CN1688614A - Aqueous polymer dispersions, method for the production thereof and use thereof, especially in anti-corrosion coatings - Google Patents
Aqueous polymer dispersions, method for the production thereof and use thereof, especially in anti-corrosion coatings Download PDFInfo
- Publication number
- CN1688614A CN1688614A CN 03819209 CN03819209A CN1688614A CN 1688614 A CN1688614 A CN 1688614A CN 03819209 CN03819209 CN 03819209 CN 03819209 A CN03819209 A CN 03819209A CN 1688614 A CN1688614 A CN 1688614A
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- weight
- copolymer
- monomer
- acid
- polymer dispersion
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- 239000006185 dispersion Substances 0.000 title claims abstract description 43
- 238000000576 coating method Methods 0.000 title claims abstract description 30
- 229920000642 polymer Polymers 0.000 title claims abstract description 17
- 238000000034 method Methods 0.000 title claims description 31
- 238000005260 corrosion Methods 0.000 title abstract description 7
- 238000004519 manufacturing process Methods 0.000 title description 6
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 51
- 239000004815 dispersion polymer Substances 0.000 claims abstract description 34
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 23
- ABLZXFCXXLZCGV-UHFFFAOYSA-N phosphonic acid group Chemical group P(O)(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims abstract 4
- 239000000178 monomer Substances 0.000 claims description 104
- -1 carboxylic acid acids Chemical class 0.000 claims description 47
- 239000000839 emulsion Substances 0.000 claims description 35
- 229920001577 copolymer Polymers 0.000 claims description 31
- 239000007788 liquid Substances 0.000 claims description 26
- 239000000126 substance Substances 0.000 claims description 18
- 150000002148 esters Chemical class 0.000 claims description 17
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 15
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 15
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 15
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 15
- 239000002585 base Substances 0.000 claims description 14
- 239000003999 initiator Substances 0.000 claims description 14
- 230000001681 protective effect Effects 0.000 claims description 12
- 150000003839 salts Chemical class 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 10
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 10
- 150000003863 ammonium salts Chemical class 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 10
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 9
- 239000000084 colloidal system Substances 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 9
- 150000003254 radicals Chemical class 0.000 claims description 9
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical compound SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000004132 cross linking Methods 0.000 claims description 8
- 230000009477 glass transition Effects 0.000 claims description 8
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 7
- 229910052783 alkali metal Inorganic materials 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 238000007720 emulsion polymerization reaction Methods 0.000 claims description 7
- 239000000243 solution Substances 0.000 claims description 7
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 claims description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 239000000654 additive Substances 0.000 claims description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 4
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 4
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 4
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 4
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 4
- 239000012965 benzophenone Substances 0.000 claims description 4
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 claims description 3
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 claims description 3
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 3
- 239000004215 Carbon black (E152) Substances 0.000 claims 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 claims description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 3
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 claims description 3
- 229910021529 ammonia Inorganic materials 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 3
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 claims description 3
- 229930195733 hydrocarbon Natural products 0.000 claims description 3
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 claims description 3
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 3
- 239000004530 micro-emulsion Substances 0.000 claims description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 3
- 159000000000 sodium salts Chemical class 0.000 claims description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 3
- LGJCFVYMIJLQJO-UHFFFAOYSA-N 1-dodecylperoxydodecane Chemical compound CCCCCCCCCCCCOOCCCCCCCCCCCC LGJCFVYMIJLQJO-UHFFFAOYSA-N 0.000 claims description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 2
- JJRUAPNVLBABCN-UHFFFAOYSA-N 2-(ethenoxymethyl)oxirane Chemical compound C=COCC1CO1 JJRUAPNVLBABCN-UHFFFAOYSA-N 0.000 claims description 2
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical class OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 claims description 2
- BWDBEAQIHAEVLV-UHFFFAOYSA-N 6-methylheptan-1-ol Chemical compound CC(C)CCCCCO BWDBEAQIHAEVLV-UHFFFAOYSA-N 0.000 claims description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 2
- 239000005977 Ethylene Substances 0.000 claims description 2
- 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 claims description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 claims description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 2
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 2
- 239000012736 aqueous medium Substances 0.000 claims description 2
- 239000008346 aqueous phase Substances 0.000 claims description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 2
- 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 claims description 2
- 239000011230 binding agent Substances 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 150000005690 diesters Chemical class 0.000 claims description 2
- WZJDBQZPEAEUMK-UHFFFAOYSA-N diethoxy-methyl-(2-triethoxysilylethyl)silane Chemical compound CCO[Si](C)(OCC)CC[Si](OCC)(OCC)OCC WZJDBQZPEAEUMK-UHFFFAOYSA-N 0.000 claims description 2
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 2
- 239000001530 fumaric acid Substances 0.000 claims description 2
- 230000002209 hydrophobic effect Effects 0.000 claims description 2
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 2
- MPQXHAGKBWFSNV-UHFFFAOYSA-N oxidophosphanium Chemical class [PH3]=O MPQXHAGKBWFSNV-UHFFFAOYSA-N 0.000 claims description 2
- 150000003009 phosphonic acids Chemical class 0.000 claims description 2
- 229920002401 polyacrylamide Polymers 0.000 claims description 2
- 229920001451 polypropylene glycol Polymers 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 239000012966 redox initiator Substances 0.000 claims description 2
- BWYYYTVSBPRQCN-UHFFFAOYSA-M sodium;ethenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C=C BWYYYTVSBPRQCN-UHFFFAOYSA-M 0.000 claims description 2
- 125000006850 spacer group Chemical group 0.000 claims description 2
- 239000000725 suspension Substances 0.000 claims description 2
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 claims description 2
- 150000003672 ureas Chemical class 0.000 claims description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 2
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims 2
- IBDVWXAVKPRHCU-UHFFFAOYSA-N 2-(2-methylprop-2-enoyloxy)ethyl 3-oxobutanoate Chemical compound CC(=O)CC(=O)OCCOC(=O)C(C)=C IBDVWXAVKPRHCU-UHFFFAOYSA-N 0.000 claims 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims 2
- 150000007513 acids Chemical class 0.000 claims 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 claims 2
- 150000008064 anhydrides Chemical class 0.000 claims 2
- 150000008366 benzophenones Chemical class 0.000 claims 2
- 150000001735 carboxylic acids Chemical class 0.000 claims 2
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 claims 2
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 claims 2
- 238000012703 microemulsion polymerization Methods 0.000 claims 2
- 150000004756 silanes Chemical class 0.000 claims 2
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 claims 2
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims 1
