JP3539678B2 - Method for producing spherical particles - Google Patents
Method for producing spherical particles Download PDFInfo
- Publication number
- JP3539678B2 JP3539678B2 JP2000181265A JP2000181265A JP3539678B2 JP 3539678 B2 JP3539678 B2 JP 3539678B2 JP 2000181265 A JP2000181265 A JP 2000181265A JP 2000181265 A JP2000181265 A JP 2000181265A JP 3539678 B2 JP3539678 B2 JP 3539678B2
- Authority
- JP
- Japan
- Prior art keywords
- spherical particles
- medium
- group
- particles
- viscous fluid
- 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
- 239000012798 spherical particle Substances 0.000 title claims description 75
- 238000004519 manufacturing process Methods 0.000 title claims description 46
- 239000012530 fluid Substances 0.000 claims description 34
- 238000000034 method Methods 0.000 claims description 27
- 229940057995 liquid paraffin Drugs 0.000 claims description 15
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- 239000003960 organic solvent Substances 0.000 claims description 9
- 229920002545 silicone oil Polymers 0.000 claims description 9
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 7
- 125000005843 halogen group Chemical group 0.000 claims description 6
- 150000003868 ammonium compounds Chemical class 0.000 claims description 5
- 150000001450 anions Chemical class 0.000 claims description 4
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical group C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 claims description 3
- 125000004183 alkoxy alkyl group Chemical group 0.000 claims description 3
- 125000004181 carboxyalkyl group Chemical group 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 125000003386 piperidinyl group Chemical group 0.000 claims description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 33
- 239000002245 particle Substances 0.000 description 31
- 238000006116 polymerization reaction Methods 0.000 description 17
- 150000001875 compounds Chemical class 0.000 description 15
- 239000000178 monomer Substances 0.000 description 13
- 238000005054 agglomeration Methods 0.000 description 12
- 230000002776 aggregation Effects 0.000 description 12
- 238000003756 stirring Methods 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 9
- NJSSICCENMLTKO-HRCBOCMUSA-N [(1r,2s,4r,5r)-3-hydroxy-4-(4-methylphenyl)sulfonyloxy-6,8-dioxabicyclo[3.2.1]octan-2-yl] 4-methylbenzenesulfonate Chemical compound C1=CC(C)=CC=C1S(=O)(=O)O[C@H]1C(O)[C@@H](OS(=O)(=O)C=2C=CC(C)=CC=2)[C@@H]2OC[C@H]1O2 NJSSICCENMLTKO-HRCBOCMUSA-N 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 7
- 239000011347 resin Substances 0.000 description 7
- 229920005989 resin Polymers 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- LXEKPEMOWBOYRF-UHFFFAOYSA-N [2-[(1-azaniumyl-1-imino-2-methylpropan-2-yl)diazenyl]-2-methylpropanimidoyl]azanium;dichloride Chemical compound Cl.Cl.NC(=N)C(C)(C)N=NC(C)(C)C(N)=N LXEKPEMOWBOYRF-UHFFFAOYSA-N 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 239000003456 ion exchange resin Substances 0.000 description 6
- 229920003303 ion-exchange polymer Polymers 0.000 description 6
- 239000000741 silica gel Substances 0.000 description 6
- 229910002027 silica gel Inorganic materials 0.000 description 6
- 239000002250 absorbent Substances 0.000 description 5
- 239000000654 additive Substances 0.000 description 5
- 239000003999 initiator Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 238000010557 suspension polymerization reaction Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 229910001873 dinitrogen Inorganic materials 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 239000000499 gel Substances 0.000 description 4
- 239000012797 inorganic spherical particle Substances 0.000 description 4
- 239000010687 lubricating oil Substances 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000003505 polymerization initiator Substances 0.000 description 4
- 230000000379 polymerizing effect Effects 0.000 description 4
- -1 siloxane structure Chemical group 0.000 description 4
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 3
- 239000001856 Ethyl cellulose Substances 0.000 description 3
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 3
- 239000003957 anion exchange resin Substances 0.000 description 3
- 238000007720 emulsion polymerization reaction Methods 0.000 description 3
- 235000019325 ethyl cellulose Nutrition 0.000 description 3
- 229920001249 ethyl cellulose Polymers 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- 239000000375 suspending agent Substances 0.000 description 3
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- IYFATESGLOUGBX-YVNJGZBMSA-N Sorbitan monopalmitate Chemical compound CCCCCCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O IYFATESGLOUGBX-YVNJGZBMSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 239000003995 emulsifying agent Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000012188 paraffin wax Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 235000019353 potassium silicate Nutrition 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000001570 sorbitan monopalmitate Substances 0.000 description 2
