JP3735990B2 - Method for producing magnetic silica gel - Google Patents
Method for producing magnetic silica gel Download PDFInfo
- Publication number
- JP3735990B2 JP3735990B2 JP01384897A JP1384897A JP3735990B2 JP 3735990 B2 JP3735990 B2 JP 3735990B2 JP 01384897 A JP01384897 A JP 01384897A JP 1384897 A JP1384897 A JP 1384897A JP 3735990 B2 JP3735990 B2 JP 3735990B2
- Authority
- JP
- Japan
- Prior art keywords
- magnetic
- silica gel
- water
- magnetic silica
- alkoxide
- 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.)
- Expired - Fee Related
Links
- 230000005291 magnetic effect Effects 0.000 title claims description 95
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims description 62
- 239000000741 silica gel Substances 0.000 title claims description 62
- 229910002027 silica gel Inorganic materials 0.000 title claims description 62
- 238000004519 manufacturing process Methods 0.000 title claims description 20
- 150000004703 alkoxides Chemical class 0.000 claims description 48
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 43
- 229920000642 polymer Polymers 0.000 claims description 38
- 239000000126 substance Substances 0.000 claims description 35
- 239000000499 gel Substances 0.000 claims description 31
- 239000011148 porous material Substances 0.000 claims description 30
- 239000002904 solvent Substances 0.000 claims description 28
- 239000003960 organic solvent Substances 0.000 claims description 25
- 239000011553 magnetic fluid Substances 0.000 claims description 19
- 239000002245 particle Substances 0.000 claims description 19
- 239000000696 magnetic material Substances 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 238000006460 hydrolysis reaction Methods 0.000 claims description 4
- 230000007062 hydrolysis Effects 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims 1
- 238000000034 method Methods 0.000 description 49
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 27
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 14
- 239000000243 solution Substances 0.000 description 14
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 11
- 239000006249 magnetic particle Substances 0.000 description 10
- 238000006116 polymerization reaction Methods 0.000 description 10
- 239000011259 mixed solution Substances 0.000 description 9
- 238000000926 separation method Methods 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 238000000605 extraction Methods 0.000 description 8
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 8
- JYVLIDXNZAXMDK-UHFFFAOYSA-N pentan-2-ol Chemical compound CCCC(C)O JYVLIDXNZAXMDK-UHFFFAOYSA-N 0.000 description 8
- 238000001179 sorption measurement Methods 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 230000000704 physical effect Effects 0.000 description 7
- 239000004094 surface-active agent Substances 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 238000001879 gelation Methods 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 150000001298 alcohols Chemical class 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- QNVRIHYSUZMSGM-UHFFFAOYSA-N hexan-2-ol Chemical compound CCCCC(C)O QNVRIHYSUZMSGM-UHFFFAOYSA-N 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 230000005389 magnetism Effects 0.000 description 4
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical group CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 239000004115 Sodium Silicate Substances 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000003463 adsorbent Substances 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000000969 carrier Substances 0.000 description 3
- 238000010790 dilution Methods 0.000 description 3
- 239000012895 dilution Substances 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 3
- 229910052911 sodium silicate Inorganic materials 0.000 description 3
- 229910000859 α-Fe Inorganic materials 0.000 description 3
- QNVRIHYSUZMSGM-LURJTMIESA-N 2-Hexanol Natural products CCCC[C@H](C)O QNVRIHYSUZMSGM-LURJTMIESA-N 0.000 description 2
- HCFAJYNVAYBARA-UHFFFAOYSA-N 4-heptanone Chemical compound CCCC(=O)CCC HCFAJYNVAYBARA-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- 239000003929 acidic solution Substances 0.000 description 2
- 150000007514 bases Chemical class 0.000 description 2
- -1 cells Proteins 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 description 2
- 238000007865 diluting Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 239000011554 ferrofluid Substances 0.000 description 2
- 239000003302 ferromagnetic material Substances 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- NGAZZOYFWWSOGK-UHFFFAOYSA-N heptan-3-one Chemical compound CCCCC(=O)CC NGAZZOYFWWSOGK-UHFFFAOYSA-N 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 2
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- QQZOPKMRPOGIEB-UHFFFAOYSA-N n-butyl methyl ketone Natural products CCCCC(C)=O QQZOPKMRPOGIEB-UHFFFAOYSA-N 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 150000007523 nucleic acids Chemical class 0.000 description 2
- 102000039446 nucleic acids Human genes 0.000 description 2
- 108020004707 nucleic acids Proteins 0.000 description 2