- LABXBOIPJOUEHG-UHFFFAOYSA-N 2-(carbamoylamino)ethyl prop-2-enoate Chemical compound NC(=O)NCCOC(=O)C=C LABXBOIPJOUEHG-UHFFFAOYSA-N 0.000 claims 1
- DMZPTAFGSRVFIA-UHFFFAOYSA-N 3-[tris(2-methoxyethoxy)silyl]propyl 2-methylprop-2-enoate Chemical compound COCCO[Si](OCCOC)(OCCOC)CCCOC(=O)C(C)=C DMZPTAFGSRVFIA-UHFFFAOYSA-N 0.000 claims 1
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 claims 1
- ZSBNXOIAJFVXMP-UHFFFAOYSA-N 5-tert-butyl-2-methylbenzenethiol Chemical compound CC1=CC=C(C(C)(C)C)C=C1S ZSBNXOIAJFVXMP-UHFFFAOYSA-N 0.000 claims 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims 1
- 239000007983 Tris buffer Substances 0.000 claims 1
- 150000008062 acetophenones Chemical class 0.000 claims 1
- 229960005070 ascorbic acid Drugs 0.000 claims 1
- 235000010323 ascorbic acid Nutrition 0.000 claims 1
- 239000011668 ascorbic acid Substances 0.000 claims 1
- 239000003638 chemical reducing agent Substances 0.000 claims 1
- 239000000470 constituent Substances 0.000 claims 1
- 239000008121 dextrose Substances 0.000 claims 1
- 125000004663 dialkyl amino group Chemical group 0.000 claims 1
- 150000001983 dialkylethers Chemical class 0.000 claims 1
- 239000002270 dispersing agent Substances 0.000 claims 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 claims 1
- ZEYMDLYHRCTNEE-UHFFFAOYSA-N ethenyl 3-oxobutanoate Chemical compound CC(=O)CC(=O)OC=C ZEYMDLYHRCTNEE-UHFFFAOYSA-N 0.000 claims 1
- MABAWBWRUSBLKQ-UHFFFAOYSA-N ethenyl-tri(propan-2-yloxy)silane Chemical compound CC(C)O[Si](OC(C)C)(OC(C)C)C=C MABAWBWRUSBLKQ-UHFFFAOYSA-N 0.000 claims 1
- WOXXJEVNDJOOLV-UHFFFAOYSA-N ethenyl-tris(2-methoxyethoxy)silane Chemical compound COCCO[Si](OCCOC)(OCCOC)C=C WOXXJEVNDJOOLV-UHFFFAOYSA-N 0.000 claims 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 claims 1
- SBGKURINHGJRFN-UHFFFAOYSA-N hydroxymethanesulfinic acid Chemical compound OCS(O)=O SBGKURINHGJRFN-UHFFFAOYSA-N 0.000 claims 1
- 239000011976 maleic acid Substances 0.000 claims 1
- 125000005397 methacrylic acid ester group Chemical group 0.000 claims 1
- 150000002763 monocarboxylic acids Chemical class 0.000 claims 1
- 125000005385 peroxodisulfate group Chemical group 0.000 claims 1
- 150000002989 phenols Chemical class 0.000 claims 1
- 239000003505 polymerization initiator Substances 0.000 claims 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 claims 1
- PNOXUQIZPBURMT-UHFFFAOYSA-M potassium;3-(2-methylprop-2-enoyloxy)propane-1-sulfonate Chemical compound [K+].CC(=C)C(=O)OCCCS([O-])(=O)=O PNOXUQIZPBURMT-UHFFFAOYSA-M 0.000 claims 1
- WBHQBSYUUJJSRZ-UHFFFAOYSA-M sodium bisulfate Chemical compound [Na+].OS([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-M 0.000 claims 1
- 229910000342 sodium bisulfate Inorganic materials 0.000 claims 1
- 125000001424 substituent group Chemical group 0.000 claims 1
- 150000003460 sulfonic acids Chemical class 0.000 claims 1
- 238000010557 suspension polymerization reaction Methods 0.000 claims 1
- 239000011975 tartaric acid Substances 0.000 claims 1
- 235000002906 tartaric acid Nutrition 0.000 claims 1
- 150000005691 triesters Chemical class 0.000 claims 1
- UDUKMRHNZZLJRB-UHFFFAOYSA-N triethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OCC)(OCC)OCC)CCC2OC21 UDUKMRHNZZLJRB-UHFFFAOYSA-N 0.000 claims 1
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 claims 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 22
- 238000002360 preparation method Methods 0.000 abstract description 15
- 238000012360 testing method Methods 0.000 abstract description 7
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 abstract description 2
- 238000009833 condensation Methods 0.000 abstract 1
- 230000005494 condensation Effects 0.000 abstract 1
- 239000011248 coating agent Substances 0.000 description 26
- 239000000463 material Substances 0.000 description 19
- 239000008267 milk Substances 0.000 description 19
- 210000004080 milk Anatomy 0.000 description 19
- 235000013336 milk Nutrition 0.000 description 19
- 239000003795 chemical substances by application Substances 0.000 description 17
- 239000003973 paint Substances 0.000 description 10
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 9
- 230000037452 priming Effects 0.000 description 9
- 238000003860 storage Methods 0.000 description 8
- 238000007334 copolymerization reaction Methods 0.000 description 6
- 239000003513 alkali Substances 0.000 description 5
- 125000005499 phosphonyl group Chemical group 0.000 description 5
- 239000002987 primer (paints) Substances 0.000 description 5
- 229920000147 Styrene maleic anhydride Polymers 0.000 description 4
- 239000002250 absorbent Substances 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- WOLATMHLPFJRGC-UHFFFAOYSA-N furan-2,5-dione;styrene Chemical compound O=C1OC(=O)C=C1.C=CC1=CC=CC=C1 WOLATMHLPFJRGC-UHFFFAOYSA-N 0.000 description 4
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 3
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000007600 charging Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000003750 conditioning effect Effects 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- ZBJVLWIYKOAYQH-UHFFFAOYSA-N naphthalen-2-yl 2-hydroxybenzoate Chemical compound OC1=CC=CC=C1C(=O)OC1=CC=C(C=CC=C2)C2=C1 ZBJVLWIYKOAYQH-UHFFFAOYSA-N 0.000 description 3
- 150000003014 phosphoric acid esters Chemical class 0.000 description 3
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- 239000012752 auxiliary agent Substances 0.000 description 2
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- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 2
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- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 1
- RCGCPJFKOPMRON-UHFFFAOYSA-N 2-(dimethylamino)ethyl but-2-enoate Chemical compound CC=CC(=O)OCCN(C)C RCGCPJFKOPMRON-UHFFFAOYSA-N 0.000 description 1
- 229920000536 2-Acrylamido-2-methylpropane sulfonic acid Polymers 0.000 description 1
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- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
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- 125000003368 amide group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
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- 239000012874 anionic emulsifier Substances 0.000 description 1
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- 239000002518 antifoaming agent Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
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- 230000008901 benefit Effects 0.000 description 1
- 125000005340 bisphosphate group Chemical group 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 244000309464 bull Species 0.000 description 1
- MPMBRWOOISTHJV-UHFFFAOYSA-N but-1-enylbenzene Chemical compound CCC=CC1=CC=CC=C1 MPMBRWOOISTHJV-UHFFFAOYSA-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
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
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- 230000008021 deposition Effects 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- FBSAITBEAPNWJG-UHFFFAOYSA-N dimethyl phthalate Natural products CC(=O)OC1=CC=CC=C1OC(C)=O FBSAITBEAPNWJG-UHFFFAOYSA-N 0.000 description 1
- 229960001826 dimethylphthalate Drugs 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 150000002081 enamines Chemical class 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N ethyl acetate Substances CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- SBRXLTRZCJVAPH-UHFFFAOYSA-N ethyl(trimethoxy)silane Chemical compound CC[Si](OC)(OC)OC SBRXLTRZCJVAPH-UHFFFAOYSA-N 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 229940042795 hydrazides for tuberculosis treatment Drugs 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000001261 hydroxy acids Chemical group 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
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- 229910052909 inorganic silicate Inorganic materials 0.000 description 1
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- 238000012423 maintenance Methods 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 1
- 229910000402 monopotassium phosphate Inorganic materials 0.000 description 1
- 235000019796 monopotassium phosphate Nutrition 0.000 description 1
- 150000007518 monoprotic acids Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- GNSKLFRGEWLPPA-UHFFFAOYSA-M potassium dihydrogen phosphate Chemical compound [K+].OP(O)([O-])=O GNSKLFRGEWLPPA-UHFFFAOYSA-M 0.000 description 1
- 235000019394 potassium persulphate Nutrition 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- AXLMPTNTPOWPLT-UHFFFAOYSA-N prop-2-enyl 3-oxobutanoate Chemical compound CC(=O)CC(=O)OCC=C AXLMPTNTPOWPLT-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