- 235000011071 sorbitan monopalmitate Nutrition 0.000 description 2
- 229940031953 sorbitan monopalmitate Drugs 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- NHRMYURRBPCILW-UHFFFAOYSA-N (3-ethenylphenyl)methyl-[2-[(3-ethenylphenyl)methylazaniumyl]ethyl]azanium;dichloride Chemical compound [Cl-].[Cl-].C=CC1=CC=CC(C[NH2+]CC[NH2+]CC=2C=C(C=C)C=CC=2)=C1 NHRMYURRBPCILW-UHFFFAOYSA-N 0.000 description 1
- QCTKMTRBYIWNQO-UHFFFAOYSA-N (4-ethenylphenyl)methyl-[1-[(4-ethenylphenyl)methylazaniumyl]propan-2-yl]azanium;dichloride Chemical compound [Cl-].[Cl-].C=1C=C(C=C)C=CC=1C[NH2+]C(C)C[NH2+]CC1=CC=C(C=C)C=C1 QCTKMTRBYIWNQO-UHFFFAOYSA-N 0.000 description 1
- POSHRBMOTNCWKL-UHFFFAOYSA-N (4-ethenylphenyl)methyl-[2-[(4-ethenylphenyl)methylazaniumyl]ethyl]azanium;dichloride Chemical compound [Cl-].[Cl-].C1=CC(C=C)=CC=C1C[NH2+]CC[NH2+]CC1=CC=C(C=C)C=C1 POSHRBMOTNCWKL-UHFFFAOYSA-N 0.000 description 1
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 1
- AVGQTJUPLKNPQP-UHFFFAOYSA-N 1,1,1-trichloropropane Chemical compound CCC(Cl)(Cl)Cl AVGQTJUPLKNPQP-UHFFFAOYSA-N 0.000 description 1
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 1
- SMBRHGJEDJVDOB-UHFFFAOYSA-N 2-methylpropanimidamide;dihydrochloride Chemical compound Cl.Cl.CC(C)C(N)=N SMBRHGJEDJVDOB-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- OSDWBNJEKMUWAV-UHFFFAOYSA-N Allyl chloride Chemical compound ClCC=C OSDWBNJEKMUWAV-UHFFFAOYSA-N 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M Thiocyanate anion Chemical compound [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000004931 aggregating effect Effects 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 150000001449 anionic compounds Chemical class 0.000 description 1
- 229950005499 carbon tetrachloride Drugs 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 description 1
- 125000000068 chlorophenyl group Chemical group 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- IOMDIVZAGXCCAC-UHFFFAOYSA-M diethyl-bis(prop-2-enyl)azanium;chloride Chemical compound [Cl-].C=CC[N+](CC)(CC)CC=C IOMDIVZAGXCCAC-UHFFFAOYSA-M 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
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- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
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- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
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- 150000002513 isocyanates Chemical class 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
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- 125000002960 margaryl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- BVWUEIUNONATML-UHFFFAOYSA-N n-benzylethenamine Chemical group C=CNCC1=CC=CC=C1 BVWUEIUNONATML-UHFFFAOYSA-N 0.000 description 1
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- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- OXUCOTSGWGNWGC-UHFFFAOYSA-N octane Chemical compound CCCCCCC[CH2-] OXUCOTSGWGNWGC-UHFFFAOYSA-N 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- HVAMZGADVCBITI-UHFFFAOYSA-M pent-4-enoate Chemical compound [O-]C(=O)CCC=C HVAMZGADVCBITI-UHFFFAOYSA-M 0.000 description 1
- 125000002958 pentadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- AEIAMRMQKCPGJR-UHFFFAOYSA-N propane-1,2-diamine;dihydrochloride Chemical compound Cl.Cl.CC(N)CN AEIAMRMQKCPGJR-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
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- 238000004062 sedimentation Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- 230000002195 synergetic effect Effects 0.000 description 1
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- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 1
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Description
【０００１】
【発明の属する技術分野】
本発明は、球状粒子の製造方法に関する。
【０００２】
【従来の技術】
球状粒子は、その形態が表面積を増大させることや、取り扱い性に優れることから、様々な工業製品に広く用いられており、現在では化学工業に欠くことができないものとなっている。代表的な球状粒子としては、例えば、有機系球状粒子としてイオン交換樹脂、吸水性樹脂等や、無機系球状粒子としてシリカゲル等の球状粒子が挙げられる。
【０００３】
このような球状粒子を製造する方法としては、例えば、媒体中への分散や、媒体中での重合体の形成により分散体を生成させる方法が簡易であり、また、均一な形状と大きさの球状粒子を生成させるのに好適な方法であることから工業的に広く行われている。しかしながら、分散体として生成する球状粒子が凝集性を有したり、球状粒子同士が粘着したりする場合には、塊状化して均一な製品を得ることができないという問題があった。そこで、媒体中で球状粒子を製造する場合には、懸濁剤等を用いたり、強い攪拌を行ったりして生成する球状粒子の塊状化を防止しているが、このような方法では、充分に均一な球状粒子とはならない場合や、懸濁剤の使用や強い攪拌を伴うため、高品質な工業製品を得るために適用できない場合もあった。また、製造コストの面でも改善する余地があるものであった。
【０００４】
特開平４−３１１７１０号公報には、水不混和性不活性有機液体中、少なくとも１種のジアリルジアルキルアンモニウムクロライド等の水溶性モノマーの水溶液の液滴を含む二相システムを調製し、沈殿防止剤及び乳化剤の組み合わせの存在下で重合を行うことにより、ホモポリマー又はコポリマーを調製する方法が開示されている。この調製方法では、粒径分布の少ないある程度均一な球状粒子を得ることができると考えられた。しかしながら、沈殿防止剤及び乳化剤を組み合わせることにより球状粒子の塊状化を防止するものであるため、高品質な工業製品を得るために適用できない場合もあり、また、これらの添加剤を用いることから製造コストの面でも改善する余地があるものであった。
【０００５】
