CN111201254B - 用于自动洗碗系统中的梯度共聚物 - Google Patents
用于自动洗碗系统中的梯度共聚物 Download PDFInfo
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- CN111201254B CN111201254B CN201880066213.0A CN201880066213A CN111201254B CN 111201254 B CN111201254 B CN 111201254B CN 201880066213 A CN201880066213 A CN 201880066213A CN 111201254 B CN111201254 B CN 111201254B
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- monomer
- acid
- monomers
- polymer
- sodium
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- 238000004851 dishwashing Methods 0.000 title claims description 9
- 229920000028 Gradient copolymer Polymers 0.000 title description 3
- 239000000178 monomer Substances 0.000 claims abstract description 82
- 229920000642 polymer Polymers 0.000 claims abstract description 39
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 15
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims abstract 4
- 239000000203 mixture Substances 0.000 claims description 59
- 239000003599 detergent Substances 0.000 claims description 13
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 claims description 13
- 235000010262 sodium metabisulphite Nutrition 0.000 claims description 13
- 238000006116 polymerization reaction Methods 0.000 claims description 12
- 150000003839 salts Chemical class 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 10
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 9
- 229920000536 2-Acrylamido-2-methylpropane sulfonic acid Polymers 0.000 claims description 8
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 8
- 239000012986 chain transfer agent Substances 0.000 claims description 8
- 229940001584 sodium metabisulfite Drugs 0.000 claims description 8
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 claims description 7
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 7
- 239000000945 filler Substances 0.000 claims description 6
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 claims description 5
- 239000003999 initiator Substances 0.000 claims description 5
- 239000002736 nonionic surfactant Substances 0.000 claims description 5
- 239000007844 bleaching agent Substances 0.000 claims description 4
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 claims description 4
- PRAMZQXXPOLCIY-UHFFFAOYSA-N 2-(2-methylprop-2-enoyloxy)ethanesulfonic acid Chemical compound CC(=C)C(=O)OCCS(O)(=O)=O PRAMZQXXPOLCIY-UHFFFAOYSA-N 0.000 claims description 2
- AGBXYHCHUYARJY-UHFFFAOYSA-N 2-phenylethenesulfonic acid Chemical compound OS(=O)(=O)C=CC1=CC=CC=C1 AGBXYHCHUYARJY-UHFFFAOYSA-N 0.000 claims description 2
- GQTFHSAAODFMHB-UHFFFAOYSA-N 2-prop-2-enoyloxyethanesulfonic acid Chemical compound OS(=O)(=O)CCOC(=O)C=C GQTFHSAAODFMHB-UHFFFAOYSA-N 0.000 claims description 2
- KFNGWPXYNSJXOP-UHFFFAOYSA-N 3-(2-methylprop-2-enoyloxy)propane-1-sulfonic acid Chemical compound CC(=C)C(=O)OCCCS(O)(=O)=O KFNGWPXYNSJXOP-UHFFFAOYSA-N 0.000 claims description 2
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 claims description 2
- NYUTUWAFOUJLKI-UHFFFAOYSA-N 3-prop-2-enoyloxypropane-1-sulfonic acid Chemical compound OS(=O)(=O)CCCOC(=O)C=C NYUTUWAFOUJLKI-UHFFFAOYSA-N 0.000 claims description 2