- AQIXEPGDORPWBJ-UHFFFAOYSA-N pentan-3-ol Chemical compound CCC(O)CC AQIXEPGDORPWBJ-UHFFFAOYSA-N 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 102000004169 proteins and genes Human genes 0.000 description 2
- 108090000623 proteins and genes Proteins 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 238000005211 surface analysis Methods 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- HNAGHMKIPMKKBB-UHFFFAOYSA-N 1-benzylpyrrolidine-3-carboxamide Chemical compound C1C(C(=O)N)CCN1CC1=CC=CC=C1 HNAGHMKIPMKKBB-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- JGFBQFKZKSSODQ-UHFFFAOYSA-N Isothiocyanatocyclopropane Chemical compound S=C=NC1CC1 JGFBQFKZKSSODQ-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 1
- 239000002156 adsorbate Substances 0.000 description 1
- 238000001042 affinity chromatography Methods 0.000 description 1
- 230000004931 aggregating effect Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- QZPSXPBJTPJTSZ-UHFFFAOYSA-N aqua regia Chemical compound Cl.O[N+]([O-])=O QZPSXPBJTPJTSZ-UHFFFAOYSA-N 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- OBNCKNCVKJNDBV-UHFFFAOYSA-N butanoic acid ethyl ester Natural products CCCC(=O)OCC OBNCKNCVKJNDBV-UHFFFAOYSA-N 0.000 description 1
- PWLNAUNEAKQYLH-UHFFFAOYSA-N butyric acid octyl ester Natural products CCCCCCCCOC(=O)CCC PWLNAUNEAKQYLH-UHFFFAOYSA-N 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001962 electrophoresis Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000005294 ferromagnetic effect Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 230000003100 immobilizing effect Effects 0.000 description 1
- 238000003018 immunoassay Methods 0.000 description 1
- 229940035429 isobutyl alcohol Drugs 0.000 description 1
- YWXYYJSYQOXTPL-SLPGGIOYSA-N isosorbide mononitrate Chemical compound [O-][N+](=O)O[C@@H]1CO[C@@H]2[C@@H](O)CO[C@@H]21 YWXYYJSYQOXTPL-SLPGGIOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000005381 magnetic domain Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- UUIQMZJEGPQKFD-UHFFFAOYSA-N n-butyric acid methyl ester Natural products CCCC(=O)OC UUIQMZJEGPQKFD-UHFFFAOYSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000002459 porosimetry Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 102000004196 processed proteins & peptides Human genes 0.000 description 1
- 108090000765 processed proteins & peptides Proteins 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000005563 spheronization Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000013076 target substance Substances 0.000 description 1
- 239000011882 ultra-fine particle Substances 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
- H01F1/44—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of magnetic liquids, e.g. ferrofluids
- H01F1/445—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of magnetic liquids, e.g. ferrofluids the magnetic component being a compound, e.g. Fe3O4
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03C—MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03C1/00—Magnetic separation
- B03C1/005—Pretreatment specially adapted for magnetic separation
- B03C1/01—Pretreatment specially adapted for magnetic separation by addition of magnetic adjuvants
Description
【０００１】
【発明の属する技術分野】
本発明は吸着剤や吸着用担体、抽出剤や抽出用担体、触媒担体等に使用することが可能な磁性及び強度を有し、その磁性体含有量や形状、粒径、細孔特性の制御が可能なシリカゲルの製造方法に関するものである。
【０００２】
【従来の技術】
従来より吸着剤や吸着用の固相担体としてはシリカゲル等が良く知られているが、これらを用いる場合、その回収のためには遠心分離法や、あるいはフィルターによる濾過等を行わなければならず、簡便な方法ではなかった。また、吸着、抽出操作においては、目的とする吸着物や抽出物とそれ以外の他の物質とを分離する必要があるが、従来の遠心分離法、カラム分離法、電気泳動法等の手法では分離のみでも長時間を要し、簡便な方法ではないという課題を有していた。
【０００３】
そのため、目的の物質を分離する手段として、特開昭６０−２４４２５１に記載のように、粒子に強磁性体を付加し、磁場を与えることにより、目的の粒子を回収するという方法はあった。しかし、この方法では、吸着、抽出、反応操作等において、粒子が均一に分散した状態にてその操作を実施したい場合においても強磁性体自身が自己会合してしまい、粒子の存在状態を自由に制御できないという欠点を有していた。
【０００４】
近年、強磁性体自身の自己会合をなくす方法として、特開昭６１−１８１９６７に記載のように、磁性体として超常磁性体を用いた方法が開示されている。また、特表平４−５０１９５７に記載のように、検体を固定する固相として超常磁性体を含んだ磁気粒子を用い、蛋白質、細胞、ＤＮＡの分離、分析等に利用できることが開示されている。更に、特許番号２５５４２５０号には、ゲルマトリックスに超常磁性磁気反応性物質を捕捉させ運動性の高い試薬担体について開示している。これらに記載の超常磁性磁気粒子は、酸化鉄等の強磁性体を永久磁性を維持するのに必要な磁区の大きさより小さい微粒子にして粒子中に含ませたもので、外部磁場により強磁性を示す性質を有する。その性質を利用し、分散させる時には外部磁場をかけず、凝集させる時に外部磁場をかけて溶液中の粒子を凝集させる方法である。しかしながら、これらの方法においても、磁性粒子の物性を充分に制御した方法により得たものとはいえず、磁性粒子を種々の用途に応じてその物性を充分に制御し、最適な磁性粒子を製造する方法が望まれていた。
【０００５】
又、磁性シリカゲルを得る方法としては特開平７−２３５４０７に記載のように、ケイ酸ナトリウムの中和反応によりシリカゾルを得て、このゾル中に磁性体を添加し、更にゲル化させる方法がある。しかし、この方法では磁性体の沈殿のために一定量の磁性体を導入することができず、更に、磁性粒子の物性を制御することができないという欠点があった。又、ケイ酸ナトリウム中に磁性粒子を添加し、ゲル化させることにより磁性ゲルを得る方法でも、目的量の磁性体を含有させることはできず、磁性粒子の物性を制御することができないという課題を有していた。
【０００６】
一方、このような磁性粒子を触媒担体として使用する時は、反応効率が良く、固定床として利用できたり、反応又は処理後に分離回収するために、その形状、物性として、球状で多孔性であり、しかも耐圧強度の大きな磁性粒子を製造する方法が望まれていた。
【０００７】
【発明が解決しようとする課題】
本発明の目的は、上記に記載した従来の課題等を解決する、すなわち、吸着剤や吸着用担体、抽出剤や抽出用担体、触媒担体等に使用できるような、形状、粒径、細孔径、強度物性を有する磁性シリカゲルの製造方法を提供するものである。
【０００８】
【課題を解決するための手段】
本発明者らは上記課題を解決するために鋭意検討を重ねた結果、一定量の磁性体をシリカゲルに含ませて磁性を付与し、その平均粒径、平均細孔径、細孔容積、ＢＥＴ比表面積といった形状、粒径、細孔特性等の物性を制御することで種々の吸着用担体、抽出用担体、触媒担体として有用となること、更にその製造方法として、Ｓｉアルコキシドポリマーと磁性体を接触させて球状化し、その後ゲル化させ、洗浄、乾燥処理を施すことで容易に製造できることを見出だし、本発明を完成させるに至った。
【０００９】
すなわち、本発明は、磁性体の含有量が全量の５〜５０重量％、平均粒径が１〜２００μｍ、平均細孔径が３〜２００ｎｍ、細孔容積が０．１〜２．５ミリリットル／ｇ、ＢＥＴ比表面積が１００〜８００ｍ２／ｇである磁性シリカゲルの製造方法である。
【００１０】
以下、本発明を詳細に説明する。
【００１１】
まず、本発明の磁性シリカゲルについて説明する。
【００１２】
