CN1250684A - 微囊包封球型聚合物的制备方法 - Google Patents
微囊包封球型聚合物的制备方法 Download PDFInfo
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- CN1250684A CN1250684A CN99121357A CN99121357A CN1250684A CN 1250684 A CN1250684 A CN 1250684A CN 99121357 A CN99121357 A CN 99121357A CN 99121357 A CN99121357 A CN 99121357A CN 1250684 A CN1250684 A CN 1250684A
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- Prior art keywords
- monomer
- hydrophilic monomer
- microencapsulation
- peroxide
- methyl
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- 238000000034 method Methods 0.000 title claims abstract description 29
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- 239000003094 microcapsule Substances 0.000 title description 4
- 239000000178 monomer Substances 0.000 claims abstract description 76
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 23
- 239000008346 aqueous phase Substances 0.000 claims abstract description 18
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 14
- 239000000203 mixture Substances 0.000 claims abstract description 13
- 239000003999 initiator Substances 0.000 claims abstract description 10
- 238000002360 preparation method Methods 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- -1 alkyl methacrylate Chemical compound 0.000 claims description 19
- 150000001875 compounds Chemical class 0.000 claims description 14
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 11
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 11
- MPMBRWOOISTHJV-UHFFFAOYSA-N but-1-enylbenzene Chemical compound CCC=CC1=CC=CC=C1 MPMBRWOOISTHJV-UHFFFAOYSA-N 0.000 claims description 8
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 6
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical class CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 claims description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 5
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 5
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 5
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 claims description 4
- NPDACUSDTOMAMK-UHFFFAOYSA-N 4-Chlorotoluene Chemical compound CC1=CC=C(Cl)C=C1 NPDACUSDTOMAMK-UHFFFAOYSA-N 0.000 claims description 4
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 4
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims description 4
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 claims description 4
- 125000005907 alkyl ester group Chemical group 0.000 claims description 4