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims description 2
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 claims description 2
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 claims description 2
- 230000000379 polymerizing effect Effects 0.000 claims description 2
- UIIIBRHUICCMAI-UHFFFAOYSA-N prop-2-ene-1-sulfonic acid Chemical compound OS(=O)(=O)CC=C UIIIBRHUICCMAI-UHFFFAOYSA-N 0.000 claims description 2
- 239000007870 radical polymerization initiator Substances 0.000 claims description 2
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 2
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 claims description 2
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000002253 acid Substances 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 37
- 239000008367 deionised water Substances 0.000 description 28
- 229910021641 deionized water Inorganic materials 0.000 description 28
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 24
- 239000000243 solution Substances 0.000 description 24
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 20
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 18
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 15
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 15
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 8
- -1 disilicate Chemical compound 0.000 description 8
- 239000011541 reaction mixture Substances 0.000 description 8
- BDHFUVZGWQCTTF-UHFFFAOYSA-N sulfonic acid Chemical compound OS(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-N 0.000 description 8
- 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 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 239000004296 sodium metabisulphite Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 229910052783 alkali metal Inorganic materials 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000011790 ferrous sulphate Substances 0.000 description 4
- 235000003891 ferrous sulphate Nutrition 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 4
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 4
- 238000006386 neutralization reaction Methods 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- MWNQXXOSWHCCOZ-UHFFFAOYSA-L sodium;oxido carbonate Chemical compound [Na+].[O-]OC([O-])=O MWNQXXOSWHCCOZ-UHFFFAOYSA-L 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- CIEZZGWIJBXOTE-UHFFFAOYSA-N 2-[bis(carboxymethyl)amino]propanoic acid Chemical compound OC(=O)C(C)N(CC(O)=O)CC(O)=O CIEZZGWIJBXOTE-UHFFFAOYSA-N 0.000 description 3
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical compound NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 3
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 3
- 150000001340 alkali metals Chemical class 0.000 description 3
- 150000003863 ammonium salts Chemical class 0.000 description 3
- 239000012736 aqueous medium Substances 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L sodium sulphate Substances [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- 235000011152 sodium sulphate Nutrition 0.000 description 3