特公平２−４１５２８号公報には、ジアリルジアルキルアンモニウムクロライドと、ジアリルアンモニウム基を同一分子内に少なくとも２個以上有する化合物若しくはパラ（又はメタ）ビニルフェニルメチルアンモニウム基を同一分子内に少なくとも２個以上有する化合物又はこれらの混合物を含む水溶液を、水に不溶性の有機溶媒中に懸濁させて共重合体を製造するに際し、親水性基と疎水性基とを有する共重合体を分散剤として用いる球状陰イオン交換樹脂の製造方法が開示されている。この製造方法でも、ある程度均一な球状粒子を得ることができると考えられた。しかしながら、この製造方法でも同様に、共重合体を分散剤として用いることから、高品質な工業製品を得るために適用できない場合もあり、また、製造コストの面でも改善する余地があるものであった。
【０００６】
【発明が解決しようとする課題】
本発明は、上記現状に鑑みてなされたものであり、均一で高品質な球状粒子を廉価にかつ簡便に、しかも、高収率で製造する方法を提供することを目的とするものである。
【０００７】
【課題を解決するための手段】
本発明は、媒体中で球状粒子を製造する方法であって、上記媒体は、粘性流体を含むものである球状粒子の製造方法である。
本発明者らは、球状粒子の製造方法についての問題点を綿密に精査したうえで鋭意研究を行った結果、上述した製造方法が生成する球状粒子の塊状化を防止して均一で高品質な製品を得ることができるとともに、廉価にかつ簡便に、しかも、高収率で製造することができることから、有機系球状粒子としてイオン交換樹脂、吸水性樹脂等や、無機系球状粒子としてシリカゲル等の球状粒子を含む工業製品に好適に適用することができるという劇的な効果が生じる事実に遭遇し、本発明に到達したものである。
以下に、本発明を詳述する。
【０００８】
本発明は、媒体中で球状粒子を製造する方法である。このような製造方法としては特に限定されるものではなく、工業的に行われる媒体中での球状粒子の製造に広く適用することができる。例えば、有機系球状粒子を製造する場合には、媒体中で単量体の重合を行う方法や、重合体を媒体中に分散する方法等に適用することができ、また、無機系球状粒子を製造する場合には、媒体中に無機物質を分散する方法等に適用することができる。
【０００９】
上記球状粒子の製造方法の具体例としては、例えば、媒体中で単量体の重合を行う方法として乳化重合や懸濁重合により媒体中でイオン交換樹脂や吸水性樹脂等の球状粒子を製造する方法や、媒体中に無機物質を分散する方法として媒体中に水ガラスを滴下してシリカゲル粒子を製造する方法等が挙げられる。
【００１０】
上記媒体中で単量体の重合を行う方法では、通常、単量体の液滴を媒体中に分散させて重合を行うことになる。この場合、単量体の液滴と媒体との極性としては特に限定されず、例えば、単量体の液滴が媒体よりも低極性のものであっても、高極性のものであってもよい。単量体の液滴が媒体よりも高極性のものであるときには逆相重合となり、この場合は生成する球状粒子同士の粘着性が高く塊状化しやすい場合がある。このような場合に、本発明の製造方法が特に好適に適用されることになる。逆相重合の形態としては、例えば、媒体として水不溶性有機溶剤を用い、水溶性の単量体の液滴又は水溶性の単量体を含む水溶液の液滴を該媒体中に分散させて懸濁重合等を行う場合等がある。
【００１１】
上記媒体中で球状粒子を製造する方法における重合条件や分散条件、単量体、重合開始剤や添加剤等の使用可能な原料等としては、製造する製品の用途や性能、品質等により適宜設定すればよく、特に限定されるものではない。例えば、通常の工業的な球状粒子の製造方法に本発明の製造方法を適用すればよい。
【００１２】
本発明においては、媒体は、粘性流体を含むものである。これにより、生成する球状粒子の凝集性を抑制したり、球状粒子同士の粘着を抑制したりして球状粒子の塊状化を抑制することができることになる。従って、均一で高品質な球状粒子を廉価にかつ簡便に、しかも、高収率で製造することができることになる。
【００１３】
本発明がなぜこのような作用効果を奏するのかについては必ずしも定かではないが、例えば、以下のような理由が挙げられ、これらの相乗的な作用によるためと考えられる。
（１）媒体中で生成する球状粒子は、通常、凝集性を有したり、球状粒子同士の粘着性を有したりして安定的に媒体中で存在しにくいものであるが、媒体が粘性流体を含むものであることにより、球状粒子の周囲に粘性流体が存在することに起因して、球状粒子の凝集性や粘着性を抑制して媒体中での安定性を向上するとともに、媒体の粘性が高くなることによっても球状粒子同士が凝集することを抑制することができること、（２）生成する球状粒子の塊状化を防止するための懸濁剤等の添加剤の使用を抑制し、また、媒体中の粘性流体は球状粒子を媒体から分離するときに容易に取り除くことができることや、強い攪拌を不要とすることができることに起因して、得られる製品をより高品質なものとすることができること、（３）添加剤の使用が抑制され、また、強い攪拌が不要であることから、球状粒子の塊状化の防止を簡便に行うことができ、製造コストを抑制することができること。
【００１４】
上記粘性流体とは、媒体中での球状粒子の製造において通常用いられる媒体よりも常温で高い粘性を有する流体であり、本発明では、媒体中において、生成する球状粒子の塊状化を防止することができるような粘性を有する流体を意味する。例えば、媒体として水を用いる場合には、水よりも常温で粘性が高いものであり、媒体として有機溶剤を用いる場合には、使用する有機溶剤よりも常温で粘性が高いものであることが必須である。また、媒体に添加する前の性状が固形であっても、媒体に添加し、必要により攪拌や加温等を行うことにより流体となり、媒体の粘性を上げる作用を有するものを用いることもできる。このようなものとしては、例えば、固形のパラフィンワックスや、シリコーンオイルの２次製品であるグリース等が挙げられる。尚、本発明の粘性流体は、例えば、２５〜５０℃で媒体より粘性が高ければよく、重合温度等の高温での粘性は特に限定されるものではない。尚、粘性は、常温での粘度や動粘度等により測定することができる。
【００１５】
上記粘性流体の種類としては、球状粒子の生成において不活性であるものが好ましく、例えば、流動パラフィン及び／又はシリコーンオイルを含むものであることが好ましい。これにより、本発明の作用効果を充分に発揮させることができ、媒体中で単量体の重合を行う方法や、重合体を媒体中に分散する方法等の有機系球状粒子の製造や、媒体中に無機物質を分散する方法等の無機系球状粒子の製造に好適に適用することができることになる。また、上記粘性流体が流動パラフィン及び／又はシリコーンオイルを含むものである場合、本発明の効果を損なうことがない限り、その他の粘性流体を含んでいてもよい。
【００１６】
上記流動パラフィンとしては、常温で液状のパラフィンであれば特に限定されず、例えば、炭素原子数が１２〜５０の液状飽和炭化水素等が挙げられ、ｎ−パラフィン、イソパラフィン、ナフテンのいずれであってもよい。また、市販品として、例えば、モレスコホワイト、モレスコバイオレス（いずれも商品名、松村石油研究所社製）、スタノール、クリストール、エッソホワイトオイル、ピュアレックス（いずれも商品名、エッソ石油社製）等を用いることができる。これらは単独で用いてもよく、２種以上を併用してもよい。これらの中でも、４０℃での動粘度が５〜５００ｍｍ2 ／ｓであるものを好適に用いることができる。より好ましくは、１０〜１００ｍｍ2 ／ｓである。
【００１７】
上記シリコーンオイルとしては、常温で液状のシロキサン構造を有するものであれば特に限定されず、例えば、ジメチルシリコーンオイル等のポリシロキサンオイル等が挙げられ、水酸基、カルボキシル基、アミノ基、エポキシ基、シアノ基、メルカプト基、トリフルオロプロピル基、クロルフェニル基、長鎖アルキル基等の官能基を有したり、ポリエーテルやアルコール等で変性したりした変性シリコーンオイルも用いることができる。これらは単独で用いてもよく、２種以上を併用してもよい。これらの中でも、４０℃での動粘度が５〜１０００００ｍｍ2 ／ｓであるものを好適に用いることができる。より好ましくは、１０〜１００００ｍｍ2 ／ｓである。
【００１８】
上記粘性流体としてはまた、流動パラフィン及び／又はシリコーンオイルを含むもの以外にも、潤滑油として用いることができるものを含むものも好ましい。
上記潤滑油として用いることができるものとしては特に限定されず、例えば、ジエステル系、ポリアルキレングリコール系、ハロゲン化炭化水素系等の合成潤滑油や、石油系潤滑油、脂肪油等の液状の潤滑油等が挙げられる。これらは単独で用いてもよく、２種以上を併用してもよい。これらの中でも、４０℃での動粘度が５〜１０００００ｍｍ2 ／ｓであるものを好適に用いることができる。より好ましくは、１０〜１００００ｍｍ2 ／ｓである。
【００１９】
上記粘性流体の媒体中における含有量は、球状粒子の凝集性や粘着性、媒体の種類、製造方法等により適宜設定すればよく、特に限定されるものではない。例えば、乳化重合や懸濁重合により媒体中でイオン交換樹脂や吸水性樹脂等の球状粒子を製造する方法では、粘性流体を含む媒体全量に対して、０．１〜５０重量％とすることが好ましく、媒体中に水ガラスを滴下してシリカゲル粒子を製造する方法では、粘性流体を含む媒体全量に対して、１０〜９５重量％とすることが好ましい。また、系中の粘性流体の量を適宜調節することで球状粒子の粒径（粒子サイズ）を調節できることになる。
【００２０】
本発明の製造方法において、上記粘性流体を含む媒体の粘度としては特に限定されず、媒体中での球状粒子の製造において一般に使用される媒体に比べて高ければよく、例えば、常温において、粘性流体を添加する前の媒体の粘度よりも添加した後の媒体の粘度が僅かでも上がればよい。
【００２１】
上記粘性流体を媒体中に含有させる方法も特に限定されるものではない。例えば、球状粒子の製造前に媒体と粘性流体とを混合して用いる方法；球状粒子の製造中に媒体中に粘性流体を滴下する方法；球状粒子の製造中に媒体中に粘性流体を段階的に添加する方法等が挙げられる。これらの方法では、媒体中における粘性流体の含有量を一定としてもよく変動させてもよい。
【００２２】
本発明の製造方法では、媒体中で球状粒子を製造した後に、通常は濾過等の方法により媒体中から球状粒子を取り出し、必要により球状粒子を洗浄、乾燥等して製品とするが、媒体中の球状粒子をそのまま製品としてもよく、製品の形態は特に限定されるものではない。また、媒体中から球状粒子を取り出す場合、粘性流体を含む媒体や、媒体から分離した粘性流体を再利用してもよい。
【００２３】
本発明により製造される球状粒子の粒径としては特に限定されるものではない。例えば、平均粒径が０．０１〜２０ｍｍである球状粒子の製造に好適に適用することができる。０．０１ｍｍ未満であると、濾過等の操作により媒体中から粒子を取り出すのが困難であり、２０ｍｍを超えると、球状粒子の製造が困難であるばかりか、塊状化が充分に防止できないおそれがある。無機粒子の場合、より好ましくは、０．１〜１０ｍｍであり、更に好ましくは、１〜５ｍｍである。有機粒子の場合、より好ましくは、０．０５〜５ｍｍであり、更に好ましくは、０．１〜２．５ｍｍである。尚、上記平均粒径は、乾燥した球状粒子又は溶媒で膨潤した球状粒子の平均粒径を表す。
【００２４】
【発明の実施の形態】