- 229940043265 methyl isobutyl ketone Drugs 0.000 claims description 4
- 238000005502 peroxidation Methods 0.000 claims description 4
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 4
- VKPSKYDESGTTFR-UHFFFAOYSA-N 2,2,4,6,6-pentamethylheptane Chemical compound CC(C)(C)CC(C)CC(C)(C)C VKPSKYDESGTTFR-UHFFFAOYSA-N 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- YOZHLACIXDCHPV-UHFFFAOYSA-N n-(methoxymethyl)-2-methylprop-2-enamide Chemical compound COCNC(=O)C(C)=C YOZHLACIXDCHPV-UHFFFAOYSA-N 0.000 claims description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 3
- SBYMUDUGTIKLCR-UHFFFAOYSA-N 2-chloroethenylbenzene Chemical compound ClC=CC1=CC=CC=C1 SBYMUDUGTIKLCR-UHFFFAOYSA-N 0.000 claims description 2
- WVYWICLMDOOCFB-UHFFFAOYSA-N 4-methyl-2-pentanol Chemical compound CC(C)CC(C)O WVYWICLMDOOCFB-UHFFFAOYSA-N 0.000 claims description 2
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 claims description 2
- 125000005250 alkyl acrylate group Chemical group 0.000 claims description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 claims description 2
- FYIBPWZEZWVDQB-UHFFFAOYSA-N dicyclohexyl carbonate Chemical class C1CCCCC1OC(=O)OC1CCCCC1 FYIBPWZEZWVDQB-UHFFFAOYSA-N 0.000 claims description 2
- LRDFRRGEGBBSRN-UHFFFAOYSA-N isobutyronitrile Chemical compound CC(C)C#N LRDFRRGEGBBSRN-UHFFFAOYSA-N 0.000 claims description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 2
- 150000002978 peroxides Chemical class 0.000 claims description 2
- 239000003361 porogen Substances 0.000 claims description 2
- 239000011148 porous material Substances 0.000 claims description 2
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 claims description 2
- 108010010803 Gelatin Proteins 0.000 description 16
- 229920000159 gelatin Polymers 0.000 description 16
- 239000008273 gelatin Substances 0.000 description 16
- 235000019322 gelatine Nutrition 0.000 description 16
- 235000011852 gelatine desserts Nutrition 0.000 description 16
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 15
- XZKRXPZXQLARHH-UHFFFAOYSA-N buta-1,3-dienylbenzene Chemical group C=CC=CC1=CC=CC=C1 XZKRXPZXQLARHH-UHFFFAOYSA-N 0.000 description 12
- 239000000126 substance Substances 0.000 description 10
- 239000000463 material Substances 0.000 description 9
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