- PQHYOGIRXOKOEJ-UHFFFAOYSA-N 2-(1,2-dicarboxyethylamino)butanedioic acid Chemical compound OC(=O)CC(C(O)=O)NC(C(O)=O)CC(O)=O PQHYOGIRXOKOEJ-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- 102000004190 Enzymes Human genes 0.000 description 2
- 108090000790 Enzymes Proteins 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 150000003926 acrylamides Chemical class 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical class C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 239000003112 inhibitor Substances 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
- 239000011976 maleic acid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229910052573 porcelain Inorganic materials 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 2
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 2
- 229910052939 potassium sulfate Inorganic materials 0.000 description 2
- 239000001120 potassium sulphate Substances 0.000 description 2
- 235000011151 potassium sulphates Nutrition 0.000 description 2
- 238000001542 size-exclusion chromatography Methods 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- MKJHAUJMSPBJTL-UHFFFAOYSA-M sodium;hydroxy-(1-hydroxy-1-phosphonoethyl)phosphinate Chemical compound [Na+].OP(=O)(O)C(O)(C)P(O)([O-])=O MKJHAUJMSPBJTL-UHFFFAOYSA-M 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- FRPJTGXMTIIFIT-UHFFFAOYSA-N tetraacetylethylenediamine Chemical compound CC(=O)C(N)(C(C)=O)C(N)(C(C)=O)C(C)=O FRPJTGXMTIIFIT-UHFFFAOYSA-N 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
- 238000005406 washing Methods 0.000 description 2
- DCCWEYXHEXDZQW-BYPYZUCNSA-N (2s)-2-[bis(carboxymethyl)amino]butanedioic acid Chemical compound OC(=O)C[C@@H](C(O)=O)N(CC(O)=O)CC(O)=O DCCWEYXHEXDZQW-BYPYZUCNSA-N 0.000 description 1
- YRIZYWQGELRKNT-UHFFFAOYSA-N 1,3,5-trichloro-1,3,5-triazinane-2,4,6-trione Chemical compound ClN1C(=O)N(Cl)C(=O)N(Cl)C1=O YRIZYWQGELRKNT-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- 239000004382 Amylase Substances 0.000 description 1
- 102000013142 Amylases Human genes 0.000 description 1
- 108010065511 Amylases Proteins 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- 235000003351 Brassica cretica Nutrition 0.000 description 1
- 244000056139 Brassica cretica Species 0.000 description 1
- 235000003343 Brassica rupestris Nutrition 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 101100117236 Drosophila melanogaster speck gene Proteins 0.000 description 1
- 102000002322 Egg Proteins Human genes 0.000 description 1
- 108010000912 Egg Proteins Proteins 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 235000007688 Lycopersicon esculentum Nutrition 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- POLBLONFVZXVPI-UHFFFAOYSA-N N-methyl-sec-pseudobrucine Natural products O=C1CC2C3C(CC4=O)OCC=C2CN(C)CCC11C3N4C2=C1C=C(OC)C(OC)=C2 POLBLONFVZXVPI-UHFFFAOYSA-N 0.000 description 1
- FLBVMURVUYAZMG-UHFFFAOYSA-N Novacin Natural products CN1CCC23C4C5C(CC(=O)N4c6cc(C)c(C)cc26)OCC=C(C1)C5CC3=O FLBVMURVUYAZMG-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 101710180316 Protease 2 Proteins 0.000 description 1