- 230000009467 reduction Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- XWGJFPHUCFXLBL-UHFFFAOYSA-M rongalite Chemical compound [Na+].OCS([O-])=O XWGJFPHUCFXLBL-UHFFFAOYSA-M 0.000 description 1
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- 239000002002 slurry Substances 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
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- 229940095064 tartrate Drugs 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- DENFJSAFJTVPJR-UHFFFAOYSA-N triethoxy(ethyl)silane Chemical compound CCO[Si](CC)(OCC)OCC DENFJSAFJTVPJR-UHFFFAOYSA-N 0.000 description 1
- QLNOVKKVHFRGMA-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical group [CH2]CC[Si](OC)(OC)OC QLNOVKKVHFRGMA-UHFFFAOYSA-N 0.000 description 1
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Paints Or Removers (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Polymerisation Methods In General (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
本发明涉及用于抗腐蚀保护的聚合物分散液，其具有良好的防锈性能，并涉及其制备方法和用途。该聚合物分散液含有包含磷酸基团和/或膦酸基团的乳化剂，并在聚合之前通过加入碱(部分地)中和。结果，生产出根据冷凝水试验DIN 50017具有改善的防锈性能的聚合物分散液，并可获得低凝结物含量。该聚合分散液还使得由其生产的抗腐蚀底漆具有改善的稳定性。使用所述聚合物分散液，可获得高光泽的涂层。The invention relates to a polymer dispersion used for anti-corrosion protection, which has good anti-rust performance, and relates to its preparation method and use. The polymer dispersion contains an emulsifier comprising phosphoric acid groups and/or phosphonic acid groups and is (partially) neutralized by adding a base before the polymerization. As a result, polymer dispersions are produced which have improved antirust properties according to the condensation water test DIN 50017, and low condensate contents can be obtained. The polymeric dispersion also allows improved stability of the anti-corrosion primers produced therefrom. Using said polymer dispersions, high-gloss coatings can be obtained.
Description
The present invention relates to novel aqueous polymer dispersion, its production method and uses thereof, especially for the purposes of protective system.
The aqueous polymer dispersion that is used for anticorrosive coating is subjected to the restriction of multiple final condition, in order to ensure in the sufficient provide protection aspect the corrosion formation, must observe these final conditions.For example, because water is a kind of key component in corrosion process, so coating must have sufficient hydrophobicity and is diffused into the interface between base material and the coating to prevent water.In addition, also should guarantee effectively bonding between base material and the coating, so as to make since on base material/coating interface that the migration of the water under the corrosionproof protection coating causes formed bubble minimize.At last, this preservative coat reply carbonic acid gas has good diffusing barrier effect.The comonomer of the increased sticking power of determining in the prior art comprises undersaturated beta-diketonate compound, for example acetoacetic acid allyl ester and methacrylic acid acetoacetoxy ethyl ester.
In WO 99/14278, solved effective adherent problem of guaranteeing between base material and the coating by means of the acetoacetoxy group in the polymer.Poly-(alkylene imine) is added in the polymer dispersion liquid, and crosslinked with the acetoacetoxy group in film process, forms enamine.The anionic emulsifier of Jia Ruing can suppress the too early crosslinking reaction in the polymer dispersion liquid subsequently.In for example WO99/14275 and WO 99/14279, disclose equally with nonionic emulsifying agent labile cross linker system.In the latter's specification sheets, add nonionic emulsifying agent subsequently as stablizer.The phosphoric acid salt emulsifying agent is used for polymerization.The foaming tendency of resulting dispersion liquid is lower.
A shortcoming of these coating is need be subsequently by adding emulsifying agent to stablize the dispersion liquid of gained.According to disclosed embodiment, must add a large amount of relatively emulsifying agents so that realize required storage stability.On the one hand, it is expensive adding poly-(alkylene imine) emulsifying agent subsequently, and on the other hand, water-absorbent also can strengthen when emulsifier content increased in coating, and this antagonism corrosive nature is deleterious.In addition, the danger that also exists emulsifying agent to move to base material/coating interface and cause it that sticking power of base material is reduced.This is strengthening the absorptive coating foaming that also caused simultaneously.
At last, the amine in the aqueous solution forms the brown degraded product easily, and this product itself is unwanted and obviously can causes coating color-changing.Use described admixture preparation dispersion liquid subsequently, and need to use buffering system to reduce final pH value, this has all further increased the manufacturing cost of this product.
In WO 98/54256, described based on the polyamines of aqueous polymer dispersion and the mechanism of crosslinking of acetoacetoxy group.
US 5,122, and 566 disclose a kind of method for preparing grid, and this method is to implement by the aqueous emulsion polymerization in the presence of the phosphoric acid salt emulsifying agent and under the condition of pH＜3.5.The described dispersion liquid of the document also comprises at least a water-fast, non-ionic tensio-active agent, and its pH value is adjusted in 7 to 10.5 the scope after polymerization.But openly can not improve the use of (methyl) acrylic acid acetoacetoxy derivative of sticking power.
EP-A-0 476 528 discloses a kind of method that is used for the preparation of industrialization grid, and the multipolymer of therein ethylene base aromatic compound and acrylate is by in the presence of seed polymer, under the condition of pH＜3.5 and carry out the aqueous emulsion polymerization prepare in the presence of phosphoric acid salt emulsifying agent and water-fast, nonionogenic tenside.Except having at least a seed polymer, this method and US 5,122,566 disclosed methods are identical.According to EP-A-0 476 528, if do not use described at least a seed polymer, promptly according to US 5,122,566 method, the polymkeric substance that obtains in commercial production scale has very high coagulum content.
Therefore, target of the present invention provides a kind of aqueous polymer dispersion, it demonstrates higher erosion resistance in anticorrosive coating in the agglutination,cold test that carries out according to DIN 50017, this dispersion liquid can and can need not the expensive inconvenient synthetic method of prior art with the technical scale preparation and be prepared.
The characteristics of this polymeric membrane also should be to have high-clarity, promptly do not have the division scattering center that produces because of formation aggregation in polymerization process, thereby also can be used for transparent coating material.
According to the present invention, can realize the target of setting by a kind of aqueous polymer dispersion, this dispersion liquid has the solids component of 20 weight % to 74 weight %, preferred 40 weight % to 70 weight %, and contains at least a copolymer A that comprises the following compound of copolymerization attitude):
A) based on the monomeric gross weight that is used to prepare this multipolymer, at least a single or oligomeric ethylenically unsaturated monomers of 40 weight % to 99.95 weight %, preferred 60 weight % to 90 weight %, this monomer can carry out polymerization by the free radical emulsion polymerized,
B) based on the monomeric gross weight that is used to prepare this multipolymer, at least a ethylenic unsaturated monocarboxylic and/or the low poly carboxylic acid of 0.05 weight % to 10 weight %, preferred 0.05 weight % to 5 weight %, and/or its salt, and
C) based on the monomeric gross weight that is used to prepare this multipolymer, at least a other unsaturated monoprotic acid of ethylenic and/or the oligomeric acid of 0 weight % to 5 weight %, preferred 0.05 weight % to 2 weight %, it is derived from phosphoric acid, phosphonic acids, sulfuric acid and/or sulfonic acid and/or its salt
Wherein, based on the monomeric gross weight that is used to prepare this multipolymer, this dispersion liquid comprises the emulsifying agent that comprises phosphate group and/or phosphonyl group of at least 0.3 weight %, preferred 0.3 weight % to 5 weight %, and wherein at least aly contains described at least a monomer b) and (if existence) described at least a monomer c) pH 〉=4.7 of initial monomer emulsion feed.