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- 239000007853 buffer solution Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000000084 colloidal system Substances 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 230000001681 protective effect Effects 0.000 description 5
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- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000011324 bead Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000002775 capsule Substances 0.000 description 3
- 229920002678 cellulose Polymers 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000009736 wetting Methods 0.000 description 3
- XWJBRBSPAODJER-UHFFFAOYSA-N 1,7-octadiene Chemical compound C=CCCCCC=C XWJBRBSPAODJER-UHFFFAOYSA-N 0.000 description 2
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical class ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229920000867 polyelectrolyte Polymers 0.000 description 2
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 229960001755 resorcinol Drugs 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000006277 sulfonation reaction Methods 0.000 description 2
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 description 1
- LGPAKRMZNPYPMG-UHFFFAOYSA-N (3-hydroxy-2-prop-2-enoyloxypropyl) prop-2-enoate Chemical compound C=CC(=O)OC(CO)COC(=O)C=C LGPAKRMZNPYPMG-UHFFFAOYSA-N 0.000 description 1
- VXMQKONTARQGPP-UHFFFAOYSA-N (ethoxyamino)oxyethane Chemical compound CCONOCC VXMQKONTARQGPP-UHFFFAOYSA-N 0.000 description 1
- WVAFEFUPWRPQSY-UHFFFAOYSA-N 1,2,3-tris(ethenyl)benzene Chemical compound C=CC1=CC=CC(C=C)=C1C=C WVAFEFUPWRPQSY-UHFFFAOYSA-N 0.000 description 1
- QLLUAUADIMPKIH-UHFFFAOYSA-N 1,2-bis(ethenyl)naphthalene Chemical compound C1=CC=CC2=C(C=C)C(C=C)=CC=C21 QLLUAUADIMPKIH-UHFFFAOYSA-N 0.000 description 1
- PRBHEGAFLDMLAL-UHFFFAOYSA-N 1,5-Hexadiene Natural products CC=CCC=C PRBHEGAFLDMLAL-UHFFFAOYSA-N 0.000 description 1
- WAEOXIOXMKNFLQ-UHFFFAOYSA-N 1-methyl-4-prop-2-enylbenzene Chemical group CC1=CC=C(CC=C)C=C1 WAEOXIOXMKNFLQ-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N 2-butenoic acid Chemical compound CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- NEJUBWVKDRSPFZ-UHFFFAOYSA-N 2-hydrazinyloxy-2-oxoacetic acid Chemical compound NNOC(=O)C(O)=O NEJUBWVKDRSPFZ-UHFFFAOYSA-N 0.000 description 1
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 description 1
- 229920001479 Hydroxyethyl methyl cellulose Polymers 0.000 description 1
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 1
