CA2844514A1 - Copolymers of isoprenol, monoethylenically unsaturated monocarboxylic acids and sulphonic acids, methods for production thereof and use thereof as deposit inhibitors in water-bearing systems - Google Patents
Copolymers of isoprenol, monoethylenically unsaturated monocarboxylic acids and sulphonic acids, methods for production thereof and use thereof as deposit inhibitors in water-bearing systems Download PDFInfo
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- CA2844514A1 CA2844514A1 CA2844514A CA2844514A CA2844514A1 CA 2844514 A1 CA2844514 A1 CA 2844514A1 CA 2844514 A CA2844514 A CA 2844514A CA 2844514 A CA2844514 A CA 2844514A CA 2844514 A1 CA2844514 A1 CA 2844514A1
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- Prior art keywords
- acid
- solution
- weight
- water
- isoprenol
- Prior art date
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- Granted
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- 229920001577 copolymer Polymers 0.000 title claims abstract description 54
- CPJRRXSHAYUTGL-UHFFFAOYSA-N isopentenyl alcohol Chemical compound CC(=C)CCO CPJRRXSHAYUTGL-UHFFFAOYSA-N 0.000 title claims abstract description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims description 59
- 238000000034 method Methods 0.000 title claims description 18
- 239000003112 inhibitor Substances 0.000 title claims description 15
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- 239000002253 acid Substances 0.000 title description 9
- 150000002763 monocarboxylic acids Chemical class 0.000 title description 9
- 150000007513 acids Chemical class 0.000 title description 4
- 239000000178 monomer Substances 0.000 claims abstract description 33
- 150000003839 salts Chemical class 0.000 claims abstract description 17
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 claims abstract description 8
- 150000008064 anhydrides Chemical class 0.000 claims abstract description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 36
- 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 29
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 25
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 25
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 22
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 19
- XWGJFPHUCFXLBL-UHFFFAOYSA-M rongalite Chemical compound [Na+].OCS([O-])=O XWGJFPHUCFXLBL-UHFFFAOYSA-M 0.000 claims description 14
- 239000000126 substance Substances 0.000 claims description 14
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical group OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 13
- 239000003999 initiator Substances 0.000 claims description 13
- UIIIBRHUICCMAI-UHFFFAOYSA-N prop-2-ene-1-sulfonic acid Chemical compound OS(=O)(=O)CC=C UIIIBRHUICCMAI-UHFFFAOYSA-N 0.000 claims description 12
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 11
- -1 mercapto compound Chemical class 0.000 claims description 11
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 claims description 11
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 9
- 239000001506 calcium phosphate Substances 0.000 claims description 9
- 229910000389 calcium phosphate Inorganic materials 0.000 claims description 9
- 235000011010 calcium phosphates Nutrition 0.000 claims description 9
- OMAAXMJMHFXYFY-UHFFFAOYSA-L calcium trioxidophosphanium Chemical compound [Ca+2].[O-]P([O-])=O OMAAXMJMHFXYFY-UHFFFAOYSA-L 0.000 claims description 8
- 239000003638 chemical reducing agent Substances 0.000 claims description 8
- 230000002401 inhibitory effect Effects 0.000 claims description 8
- 239000012986 chain transfer agent Substances 0.000 claims description 7
- 238000010612 desalination reaction Methods 0.000 claims description 6
- 150000002978 peroxides Chemical class 0.000 claims description 5
- 238000001556 precipitation Methods 0.000 claims description 5
- 239000013535 sea water Substances 0.000 claims description 5
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 claims description 5
- 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 4
- XEEYSDHEOQHCDA-UHFFFAOYSA-N 2-methylprop-2-ene-1-sulfonic acid Chemical compound CC(=C)CS(O)(=O)=O XEEYSDHEOQHCDA-UHFFFAOYSA-N 0.000 claims description 4
- 238000004062 sedimentation Methods 0.000 claims description 4
- IAUGBVWVWDTCJV-UHFFFAOYSA-N 1-(prop-2-enoylamino)propane-1-sulfonic acid Chemical compound CCC(S(O)(=O)=O)NC(=O)C=C IAUGBVWVWDTCJV-UHFFFAOYSA-N 0.000 claims description 3
- WROUWQQRXUBECT-UHFFFAOYSA-N 2-ethylacrylic acid Chemical compound CCC(=C)C(O)=O WROUWQQRXUBECT-UHFFFAOYSA-N 0.000 claims description 3
- XMWLVXXYIYBETQ-UHFFFAOYSA-N 2-hydroxy-3-(2-methylprop-2-enoylamino)propane-1-sulfonic acid Chemical compound CC(=C)C(=O)NCC(O)CS(O)(=O)=O XMWLVXXYIYBETQ-UHFFFAOYSA-N 0.000 claims description 3
