或聚乙二醇,使用浓度为1~5wt%;所述碱性沉淀剂为浓氨水或NaOH溶液并调整反应体系pH为10~12;所述反应温度为70~80℃,加入沉淀剂后继续熟化1~1.5h。
9.根据权利要求6所述的聚合物夹心复合磁性微球的制备方法,其特征在于,步骤(4)中:所述氨基化硅烷偶联剂为3-氨丙基三甲氧基硅烷、3-氨丙基三乙氧基硅烷中至少一种;所述法沉积SiO2层的反应时间为12~24h;所述正硅酸四乙酯的乙醇溶液滴加时间为45~60min,磁性微球、正硅酸四乙酯与氨基化硅烷偶联剂的质量比为1:0.5~1.5:0.25~0.5,加入硅烷偶联剂后继续保持反应6~12h。
10.根据权利要求6所述的聚合物夹心复合磁性微球的制备方法,其特征在于,步骤(5)中:所述酸酐为丁二酸酐、顺丁烯二酸酐、戊二酸酐、己二酸酐中至少一种;所述反应前酸酐的DMF溶液需磁力搅拌4~6h;所述磁性微球与酸酐的质量比为1:0.5~1.5,磁性微球的DMF溶液滴加时间为5~10min,酰胺化反应时间为10~15h。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202310909657.9A CN117106149A (zh) | 2023-07-24 | 2023-07-24 | 一种聚合物夹心复合磁性微球及其制备方法 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202310909657.9A CN117106149A (zh) | 2023-07-24 | 2023-07-24 | 一种聚合物夹心复合磁性微球及其制备方法 |
Publications (1)
Publication Number | Publication Date |
---|---|
CN117106149A true CN117106149A (zh) | 2023-11-24 |
Family
ID=88808232
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202310909657.9A Pending CN117106149A (zh) | 2023-07-24 | 2023-07-24 | 一种聚合物夹心复合磁性微球及其制备方法 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN117106149A (zh) |
-
2023
- 2023-07-24 CN CN202310909657.9A patent/CN117106149A/zh active Pending
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US4654267A (en) | Magnetic polymer particles and process for the preparation thereof | |
CN108467461B (zh) | 表面羧基核壳超顺磁性微球的制备方法 | |
Ma et al. | Synthesis and characterization of micron‐sized monodisperse superparamagnetic polymer particles with amino groups | |
Horák | Magnetic polyglycidylmethacrylate microspheres by dispersion polymerization | |
US7754278B2 (en) | Magnetic polymer microbeads and method for preparing the same | |
Zengin et al. | Molecularly imprinted superparamagnetic iron oxide nanoparticles for rapid enrichment and separation of cholesterol | |
CN111393574B (zh) | 一种表面带有功能基团的磁性微球及其制备方法和用途 | |
CN111375360B (zh) | 一种粒径均一的磁性微球的制备方法 | |
CN108129614B (zh) | 一种磁性微球及其制备方法和应用 | |
CN102744048A (zh) | 酵母菌微球体磁性复合材料表面印迹吸附剂的制备方法 | |
Li et al. | Preparation of novel bovine hemoglobin surface-imprinted polystyrene nanoparticles with magnetic susceptibility | |
Ma et al. | Preparation and surface modification of non-porous micron-sized magnetic poly (methyl acrylate) microspheres | |
Bilalis et al. | Multi‐responsive polymeric microcontainers for potential biomedical applications: synthesis and functionality evaluation | |
Rahman et al. | Organic–inorganic hybrid magnetic latex | |
CN117106149A (zh) | 一种聚合物夹心复合磁性微球及其制备方法 | |
Cao et al. | Raft polymerization of N, N‐dimethylacrylamide from magnetic poly (2‐hydroxyethyl methacrylate) microspheres to suppress nonspecific protein adsorption | |
EP2000484B1 (en) | Process for producing polymer-coated ferromagnetic particle, and polymer-coated ferromagnetic particle | |
Xie et al. | Double-sided coordination assembly: superparamagnetic composite microspheres with layer-by-layer structure for protein separation | |
CN116082669A (zh) | 一种聚合物基纳米磁珠及其制备方法 | |
US20230352218A1 (en) | Superparamagnetic monodisperse particles and method for the production thereof | |
CN110935405B (zh) | 一种表面富含双键的磁性聚苯乙烯微球的制备方法 | |
JPH08176461A (ja) | 単分散性微粒子及びその製造方法 | |
CN115975252B (zh) | 一种具有双层壳体结构的磁性聚合物微球的制备方法 | |
JPH07320916A (ja) | 磁性粒子の製造方法 | |
CN111116851A (zh) | 一种核壳结构的多聚季铵盐磁性微球的制备方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination |