CN1162963A - Process for preparing an aqueous polymer dispersion - Google Patents
Process for preparing an aqueous polymer dispersion Download PDFInfo
- Publication number
- CN1162963A CN1162963A CN 95196128 CN95196128A CN1162963A CN 1162963 A CN1162963 A CN 1162963A CN 95196128 CN95196128 CN 95196128 CN 95196128 A CN95196128 A CN 95196128A CN 1162963 A CN1162963 A CN 1162963A
- Authority
- CN
- China
- Prior art keywords
- monomer
- polymer dispersion
- content
- aqueous polymer
- radical
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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- 239000004815 dispersion polymer Substances 0.000 title claims description 105
- 238000004519 manufacturing process Methods 0.000 title description 3
- 239000000178 monomer Substances 0.000 claims abstract description 202
- 238000000034 method Methods 0.000 claims abstract description 123
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 80
- 229920000642 polymer Polymers 0.000 claims abstract description 64
- 239000000126 substance Substances 0.000 claims abstract description 50
- 230000002829 reductive effect Effects 0.000 claims abstract description 38
- 239000007788 liquid Substances 0.000 claims abstract description 29
- 239000003999 initiator Substances 0.000 claims abstract description 18
- 150000001875 compounds Chemical class 0.000 claims abstract description 13
- 230000000694 effects Effects 0.000 claims abstract description 12
- 239000000839 emulsion Substances 0.000 claims description 45
- 239000000203 mixture Substances 0.000 claims description 45
- 239000003795 chemical substances by application Substances 0.000 claims description 43
- 238000006116 polymerization reaction Methods 0.000 claims description 42
- 238000007720 emulsion polymerization reaction Methods 0.000 claims description 41
- 239000012966 redox initiator Substances 0.000 claims description 36
- 239000007864 aqueous solution Substances 0.000 claims description 34
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical group OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 27
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 27
- -1 alkali metal salt Chemical class 0.000 claims description 27
- FYOWZTWVYZOZSI-UHFFFAOYSA-N thiourea dioxide Chemical compound NC(=N)S(O)=O FYOWZTWVYZOZSI-UHFFFAOYSA-N 0.000 claims description 22
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 20
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 18
- 239000002612 dispersion medium Substances 0.000 claims description 18
- XEKOWRVHYACXOJ-UHFFFAOYSA-N ethyl acetate Substances CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 17
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 16
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 16
- 230000008569 process Effects 0.000 claims description 16
- 239000007787 solid Substances 0.000 claims description 14
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 13
- 125000004432 carbon atom Chemical group C* 0.000 claims description 13
- 150000002148 esters Chemical class 0.000 claims description 13
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 11
- 229910052799 carbon Inorganic materials 0.000 claims description 9
- 239000002609 medium Substances 0.000 claims description 9
- 238000005502 peroxidation Methods 0.000 claims description 9
- 238000002360 preparation method Methods 0.000 claims description 8
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 7
- 150000003839 salts Chemical class 0.000 claims description 7
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 5
- 229910052783 alkali metal Inorganic materials 0.000 claims description 5
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims description 5
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 4
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 claims description 4
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims description 4
- 230000008859 change Effects 0.000 claims description 4
- VFNGKCDDZUSWLR-UHFFFAOYSA-N disulfuric acid Chemical compound OS(=O)(=O)OS(O)(=O)=O VFNGKCDDZUSWLR-UHFFFAOYSA-N 0.000 claims description 4
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 claims description 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 3
- 150000003863 ammonium salts Chemical class 0.000 claims description 3
- 229910001882 dioxygen Inorganic materials 0.000 claims description 3
- 229910000765 intermetallic Inorganic materials 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 claims description 3
- 230000007704 transition Effects 0.000 claims description 2
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims 1
- 150000003254 radicals Chemical class 0.000 abstract description 57
- 239000003638 chemical reducing agent Substances 0.000 abstract description 8
- 239000007800 oxidant agent Substances 0.000 abstract description 7
- 230000001590 oxidative effect Effects 0.000 abstract description 5
- 230000033116 oxidation-reduction process Effects 0.000 abstract 2
- 239000002994 raw material Substances 0.000 description 22
- 239000003995 emulsifying agent Substances 0.000 description 20
- 239000000243 solution Substances 0.000 description 18
- 239000006185 dispersion Substances 0.000 description 15
- 238000007046 ethoxylation reaction Methods 0.000 description 15
- 239000012298 atmosphere Substances 0.000 description 14
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 13
- 239000011261 inert gas Substances 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 12
- 230000009467 reduction Effects 0.000 description 11
- 239000002253 acid Substances 0.000 description 10
- 150000001721 carbon Chemical group 0.000 description 9
- 239000012071 phase Substances 0.000 description 9
- 238000010526 radical polymerization reaction Methods 0.000 description 9
- XWGJFPHUCFXLBL-UHFFFAOYSA-M rongalite Chemical compound [Na+].OCS([O-])=O XWGJFPHUCFXLBL-UHFFFAOYSA-M 0.000 description 9
- 125000000217 alkyl group Chemical group 0.000 description 8
- 150000001408 amides Chemical class 0.000 description 8
- YACLQRRMGMJLJV-UHFFFAOYSA-N chloroprene Chemical compound ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 description 8
- 150000002500 ions Chemical class 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 239000011324 bead Substances 0.000 description 7
- 230000002349 favourable effect Effects 0.000 description 7
- JXAZAUKOWVKTLO-UHFFFAOYSA-L sodium pyrosulfate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)OS([O-])(=O)=O JXAZAUKOWVKTLO-UHFFFAOYSA-L 0.000 description 7
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 150000002191 fatty alcohols Chemical class 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- SBGKURINHGJRFN-UHFFFAOYSA-N hydroxymethanesulfinic acid Chemical compound OCS(O)=O SBGKURINHGJRFN-UHFFFAOYSA-N 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 5
- 159000000000 sodium salts Chemical class 0.000 description 5
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 5
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 4
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 4
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 4
- 239000000084 colloidal system Substances 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- LVHBHZANLOWSRM-UHFFFAOYSA-N itaconic acid Chemical compound OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 230000001681 protective effect Effects 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- CCJAYIGMMRQRAO-UHFFFAOYSA-N 2-[4-[(2-hydroxyphenyl)methylideneamino]butyliminomethyl]phenol Chemical compound OC1=CC=CC=C1C=NCCCCN=CC1=CC=CC=C1O CCJAYIGMMRQRAO-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910052728 basic metal Inorganic materials 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- BWYYYTVSBPRQCN-UHFFFAOYSA-M sodium;ethenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C=C BWYYYTVSBPRQCN-UHFFFAOYSA-M 0.000 description 3
- 230000009466 transformation Effects 0.000 description 3
- KUDUQBURMYMBIJ-UHFFFAOYSA-N 2-prop-2-enoyloxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC(=O)C=C KUDUQBURMYMBIJ-UHFFFAOYSA-N 0.000 description 2
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 239000012874 anionic emulsifier Substances 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- 150000003818 basic metals Chemical class 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 2
- 239000000920 calcium hydroxide Substances 0.000 description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- FDENMIUNZYEPDD-UHFFFAOYSA-L disodium [2-[4-(10-methylundecyl)-2-sulfonatooxyphenoxy]phenyl] sulfate Chemical compound [Na+].[Na+].CC(C)CCCCCCCCCc1ccc(Oc2ccccc2OS([O-])(=O)=O)c(OS([O-])(=O)=O)c1 FDENMIUNZYEPDD-UHFFFAOYSA-L 0.000 description 2
- 239000001530 fumaric acid Substances 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 125000003010 ionic group Chemical group 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 2
- DNTMQTKDNSEIFO-UHFFFAOYSA-N n-(hydroxymethyl)-2-methylprop-2-enamide Chemical compound CC(=C)C(=O)NCO DNTMQTKDNSEIFO-UHFFFAOYSA-N 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 230000008719 thickening Effects 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- 229910001428 transition metal ion Inorganic materials 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (1R)-1,3-butanediol Natural products CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 1
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 description 1
- WERYXYBDKMZEQL-UHFFFAOYSA-N 1,4-butanediol Substances OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 1
- NDGXZYRXRPWLOE-UHFFFAOYSA-N 2-(prop-2-enoylamino)oxyacetic acid Chemical compound OC(=O)CONC(=O)C=C NDGXZYRXRPWLOE-UHFFFAOYSA-N 0.000 description 1
- SBYMUDUGTIKLCR-UHFFFAOYSA-N 2-chloroethenylbenzene Chemical compound ClC=CC1=CC=CC=C1 SBYMUDUGTIKLCR-UHFFFAOYSA-N 0.000 description 1
- TWYISXLZCIVDDW-UHFFFAOYSA-N 2-methyl-n-(2-methylpropoxymethyl)prop-2-enamide Chemical compound CC(C)COCNC(=O)C(C)=C TWYISXLZCIVDDW-UHFFFAOYSA-N 0.000 description 1
- DUIOKRXOKLLURE-UHFFFAOYSA-N 2-octylphenol Chemical compound CCCCCCCCC1=CC=CC=C1O DUIOKRXOKLLURE-UHFFFAOYSA-N 0.000 description 1
- NYYSPVRERVXMLJ-UHFFFAOYSA-N 4,4-difluorocyclohexan-1-one Chemical compound FC1(F)CCC(=O)CC1 NYYSPVRERVXMLJ-UHFFFAOYSA-N 0.000 description 1
- JYCQQPHGFMYQCF-UHFFFAOYSA-N 4-tert-Octylphenol monoethoxylate Chemical compound CC(C)(C)CC(C)(C)C1=CC=C(OCCO)C=C1 JYCQQPHGFMYQCF-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- JGLMVXWAHNTPRF-CMDGGOBGSA-N CCN1N=C(C)C=C1C(=O)NC1=NC2=CC(=CC(OC)=C2N1C\C=C\CN1C(NC(=O)C2=CC(C)=NN2CC)=NC2=CC(=CC(OCCCN3CCOCC3)=C12)C(N)=O)C(N)=O Chemical compound CCN1N=C(C)C=C1C(=O)NC1=NC2=CC(=CC(OC)=C2N1C\C=C\CN1C(NC(=O)C2=CC(C)=NN2CC)=NC2=CC(=CC(OCCCN3CCOCC3)=C12)C(N)=O)C(N)=O JGLMVXWAHNTPRF-CMDGGOBGSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical class [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- 229930091371 Fructose Natural products 0.000 description 1
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 description 1
- 239000005715 Fructose Substances 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 229910021550 Vanadium Chloride Inorganic materials 0.000 description 1
- QLVHFTGKDGTJDH-UHFFFAOYSA-N acetic acid;ethenyl acetate Chemical compound CC(O)=O.CC(=O)OC=C QLVHFTGKDGTJDH-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 238000012644 addition polymerization Methods 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- YCOXTKKNXUZSKD-UHFFFAOYSA-N as-o-xylenol Natural products CC1=CC=C(O)C=C1C YCOXTKKNXUZSKD-UHFFFAOYSA-N 0.000 description 1
- 235000015278 beef Nutrition 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 239000003139 biocide Substances 0.000 description 1
- ZPOLOEWJWXZUSP-AATRIKPKSA-N bis(prop-2-enyl) (e)-but-2-enedioate Chemical compound C=CCOC(=O)\C=C\C(=O)OCC=C ZPOLOEWJWXZUSP-AATRIKPKSA-N 0.000 description 1
- ZPOLOEWJWXZUSP-WAYWQWQTSA-N bis(prop-2-enyl) (z)-but-2-enedioate Chemical compound C=CCOC(=O)\C=C/C(=O)OCC=C ZPOLOEWJWXZUSP-WAYWQWQTSA-N 0.000 description 1
- XZKRXPZXQLARHH-UHFFFAOYSA-N buta-1,3-dienylbenzene Chemical compound C=CC=CC1=CC=CC=C1 XZKRXPZXQLARHH-UHFFFAOYSA-N 0.000 description 1