- VSSGDAWBDKMCMI-UHFFFAOYSA-N 2-methyl-2-(2-methylprop-2-enoylamino)propane-1-sulfonic acid Chemical compound CC(=C)C(=O)NC(C)(C)CS(O)(=O)=O VSSGDAWBDKMCMI-UHFFFAOYSA-N 0.000 claims description 3
- AGBXYHCHUYARJY-UHFFFAOYSA-N 2-phenylethenesulfonic acid Chemical compound OS(=O)(=O)C=CC1=CC=CC=C1 AGBXYHCHUYARJY-UHFFFAOYSA-N 0.000 claims description 3
- PVEOYINWKBTPIZ-UHFFFAOYSA-N but-3-enoic acid Chemical compound OC(=O)CC=C PVEOYINWKBTPIZ-UHFFFAOYSA-N 0.000 claims description 3
- 159000000007 calcium salts Chemical class 0.000 claims description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 3
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 claims description 3
- 150000002505 iron Chemical class 0.000 claims description 3
- HVAMZGADVCBITI-UHFFFAOYSA-N pent-4-enoic acid Chemical compound OC(=O)CCC=C HVAMZGADVCBITI-UHFFFAOYSA-N 0.000 claims description 3
- XXIJLZCMICIETD-UHFFFAOYSA-M sodium;1,2-dihydroxy-2-oxoethanesulfinate Chemical compound [Na+].OC(=O)C(O)S([O-])=O XXIJLZCMICIETD-UHFFFAOYSA-M 0.000 claims description 3
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 claims description 3
- AIIITCMZOKMJIM-UHFFFAOYSA-N 2-(prop-2-enoylamino)propane-2-sulfonic acid Chemical compound OS(=O)(=O)C(C)(C)NC(=O)C=C AIIITCMZOKMJIM-UHFFFAOYSA-N 0.000 claims description 2
- 239000000498 cooling water Substances 0.000 claims description 2
- 159000000003 magnesium salts Chemical class 0.000 claims description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-N sulfonic acid Chemical group OS(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-N 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 177
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 42
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 36
- 229920000642 polymer Polymers 0.000 description 31
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 30
- 238000006116 polymerization reaction Methods 0.000 description 24
- 239000000203 mixture Substances 0.000 description 17
- 230000005764 inhibitory process Effects 0.000 description 13
- 239000007787 solid Substances 0.000 description 13
- 229920001897 terpolymer Polymers 0.000 description 12
- 229920002125 Sokalan® Polymers 0.000 description 11
- 239000008367 deionised water Substances 0.000 description 11
- 229910021641 deionized water Inorganic materials 0.000 description 11
- 235000010216 calcium carbonate Nutrition 0.000 description 10
- 239000011521 glass Substances 0.000 description 10
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 description 10
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 10
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 9
- 239000011976 maleic acid Substances 0.000 description 8
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 7
- 239000013049 sediment Substances 0.000 description 7
- 239000004584 polyacrylic acid Substances 0.000 description 6
- 239000002244 precipitate Substances 0.000 description 6
- 229920000536 2-Acrylamido-2-methylpropane sulfonic acid Polymers 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 5
- JHUFGBSGINLPOW-UHFFFAOYSA-N 3-chloro-4-(trifluoromethoxy)benzoyl cyanide Chemical compound FC(F)(F)OC1=CC=C(C(=O)C#N)C=C1Cl JHUFGBSGINLPOW-UHFFFAOYSA-N 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 4
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical class OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- 239000011575 calcium Substances 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- 150000003460 sulfonic acids Chemical class 0.000 description 4
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000001636 atomic emission spectroscopy Methods 0.000 description 3
- 239000001110 calcium chloride Substances 0.000 description 3
- 235000011148 calcium chloride Nutrition 0.000 description 3
- 229910001628 calcium chloride Inorganic materials 0.000 description 3
- 235000011132 calcium sulphate Nutrition 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 238000009616 inductively coupled plasma Methods 0.000 description 3
- 239000008235 industrial water Substances 0.000 description 3
- XFHJDMUEHUHAJW-UHFFFAOYSA-N n-tert-butylprop-2-enamide Chemical compound CC(C)(C)NC(=O)C=C XFHJDMUEHUHAJW-UHFFFAOYSA-N 0.000 description 3
- 235000021317 phosphate Nutrition 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 238000010526 radical polymerization reaction Methods 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000003643 water by type Substances 0.000 description 3
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 2