- 239000005708 Sodium hypochlorite Substances 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 240000003768 Solanum lycopersicum Species 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- WDJHALXBUFZDSR-UHFFFAOYSA-N acetoacetic acid Chemical compound CC(=O)CC(O)=O WDJHALXBUFZDSR-UHFFFAOYSA-N 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 235000019418 amylase Nutrition 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 239000004599 antimicrobial Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- QKSKPIVNLNLAAV-UHFFFAOYSA-N bis(2-chloroethyl) sulfide Chemical compound ClCCSCCCl QKSKPIVNLNLAAV-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- VTIIJXUACCWYHX-UHFFFAOYSA-L disodium;carboxylatooxy carbonate Chemical compound [Na+].[Na+].[O-]C(=O)OOC([O-])=O VTIIJXUACCWYHX-UHFFFAOYSA-L 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 235000013345 egg yolk Nutrition 0.000 description 1
- 210000002969 egg yolk Anatomy 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 235000013882 gravy Nutrition 0.000 description 1
- 239000008233 hard water Substances 0.000 description 1
- PMYUVOOOQDGQNW-UHFFFAOYSA-N hexasodium;trioxido(trioxidosilyloxy)silane Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[O-][Si]([O-])([O-])O[Si]([O-])([O-])[O-] PMYUVOOOQDGQNW-UHFFFAOYSA-N 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000003264 margarine Substances 0.000 description 1
- 235000013310 margarine Nutrition 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical class CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 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
- 235000010460 mustard Nutrition 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- DWSGLSZEOZQMSP-UHFFFAOYSA-N potassium;sodium Chemical class [Na+].[K+] DWSGLSZEOZQMSP-UHFFFAOYSA-N 0.000 description 1
- 229920001592 potato starch Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 235000015067 sauces Nutrition 0.000 description 1
- 229940071207 sesquicarbonate Drugs 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 229940045872 sodium percarbonate Drugs 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
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Abstract
本公开涉及一种聚合物，其包含第一级分和第二级分，其中所述第一级分包含90至100wt％的聚合的C3‑C6羧酸单体单元；并且所述第二级分包含30至80wt％的聚合的C3‑C6羧酸单体单元和20至70wt％的聚合的磺酸单体单元；其中所述第一级分占所述聚合物的10至40wt％，并且所述第二级分占所述聚合物的60至90wt％；所述聚合物的Mw是3,000至30,000；并且单体随机分布在每个级分中。
Description
背景技术
本发明大体上涉及在自动洗碗中可用作添加剂的梯度共聚物。
自动洗碗洗涤剂通常被认为是与用于织物洗涤或水处理的洗涤剂组合物不同的一类洗涤剂组合物。需要自动洗碗洗涤剂以在彻底的清洁循环之后在洗涤过的物品上产生无斑和无膜外观。不含磷酸盐的组合物依赖于非磷酸盐助洗剂，如柠檬酸盐、碳酸盐、硅酸盐、二硅酸盐、碳酸氢盐、氨基羧酸盐和其它盐以螯合来自硬水中的钙和镁，并且在干燥后留下不溶性可见沉积物。已知(甲基)丙烯酸和磺酸单体的聚合物用于自动洗碗系统中。举例来说，WO2017013158A1公开洗涤剂组合物中丙烯酸均聚物和丙烯酸/AMPS共聚物的混合物。然而，这个参考未公开本发明的组合物。
发明内容
本发明涉及一种聚合物，其包含第一级分和第二级分，其中第一级分包含90至100wt％的聚合的C3-C6羧酸单体单元，并且第二级分包含30至80wt％的聚合的羧酸单体单元和20至70wt％的聚合的磺酸单体单元；其中第一级分占聚合物的10至40wt％，并且第二级分占聚合物的60至90wt％；聚合物的Mw是3,000至30,000；并且单体随机分布在每个级分中。
本发明另外涉及用于生产聚合物的方法；所述方法包含以下步骤：(a)在初始聚合相中聚合包含90至100wt％的C3-C6羧酸单体的第一单体组合物；和(b)在第二聚合相中聚合包含30至80wt％的C3-C6羧酸单体和20至70wt％的磺酸单体的第二单体混合物；其中在添加第一和第二单体组合物期间添加链转移剂。
具体实施方式