- UTOVMEACOLCUCK-PLNGDYQASA-N butyl maleate Chemical compound CCCCOC(=O)\C=C/C(O)=O UTOVMEACOLCUCK-PLNGDYQASA-N 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 125000004386 diacrylate group Chemical group 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- LDCRTTXIJACKKU-ARJAWSKDSA-N dimethyl maleate Chemical compound COC(=O)\C=C/C(=O)OC LDCRTTXIJACKKU-ARJAWSKDSA-N 0.000 description 1
- HRKQOINLCJTGBK-UHFFFAOYSA-L dioxidosulfate(2-) Chemical compound [O-]S[O-] HRKQOINLCJTGBK-UHFFFAOYSA-L 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- GRWZHXKQBITJKP-UHFFFAOYSA-N dithionous acid Chemical compound OS(=O)S(O)=O GRWZHXKQBITJKP-UHFFFAOYSA-N 0.000 description 1
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical class CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- GLVVKKSPKXTQRB-UHFFFAOYSA-N ethenyl dodecanoate Chemical compound CCCCCCCCCCCC(=O)OC=C GLVVKKSPKXTQRB-UHFFFAOYSA-N 0.000 description 1
- AFSIMBWBBOJPJG-UHFFFAOYSA-N ethenyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC=C AFSIMBWBBOJPJG-UHFFFAOYSA-N 0.000 description 1
- BLCTWBJQROOONQ-UHFFFAOYSA-N ethenyl prop-2-enoate Chemical compound C=COC(=O)C=C BLCTWBJQROOONQ-UHFFFAOYSA-N 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000005562 fading Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 229940017705 formaldehyde sulfoxylate Drugs 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 235000003642 hunger Nutrition 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- SNHMUERNLJLMHN-UHFFFAOYSA-N iodobenzene Chemical compound IC1=CC=CC=C1 SNHMUERNLJLMHN-UHFFFAOYSA-N 0.000 description 1
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- JEHCHYAKAXDFKV-UHFFFAOYSA-J lead tetraacetate Chemical compound CC(=O)O[Pb](OC(C)=O)(OC(C)=O)OC(C)=O JEHCHYAKAXDFKV-UHFFFAOYSA-J 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 244000144972 livestock Species 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 235000013336 milk Nutrition 0.000 description 1
- 239000008267 milk Substances 0.000 description 1
- 210000004080 milk Anatomy 0.000 description 1
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 1
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 description 1
- KCTMTGOHHMRJHZ-UHFFFAOYSA-N n-(2-methylpropoxymethyl)prop-2-enamide Chemical compound CC(C)COCNC(=O)C=C KCTMTGOHHMRJHZ-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 229920002113 octoxynol Polymers 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- RPESBQCJGHJMTK-UHFFFAOYSA-I pentachlorovanadium Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[V+5] RPESBQCJGHJMTK-UHFFFAOYSA-I 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical class OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 230000037048 polymerization activity Effects 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000012286 potassium permanganate 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
- QTECDUFMBMSHKR-UHFFFAOYSA-N prop-2-enyl prop-2-enoate Chemical compound C=CCOC(=O)C=C QTECDUFMBMSHKR-UHFFFAOYSA-N 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-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
- 239000007870 radical polymerization initiator Substances 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 230000019635 sulfation Effects 0.000 description 1
- 238000005670 sulfation reaction Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 239000003760 tallow Substances 0.000 description 1
- 238000003419 tautomerization reaction Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 231100000027 toxicology Toxicity 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Polymerisation Methods In General (AREA)
Abstract
The invention provides a preparing method for polymer water miscible liquid, wherein the polymer water miscible liquid is prepared in known mode, and the polymer contains at least a chemical bonded monomer having at least one olefinic unsaturated group, therefore, in the polymer water miscible liquid, the total content of free monomer having at least an olefinic unsaturated bond, i.e. the monomer has not chemical bonded, is no more than 1% (by the polymer content of polymer water miscible liquid), and residual monomer content is reduced by effect of a free radical oxidation reduction initiator system containing at least an oxidant and at least a reductant, wherein the oxidation reduction initiator system includes a compound as reductant which exists in water solution in at least two intercoversion forms which are balanced each other.
Description
The present invention relates to a kind of method for preparing aqueous polymer dispersion, wherein produce aqueous polymer dispersion by known mode own, described polymkeric substance contains the monomer with at least one ethylenically unsaturated group of at least a chemical bonding, make free monomer with at least one ethylenic unsaturated bond, promptly the total content of this class monomer (being meant the content of residual monomer in this manual) in aqueous polymer dispersion of chemical bonding is not＞0 to≤1% (by the polymer content of aqueous polymer dispersion), and the effect of the radical redox initiator system of this residual monomer content by comprising at least a oxygenant and at least a reductive agent reduces.
Aqueous polymer dispersion is the fluid systems that contains the polymer beads that exists with the stable dispersion form, this polymer beads in water dispersion medium as disperse phase.The diameter major part of polymer beads is generally 0.01 to 5 μ m, and major part usually is 0.01 to 1 μ m.The stability of disperse phase usually continued more than 1 month, usually even continue more than 3 months.The volume ratio of polymkeric substance in aqueous polymer dispersion is generally 10 to 70% (volumes) (by the cumulative volume of aqueous polymer dispersion).
Situation when being evaporated with the solvent of polymers soln is the same, and aqueous polymer dispersion has the performance that forms polymeric film when water dispersion medium is evaporated, and therefore described emulsion is widely used as tackiness agent, for example is used as the coating of topcoating or coating leather.
In principle, those skilled in the art are divided into secondary water miscible liquid and a water miscible liquid with aqueous polymer dispersion.The secondary water miscible liquid be wherein polymkeric substance outside dispersion medium (for example in the solution of suitable non-aqueous solvent) preparation those water miscible liquids.Then this solution is transferred to from dispersion, to separate in the water dispersion medium and with solvent and removes (general) by distillation.Otherwise one time water miscible liquid is meant wherein these those water miscible liquids of producing and existing with the disperse phase form at once of polymkeric substance in water dispersion medium.A common feature of all these methods is the monomer with at least one ethylenically unsaturated group to be followed be used for synthetic polymer basically, or this synthesizing undertaken by these monomers fully.
Usually undertaken by initiated polymerization in conjunction with these monomers with at least one ethylenically unsaturated group, the type of initiation is specifically determined by the required performance characteristics of the finished product, is therefore adapted therewith.For example, the initiation of ion or radical is suitable.Yet, also can cause similar polymer reaction (polymer-analogous reaction) in conjunction with monomer and carry out by catalysis.It is the most frequently used that radical causes, therefore under a water miscible liquid situation, generally undertaken, under secondary water miscible liquid situation, generally undertaken by the radical solution polymerization process by the radical aqueous emulsion polymerization process in conjunction with one or more monomers with at least one ethylenically unsaturated group.
Because when considering required time, it is inappropriate attempting to reach the conversion fully that is incorporated into about one or more monomers that contain at least one ethylenically unsaturated group under the actual polymerizing condition that keeps decision the finished product desired properties (as molecular weight, molecular weight distribution, degree of branching etc.).After main polyreaction finished, the aqueous polymer dispersion that makes contained free monomer usually, and these free monomers have at least one ethylenical unsaturated double bonds and not by chemical bond be incorporated in the finished product.Because the hyperergy of ethylenical unsaturated double bonds, therefore therefore incomplete safety on toxicology consider producers and consumers's safety, and these monomers such as vinyl cyanide and vinyl-acetic ester are inappropriate.
Existing a lot of methods are used to reduce the residual monomer content of aqueous polymer dispersion.
EP-A 584 458 discloses by can reduce the residual monomer content of aqueous polymer dispersion by steam stripped.EP-B 327 006 recommends to use conventional distillating method.
The shortcoming of these methods is, although they can reduce the residual monomer content of aqueous polymer dispersion, does not handle the depleted residual monomer.Just back one problem is transferred to another state.
In addition, their use causes the solid content of water miscible liquid to change usually, and the stability of disperse phase is caused disadvantageous effect.
EP-A 505 959 relates to the method that reduces the vinyl acetate content in the polyvinyl acetate water miscible liquid.In the method for EP-A 505 959, the residual monomer vinyl-acetic ester is generated acetate and acetaldehyde with the weak alkaline medium hydrolysis, the latter is an acetate by adding hydrogen peroxide oxidation.Yet the shortcoming of this method is because another kind of ionogen load causes disadvantageous effect to the stability of aqueous polymer dispersion.
DE-A 42 10 208 relates to the free acetic acid vinyl acetate that reduces in the aqueous polymer dispersion and the method for vinyl propionate ester content.Basically these monomericly are used in combination consistently this method with stripping and hydrolysis, so the shortcoming of aforesaid method also is applicable to the method for DE-A 42 10 208.
DE-A 30 06 172 relates to the method that reduces the free acrylonitrile content in the aqueous polymer dispersion, in the method, other are had the monomer that carries out the remarkable trend of radical copolymerization with vinyl cyanide add in the aqueous polymer dispersion, proceed main radical polymerization.
DE-A 38 34 737, EP-A 379 892 and EP-A 327 006 disclose the residual monomer content in the aqueous polymer dispersion can be reduced by the radical post polymerization after main polyreaction finishes in the effect by special radical redox initiator system (these systems are because a variety of causes usually not too is fit to main polymerization), and these redox systems comprise at least a oxygenant, at least a reductive agent and (if needs) one or more transition metal ions that exist with various valence states.At this, consider the post polymerization activity of this radical redox initiator system in aqueous polymer dispersion, reductive agent plays a crucial role.When being used for the redox initiator system and playing in aqueous polymer dispersion the radical polymerization finishing, described reductive agent should be particularly :-do not influence the stability of disperse phase in aqueous polymer dispersion basically,-this redox initiator system especially in pH 〉=6 of water dispersion medium to 10, showed its advantageous effect at preferred 7 to 9 o'clock, reason is that most aqueous polymer dispersions are that negatively charged ion is stable, the effect of following of-transition metal ion is not main, because the latter remaines in the aqueous polymer dispersion after post polymerization finishes.-do not produce unwanted volatile auxiliary product as far as possible ,-make the film of non-discoloring aqueous polymer dispersion basically.