- HNVRRHSXBLFLIG-UHFFFAOYSA-N 3-hydroxy-3-methylbut-1-ene Chemical compound CC(C)(O)C=C HNVRRHSXBLFLIG-UHFFFAOYSA-N 0.000 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 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical class NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- 238000005684 Liebig rearrangement reaction Methods 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 2
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- YDONNITUKPKTIG-UHFFFAOYSA-N [Nitrilotris(methylene)]trisphosphonic acid Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CP(O)(O)=O YDONNITUKPKTIG-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 229910052925 anhydrite Inorganic materials 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 238000002144 chemical decomposition reaction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 239000003599 detergent Substances 0.000 description 2
- 150000001991 dicarboxylic acids Chemical class 0.000 description 2
- DUYCTCQXNHFCSJ-UHFFFAOYSA-N dtpmp Chemical compound OP(=O)(O)CN(CP(O)(O)=O)CCN(CP(O)(=O)O)CCN(CP(O)(O)=O)CP(O)(O)=O DUYCTCQXNHFCSJ-UHFFFAOYSA-N 0.000 description 2
- NFDRPXJGHKJRLJ-UHFFFAOYSA-N edtmp Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CCN(CP(O)(O)=O)CP(O)(O)=O NFDRPXJGHKJRLJ-UHFFFAOYSA-N 0.000 description 2
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethyl mercaptane Natural products CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 2
- 239000001530 fumaric acid Substances 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 2
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 2
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 2
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- 229910000391 tricalcium phosphate Inorganic materials 0.000 description 2
- 235000019731 tricalcium phosphate Nutrition 0.000 description 2
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 1
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 description 1
- 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 1
- KOQQKLZTINXBAS-UHFFFAOYSA-N 2-hydroxy-3-prop-2-enoxypropane-1-sulfonic acid Chemical compound OS(=O)(=O)CC(O)COCC=C KOQQKLZTINXBAS-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- ZRKSKKQONQUFMR-UHFFFAOYSA-N 3-amino-2-methyl-3-oxoprop-1-ene-1-sulfonic acid Chemical compound NC(=O)C(C)=CS(O)(=O)=O ZRKSKKQONQUFMR-UHFFFAOYSA-N 0.000 description 1
- ATBDZSAENDYQDW-UHFFFAOYSA-N 3-ethenylbenzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC(C=C)=C1 ATBDZSAENDYQDW-UHFFFAOYSA-N 0.000 description 1
- NYUTUWAFOUJLKI-UHFFFAOYSA-N 3-prop-2-enoyloxypropane-1-sulfonic acid Chemical compound OS(=O)(=O)CCCOC(=O)C=C NYUTUWAFOUJLKI-UHFFFAOYSA-N 0.000 description 1
- CMGDVUCDZOBDNL-UHFFFAOYSA-N 4-methyl-2h-benzotriazole Chemical compound CC1=CC=CC2=NNN=C12 CMGDVUCDZOBDNL-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical class [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- UDPYEFRYPGXIAL-UHFFFAOYSA-N NC(=O)C(C)=CCS(O)(=O)=O Chemical compound NC(=O)C(C)=CCS(O)(=O)=O UDPYEFRYPGXIAL-UHFFFAOYSA-N 0.000 description 1
- 239000007832 Na2SO4 Substances 0.000 description 1
- RORDFOUPNSOFRP-UHFFFAOYSA-N O[PH2]=O.O[PH2]=O Chemical compound O[PH2]=O.O[PH2]=O RORDFOUPNSOFRP-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- 229920000388 Polyphosphate Polymers 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical class OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- ACIAHEMYLLBZOI-ZZXKWVIFSA-N Unsaturated alcohol Chemical compound CC\C(CO)=C/C ACIAHEMYLLBZOI-ZZXKWVIFSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 150000003926 acrylamides Chemical class 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 1
- 150000008041 alkali metal carbonates Chemical class 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 125000005250 alkyl acrylate group Chemical group 0.000 description 1
- 125000006295 amino methylene group Chemical group [H]N(*)C([H])([H])* 0.000 description 1
- VZTDIZULWFCMLS-UHFFFAOYSA-N ammonium formate Chemical compound [NH4+].[O-]C=O VZTDIZULWFCMLS-UHFFFAOYSA-N 0.000 description 1
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 1
- 239000012935 ammoniumperoxodisulfate Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 239000003139 biocide Substances 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- YQHLDYVWEZKEOX-UHFFFAOYSA-N cumene hydroperoxide Chemical compound OOC(C)(C)C1=CC=CC=C1 YQHLDYVWEZKEOX-UHFFFAOYSA-N 0.000 description 1
- 238000006114 decarboxylation reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000000909 electrodialysis Methods 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 239000012527 feed solution Substances 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical class CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- DCUFMVPCXCSVNP-UHFFFAOYSA-N methacrylic anhydride Chemical compound CC(=C)C(=O)OC(=O)C(C)=C DCUFMVPCXCSVNP-UHFFFAOYSA-N 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical class [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 235000011007 phosphoric acid Nutrition 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- ASUAYTHWZCLXAN-UHFFFAOYSA-N prenol Chemical compound CC(C)=CCO ASUAYTHWZCLXAN-UHFFFAOYSA-N 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- TVDSBUOJIPERQY-UHFFFAOYSA-N prop-2-yn-1-ol Chemical compound OCC#C TVDSBUOJIPERQY-UHFFFAOYSA-N 0.000 description 1