除非另外指示，否则所有百分比均是重量百分比(wt％)，并且所有温度均以℃为单位。除非另外说明，否则操作在室温(20-25℃)下执行。通过凝胶渗透色谱法(GPC)使用聚丙烯酸标准物测量重均分子量Mw，如本领域中已知。GPC技术在以下文献中详细地讨论：《现代尺寸排阻色谱(Modern Size Exclusion Chromatography)》,W.W.Yau,J.J.Kirkland,D.D.Bly；威利跨学科出版社(Wiley-Interscience),1979和《材料表征和化学分析指南(AGuide to Materials Characterization and Chemical Analysis)》,J.P.Sibilia；德国化学学会出版社(VCH),1988,第81-84页。本文所报告的分子量以道尔顿为单位。如本文所用，术语“(甲基)丙烯酸”是指丙烯酸或甲基丙烯酸。磺酸单体是具有磺酸基团或其盐并且具有两个至八个碳原子的单体。优选的磺酸单体包括例如2-丙烯酰胺基-2-甲基丙磺酸(AMPS)、乙烯基磺酸、丙烯酸2-磺乙酯、甲基丙烯酸2-磺乙酯、丙烯酸磺丙酯、甲基丙烯酸磺丙酯、苯乙烯磺酸、3-烯丙氧基-2-羟基-1-丙磺酸和2-丙烯-1-磺酸以及其盐和其组合；优选AMPS。C3-C6羧酸单体是具有一个或两个羧酸基团(优选一个)和3至6个碳原子的单体。优选地，C3-C6羧酸单体具有3或4个碳原子；优选地，其选自由以下组成的组：丙烯酸(AA)、甲基丙烯酸(MAA)、马来酸和衣康酸；优选(甲基)丙烯酸，优选丙烯酸。
术语“碳酸盐”是指碳酸盐、碳酸氢盐或倍半碳酸盐的碱金属盐或铵盐；术语“硅酸盐”是指硅酸盐、二硅酸盐、偏硅酸盐的碱金属盐或铵盐；并且术语“柠檬酸盐”是指碱金属柠檬酸盐。优选地，碳酸盐、硅酸盐或柠檬酸盐是钠盐、钾盐或锂盐；优选钠盐或钾盐；优选钠盐。术语“过碳酸盐”和“过硼酸盐”是指这些阴离子的碱金属盐或铵盐，优选钾盐或钠盐，优选钠盐。碳酸盐或柠檬酸盐的重量百分比按盐的实际重量计，包括金属离子。术语“不含磷酸盐”是指组合物含有小于0.5wt％的磷酸盐(以元素磷的形式)，优选小于0.2wt％，优选小于0.1wt％，优选不含可检测的磷酸盐。洗涤剂组合物中的重量百分比按整个组合物计，包括可存在的任何水。
本发明的聚合物通过多阶段聚合方法生产，其中单体组成随着制备聚合物而改变。在制备中，使第一单体组合物聚合，随后使第二单体组合物聚合。如本文中使用的短语，聚合物的第一级分是指由第一单体形成的聚合物。第一和第二级分的组成和量分别定义为第一和第二单体组合物的组成和量。在一些情况下，第一和第二级分可对应于分离的第一和第二相。通常，执行聚合的第一阶段，任选地随后执行残留单体还原步骤以消耗任何未反应的单体。然后添加第二单体组合物，并且允许聚合继续进行，优选随后进行最终的残留单体还原步骤。通常，聚合是溶液聚合，优选在水性介质中。优选地，水性介质是至少75wt％，优选至少90wt％，优选至少95wt％的水。优选地，将聚合物与水性介质分离；优选地，聚合物是30-65％，替代地35-60％，替代地38-57％的固体。
优选地，第一单体组合物包含95至100wt％，优选97至100wt％，优选98至100wt％，优选99至100wt％的C3-C6羧酸单体。优选地，第二单体组合物包含至少35wt％，优选至少40wt％，优选至少45wt％，优选至少50wt％；优选不超过75wt％，优选不超过70wt％，优选不超过65wt％的C3-C6羧酸单体。优选地，第二单体组合物包含至少25wt％，优选至少30wt％，优选至少35wt％；优选不超过65wt％，优选不超过60wt％，优选不超过55wt％，优选不超过50wt％的磺酸单体。优选地，第二单体组合物包含至少35wt％，优选至少40wt％，优选至少45wt％；优选不超过75wt％，优选不超过70wt％，优选不超过65wt％，优选不超过60wt％的C3-C6羧酸单体。优选地，第一单体组合物占总单体的至少13wt％，优选至少16wt％，优选至少18wt％；优选不超过35wt％，优选不超过32wt％，优选不超过29wt％，优选不超过26wt％。优选地，第二单体组合物占总单体的至少65wt％，优选至少68wt％，优选至少71wt％；优选不超过87wt％，优选不超过84wt％，优选不超过82wt％。术语“总单体”意指第一和第二组合物以及用于形成聚合物的任何其它单体的总量。
优选地，链转移剂在至少90％，优选至少95％的单体添加时间内，优选在整个单体添加时间内与单体一起连续添加。优选的链转移剂包括例如偏亚硫酸氢钠、次磷酸钠、亚磷酸、2-巯基乙醇、3-巯基丙酸和1-十二烷硫醇。优选地，至少50wt％，优选至少75wt％，优选至少85wt％的链转移剂与单体一起连续添加。优选地，链转移剂的量是第一和第二单体组合物的总质量的0.1至25wt％，优选至少0.5wt％，优选至少1wt％，优选至少1.5wt％，优选至少2wt％，优选至少2.5wt％，优选至少3wt％，优选至少3.5wt％；优选不超过20wt％，优选不超过15wt％，优选不超过10wt％，优选不超过8wt％。任选地，使用至少两种添加速率添加链转移剂，其中两种速率中的较大速率是下一最快速率的至少两倍(优选不超过十倍)。
在聚合期间存在自由基聚合引发剂，其量优选是第一和第二单体组合物的总质量的0.1至10wt％，优选至少0.2wt％，优选至少0.25wt％，优选至少0.3wt％，优选至少0.35wt％；优选不超过5wt％，优选不超过3wt％，优选不超过2.5wt％，优选不超过2wt％，优选不超过1.5wt％。优选地，至少50wt％，优选至少75wt％，优选至少85wt％的引发剂与单体一起连续添加。优选地，引发剂不含磷。优选的引发剂包括例如过硫酸钠、过硫酸钾和过硫酸铵。
优选地，聚合物的第一级分包含95至100wt％，优选97至100wt％，优选98至100wt％，优选99至100wt％的聚合的C3-C6羧酸单体单元。优选地，第二级分包含至少35wt％，优选至少40wt％，优选至少45wt％，优选至少50wt％；优选不超过75wt％，优选不超过70wt％，优选不超过65wt％，优选不超过60wt％的聚合的C3-C6羧酸单体单元。优选地，第二级分包含至少25wt％，优选至少30wt％，优选至少35wt％；优选不超过65wt％，优选不超过60wt％，优选不超过55wt％，优选不超过50wt％的聚合的磺酸单体单元。优选地，第一级分占聚合物的至少13wt％，优选至少16wt％，优选至少18wt％；优选不超过35wt％，优选不超过32wt％，优选不超过29wt％，优选不超过26wt％。优选地，第二级分占聚合物的至少65wt％，优选至少68wt％，优选至少71wt％；优选不超过87wt％，优选不超过84wt％，优选不超过82wt％。优选地，聚合物包含至少40wt％，优选至少45wt％，优选至少50wt％，优选至少55wt％；优选不超过95wt％，优选不超过90wt％，优选不超过85wt％，优选不超过80wt％的聚合的C3-C6羧酸单体单元。
聚合物可包含0至10wt％，优选不超过8wt％，优选不超过6wt％，优选不超过4wt％，优选不超过2wt％的除了C3-C6羧酸单体和磺酸单体以外的额外单体。合适的额外单体的实例包括例如(甲基)丙烯酸C1-C16烷基酯、(甲基)丙烯酸2-羟烷基酯、烷酸乙烯基酯和丙烯酰胺。
优选地，本发明的聚合物包含不超过0.3wt％，优选不超过0.1wt％，优选不超过0.05wt％，优选不超过0.03wt％，优选不超过0.01wt％的交联单体的聚合单元。交联单体是多烯键式不饱和单体。