本発明の球状粒子の製造方法は、有機系球状粒子としてイオン交換樹脂、吸水性樹脂等や、無機系球状粒子としてシリカゲル等の各種の球状粒子の製造に広く適用することができるが、特に、アミン系化合物を単量体として逆相懸濁重合または逆相乳化重合により球状粒子を製造する場合に好適に適用することができる。このような製造方法としては、例えば、（１）下記一般式で表されるアンモニウム化合物を含む水溶液を水不溶性有機溶剤を媒体として共重合または単独重合する方法；（２）下記一般式で表されるアンモニウム化合物とアリルアンモニウム基を分子内に２個以上有する化合物とを含む水溶液を水不溶性有機溶剤を媒体として共重合または単独重合する方法等が挙げられる。本発明では、媒体である水不溶性有機溶剤中に粘性流体を含むことになる。
【００２５】
【化１】
上記一般式中、Ｒ1 及びＲ2 は、同一若しくは異なって、水素原子、メチル基、エチル基又はハロゲン原子を表す。Ｒ3 及びＲ4 は、同一若しくは異なって、水素原子、アルキル基、ヒドロキシアルキル基、カルボキシアルキル基、カルボキシアミドアルキル基又はアルコキシアルキル基を表すか、又は、Ｒ3 −Ｎ+ −Ｒ4 は、Ｒ3 とＲ4 とが結合してピペリジン環又はモルホリニウム環を表す。Ｘ1 及びＸ2 は、同一若しくは異なって、水素原子、アルキル基又はハロゲン原子を表す。Ｙ- は、アニオンを表す。
【００２７】
上記ハロゲン原子としては特に限定されず、例えば、フッ素、塩素、臭素、ヨウ素等が挙げられる。
上記アルキル基、ヒドロキシアルキル基、カルボキシアルキル基、カルボキシアミドアルキル基及びアルコキシアルキル基のアルキル基は、炭素原子数が１〜１８個であることが好ましい。このようなアルキル基としては特に限定されず、例えば、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、イソブチル基、ｔｅｒｔ−ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基、ウンデシル基、ドデシル基、トリデシル基、テトラデシル基、ペンタデシル基、ヘキサデシル基、ヘプタデシル基、オクタデシル基等が挙げられる。より好ましくは、炭素原子数が１〜１２個のものであり、更に好ましくは、炭素原子数が１〜８個のものであり、最も好ましくは、炭素原子数が１〜６個のものである。
【００２８】
上記ピペリジン環及びモルホリニウム環は、炭素原子数が１〜１３個であるアルキル基により１個又は２個以上の水素原子が置換されていてもよい
上記アニオンとしては特に限定されず、例えば、フッ素、塩素、臭素、ヨウ素等のハロゲン原子のハリドイオンや、スルフェート、スルホネート、ホスホネート、ヒドロキシド、ボレート、シアニド、カーボネート（炭酸イオン）、ヒドロゲンカーボネート（炭酸水素イオン）、チオシアネート、チオスルフェート、イソシアネート、スルフィト、ビスルフィト、ニトレート、オキサレート、シリケート、スルフィド、シアネート、アセテート等の無機及び有機アニオン等が挙げられる。
【００２９】
上記一般式で表されるアンモニウム化合物の好ましい例としては、例えば、ジアリルジメチルアンモニウムクロライド、ジアリルジエチルアンモニウムクロライド、ジアリルメチル−β−ヒドロキシエチルアンモニウムクロライド等のジアリルジアルキルアンモニウムクロライド；ジメタリルジメチルアンモニウムクロライド等のジメタリルジアルキルアンモニウムクロライド等が挙げられる。これらは単独で用いてもよく、２種以上を併用してもよい。
【００３０】
上記アリルアンモニウム基を分子内に２個以上有する化合物としては特に限定されず、例えば、下記式（１）〜（１４）に表される化合物の他、Ｎ，Ｎ′−ジメチル−Ｎ，Ｎ′−テトラアリル−２−ブテン−１，４−ジアンモニウムジクロライド等が挙げられる。また、これらの化合物に代えて、又は、これらの化合物とともに、パラビニルフェニルメチルアンモニウム基及び／又はメタビニルフェニルメチルアンモニウム基を分子内に２個以上有する化合物として、例えば、Ｎ，Ｎ′−ジ（パラビニルフェニルメチル）エチレンジアンモニウムジクロライド、Ｎ，Ｎ′−ジ（メタビニルフェニルメチル）エチレンジアンモニウムジクロライド、Ｎ，Ｎ′−ジ（パラビニルフェニルメチル）プロピレンジアンモニウムジクロライド、Ｎ，Ｎ′−ジ（メタビニルフェニルメチル）プロピレンジアンモニウムジクロライド等が挙げられる。ここに掲げたものは代表例であり、これら以外にも例えば、フェニレンジアミンやその他ジアミン類と塩化アリルまたは酢酸アリルで合成される化合物が挙げられる。これらはそれぞれ単独で用いてもよく、２種以上を併用してもよい。尚、これらの化合物が有するカウンターアニオンは、クロライド系に限らず、他のものでも良い。
【００３１】
【化２】
上記（２）の製造方法においては、アンモニウム化合物とアリルアンモニウム基を分子内に２個以上有する化合物との共重合比率としては特に限定されず、例えば、重量比で４０〜９９．９／６０〜０．１となるようにすることが好ましい。上記（１）及び（２）の製造方法においては、上記化合物以外の他の化合物を適宜重合させてもよい。また、水溶液における化合物の濃度としては特に限定されず、例えば、仕込時の水溶液濃度は取扱の上で３０〜８０重量％とすることが好ましいが、重合開始前、あるいは重合中に脱水操作によりさらに濃縮しても良い。
【００３３】
上記媒体として用いられる水不溶性有機溶剤としては特に限定されず、例えば、トルエン、キシレン、ベンゼン、ｎ−ヘキサン、シクロヘキサン、オクタン、鉱酸、ミネラルスピリット、ケロシンや、１，１，１−トリクロロエタン、１，２−ジクロロプロパン、テトラクロロエタン、トリクロロプロパン、テトラクロロメタン等の臭素化及び／又は塩素化された炭化水素等が挙げられる。これらは単独で用いてもよく、２種以上を併用してもよい。これらの中でも、トルエン、キシレンを用いることが工業的に好適である。
【００３４】
上記粘性流体として流動パラフィン及び／又はシリコーンオイルを用いる場合には、粘性流体の媒体中の含有量としては、例えば、粘性流体を含む媒体全量に対して、０．１〜５０重量％とすることが好ましい。０．１重量％未満であると、生成する球状粒子の塊状化を充分に防止できないおそれがあり、５０重量％を超えると、粒子径が低下するおそれがある。より好ましくは、１〜４０重量％であり、更に好ましくは、５〜３０重量％である。また、粘性流体を含む媒体の粘度は、粘性流体添加前後で粘度が上がりさえすれば良い。
【００３５】
上記共重合における重合条件、すなわち重合温度、重合時間、攪拌条件や、使用する重合開始剤、添加剤等は、生成する球状粒子の大きさや性能、品質等により適宜設定すればよく、特に限定されるものではない。例えば、重合温度は、２０〜１５０℃とすることが好ましい。より好ましくは、５０〜１２０℃である。また、常圧または減圧系で共沸脱水を併用しても良い。重合時間は、他の条件により適宜設定すればよく、４〜１０時間とすることが好ましい。攪拌条件は、通常の重合における攪拌速度とすればよい。使用する重合開始剤は水溶性、油溶性を問わず、ペルオキシド系やアゾ系の一般的な開始剤を用いることができる。添加剤は、一般的な分散安定剤等を用いることができる。その他の重合条件は、特に限定されるものではない。
【００３６】
上記（２）の製造方法の代表例として、ジアリルジメチルアンモニウムクロライド及びＮ，Ｎ′−テトラアリルジピペリジニルプロパニウムジクロライドの水溶液と重合開始剤の水溶液とをトルエンと流動パラフィンとを混合し分散安定剤を添加した媒体中に滴下し、逆相懸濁重合を行う場合を下記反応式に示す。
【００３７】
【化３】
上記逆相懸濁重合により得られる粒状粒子は、平均粒径が０．０５〜５ｍｍである陰イオン交換樹脂であり、工業的に有用なものである。また、これらの粒子はイオン交換樹脂が利用される用途、例えば水処理、廃水処理、有価物回収、薬液の精製、触媒等に好適に用いられる。このような陰イオン交換樹脂粒子が、本発明により、均一で高品質な球状粒子として、廉価にかつ簡便に、しかも、高収率で製造することができることになる。
【００３９】
【実施例】
以下に実施例を掲げて本発明を更に詳細に説明するが、本発明はこれら実施例のみに限定されるものではない。
【００４０】
実施例１
攪拌機、還流冷却管、水分離管、減圧一定装置、温度計、窒素ガス導入管及び滴下ロートを備えた１Ｌのセパラブルフラスコに、トルエン３５０ｍｌと流動パラフィン５０ｍｌを入れ、分散安定剤としてソルビタンモノパルミテート０．６４ｇ、及び、エチルセルロース０．２１ｇを添加して４０℃で溶解させた。このとき、窒素ガスを吹き込んで溶存酸素を追い出した。
【００４１】
別に、１００ｍｌのビーカーで６５％ジアリルジメチルアンモニウムクロライド（ＤＡＤＭＡＣ）４１．７４ｇとテトラアリルジピペリジニルプロパニウムクロライド（ＴＡＤＰＰＣ）８．２６ｇ及び水２０．７８ｇを混合溶解し、更に重合開始剤２，２′−アゾビス（２−アミジノプロパン）ジクロリド（「Ｖ−５０」、商品名、和光純薬工業社製）０．３２ｇ及び水２．４ｇを混合した溶液を添加した。
【００４２】
この溶液を３０℃で反応容器中に３０分かけて滴下し、滴下終了後５５℃で４時間、更に昇温し、７５℃で３時間反応させた。途中２時間経過した時点で攪拌速度を２２０ｒｐｍから２５０ｒｐｍに上昇させ、更に流動パラフィン５０ｍｌを滴下した。また、５５℃から７５℃への昇温時にトルエン５０ｍｌを追加し、更に反応系内を減圧にして留出水を分離しながら重合させた。
【００４３】
所定時間反応後、冷却し生成粒子を減圧濾過により分離した。濾別した粒子をメタノール８００ｍｌで３０分間、３回洗浄し、６０℃で一晩減圧乾燥させ、乾燥粒子３２．９ｇ（ゲル収率９２．８％）を得た。
得られた乾燥粒子は、直径０．２ｍｍ程度の独立した粒子であった。
【００４４】
実施例２
実施例１で初期仕込をトルエン３７５ｍｌ、流動パラフィン２５ｍｌ、開始剤（Ｖ−５０）０．２１ｇ、開始剤を溶解させるための水１．６ｇその他同条件とし、途中２時間経過した時点でトルエン２５ｍｌと流動パラフィン２５ｍｌとの混合液を滴下し、４時間経過した時点でトルエン５０ｍｌ滴下した。
その他同様に行い、乾燥粒子２９．５ｇ（ゲル収率８３．３％）を得た。得られた乾燥粒子は、直径０．３ｍｍ程度の独立した粒子であった。
【００４５】
実施例３
実施例１でソルビタンモノパルミテート０．６０ｇ、エチルセルロース０．２０ｇ、６５％ジアリルジメチルアンモニウムクロライド（ＤＡＤＭＡＣ）４８．０９ｇ、テトラアリルピペラジニウムジクロライド（ＴＡＰＣ）１．９１ｇ、水０ｇ、開始剤（Ｖ−５０）０．２０ｇ及び水１．５ｇとした以外は同様に行った。乾燥粒子３１．８ｇ（ゲル収率９７．２％）を得た。得られた乾燥粒子は、直径０．２ｍｍ程度の独立した粒子であった。
【００４６】
実施例４
攪拌機、還流冷却管、温度計、窒素ガス導入管及び滴下ロートを備えた１Ｌのセパラブルフラスコに、トルエン３５０ｍｌと流動パラフィン５０ｍｌを入れ、分散安定剤としてソルビタンモノパルミテート０．６０ｇ、及び、エチルセルロース０．２０ｇを添加して４０℃で溶解させた。このとき、窒素ガスを吹き込んで溶存酸素を追い出した。
【００４７】
別に、１００ｍｌのビーカーで６５％ジアリルジメチルアンモニウムクロライド（ＤＡＤＭＡＣ）４０．３２ｇ、トリアリルアミン塩酸塩９．６８ｇを混合し、更に開始剤（Ｖ−５０）０．４０ｇ及び水３．０ｇを混合した溶液を添加した。