- WZNGETBJLYZXRB-UHFFFAOYSA-N NOC1=CC=CC=C1.N Chemical compound NOC1=CC=CC=C1.N WZNGETBJLYZXRB-UHFFFAOYSA-N 0.000 description 1
- SYNHCENRCUAUNM-UHFFFAOYSA-N Nitrogen mustard N-oxide hydrochloride Chemical compound Cl.ClCC[N+]([O-])(C)CCCl SYNHCENRCUAUNM-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 229920002396 Polyurea Polymers 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 description 1
- AZFNGPAYDKGCRB-XCPIVNJJSA-M [(1s,2s)-2-amino-1,2-diphenylethyl]-(4-methylphenyl)sulfonylazanide;chlororuthenium(1+);1-methyl-4-propan-2-ylbenzene Chemical compound [Ru+]Cl.CC(C)C1=CC=C(C)C=C1.C1=CC(C)=CC=C1S(=O)(=O)[N-][C@@H](C=1C=CC=CC=1)[C@@H](N)C1=CC=CC=C1 AZFNGPAYDKGCRB-XCPIVNJJSA-M 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001263 acyl chlorides Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910000329 aluminium sulfate Inorganic materials 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- SOIFLUNRINLCBN-UHFFFAOYSA-N ammonium thiocyanate Chemical compound [NH4+].[S-]C#N SOIFLUNRINLCBN-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000000889 atomisation Methods 0.000 description 1
- 210000001124 body fluid Anatomy 0.000 description 1
- 239000010839 body fluid Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 230000021523 carboxylation Effects 0.000 description 1
- 238000006473 carboxylation reaction Methods 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 229920003086 cellulose ether Polymers 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- ZRRLFMPOAYZELW-UHFFFAOYSA-N disodium;hydrogen phosphite Chemical compound [Na+].[Na+].OP([O-])[O-] ZRRLFMPOAYZELW-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000008394 flocculating agent Substances 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- PYGSKMBEVAICCR-UHFFFAOYSA-N hexa-1,5-diene Chemical compound C=CCCC=C PYGSKMBEVAICCR-UHFFFAOYSA-N 0.000 description 1
- 150000002429 hydrazines Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 150000002832 nitroso derivatives Chemical class 0.000 description 1
- UOKZUTXLHRTLFH-UHFFFAOYSA-N o-phenylhydroxylamine Chemical compound NOC1=CC=CC=C1 UOKZUTXLHRTLFH-UHFFFAOYSA-N 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- DBSDMAPJGHBWAL-UHFFFAOYSA-N penta-1,4-dien-3-ylbenzene Chemical compound C=CC(C=C)C1=CC=CC=C1 DBSDMAPJGHBWAL-UHFFFAOYSA-N 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 230000005501 phase interface Effects 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- 235000010289 potassium nitrite Nutrition 0.000 description 1