优选地，聚合物是无规共聚物。优选地，聚合物的Mw是至少3,000，优选至少4,000，优选至少5,000；优选不超过30,000，优选不超过50,000，优选不超过30,000，优选不超过25,000，优选不超过20,000，优选不超过15,000。优选地，聚合物的Mn是至少1,000，优选至少1,500，优选至少2,000；优选不超过10,000，优选不超过5,000，优选不超过4,000，优选不超过3,000。优选地，Mw/Mn是1.5至10，优选至少2，优选至少2.2；优选不超过8，优选不超过7，优选不超过6，优选不超过5，优选不超过4。
优选地，本发明的聚合物以至少1wt％，优选至少1.5wt％，优选至少2wt％，优选至少2.5wt％，优选至少3wt％，优选至少3.5wt％；优选不超过8wt％，优选不超过7.5wt％，优选不超过7wt％，优选不超过6.5wt％的量存在于洗涤剂组合物中。
聚合物可与其它聚合物组合使用，所述其它聚合物可用于控制自动洗碗机中的不溶性沉积物，包括例如包含丙烯酸、甲基丙烯酸、马来酸或其它二酸单体的残基，丙烯酸或甲基丙烯酸的酯(包括聚乙二醇酯)、苯乙烯单体、AMPS和其它磺化单体，以及经取代的丙烯酰胺或甲基丙烯酰胺的组合的聚合物。特别有用的聚合物是能够改善斑点的那些聚合物，例如RO-(M)x-(N)y-OH或R-O-(M)x-(N)y-(P)z-OH，其中参数在本文中定义。
优选地，洗涤剂组合物包含碳酸盐、柠檬酸盐、硅酸盐或其组合，其量是至少25wt％，优选至少30wt％，优选至少33wt％，优选至少36wt％；优选不超过70wt％，优选不超过65wt％，优选不超过60wt％，优选不超过55wt％。优选地，碳酸盐的量是至少5wt％，优选至少10wt％，优选至少15wt％；优选不超过45wt％，优选不超过40wt％，优选不超过35wt％，优选不超过30wt％。优选地，柠檬酸盐的量是至少5wt％，优选至少10wt％，优选至少15wt％；优选不超过4wt％，优选不超过35wt％，优选不超过30wt％，优选不超过25wt％。优选地，硅酸盐的量不超过15wt％，优选不超过10wt％，优选不超过6wt％，优选不超过4wt％。
优选地，洗涤剂组合物包含漂白剂，优选过碳酸盐、过硼酸盐、次氯酸钠或三氯氰尿酸；优选过碳酸盐或过硼酸盐；优选过碳酸盐。优选地，漂白剂的量是至少8wt％，优选至少11wt％，优选至少12wt％；优选不超过25wt％，优选不超过22wt％，优选不超过20wt％，优选不超过18wt％。
洗涤剂组合物包含0.1至8wt％；优选至少0.4wt％，优选至少0.7wt％，优选至少1wt％，优选至少1.3wt％，优选至少1.5wt％；优选不超过6wt％，优选不超过4wt％，优选不超过3wt％，优选不超过2.5wt％的1-羟基乙烷二膦酸或其盐。
任选地，洗涤剂组合物包含至少3wt％；优选至少5wt％，优选至少6wt％，优选至少7wt％，优选至少8wt％；优选不超过40wt％，优选不超过30wt％，优选不超过25wt％，优选不超过20wt％，优选不超过15wt％的量的一种或多种氨基羧酸盐助洗剂。优选的氨基羧酸盐助洗剂包括甲基甘氨酸二乙酸(MGDA)以及其盐、谷氨酸二乙酸(GLDA)以及其盐、亚氨基二琥珀酸(IDSA)以及其盐和天冬氨酸二乙酸(ASDA)以及其盐。MGDA是尤其优选的。
片剂或粉末中的填料是惰性的水溶性物质，通常是钠盐或钾盐，例如钠或钾的硫酸盐和/或氯化物，并且通常以在0wt％至70wt％；优选不超过50wt％，优选不超过40wt％，优选不超过30wt％，优选不超过20wt％，优选不超过15wt％；优选至少2wt％，优选至少4wt％范围内的量存在。
优选地，非离子表面活性剂具有式RO-(M)x-(N)y-H或R-O-(M)x-(N)y-(P)z-H，其中M代表环氧乙烷的聚合单元，N代表C3-C18 1,2-环氧烷烃的聚合单元，P代表C6-C18-烷基缩水甘油醚，x是5-40，y是0-20，z是0-3，并且R代表C6-C22直链或支链烷基。
优选地，非离子表面活性剂具有化学式RO-(M)x-(N)y-H或R-O-(M)x-(N)y-R'，其中M和N是衍生自环氧烷(其中一个是环氧乙烷)的单元，R代表C6-C22直链或支链烷基，并且R'代表衍生自醇前体与C6-C22直链或支链烷基卤化物、环氧烷烃或缩水甘油醚的反应的基团。优选地，表面活性剂具有式RO-(M)x-H，其中M代表聚合的环氧乙烷单元。优选地，x是至少三，优选至少五；优选不超过十，优选不超过八。优选地，R和R'具有至少八个碳原子，优选至少十个碳原子。优选地，组合物包含至少2wt％，优选至少3wt％；优选不超过12wt％，优选不超过9wt％，优选不超过8wt％的一种或多种非离子表面活性剂。
自动洗碗洗涤剂组合物的其它组分可包括，例如，无机助洗剂、螯合剂化合物、腐蚀抑制剂、表面活性剂、氧和/或氯漂白剂、漂白剂活化剂、酶、泡沫抑制剂、颜料、芳香剂、抗菌剂和填料。片剂或粉末中的填料是惰性的水溶性物质，通常是钠盐或钾盐，例如钠或钾的硫酸盐和/或氯化物，并且通常以在0wt％至70wt％；优选不超过50wt％，优选不超过40wt％，优选不超过30wt％，优选不超过20wt％，优选不超过15wt％；优选至少2wt％，优选至少4wt％范围内的量存在。凝胶配制物中的填料可包括上文提到的那些并且还包括水。芳香剂、染料、泡沫抑制剂、酶和抗菌剂通常总计不超过组合物的5wt％。
优选地，洗涤剂组合物的pH(在水中在1wt％下)是至少8.5，优选至少9.5；在一些实施例中，pH不大于12。
组合物可配制成任何典型形式，例如作为片剂、粉末、单剂、小袋、糊剂、液体或凝胶。在典型操作条件下组合物可用于任何典型自动洗碗机。在洗涤过程期间的典型水温优选是20℃至85℃，优选30℃至70℃。按在洗碗机中总液体的百分比计，组合物的典型浓度优选是0.1至1wt％，优选0.2至0.7wt％。在选择适当的产品形态和添加时间的情况下，组合物可存在于预洗、主洗、倒数第二次冲洗、最后一次冲洗或这些循环的任何组合中。
实例
合成
聚合物C1的合成向配备有热电偶、顶置式搅拌器、回流冷凝器和用于引入液体试剂的端口的圆底烧瓶中装入206g去离子水(DI)和2.5g的0.15wt％硫酸亚铁溶液。将混合物在搅拌下加热至73℃，此时立即添加偏亚硫酸氢钠溶液(0.84g在5.25g DI中)。然后，启动进料丙烯酸(240g)和AMPS钠盐(120g的50wt％水溶液)的混合物，并且以4克/分钟的速率进行直至耗尽(90分钟)。同时开始，起始进料过硫酸钠溶液(0.96g在30g DI中)并且持续至耗尽(95分钟)。还同时开始，起始进料偏亚硫酸氢钠(19.43g在45g DI中)并且持续至耗尽(80分钟)。在最长进料(引发剂)完成后，将反应在73℃下保持10分钟，随后在10分钟内添加追加的过硫酸钠溶液(0.39g在7g DI中)，随后再保持20分钟。使反应混合物冷却，并且在此相期间，通过添加75g的50wt％氢氧化钠溶液来部分中和反应混合物。然后添加少量过氧化氢(4.8g的35wt％溶液)以帮助减少残留亚硫酸盐。接着通过再添加150g的50％氢氧化钠来完成中和。倾析聚合物，用30g DI冲洗，并且在冷却后进行分析。固体含量(wt％)：41.66；pH＝6.1；残留AA<17ppm；Mw/1000＝6.7；Mn/1000＝2.5。