【００４８】
この溶液を３０℃で反応容器中に３０分かけて滴下し、滴下終了後５５℃で４時間、更に昇温し、７５℃で２時間反応させた。途中２時間経過した時点で攪拌速度を２２０ｒｐｍから２５０ｒｐｍに上昇させ、更に流動パラフィン５０ｍｌを滴下した。また、５５℃から７５℃への昇温時にトルエン５０ｍｌを追加した。
【００４９】
所定時間反応後、冷却し生成粒子を減圧濾過により分離した。濾別した粒子をメタノール８００ｍｌで３０分間、３回洗浄し、６０℃で一晩減圧乾燥させ、乾燥粒子２２．１ｇ（ゲル収率６６．４％）を得た。
得られた乾燥粒子は、直径０．５ｍｍ程度の独立した粒子であった。
【００５０】
比較例１
実施例４において、流動パラフィンの代わりにトルエンを用いて媒体をすべてトルエンとしたこと以外は同様にして反応を試みたが、反応途中で凝集塊状物となり、攪拌が困難となったため、反応を中断した。
【００５１】
【発明の効果】
本発明の球状粒子の製造方法は、上述の構成よりなるので、均一で高品質な球状粒子を廉価にかつ簡便に、しかも、高収率で製造することができ、有機系球状粒子としてイオン交換樹脂、吸水性樹脂等や、無機系球状粒子としてシリカゲル等の各種の球状粒子の製造に広く適用することができる。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a method for producing spherical particles.
[0002]
[Prior art]
Spherical particles are widely used in various industrial products because their morphology increases the surface area and are excellent in handleability, and are now indispensable to the chemical industry. Typical spherical particles include, for example, organic-type spherical particles such as ion-exchange resins and water-absorbing resins, and inorganic-type spherical particles such as silica gel.
[0003]
As a method of producing such a spherical particle, for example, a method of dispersing in a medium or forming a polymer by forming a polymer in the medium is simple, and a method of forming a uniform shape and size. It is widely used industrially because it is a suitable method for producing spherical particles. However, when the spherical particles formed as a dispersion have a cohesive property or the spherical particles stick to each other, there is a problem that a uniform product cannot be obtained by agglomeration. Therefore, when manufacturing spherical particles in a medium, or using a suspending agent or the like, to prevent agglomeration of the spherical particles generated by performing strong stirring, but such a method is sufficient In some cases, uniform spherical particles may not be obtained, or the use of a suspending agent or strong stirring may not be possible in order to obtain high-quality industrial products. There is also room for improvement in terms of manufacturing costs.
[0004]
JP-A-4-31710 discloses a two-phase system comprising a droplet of an aqueous solution of a water-soluble monomer such as at least one diallyldialkylammonium chloride in a water-immiscible inert organic liquid. And a method for preparing a homopolymer or copolymer by conducting polymerization in the presence of a combination of emulsifiers. It was considered that this preparation method could obtain spherical particles having a small particle size distribution and a certain degree of uniformity. However, since the agglomeration of the spherical particles is prevented by combining the sedimentation inhibitor and the emulsifier, it may not be applicable to obtain high-quality industrial products. There was also room for improvement in cost.
[0005]
Japanese Patent Publication No. 2-41528 discloses a diaryldialkylammonium chloride and a compound having at least two diallylammonium groups in the same molecule or at least two para (or meth) vinylphenylmethylammonium groups in the same molecule. In producing a copolymer by suspending an aqueous solution containing a compound having the above or a mixture thereof, in a water-insoluble organic solvent, using a copolymer having a hydrophilic group and a hydrophobic group as a dispersant A method for producing an anion exchange resin is disclosed. It was thought that even with this production method, spherical particles having a certain degree of uniformity could be obtained. However, in this production method, similarly, since the copolymer is used as a dispersant, it may not be applicable to obtain high-quality industrial products, and there is still room for improvement in production cost. Was.
[0006]
[Problems to be solved by the invention]
The present invention has been made in view of the above situation, and has as its object to provide a method for producing uniform, high-quality spherical particles at low cost, easily, and with high yield.
[0007]
[Means for Solving the Problems]
The present invention is a method for producing spherical particles in a medium, wherein the medium contains a viscous fluid.
The present inventors have conducted a thorough study after closely examining the problems with the method for producing spherical particles, and as a result, the above-described production method has prevented uniform agglomeration of spherical particles generated by the above-described production method. Since products can be obtained, and inexpensive and simple, and can be produced in high yield, ion-exchange resins and water-absorbent resins as organic spherical particles, and silica gel and the like as inorganic spherical particles. The present invention has been achieved by encountering the dramatic effect of being able to be suitably applied to industrial products containing spherical particles.