- 239000004304 potassium nitrite Substances 0.000 description 1
- FBCQUCJYYPMKRO-UHFFFAOYSA-N prop-2-enyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC=C FBCQUCJYYPMKRO-UHFFFAOYSA-N 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 229940079877 pyrogallol Drugs 0.000 description 1
- JVBXVOWTABLYPX-UHFFFAOYSA-L sodium dithionite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])=O JVBXVOWTABLYPX-UHFFFAOYSA-L 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 235000010288 sodium nitrite Nutrition 0.000 description 1
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 1
- VGTPCRGMBIAPIM-UHFFFAOYSA-M sodium thiocyanate Chemical compound [Na+].[S-]C#N VGTPCRGMBIAPIM-UHFFFAOYSA-M 0.000 description 1
- PODWXQQNRWNDGD-UHFFFAOYSA-L sodium thiosulfate pentahydrate Chemical compound O.O.O.O.O.[Na+].[Na+].[O-]S([S-])(=O)=O PODWXQQNRWNDGD-UHFFFAOYSA-L 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/18—Suspension polymerisation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/04—Acids; Metal salts or ammonium salts thereof
- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/42—Nitriles
- C08F220/44—Acrylonitrile
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F220/56—Acrylamide; Methacrylamide
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Manufacturing Of Micro-Capsules (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Polymerisation Methods In General (AREA)
Abstract
本发明涉及通过含有引发剂的悬浮在水相中的疏水性单体的微囊包封液滴和加入到该水相中的亲水性单体的混合物的聚合作用来制备微囊包封球形聚合物的方法。
Description
本发明涉及通过含有引发剂的悬浮在水相中的疏水性单体的微囊包封液滴和加入到该水相中的亲水性单体的混合物的聚合作用来制备微囊包封球形聚合物的方法。
近来,具有尽可能均一粒度的离子交换剂(以下称为“单分散”)变得越来越重要,因为,由于单分散离子交换剂的交换剂床具有更有利的流体力学性能,使其在许多应用中能获得经济上的好处,关于这点可参考EP-A-0046535和EP-A-0051210。
单分散离子交换剂可以通过使单分散珠状聚合物官能化得到。制备单分散珠状聚合物的一种可能的方法是采用特殊的雾化技术产生单分散单体液滴,然后通过聚合作用使这些液滴固化。均一液滴的形成得到振动激发的支持,例如EP-A-0051210叙述了一种生产具有均一粒度的球形粒子的方法,其中均一单体液滴是通过层状单体流中的振动激发而产生的。如果想在聚合过程中保持单体液滴的单分散性,则必须确保消除液滴的聚集和聚结以及新液滴的形成。防止液滴聚结及新液滴形成的一种特别有效的方法是按照EP-A-0046535的液滴微囊包封技术。
对于珠状聚合物的性能,往往有利的作法是,除了使用疏水性单体外,还使用易溶于水的亲水性单体。上述先有技术的缺点在于其中所有单体都是微囊包封的。按照这种方法,一部分水溶性单体就有可能从微囊中跑到水相中去。如果水相被取代,例如被逆流水洗取代,则水溶性单体也会部分地被除去。
因此,本发明的目的是制备疏水性单体和易溶于水的亲水性单体这两者的微囊包封共聚物。现已发现,如果在与悬浮于水相中的微囊包封的疏水性单体进行聚合的同时往该水相中添加亲水性单体,就可得到疏水性及亲水性单体的微囊包封共聚物。
因此本发明涉及制备疏水性和亲水性单体的微囊包封聚合物的方法,其特征在于使悬浮于水相中的微囊包封的疏水性单体进行聚合,同时往水相中加入亲水性单体。