The copolymer A that the present invention is used) glass transition temperature T
gUsually in-35 ℃ to 80 ℃ scope, a preferred Tg is in 0 ℃ to 40 ℃ scope or two T
gAt-30 ℃ to+20 ℃ (T
g) and+40 ℃ to+80 ℃ (the 2nd T
g) scope in.
The used copolymer A of property quality and quantity adjusting the present invention by the selection comonomer) glass transition temperature.
Monomer is a) to c) weight part preferably select to such an extent that only can make the glass transition temperature T of the multipolymer that constitutes by them
gIn-35 ℃ to 80 ℃ scope.
Be surprised to find that aqueous dispersions of the present invention has the erosion resistance of remarkable improvement in according to the agglutination,cold test of DIN 50017 in the protective system that obtains.In addition, aqueous dispersions of the present invention less coagulum that occurs in polymerization process.Institute's dispersion liquid that obtains can be produced with technical scale zero defect ground, and (storage) stability of the anti-corrosive primer coating of preparing with their is improved.At last, use dispersion liquid of the present invention can produce coating with high gloss.
The preferred construction unit of this at least a multipolymer is α a), β-ethylenic unsaturated carboxylic acid and the ester that contains the alkanol of 1 to 18 carbon atom, the ester of preferred acrylic or methacrylic acid and methyl alcohol, ethanol, propyl alcohol, butanols, amylalcohol, 2-Ethylhexyl Alcohol, isooctyl alcohol, nonylcarbinol and n-dodecane alcohol.Other preferred monomer comprises vi-ny l aromatic monomers, for example vinylbenzene and alkyl derivative thereof, for example vinyl toluene, ethyl styrene and oligomeric (alkyl) vinylbenzene.In addition, the alkene of ethene, propylene, iso-butylene and so on, and the derivative of these compounds, for example ester of vinylchlorid, Vinyl Ether and (aliphatics) carboxylic acid and alkene, the ethylenic unsaturated ester of preferred vinyl-acetic ester or Versatic acid also can be used as structural unit a).
Used structural unit b) is undersaturated monocarboxylic acid of single or oligomeric ethylenic or low poly carboxylic acid and acid anhydrides thereof and/or their salt.Preferred vinylformic acid, methacrylic acid, methylene-succinic acid, toxilic acid and/or fumaric acid and their salt of using.If comprise structural unit b) and pH value＜4.7 of water-based initial monomer emulsion feed c), just it must be increased to pH 〉=4.7 at least.This can finish as follows: with the structural unit b in the water) and (if use) c) structural unit d when suitable) and emulsifying agent and non-essential initiator add water-based initial monomer emulsion feed, and before remaining monomer of adding, the pH value is adjusted to pH 〉=4.7 with alkali.Can be in advance in the initial monomer emulsion feed, add the water miscible structural unit d of part), AAEMA for example.
The initial monomer emulsion feed is meant the mixture of the following material that is used to prepare monomer milk sap in the feed chute in the specification sheets: water, structural unit b), structural unit c) (if existence), emulsifying agent and non-essential structural unit d when suitable) and initiator.
For improving the pH value of initial monomer emulsion feed, preferably use sodium hydroxide and potassium hydroxide.Especially preferably use ammonia with in and the initial monomer emulsion feed because this alkali can volatilize the film forming of polymkeric substance after, the reduction polymer moieties water-absorbent.
Preferred construction unit c) is sodium, potassium and the ammonium salts of sulfuric acid, sulfonic acid, phosphoric acid and/or the unsaturated derivative of phosphonic ethylenic.Especially preferably use vinyl sulfonic acid sodium, 2-acrylamido-2-methyl propane sulfonic acid (
AMPS) salt and methacrylic acid sulfopropyl ester potassium.Especially preferably use ammonium salt, contain free acid because solidify the post polymerization thing at film, this free acid produces lower water-absorbent with respect to corresponding salt at polymer moieties.
When the weight part of mentioning as various (comonomer) structural unit of the ratio of at least a multipolymer, suppose that all comonomers are sneaked in this multipolymer by 100% ground.
Based on the monomeric gross weight that is used to prepare this multipolymer, aqueous polymer dispersion of the present invention also comprises the emulsifying agent that comprises phosphate group and/or phosphonyl group of at least 0.3 weight %, preferred 0.3 weight % to 5 weight %.This emulsifying agent preferably uses the form of ammonium, sodium and the sylvite of phosphoric acid ester and/or phosphonic acid ester.But the salt that also can use these compounds and other alkali to form.When using free phosphoric acid ester and/or phosphonic acid ester, can their (partly) original positions be neutralized to pH 〉=7 by the aqueous solution and alkali (preferably with the ammonia) reaction of emulsifying agent as base material.
The preferred ester of the adducts that comprises the emulsifying agent, particularly phosphoric acid of phosphate group and the ester of pure and mild phenol (also can be the form of mixture of monoesters, diester and three esters of phosphoric acid), phosphoric acid and pure and/or (alkyl) phenol and oxyethane and/or propylene oxide and sodium salt, sylvite and the ammonium salt of these compounds of using.These compounds can obtain from the commercial channel usually, and are for example commercial by name
Berol 522 (alkylphosphonic acid carboxylic acid sylvite),
Hostaphat 1306 (alkyl hangs down the polyethoxye phosphoric acid ester) and
Berol 733 (alkylphenol hangs down the polyethoxye potassium phosphate salt).As the emulsifying agent that comprises phosphate group, can also use the ethylenic unsaturated ester of phosphoric acid and hydrocarbon and by the neutralized reaction product of its deutero-and alkali.
In a preferred embodiment; based on the monomeric gross weight that is used to prepare this multipolymer, at least a multipolymer of described aqueous dispersions also comprises 0.05 weight % to 10 weight %, the more preferably monomer d of the free redical polymerization that comprises at least one acetoacetoxy of 0.5 weight % to 3 weight % with the copolymerization attitude).
Preferred monomer d) be methacrylic acid acetoacetoxy ethyl ester (AAEMA) and vinylformic acid acetoacetoxy ethyl ester (AAEA).Can also use the etheric acid Vinyl Ether.According to the present invention, if monomer d) be that part is water miscible, for example under the situation that is AAEMA, they can also be with monomer b) to c) be included in the initial monomer emulsion feed.
Respectively based on the monomeric gross weight that is used to prepare this multipolymer, at least a multipolymer of described aqueous dispersions can also comprise 0 weight % to 10 weight % of copolymerization attitude, preferred 0 weight % to 2 weight %, the more preferably unsaturated reactive cross-linking monomer e of 0.05 weight % to 1 weight % at least a (list) or (oligomeric) ethylenic), and 0 weight % to 30 weight % of copolymerization attitude, but (list) or (oligomeric) ethylenically unsaturated monomers f of other copolymerization of preferred 0 weight % to 5 weight %) and 0 weight % to 5 weight %, preferred 0 weight % to 2 weight %, more preferably 0 weight % to 0.5 weight %'s can have reactive molecule g to polymkeric substance by similar polymer reaction).