Reducing sugar and its acid derivative are recommended in US-A 4 529 753 the 3rd and 4 hurdles, for example xitix and basic metal hydrosulphite can be picked out sodium bisulfite as specially suitable reductive agent as the reductive agent that is adapted at being used as in the aqueous polymer dispersion radical redox initiator system.EP-B 327 006, supported this suggestion among the US-A 4 529 753 for the 7th page, mention sulfoxylate simultaneously, as the sodium salt (Rongalit of hydroxyl methane-sulfinic acid
C) as another kind of appropriate reductant.In the embodiment 1 and DE-A 38 34 734 of EP-A 379 892, will comprise that also the redox initiator system of RongalitC is used for carrying out the radical post polymerization at aqueous polymer dispersion.
Yet the shortcoming of these reductive agents of recommending in the prior art is that they can not satisfy described requirement fully.
Another shortcoming of the reductive agent of recommending in the prior art is that their necessity is used in combination with the oxygenant with high oxidation potential.If this oxygenant residues in the aqueous polymer dispersion on a small quantity, then they are handled described emulsion for (for example) with sanitas and have disadvantageous effect, reason is that biocide is responsive especially (for example to the oxygenant with high oxidation gesture usually, referring to L.Conquer, Polymer PaintCol.J.Vol.183, No.4335 (1993), 421-423).
In addition, according to F.Holscher, Dispersionen synthetischer Hochpolymer, Part I, Springer-Verlag, New York (1969), p117, there is disadvantageous effect in the resistates of oxygenant (for example under the situation of peroxide oxidant) to the performance of dispersion system.
US-A 4 529 753 recommends to use the post polymerization method simultaneously and relates to the method for using steam stripped, so this suggestion also has the shortcoming of having described.
Simultaneously, although utilize the method for residual monomer content of the reduction aqueous polymer dispersion of prior art can reach 1% (weight) or residual monomer content still less (by the polymer content of aqueous polymer dispersion) usually, but when residual monomer content being reduced to be lower than the limit of 1% (weight), run into bigger difficulty.This thinks because the fact in the place that dispersed polymer beads and water dispersion medium all are the residual monomers in the aqueous polymer dispersion can be existed.Between this two-phase, set up distribution equilibrium.The shortcoming of the method for the residual monomer content of known reduction aqueous polymer dispersion seemingly is only applicable to water dispersion medium basically based on them or is only applicable to the fact of polymer beads.Therefore, when using currently known methods, the residual monomer content that fully reduces aqueous polymer dispersion is (the setting up partition equilibrium repeatedly) that is subjected to diffusion control basically, and this might cause the dissatisfied speed that residual monomer reduces in the aqueous polymer dispersion.
Two distribution possibilities between the homophase not; also may be to comprise under the situation of at least two kinds of different monomers A and B at the residual monomer mixture; by the reason that existing method can not make the reduction of residual monomer in the aqueous polymer dispersion evenly carry out for different monomers, the difference of described monomer A and B also can cause its different solvabilities in water dispersion medium and dispersed polymer beads usually.
The object of the invention is to provide the method that reduces the residual monomer content of aqueous polymer dispersion by the effect of the radical redox initiation system that comprises at least a oxygenant and at least a reductive agent, and this method does not have the shortcoming that the known method that is used to reduce the aqueous polymer dispersion residual monomer content exists.
We find, the object of the invention can realize by the method for preparing aqueous polymer dispersion, wherein press known way and produce aqueous polymer dispersion, described polymkeric substance contains the monomer with at least one ethylenically unsaturated group of at least a chemical bonding, make free monomer with at least one ethylenic unsaturated bond, be this class not the total content of monomer in aqueous polymer dispersion of chemical bonding be＞0 to≤1wt% (by the polymer content of aqueous polymer dispersion), and the effect of the radical redox initiator system of this residual monomer content by comprising at least a oxygenant and at least a reductive agent reduces, wherein the redox initiator system comprises a kind of compound as reductive agent, this compound exists with two kinds of change forms of mutual equilibrated in the aqueous solution at least, and this compound is preferably amino imino methane-sulfinic acid and/or its salt.Certainly, novel method also can be at residual monomer content 10
-3To 0.5wt% or 10
-3To 0.1wt% (by the polymer content of aqueous polymer dispersion) use down.
Following prior art can be used as the basis that reaches the object of the invention.
R mpp, chemical dictionary (Chemie Lexikon), Cm-G, the 9th edition, GerogThieme Verlag, Stuttgart (1990), p1426 discloses amino imino methane-sulfinic acid and has been present in the aqueous solution with two kinds of forms of mutual equilibrated (tautomerism):
Thiourea peroxide amino imino methane-sulfinic acid
(formamidine sulfinic acid)
Degussa AG has sold the material that is used as reductive agent F in textile industry.
The German patent application F 2886 (1944) of Farbf.Bayer discloses amino imino methane-sulfinic acid can cause radical master aqueous emulsion polymerization in the presence of oxygen.Provided 60,80 and 100% yield (embodiment 6) in an embodiment.We repeat embodiment 6 and reach 5% polymerisation conversion (by wanting the polymeric monomer weight).
US-A 3 344 128 recommends amino imino methane-sulfinic acid is used as reductive agent in the redox initiator of the radical master aqueous emulsion polymerization of the mixture that causes conjugated diolefine and conjugated diolefine and vinyl-arene.The polymerisation conversion of report all is lower than 70%.
JP 60/118706 relates to the method that in the presence of amino imino methane-sulfinic acid radical master aqueous emulsion polymerization prepares chloroprene polymer.Polymerisation conversion reaches 70%.Residual monomer is removed by steam stripped.
DE-A 36 05 331 relates to the radical master aqueous emulsion polymerization of chloroprene equally, and the redox initiator system of recommendation comprises that those contain the material of amino imino methane-sulfinic acid.Mention that in specification sheets monomeric transformation efficiency can reach 50 to 99%.In embodiments, monomer conversion in all cases all＜70%.The disclosure document is very usually recommended by remove unreacted organic compound by vapor distillation in radical master aqueous emulsion polymerization process.Take corresponding method in an embodiment.
EP-B 155 805 also relates to the method that radical master aqueous emulsion polymerization prepares chloroprene polymer.Embodiment carries out under nitrogen atmosphere and comprises following and use amino imino methane-sulfinic acid.EP-B 155 805 does not provide and follows the explanation of using oxygenant.In addition, all limit based on the polymerisation conversion of chloroprene in all embodiments to≤95%.EP-B 155 805 recommends to remove unconverted monomer by steam stripped.
DE-A 36 05 334 discloses equally and has used the radical redox initiator that contains amino imino methane-sulfinic acid to carry out the method that radical master aqueous emulsion polymerization prepares chloroprene polymer.The monomeric transformation efficiency that provides reaches 63 to 85% usually.Recommend to use vapor distillation to remove unconverted organic compound.
DE-A 36 05 332 also relates to the radical master aqueous emulsion polymerization of chloroprene.The redox initiator system of recommending comprises that also those contain the material of amino imino methane-sulfinic acid.Mention that in specification sheets monomeric transformation efficiency can reach 50 to 99%.In embodiments, monomer conversion all be restricted in all cases＜70%.The disclosure document is with recommending to remove residual monomer by vapor distillation.
EP-B 505 163 relates to the method for the residual monomer content in the water-absorbing polymer (superabsorbents) that reduction mainly is made up of poly-(methyl) vinylformic acid, and wherein the polymkeric substance of solid water gel form, water-in-oil gel form or anhydrous form usefulness itself comprises the redox initiator system processing of amino imino methane-sulfinic acid.
DE-A 40 15 085 discloses the method for preparing superabsorbents by the vinyl monomer that mainly has acid functional group with the redox initiator system radical polymerization in the aqueous solution that comprises amino imino methane-sulfinic acid.The finished product that make are the polymer gel with high strength and low residual monomer content.
None provides these existing methods when free radical redox initiator system and is containing≤any prompting of the well-formedness of amino imino methane-sulfinic acid when reducing residual monomer in the aqueous polymer dispersion of the residual monomer of 1wt% (by the polymkeric substance that exists), reason be the specific two-phase of the residual monomer of aqueous polymer dispersion distribute (polymer beads/water dispersion medium) irrelevant with any currently known methods.This is so same for DE-A 39 09 790.
Therefore, according to " superpolymer ", vol.IX, letex polymerization, Interscience Publisher, Inc., New York, the 3rd edition (1965), p14/16, it is important that radical is formed at aqueous phase not in the emulsified monomer drop, and radical aqeous suspension polymeric is characterised in that radical forms in monomer droplet.When these two kinds of methods of use, this difference causes the molecular weight of (for example) resulting polymers obviously different with another kind.Therefore, the free-radical initiator system of suitable these two kinds of methods is highly-hydrophilic or highly lipophilic those initiators (depending on method).
EP-A 590 468 has confirmed these relations.
The initiator system that on the contrary, can be in water and lipophilic polymer particle form radical simultaneously on the spot is more suitable for effectively carrying out for reducing the radical post polymerization of the residual monomer content in the aqueous polymer dispersion.
Therefore, we the advantageous results of using novel method when finishing (definitional part of this novel method starts from radical master aqueous emulsion polymerization process) to find especially owing to such fact (its legitimacy is not had any requirement), be that amino imino methane-sulfinic acid in the aqueous solution exists with two kinds of forms of mutual equilibrated, wherein a kind of (amino imino methane-sulfinic acid) is more hydrophilic relatively form, and another kind of (thiourea peroxide) is relatively more hydrophobic.Think that tautomeric equilibrium can be favourable with the specific hydrophilic this point that natural way is adapted to the particular polymers emulsion by equilibrium displacement.
To this, should point out once more: the polymer properties that is scattered in the water medium is inoperative basically to the success of novel method, promptly here term polymer comprise polycondensate (as polyester) and addition polymer as urethane and can by ion or radical polymerization have at least one ethylenical unsaturated double bonds monomer and as described in the polymkeric substance that makes of the mixture of monomer type.The most important thing is when synthesizing the polymkeric substance that is scattered in the water medium, to relate at least a monomer, make not have any problem for removing residual monomer with at least one ethylenically unsaturated group.According to the present invention, it is unimportant to introduce one or more monomer methods with at least one ethylenical unsaturated double bonds in by dispersed polymeres.This method can directly be passed through ion or radical polymerization, carries out by the reaction of similar polymkeric substance or by direct addition polymerization or polycondensation.In addition, emphasize once more in the present invention that if do not further specify, the term polymer water miscible liquid comprises water miscible liquid and secondary water miscible liquid.
The preparation method of the aqueous polymer dispersion of above-mentioned dissimilar polymkeric substance has been described in a lot of documents, therefore be those skilled in the art known fully (for example referring to, " polymer science and engineering encyclopedia ", Vol.8, p659 following (1987); D.C.Blackley, " superpolymer latex ", Vol.1, p35 following (1966); H.Warson, " application of synthetic resin emulsion ", below the p246, the 5th chapter (1972); D.Diederich, Chemie in unserer Zeit, 24, (1990), 135-142; " letex polymerization ", interdisciplinary science press, New York (1965); DE-A 40 03 422 and Dispersionen Synthetischer Hochpolymer, F.H lscher, Springer-Verlag, Berlin (1969)).