本発明の磁性シリカゲルにおいて用いられる磁性体とは、磁力を与えられることで強い磁性を発生し、磁力が無くなるとその磁性も無くなる、いわゆる超常磁性を示すものである。このような性質を示すものとしては、例えば、スピネル型やプランバイト型のフェライトや、鉄，ニッケル，コバルト等を主成分とした合金が挙げられる。これらの中でも、マグネタイトやフェライトの超微粒子を水や有機溶媒に懸濁させて得られる磁性流体が好ましく用いられる。
【００１３】
ここで、本発明で使用される磁性流体について更に詳しく述べると、磁性流体とは、その直径が約１０ｎｍ以下のマグネタイトやフェライトなどの磁性微粒子を水や有機溶媒中に懸濁させたコロイド状の流体であり、以下で述べる本発明の磁性シリカゲルを製造する方法においては、磁性流体中の磁性微粒子を溶媒中に安定化させるために界面活性剤を添加して使用することもできる。
【００１４】
この磁性体をシリカゲルに含ませ、磁性を有したシリカゲルが得られるわけであるが、磁性体の含有量としては、磁性シリカゲル全量の５〜５０重量％の範囲であることが必須である。磁性体の含有量が５重量％未満である場合には、得られた磁性シリカゲルの磁性が充分ではないため、実際の用途面において反応効率、分離操作において問題となり、５０重量％を越える場合には、磁性シリカゲルの形状が球状化できなかったり、充分な多孔性を付与できなかったりといった物性面で問題があり、更に、得られる磁性シリカゲルの表面を化学的に修飾させることが困難となることがあるため好ましくない。
【００１５】
本発明の磁性シリカゲルの平均粒径の範囲としては、１〜２００μｍである。平均粒径が１μｍ未満の場合には、粒子が小さすぎるため、分離の際に時間がかかり過ぎたり、触媒用担体として固定床にて利用する際に望ましい流速が得られないなどの問題があるため、好ましくなく、２００μｍを越える場合には、実際の使用面においてゲルが破壊されたりしてその形状を維持できなるなどの問題が生じ、好ましくない。
【００１６】
本発明の磁性シリカゲルの平均細孔径の範囲としては、３〜２００ｎｍである。平均細孔径が３ｎｍ未満の場合には径が小さすぎて吸着、抽出、触媒等の担体としての反応効率が悪くなり、２００ｎｍを越える場合にはその形状保持性が悪くなるため好ましくない。
【００１７】
本発明の磁性シリカゲルの細孔容積の範囲としては、０．１〜２．５ミリリットル／ｇである。細孔容積が０．１ミリリットル／ｇ未満の場合にはその用途面である担体としての性能、特に反応効率が悪くなり、２．５ミリリットル／ｇを越える場合にはその形状保持性が悪くなるため好ましくない。
【００１８】
本発明の磁性シリカゲルのＢＥＴ比表面積の範囲としては、１００〜８００ｍ2／ｇである。ＢＥＴ比表面積が１００ｍ2／ｇ未満の場合は磁性シリカゲルの表面積が小さいため、その用途面である担体としての性能、特に反応効率が悪くなり、８００ｍ2／ｇを越える場合にはその形状保持性が悪くなるため好ましくない。
【００１９】
次に、本発明の磁性シリカゲルの製造方法について説明する。
【００２０】
本発明の磁性シリカゲル中の磁性体の出発原料としては、磁性流体であることが望ましく、その製造方法は公知の方法により実施できるが、以下の工程からなる製造方法により、更に容易に製造できる。
【００２１】
ａ）Ｓｉアルコキシドを酸で加水分解しＳｉアルコキシドポリマーを生成する工程
ｂ）アルコキシドポリマーに磁性体を加える工程
ｃ）アルコキシドポリマーと磁性体の混合溶液を水に分散させ球状化し、アルカリでゲル化する工程
ｄ）ゲルを水洗後、溶媒置換し、乾燥させる工程
ここで、本発明の製造方法において使用されるＳｉアルコキシドとしては、以下に示す製造方法において、加水分解によりポリマーを生成するものであれば特に制限なく用いることができ、例えば、Ｓｉ（ＯＣＨ3）4、Ｓｉ（ＯＣ2Ｈ5）4、Ｓｉ（Ｏ−ｎ−Ｃ3Ｈ7）4、Ｓｉ（Ｏ−ｉ−Ｃ3Ｈ7）4、Ｓｉ（Ｏ−ｎ−Ｃ4Ｈ9）4、Ｓｉ（Ｏ−ｉ−Ｃ4Ｈ9）4等を挙げることができる。また、本発明の製造方法においては、Ｓｉアルコキシド以外に、他の金属アルコキシドを添加してもよい。
【００２２】
まずＳｉのアルコキシドを酸性溶液中でゲル化しない程度に部分的に加水分解する。酸性溶液としては酸、水および有機溶媒の混合溶液が好ましい。このとき使用される酸としては、塩酸，硫酸，硝酸等の無機酸、酢酸，ギ酸等の有機酸が挙げられる。有機溶媒としては酸、水及びＳｉアルコキシドと均一に混合するものが好ましく、特にメタノール，エタノール等のアルコールが好ましい。添加する水の量はＳｉアルコキシドを部分的に加水分解する量、すなわちＳｉアルコキシド１モルに対して４モル以内であることが好ましい。加水分解反応の条件としては、Ｓｉアルコキシドの加水分解を均一に行わせるため、混合溶液を１０〜８０℃の温度の範囲で、３０分〜５時間撹拌させることで良い。
【００２３】
Ｓｉアルコキシドの加水分解終了後、次に上記Ｓｉアルコキシド溶液を重合する。重合条件としては、１０〜２００℃の温度の範囲で1 〜４８時間行なうことで良く、反応後、溶媒あるいは反応で生成したアルコール等を留去してＳｉアルコキシドポリマーを得る。Ｓｉアルコキシドポリマーの重合度は水の量、重合温度、重合時間等により制御することができる。Ｓｉアルコキシドポリマーの重合度と粘度の間には相関があり、Ｓｉアルコキシドポリマーの重合度が高くなるほど粘度は高くなる。Ｓｉアルコキシドポリマーの重合度は室温における粘度で１０センチポイズ以上でゲル化が起こらない程度であればよい。例えば、ＪＩＳ−Ｋ−７１１７−１９８７に準拠し、２５℃における粘度を測定することで確認できる。更に、磁性体を添加する際に均一に分散させるためにはＳｉアルコキシドポリマーの重合度は２５℃における粘度が２０〜１０００ｍＰａ・ｓ（＝センチポイズ）であることが好ましい。粘度がこの範囲にあればゲル化時において球状のゲルを得ることできる。
【００２４】
得られたＳｉアルコキシドポリマーはそのままあるいは有機溶媒で希釈する。Ｓｉアルコキシドポリマーを有機溶媒で希釈する場合に用いる有機溶媒としては、シクロヘキサン，ベンゼン等の炭化水素、１−ブタノール，２−ブタノ−ル，１−ペンタノール，２−ペンタノール，１−ヘキサノール，２−ヘキサノール等のアルコール等の、水にほとんど溶解しないものが好ましい。また、有機溶媒で希釈する場合のＳｉアルコキシドポリマーの濃度としては、球状のゲルを得るために希釈された溶液全量に対して２０重量％以上であることが好ましい。
【００２５】
次にＳｉアルコキシドポリマーに磁性体を加える。使用される磁性体は水又は有機溶媒に分散させて懸濁液状又は溶液状としたものを使用できる。磁性体としては、Ｓｉアルコキシドポリマーへの分散性の面から磁性流体が好ましく用いられ、この磁性流体としては、市販品等をそのままあるいは溶媒置換等を実施して用いることができる。
【００２６】
ここで、磁性体をポリマーへ分散させるにあたっては、Ｓｉアルコキシドポリマーやその希釈溶媒との混合溶液に磁性体を均一に分散させることが好ましく、このため、磁性体と混合する溶媒としては、極性の低い有機溶媒を用いると良い。この有機溶媒としては、例えば、シクロヘキサン，ベンゼン等の炭化水素、１−ブタノール，２−ブタノ−ル，１−ペンタノール，２−ペンタノール，１−ヘキサノール，２−ヘキサノール等のアルコール等が挙げられる。
【００２７】
更に、溶媒と混合された磁性体や磁性流体中の磁性体を分散させ、安定化させるために、磁性体の表面や表面付近を界面活性剤等で処理したり、界面活性剤を添加するすることが好ましい。又、磁性体をＳｉアルコキシドポリマーと混合する際に、磁性体を均一に分散させるために、Ｓｉアルコキシドポリマーは、その重合度を低くすることが好ましく、特にＳｉアルコキシドポリマーの２５℃における粘度として、２０〜２００ｍＰａ・ｓにすることが好ましい。
【００２８】
このように、磁性体の選択、Ｓｉアルコキシドポリマーの重合度、Ｓｉアルコキシドポリマーの希釈溶媒を組み合わせることにより、磁性体をＳｉアルコキシドポリマーへ均一に分散させることができる。
【００２９】
次に、Ｓｉアルコキシドポリマー又はこれに希釈溶媒を加えた混合溶液と磁性体との混合液又は混合物を、撹拌下に水中に分散させ球状化する。ここで、この混合物を分散させる水へ界面活性剤、ポリビニルアルコール等の分散剤を添加してもよい。
【００３０】
球状化後、上記記載の混合液又は混合物へ塩基性物質を添加してゲル化する。こので使用される塩基性物質としては、アンモニア，水酸化ナトリウム，水酸化カリウム等の無機塩基性化合物、アミン，尿素等の有機塩基性化合物が挙げられる。ゲル化の際にＳｉアルコキシドポリマー中のアルコキシ基を完全に加水分解するためには、ｐＨ８〜１１、３０〜１００℃の温度範囲で、１〜１０時間撹拌することで良い。
【００３１】
生成したゲルは濾過、遠心分離等により分離し、水洗後乾燥する。濾過、分離の方法としては公知の方法を用いることができる。又、洗浄の際に使用する水としては、水、温水等の通常使用できる水であれば良い。
【００３２】
更に、乾燥条件としては、ゲル内部及びゲル表面の水分を直接蒸発させるとゲルが収縮し、凝集するため以下の３つのいずれかの方法で乾燥する。
【００３３】
第一の方法は、ゲル中の水分を有機溶媒で置換した後、有機溶媒を加熱除去する方法である。ここで用いられる有機溶媒としては、水より低表面張力の溶媒が好ましく、水と任意の割合で溶け合うものが更に好ましい。ここで、水より低表面張力の溶媒とは、水のＷｉｌｈｅｌｍ法による２５℃における空気に対する表面張力が７２ｄｙｎ／ｃｍ（＝１０-3Ｎｍ-1）であることから、これより小さい表面張力を有する溶媒が選択できる。この溶媒の選択については、以下に示す第一の方法や第二の方法においても同様である。水、溶媒の留去は通常、常圧で行なうが減圧下で行なってもよい。また、この方法で、ゲルの凝集が強い場合は再度、水や有機溶媒中に分散させた後、有機溶媒に置換し、有機溶媒を加熱除去することにより、ゲルの凝集をなくすことができる。
【００３４】
第二の方法は、ゲル中の水分を有機溶媒で置換した後、有機溶媒を加熱除去する方法である。ここで用いられる有機溶媒としては、水より高沸点、低表面張力の溶媒が好ましく、水と任意の割合で溶け合うものが更に好ましい。例えば、ホルムアミド、Ｎ，Ｎ−ジメチルホルムアミド、エチレングリコール、プロピレングリコール等が挙げられる。水と任意の割合で溶け合わない溶媒の場合は水および置換溶媒と任意の割合で溶け合う溶媒と混合することにより使用できる。このような溶媒の組み合わせとしては、１−ブタノール，１−ペンタノール，２−ペンタノール，１−ヘキサノール，２−ヘキサノール等の高沸点アルコールと、メタノール，エタノール等の低沸点アルコールとの組み合わせが挙げられる。
【００３５】
第三の方法は、有機溶媒を加えて加熱して、その溶媒と共にゲル中の水を留去する方法である。ここで用いられる有機溶媒としては、水より高沸点、低表面張力の溶媒が好ましく、水と共沸するものが更に好ましい。例えば１−ブタノール，イソブチルアルコール，１−ペンタノール，２−ペンタノール，３−ペンタノール，イソアミルアルコール等のアルコール、酪酸メチル，酪酸エチル等のエステル、シクロペンタノン，３−ヘプタノン，４−ヘプタノン等のケトン等が挙げられる。水、溶媒の留去は通常、常圧で行なうが減圧下で行なってもよい。
【００３６】
また、ゲルの乾燥前や後にゲルと同容量程度の水と共にオートクレーブ中で１００〜３００℃に加熱して１〜２４時間水熱処理を行なうこともできる。この処理の際に、温度、時間、液のｐＨを変えることにより細孔分布、細孔容積を制御することができる。
【００３７】
以上の手法により、磁性体の含有量が全量の５〜５０重量％、平均粒径が1 〜２００μｍ、平均細孔径が３〜２００ｎｍ、細孔容積が０．１〜２．５ミリリットル／ｇ、比表面積が１００〜８００ｍ2／ｇである本発明の磁性シリカゲルが得られる。
【００３８】
また、本発明の磁性シリカゲルは吸着、抽出、反応用として、そのまま使用することができると共に、表面を化学修飾し、生物由来材料である、抗体、酵素等の蛋白質、ペプチドや核酸などと結合させ、免疫測定、核酸の測定等の各種の測定法やアフィニティークロマトグラフィー等の分離手段などに用いられる固定化担体として使用することもできる。