As reactive cross-linking monomer e), i.e. crosslinked monomer in film process, the preferred unsaturated derivative of ethylenic that uses silane, for example vinyltrimethoxy silane, vinyltriethoxysilane, vinyl silane triisopropoxide, (γ-methacryloxypropyl) Trimethoxy silane, vinyl three (2-methoxy ethoxy) silane and γ-methacryloxypropyl three (2-methoxy ethoxy) silane.
Other suitable monomers e) the unsaturated derivative of other ethylenic of (methyl) glycidyl acrylate and/or Racemic glycidol is arranged, for example the glycidyl vinyl ether.
As monomer e), can also use diacetone-acryloamide(DAA).But should add two hydrazides co-crosslinkers in this case.Also can use the derivative of sheltering of N hydroxymethyl acrylamide, for example N-tert.-butoxy methyl acrylamide crosslinkedly.
As other monomer f), can use undersaturated nitrogen containing monomer, for example Methacrylamide and (methyl) vinylformic acid dimethylaminoethyl ester; The derivative of urea, for example vinylformic acid beta-carbamido ethyl ester, beta-carbamido Vinyl Ether and (methyl) vinylformic acid -hydroxy alkyl ester preferably use Methacrylamide.
Can also use dual functional (methyl) acrylate, two (methyl) vinylformic acid 1 for example, 4-and 1,3-butanediol ester and two (methyl) vinylformic acid 1,6-hexylene glycol ester, dual functional ethene derivatives, for example Vinylstyrene and divinyl, with (methyl) acrylate of trifunctional, trimethylolpropane trimethacrylate for example is as other unsaturated monomer f) to increase the elasticity of coating.
As structural unit g), generally can use material by the functional group reactions of similar polymer reaction and polymkeric substance.The present invention preferably uses epoxy silane, more preferably glycidoxypropyltrimewasxysilane, β-(3, the 4-epoxycyclohexyl) ethyl triethoxysilane, β-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane, perhaps oligomeric functional silane, for example 1-(triethoxysilyl)-2-(diethoxymethyl silyl) ethane or isocyanuric acid three [3-(trimethoxysilyl) propyl group] ester.
In another embodiment, based on the monomeric gross weight that is used to prepare this multipolymer, aqueous polymer dispersion of the present invention comprises 0 weight % to 5 weight %, preferred 0 weight % to 0.5 weight %, the more preferably UV-crosslinked material of 0 weight % to 0.3 weight %, and this material is not that ethylenic is undersaturated.Preferred ultraviolet-crosslinkable agent is methyl phenyl ketone, benzophenone and acetophenone derivs or the benzophenone derivates that does not comprise ethylenic unsaturated polymerizable group.The preferred especially derivative that uses at room temperature the benzophenone that exists with the liquid mixture form adds proper assistant where necessary, and reason is that these derivatives have the advantage on the performance.Can also use the phosphine oxide derivative.
Except comprising the emulsifying agent of phosphate group and/or phosphonyl group, aqueous polymer dispersion of the present invention can also comprise other emulsifying agent.Based on the monomeric total amount of polymkeric substance, the total amount of emulsifying agent is preferably at 0.3 weight % to 10 weight %, more preferably in the scope of 0.3 weight % to 3.5 weight %.Preferred other emulsifying agent is the emulsifying agent that comprises alkyl, aryl or alkylaryl group.Can use poly-(oxyethane), poly-(propylene oxide) or poly-(ethylene oxide/propylene oxide) as the spacer groups between hydrocarbon free radical and the terminal polar group.Outside phosphate group and/or phosphonyl group emulsifying agent, other ionic emulsifying agent of less preferred use based on vitriol/ester, sulfonate/ester and/or carboxylate salt/ester.Except phosphate group and/or phosphonyl group emulsifying agent, also can use non-ionic co-emulsifier.Preferably adding emulsifying agent before the polymerization and/or between polymerization period.But can also in final dispersion liquid, add ionic and emulsifying agent nonionic, to increase its stability.It is low as far as possible that the amount of used emulsifying agent should keep, so that the water-absorbent of coating minimizes.
In another embodiment, based on the monomeric gross weight that is used to prepare this multipolymer, aqueous polymer dispersion of the present invention comprises the protective colloid of 0 weight % to 5 weight %, preferred 0 weight % to 1 weight %.Can use the protective colloid of the known and suitable the object of the invention of all those skilled in the art.But preferably use water miscible carboxymethyl cellulose, more preferably use the form of its ammonium salt or an alkali metal salt.The example of commercially available prod comprises
Blanose 7M,
Blanose 7UL,
Blanose 7EL and
Ambergum 3021 (Aqualon).In due course, this carboxymethyl cellulose also can have other substituting group, for example alkyl or hydroxyalkyl, alkoxyalkyl and dialkyl amido.Example has methyl carboxymethyl cellulose, ethyl carboxymethyl cellulose, hydroxyethyl carboxymethyl cellulose, hydroxypropyl carboxy methyl Mierocrystalline cellulose, methoxyethyl carboxymethyl cellulose and ethoxyethyl carboxymethyl cellulose.
In addition,, also can use macromolecular compound, for example polyvinyl alcohol, polyvinylpyrrolidone, polyacrylamide, PMAm or poly carboxylic acid, and their an alkali metal salt and/or ammonium salt as protective colloid.
In another embodiment preferred, based on the monomeric gross weight that is used to prepare this multipolymer, aqueous polymer dispersion of the present invention comprises the dispersion agent of 0 weight % to 10 weight %, preferred 0.05 weight % to 3 weight %, preferred polymeric dispersion agent.As dispersion agent, can use well known by persons skilled in the art and be suitable for any dispersion agent of the object of the invention.The example is water-soluble poly-(methyl) vinylformic acid and/or their alkali metal salts or ammonium salt.But the preferred dispersion agent that uses, for example water solubility copolymer of vinyl aromatic compound (particularly vinylbenzene) and ethylenic unsaturated carboxylic acid and/or their acid anhydrides (particularly maleic anhydride) with hydrophobic parts.The form of preferred especially corresponding ammonium salt of these multipolymers and an alkali metal salt.Can between polymerization period or even before polymerization with they part or all of addings.According to its trade(brand)name, can for example use
The SMA resin, for example Cray Valley produces
SMA 3000HNa.
If desired, aqueous polymer dispersion of the present invention can also comprise film coalescence aid, for example butyldiglycol and petroleum solvent, such as softening agent and/or other auxiliary agent of dimethyl phthalate and dibutyl phthalate, for example inhibiter, urethane and Polyacrylate thickeners, sanitas, the defoamer such as mineral oil antifoam agent or silicon oil foam killer, wetting agent and other for example often are used to prepare the additive of coating material.
The present invention not only provides aqueous polymer dispersion, but also Its Preparation Method And Use is provided, especially for the purposes of rust proof paint.
Can prepare this multipolymer according to the method for free radical suspension well known by persons skilled in the art, miniemulsion, microemulsion and emulsion polymerized.But preferred manufacturing procedure is the emulsion polymerized method of carrying out in water.Aqueous polymer dispersion by the preparation of this method be multipolymer of the present invention form preferably is provided.
Therefore; preferably under condition well known by persons skilled in the art, in aqueous medium, in the presence of free radical formation initiator and emulsifying agent; and suitably the time in the presence of protective colloid, conditioning agent and other auxiliary agent, prepare described at least a multipolymer by the free radical emulsion polymerized.