- 229920006296 quaterpolymer Polymers 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- DIKJULDDNQFCJG-UHFFFAOYSA-M sodium;prop-2-ene-1-sulfonate Chemical compound [Na+].[O-]S(=O)(=O)CC=C DIKJULDDNQFCJG-UHFFFAOYSA-M 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- CSABAZBYIWDIDE-UHFFFAOYSA-N sulfino hydrogen sulfite Chemical class OS(=O)OS(O)=O CSABAZBYIWDIDE-UHFFFAOYSA-N 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 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 description 1
- 230000008719 thickening Effects 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 229910001456 vanadium ion Inorganic materials 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 150000003751 zinc Chemical class 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
- C08F216/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
- C08F216/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an alcohol radical
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
- C02F5/08—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents
- C02F5/10—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances
-
- 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
- C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/04—Acids; Metal salts or ammonium salts thereof
- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F220/58—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing oxygen in addition to the carbonamido oxygen, e.g. N-methylolacrylamide, N-(meth)acryloylmorpholine
- C08F220/585—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing oxygen in addition to the carbonamido oxygen, e.g. N-methylolacrylamide, N-(meth)acryloylmorpholine and containing other heteroatoms, e.g. 2-acrylamido-2-methylpropane sulfonic acid [AMPS]
-
- 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
- C08F228/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a bond to sulfur or by a heterocyclic ring containing sulfur
- C08F228/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a bond to sulfur or by a heterocyclic ring containing sulfur by a bond to sulfur
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/37—Polymers
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
-
- 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
- C08F216/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
- C08F216/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an alcohol radical
- C08F216/04—Acyclic compounds
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- C—CHEMISTRY; METALLURGY
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/08—Anhydrides
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
- F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
- F16L58/00—Protection of pipes or pipe fittings against corrosion or incrustation
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- General Chemical & Material Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Polymerization Catalysts (AREA)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
Abstract
The invention relates to copolymers of (a) from 5 to 40% by weight of isoprenol, (b) from 5 to 93% by weight of at least one monoethylenically unsaturated C3 to C8 monocarboxylic acid, or of an anhydride or salt of same, (c) from 2 to 90% by weight of one or more monomers containing sulphonic acid groups.
Description
COPOLYMERS OF ISOPRENOL, MONOETHYLENICALLY UNSATURATED
MONOCARBOXYLIC ACIDS AND SULFONIC ACIDS, METHODS FOR PRODUCTION
THEREOF AND USE THEREOF AS DEPOSIT INHIBITORS IN WATER-BEARING
SYSTEMS
The invention relates to copolymers of isoprenol, monoethylenically unsaturated monocarboxylic acids and sulfonic acids, methods for production thereof and use thereof as deposit inhibitors in water-bearing systems.
The solubility of most substances in water is restricted. In particular, in industrial water treatment, the prevention of mineral sediments in water-bearing systems is an essential task.
Inorganic salts such as calcium carbonate, magnesium hydroxide, calcium sulfate and barium sulfate, and calcium phosphate or calcium phosphonate have a low solubility in water. If these dissolved components are concentrated in aqueous systems (thickening), the solubility product is exceeded with the consequence that these substances precipitate out and cause sediments.