【００３９】
【実施例】
以下、実施例により本発明を具体的に説明するが、これらに実施例により本発明はなんら限定されるものでない。なお、各評価は以下に示した方法によって実施した。
【００４０】
実施例で使用した磁性流体について、その磁気ヒステリシスを振動試料型磁力計（ＶＳＭ）（理研電子製、型式：ＢＨＶ−５０）を用いて、その磁気ヒステリシスを測定したところ、超常磁性を示すものであった。
【００４１】
（１）磁性体の含有量
Ｓｉについては、磁性シリカゲルを王水により分解後、過塩素酸処理し、重量法により測定した。Ｆｅ（鉄）については、硝酸・フッ化水素酸により分解後、過塩素酸処理し、ＩＣＰ発光法により測定した。
【００４２】
（２）平均粒径
磁性シリカゲルの一部を、走査型電子顕微鏡ＩＳＩ−１３０（ＣＯＵＬＴＥＲ社製）で観察し、インタセプト法により求めた。
【００４３】
（３）平均細孔径及び細孔容積
ポアサイザ９３２０（ＭＩＣＲＯＭＥＲＩＴＩＣＳ社製）を用い、水銀圧入法により０〜２０７ＭＰａの圧力範囲で測定した。
【００４４】
（４）ＢＥＴ比表面積
ＭＯＮＯＳＯＲＢ（米国ＱＵＡＮＴＡＣＨＲＯＭＥ社製）を用い、ＢＥＴ式１点法により測定した。
【００４５】
（５）粘度
ＪＩＳ−Ｋ−７１１８−１９８７に準拠し、Ｂ型粘度計（東京計器社製、型式：ＢＨ）により、２５℃における粘度を測定した。
【００４６】
（６）ゲルの表面分析
Ｘ線光電子分光分析装置（Ｐｅｒｋｉｎ−Ｅｌｍｅｒ社製、ＥＳＣＡ５４００ＭＣ）により、表面のＦｅとＳｉを分析した。
【００４７】
（７）ゲルの内部分析
磁性体が磁性シリカゲルの内部に分布していることを以下の方法により測定した。すなわち、磁性シリカゲルをエポキシ樹脂で包埋し、ミクロトームにて切断した。ここ後、表面をＣ（カーボン）蒸着し、これをＪＣＭＡ−７３３（日本電子社製）を用いて、先ず走査型電子顕微鏡（ＳＥＭ）観察し、更にＸＭＡによるＳｉ、Ｆｅの面分析を行なった。
【００４８】
実施例１
Ｓｉ（ＯＣ2Ｈ5）4 １５０．０ｇとエタノール ６２．７ｇの混合溶液を４０℃で３０分撹拌した。この混合溶液を４０℃で撹拌しながら１／１００Ｎ−塩酸水溶液 １４．９ｇを滴下した。この溶液を１時間撹拌した後、９０℃で４時間、更に１６５℃で１２時間撹拌して留出物を除去し、Ｓｉアルコキシドポリマーを得た。この操作は窒素雰囲気中で行なった。得られたＳｉアルコキシドポリマーの粘度を前記した方法により測定したところ、粘度は室温で５０センチポイズであった。得られたＳｉアルコキシドポリマーのうち７０．０ｇを１−ペンタノール７０．０ｇに溶解した。この溶液に市販の磁性流体（（株）フェローテック製、：全量に対して、磁性体量３５重量％、界面活性剤量１０重量％、１−ブタノール溶液含有） ２０ｍｌを添加し、均一溶液を得た。この溶液を撹拌しながら８０℃の５％ポリビニルアルコール水溶液 ５６０．０ｇに投入した。３０分撹拌後、５％のＮＨ4ＯＨ水溶液 １２．５ミリリットルを加え、８０℃で３時間撹拌した。得られた懸濁液を７０℃の温水 １０００ミリリットルに投入し、固体を濾取後、温水で洗浄した。洗浄後、２−プロパノールで３回置換し、真空乾燥し、球状の磁性シリカゲルを得た。得られた磁性シリカゲルのＦｅ含有量、Ｓｉ／Ｆｅ組成（Ａ）、ＥＳＣＡによる表面組成分析からの表面Ｓｉ／Ｆｅモル比（Ｂ）、表面Ｓｉ分布を示す表面Ｓｉ／Ｆｅモル比とＳｉ／Ｆｅ組成の比（Ｂ／Ａ）、平均粒径、ＢＥＴ比表面積、水銀圧入法による平均細孔径、細孔容積等を前記した方法により測定し、その結果を表１に示した。
【００４９】
【表１】
実施例２
実施例１と同様の方法により、水洗処理まで行なったゲルに１−ブタノール
１０００ミリリットルを加え、１３０℃に加熱して水を共沸留去後、１−ブタノールを留去した。得られた粉末を真空乾燥することにより、球状の磁性シリカゲルを得た。得られた磁性シリカゲルを実施例と同様の方法により測定し、その結果を表１に示した。
【００５１】
実施例３
実施例１と同様の方法により、水洗処理まで行なったゲルをＮ，Ｎ−ジメチルホルムアミドで溶媒置換し、真空乾燥を行なうことにより、球状の磁性シリカゲルを得た。得られた磁性シリカゲルを実施例と同様の方法により測定し、その結果を表１に示した。
【００５２】
実施例４
１／１００Ｎ−塩酸水溶液の添加量を１６．８ｇにした以外は実施例１と同様にし、球状の磁性シリガゲルを得た。この時、得られたＳｉアルコキシドポリマーの粘度を前記した方法により測定したところ、粘度は室温で９５０センチポイズであった。得られた磁性シリカゲルを実施例と同様の方法により測定し、その結果を表１に示した。
【００５３】
実施例５
Ｓｉアルコキシドポリマーの希釈溶液として１−ペンタノールを３０ｇ使用した以外は実施例１と同様にし、球状の磁性シリガゲルを得た。得られた磁性シリカゲルを実施例と同様の方法により測定し、その結果を表１に示した。
【００５４】
実施例６
磁性流体の添加量を１０ｍｌにした以外は実施例１と同様にし、球状の磁性シリガゲルを得た。得られた磁性シリカゲルを実施例と同様の方法により測定し、その結果を表１に示した。
【００５５】
実施例７
磁性流体の添加量を３０ｍｌにした以外は実施例１と同様にし、球状の磁性シリカゲルを得た。得られた磁性シリカゲルを実施例と同様の方法により測定し、その結果を表１に示した。
【００５６】
比較例１
１／１００Ｎ−塩酸水溶液の添加量を１２．０ｇにした以外は実施例１と同様にした。この時、得られたＳｉアルコキシドポリマーの粘度を前記した方法により測定したところ、粘度は室温で８センチポイズであった。得られたゲルは球状にはならず、不定形であった。得られた磁性シリカゲルを平均細孔径及び細孔容積を除いて実施例と同様の方法により測定し、その結果を表１に示した。
【００５７】
比較例２
Ｓｉアルコキシドポリマーの希釈溶媒としてエタノールを使用した以外は実施例１と同様にした。この場合は磁性流体を添加したとき、磁性流体中の磁性体が沈殿してしまった。得られた磁性シリカゲルを実施例と同様の方法により測定し、その結果を表１に示した。
【００５８】
比較例３
磁性体量が３５重量％、界面活性剤の量が０重量％、溶媒が１−ブタノールである磁性流体を使用した以外は実施例１と同様にした。この場合は磁性流体を添加したとき、磁性流体中の磁性体が沈殿してしまった。得られた磁性シリカゲルを実施例と同様の方法により測定し、その結果を表１に示した。
【００５９】
比較例４
Ｓｉアルコキシドポリマーの希釈溶媒の１−ペンタノールの量を２８０ｇとした以外は実施例１と同様にした。得られたゲルは球状にはならず、不定形であった。得られた磁性シリカゲルを平均細孔径及び細孔容積を除いて実施例と同様の方法により測定し、その結果を表１に示した。
【００６０】
比較例５
１５重量％の硫酸水溶液２５ｇが入った反応容器を２０℃に設定し撹拌した。この反応容器に、撹拌しながらＳｉＯ2濃度が１２重量％のケイ酸ナトリウム水溶液を７１ｇ添加し、ケイ酸を得た。更に、この溶液に市販の磁性流体（（株）フェローテック製：全量に対して、磁性体量３５重量％、界面活性剤量１０重量％、１−ブタノール溶液含有）を２２ｍｌを添加し、１時間反応させてゲル化させ、更に８０℃に昇温して２時間反応させてゲル化を完了させた。温水にて洗浄後、乾燥させ、磁性ゲルを得た。この時、磁性流体を添加した際に磁性体が凝集して沈殿してしまい、シリカゲル中に分散しなかった。又、ゲルも球状にならず不定形であった。得られた磁性シリカゲルを平均細孔径及び細孔容積を除いて実施例と同様の方法により測定し、その結果を表１に示した。
【００６１】
比較例６
比較例５と同様にしてゲル化を完了させ、温水にて洗浄後、水に分散させ、湿式粉砕し、次いで、入り口温度１００℃、出口温度６０℃にセットしたディスク式のスプレードライヤーにより噴霧乾燥し、磁性シリカゲルを得た。この時、磁性流体を添加した際に磁性体が凝集して沈殿してしまい、シリカゲル中に分散しなかった。得られた磁性シリカゲルを実施例と同様の方法により測定し、その結果を表１に示した。
【００６２】
【発明の効果】
本発明で得られる磁性シリカゲルは球状であり、その内部に充分な量の磁性体を含有し、かつ大きな細孔容積を持ち、更にその強度も大きいことが明らかであることから吸着剤や吸着用担体、抽出剤や抽出用担体、触媒担体として好適に使用できる。また、本発明の製造方法によれば、種々の用途に応じた細孔特性を有する磁性シリカゲルを容易に製造することが可能である。[0001]
BACKGROUND OF THE INVENTION
The present invention has magnetism and strength that can be used for an adsorbent, an adsorption carrier, an extractant, an extraction carrier, a catalyst carrier, etc., and controls the content, shape, particle size, and pore characteristics of the magnetic substance. Silica gel capable of of It relates to a manufacturing method.
[0002]
[Prior art]
Conventionally, silica gel or the like is well known as an adsorbent or an adsorption solid phase carrier. However, when these are used, a centrifugal separation method or filtration with a filter or the like must be performed for the recovery. It was not a simple method. In addition, in the adsorption and extraction operations, it is necessary to separate the target adsorbate or extract from other substances, but in conventional techniques such as centrifugation, column separation, and electrophoresis Separation alone requires a long time and has a problem that it is not a simple method.
[0003]
Therefore, as a means for separating the target substance, there has been a method of recovering the target particle by adding a ferromagnetic substance to the particle and applying a magnetic field as described in JP-A-60-244251. However, in this method, even if it is desired to perform the operation in a state where the particles are uniformly dispersed in the adsorption, extraction, reaction operation, etc., the ferromagnet itself self-associates, so that the existence state of the particles can be freely set. It had the disadvantage that it could not be controlled.