By the emulsion polymerized method of routine, in the presence of the protective colloid of monomer at emulsifying agent, initiator and suitably the time in aqueous phase emulsification, and preferably polymerization in 25 to 95 ℃ temperature range of this milk sap.Can be according to method known to those skilled in the art, for example in batches or the emulsion feed method carry out this emulsion polymerized, preferred emulsion feed method, wherein add partial monosomy milk sap as initial charge, and before the form with the monomer aqueous emulsion is metered into residual monomers, finish polymerization.Preferred list (milk sap) chargings that are metered into two or more different compositions continuously.This generation makes the polymeric film of gained have the multistage polymkeric substance of variform.The preparation method of this multistage polymkeric substance is for example having description among the EP-A-0 795 568.Suitable multistage polymkeric substance has lower minimum film-forming temperature (MFFTs) than the homogeneity polymkeric substance of same monomer component, so more preferably.Because MFFT is lower, consequently can significantly reduce consumption volatile, environmentally harmful film coalescence aid.In addition, can prepare multistage polymkeric substance with form with special resistance to blocking.Perhaps, can be metered into monomer with constant or the rapid monomer composition that changes as known according to the power feed method.One or more emulsifying agents not only, and the protective colloid that uses when suitable can be included in the initial charge that (partly) add reactor, and/or are metered into monomer milk sap (partly).
In the method for the invention, can use one or more initial monomer emulsion feed.According to the present invention, comprise described at least a monomer b) and the described at least a monomer c suitably the time) pH value 〉=4.7 of initial emulsion feed, preferred 4.7 to 11, more preferably 4.7 to 8, and preferred especially 5 to 7.
Usually emulsifying agent is added with the initial monomer emulsion feed, different initial monomer emulsion feed can comprise different emulsifying agents.
Contain described at least a monomer b) the initial monomer charging preferably contain the emulsifying agent of phosphoric acid group.
Preferred especially use comprise monomer a), b) and (if use) c) and the initial monomer charging of the emulsifying agent of phosphoric acid group.
In the initial monomer emulsion feed is under two or more the situation, preferably its pH value all 〉=4.7, preferred 4.7 to 11, and more preferably 5 to 7.
Preferably in pH value 〉=4.7, preferred 4.7 to 11, and more preferably carry out polymerization under 5 to 7 the condition.
Use oil soluble and/or water miscible radical initiator or redox initiator system to cause and carry out polymerization.Preferably use for example Potassium Persulfate, Sodium persulfate or ammonium peroxydisulfate, hydrogen peroxide, dibenzoyl peroxide, lauryl peroxide, tertbutyl peroxide, azo isobutyronitrile and other azo initiators, use with reductive agent in due course, for example sodium bisulfite,
Rongalit, glucose, xitix or tartrate.Based on the monomeric gross weight that is used to prepare multipolymer, the amount of used polymerization starter is 0.1 weight % to 10 weight % respectively, preferred 0.1 weight % to 1 weight %.
In addition, can also use conditioning agent, for example mercaptan preferably uses n-dodecane mercaptan, thiophenol and 2-methyl-5-tert.-butylbenzene thiophenol in the case.Based on the monomeric gross weight that is used to prepare multipolymer, the amount of used one or more conditioning agents is generally 0 weight % to 1 weight %.
Usually use ammoniacal liquor or alkali hydroxide soln that the final pH value of aqueous dispersions is adjusted to 6 to 10.
Can be by adding common additive, pigment, softening agent and other additive suitably the time, for example weighting agent, dispersion agent, thickening material, corrosion-inhibiting pigment, inhibiter, wetting agent, ultraviolet inhibitor, ultraviolet initiator and/or other polymeric binder are mixed with coating composition with aqueous dispersions of the present invention.They especially are suitable for producing and using undyed or painted coating, for example antirust coating, transparent coating material, gloss varnish and decorative coveringn, and these coatings require to improve base material sticking power.Owing in the synthetic resins preparation, have phosphate group, and may have wet adhesion promoter (for example acetoacetoxy) in due course, thereby guarantee that base material sticking power is improved.Especially preferably use AAEMA and/or AAEA functional monomer in this article as described at least a multipolymer.The suitable substrates preferable alloy, more preferably steel, but also inorganic silicate surface and timber.In addition, the acetoacetoxy of any existence has guaranteed that coating of the present invention has lower bonding tendency, promptly when the desiccated surface that two have been handled through coating is pressed together, seldom might bond.If use reactive cross-linking monomer e) replacement monomer d), also can realize effective base material sticking power.Measure the minimum film-forming temperature (MFFT) of polymkeric substance according to DIN-ISO 2115.Measure the glass transition temperature (T of polymkeric substance by DSC (dsc)
g).Heating and cooling speed is respectively 200 ℃/min, and the temperature range that covers is-60 ℃ to+130 ℃.In second heating period, measure the glass transition temperature (mid point evaluation) of polymkeric substance.By using the Fox equation, can estimate the glass transition temperature (consult T.G.Fox, Bull.Am.Phys.Soc. (Ser.II), 1,123[1956]) of this polymkeric substance highly approx.By monomer a), b) and the multiple glass transition temperature of the homopolymer that c) constitutes all be known, and at for example J.Brandrup, E.M.Immergut, " polymer handbook " (Polymer Handbook), second edition in 1975, J.Wiley lists among the NewYork.
Explain the present invention below with reference to exemplary example approach, but these embodiments not limitations of the present invention.
Embodiment 1 to 10:
The preparation of multipolymer aqueous dispersions:
A) preparation of initiator solution:
The 3.75g Potassium Persulphate is dissolved in 96.25g deionized water (DI water).
B) polymerization
The preparation of monomer milk sap
Monomer milk sap (initial monomer emulsion feed): use the stirrer have propeller stirrer with the speed of 1000rpm the 28.8g AAEMA thorough mixing with the emulsifying agent that is used for monomer milk sap (seeing Table 1) of successive 491.2g deionized water, described amount, 19.2g methacrylic acid and suitably the time.Subsequently, where necessary, use the NH of 12.5% concentration of described amount (seeing Table 1)
4OH adjusts to 5 with the pH value.
Final monomer solution: add the mixture of 480g methyl methacrylate and 480g n-butyl acrylate subsequently, and with the speed of 1000rpm with resulting emulsifying mixture 10 minutes.
Have in the glass reactor of anchor stirrer at 3L, under the stirring velocity of 120rpm, the emulsifying agent that is used for initial charge of successive 526.4g deionized water and described amount (seeing Table 1) is heated to 80 ℃, add 15.1g initiator solution (a) and 37g monomer milk sap then, and stirred this mixture 15 minutes.Can observe reaction significantly from the heat of emitting.By outside water-bath the internal temperature of this reactor is remained on 80 to 82 ℃ continuously.Subsequently, add residual monomers milk sap by isolating dropping funnel continuous measurement in 180 minutes time, continuous measurement adds remaining initiator solution in 195 minutes time.After being metered into end, continue heating 1 hour at 80 ℃ again, then this milk sap is cooled to room temperature.Under 30 ℃ of temperature, use the ammoniacal liquor of 12.5% concentration that the pH value is adjusted to 7 to 8.