The monomer with at least one ethylenically unsaturated group that is fit to this novel method especially comprises the monomer that can carry out radical polymerization with plain mode, for example alkene such as ethene, vinyl-arene such as vinylbenzene, alpha-methyl styrene, chloro styrene or Vinyl toluene, ester such as vinyl-acetic ester, propionate, vinyl propionate, vinyl laurate, new vinyl acetate acid and stearic acid vinyl ester that the monocarboxylic acid of vinyl alcohol and 1 to 18 carbon atom forms, and commercial monomer VEOVA
(VEOVA X is the trade(brand)name of Shell Co. Ltd to 9-11, represents the vinyl acetate of carboxylic acid, and described carboxylic acid is also referred to as Versatic
X acid), the α of preferred 3 to 6 carbon atoms, β-monoene belongs to unsaturated list and dicarboxylic acid, particularly vinylformic acid, methacrylic acid, toxilic acid, fumaric acid and methylene-succinic acid and common 1 to 12, preferred 1 to 8, the more preferably ester that forms of the alkanol of 1 to 4 carbon atom, especially the methyl esters of vinylformic acid and methacrylic acid, ethyl ester, positive butyl ester, isobutyl ester, the tert-butyl ester and 2-ethylhexyl, dimethyl maleate or n-butyl maleate, α, β-monoene belongs to the nitrile such as the vinyl cyanide of insatiable hunger carboxylic acid, and conjugation C
4-C
8-diolefine such as 1,3-butadiene and isoprene.For the aqueous polymer dispersion of being produced by the radical aqueous emulsion polymerization process fully, described monomer is generally principal monomer, and by will be by radical aqueous emulsion polymerization process polymeric total monomer weight, the total amount of this principal monomer be more than the 50wt%.These monomers are standard temperature and pressure (STP) condition (25 ℃ 1atm) only have medium extremely slight water-soluble down usually.
The monomer that has higher water-soluble under these conditions is (for example) α, β-monoene belongs to unsaturated list and dicarboxylic acid and acid amides thereof, as vinylformic acid, methacrylic acid, toxilic acid, fumaric acid, methylene-succinic acid, acrylamide and Methacrylamide, and vinyl sulfonic acid and its water-soluble salt and N-vinyl pyrrolidone.
For the aqueous polymer dispersion of producing by the radical aqueous emulsion polymerization process fully, above-mentioned monomer with higher water-soluble usually only as modified monomer to be lower than 50, common 0.5 to 20, preferred 1 to 10wt% (by wanting the polymeric total monomer weight) carried out polymerization in addition.
Usually the monomer that improves the film intrinsic strength of aqueous polymer dispersion generally has at least one epoxy group(ing), hydroxyl, N-methylol or carbonyl, or at least two non-conjugated ethylenical unsaturated double bonds.These monomeric examples are α of 3 to 10 carbon atoms, the ester (wherein N hydroxymethyl acrylamide and N-methylol methacrylamide are particularly preferred) of the alkenols of the N-hydroxyalkyl amide of β-monoethylenically unsaturated carboxylic acid and itself and 1 to 4 carbon atom, have the monomer of two vinyl, the monomer that has the monomer of two vinylidenes and have two alkenyls.Dibasic alcohol and α, the diester of β-monoethylenically unsaturated carboxylic acid (wherein preferred vinylformic acid and methacrylic acid) is particularly advantageous.The monomeric example of this class with two non-conjugated ethylenical unsaturated double bonds is the diacrylate and the dimethacrylate of aklylene glycol, as ethylene glycol diacrylate, diacrylate 1,3-butanediol ester, diacrylate 1,4-butanediol ester and diacrylate propylene glycol ester, Vinylstyrene, methacrylic vinyl acetate, vinyl acrylate, allyl methacrylate(AMA), allyl acrylate, diallyl maleate, diallyl fumarate, methylene-bisacrylamide, vinylformic acid cyclopentadiene ester or triallyl isocyanurate.Methacrylic acid and acrylic acid hydroxyl-C
1-C
8-alkyl ester; as hydroxyethyl ester, the hydroxyl-n-propyl ester or the hydroxyl-n-butyl of vinylformic acid and methacrylic acid, and compound also is particularly important as diacetone-acryloamide(DAA) and acrylic or methacrylic acid acetoacetoxy ethyl ester, methacrylic acid urea groups ethyl ester and acrylamido oxyacetic acid at this.For the aqueous polymer dispersion of being produced by the radical aqueous emulsion polymerization process fully, above-mentioned monomer carries out polymerization in addition in 0.5 to 10wt% amount (by wanting the polymeric total monomer weight) usually.
When the residual monomer that will remove comprised mutually different and that have at least one ethylenically unsaturated group two or more monomers, it was particularly advantageous that novel method evenly reduces monomeric advantage.As a result, when mutually different three kinds or four kinds or five kinds or six kinds or more kinds of residual monomer are the integral part of the aqueous polymer dispersion to be processed according to the present invention, prove that this method is suitable for.
Especially the residual monomer in being present in aqueous polymer dispersion satisfies their when having the such condition of visibly different molar solubility S (=in water molar solubility) under the post polymerization condition mutually in 1000g water (these solubleness are usually with closely similar at 25 ℃, solubleness during 1ba), and situation also is like this.
If in the residual monomer mixture, have the residual monomer of the highest molar solubility SA and represent to have minimum molar solubility S with A
BResidual monomer represent with B, then the success that obtains according to the present invention basically with S
A/ S
BWhether 〉=1.1, or 〉=1.5 or 〉=2 or 〉=5 or 〉=10 or 〉=50 or 〉=100 or 〉=1000 or 〉=100000 irrelevant.
Therefore, if residual monomer contains at least a residual monomer that is classified as by the medium group of forming to slight water-soluble monomer in above-mentioned possible residual monomer, in above-mentioned possible residual monomer, be classified as residual monomer with at least a, then generally can succeed according to the present invention with higher water-soluble group.
When the residual monomer mixture does not comprise chloroprene, also can succeed according to the present invention.
When the residual monomer mixture contains at least a at least a and following monomer with good especially water solubility in the following monomer with slight especially water solubility, can succeed especially according to the present invention.The monomer of described slight especially water solubility is: vinylbenzene, divinyl, n-butyl acrylate and 2-EHA, the monomer of described good especially water solubility is: vinylformic acid, methacrylic acid, acrylamide and Methacrylamide.Yet, even being called especially easily the dissolved monomer except above-mentioned when the residual monomer mixture, when also containing the monomer of medium water solubility such as vinyl-acetic ester and/or vinyl cyanide, this novel method is preferred.
By using this novel method, the remaining vinyl cyanide of satisfied fully reduction, vinyl-acetic ester and acrylic acid content are significant especially.These materials are considered to be difficult to eliminate usually.
Simultaneously, the auxiliary product that forms in reduce consuming the compound process that the present invention will use reduces the quality (particularly stable) of aqueous polymer dispersion in not half ground at least.This causes using simultaneously the possibility of the gas stripping process of novel method and strengthening stability, promptly directly reduces residual monomer in conjunction with chemistry and physics, as recommendation among the US-A 4 529 753.In addition and for example, with opposite by steam stripped reduction residual monomer, this novel method can be used without difficulty, basically with the irrelevant (solid volume of solids content in volume, press the volumeter of aqueous polymer dispersion), be that solids content in volume can be 10 to 50, or 20 to 60 or 30 to 70% (volume) (as the situation in the aqueous polymer dispersion of DE-A 42 13 965), it is interested especially wherein using down in high solid volumetric concentration (50 to 70% (volumes) or higher).
When using this novel method, even exist a class can not improve the aqueous polymer dispersion of its quality by simple reduction residual monomer content.These aqueous polymer dispersions are by following the aqueous polymer dispersion of use as the material preparation in free formaldehyde source.Described examples of substances is the N-hydroxyalkyl amide and the N-alkoxyalkyl acid amides of ethylenically unsaturated carboxylic acids, as N hydroxymethyl acrylamide, N-methylol methacrylamide, N-(isobutoxy methyl) acrylamide and N-(isobutoxy methyl) Methacrylamide.These monomers of copolymerization can increase the intrinsic strength of (for example) film prepared therefrom, and this is favourable for the tackiness agent as (for example) non-woven fabrics.
Yet in water medium, these auxiliary monomers are and free formaldehyde such as hydroxyl methane-sulfinic acid (formaldehydesulfoxylate) or its salt (these materials are used as reductive agent at the radical redox initiator that is used for preparing aqueous polymer dispersion) equilibrated.
Obviously, these aqueous polymer dispersions (as disclosed among DE-C 40 40 959, EP-A 311 908 and the EP-A 147 759) that contain free formaldehyde have the free formaldehyde content of reduction after using this novel method.
This novel method can be used in alkalescence and sour water dispersion medium, promptly uses scope to extend to pH12 from pH1.
Under acid pH, for example when aqueous polymer dispersion contain 〉=vinylformic acid of 5 to 60wt% (by polymkeric substance) is during as the unit of copolymerization, it is important using this novel method under acid pH.The pH value of the aqueous polymer dispersion that has the aforesaid propylene acid content if raise, then its dynamic viscosity significantly increases.Therefore these aqueous polymer dispersions are advantageously used for thickening material emulsion (for example referring to German Patent 1,164,095,1,264,945,1,258,721,1,546,315 and 1,265,752).To this, they can be with low relatively viscosity production in acidic medium.Thickening effectiveness increases the pH value by user oneself to be realized.Therefore this is wherein to be lower than 7 by the aqueous polymer dispersion producer in the pH of water dispersion medium value (be generally＜7 to 2) implements one of situation of reduction residual monomer content down.
Yet this novel method is preferably at the pH6 to 10 of water dispersion medium, uses for preferred especially 7 to 9 times.This is to be favourable by the anionic group stable polymer water miscible liquid that exists for its disperse phase.These aqueous polymer dispersions are that (for example) is by anionic emulsifier stable polymer water miscible liquid that exists or the α that contains 3 to 6 carbon atoms, β-monoethylenically unsaturated carboxylic acid such as vinylformic acid (are generally 0.1 to 5 by dispersed polymkeric substance, preferred 0.5 to 4wt%) as the aqueous polymer dispersion of polymerized unit, with separately or follow the stable dispersion phase.
(even when when using down for 20 to 50 ℃) under the situation that novel residual monomer reduces, obviously can occur in the presence of the metallic compound of multiple valence state dissolving in water-based reaction medium and its metal component (for example iron, vanadium or its mixture), needn't use new redox initiator system.Yet it also can use in the presence of this compounds certainly.If this situation, its consumption are calculated by oxygenant or reductive agent (substoichiometric component in each case) and by the metallic compound that will add and are generally 0.01 to 1wt%.The example of this type of suitable combination thing is ferric sulfate (II), iron(ic) chloride (II), iron nitrate (II), ironic acetate (II) and corresponding iron (III) salt, ammonium and basic metal vanadate (V (V)), vanadium chloride (III), vanadylic chloride (V), particularly five hydration vanadylic sulfates (IV).Usually also add and make metal under reaction conditions, remain in coordination agent in the solution.