聚合物1的合成在C1中描述的聚合反应器中装入206g去离子水(DI)和2.5g的0.15wt％硫酸亚铁溶液。将混合物在搅拌下加热至73℃，此时添加偏亚硫酸氢钠溶液(0.84g在5.25g DI中)。此时以2.667克/分钟的速率起始丙烯酸(240g)进料直至耗尽(90分钟)。同时开始，起始进料过硫酸钠溶液(0.96g在30g DI中)并且持续至耗尽(95分钟)。还同时开始，起始进料偏亚硫酸氢钠(19.43g在45g DI中)并且持续至耗尽(80分钟)。在启动同时进料AA、过硫酸钠和偏亚硫酸氢钠三十分钟后，起始进料AMPS钠盐(120g的50wt％水溶液)，并且以2克/分钟的速率进行直至耗尽(60分钟)。在过硫酸钠进料完成后，将反应在73℃下保持10分钟，随后在10分钟内添加追加的过硫酸钠溶液(0.39g在5.2g DI中)，随后再保持20分钟。使反应混合物冷却，并且在此相期间，通过添加75g的50wt％氢氧化钠溶液来部分中和反应混合物。然后添加少量过氧化氢(7.25g的35wt％溶液)。接着通过再添加150g的50％氢氧化钠来完成中和。倾析聚合物，用30g DI冲洗，并且在冷却后进行分析。固体含量(wt％)：42.03；pH＝6.1；残留AA<17ppm；Mw/1000＝6.3；Mn/1000＝2.4。
聚合物2的合成在C1中描述的聚合反应器中装入206g去离子水(DI)和2.5g的0.15wt％硫酸亚铁溶液。将混合物在搅拌下加热至73℃，此时添加偏亚硫酸氢钠溶液(0.84g在5.25g DI中)。此时以2.667克/分钟的速率起始丙烯酸(240g)进料直至耗尽(90分钟)。同时开始，起始进料过硫酸钠溶液(0.96g在30g DI中)并且持续至耗尽(95分钟)。还同时开始，以1.87毫升/分钟的速率起始进料偏亚硫酸氢钠(19.43g在45g DI中)，并且以此速率持续20分钟，此时速率经60分钟降低至0.21毫升/分钟。在启动同时进料AA、过硫酸钠和偏亚硫酸氢钠三十分钟后，起始进料AMPS钠盐(120g的50wt％水溶液)，并且以2克/分钟的速率进行直至耗尽(60分钟)。在过硫酸钠进料完成后，将反应在73℃下保持10分钟，随后在10分钟内添加追加的过硫酸钠溶液(0.39g在5.2g DI中)，随后再保持20分钟。使反应混合物冷却，并且在此相期间，通过添加75g的50wt％氢氧化钠溶液来部分中和反应混合物。然后添加少量过氧化氢(5.4g的35wt％溶液)。接着通过再添加150g的50％氢氧化钠来完成中和。倾析聚合物，用30g DI冲洗，并且在冷却后进行分析。固体含量(wt％)：42.37；pH＝6.2；残留AA<16ppm；Mw/1000＝10.5；Mn/1000＝2.4。
聚合物3的合成在C1中描述的聚合反应器中装入206g去离子水(DI)和2.5g的0.15wt％硫酸亚铁溶液。将混合物在搅拌下加热至73℃，此时添加偏亚硫酸氢钠溶液(0.84g在5.25g DI中)。此时以2.667克/分钟的速率起始丙烯酸(240g)进料直至耗尽(90分钟)。同时开始，起始进料过硫酸钠溶液(0.96g在30g DI中)并且持续至耗尽(95分钟)。还同时开始，以0.93毫升/分钟的速率起始进料偏亚硫酸氢钠(19.43g在45g DI中)，并且以此速率持续40分钟，此时速率经40分钟降低至0.32毫升/分钟。在启动同时进料AA、过硫酸钠和偏亚硫酸氢钠三十分钟后，起始进料AMPS钠盐(120g的50wt％水溶液)，并且以2克/分钟的速率进行直至耗尽(60分钟)。在过硫酸钠进料完成后，将反应在73℃下保持10分钟，随后在10分钟内添加追加的过硫酸钠溶液(0.39g在5.2g DI中)，随后再保持20分钟。使反应混合物冷却，并且在此相期间，通过添加75g的50wt％氢氧化钠溶液来部分中和反应混合物。然后添加少量过氧化氢(4.7g的35wt％溶液)。接着通过再添加150g的50％氢氧化钠来完成中和。倾析聚合物，用30g DI冲洗，并且在冷却后进行分析。固体含量(wt％)：42.25；pH＝6.2；残留AA<22ppm；Mw/1000＝7.2；Mn/1000＝2.3。
用于自动洗碗(ADW)测试的配制物：
总配制物重量：20g。
| 成分 | 重量％(以固体材料计) |
| 柠檬酸钠 | 30 |
| 碳酸钠 | 25 |
| 二硅酸钠 | 2 |
| 过碳酸钠 | 15 |
| 四乙酰基乙二胺(TAED) | 4 |
| 非离子表面活性剂* | 5 |
| 分散剂聚合物 | 5 |
| 蛋白酶** | 2 |
| 淀粉酶*** | 1 |
| 1-羟基乙烷二膦酸钠盐(HEDP)**** | 2 |
| 硫酸钠(填料) | 9 |
*DOWFAXTM20B102，可购自陶氏化学公司(The Dow Chemical Company)；**
12T，可购自诺维信(Novozymes)；***
12T，可购自诺维信；****
2016DG，可购自意特化工集团(Italmatch Chemicals)。
ADW 30-循环累积性能测试
Miele G1222 SC机器在65℃下运行，具有预洗的30分钟循环，法国水硬度是37°，Ca:Mg＝3:1，临时硬度(法国)是25°，压载载荷是瓷器、玻璃和餐具。冷冻添加食物类污垢(50g，参见下表)。评级由经训练的小组成员观察在暗室中的灯箱中从下方照亮的玻璃来执行，并且范围是1(无成膜或斑点)至5(重度成膜或斑点)。
食物类污垢：
| 成分 | 制备3L所需的数量 |
| 水 | 2.1L |
| 人造黄油 | 300g |
| 马铃薯淀粉 | 15g |
| 即食肉汁 | 75.g |
| 苯甲酸 | 3g |
| 牛奶 | 150g |
| 蛋黄 | 9(约162g) |
| 调味蕃茄酱 | 75g |
| 芥末 | 75g |
成膜和斑点等级：
ADW 5-循环冲洗性能测试
Miele G1223 SC L2机器在50℃下运行，8分钟循环，法国水硬度是37°，Ca:Mg＝3:1，临时硬度(法国)是25°，压载载荷是瓷器、玻璃和餐具。冷冻添加食物类污垢(50g，与累积测试相同)。评级由经训练的小组成员观察在暗室中的灯箱中从下方照亮的玻璃来执行，并且范围是1(无成膜或斑点)至5(重度成膜或斑点)。
成膜和斑点等级：
Claims (7)
1.一种用于制备聚合物的方法，所述方法包含以下步骤：(a)在初始聚合相中聚合包含90至100wt％的C3-C6羧酸单体的第一单体组合物；和(b)在第二聚合相中聚合包含30至80wt％的C3-C6羧酸单体和20至70wt％的磺酸单体的第二单体组合物；其中在添加所述第一和第二单体组合物期间添加链转移剂，其中所述链转移剂在整个单体添加时间内与单体一起连续添加。
2.根据权利要求1所述的方法，其中所述磺酸单体选自由以下组成的组：2-丙烯酰胺基-2-甲基丙磺酸、乙烯基磺酸、丙烯酸2-磺乙酯、甲基丙烯酸2-磺乙酯、丙烯酸磺丙酯、甲基丙烯酸磺丙酯、苯乙烯磺酸、3-烯丙氧基-2-羟基-1-丙磺酸和2-丙烯-1-磺酸以及其盐和其组合。
3.根据权利要求2所述的方法，其中所述第一单体组合物包含95至100wt％的(甲基)丙烯酸；并且所述第二单体组合物包含40至70wt％的(甲基)丙烯酸和30至60wt％的磺酸单体。
4.根据权利要求3所述的方法，其中所述第一单体组合物占总单体的13至32wt％，并且所述第二单体组合物占总单体的68至87wt％。
5.根据权利要求4所述的方法，其中自由基聚合引发剂的添加量是所述第一和第二单体组合物的总质量的0.1至5wt％，并且至少50wt％的引发剂与所述单体一起连续添加。