Hereinafter, the present invention will be described in detail.
[0008]
The present invention is a method for producing spherical particles in a medium. Such a production method is not particularly limited, and can be widely applied to the production of spherical particles in a medium which is industrially performed. For example, when producing organic spherical particles, it can be applied to a method of polymerizing a monomer in a medium, a method of dispersing a polymer in a medium, and the like. In the case of manufacturing, the present invention can be applied to a method of dispersing an inorganic substance in a medium and the like.
[0009]
Specific examples of the method for producing the spherical particles include, for example, producing spherical particles such as an ion-exchange resin and a water-absorbent resin in a medium by emulsion polymerization or suspension polymerization as a method of polymerizing a monomer in a medium. Examples of the method and a method of dispersing an inorganic substance in a medium include a method of dropping water glass into a medium to produce silica gel particles.
[0010]
In the method of polymerizing the monomer in the medium, the polymerization is generally performed by dispersing the monomer droplets in the medium. In this case, the polarity between the monomer droplet and the medium is not particularly limited.For example, even if the monomer droplet has a lower polarity than the medium, it may have a higher polarity. Good. When the monomer droplets have a higher polarity than the medium, reverse-phase polymerization occurs. In this case, the generated spherical particles have high tackiness and may easily be aggregated. In such a case, the manufacturing method of the present invention is particularly suitably applied. As a form of reverse phase polymerization, for example, a water-insoluble organic solvent is used as a medium, and droplets of a water-soluble monomer or droplets of an aqueous solution containing a water-soluble monomer are dispersed in the medium and suspended. In some cases, turbid polymerization is performed.
[0011]
Polymerization conditions and dispersion conditions in the method for producing spherical particles in the above medium, monomers, usable raw materials such as polymerization initiators and additives, etc. are appropriately set according to the use, performance, quality, etc. of the product to be produced. What is necessary is just to do and it does not specifically limit. For example, the production method of the present invention may be applied to a general industrial production method of spherical particles.
[0012]
In the present invention, the medium contains a viscous fluid. This makes it possible to suppress agglomeration of the spherical particles to be generated or to suppress adhesion of the spherical particles, thereby suppressing agglomeration of the spherical particles. Therefore, uniform and high-quality spherical particles can be produced inexpensively, easily, and in high yield.
[0013]
Although it is not always clear why the present invention exerts such effects, it is considered that, for example, the following reasons are given, and these are synergistic effects.
(1) Spherical particles formed in a medium are generally hard to be stably present in a medium due to aggregating properties and adhesion between the spherical particles. By containing a fluid, due to the existence of a viscous fluid around the spherical particles, the cohesiveness and stickiness of the spherical particles are suppressed, the stability in the medium is improved, and the viscosity of the medium is reduced. Agglomeration of the spherical particles can be suppressed even when the height is increased. (2) Use of an additive such as a suspending agent for preventing agglomeration of the generated spherical particles is suppressed. The viscous fluid inside can be easily removed when the spherical particles are separated from the medium, and the resulting product can be of higher quality due to the elimination of strong stirring. , (3) additives Use is suppressed, also since the strong stirring is not required, it is possible to easily perform the prevention of agglomeration of spherical particles, it is possible to suppress the manufacturing cost.
[0014]
The above-mentioned viscous fluid is a fluid having a higher viscosity at room temperature than a medium usually used in the production of spherical particles in a medium.In the present invention, it is intended to prevent agglomeration of generated spherical particles in a medium. Means a fluid having a viscosity such that For example, when water is used as a medium, the viscosity is higher at room temperature than water, and when an organic solvent is used as a medium, it is essential that the viscosity is higher at room temperature than the organic solvent used. It is. Further, even if the properties before the addition to the medium are solid, it is possible to use a substance which becomes a fluid by being added to the medium and stirring or heating as necessary, and having an action of increasing the viscosity of the medium. Examples of such a material include solid paraffin wax and grease which is a secondary product of silicone oil. The viscosity of the viscous fluid of the present invention may be higher than that of the medium at, for example, 25 to 50 ° C., and the viscosity at a high temperature such as a polymerization temperature is not particularly limited. In addition, the viscosity can be measured by viscosity at room temperature, kinematic viscosity, and the like.
[0015]
The type of the viscous fluid is preferably one that is inert in producing spherical particles, and for example, preferably contains liquid paraffin and / or silicone oil. Thereby, the effects of the present invention can be sufficiently exhibited, and a method of polymerizing a monomer in a medium, a method of manufacturing organic spherical particles such as a method of dispersing a polymer in a medium, and a medium. It can be suitably applied to the production of inorganic spherical particles such as a method of dispersing an inorganic substance therein. When the above-mentioned viscous fluid contains liquid paraffin and / or silicone oil, other viscous fluids may be contained as long as the effects of the present invention are not impaired.
[0016]
The liquid paraffin is not particularly limited as long as it is a liquid paraffin at room temperature, and examples thereof include liquid saturated hydrocarbons having 12 to 50 carbon atoms, and n-paraffin, isoparaffin, and naphthene. Is also good. Commercial products include, for example, Moresco White, Moresco Bioless (all trade names, manufactured by Matsumura Petroleum Institute), Stanol, Christol, Esso White Oil, Pure Rex (all trade names, Esso Oil Co., Ltd.) Manufactured) can be used. These may be used alone or in combination of two or more. Among them, the kinematic viscosity at 40 ° C. is 5 to 500 mm. Two / S can be suitably used. More preferably, 10 to 100 mm Two / S.
[0017]
The silicone oil is not particularly limited as long as it has a siloxane structure which is liquid at normal temperature, and examples thereof include polysiloxane oils such as dimethyl silicone oil and the like, and include a hydroxyl group, a carboxyl group, an amino group, an epoxy group, and a cyano oil. A modified silicone oil having a functional group such as a group, a mercapto group, a trifluoropropyl group, a chlorophenyl group, or a long-chain alkyl group, or modified with a polyether, alcohol, or the like can also be used. These may be used alone or in combination of two or more. Among these, the kinematic viscosity at 40 ° C. is 5 to 100000 mm Two / S can be suitably used. More preferably, 10 to 10000 mm Two / S.
[0018]
As the above-mentioned viscous fluid, in addition to those containing liquid paraffin and / or silicone oil, those containing a fluid that can be used as a lubricating oil are also preferable.
No particular limitation is imposed on the lubricating oil, and examples thereof include synthetic lubricating oils such as diesters, polyalkylene glycols, and halogenated hydrocarbons, and liquid lubricating oils such as petroleum-based lubricating oils and fatty oils. Oil and the like. These may be used alone or in combination of two or more. Among these, the kinematic viscosity at 40 ° C. is 5 to 100000 mm Two / S can be suitably used. More preferably, 10 to 10000 mm Two / S.
[0019]
The content of the viscous fluid in the medium is not particularly limited, and may be appropriately set depending on the cohesiveness and tackiness of the spherical particles, the type of the medium, the production method, and the like. For example, in a method for producing spherical particles such as an ion-exchange resin and a water-absorbent resin in a medium by emulsion polymerization or suspension polymerization, the amount is preferably 0.1 to 50% by weight based on the total amount of the medium including the viscous fluid. Preferably, in the method of producing silica gel particles by dropping water glass into a medium, the content is preferably 10 to 95% by weight based on the total amount of the medium including the viscous fluid. Also, by appropriately adjusting the amount of the viscous fluid in the system, the particle size (particle size) of the spherical particles can be adjusted.
[0020]
In the production method of the present invention, the viscosity of the medium containing the viscous fluid is not particularly limited, and may be higher than a medium generally used in the production of spherical particles in the medium. It is sufficient that the viscosity of the medium after the addition is slightly higher than the viscosity of the medium before the addition.
[0021]
The method for causing the viscous fluid to be contained in the medium is not particularly limited. For example, a method of mixing and using a medium and a viscous fluid before the production of spherical particles; a method of dropping a viscous fluid into a medium during the production of spherical particles; And the like. In these methods, the content of the viscous fluid in the medium may be constant or may be varied.