The temperature of recommending to use in novel reduction residual monomer is 0 to 100 ℃, preferred 20 to 90 ℃, and preferred especially 50 to 80 ℃.Yet depress adding, corresponding higher temperature also is feasible.Suitable working pressure is 〉=1 to 15 crust.To carry out novel post polymerization under the minimum film-forming temperature MFT of resulting polymers emulsion (white point temperature) be particularly advantageous being higher than.Be lower than 0 ℃ aqueous polymer dispersion for MFT, with the statistics second-order transition temperature T of polymer dispersion
g(DSC, neutral temperature) replacement MFT (referring to " Ullmann industrial chemistry encyclopaedia ", VCH, Weinheim, Vol.A21 (1992), p169).Processing temperature preferably is higher than corresponding MFT or T
gThe value at least 20 ℃, preferably at least 40 ℃,, advantageously at least 60 ℃, especially preferably at least 80 ℃, more particularly advantageous at least 100 ℃ (it is believed that this relation generally is applicable to post polymerization).For having more than a T
gPolymer emulsion, should use the Schwellenwert in these values.
Usually for the radical polymerization method, this novel method can be at inert gas atmosphere (for example, N
2, Ar) and oxygen containing atmosphere (as air) use down.The fact that reductive agent used according to the invention can be only obviously reduces residual monomer content at molecular oxygen in the presence of as oxygenant is quite favourable.Consider the residual monomer content that reduces the described emulsion in the aqueous polymer dispersion hold tank, this is true to be to make us interested especially with using required lesser temps.Opened up the favourable condition that the possibility that limits other oxygenant that must add so provides (for example) to kill livestock thing processing aqueous polymer dispersion in addition.
It also is favourable that the novel method of using can not cause any the fading of resulting polymers water miscible liquid usually.The fabulous operability and the storage life of the reductive agent that the present invention uses also are favourable.
As mentioned above, this novel method be particularly suitable for dispersed polymkeric substance by the radical aqueous emulsion polymerization by in the aqueous polymer dispersion with at least one ethylenically unsaturated group production (this polymkeric substance does not carry out novel residual monomer to be eliminated), and just because of this reason, all viewpoints that provide among the present invention are particularly related to a water miscible liquid of being produced by the radical aqueous emulsion polymerization.The radical aqueous emulsion polymerization is preferably undertaken by charging process, promptly will account for 50 to 100 of gross weight by polymeric usually, preferred 70 to 100, preferred especially 80 to 100, preferred more especially 90 to the 100wt% monomers of mainly measuring are after radical polymerization begins, and the monomeric speed that has been present in the polymerization reactor with polymerization adds in the polymerization reactor.Usually, reinforced so that be present at least 80 in the polymerization reactor, preferably at least 90, the speed that preferred especially 95wt% monomer at least has been incorporated in the polymerized unit is undertaken by continuously feeding (be generally pure monomer or at the pre-emulsified monomer of aqueous phase).The seed polymer water miscible liquid can be followed be used to set up by the particle size of dispersed polymeres particle (referring to, EP-B 40419 and " polymer science and technology encyclopedia ", Vol.5, John Wiley and Sons Inc., NewYork (1966), p847).
The suitable free radical polymerization initiator that is used for above-mentioned main polyreaction is those all initiators that can cause the radical letex polymerization.These initiators can be superoxide and azo-compound.Yet the redox initiator system also is suitable.Usually to be used for the free-radical initiator system of post polymerization different with the present invention to be used for main polymeric free-radical initiator.Simultaneously, will be in the main emulsion polymerization polymeric generally at least 50, more general at least 75, the monomer polymerization in the presence of no novel reductive agent usually of 90wt% at least usually, promptly main polymerization does not comprise any novel reductive agent usually.For from desired properties and consider the cost-effectiveness that reaches high, carry out radical aqueous emulsion polymerization as main polyreaction with special efficient manner, using peroxidation pyrosulfuric acid and/or its an alkali metal salt and/or its ammonium salt is preferred as free-radical initiator.The consumption of free-radical initiator is by wanting polymeric monomer total amount to be preferably 0.1 to 2wt%.The mode that adds the free-radical initiator system in described radical master aqueous emulsion polymerization process is unimportant.Initiator system can all add in the polymerization reactor or with its speed that consumes in radical aqueous emulsion polymerization process when beginning and add continuously or stage by stage.According to the known mode of those skilled in the art itself, this specifically depends on the chemical property and the polymerization temperature of initiator system.
The direct result of the above-mentioned fact is, 0 to 100 ℃ of temperature of reaction that is suitable as above-mentioned radical master aqueous emulsion polymerization of total size, but 70 to 100 ℃ of temperature, preferred 80 to 100 ℃, preferred especially＞85 to 100 ℃ be preferred the use.
Can use super-atmospheric pressure or decompression, polymerization temperature also can surpass 100 ℃ and can be up to 130 ℃ or higher like this.With easy volatile monomer such as the preferably polymerization under super-atmospheric pressure of ethene, divinyl or vinylchlorid.Certainly in radical master aqueous emulsion polymerization, can follow and use molecular weight regulator such as uncle's lauryl mercaptan.
In radical aqueous emulsion polymerization process, follow usually and use the dispersion agent guarantee the aqueous polymer dispersion stability of producing.Suitable dispersion agent is protective colloid and the emulsifying agent that is generally used for carrying out described letex polymerization.
The example of suitable protective colloid is polyvinyl alcohol, derivatived cellulose or contains vinylpyrrolidone copolymers.Other appropriate protection colloidal are described in detail and are appeared at Houben-Weyl, Methoden der organischen Chemie, Volume XIV/1; MakromolekulareStoffe, Georg-Thieme-Verlag, Stuttgart; 1961, among the p411-420.Certainly, can also use the mixture of emulsifying agent and/or protective colloid.Opposite with protective colloid, only relative molecular weight is usually less than 1000 emulsifying agent as dispersion agent.They can be negatively charged ion, positively charged ion or non-ionic.When using surfactant mixture, each component certainly must be compatible mutually, can detect by preliminary experiment several times when having a question.Usually, anionic emulsifier can be compatible mutually and compatible with nonionic emulsifying agent.This is fit to cationic emulsifier equally, and negatively charged ion and the common objectionable intermingling mutually of nonionic emulsifying agent.Conventional emulsifier be (for example) ethoxylation list-, two-and trialkyl phenol (degree of ethoxylation: 3 to 100, alkyl: C
4To C
12), the Fatty Alcohol(C12-C14 and C12-C18) of ethoxylation (degree of ethoxylation: 3 to 10, alkyl C
8To C
18), and alkylsurfuric acid (alkyl: C
8To C
16), the ethoxylation alkanol (degree of ethoxylation: 1 to 70, alkyl: C
12To C
18) and ethoxylated alkyl phenols (degree of ethoxylation: 3 to 100, alkyl: C
4To C
12) sulfate hemiester, alkylsulphonic acid (alkyl: C
12To C
18) and an alkarylsulphonic acid (alkyl: C
9To C
18) basic metal and ammonium salt.Emulsifying agent such as sulfosuccinic ester that other are suitable are described in Houben-Weyl, Methoden derorganischen Chemie, Volume XIV/1, Makromolekulare Stoffe, Georg-Thieme-Verlag, Stuttgart, 1961, among the p192-208.
Having proved other suitable tensio-active agent is the compound of following general formula I:
R wherein
1And R
2Respectively be hydrogen or C
4-C
24-alkyl and be not hydrogen simultaneously, X and Y are alkalimetal ion and/or ammonium ion.In general formula I, R
1And R
2Respectively be preferably 6 to 18, the particularly straight chain of 6,12 or 16 carbon atoms or branched-alkyl or hydrogen, R
1And R
2Be not hydrogen simultaneously.X and Y are preferably sodium, potassium or ammonium ion, and sodium is particularly preferred.Wherein X and Y are sodium, R
1Be the branched-alkyl and the R of 12 carbon atoms
2Be hydrogen or R
1Compound I be particularly advantageous.Usually use the cuts that contains 50 to 90wt% monoalkylation products, for example Dowfax 2A1 (trade mark of Dow Chemical).In this novel method, Compound I itself is preferably used as dispersion, be preferably used as especially with ethoxylized fatty alcohol (degree of ethoxylation: 3 to 50, alkyl: C
8To C
36) mixture.Compound I is normally known and commercially available from (for example) US-A 4,269,749.
Used dispersion dosage is generally 0.5 to 6, preferred 1 to 3wt% (by the monomer that will carry out radical polymerization).
Above-mentioned dispersion agent is suitable for stablizing the direct novel product of this method certainly very much.Yet described product comprises the aqueous polymer dispersion of self-emulsifying polymkeric substance (polymkeric substance that promptly has ionic group), described ionic group since with the repulsive interaction of identical charges, therefore can carry out stabilization.Described product is negatively charged ion stable (containing anionic dispersing agents) especially preferably.
If by the radical aqueous emulsion polymerization by comprising that the monomer composition with at least one ethylenically unsaturated group prepares the aqueous polymer dispersion that its residual monomer content reduces by mode of the present invention, be to comprise different mutually and have at least two kinds of monomers of at least one ethylenically unsaturated group and also contain those compositions of following component for the monomer composition of this novel method particularly important then, described component is :-70 to 99.9wt% vinylformic acid and/or methacrylic acid and 1 to 12 carbon atom
The ester and/or the vinylbenzene of alkanol,
Or-70 to 99.9wt% vinylbenzene and/or divinyl
Or-70 to 99.9wt% vinylchlorid and/or vinylidene chloride
Or-40 vinyl-acetic esters, propionate and/or ethene to 99.9wt%.
The monomer composition relevant especially with this novel method comprises:
0.1 to the α of at least a 3 to 6 carbon atoms of 5wt%, β-monoethylenically unsaturated carboxylic acid and/or its acid amides (monomer A) and
The ester of the alkanol of 70 to 99.9wt% vinylformic acid and/or methacrylic acid and 1 to 12 carbon atom and/or vinylbenzene (monomers B)
0.1 to the α of at least a 3 to 6 carbon atoms of 5wt%, β-monoethylenically unsaturated carboxylic acid and/or its acid amides (monomer A) and
70 to 99.9wt% vinylbenzene and/or divinyl (monomers B ') or
0.1 to the α of at least a 3 to 6 carbon atoms of 5wt%, β-monoethylenically unsaturated carboxylic acid and/or its acid amides (monomer A) and
70 to 99.9wt% vinylchlorid and/or vinylidene chloride (monomers B ") or
0.1 to the α of at least a 3 to 6 carbon atoms of 5wt%, β-monoethylenically unsaturated carboxylic acid and/or its acid amides (monomer A) and
40 to 99.9wt% vinyl-acetic ester, propionate and/or ethene (B ).