The solubility of the substances is, in addition, dependent on temperature and the pH. In particular, many substances such as calcium carbonate, or calcium sulfate, exhibit an inverse solubility, i.e. their solubility decreases with increasing temperature. This leads to high process temperatures frequently being the cause of unwanted precipitates and formation of deposits in cooling and boiler feed water systems on heat-exchange surfaces or in pipelines.
Precipitates and sediments of inorganic substances and salts in water-bearing systems may only be removed again with great effort. Each mechanical and chemical cleaning is costly and time consuming and inescapably leads to production failures.
Not only in cooling and boiler feed water systems are attempts made to prevent the formation of calcium carbonate deposits, calcium sulfate deposits and other salt deposits. Also in seawater desalination by distillation and by membrane methods such as reverse osmosis or electrodialysis, efforts are made to prevent formation of these solid deposits.
MONOCARBOXYLIC ACIDS AND SULFONIC ACIDS, METHODS FOR PRODUCTION
THEREOF AND USE THEREOF AS DEPOSIT INHIBITORS IN WATER-BEARING
SYSTEMS
The invention relates to copolymers of isoprenol, monoethylenically unsaturated monocarboxylic acids and sulfonic acids, methods for production thereof and use thereof as deposit inhibitors in water-bearing systems.
The solubility of most substances in water is restricted. In particular, in industrial water treatment, the prevention of mineral sediments in water-bearing systems is an essential task.
Inorganic salts such as calcium carbonate, magnesium hydroxide, calcium sulfate and barium sulfate, and calcium phosphate or calcium phosphonate have a low solubility in water. If these dissolved components are concentrated in aqueous systems (thickening), the solubility product is exceeded with the consequence that these substances precipitate out and cause sediments.
The solubility of the substances is, in addition, dependent on temperature and the pH. In particular, many substances such as calcium carbonate, or calcium sulfate, exhibit an inverse solubility, i.e. their solubility decreases with increasing temperature. This leads to high process temperatures frequently being the cause of unwanted precipitates and formation of deposits in cooling and boiler feed water systems on heat-exchange surfaces or in pipelines.
Precipitates and sediments of inorganic substances and salts in water-bearing systems may only be removed again with great effort. Each mechanical and chemical cleaning is costly and time consuming and inescapably leads to production failures.
Not only in cooling and boiler feed water systems are attempts made to prevent the formation of calcium carbonate deposits, calcium sulfate deposits and other salt deposits. Also in seawater desalination by distillation and by membrane methods such as reverse osmosis or electrodialysis, efforts are made to prevent formation of these solid deposits.
- 2 -There is particular interest in multifunctional deposit inhibitors which exhibit good inhibition properties for calcium carbonate, calcium sulfate, calcium phosphate and calcium phosphonate deposits. This is a problem for conventional deposit inhibitors such as, e.g., polyacrylic acids. Such homopolymers are frequently good deposit inhibitors for calcium carbonate or calcium sulfate, but have scarcely any inhibitory activity, in particular for calcium phosphate and calcium phosphonate deposits.
It is known to employ low-molecular-weight polyacrylic acids and salts thereof produced by means of free-radical polymerization as deposit inhibitors in industrial water treatment and in seawater desalination owing to the dispersant properties and properties inhibiting crystal growth thereof. For a good activity, the mean molecular weight (Mw) of these polymers should be <50 000 g/mol. Frequently, polyacrylic acids having Mw < 10 000 g/mol are described as particularly effective. A disadvantage of these polymers is their sensitivity to hardness rising with increasing temperature, i.e. the risk that the polymers precipitate as Ca or Mg polyacrylates increases. In addition, the polyacrylic acids have only a very low inhibitory activity against sediments of calcium phosphate or calcium phosphonate.
Corrosion protection is indispensible in industrial aqueous processes. Among the customary corrosion inhibitors, phosphates and phosphonates are assuming an outstanding importance.
However, with the use of phosphates or phosphonates as corrosion inhibitors, the risk of sediments from calcium phosphate or calcium phosphonate increases. These sediments are particularly problematic, since they can only be removed again with great effort.
In addition to pure polyacrylic acids, numerous copolymers, terpolymers and quater polymers have been described as deposit inhibitors. In this case, generally copolymers of unsaturated carboxylic acids such as acrylic acid, sulfonate-comprising monomers such as 2-acrylamido-2-methylpropanesulfonate, styrenesulfonate or sulfoethyl methacrylate, and optionally, nonionic monomers are described. The nonionic monomers are frequently acrylamide, acrylamide derivatives_ such as N-alkylacylamides, methacrylamide derivatives, alkyl acrylates, hydroxyalkyl acrylates, alkyl methacrylates or vinyl acetate.