[0004]
In recent years, as a method for eliminating self-association of a ferromagnetic material itself, a method using a superparamagnetic material as a magnetic material has been disclosed as described in JP-A-61-1181967. Further, as disclosed in JP-A-4-501957, it is disclosed that magnetic particles containing a superparamagnetic substance can be used as a solid phase for immobilizing a specimen and can be used for separation, analysis, etc. of proteins, cells, and DNA. . Furthermore, Japanese Patent No. 2554250 discloses a reagent carrier having a high mobility by capturing a superparamagnetic magnetic reactive substance in a gel matrix. The superparamagnetic magnetic particles described in these are particles in which a ferromagnetic material such as iron oxide is made smaller than the size of a magnetic domain necessary for maintaining permanent magnetism and contained in the particles. It has the properties shown. By utilizing this property, the particles in the solution are aggregated by applying an external magnetic field when aggregating without applying an external magnetic field when dispersing. However, even these methods cannot be obtained by a method in which the physical properties of the magnetic particles are sufficiently controlled, and the magnetic particles are sufficiently controlled according to various uses to produce optimal magnetic particles. A way to do it was desired.
[0005]
As a method for obtaining magnetic silica gel, there is a method in which a silica sol is obtained by a neutralization reaction of sodium silicate, a magnetic substance is added to the sol, and gelled, as described in JP-A-7-235407. . However, this method has a drawback that a certain amount of magnetic substance cannot be introduced due to precipitation of the magnetic substance, and further, physical properties of the magnetic particles cannot be controlled. In addition, even in a method of obtaining a magnetic gel by adding magnetic particles to sodium silicate and making it gel, a target amount of a magnetic substance cannot be contained, and physical properties of the magnetic particles cannot be controlled. Had.
[0006]
On the other hand, when using such magnetic particles as a catalyst carrier, the reaction efficiency is good, and it can be used as a fixed bed, or it is spherical and porous as its shape and physical properties for separation and recovery after reaction or treatment. In addition, there has been a demand for a method for producing magnetic particles having high pressure resistance.
[0007]
[Problems to be solved by the invention]
The object of the present invention is to solve the conventional problems described above, that is, the shape, the particle diameter, the pore diameter, which can be used for the adsorbent, the adsorption carrier, the extractant, the extraction carrier, the catalyst carrier, etc. Magnetic silica gel with strong physical properties of A manufacturing method is provided.
[0008]
[Means for Solving the Problems]
As a result of intensive studies to solve the above problems, the present inventors have added a certain amount of magnetic substance to silica gel to impart magnetism, and the average particle diameter, average pore diameter, pore volume, BET ratio Controlling physical properties such as surface area, particle size, pore characteristics, etc. makes it useful as various adsorption carriers, extraction carriers, and catalyst carriers. In addition, Si alkoxide polymer and magnetic material are contacted as a manufacturing method. It was found to be easily spheronized, then gelled, washed and dried to complete the present invention.
[0009]
That is, according to the present invention, the content of the magnetic material is 5 to 50% by weight of the total amount, the average particle size is 1 to 200 μm, the average pore size is 3 to 200 nm, and the pore volume is 0.1 to 2.5 ml / g. , BET specific surface area is 100-800m 2 / G magnetic silica gel of It is a manufacturing method.
[0010]
Hereinafter, the present invention will be described in detail.
[0011]
First, the magnetic silica gel of the present invention will be described.
[0012]
The magnetic material used in the magnetic silica gel of the present invention exhibits so-called superparamagnetism, which generates strong magnetism when given a magnetic force and disappears when the magnetic force is lost. Examples of such properties include spinel-type and plumbite-type ferrites, and alloys mainly composed of iron, nickel, cobalt, and the like. Among these, a magnetic fluid obtained by suspending ultrafine particles of magnetite or ferrite in water or an organic solvent is preferably used.
[0013]
Here, the magnetic fluid used in the present invention will be described in more detail. The magnetic fluid is a colloidal form in which magnetic fine particles such as magnetite and ferrite having a diameter of about 10 nm or less are suspended in water or an organic solvent. In the method for producing the magnetic silica gel of the present invention described below, which is a fluid, a surfactant may be added to stabilize the magnetic fine particles in the magnetic fluid in the solvent.