When monomer A was vinylformic acid, this novel method was particularly suitable for for above-mentioned monomer composition.
This novel method comprises that for the radical aqueous emulsion polymerization monomer composition of following component also is preferred, and described component is:
0.1 to the vinyl cyanide of 30 (preferred 0.5 to 15) wt% and
The ester of the alkanol of 70 to 99.9wt% vinylformic acid and/or methacrylic acid and 1 to 12 carbon atom and/or vinylbenzene or
0.1 to the vinyl cyanide of 30 (preferred 0.5 to 15) wt% and
70 to 99.9wt% vinylbenzene and/or divinyl or
0.1 to the vinyl-acetic ester of 40wt% and/or propionate and
The ester and/or the vinylbenzene of the alkanol of 60 to 99.9wt% vinylformic acid and/or methacrylic acid and 1 to 12 carbon atom.
Yet this novel method comprises that for the radical aqueous emulsion polymerization monomer composition of following component is particularly preferred, and described component is:
0.1 to the α of at least a 3 to 6 carbon atoms of 5wt%, β-monoethylenically unsaturated carboxylic acid and/or its acid amides, particularly vinylformic acid,
0.1 to the vinyl cyanide of 30 (preferred 0.5 to 15) wt% and
69.9 to the ester of the alkanol of the vinylformic acid of 99.9wt% and/or methacrylic acid and 1 to 12 carbon atom and/or vinylbenzene or
0.1 to the α of at least a 3 to 6 carbon atoms of 5wt%, β-monoethylenically unsaturated carboxylic acid and/or its acid amides, particularly vinylformic acid,
0.1 to the vinyl cyanide of 30 (preferred 0.5 to 15) wt% and
69.9 to the vinylbenzene of 99.9wt% and/or divinyl or
0.1 to the α of at least a 3 to 6 carbon atoms of 5wt%, β-monoethylenically unsaturated carboxylic acid and/or its acid amides, particularly vinylformic acid,
0.1 to the vinyl-acetic ester of 40wt% and/or propionate and
59.9 ester and/or vinylbenzene to the alkanol of the vinylformic acid of 99.9wt% and/or methacrylic acid and 1 to 12 carbon atom.
Described monomer composition does not preferably contain chloroprene and the monomer composition chosen should make gained be lower than 50 ℃ by the Tg value of dispersed polymeres, preferably is lower than 25 ℃, especially preferably is lower than 0 ℃ (being low to moderate-70 ℃).
For containing residual monomer and its aqueous polymer dispersion of being produced by the radical aqueous emulsion polymerization by monomer by dispersed polymeres with at least one ethylenically unsaturated group, in this radical master aqueous emulsion polymerization itself, residual monomer content reaches or keeps below the limit (by total water miscible liquid) of 1wt% usually.When residual monomer content not for this reason during limit, as mentioned above, can directly use the novel method that reduces residual monomer subsequently, or use conventional existing residual monomer to reduce method earlier, then use novel method of the present invention again to utilize the advantage of this novel method until reaching described limit.Usually after main polyreaction, can reduce the new step of residual monomer reposefully.In addition, new radical redox system has been used for main polyreaction.
Except above-mentioned amino imino methane-sulfinic acid, the radical redox initiator that the present invention uses also can comprise other reductive agent certainly, for example reducing sugar such as glucose and fructose, their derivative such as xitix, or-sulfinic acid such as hydroxyl methane-sulfinic acid, or alkane-sulfinic acid such as sec.-propyl-sulfinic acid (or its salt).Yet amino imino methane-sulfinic acid is preferably more than the 50wt% of used reductive agent total amount, and more preferably more than the 75wt%, it is particularly preferred that amino imino methane-sulfinic acid uses as single reductive agent.Except direct adding amino imino methane-sulfinic acid, this novel reductive agent also can (for example) produce by adding thiocarbamide and hydrogen peroxide in position.
The example of the suitable oxidation component of the radical redox initiator that the present invention uses is a molecular oxygen, ozone, the reagent such as alkali metal chlorates and perchlorates, transition metal oxide such as potassium permanganate, Manganse Dioxide and the plumbous oxide that when forming radical, oxygen are provided and do not have the superoxide structure, and lead tetraacetate and iodobenzene.Yet, preferably use superoxide, hydrogen peroxide or its mixture.
Use with hydrogen peroxide, peroxidation pyrosulfuric acid and its salt (particularly an alkali metal salt), tertbutyl peroxide and with oxygen and to prove particularly advantageous.It is preferred only using tertbutyl peroxide or tertbutyl peroxide and oxygen.
The oxygenant that uses in novel method and the mol ratio of reductive agent should be 0.1: 1 to 1: 0.1 usually, and preferred 0.5: 1 to 1: 0.5, preferred especially 0.75: 1 to 1: 0.75.They are preferably to wait mole to use.
In novel method, all radical redox initiator systems that the present invention uses once can be added in the aqueous polymer dispersion that contains residual monomer in principle.Yet, also all oxygenants once can be added, add reductive agent then continuously.Oxidizing and Reducing Agents can also be added in the aqueous polymer dispersion to be processed in several hours continuously by feeding in raw material respectively.Usually these two kinds of raw materials begin reinforced and finish simultaneously to feed in raw material simultaneously, promptly feed in raw material and carry out synchronously basically.Feed in raw material and advantageously carry out with aqueous solution form.
Certainly, the consumption of the radical redox initiator system of the present invention's use depends on the amount of the residual monomer that still exists and the degree that described monomer reduces.
Usually its consumption is 0.01 to 5, advantageously 0.1 to 1wt% (by dispersed polymkeric substance).Certainly, after this novel method, can then reduce other program of residual monomer content.
At last, be also pointed out that the radical redox initiator system that the present invention uses can reduce residual monomer content at short notice effectively.The residual monomer content of measuring in the following example is based on the gas chromatographic measurement method.Embodiment and Comparative examples A) preparation contains the aqueous polymer dispersion (inert gas atmosphere) of residual monomer
At first, under agitation with the ethoxylized fatty alcohol mixture (C of 200g softening water, 40g raw material 1,12.5g concentration 20wt%
16/ C
18, degree of ethoxylation: the aqueous solution 18), the mixture of the active ingredient of 5g concentration 20wt% (corresponding to the Dowfax 2A1) aqueous solution and 10g raw material 2 add in the polymerization reactor and are heated to 85 ℃.After 15 minutes, the raw material 1 (in 3 hours) of residual content and the raw material 2 (in 3.5 hours) of residual content are begun to add continuously (and keeping 85 ℃ of temperature) in the polymerization reactor by reinforced respectively simultaneously.After raw material 2 adds, continue down to stir 1 hour at 85 ℃.Raw material 1 (in adition process, stirring)
The 165g softening water,
Ethoxylized fatty alcohol mixture (the C of 25g concentration 20wt%
16/ C
18, ethoxy
The baseization degree: the aqueous solution 18),
32.5g the active ingredient of concentration 20wt% (corresponding to the Dowfax 2A1) aqueous solution,
The acrylamide solution of 10g concentration 50wt%,
12.5g vinylformic acid
250g vinylbenzene
The 250g n-butyl acrylate.Raw material 2:
The 100g softening water and
1g peroxidation sodium pyrosulfate.
When the solid content that makes was diluted to solid content 0.01wt% for the 48.3wt% aqueous polymer dispersion, its transmittance (LT) with respect to pure water under 25 ℃ (2.5cm path lengths) was 81%.
The pH value of water dispersion medium is 2.7.Above-mentioned six batch materials are mixed.This mixture has following residual monomer content:
N-butyl acrylate: 12000mg/kg emulsion
Vinylbenzene: 2000mg/kg emulsion B) by reducing polymkeric substance water and milk with various radical redox initiator system post polymerization
The residual monomer content of liquid A (under each situation, using the 200g said mixture)
Under the given initial pH of water dispersion medium, one of three kinds of methods below using under each situation (initial pH value is by the NaOH aqueous solution increase of concentration 10wt%): all Oxidizing and Reducing Agents that a) will select (described amount under each situation all be by by the wt% of dispersed polymeres) add among the aqueous polymer dispersion A simultaneously with the aqueous solution of concentration 2wt%, then this mixture is left standstill for some time X (inert gas atmosphere, N under 23 ℃ in encloses container
2).Then, measure residual monomer at once.B) aqueous polymer dispersion A being heated to 70 ℃ and all oxygenants that will select adds simultaneously with the aqueous solution of concentration 2wt%.Under temperature keeps 70 ℃, reductive agent aqueous solution continuous measurement with concentration 2wt% in 30 minutes is added.Then, this mixture was further stirred 30 minutes down at 70 ℃.Subsequently, by add that the 10mg quinhydrones stops post polymerization and with this mixture with gas chromatographic analysis (variable b
*), or these samples are left standstill 3 days (variable b) again analyze (inert gas atmosphere, N then under 23 ℃ in encloses container
2).Described Oxidizing and Reducing Agents amount also is by by the wt% of dispersed polymeres.C) only the aqueous solution of reductive agent with concentration 2wt% is all added among the aqueous polymer dispersion A, then with emulsion under 23 ℃ with reactor that air communicates in left standstill 3 days.Carry out gas chromatographic analysis then.The reduction dosage of described adding is also for by by the wt% of dispersed polymeres.
Under all situations of the present invention, the total residual monomer content of gained all is significantly less than 1wt% (by dispersed polymkeric substance).
The gained result provides in following table 1.