It is known to employ low-molecular-weight polyacrylic acids and salts thereof produced by means of free-radical polymerization as deposit inhibitors in industrial water treatment and in seawater desalination owing to the dispersant properties and properties inhibiting crystal growth thereof. For a good activity, the mean molecular weight (Mw) of these polymers should be <50 000 g/mol. Frequently, polyacrylic acids having Mw < 10 000 g/mol are described as particularly effective. A disadvantage of these polymers is their sensitivity to hardness rising with increasing temperature, i.e. the risk that the polymers precipitate as Ca or Mg polyacrylates increases. In addition, the polyacrylic acids have only a very low inhibitory activity against sediments of calcium phosphate or calcium phosphonate.
Corrosion protection is indispensible in industrial aqueous processes. Among the customary corrosion inhibitors, phosphates and phosphonates are assuming an outstanding importance.
However, with the use of phosphates or phosphonates as corrosion inhibitors, the risk of sediments from calcium phosphate or calcium phosphonate increases. These sediments are particularly problematic, since they can only be removed again with great effort.
In addition to pure polyacrylic acids, numerous copolymers, terpolymers and quater polymers have been described as deposit inhibitors. In this case, generally copolymers of unsaturated carboxylic acids such as acrylic acid, sulfonate-comprising monomers such as 2-acrylamido-2-methylpropanesulfonate, styrenesulfonate or sulfoethyl methacrylate, and optionally, nonionic monomers are described. The nonionic monomers are frequently acrylamide, acrylamide derivatives_ such as N-alkylacylamides, methacrylamide derivatives, alkyl acrylates, hydroxyalkyl acrylates, alkyl methacrylates or vinyl acetate.
- 3 -US 4,711,725 describes terpolymers of (1) (meth)acrylic acid, (2) acrylamidoalkyl- or -arylsulfonates, in particular 2-acrylamido-2-methylpropanesulfonate (AMPS), and (3) vinyl esters such as ethyl acrylate and hydroxyethyl methacrylate, or acrylamides such as tert-butylacrylamide as deposit inhibitors for aqueous systems.
US 4,952,327 describes terpolymers of (1) (meth)acrylic acid or maleic acid, (2) acrylamidoalkanesulfonic acid, in particular AMPS, and (3) styrenesulfonic acid as deposit inhibitors for aqueous systems.
JP 59102496 describes the production of copolymers of 0.5 to 50% by weight of an unsaturated alcohol such as isoprenol with 50 to 99.5% by weight of an olefinic mono- or dicarboxylic acid, such as, e.g., acrylic acid or maleic acid, and optionally with 0 to 40% by weight of a third monomer which comprises, inter alia, styrenesulfonate, acrylonitrile or vinyl acetate. The resultant polymers are described as encrustation inhibitors in industrial water treatment. The monomers are used as initiator at 95 C with a mixture of hydrogen peroxide and sodium persulfate. The molecular weight of the resultant polymers is between 3200 and 4000 g/mol.
EP-A 337 694 relates to the production of maleic acid copolymers having a number-average molecular weight Mn from 300 to 5000 g/mol and a polydispersity of <2.5 of 50 to 99.9% by weight of maleic acid and 50 to 0.1% by weight of a water-soluble unsaturated comonomer, and also use thereof for the water treatment. The use as antiscalant and as builder in detergent formulations is explicitly mentioned. Comonomers described are, inter alia, monoethylenically unsaturated monocarboxylic acids such as acrylic acid and methacrylic acid, unsaturated dicarboxylic acids such as fumaric acid and itaconic acid, unsaturated alcohols such as isoprenol, (meth)ally1 ether and monoethylenically unsaturated sulfonic acid group-comprising compounds such as vinylsulfonic acid and 2-acrylamido-2-methylpropanesulfonic acid. The copolymers are described by aqueous polymerization with H202 as initiator in the presence of 0.5 to 500 ppm of a metal catalyst comprising iron, copper or vanadium ions. A
chain-transfer agent is not used. During the polymerization, carbon dioxide is released, wherein the amount of carbon dioxide is proportional to the amount of H202. In the examples, maleic acid-isoprenol copolymers having number-average molecular weights between 1090
US 4,952,327 describes terpolymers of (1) (meth)acrylic acid or maleic acid, (2) acrylamidoalkanesulfonic acid, in particular AMPS, and (3) styrenesulfonic acid as deposit inhibitors for aqueous systems.