[0014]
This magnetic material is contained in silica gel to obtain magnetic silica gel, but the content of the magnetic material is essential to be in the range of 5 to 50% by weight of the total amount of magnetic silica gel. When the content of the magnetic substance is less than 5% by weight, the magnetic silica gel thus obtained is not sufficiently magnetized, which causes problems in reaction efficiency and separation operation in actual use, and exceeds 50% by weight. Has problems in terms of physical properties such as the shape of the magnetic silica gel cannot be spheroidized or sufficient porosity cannot be imparted, and it is difficult to chemically modify the surface of the obtained magnetic silica gel. This is not preferable.
[0015]
The range of the average particle diameter of the magnetic silica gel of the present invention is 1 to 200 μm. When the average particle size is less than 1 μm, the particles are too small, so that it takes too much time for separation, or a desirable flow rate cannot be obtained when used in a fixed bed as a catalyst support. Therefore, it is not preferable, and when it exceeds 200 μm, there is a problem in that the gel is broken on the actual use surface and the shape cannot be maintained, which is not preferable.
[0016]
The range of the average pore diameter of the magnetic silica gel of the present invention is 3 to 200 nm. If the average pore diameter is less than 3 nm, the diameter is too small and the reaction efficiency as a support for adsorption, extraction, catalyst, etc. is deteriorated, and if it exceeds 200 nm, the shape retention is deteriorated.
[0017]
The range of the pore volume of the magnetic silica gel of the present invention is 0.1 to 2.5 ml / g. When the pore volume is less than 0.1 ml / g, the performance as a carrier, particularly the reaction efficiency, is deteriorated, and when it exceeds 2.5 ml / g, the shape retention is deteriorated. Therefore, it is not preferable.
[0018]
The range of the BET specific surface area of the magnetic silica gel of the present invention is 100 to 800 m. 2 / G. BET specific surface area is 100m 2 In the case of less than / g, since the surface area of the magnetic silica gel is small, the performance as a carrier, particularly the reaction efficiency, is deteriorated. 2 When the amount exceeds / g, the shape retention is deteriorated, which is not preferable.
[0019]
Next, the manufacturing method of the magnetic silica gel of this invention is demonstrated.
[0020]
The starting material of the magnetic substance in the magnetic silica gel of the present invention is preferably a magnetic fluid, and the production method can be carried out by a known method, but can be more easily produced by a production method comprising the following steps.
[0021]
a) Step of hydrolyzing Si alkoxide with acid to produce Si alkoxide polymer
b) Adding a magnetic substance to the alkoxide polymer
c) A step of dispersing a mixed solution of an alkoxide polymer and a magnetic substance in water, spheronizing, and gelling with an alkali
d) Step of washing the gel with water, replacing the solvent, and drying
Here, the Si alkoxide used in the production method of the present invention can be used without particular limitation as long as it produces a polymer by hydrolysis in the production method shown below. For example, Si (OCH Three ) Four , Si (OC 2 H Five ) Four , Si (On-C Three H 7 ) Four , Si (O-i-C Three H 7 ) Four , Si (On-C Four H 9 ) Four , Si (O-i-C Four H 9 ) Four Etc. Moreover, in the manufacturing method of this invention, you may add another metal alkoxide other than Si alkoxide.
[0022]
First, Si alkoxide is partially hydrolyzed to an extent that it does not gel in an acidic solution. As the acidic solution, a mixed solution of an acid, water and an organic solvent is preferable. Examples of the acid used at this time include inorganic acids such as hydrochloric acid, sulfuric acid and nitric acid, and organic acids such as acetic acid and formic acid. As the organic solvent, those uniformly mixed with acid, water and Si alkoxide are preferable, and alcohols such as methanol and ethanol are particularly preferable. The amount of water to be added is preferably within 4 mol with respect to 1 mol of the Si alkoxide, that is, the amount by which the Si alkoxide is partially hydrolyzed. As a condition for the hydrolysis reaction, the mixed solution may be stirred in the temperature range of 10 to 80 ° C. for 30 minutes to 5 hours in order to uniformly hydrolyze the Si alkoxide.
[0023]
After completion of the hydrolysis of the Si alkoxide, the Si alkoxide solution is then polymerized. The polymerization conditions may be carried out in the temperature range of 10 to 200 ° C. for 1 to 48 hours. After the reaction, the solvent or alcohol produced by the reaction is distilled off to obtain a Si alkoxide polymer. The degree of polymerization of the Si alkoxide polymer can be controlled by the amount of water, polymerization temperature, polymerization time, and the like. There is a correlation between the degree of polymerization of the Si alkoxide polymer and the viscosity, and the higher the degree of polymerization of the Si alkoxide polymer, the higher the viscosity. The degree of polymerization of the Si alkoxide polymer may be such that gelation does not occur at a viscosity at room temperature of 10 centipoise or more. For example, it can confirm by measuring the viscosity in 25 degreeC based on JIS-K-7117-1987. Further, in order to uniformly disperse the magnetic substance, the degree of polymerization of the Si alkoxide polymer is preferably 20 to 1000 mPa · s (= centipoise) at 25 ° C. If the viscosity is within this range, a spherical gel can be obtained during gelation.
[0024]
The obtained Si alkoxide polymer is diluted as it is or with an organic solvent. Examples of the organic solvent used when the Si alkoxide polymer is diluted with an organic solvent include hydrocarbons such as cyclohexane and benzene, 1-butanol, 2-butanol, 1-pentanol, 2-pentanol, 1-hexanol, 2 -Those which hardly dissolve in water, such as alcohols such as hexanol, are preferred. The concentration of the Si alkoxide polymer when diluted with an organic solvent is preferably 20% by weight or more based on the total amount of the solution diluted to obtain a spherical gel.
[0025]
Next, a magnetic substance is added to the Si alkoxide polymer. The magnetic material used can be a suspension or solution dispersed in water or an organic solvent. As the magnetic material, a magnetic fluid is preferably used from the viewpoint of dispersibility in the Si alkoxide polymer. As this magnetic fluid, a commercially available product or the like can be used as it is or after solvent substitution or the like.
[0026]
Here, when dispersing the magnetic material in the polymer, it is preferable to uniformly disperse the magnetic material in a mixed solution of the Si alkoxide polymer and its dilution solvent. For this reason, the solvent mixed with the magnetic material is a polar solvent. A low organic solvent may be used. Examples of the organic solvent include hydrocarbons such as cyclohexane and benzene, alcohols such as 1-butanol, 2-butanol, 1-pentanol, 2-pentanol, 1-hexanol and 2-hexanol. .
[0027]
Furthermore, in order to disperse and stabilize the magnetic substance mixed with the solvent or the magnetic fluid, the surface of the magnetic substance or the vicinity of the surface is treated with a surfactant or the like, or a surfactant is added. It is preferable. Further, in order to uniformly disperse the magnetic substance when the magnetic substance is mixed with the Si alkoxide polymer, the Si alkoxide polymer preferably has a low degree of polymerization. In particular, the viscosity of the Si alkoxide polymer at 25 ° C. It is preferable to set it as 20-200 mPa * s.
[0028]
Thus, the magnetic substance can be uniformly dispersed in the Si alkoxide polymer by combining the selection of the magnetic substance, the polymerization degree of the Si alkoxide polymer, and the dilution solvent of the Si alkoxide polymer.
[0029]
Next, a mixed solution or a mixture of a Si alkoxide polymer or a mixed solution obtained by adding a dilution solvent to the Si alkoxide polymer and a magnetic material is dispersed in water with stirring and spheroidized. Here, you may add dispersing agents, such as surfactant and polyvinyl alcohol, to the water which disperse | distributes this mixture.
[0030]
After spheronization, a basic substance is added to the above-described mixed solution or mixture to gelate. Examples of the basic substance used here include inorganic basic compounds such as ammonia, sodium hydroxide, and potassium hydroxide, and organic basic compounds such as amine and urea. In order to completely hydrolyze the alkoxy group in the Si alkoxide polymer at the time of gelation, it may be stirred for 1 to 10 hours in a temperature range of pH 8 to 11 and 30 to 100 ° C.