Table 1
T-BHP tertbutyl peroxide Rongalite C: the sodium salt AIMS of hydroxyl methane-sulfinic acid: amino imino methane-sulfinic acid NaPS: main emulsion polymerization (inert gas atmosphere) peroxidation sodium pyrosulfate C):
| Oxygenant/amount | Reductive agent/amount | Initial pH | Method | Residual monomer content (mg/kg emulsion) | |
| N-butyl acrylate | Vinylbenzene | ||||
| ????0.1????t- BHP | 0.1 sodium pyrosulfate | ????2.7 | b | ????7100 | ????660 |
| ????0.1????t- BHP | ?0.1AIMS | ????2.7 | b | ????3400 | ????110 |
| ????0.2????t- BHP | ?0.2AIMS | ????2.7 | b | ????730 | ????20 |
| ????0.1????t- BHP | ?????????0.1 ?Rongalite?C | ????8 | b * | ????5840 | ????490 |
| ????0.1????t- BHP | ?0.1AIMS | ????8 | b * | ????560 | ????36 |
| ???????????0.1 NaPS | ?0.1AIMS | ????8 | b * | ????1168 | ????10 |
| ????0.1????t- BHP | ?????????0.1 ?Rongalite?C | ????8 | A, X=4 days | ????414 | ????21 |
| ????0.1????t- BHP | 0.1 sodium pyrosulfate | ????8 | A, X=4 days | ????234 | ????21 |
| ????0.1????t- BHP | 0.1 xitix | ????8 | A, X=4 days | ????212 | ????21 |
| ????0.1????t- BHP | ?0.1?AIMS | ????8 | A, X=4 days | ????180 | ????10 |
| ???????????0.1 NaPS | ???????????0.1 ?Rongalite?C | ????8 | A, X=4 days | ????2120 | ????149 |
| ???????????0.1 NaPS | ?0.1AIMS | ????8 | A, X=4 days | ????998 | ????42 |
| ???????????0.2 NaPS | ?0.1AIMS | ????8 | A, X=4 days | ????550 | ????21 |
| ????0.1????t- BHP | ?0.1AIMS | ????6 | A, X=4 days | ????1020 | ????110 |
| ????0.1????t- BHP | ?0.1AIMS | ????7 | A, X=4 days | ????369 | ????30 |
| ????0.1????t- BHP | ?0.1AIMS | ????8 | A, X=4 days | ????180 | ????10 |
| ????0.1????t- BHP | ?0.1AIMS | ????8 | a，X＝1 h | ????1168 | ????63 |
| ????0.1????t- BHP | ?0.1AIMS | ????8 | a，X＝2 h | ????955 | ????24 |
| ????0.1????t- BHP | ?0.1AIMS | ????8 | a，X＝4 h | ????541 | ????16 |
| ????- | ?- | ????8 | c | ????11250 | ????1770 |
| ????- | ?0.1AIMS | ????8 | c | ????4425 | ????103 |
| ????- | ?0.1AIMS | ????10 | c | ????3525 | ????57 |
| ????- | ?0.1AIMS | ????12 | c | ????2850 | ????34 |
| ????- | ???????????0.1 ?Rongalite?C | ????8 | c | Agglomerative emulsion within a certain period of time | |
| ????- | ???????????0.1 ?Rongalite?C | ????10 | c | ????10500 | ????1720 |
| ??????- | ?????????0.1 Rongalite?C | ????12 | ????c | ????9800 | ????1542 |
| ????0.1????t- BHP | ?0.1AIMS | ????8 | ????c | ????68 | ????7 |
With the mixture heating up to 60 of aqueous hydrogen peroxide solution, 48g raw material and the 500g softening water of 10g concentration 30wt% ℃.Then, keeping temperature all to add next time and stirred 15 minutes down for 50 ℃ the 10g solution of 3g xitix in 200g water at 50 ℃.Under temperature keeps 60 ℃, the raw material of residual content was added in 120 minutes continuously then, behind reinforced the end with reaction mixture 60 ℃ of following restir 60 minutes.
The solid content of resulting polymers water miscible liquid is 48.2wt%.
The pH value of dispersion medium is 2.9.
Raw material is formed:
The 1190g ethyl propenoate,
The 150g vinyl cyanide,
The 120g methyl acrylate,
N-methylol-methacryloyl amine aqueous solution of 78g concentration 48wt%,
The sulfation octyl phenol ethoxylate (ethoxylation of 64g concentration 35wt%
Degree: sodium-salt aqueous solution=emulsifier solution 1 25),
The ethoxylation octyl phenol of 112g concentration 20wt% (degree of ethoxylation:
25) aqueous solution=emulsifier solution 2,
The 670g softening water.
The residual monomer content of aqueous polymer dispersion comprises:
6500mg ethyl propenoate/kg emulsion,
800mg methyl acrylate/kg emulsion and
770mg vinyl cyanide/kg emulsion.Post polymerization (inert gas atmosphere)
The pH value of each aqueous polymer dispersion of 200g of making in the main emulsion polymerization is increased to 7.1 with strong aqua.Then oxygenant is all added next time (described amount is the wt% by dispersed polymkeric substance) at 25 ℃.Stir after 10 minutes, the amino imino methanesulfonic is once all added (described amount is wt%, by dispersed polymkeric substance) and adds 20mg FeSO
47H
2O connects and sees 25 ℃ of following stirrings 2 hours.Then aqueous polymer dispersion was left standstill under 25 ℃ 24 hours again.The residual monomer content that records in all cases all is lower than 1wt% (by dispersed polymkeric substance).
Concrete outcome and consumption provide in table 2.
Table 2
(it is identical with table 1 to abridge) D) and C) the same, but reinforced and post polymerization under 60 ℃, carry out.Result and consumption provide in table 3.Similar in abbreviation of selecting for use and the table 1.
| Oxygenant/amount | Reductive agent/amount | Residual monomer content (mg/kg emulsion) | ||
| Ethyl propenoate | Methyl acrylate | Vinyl cyanide | ||
| ?0.2t-BHP | ?0.24AIMS | ????760 | ????150 | ????72 |
| ?0.076H 2O 2 | ?0.24AIMS | ????780 | ????160 | ????77 |
| ?0.53NaPS | ?0.24AIMS | ????1000 | ????190 | ????100 |
| ?0.2t-BHP | ?0.48AIMS | ????220 | ????90 | ????12 |
| ?0.076H 2O 2 | ?0.48AIMS | ????520 | ????120 | ????40 |
| ?0.53NaPS | ?0.48AIMS | ????690 | ????150 | ????60 |
Table 3
E) main emulsion polymerization (inert gas atmosphere)
| Oxygenant/amount | Reductive agent/amount | Residual monomer content (mg/kg emulsion) | ||
| Ethyl propenoate | Methyl acrylate | Vinyl cyanide | ||
| ?0.2t-BHP | ?0.24AIMS | ????＜10 | ????36 | ??＜10 |
| ?0.076H 2O 2 | ?0.24AIMS | ????126 | ????10 | ??＜10 |
With 2.6g concentration is the C of 40wt%
16The sodium-salt aqueous solution of-paraffinic hydrocarbons sulfonic acid (emulsifier solution 3), 4.2g sodium vinyl sulfonate, 15mg FeSO
47H
2The mixture heating up to 85 of O, 625g softening water and 80g raw material 1 ℃.Then, under temperature keeps 70 ℃, add 58g raw material 2 simultaneously and stirred 15 minutes.Begin to add continuously the raw material 2 (in 135 minutes) of the raw material 1 (in 120 minutes) of residual content and residual content in the polymerization reactor simultaneously and keep 85 ℃ of temperature.After raw material 2 adds, continue down to stir 60 minutes at 85 ℃.Stablize and make the pH value increase to 8.0 with the 12g emulsifier solution 3 that adds by the moisture calcium hydroxide mashed prod of adding (the 97g calcium hydroxide in 85g water).The solid content of resulting polymers water miscible liquid is 48.1wt%.Raw material 1
The 1170g n-butyl acrylate,
The 105g vinyl cyanide,
The 225g methacrylic acid,
0.5g sodium vinyl sulfonate,
15g emulsifier solution 3,
The 510g softening water.Raw material 2:
12g peroxidation sodium pyrosulfate
The 375g softening water
The residual monomer content of aqueous polymer dispersion comprises:
260mg vinyl cyanide/kg emulsion and
3800mg n-butyl acrylate/kg emulsion.Post polymerization (inert gas atmosphere)
T-BHP or the NaPS (under 25 ℃) of 0.1wt% are added in each the 450g aqueous polymer dispersion that makes in the main emulsion polymerization.Then, adding the 21.6g AIMS aqueous solution of concentration 1wt% under 25 ℃ and under each situation, mixture being kept 24 hours, measure residual monomer content then under 25 ℃.This content＜＜1wt% (by dispersed polymkeric substance), it comprises:
17mg vinyl cyanide/kg emulsion
280mg n-butyl acrylate/kg emulsion (t-BHP is as oxygenant) or
60mg vinyl cyanide/kg emulsion
770mg n-butyl acrylate/kg emulsion (NaPS is as oxygenant) F) main emulsion polymerization (inert gas atmosphere)
With 3.5kg vinyl-acetic ester, 2.5kg emulsifier solution 2,0.25kg sodium vinyl sulfonate, 1g FeSO
47H
2The mixture heating up to 60 of O and 19kg softening water ℃.Then, under temperature kept 30 ℃, continuous measurement added in the solution of 0.15kg peroxidation sodium pyrosulfate in 5.8kg water in 3 hours.Begin in 2 hours, to add continuously monomer emulsion during in addition, from the beginning polymerization.After initiator charge adds, mixture was kept under 60 ℃ 1 hour again, stable with 0.7kg emulsifier aqueous solution 1, be cooled to room temperature and pass through the filtration of 120 μ m strainers.The solid content of resulting polymers water miscible liquid is 49.2wt%, and the pH value of dispersion medium is 4.7.
Consisting of of monomer emulsion:
37.5kg vinyl-acetic ester
7.5kg n-butyl acrylate
3.2kg the N hydroxymethyl acrylamide solution of concentration 48wt%
1.1kg emulsifier aqueous solution 1
1.9kg emulsifier aqueous solution 2
17.9kg softening water.
The residual monomer content of aqueous polymer dispersion comprises 2,800mg vinyl-acetic ester/kg emulsion.Post polymerization (inert gas atmosphere)
The pH value of the 600g aqueous polymer dispersion that makes in the main emulsion polymerization is increased to 7.1 with strong aqua.T-BHP with 0.2wt% (by dispersed polymkeric substance) all adds at 25 ℃ with 2wt% aqueous solution form next time then.Then at the AIMS aqueous solution that in 30 minutes, adds 35g concentration 2% under 25 ℃.Then aqueous polymer dispersion was left standstill under 25 ℃ 6 days.
The residual monomer content of the vinyl-acetic ester of measuring only is 30mg vinyl-acetic ester/kg emulsion.The total content of residual monomer all is significantly less than 1wt% (by dispersed polymkeric substance).G) main emulsion polymerization (inert gas atmosphere)
Under agitation the 45g monomer emulsion is added in the 615g water and with this mixture heating up to 60 ℃.Then, stirred 15 minutes under this temperature at the reductant solution that in 100g water, contains 2.7g Rongalite of 50 ℃ of oxidizing agent solutions that in 100g water, contain 4g peroxidation sodium pyrosulfate that add down 5wt% and 5wt% and with this mixture.Beginning continuous measurement adding residual monomers emulsion (in 120 minutes), remaining oxidizing agent solution and remaining reductant solution (each situation is all in 135 minutes) under 60 ℃ simultaneously then.Then with this reaction mixture 60 ℃ of following restir 60 minutes.Making solid content is that 43.9wt% and pH value are 2.3 aqueous polymer dispersion.
Consisting of of monomer emulsion:
The 1200g n-butyl acrylate
The 135g vinyl cyanide
13.5g vinylformic acid
Sulfated lauryl alcohol ethoxylate (the ethoxylation of 90g concentration 30wt%
Degree: sodium-salt aqueous solution=emulsifier solution 4 30)
The ethoxylation Tallow, beef Fatty Alcohol(C12-C14 and C12-C18) (ethoxylation of 68g concentration 20wt%
Degree: the 30) aqueous solution
The 770g softening water
The residual monomer content of aqueous polymer dispersion comprises:
13000mg n-butyl acrylate/kg emulsion
2700mg vinyl cyanide/kg emulsion.