Table 1
| Embodiment | ??1 ??(comp.) | ??2 | ??3 ??(comp.) | ?4 ?(comp.) | ??5 ??(comp.) | ??6 | ??7 ??(comp.) | ??8 ??(comp.) | ??9 ??(comp.) | ??10 |
| The pH value of monomer milk sap (is used for neutral concentration and is 12.5% NH 4The amount of OH [g]) | ??＜4.5 | ??5/29.25 | ??＜4.5 | ??5/27.4 | ??＜4.5 | ??5/28.7 | ??＜4.5 | ??5/30.08 | ??＜4.5 | ??5/32.6 |
| Hostaphat?BV 1(amount of monomer milk sap/initial charge [g]) | ??13.82/ ??6.91 | ??13.82/ ??6.91 | ??13.82/ ??6.91 | ??13.82/ ??6.91 | ||||||
| Hostaphat?1308 2(amount of monomer milk sap/initial charge [g]) | ??9.6/4.8 | ??9.6/4.8 | ??9.6/4.8 | ??9.6/4.8 | ||||||
| Berol?733 3(amount of monomer milk sap/initial charge [g]) | ??21.89/ ??10.94 | ??21.89/ ??10.94 | ||||||||
| AAEMA[g] | ??28.8 | ??28.8 | ??28.8 | ??28.8 | ??28.8 | ??28.8 | ||||
| The particle diameter of aerosil dw [mm] | ??164 | ??116 | ??111 | ??112 | ??158 | ??118 | ??113 | ??122 | ??118 | ??118 |
| Wet coagulum [g] | ??88.7 | ??0.6 | ??6.23 | ??7.29 | ??1.5 | ??0 | ??0 | ??0 | ??0 | ??0 |
| Tg：[℃] | ??18.3 | ??15.2 | ??19.9 | ??17.9 | ??20.6 | ??20.6 | ??17.0 | ??14.2 | ??22.9 | ??18.5 |
| MFFT：[℃] | ??10 | ??6 | ??9 | ??9 | ??10 | ??10 | ??10 | ??9 | ??9 | ??9 |
| The solids content of measuring [%] | ??46.5 | ??46.4 | ??46.2 | ??46.7 | ??47.2 | ??47.2 | ??47.4 | ??46.9 | ??46.8 | ??46.5 |
Comp.: Comparative Examples
1: three sec-butyl phenol seven (ethylene glycol) ether sodium sulfates (about 50% form)
2: isotridecyl eight (ethylene glycol) ether list or bisphosphate (about 100% form)
3: the 4-nonylphenol gathers (ethylene glycol) ether phosphoric acid monopotassium salt (about 35% form)
Be increased to 5 by pH value, and AAEMA be incorporated into polymkeric substance, significantly reduced the coagulum part (comprising) of sieving and removing by 180 μ m sieve attached to the coagulum on the agitator by copolymerization with monomer milk sap solution.By comparative example 1 and example 2 and example 1 and example 6 this point as can be seen.
Embodiment 11
Use the copolymer dispersion of embodiment 1 to 10 to prepare antirust linging formulation.
Table 2:
| Mashed prod | Weight part |
| Borchigel L 75 (aqueous solution of 5% concentration) | ?4.40 |
| Water | ?8.00 |
| ?AMP?90 | ?0.15 |
| ?Surfynol?SE-F | ?0.30 |
| ?Additol?VXW?4973 | ?0.30 |
| ?Ser?Ad?FA?179 | ?0.15 |
| ?Heucophos?Zp?10 | ?6.40 |
| ?Microtalc?AT?extra | ?6.40 |
| ?Bayferrox?130?M | ?5.50 |
| ?Millicarb | ?4.00 |
| ?35.60 | |
| Tackiness agent | |
| Embodiment 1 to 10 (about 47%) | ?47.20 |
| Water | ?15.80 |
| ?Texanol | ?1.40 |
| ?100.00 |
Under agitation in 8g water, add 4.4g concentration and be the aqueous solution of 5% Borchigel L 75.Add AMP 90, Surfynol SE-F, Additol VXW 4973 and Ser Ad FA 179 then.Add Heucophos ZPIO, Microtalc AT extra, Bayferrox 130 M and Millicarb continuously according to the amount shown in the table 2 then, then in dissolver with this mixture of VELOCITY SHEAR of 5000rpm 20 minutes.
After at room temperature storing 1 day, dispersion liquid (solids content is about 47%), water and the Texanol with embodiment 1 to 10 adds in the described mashed prod with described amount, and stirs final coating 10 minutes under 500rpm.In embodiment 11k to 11l, (see Table 3), before the preparation lacquering, with the SMA of 1.44 weight % (based on thick attitude polymer dispersion liquid)
(CrayValley provides form to 3000HNa solution: about 25% solid) add in each dispersion liquid.
Table 3
| Priming paint | ??11a | ??11b | ??11c | ??11d | ??11e | ????11f | ??11g | ??11h | ??11i | ??11j | ??11k | ????11l |
| Dispersion liquid embodiment | ??1 | ??2 | ??3 | ??4 | ??5 | ????6 | ??7 | ??8 | ??9 | ??10 | ??5 | ????6 |
| Additive in the dispersion liquid | ??- | ??- | ??- | ??- | ??- | ????- | ??- | ??- | ??- | ??- | 1.44 SMA 3000 HNa of weight % | 1.44 SMA 3000 HNa of weight % |
Embodiment 12:
The antirust coating test under the constant condensing condition of DIN 50017 and the storage stability of priming paint formulation
The Wound-rotor type scraping blade (the about 100 μ m of wet-film thickness, the about 50 μ m of build) that uses 100 μ m is administered to the priming paint of embodiment 11 on the steel plate galvanized, and dry under the relative humidity of 23 ℃ temperature and 50%.Measure build then, and use the cut stylus the center, whole length upper edge of specimen and the longitudinal axis abreast onboard cut make the distance of itself and panel edges maintenance 30mm to base material.In deriving from the alternately climatic test device of Weiss, under the relative humidity of 40 ℃ temperature and 100%, experimentize, exposure duration is 864 hours.Calculate corrosion control index as referred to herein (CCI) by following formula:
CCI=(4 * bubbles volume+1 * bubble size+1 * rusting rate)/6
Each evaluation is to carry out to the rank of 5 (non-constants) from 0 (very good), and therefore, best CCI is 0, and the poorest CCI is 5.Bubbles volume, bubble size and rusting rate are measured according to DIN 53209 and DIN 53210.
Priming paint was at room temperature stored 3 months in the PE container of sealing, measured its storage stability.Estimate on 1 to 5 rank, wherein the excellent storage stability of 1 expression does not deposit any weighting agent and pigment, and the very serious deposition of 5 expressions, and can form slurries.
Table 4
| Priming paint | ??11a | ??11b | ?11c | ????11d | ?11e | ????11f | ??11g | ????11h | 11i | ??11j | ?11k | ?11l |
| ??V 1 | ??P 1 | ?V 1 | ????V 1 | ?V 1 | ????P 2 | ??V 1 | ????V 1 | V 1 | ??P 2 | ?V 2 | ?P 2 | |
| Dispersion liquid embodiment | ??1 | ??2 | ?3 | ????4 | ?5 | ????6 | ??7 | ????8 | 9 | ??10 | 5+1.44 SMA 3000 HNa of weight % | 6+1.44 SMA 3000 HNa of weight % |
| The pH value of monomer milk sap | ??＜4.5 | ??5 | ?＜4.5 | ????5 | ?＜4.5 | ????5 | ??＜4.5 | ????5 | ＜4.5 | ??5 | ?＜4.5 | ?5 |
| The milk sap dispersion liquid | ??Ph 3 | ??Ph 3 | ?S 4 | ????S 4 | ?Ph 3 | ????Ph 3 | ??S 4 | ????S 4 | Ph 3 | ??Ph 3 | ?Ph 3 | ?Ph 3 |
| AAEMA | ??- | ??- | ?- | ????- | ?+ | ????+ | ??+ | ????+ | + | ??+ | ?+ | ?+ |
| CCI | ??0.58 | ??0.54 | ?1.5 | ????1.25 | ?1 | ????0.6 | ??1.42 | ????0.9 | - | ??0.29 | ?0.54 | ?0.5 |
| The storage stability of priming paint | ??5 | ??4 | ?4 | ????2 | ?4 | ????3 | ??4 | ????3 | Coagulum | ??3 | ?4 | ?1 |
1: the V=Comparative Examples;
2: the P=inventive embodiments;
3: the phosphate group emulsifying agent;
4: vitriol/ester emulsifying agent
Have been found that the stability of using dispersion liquid of the present invention to improve rust-proofing primer.This dispersion liquid the pH value be 5 and therefore with carboxylic acid monomer's group (partly) neutral condition under use the preparation of monomer milk sap.Priming paint 11i just condenses just added tackiness agent in preparation priming paint process after, and formulation 11j of the present invention is stable.