在本发明的上下文中,单体应理解为表示单烯类不饱和化合物和通常起交联剂作用的多烯类不饱和化合物,以及它们的混合物。就本发明的意义上讲,疏水性单体应理解为表示能在水相中形成另一相、且在25℃的溶解度<2%(重量)的单体。疏水性单烯类不饱和化合物的例子有苯乙烯、乙烯基甲苯、乙基苯乙烯、α-甲基苯乙烯、氯代苯乙烯、氯甲基苯乙烯、丙烯酸烷基酯和甲基丙烯酸烷基酯。优选的是苯乙烯以及苯乙烯与上述单体的混合物。疏水性多官能单烯类不饱和化合物的例子是二乙烯基苯、二乙烯基甲苯、三乙烯基苯、二乙烯基萘、三乙烯基萘、1,7-辛二烯、1,5-己二烯、乙二醇二甲基丙烯酸酯、三羟甲基丙烷三甲基丙烯酸酯和甲基丙烯酸烯丙酯。
在本发明的上下文中,亲水性单体应理解为表示在25℃在水中的溶解度至少为2%(重量)的单体。亲水性单烯类不饱和化合物的例子有丙烯酸、甲基丙烯酸、丙烯腈、甲基丙烯腈、丙烯酰胺、甲基丙烯酰胺、丙烯酸羟烷基酯、丙烯酸烷氧基烷基酯、丙烯酸氨烷氧基烷基酯、甲基丙烯酸羟烷基酯、甲基丙烯酸烷氧基烷基酯和甲基丙烯酸氨烷氧基烷基酯,以及氮原子上有取代的丙烯酰胺或甲基丙烯酰胺的衍生物,例如N-甲氧基甲基甲基丙烯酰胺。优选的是丙烯腈、甲基丙烯酰胺以及氮原子上有取代的甲基丙烯酰胺的衍生物。亲水性多官能烯类不饱和化合物的例子是二丙烯酸甘油酯。
单烯类不饱和化合物的用量一般为疏水性和亲水性单体混合物重量的0.05~20%,优选0.1~10%,特别优选0.2~5%。多烯类不饱和化合物(交联剂)的类型要根据球形聚合物随后的用途来选择。例如,如果想通过磺化从聚合物制备阳离子交换剂,则丙烯酸酯和甲基丙烯酸酯均不合适,因为酯键在磺化条件下会断裂。在许多情况下,尤其对于制备强酸性阳离子交换剂来说,二乙烯基苯是合适的。对大多数用途而言,工业纯的二乙烯基苯就足够了,这种产品除了含有二乙烯基苯的各种异构体外,也还含有乙基乙烯基苯。
可用各种方法加入亲水性单体。例如,可以一开始就将亲水性单体加入到反应器中,然后再充入分散在水相中的微囊包封的单体液滴。也可以在开始时先将分散的微囊包封的单体液滴加入到水相中,然后再加入亲水性单体。同样地,也可以同时加入亲水性单体和分散的微囊包封的单体液滴。亲水性单体也可以以水溶液或水相形式使用。优选的是,将亲水性单体加入到分散在水相中的微囊包封单体液滴中,特别优选的是,以优选的方式加入水含量<5%(重量)的亲水性单体。
加入亲水性单体的时间也可以在宽范围内变化。因此,例如,可以在聚合开始之前加入该单体。然而,也可以在聚合过程中加入该单体,或者也可以在一段较长的时间内以计量方式加入。优选的是在聚合开始之前加入该单体。
用于这种预期用途的已知材料,尤其是聚酯、天然与合成聚酰胺、聚氨酯、聚脲均适用于单体液滴的微囊包封。特别适用的天然聚酰胺是明胶。明胶特别用作凝聚层和复合凝聚层。就本发明的意义上讲,含明胶的复合凝聚层应理解为尤其表示明胶和合成聚电解质的结合。适用的合成聚电解质是含有例如加入的马来酸、丙烯酸、甲基丙烯酸、丙烯酰胺和甲基丙烯酰胺单元的共聚物。含明胶的胶囊可用通常的固化剂,例如甲醛或戊二醛进行固化。有关用明胶、含明胶的凝聚剂和含明胶的复合凝聚剂包封单体液滴的方法详细叙述于EP-A-0046535中。用合成聚合物进行包封的方法是已知的。例如,相界面缩聚是一种合适的方法,在该方法中,使溶解在单体液滴中的一种反应性组分(例如异氰酸酯或酰氯)与溶解在水相中的第二反应性组分(例如胺)反应。
被包封的单体液滴含有引发剂,用于引发聚合反应。适用于本发明方法的引发剂有,例如过氧化合物,如过氧化二苯甲酰、过氧化二月桂基、过氧化二(对氯苯甲酰)、过氧二碳酸二环己基酯、过辛酸叔丁酯、过氧-2-乙基-己酸叔丁酯、2,5-二(2-乙基己酰基过氧)-2,5-二甲基己烷和叔戊基过氧-2-乙基己烷,以及偶氮化合物,例如,2,2′-偶氮二(异丁腈)和2,2′-偶氮二(2-甲基异丁腈)。
亲水性单体也可以含有引发剂。上述引发剂同样适合于此目的。优选的是添加不含引发剂的亲水性单体。
引发剂的用量一般为亲水性和疏水性单体混合物重量的0.05-2.5%,优选0.1-1.5%。
所谓成孔剂(porogens)可以作为进一步的添加剂用于微囊包封液滴中,以便在球形聚合物中产生大孔结构。对于此目的而言,合适的溶剂是所生成的聚合物在其中溶解性差或只能溶胀的那些溶剂。可以提及的例子有己烷、辛烷、异辛烷、异十二烷、甲乙酮、甲基异丁基酮、甲基异丁基甲醇和辛醇。
微囊包封单体液滴可以含有至多30%(以单体重量计)的交联或未交联的聚合物。优选的聚合物是从上述单体衍生的,特别优选的是从苯乙烯衍生的。
包封单体液滴的平均粒度是10-1000μm,优选100-1000μm。本发明的方法也适用于制备单分散球形聚合物。
水相可以含有溶解的聚合引发剂。合适的阻聚剂既可以是无机物质也可以是有机物质。无机阻聚剂的例子有含氮化合物,如羟基胺、肼、亚硝酸钠和亚硝酸钾,亚磷酸盐如亚磷酸氢钠,以及含硫化合物,如连二亚硫酸钠、硫代硫酸钠、亚硫酸钠、亚硫酸氢钠、硫氰酸钠和硫氰酸铵。有机阻聚剂的例子有酚类化合物,如氢醌、对苯二酚单甲基醚、雷琐酚、焦儿茶酚、叔丁基焦儿茶酚、焦棓酚以及酚醛缩合物。其它合适的有机阻聚剂是含氮化合物。这类化合物包括羟基胺衍生物,如N,N-二乙基羟基胺、N-异丙基羟基胺和磺化或羧化N-烷基羟基胺或N,N-二烷基羟基胺衍生物,肼衍生物如N,N-肼基二乙酸,亚硝基化合物如N-亚硝基苯基羟基胺、N-亚硝基苯基羟基胺铵盐或N-亚硝基苯基羟基胺铝盐。阻聚剂的浓度为5-1000ppm(以水相为基准计),优选10-500ppm,特别优选10-250ppm。
在一种或几种保护性胶体以及任选的缓冲体系的存在下,可以方便地实现包封单体液滴在水相中的聚合作用,得到球形聚合物。适用的保护性胶体是天然和合成的水溶性聚合物,例如明胶、淀粉、聚乙烯醇、聚乙烯基吡咯烷酮、聚丙烯酸、聚甲基丙烯酸和(甲基)丙烯酸与(甲基)丙烯酸酯的共聚物。纤维素衍生物也是非常合适的,尤其是纤维素酯和纤维素醚,如羧甲基纤维素、甲基羟乙基纤维素、甲基羟丙基纤维素和羟乙基纤维素。特别合适的是明胶。保护性胶体的用量一般为水相重量的0.05-1%,优选0.05-0.5%。