[0022]
In the production method of the present invention, after the spherical particles are produced in the medium, the spherical particles are usually taken out of the medium by a method such as filtration, and if necessary, the spherical particles are washed and dried to obtain a product. May be used as a product as it is, and the form of the product is not particularly limited. In the case of extracting spherical particles from a medium, a medium containing a viscous fluid or a viscous fluid separated from the medium may be reused.
[0023]
The particle size of the spherical particles produced according to the present invention is not particularly limited. For example, it can be suitably applied to the production of spherical particles having an average particle size of 0.01 to 20 mm. If it is less than 0.01 mm, it is difficult to take out the particles from the medium by an operation such as filtration, and if it is more than 20 mm, not only the production of spherical particles is difficult, but also the agglomeration may not be sufficiently prevented. is there. In the case of inorganic particles, it is more preferably from 0.1 to 10 mm, and still more preferably from 1 to 5 mm. In the case of organic particles, it is more preferably 0.05 to 5 mm, and still more preferably 0.1 to 2.5 mm. In addition, the said average particle diameter represents the average particle diameter of the dried spherical particle or the spherical particle swollen with the solvent.
[0024]
BEST MODE FOR CARRYING OUT THE INVENTION
The method for producing spherical particles of the present invention can be widely applied to the production of various spherical particles such as silica gel and the like as ion-exchange resins and water-absorbent resins as organic spherical particles, and inorganic spherical particles. It can be suitably applied to the case where spherical particles are produced by reverse phase suspension polymerization or reverse phase emulsion polymerization using an amine compound as a monomer. As such a production method, for example, (1) a method of copolymerizing or homopolymerizing an aqueous solution containing an ammonium compound represented by the following general formula using a water-insoluble organic solvent as a medium; (2) a method represented by the following general formula And a method of copolymerizing or homopolymerizing an aqueous solution containing an ammonium compound and a compound having two or more allylammonium groups in a molecule using a water-insoluble organic solvent as a medium. In the present invention, a viscous fluid is contained in a water-insoluble organic solvent as a medium.
[0025]
Embedded image
In the above general formula, R 1 And R Two Represents the same or different and represents a hydrogen atom, a methyl group, an ethyl group or a halogen atom. R Three And R Four Is the same or different and represents a hydrogen atom, an alkyl group, a hydroxyalkyl group, a carboxyalkyl group, a carboxamidoalkyl group or an alkoxyalkyl group, or R Three -N + -R Four Is R Three And R Four And bond to form a piperidine ring or a morpholinium ring. X 1 And X Two Represents the same or different and represents a hydrogen atom, an alkyl group or a halogen atom. Y - Represents an anion.
[0027]
The halogen atom is not particularly limited, and includes, for example, fluorine, chlorine, bromine, iodine and the like.
The alkyl group of the alkyl group, hydroxyalkyl group, carboxyalkyl group, carboxamidoalkyl group and alkoxyalkyl group preferably has 1 to 18 carbon atoms. Such an alkyl group is not particularly limited, and includes, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, a hexyl group, a heptyl group, Examples include octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, and octadecyl. More preferably, it has 1 to 12 carbon atoms, still more preferably, it has 1 to 8 carbon atoms, and most preferably, it has 1 to 6 carbon atoms. .
[0028]
In the piperidine ring and the morpholinium ring, one or more hydrogen atoms may be substituted by an alkyl group having 1 to 13 carbon atoms.
The anion is not particularly restricted but includes, for example, halide ions of halogen atoms such as fluorine, chlorine, bromine and iodine, sulfate, sulfonate, phosphonate, hydroxide, borate, cyanide, carbonate (carbonate ion), hydrogen carbonate (carbonate). Hydrogen ion), thiocyanate, thiosulfate, isocyanate, sulfite, bisulfite, nitrate, oxalate, silicate, sulfide, cyanate, acetate, and other inorganic and organic anions.
[0029]
Preferred examples of the ammonium compound represented by the above general formula include, for example, diallyldimethylammonium chloride, diallyldialkylammonium chloride such as diallyldiethylammonium chloride, diallylmethyl-β-hydroxyethylammonium chloride; and dimethallyldimethylammonium chloride. Dimethallyl dialkyl ammonium chloride and the like. These may be used alone or in combination of two or more.
[0030]
The compound having two or more allyl ammonium groups in the molecule is not particularly limited. For example, in addition to the compounds represented by the following formulas (1) to (14), N, N′-dimethyl-N, N ′ -Tetraallyl-2-butene-1,4-diammonium dichloride and the like. Further, instead of these compounds or together with these compounds, compounds having two or more paravinylphenylmethylammonium groups and / or metavinylphenylmethylammonium groups in the molecule, for example, N, N'-di- (Paravinylphenylmethyl) ethylenediammonium dichloride, N, N'-di (metavinylphenylmethyl) ethylenediammonium dichloride, N, N'-di (paravinylphenylmethyl) propylenediammonium dichloride, N, N'- And di (methvinylphenylmethyl) propylenediammonium dichloride. The compounds listed here are representative examples. In addition to these, for example, compounds synthesized with phenylenediamine or other diamines and allyl chloride or allyl acetate can be mentioned. These may be used alone or in combination of two or more. The counter anion of these compounds is not limited to chloride, but may be other.
[0031]
Embedded image
In the production method (2), the copolymerization ratio of the ammonium compound and the compound having two or more allylammonium groups in the molecule is not particularly limited, and is, for example, 40 to 99.9 / 60 by weight. It is preferable to set it to 0.1. In the production methods (1) and (2), a compound other than the above compound may be appropriately polymerized. The concentration of the compound in the aqueous solution is not particularly limited. For example, the concentration of the aqueous solution at the time of preparation is preferably 30 to 80% by weight after handling, but it is further increased by a dehydration operation before the start of polymerization or during the polymerization. It may be concentrated.
[0033]
The water-insoluble organic solvent used as the medium is not particularly limited, and examples thereof include toluene, xylene, benzene, n-hexane, cyclohexane, octane, mineral acid, mineral spirit, kerosene, 1,1,1-trichloroethane, , 2-dichloropropane, tetrachloroethane, trichloropropane, tetrachloromethane, and other brominated and / or chlorinated hydrocarbons. These may be used alone or in combination of two or more. Among them, it is industrially preferable to use toluene and xylene.
[0034]
When liquid paraffin and / or silicone oil is used as the viscous fluid, the content of the viscous fluid in the medium is, for example, 0.1 to 50% by weight based on the total amount of the medium including the viscous fluid. Is preferred. If the amount is less than 0.1% by weight, the resulting spherical particles may not be sufficiently prevented from agglomerating. If the amount exceeds 50% by weight, the particle diameter may be reduced. More preferably, it is 1 to 40% by weight, still more preferably 5 to 30% by weight. Further, the viscosity of the medium containing the viscous fluid only needs to increase before and after the addition of the viscous fluid.
[0035]
The polymerization conditions in the copolymerization, that is, the polymerization temperature, the polymerization time, the stirring conditions, the polymerization initiator to be used, the additives, and the like may be appropriately set according to the size, performance, quality, and the like of the generated spherical particles, and are particularly limited. Not something. For example, the polymerization temperature is preferably set to 20 to 150 ° C. More preferably, it is 50 to 120 ° C. Further, azeotropic dehydration may be used in combination with a normal pressure or reduced pressure system. The polymerization time may be appropriately set according to other conditions, and is preferably 4 to 10 hours. The stirring conditions may be the stirring speed in ordinary polymerization. Regarding the polymerization initiator to be used, a common peroxide-based or azo-based initiator can be used regardless of whether it is water-soluble or oil-soluble. As the additive, a general dispersion stabilizer or the like can be used. Other polymerization conditions are not particularly limited.