JP 59102496 describes the production of copolymers of 0.5 to 50% by weight of an unsaturated alcohol such as isoprenol with 50 to 99.5% by weight of an olefinic mono- or dicarboxylic acid, such as, e.g., acrylic acid or maleic acid, and optionally with 0 to 40% by weight of a third monomer which comprises, inter alia, styrenesulfonate, acrylonitrile or vinyl acetate. The resultant polymers are described as encrustation inhibitors in industrial water treatment. The monomers are used as initiator at 95 C with a mixture of hydrogen peroxide and sodium persulfate. The molecular weight of the resultant polymers is between 3200 and 4000 g/mol.
EP-A 337 694 relates to the production of maleic acid copolymers having a number-average molecular weight Mn from 300 to 5000 g/mol and a polydispersity of <2.5 of 50 to 99.9% by weight of maleic acid and 50 to 0.1% by weight of a water-soluble unsaturated comonomer, and also use thereof for the water treatment. The use as antiscalant and as builder in detergent formulations is explicitly mentioned. Comonomers described are, inter alia, monoethylenically unsaturated monocarboxylic acids such as acrylic acid and methacrylic acid, unsaturated dicarboxylic acids such as fumaric acid and itaconic acid, unsaturated alcohols such as isoprenol, (meth)ally1 ether and monoethylenically unsaturated sulfonic acid group-comprising compounds such as vinylsulfonic acid and 2-acrylamido-2-methylpropanesulfonic acid. The copolymers are described by aqueous polymerization with H202 as initiator in the presence of 0.5 to 500 ppm of a metal catalyst comprising iron, copper or vanadium ions. A
chain-transfer agent is not used. During the polymerization, carbon dioxide is released, wherein the amount of carbon dioxide is proportional to the amount of H202. In the examples, maleic acid-isoprenol copolymers having number-average molecular weights between 1090
- 4 -and 4780 g/mol are produced, wherein the polymerization is carried out at the boiling point of the aqueous monomer solution.
EP-A 396 303 relates to producing maleic acid polymers of 75 to 100% by weight of maleic acid and 0 to 25% by weight of a further water-soluble monomer by aqueous polymerization with 12 to 150 g of H202 per mole of the monomer components, 0.3 to 500 ppm of a metal salt of iron, vanadium or copper and an alkaline substance such as alkali metal hydroxide or alkali metal carbonate in order to neutralize up to 45% by weight monomers having acid groups.
Comonomers described are, inter alia, unsaturated monocarboxylic acids such as acrylic acid and methacrylic acid, unsaturated dicarboxylic acids such as fumaric acid and itaconic acid, unsaturated alcohols such as isoprenol, (meth)ally1 ether and unsaturated sulfonic acid group-comprising compounds such as vinylsulfonic acid and 2-acrylamido-2-methylpropanesulfonic acid. A chain-transfer agent is not used. The polymerization temperature is said to be in the range from 85 to 160 C. In the examples, copolymers of 80% by weight of maleic acid and 20% by weight of isoprenol having number-average molecular weights between 2400 and 4100 g/mol are produced. The polymerization is carried out at the boiling point of the monomer mixture. The use of the copolymers as detergent builders and antiscalants is described.
A disadvantage of the methods of the prior art is the relatively narrow molecular weight range of the isoprenol-comprising copolymers thus obtainable, and also the high polymerization temperatures, at which olefinic alcohols such as isoprenol are subject to chemical degradation (see F. Lynen, Liebigs Ann. Chem. 1960, 360, 58 to 70). Associated therewith is a reduced activity of the isoprenol-comprising polymers corresponding to the prior art.
It is an object of the invention to provide multifunctional deposit-inhibiting polymers which have an activity as broad as possible against precipitates and sediments of calcium and magnesium salts and, in particular, effectively inhibit precipitates and deposits of calcium carbonate, calcium sulfate, calcium phosphate and calcium phosphonate in water-bearing systems. In addition, it is an object of the present invention to provide a suitable method for producing the copolymers.
EP-A 396 303 relates to producing maleic acid polymers of 75 to 100% by weight of maleic acid and 0 to 25% by weight of a further water-soluble monomer by aqueous polymerization with 12 to 150 g of H202 per mole of the monomer components, 0.3 to 500 ppm of a metal salt of iron, vanadium or copper and an alkaline substance such as alkali metal hydroxide or alkali metal carbonate in order to neutralize up to 45% by weight monomers having acid groups.