聚合可以在缓冲体系存在下进行。优选的缓冲体系是在聚合开始时能将水相的pH值调节在14-6之间,优选在12~8之间的缓冲体系。在这些条件下,保护性胶体中全部或一部分羧基以盐的形式存在。以这种方式能有利地影响保护性胶体的作用。特别适用的缓冲体系含有硫酸盐或硼酸盐。就本发明的意义上讲,磷酸盐和硼酸盐这两个术语也包括原形式的相应酸和盐的缩合物。水相中硫酸盐或硼酸盐的浓度是0.5-500mmol/l,优选2.5-100mmol/l。
聚合过程中的搅拌速度并不很严格,与传统珠状聚合相比,本方法中的搅拌速度对粒度没有任何影响。应当采用能足以使悬浮的单体液滴处于悬浮状态并能足以使聚合热除去的低搅拌速度。可以采用各种类型搅拌器。特别适合的是具有轴向搅拌作用的框式搅拌器。
包封单体液滴与水相的体积比是1∶0.75-1∶20,优选1∶1-1∶6。
聚合温度取决于所用引发剂的分解温度。该温度一般为50-150℃,优选为55-100℃。聚合时间为0.5小时至几小时。已经证明采用下述的温度程序是有益的:在低温,例如60℃,开始聚合,然后随着聚合转化率的增加,反应温度不断提高。例如,按照这个方法可以非常容易地满足对反应过程的安全性和高聚合转化率的要求。聚合完毕后,可用常规方法分离出聚合物,例如采用过滤或倾析的方法,并任选地将聚合物进行洗涤。
按照本发明方法制备的微囊包封聚合物是由疏水性和亲水性单体构成的。这是令人惊奇的,因为亲水性单体并没有由于微囊包封的结果与疏水性单体液滴分开,保持独立,而是穿过包围疏水性单体液滴的胶囊壁,只在该液滴中进行共聚。
实例1(按照本发明)
先将3000g软化水加入到10升的玻璃反应器中,然后加入10g明胶、16g硫酸氢钠十二水合物和0.73g雷琐酚在320g软化水中的溶液,并进行充分混合。
然后在搅拌下加入3200g微囊包封窄粒度分布单体液滴和3200gpH为12的水相的混合物。所述单体液滴含有10.4%(重量)的二乙烯基苯和2.6%(重量)的乙基苯乙烯(以二乙烯基苯和乙基苯乙烯的工业异构体混合物形式使用,其中二乙烯基苯含量为80%重量)、0.75%(重量)的过氧化二苯甲酰和86.25%(重量)的苯乙烯。所述微胶囊由用甲醛固化的复合凝聚层组成,并含有明胶和丙烯酰胺与丙烯酸的共聚物。该单体液粒的平均粒度为430μm。
在搅拌下将136g丙烯加入到该批料中。
在搅拌下按照开始25℃和最终95℃的温度程序升温,使该物料聚合。将物料冷却,在32μm筛网上洗涤,然后干燥。得到3250g平均粒度为410μm、具有窄粒度分布和平滑表面的球形聚合物。氮含量为0.9%(重量)。
实例2(按照本发明)
先将1185g软化水加入到4升的玻璃反应器中,然后加入2.4g明胶和4g硫酸氢钠十二水合物在80g软化水中的溶液和12.8g丙烯腈,并进行充分混合。然后在搅拌下加入640g微囊包封窄粒度分布的单体液滴和790g pH为12含有0.065%(重量)的甲醛和氢氧化钠溶液的水相的混合物。所述单体液滴含有0.5%(重量)的二乙烯基苯和0.3%(重量)的乙基苯乙烯(以二乙烯基苯和乙基苯乙烯的工业异构体混合物形式使用,其中二乙烯基苯的含量为63%重量)、0.75%(重量)的过氧化二苯甲酰和98.45%(重量)的苯乙烯。所述微胶囊由用甲醛固化的复合凝聚层构成,并含有明胶和丙烯酰胺与丙烯酸的共聚物。平均粒度是231μm。在搅拌下按照开始25℃和最终95℃的温度程序升温,使该物料聚合。将物料冷却,在32μm筛网上洗涤,然后干燥。得到620g平均粒度为220μm、具有窄粒度分布和平滑表面的球形聚合物。氮含量为0.5%(重量)。
实例3(按照本发明)
先将3000g软化水加入到10升的玻璃反应器中,然后加入10g明胶、16g硫酸氢钠十二水合物在320g软化水中的溶液,并进行充分混合。
然后在搅拌下加入微囊包封窄粒度分布单体液滴和4000g pH为12的水相的混合物。所述单体液滴含有112g二乙烯基苯重量含量为80%的二乙烯基苯和乙基苯乙烯的工业异构体混合物、1008g苯乙烯、896g异十二烷和9.6g重量含量为75%的过氧化二苯甲酰。所述胶囊由用甲醛固化的复合凝聚层构成,并含有明胶和丙烯酰胺与丙烯酸的共聚物。该单体液滴的平均粒度为220μm。
在搅拌下将56g N-甲氧基甲基甲基丙烯酰胺加入到该批物料中。
在搅拌下按照开始25℃和最终95℃的温度程序升温,使该物料聚合。将物料冷却,在32μm筛网上洗涤,然后干燥。得到1065g平均粒度为210μm、具有窄粒度分布和平滑表面的球形聚合物。氮含量为0.34%(重量)。
Claims (9)
1.制备疏水性和亲水性单体的微囊包封共聚物的方法,其特征在于使悬浮于水相中的微囊包封的疏水性单体进行聚合,同时往水相中加入亲水性单体。
2.按照权利要求1的方法,其特征在于用25℃时在水中的溶解度<2%(重量)的单烯类不饱和化合物作为疏水性单体。
3.按照权利要求1的方法,其特征在于用25℃时在水中的溶解度为至少2%的单烯类不饱和化合物作为亲水性单体。
4.按照权利要求2的方法,其特征在于用苯乙烯、乙烯基甲苯、乙基苯乙烯、α-甲基苯乙烯、氯苯乙烯、氯甲基苯乙烯、丙烯酸烷基酯和甲基丙烯酸烷基酯作为疏水性单体。
5.按照权利要求3的方法,其特征在于用丙烯酸、甲基丙烯酸、丙烯腈、甲基丙烯腈、丙烯酸羟烷基酯、丙烯酸烷氧基烷基酯、丙烯酸氨烷氧基烷基酯、甲基丙烯酸羟烷基酯、甲基丙烯酸烷氧基烷基酯和甲基丙烯酸氨烷氧基烷基酯,以及氮原子上有取代的丙烯酰胺或甲基丙烯酰胺的衍生物,例如N-甲氧基甲基甲基丙烯酰胺作为亲水性单体。