[0036]
As a typical example of the production method (2), an aqueous solution of diallyldimethylammonium chloride and N, N'-tetraallyldipiperidinylpropanium dichloride and an aqueous solution of a polymerization initiator are mixed by mixing toluene and liquid paraffin. The following reaction formula shows a case where the suspension is added dropwise to a medium to which a stabilizer is added to perform reverse phase suspension polymerization.
[0037]
Embedded image
The granular particles obtained by the reverse phase suspension polymerization are anion exchange resins having an average particle size of 0.05 to 5 mm and are industrially useful. Further, these particles are suitably used for applications in which an ion exchange resin is used, for example, water treatment, wastewater treatment, valuable resource recovery, chemical solution purification, and catalyst. According to the present invention, such anion-exchange resin particles can be produced as uniform and high-quality spherical particles at low cost, easily and with high yield.
[0039]
【Example】
Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to only these Examples.
[0040]
Example 1
In a 1 L separable flask equipped with a stirrer, a reflux condenser, a water separator, a decompression device, a thermometer, a nitrogen gas inlet tube and a dropping funnel, 350 ml of toluene and 50 ml of liquid paraffin are placed. 0.64 g of tate and 0.21 g of ethyl cellulose were added and dissolved at 40 ° C. At this time, dissolved oxygen was driven out by blowing nitrogen gas.
[0041]
Separately, 41.74 g of 65% diallyldimethylammonium chloride (DADMAC), 8.26 g of tetraallyldipiperidinylpropanium chloride (TADPPC) and 20.78 g of water were mixed and dissolved in a 100 ml beaker. A solution obtained by mixing 0.32 g of 2'-azobis (2-amidinopropane) dichloride ("V-50", trade name, manufactured by Wako Pure Chemical Industries, Ltd.) and 2.4 g of water was added.
[0042]
This solution was dropped into the reaction vessel at 30 ° C. over 30 minutes, and after completion of the dropping, the temperature was further raised at 55 ° C. for 4 hours, followed by a reaction at 75 ° C. for 3 hours. At the time when two hours had passed halfway, the stirring speed was increased from 220 rpm to 250 rpm, and 50 ml of liquid paraffin was further added dropwise. Further, at the time of raising the temperature from 55 ° C. to 75 ° C., 50 ml of toluene was added, and the pressure inside the reaction system was further reduced to effect polymerization while distilling water was separated.
[0043]
After reacting for a predetermined time, the mixture was cooled and the produced particles were separated by filtration under reduced pressure. The particles separated by filtration were washed three times with 800 ml of methanol for 30 minutes and dried under reduced pressure at 60 ° C. overnight to obtain 32.9 g of dried particles (gel yield: 92.8%).
The obtained dried particles were independent particles having a diameter of about 0.2 mm.
[0044]
Example 2
In Example 1, the initial charge was 375 ml of toluene, 25 ml of liquid paraffin, 0.21 g of an initiator (V-50), 1.6 g of water for dissolving the initiator, and other conditions were the same. And a mixed liquid of 25 ml of liquid paraffin and 50 ml of toluene were dropped after 4 hours.
In the same manner as above, 29.5 g of dry particles (gel yield: 83.3%) were obtained. The obtained dried particles were independent particles having a diameter of about 0.3 mm.
[0045]
Example 3
In Example 1, sorbitan monopalmitate 0.60 g, ethyl cellulose 0.20 g, 65% diallyldimethylammonium chloride (DADMAC) 48.09 g, tetraallylpiperazinium dichloride (TAPC) 1.91 g, water 0 g, initiator (V -50) The same operation was performed except that 0.20 g and 1.5 g of water were used. 31.8 g of dry particles (gel yield 97.2%) were obtained. The obtained dried particles were independent particles having a diameter of about 0.2 mm.
[0046]
Example 4
In a 1 L separable flask equipped with a stirrer, a reflux condenser, a thermometer, a nitrogen gas inlet tube and a dropping funnel, 350 ml of toluene and 50 ml of liquid paraffin were placed, and 0.60 g of sorbitan monopalmitate as a dispersion stabilizer and ethyl cellulose were added. 0.20 g was added and dissolved at 40 ° C. At this time, dissolved oxygen was driven out by blowing nitrogen gas.
[0047]
Separately, a solution obtained by mixing 40.32 g of 65% diallyldimethylammonium chloride (DADMAC) and 9.68 g of triallylamine hydrochloride in a 100 ml beaker, and further mixing 0.40 g of an initiator (V-50) and 3.0 g of water. Was added.
[0048]
This solution was dropped into the reaction vessel at 30 ° C. over 30 minutes, and after completion of the dropping, the temperature was further raised at 55 ° C. for 4 hours, and the reaction was carried out at 75 ° C. for 2 hours. At the time when two hours had passed halfway, the stirring speed was increased from 220 rpm to 250 rpm, and 50 ml of liquid paraffin was further added dropwise. Further, 50 ml of toluene was added when the temperature was raised from 55 ° C to 75 ° C.
[0049]
After reacting for a predetermined time, the mixture was cooled and the produced particles were separated by filtration under reduced pressure. The particles separated by filtration were washed three times with 800 ml of methanol for 30 minutes and dried under reduced pressure at 60 ° C. overnight to obtain 22.1 g of dry particles (gel yield: 66.4%).
The obtained dried particles were independent particles having a diameter of about 0.5 mm.
[0050]
Comparative Example 1
In Example 4, the reaction was attempted in the same manner except that toluene was used instead of liquid paraffin, and the medium was changed to toluene. However, the reaction was interrupted due to agglomeration during the reaction and difficulty in stirring. did.
[0051]
【The invention's effect】
Since the method for producing spherical particles of the present invention has the above-described configuration, uniform and high-quality spherical particles can be produced at low cost and simply, and at a high yield, and ion exchange can be performed as organic spherical particles. It can be widely applied to the production of resins, water-absorbent resins and the like, and various spherical particles such as silica gel as inorganic spherical particles.
Claims (2)
該媒体は、粘性流体を含むものであり、
該製造方法は、下記一般式で表されるアンモニウム化合物を含む水溶液を水不溶性有機溶剤を媒体として共重合または単独重合する方法である
ことを特徴とする球状粒子の製造方法。
The medium includes a viscous fluid ,
The method for producing spherical particles is a method of copolymerizing or homopolymerizing an aqueous solution containing an ammonium compound represented by the following general formula using a water-insoluble organic solvent as a medium .
ことを特徴とする請求項１記載の球状粒子の製造方法。The method for producing spherical particles according to claim 1, wherein the viscous fluid contains liquid paraffin and / or silicone oil.
Priority Applications (8)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000181265A JP3539678B2 (en) | 2000-06-16 | 2000-06-16 | Method for producing spherical particles |
| GB0114689A GB2374072B (en) | 2000-06-16 | 2001-06-15 | Crosslinked polymer method for manufacturing it and use thereof |
| CNB011210737A CN1254511C (en) | 2000-06-16 | 2001-06-15 | Cross-linked polymer and its preparation method and use |
| CN 200610059594 CN1837249A (en) | 2000-06-16 | 2001-06-15 | Crosslinked polymer, method for manufacturing it and use thereof |
| US09/880,876 US6646083B2 (en) | 2000-06-16 | 2001-06-15 | Crosslinked polymers containing tertiary amine and/or quaternary ammonium salt structures, processes for making and uses thereof |
| MYPI20012838 MY133977A (en) | 2000-06-16 | 2001-06-15 | Crosslinked polymers containing tertiary amine and/or quaternary ammonium salt structures, processes for making and uses thereof |
| CA002350728A CA2350728A1 (en) | 2000-06-16 | 2001-06-15 | Crosslinked polmer, method for manufacturing it and use thereof |
| KR1020010033867A KR100558119B1 (en) | 2000-06-16 | 2001-06-15 | Crosslinked polymers, methods of making and uses thereof |
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| JP2000181265A JP3539678B2 (en) | 2000-06-16 | 2000-06-16 | Method for producing spherical particles |
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| JP3539678B2 true JP3539678B2 (en) | 2004-07-07 |
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