Show (referring to table 4) as the result, owing to have AAEMA in the polymkeric substance, the stability of coating is further enhanced, and, in this dispersion liquid, add the storage stability that styrene-maleic anhydride copolymer has further improved the rust-proofing primer that comprises tackiness agent.This material that adds has subsequently obviously improved the stability of this anti-corrosive primer.
With comprise hydroxy-acid group b) the initial monomer emulsion feed be not adjusted to pH 〉=4.7 and the polymer phase ratio of preparation, the dispersion liquid of the present invention in the rust-proofing primer has significantly improved rust-proof effect surprisingly in the test of constant condensing condition.Only comprise unit b with use by existing this feature of phosphate group emulsifying agent) and the combining of the initial monomer emulsion feed of pH 〉=4.7, just obtained dispersion liquid of the present invention, it has low coagulum content, and in priming paint, demonstrate good storage stability, extraordinary rustless property in constant condensing condition test.
Claims (26)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE10236395.1 | 2002-08-08 | ||
| DE2002136395 DE10236395A1 (en) | 2002-08-08 | 2002-08-08 | An aqueous polymer dispersion containing copolymerisate obtained by free radical polymerization useful for coatings having high corrosion and condensation resistance |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1688614A true CN1688614A (en) | 2005-10-26 |
| CN100345869C CN100345869C (en) | 2007-10-31 |
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| Application Number | Title | Priority Date | Filing Date |
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| CNB038192098A Expired - Fee Related CN100345869C (en) | 2002-08-08 | 2003-07-21 | Aqueous polymer dispersions, method for the production thereof and use thereof, especially in anti-corrosion coatings |
Country Status (4)
| Country | Link |
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| JP (2) | JP4979192B2 (en) |
| CN (1) | CN100345869C (en) |
| DE (1) | DE10236395A1 (en) |
| WO (1) | WO2004020477A1 (en) |
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| CN107619456A (en) * | 2016-07-14 | 2018-01-23 | 陶氏环球技术有限责任公司 | With phosphoric acid and the latex of photoinitiator group functionalization |
| WO2018218631A1 (en) | 2017-06-02 | 2018-12-06 | Dow Global Technologies Llc | Waterborne epoxy coating composition |
| CN112513173A (en) * | 2018-04-02 | 2021-03-16 | 聚合物绿色有限责任公司 | Method for producing biodegradable superabsorbent polymers with high absorbency under load based on styrene maleic acid copolymers and biopolymers |
| CN114341217A (en) * | 2019-10-07 | 2022-04-12 | Dic株式会社 | Water-based resin composition, water-based paint, and plastic molded article coated with the water-based paint |
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| EP1582567B2 (en) * | 2004-04-01 | 2011-11-16 | Rohm And Haas Company | Aqueous coating composition |
| ES2340197T3 (en) | 2005-07-01 | 2010-05-31 | F. Hoffmann-La Roche Ag | CARBOXILATED LATEX PARTICLES. |
| EP1762601A1 (en) † | 2005-09-12 | 2007-03-14 | Basf Aktiengesellschaft | Method to increase resistance against stain penetration of aqueous coating compositions |
| DE102007033596A1 (en) | 2007-07-19 | 2009-01-22 | Celanese Emulsions Gmbh | Coatings with high weathering resistance, process for their preparation and their use |
| DE102007033595A1 (en) | 2007-07-19 | 2009-01-22 | Celanese Emulsions Gmbh | Polyvinyl ester dispersions, process for their preparation and their use |
| DE102007059844A1 (en) * | 2007-12-12 | 2009-06-25 | Basf Construction Polymers Gmbh | Copolymer based on a sulfonic acid-containing compound |
| US9102848B2 (en) | 2011-02-28 | 2015-08-11 | Basf Se | Environmentally friendly, polymer dispersion-based coating formulations and methods of preparing and using same |
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Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4968741A (en) * | 1989-10-06 | 1990-11-06 | The Goodyear Tire & Rubber Company | Latex for coatings having reduced blushing characteristics |
| US5990224A (en) * | 1997-09-18 | 1999-11-23 | Eastman Chemical Company | Stable low foam waterborne polymer compositions containing poly(alkyleneimines) |
| DE19810658A1 (en) * | 1998-03-12 | 1999-11-25 | Basf Ag | Aqueous polymer dispersion containing an emulsifier with phosphate groups |
-
2002
- 2002-08-08 DE DE2002136395 patent/DE10236395A1/en not_active Withdrawn
-
2003
- 2003-07-21 JP JP2004531809A patent/JP4979192B2/en not_active Expired - Fee Related
- 2003-07-21 WO PCT/EP2003/007931 patent/WO2004020477A1/en active Application Filing
- 2003-07-21 CN CNB038192098A patent/CN100345869C/en not_active Expired - Fee Related
-
2011
- 2011-08-05 JP JP2011172235A patent/JP2011225893A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107619456A (en) * | 2016-07-14 | 2018-01-23 | 陶氏环球技术有限责任公司 | With phosphoric acid and the latex of photoinitiator group functionalization |
| CN107619456B (en) * | 2016-07-14 | 2022-03-29 | 陶氏环球技术有限责任公司 | Latex functionalized with phosphoric acid and photoinitiator groups |
| WO2018218631A1 (en) | 2017-06-02 | 2018-12-06 | Dow Global Technologies Llc | Waterborne epoxy coating composition |
| CN110612335A (en) * | 2017-06-02 | 2019-12-24 | 陶氏环球技术有限责任公司 | Aqueous epoxy coating composition |
| AU2017416631B2 (en) * | 2017-06-02 | 2020-10-22 | Dow Global Technologies Llc | Waterborne epoxy coating composition |
| US11186743B2 (en) | 2017-06-02 | 2021-11-30 | Dow Global Technologies Llc | Waterborne epoxy coating composition |
| CN112513173A (en) * | 2018-04-02 | 2021-03-16 | 聚合物绿色有限责任公司 | Method for producing biodegradable superabsorbent polymers with high absorbency under load based on styrene maleic acid copolymers and biopolymers |
| CN114341217A (en) * | 2019-10-07 | 2022-04-12 | Dic株式会社 | Water-based resin composition, water-based paint, and plastic molded article coated with the water-based paint |
Also Published As
| Publication number | Publication date |
|---|---|
| CN100345869C (en) | 2007-10-31 |
| JP4979192B2 (en) | 2012-07-18 |
| DE10236395A1 (en) | 2004-02-19 |
| JP2005534799A (en) | 2005-11-17 |
| JP2011225893A (en) | 2011-11-10 |
| WO2004020477A1 (en) | 2004-03-11 |
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