6.按照权利要求1的方法,其特征在于单烯类不饱和化合物的用量是疏水性和亲水性单体混合物重量的0.05~20%。
7.按照权利要求1的方法,其特征在于使用下列引发剂:过氧化二苯甲酰、过氧化二月桂基、过氧化二(对氯苯甲酰)、过氧二碳酸二环己基酯、过辛酸叔丁酯、过氧-2-乙基-己酸叔丁酯、2,5-二(2-乙基己酰基过氧)-2,5-二甲基己烷、叔戊基过氧-2-乙基己烷、2,2′-偶氮二(异丁腈)和2,2′-偶氮二(2-甲基异丁腈)。
8.按照权利要求1的方法,其特征在于另外还使用下列成孔剂(porogens):己烷、辛烷、异辛烷、异十二烷、甲乙酮、甲基异丁基酮、甲基异丁基甲醇和辛醇。
9.按照权利要求1的方法,其特征在于该微囊包封疏水性单体含有至多30%的苯乙烯或基于苯乙烯的共聚物。
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DE19847050A DE19847050A1 (de) | 1998-10-13 | 1998-10-13 | Verfahren zur Herstellung mikroverkapselter kugelförmiger Polymerisate |
DE19847050.9 | 1998-10-13 |
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JP (1) | JP2000119305A (zh) |
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DE (2) | DE19847050A1 (zh) |
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CN110483838A (zh) * | 2015-05-29 | 2019-11-22 | 赛鲁斯股份有限公司 | 包封的聚合引发剂、聚合体系以及使用所述体系的方法 |
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MXPA00012167A (es) | 1999-12-24 | 2002-08-06 | Bayer Ag | Procedimiento para la obtencion de polimeros en perlas, reticulados, monodispersados. |
US6715674B2 (en) * | 2002-08-27 | 2004-04-06 | Ultra-Scan Corporation | Biometric factor augmentation method for identification systems |
US7566498B2 (en) | 2002-12-25 | 2009-07-28 | Matsumoto Yushi-Seiyaku Co., Ltd. | Thermo-expansive microcapsule, production process of expanded product and expanded product thereof |
DE102005021335A1 (de) * | 2005-05-04 | 2006-11-09 | Röhm Gmbh | Verfahren zur Herstellung von Perlpolymerisaten mit einer mittleren Teilchengröße im Bereich von 1 µm bis 40 µm sowie Perlpolymerisat aufweisende Formmassen und Formkörper |
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US4259465A (en) * | 1978-05-01 | 1981-03-31 | Gaf Corporation | Bimodal coextendant suspension polymerization system |
DE3031737A1 (de) * | 1980-08-22 | 1982-04-01 | Bayer Ag, 5090 Leverkusen | Verfahren zur herstellung von perlpolymerisaten einheitlicher teilchengroesse |
CA1166413A (en) * | 1980-10-30 | 1984-05-01 | Edward E. Timm | Process and apparatus for preparing uniform size polymer beads |
DE19647291A1 (de) * | 1996-11-15 | 1998-05-20 | Bayer Ag | Verfahren zur Herstellung mikroverkapselter Polymerisate |
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DE19847050A1 (de) | 2000-04-20 |
TW512147B (en) | 2002-12-01 |
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JP2000119305A (ja) | 2000-04-25 |
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