6.根据权利要求1所述的方法，其中所述链转移剂选自下组：偏亚硫酸氢钠、次磷酸钠、亚磷酸、2-巯基乙醇、3-巯基丙酸和1-十二烷硫醇。
7.一种用于自动洗碗的洗涤剂组合物，其包含：
a)1至8wt％的根据权利要求1所述的方法制备得到的聚合物；
b)25至70wt％的碳酸盐、柠檬酸盐、硅酸盐或其组合；
c)2至12wt％的非离子表面活性剂；
d)8至25wt％的漂白剂；
e)0至50wt％的填料；和
f)0.1至8wt％的1-羟基乙烷二膦酸或其盐。
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| US201762575678P | 2017-10-23 | 2017-10-23 | |
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| PCT/US2018/054968 WO2019083718A1 (en) | 2017-10-23 | 2018-10-09 | GRADIENT COPOLYMERS FOR USE IN AUTOMATIC DISHWASHING SYSTEMS |
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| EP2228428A1 (en) * | 2009-03-13 | 2010-09-15 | Rohm and Haas Company | Scale-reducing additive for automatic dishwashing systems |
| EP2896637A1 (en) * | 2014-01-21 | 2015-07-22 | Rhodia Operations | Copolymer comprising units of type A deriving from carboxylic acid monomers and units of type B deriving from sulfonic acid monomers |
| WO2017013158A1 (de) * | 2015-07-23 | 2017-01-26 | Henkel Ag & Co. Kgaa | Maschinelles geschirrspülmittel enthaltend bleichmittel und polymere |
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| WO2017176501A1 (en) * | 2016-04-08 | 2017-10-12 | The Procter & Gamble Company | Automatic dishwashing cleaning composition |
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| WO2003068899A1 (en) * | 2002-02-11 | 2003-08-21 | Rhodia Chimie | Detergent composition comprising a block copolymer |
| CN101362811B (zh) | 2008-08-28 | 2012-01-04 | 广州星业科技股份有限公司 | 用于洗涤助剂的丙烯酸类共聚物的合成方法 |
| EP2228426A1 (en) | 2009-03-13 | 2010-09-15 | Rohm and Haas Company | Scale-reducing additive for automatic dishwashing systems |
| CN102284247A (zh) | 2010-06-21 | 2011-12-21 | 中国石油化工股份有限公司 | 一种反渗透系统的清洗方法 |
| FR2998571B1 (fr) * | 2012-11-23 | 2015-08-21 | Henkel Ag & Co Kgaa | Copolymeres sequences amphiphiles et detergents pour lave-vaisselle les contenant |
| WO2015042026A1 (en) | 2013-09-18 | 2015-03-26 | The Lubrizol Corporation | High temperature stable linear polymers |
| FR3040294B1 (fr) | 2015-08-28 | 2017-08-18 | Oreal | Composition cosmetique comprenant un compose d'acide salicylique |
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| EP2228428A1 (en) * | 2009-03-13 | 2010-09-15 | Rohm and Haas Company | Scale-reducing additive for automatic dishwashing systems |
| EP2896637A1 (en) * | 2014-01-21 | 2015-07-22 | Rhodia Operations | Copolymer comprising units of type A deriving from carboxylic acid monomers and units of type B deriving from sulfonic acid monomers |
| CN107075425A (zh) * | 2014-10-09 | 2017-08-18 | 罗门哈斯公司 | 用于在自动餐具洗涤体系中减少污渍的添加剂 |
| WO2017013158A1 (de) * | 2015-07-23 | 2017-01-26 | Henkel Ag & Co. Kgaa | Maschinelles geschirrspülmittel enthaltend bleichmittel und polymere |
| WO2017176501A1 (en) * | 2016-04-08 | 2017-10-12 | The Procter & Gamble Company | Automatic dishwashing cleaning composition |
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| EP3700949A1 (en) | 2020-09-02 |
| US11292992B2 (en) | 2022-04-05 |
| BR112020006910A2 (pt) | 2020-10-06 |
| JP2023078172A (ja) | 2023-06-06 |
| JP2021500424A (ja) | 2021-01-07 |
| CN111201254A (zh) | 2020-05-26 |
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