[0031]
The produced gel is separated by filtration, centrifugation, etc., washed with water and dried. Known methods can be used as filtration and separation methods. The water used for washing may be water that can be normally used, such as water and warm water.
[0032]
Furthermore, as drying conditions, when the moisture inside the gel and the gel surface is directly evaporated, the gel contracts and aggregates, so that the gel is dried by any of the following three methods.
[0033]
The first method is a method in which the organic solvent is removed by heating after replacing the moisture in the gel with the organic solvent. As the organic solvent used here, a solvent having a lower surface tension than water is preferable, and an organic solvent that dissolves in water at an arbitrary ratio is more preferable. Here, the solvent having a surface tension lower than that of water means that the surface tension of air at 25 ° C. by water using the Wilhelm method is 72 dyn / cm (= 10 -3 Nm -1 Therefore, a solvent having a smaller surface tension can be selected. The selection of this solvent is the same in the first method and the second method described below. The distillation of water and solvent is usually performed at normal pressure, but may be performed under reduced pressure. Further, in this method, when the gel is strongly aggregated, the gel is dispersed again in water or an organic solvent, and is then replaced with the organic solvent, and the organic solvent is removed by heating to eliminate the gel aggregation.
[0034]
The second method is a method in which the organic solvent is removed by heating after replacing water in the gel with the organic solvent. As the organic solvent used here, a solvent having a higher boiling point and lower surface tension than water is preferable, and an organic solvent that is soluble in water at an arbitrary ratio is more preferable. For example, formamide, N, N-dimethylformamide, ethylene glycol, propylene glycol and the like can be mentioned. In the case of a solvent that does not dissolve in water at an arbitrary ratio, the solvent can be used by mixing with water and a solvent that dissolves at an arbitrary ratio with a substitution solvent. Examples of such solvent combinations include a combination of a high boiling alcohol such as 1-butanol, 1-pentanol, 2-pentanol, 1-hexanol, and 2-hexanol and a low boiling alcohol such as methanol and ethanol. It is done.
[0035]
The third method is a method in which an organic solvent is added and heated, and water in the gel is distilled off together with the solvent. The organic solvent used here is preferably a solvent having a higher boiling point and lower surface tension than water, and more preferably an azeotropic solvent with water. For example, alcohols such as 1-butanol, isobutyl alcohol, 1-pentanol, 2-pentanol, 3-pentanol and isoamyl alcohol, esters such as methyl butyrate and ethyl butyrate, cyclopentanone, 3-heptanone and 4-heptanone And the like. The distillation of water and solvent is usually performed at normal pressure, but may be performed under reduced pressure.
[0036]
Moreover, it can also heat-heat-treat for 1 to 24 hours by heating to 100-300 degreeC in an autoclave with the water about the same capacity | capacitance as a gel before and after drying of a gel. During this treatment, the pore distribution and pore volume can be controlled by changing the temperature, time, and pH of the liquid.
[0037]
By the above method, the content of the magnetic material is 5 to 50% by weight of the total amount, the average particle size is 1 to 200 μm, the average pore size is 3 to 200 nm, the pore volume is 0.1 to 2.5 ml / g, Specific surface area of 100-800m 2 / G of the magnetic silica gel of the present invention is obtained.
[0038]
In addition, the magnetic silica gel of the present invention can be used as it is for adsorption, extraction and reaction, and its surface is chemically modified to bind to biological materials such as antibodies, enzymes and other proteins, peptides and nucleic acids. It can also be used as an immobilization carrier used in various measurement methods such as immunoassay and nucleic acid measurement, and separation means such as affinity chromatography.
[0039]
【Example】
EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited to an Example at all by these. In addition, each evaluation was implemented by the method shown below.
[0040]
Regarding the magnetic fluid used in the examples, the magnetic hysteresis was measured using a vibrating sample magnetometer (VSM) (manufactured by Riken Electronics Co., Ltd., model: BHV-50). there were.
[0041]
(1) Content of magnetic substance
For Si, magnetic silica gel was decomposed with aqua regia, treated with perchloric acid, and measured by a gravimetric method. Fe (iron) was decomposed with nitric acid / hydrofluoric acid, treated with perchloric acid, and measured by the ICP emission method.
[0042]
(2) Average particle size
A part of the magnetic silica gel was observed with a scanning electron microscope ISI-130 (manufactured by COULTER) and determined by the intercept method.
[0043]
(3) Average pore diameter and pore volume
Using a pore sizer 9320 (manufactured by MICROMERITICS), measurement was performed in a pressure range of 0 to 207 MPa by a mercury intrusion method.
[0044]
(4) BET specific surface area
MONOSORB (manufactured by QUANTACHROME, USA) was used, and measurement was performed by the BET one-point method.
[0045]
(5) Viscosity
Based on JIS-K-7118-1987, the viscosity at 25 ° C. was measured with a B-type viscometer (manufactured by Tokyo Keiki Co., Ltd., model: BH).
[0046]
(6) Gel surface analysis
Surface Fe and Si were analyzed with an X-ray photoelectron spectroscopic analyzer (Perkin-Elmer, ESCA5400MC).
[0047]
(7) Internal analysis of gel
The distribution of the magnetic material inside the magnetic silica gel was measured by the following method. That is, magnetic silica gel was embedded with an epoxy resin and cut with a microtome. After that, C (carbon) was vapor-deposited on the surface, and this was first observed with a scanning electron microscope (SEM) using JCMA-733 (manufactured by JEOL Ltd.), and further surface analysis of Si and Fe by XMA was performed. .
[0048]
Example 1
Si (OC 2 H Five ) Four A mixed solution of 150.0 g and ethanol 62.7 g was stirred at 40 ° C. for 30 minutes. While stirring this mixed solution at 40 ° C., 14.9 g of a 1 / 100N aqueous hydrochloric acid solution was added dropwise. After stirring this solution for 1 hour, it stirred at 90 degreeC for 4 hours, and also at 165 degreeC for 12 hours, and the distillate was removed, and Si alkoxide polymer was obtained. This operation was performed in a nitrogen atmosphere. When the viscosity of the obtained Si alkoxide polymer was measured by the method described above, the viscosity was 50 centipoise at room temperature. 70.0 g of the obtained Si alkoxide polymer was dissolved in 70.0 g of 1-pentanol. To this solution, 20 ml of a commercially available ferrofluid (manufactured by Ferrotec Co., Ltd .: 35% by weight of magnetic substance, 10% by weight of surfactant, containing 1-butanol solution) is added to the total amount, and a uniform solution is obtained. Obtained. This solution was added to 560.0 g of a 5% polyvinyl alcohol aqueous solution at 80 ° C. while stirring. After stirring for 30 minutes, 5% NH Four 12.5 mL of OH aqueous solution was added, and it stirred at 80 degreeC for 3 hours. The obtained suspension was poured into 1000 ml of warm water at 70 ° C., and the solid was collected by filtration and washed with warm water. After washing, it was replaced with 2-propanol three times and vacuum-dried to obtain spherical magnetic silica gel. Fe content of the obtained magnetic silica gel, Si / Fe composition (A), surface Si / Fe molar ratio (B) from surface composition analysis by ESCA, surface Si / Fe molar ratio and Si / Fe showing surface Si distribution The composition ratio (B / A), average particle diameter, BET specific surface area, average pore diameter by mercury porosimetry, pore volume and the like were measured by the methods described above, and the results are shown in Table 1.
[0049]
[Table 1]
Example 2
In the same manner as in Example 1, 1-butanol was applied to the gel that had been subjected to washing treatment.
1000 ml was added and heated to 130 ° C. to distill off water azeotropically, and then 1-butanol was distilled off. The obtained powder was vacuum-dried to obtain spherical magnetic silica gel. The obtained magnetic silica gel was measured by the same method as in the Examples, and the results are shown in Table 1.
[0051]
Example 3
In the same manner as in Example 1, the gel which had been subjected to the water washing treatment was substituted with N, N-dimethylformamide and vacuum-dried to obtain spherical magnetic silica gel. The obtained magnetic silica gel was measured by the same method as in the Examples, and the results are shown in Table 1.