Aqueous polymer dispersion also contains 71mg formaldehyde/kg emulsion.Post polymerization (inert gas atmosphere)
The 300g aqueous polymer dispersion that will make in the main emulsion polymerization is heated to 70 ℃ with reflux exchanger.Then 0.4wt% (by dispersed polymkeric substance) NaPS (with the aqueous solution of concentration 5wt%) is once all added.Then in 10 minutes, be metered into the AIMS aqueous solution (, being total up to the AIMS of 0.2wt%) of concentration 1wt%, then this mixture further stirred 3 hours down at 70 ℃ based on dispersed polymkeric substance meter.This water miscible liquid also contains:
2000mg n-butyl acrylate/kg emulsion
6mg vinyl cyanide/kg emulsion
8mg formaldehyde/kg emulsion.
Total residual monomer content is lower than 1wt% (by dispersed polymkeric substance).H) repeat embodiment G, but the consisting of of monomer emulsion:
The 1000g ethyl propenoate
The 335g vinyl-acetic ester
13.5g vinylformic acid
90g emulsifier aqueous solution 4
68g emulsifier aqueous solution 5
The 770g softening water.
Making solid content is that 43.6wt% and pH value are 2.2 aqueous polymer dispersion.
The residual monomer content of aqueous polymer dispersion comprises:
7300mg vinyl-acetic ester/kg emulsion
180mg ethyl propenoate/kg emulsion
Aqueous polymer dispersion also contains 86mg formaldehyde/kg emulsion.Post polymerization (inert gas atmosphere)
The 300g aqueous polymer dispersion that will make in the main emulsion polymerization is heated to 70 ℃ with reflux exchanger.Then 0.4wt% (by dispersed polymkeric substance) NaPS (with the aqueous solution of concentration 5wt%) is once all added.Then in 10 minutes, be metered into the AIMS aqueous solution (amount to 0.2wt%AIMS, by by dispersed polymeres) of concentration 1wt%, then this mixture further stirred 3 hours down at 70 ℃.Total residual monomer content is lower than 1wt% (by dispersed polymkeric substance), and it comprises:
30mg vinyl-acetic ester/kg emulsion
＜10mg ethyl propenoate/kg emulsion
8mg formaldehyde/kg emulsion.
Claims (33)
1. method for preparing aqueous polymer dispersion, wherein produce aqueous polymer dispersion by known mode own, described polymkeric substance contains the monomer with at least one ethylenically unsaturated group of at least a chemical bonding, feasible free monomer with at least one ethylenic unsaturated bond, be this class not chemical bonding the total content of monomer in aqueous polymer dispersion by the polymer content of aqueous polymer dispersion count＞0 to≤1%, and the effect of the radical redox initiator system of this residual monomer content by comprising at least a oxygenant and at least a reductive agent reduces, wherein the redox initiator system comprises a kind of compound as reductive agent, and this compound exists with two kinds of change forms of mutual equilibrated in the aqueous solution at least.
2. method as claimed in claim 1, wherein the redox initiator system comprises that amino imino methane-sulfinic acid or its salt are as reductive agent.
3. as the method for claim 1 or 2, wherein the residual monomer content that will reduce is＞0 to≤0.5wt%.
4. as any one method of claim 1 to 3, wherein the residual monomer content that will reduce is＞0 to≤0.1wt%.
5. as any one method of claim 1 to 4, wherein dispersed polymkeric substance contains at least two kinds of mutual different and monomers that have at least one ethylenically unsaturated group that are incorporated into the chemical bonding form.
6. method as claimed in claim 5, wherein, dispersed polymkeric substance contains at least two kinds of mutual different and monomer that have at least one ethylenically unsaturated group, ratio S on the other hand that are incorporated into the chemical bonding form on the one hand
A/ S
B〉=1.1, S wherein
AThe highest monomeric molar solubility of molar solubility under these conditions in water in the residual monomer mixture that will reduce for the content of under 25 ℃ and 1 crust, measuring, S
BThe minimum monomeric corresponding solubleness of molar solubility under these conditions in water in the residual monomer mixture that will reduce for content.
7. method as claimed in claim 7, wherein S
A/ S
B〉=1.5.
8. as any one method of claim 1 to 7, wherein its content residual monomer mixture that will reduce contains at least a monomer and at least a monomer that is selected from vinylformic acid, methacrylic acid, acrylamide and Methacrylamide that is selected from vinylbenzene, divinyl, n-butyl acrylate and 2-EHA.
9. as any one method of claim 1 to 7, wherein its content residual monomer mixture that will reduce comprises vinyl cyanide.
10. as any one method of claim 1 to 7, wherein its content residual monomer mixture that will reduce comprises vinyl-acetic ester or propionate.
11. as any one method of claim 1 to 7, wherein its content residual monomer mixture that will reduce comprises vinylformic acid.
12. as any one method of claim 1 to 11, wherein the solids content in volume of the aqueous polymer dispersion of producing by known mode itself is 30 to 70% (volumes).
13., wherein the source thing of free formaldehyde is followed to be used for the process of producing aqueous polymer dispersion by known mode itself as any one method of claim 1 to 12.
14. as any one method of claim 1 to 13, wherein the redox initiator system works for 6 to 10 times in the pH of water dispersion medium value.
15. as any one method of claim 1 to 14, wherein the redox initiator system works under 50 to 80 ℃.
16. as any one method of claim 1 to 15, wherein molecular oxygen is the component of redox initiator system.
17. as any one method of claim 1 to 16, wherein the redox initiator system is higher than in temperature under the minimum film-forming temperature of resulting polymers water miscible liquid and works.
18. as any one method of claim 1 to 16, wherein redox system works under temperature is higher than by the statistics second-order transition temperature of dispersed polymeres.
19. as any one method of claim 1 to 18, wherein the aqueous polymer dispersion of producing by known mode itself is the secondary emulsion.
20. as any one method of claim 1 to 19, wherein the aqueous polymer dispersion of producing by known mode itself by dispersed polymeres by the radical aqueous emulsion polymerization by monomer preparation with at least one ethylenically unsaturated group.
21. as the method for claim 20, wherein the radical aqueous emulsion polymerization is undertaken by reinforced method.
22. as the method for claim 21, monomer that wherein will polymeric 50 to 100wt% adds in the polymerization reactor when the radical aqueous emulsion polymerization begins.
23. as the method for claim 20 or 21, wherein will polymeric at least the monomer of 50wt% in the presence of no amino imino methane-sulfinic acid, carry out polymerization.
24., wherein be used to prepare and comprise peroxidation pyrosulfuric acid or its an alkali metal salt by the free-radical initiator system of dispersed polymeres as any one method of claim 20 to 23.
25. as any one method of claim 20 to 24, wherein only with peroxidation pyrosulfuric acid or its an alkali metal salt or its ammonium salt as preparation by the free-radical initiator system of dispersed polymeres.
26., wherein 70 to 100 ℃ polymerization temperature is used for preparation by dispersed polymeres as any one method of claim 20 to 25.
27. as any one method of claim 20 to 26, wherein be used to prepare by dispersed polymeres want the polymeric monomer composition comprise at least two kinds different mutually and have the monomer of at least one ethylenically unsaturated group and also contain :-70 to 99.9wt% vinylformic acid and/or methacrylic acid and 1 to 12 carbon atom
The alkanol ester and/or the vinylbenzene that form,
Or-70 to 99.9wt% vinylbenzene and/or divinyl
Or-70 to 99.9wt% vinylchlorid and/or vinylidene chloride
Or-40 vinyl-acetic esters, propionate and/or ethene to 99.9wt%.
28., wherein superoxide or hydrogen peroxide are followed oxygenant as radical redox initiator system as any one method of claim 1 to 27.
29., wherein tertbutyl peroxide is followed as oxygenant as any one method of claim 1 to 28.
30. as any one method of claim 1 to 29, wherein radical redox initiator system also comprises and dissolves in the metallic compound that multiple valence state can appear in water-containing reacting medium and its metal component.
31. the purposes of a radical redox initiator system in aqueous polymer dispersion, described initiator system comprises a kind of compound as reductive agent that exists with at least two kinds of change forms of mutual equilibrated at the aqueous solution that is used for reducing free monomer content, described free monomer be non-chemical bonding and have at least one ethylenic unsaturated bond, described content by the polymer content of aqueous polymer dispersion count＞0 to≤1%.
32. as the purposes of claim 31, wherein reductive agent comprises amino imino methane-sulfinic acid or its salt.
33. according to any one the aqueous polymer dispersion of method preparation of claim 1 to 30.
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|---|---|---|---|
| CN 95196128 CN1162963A (en) | 1994-10-04 | 1995-09-23 | Process for preparing an aqueous polymer dispersion |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP4435422.3 | 1994-10-04 | ||
| CN 95196128 CN1162963A (en) | 1994-10-04 | 1995-09-23 | Process for preparing an aqueous polymer dispersion |
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| Publication Number | Publication Date |
|---|---|
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ID=5083122
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|---|---|---|---|
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1839159B (en) * | 2003-08-21 | 2010-10-13 | 巴斯福股份公司 | Use of 2-hydroxy-2-sulfinato acetic acid or the salts thereof as an initiator in w/o emulsions |
| CN103443130A (en) * | 2006-07-18 | 2013-12-11 | 赛拉尼斯国际公司 | Emulsion polymerisation process |
| CN106883326A (en) * | 2017-03-22 | 2017-06-23 | 美巢集团股份公司 | A kind of method for reducing polyvinyl acetate emulsion VOC content |
| CN109589903A (en) * | 2018-12-28 | 2019-04-09 | 浙江中科立德新材料有限公司 | A kind of de- one-pot of reaction-suitable for the production of high-viscosity polymer emulsion/solution and its application method |
| CN112574354A (en) * | 2020-12-10 | 2021-03-30 | 巴斯夫新材料有限公司 | Emulsion polymerization process |
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1995
- 1995-09-23 CN CN 95196128 patent/CN1162963A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1839159B (en) * | 2003-08-21 | 2010-10-13 | 巴斯福股份公司 | Use of 2-hydroxy-2-sulfinato acetic acid or the salts thereof as an initiator in w/o emulsions |
| CN103443130A (en) * | 2006-07-18 | 2013-12-11 | 赛拉尼斯国际公司 | Emulsion polymerisation process |
| CN103443130B (en) * | 2006-07-18 | 2016-01-20 | 赛拉尼斯国际公司 | Emulsion polymerisation process |
| CN106883326A (en) * | 2017-03-22 | 2017-06-23 | 美巢集团股份公司 | A kind of method for reducing polyvinyl acetate emulsion VOC content |
| CN109589903A (en) * | 2018-12-28 | 2019-04-09 | 浙江中科立德新材料有限公司 | A kind of de- one-pot of reaction-suitable for the production of high-viscosity polymer emulsion/solution and its application method |
| CN112574354A (en) * | 2020-12-10 | 2021-03-30 | 巴斯夫新材料有限公司 | Emulsion polymerization process |
| CN112574354B (en) * | 2020-12-10 | 2023-03-28 | 巴斯夫新材料有限公司 | Emulsion polymerization process |
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