[0052]
Example 4
A spherical magnetic silica gel was obtained in the same manner as in Example 1 except that the addition amount of the 1 / 100N hydrochloric acid aqueous solution was changed to 16.8 g. At this time, when the viscosity of the obtained Si alkoxide polymer was measured by the method described above, the viscosity was 950 centipoise at room temperature. The obtained magnetic silica gel was measured by the same method as in the Examples, and the results are shown in Table 1.
[0053]
Example 5
A spherical magnetic silica gel was obtained in the same manner as in Example 1 except that 30 g of 1-pentanol was used as a diluted solution of the Si alkoxide polymer. The obtained magnetic silica gel was measured by the same method as in the Examples, and the results are shown in Table 1.
[0054]
Example 6
A spherical magnetic silica gel was obtained in the same manner as in Example 1 except that the amount of magnetic fluid added was 10 ml. The obtained magnetic silica gel was measured by the same method as in the Examples, and the results are shown in Table 1.
[0055]
Example 7
A spherical magnetic silica gel was obtained in the same manner as in Example 1 except that the amount of magnetic fluid added was 30 ml. The obtained magnetic silica gel was measured by the same method as in the Examples, and the results are shown in Table 1.
[0056]
Comparative Example 1
Example 1 was repeated except that the addition amount of 1 / 100N hydrochloric acid aqueous solution was 12.0 g. At this time, when the viscosity of the obtained Si alkoxide polymer was measured by the method described above, the viscosity was 8 centipoise at room temperature. The obtained gel was not spherical and was indefinite. The obtained magnetic silica gel was measured by the same method as in Examples except for the average pore diameter and pore volume, and the results are shown in Table 1.
[0057]
Comparative Example 2
Example 1 was repeated except that ethanol was used as a diluting solvent for the Si alkoxide polymer. In this case, when the magnetic fluid was added, the magnetic substance in the magnetic fluid was precipitated. The obtained magnetic silica gel was measured by the same method as in the Examples, and the results are shown in Table 1.
[0058]
Comparative Example 3
Example 1 was repeated except that a magnetic fluid having a magnetic substance amount of 35% by weight, a surfactant amount of 0% by weight and a solvent of 1-butanol was used. In this case, when the magnetic fluid was added, the magnetic substance in the magnetic fluid was precipitated. The obtained magnetic silica gel was measured by the same method as in the Examples, and the results are shown in Table 1.
[0059]
Comparative Example 4
Example 1 was repeated except that the amount of 1-pentanol as a diluting solvent for the Si alkoxide polymer was changed to 280 g. The obtained gel was not spherical and was indefinite. The obtained magnetic silica gel was measured by the same method as in Examples except for the average pore diameter and pore volume, and the results are shown in Table 1.
[0060]
Comparative Example 5
A reaction vessel containing 25 g of a 15 wt% aqueous sulfuric acid solution was set at 20 ° C. and stirred. In this reaction vessel, while stirring, SiO 2 71 g of a sodium silicate aqueous solution having a concentration of 12% by weight was added to obtain silicic acid. Further, 22 ml of a commercially available ferrofluid (manufactured by Ferrotec Co., Ltd .: 35% by weight of magnetic substance, 10% by weight of surfactant, containing 1-butanol solution) is added to this solution. Gelation was completed by reacting for a period of time and then raising the temperature to 80 ° C. and reacting for 2 hours. After washing with warm water and drying, a magnetic gel was obtained. At this time, when the magnetic fluid was added, the magnetic material aggregated and precipitated and did not disperse in the silica gel. Further, the gel was not spherical and was indefinite. The obtained magnetic silica gel was measured by the same method as in Examples except for the average pore diameter and pore volume, and the results are shown in Table 1.
[0061]
Comparative Example 6
In the same manner as in Comparative Example 5, gelation was completed, washed with warm water, dispersed in water, wet pulverized, and then spray-dried with a disk-type spray dryer set at an inlet temperature of 100 ° C and an outlet temperature of 60 ° C. As a result, magnetic silica gel was obtained. At this time, when the magnetic fluid was added, the magnetic material aggregated and precipitated and did not disperse in the silica gel. The obtained magnetic silica gel was measured by the same method as in the Examples, and the results are shown in Table 1.
[0062]
【The invention's effect】
The present invention Obtained in Magnetic silica gel has a spherical shape, contains a sufficient amount of magnetic substance inside, has a large pore volume, and further has a high strength. It can be suitably used as an extraction carrier and a catalyst carrier. Moreover, according to the production method of the present invention, it is possible to easily produce magnetic silica gel having pore characteristics corresponding to various uses.
Claims (4)
ａ）Ｓｉアルコキシドを酸で加水分解し、２５℃において２０〜１０００ｍＰａ・ｓの粘度を有するＳｉアルコキシドポリマーを生成する工程
ｂ）アルコキシドポリマーに磁性体を加える工程
ｃ）アルコキシドポリマーと磁性体の混合物を水と接触させて球状化し、さらにアルカリと接触させてゲル化する工程
ｄ）ゲルを洗浄後、溶媒置換し、乾燥させる工程 The production process of magnetic silica gel comprises the following steps , the magnetic substance content is 5 to 50% by weight of the total amount, the average particle size is 1 to 200 μm, the average pore size is 3 to 200 nm, the pore volume Of magnetic silica gel having a BET specific surface area of 100 to 800 m 2 / g .
a) Hydrolysis of Si alkoxide with acid to produce Si alkoxide polymer having a viscosity of 20 to 1000 mPa · s at 25 ° C. b) Step of adding magnetic substance to alkoxide polymer c) Mixture of alkoxide polymer and magnetic substance Step of spheroidizing by contacting with water and further gelling by contacting with alkali d) Step of washing the gel, replacing the solvent, and drying
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| ES2182731T1 (en) * | 1999-10-18 | 2003-03-16 | Ferx Inc | MAGNETIC VEHICLE TO DIRECT A BIOLOGICALLY ACTIVE AGENT TO A SPECIFIC SITE. |
| AU2001263800B2 (en) * | 2000-03-24 | 2006-03-09 | Qiagen Gmbh | Porous ferro- or ferrimagnetic glass particles for isolating molecules |
| KR100406851B1 (en) * | 2001-08-21 | 2003-11-21 | 이종협 | Production Method of Mesoporous Silica comprising Magnetite used for Heavy Metal Ion Adsorbents |
| JP3653572B2 (en) * | 2001-09-06 | 2005-05-25 | 福井県 | Method for producing porous photocatalyst |
| DE10355409A1 (en) * | 2003-11-25 | 2005-06-30 | Magnamedics Gmbh | Spherical, magnetic silica gel carriers with increased surface area for the purification of nucleic acids |
| JP4912190B2 (en) * | 2007-03-15 | 2012-04-11 | 独立行政法人科学技術振興機構 | Method for producing porous silica gel and silica glass |
| JP5443723B2 (en) * | 2008-10-02 | 2014-03-19 | Ｄｏｗａエレクトロニクス株式会社 | Magnetic particles, carrier core material, method for producing the same, carrier and developer |
| KR100995981B1 (en) | 2008-12-30 | 2010-11-23 | 서울대학교산학협력단 | Fabrication method of nano-fenton system waste water treatment reagent Using magnetic nanoparticle/polymer core-shell nanoparticles |
| JP5658666B2 (en) * | 2009-07-29 | 2015-01-28 | 株式会社東芝 | Oil adsorbent |
| ES2365082B1 (en) * | 2010-03-08 | 2012-08-08 | Consejo Superior De Investigaciones Científicas (Csic) | PROCEDURE FOR OBTAINING MATERIALS WITH SUPERPARAMAGNETIC BEHAVIOR |
| WO2013184214A1 (en) * | 2012-05-07 | 2013-12-12 | Massachusetts Institute Of Technology | Compositions, methods, and systems for separating carbon-based nanostructures |
| JP6262449B2 (en) * | 2013-05-17 | 2018-01-17 | 学校法人慈恵大学 | Aggregates of radioactive cesium decontamination particles, method for producing the same, and method for decontamination of radioactive cesium |
| JP2015024407A (en) * | 2014-09-12 | 2015-02-05 | 株式会社東芝 | Oil adsorbent and method for manufacturing oil adsorbent |
| CN113559830B (en) * | 2021-08-11 | 2023-08-18 | 天津博蕴纯化装备材料科技有限公司 | Magnetic porous spherical silica gel microsphere and preparation method thereof |
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