Comonomers described are, inter alia, unsaturated monocarboxylic acids such as acrylic acid and methacrylic acid, unsaturated dicarboxylic acids such as fumaric acid and itaconic acid, unsaturated alcohols such as isoprenol, (meth)ally1 ether and unsaturated sulfonic acid group-comprising compounds such as vinylsulfonic acid and 2-acrylamido-2-methylpropanesulfonic acid. A chain-transfer agent is not used. The polymerization temperature is said to be in the range from 85 to 160 C. In the examples, copolymers of 80% by weight of maleic acid and 20% by weight of isoprenol having number-average molecular weights between 2400 and 4100 g/mol are produced. The polymerization is carried out at the boiling point of the monomer mixture. The use of the copolymers as detergent builders and antiscalants is described.
A disadvantage of the methods of the prior art is the relatively narrow molecular weight range of the isoprenol-comprising copolymers thus obtainable, and also the high polymerization temperatures, at which olefinic alcohols such as isoprenol are subject to chemical degradation (see F. Lynen, Liebigs Ann. Chem. 1960, 360, 58 to 70). Associated therewith is a reduced activity of the isoprenol-comprising polymers corresponding to the prior art.
It is an object of the invention to provide multifunctional deposit-inhibiting polymers which have an activity as broad as possible against precipitates and sediments of calcium and magnesium salts and, in particular, effectively inhibit precipitates and deposits of calcium carbonate, calcium sulfate, calcium phosphate and calcium phosphonate in water-bearing systems. In addition, it is an object of the present invention to provide a suitable method for producing the copolymers.
- 5 -The object is achieved by copolymers of (a) 5 to 40% by weight of isoprenol, (b) 5 to 93% by weight of at least one monoethylenically unsaturated C3 to C8 monocarboxylic acid, an anhydride or salt of same, (c) 2 to 90% by weight of one or more sulfonic acid group-comprising monomers.
Suitable monoethylenically unsaturated C3-C8 monocarboxylic acids which can be used as monomers (b) are, for example, acrylic acid, methacrylic acid, ethacrylic acid, vinylacetic acid, allylacetic acid and crotonic acid and also the water-soluble salts thereof.
If said unsaturated C3-C8 monocarboxylic acids can form anhydrides, these are also suitable as monomers (b), for example methacrylic anhydride.
Preferred monoethylenically unsaturated C3-C8 monocarboxylic acids (b) are acrylic acid, methacrylic acid, ethacrylic acid, vinylacetic acid, allylacetic acid and crotonic acid, particular preference is given to acrylic acid and methacrylic acid.
Sulfonic acid group-comprising monomers (c) are preferably those of the formulae (la) and (lb) H2C=CH-X-503H (la), H2C=C(CH3)-X-S03H (lb), where X is an optionally present spacer group which can be selected from -(CH2)n- where n = 0 to 4, -C6H4-, -CH2-0-C6H4-, -C(0)-NH-C(C1-102-, -C(0)-NH-CH(CH2CH3)-, -C(0)NH-CH(CH3)CH2-, -C(0)NH-C(CH3)2CH2-, -C(0)NH-CH2CH(OH)CH2-, -C(0)NH-CH2-, -C(0)NH-CH2CH2- and -C(0)NH-CH2CH2CH2-.
Particularly preferred sulfonic acid group-comprising monomers are in this case 1-acrylamido-1-propanesulfonic acid (X = -C(0)NH-CH(CH2CH3)- in formula 11a), 2-acrylamido-
Suitable monoethylenically unsaturated C3-C8 monocarboxylic acids which can be used as monomers (b) are, for example, acrylic acid, methacrylic acid, ethacrylic acid, vinylacetic acid, allylacetic acid and crotonic acid and also the water-soluble salts thereof.
If said unsaturated C3-C8 monocarboxylic acids can form anhydrides, these are also suitable as monomers (b), for example methacrylic anhydride.
Preferred monoethylenically unsaturated C3-C8 monocarboxylic acids (b) are acrylic acid, methacrylic acid, ethacrylic acid, vinylacetic acid, allylacetic acid and crotonic acid, particular preference is given to acrylic acid and methacrylic acid.
Sulfonic acid group-comprising monomers (c) are preferably those of the formulae (la) and (lb) H2C=CH-X-503H (la), H2C=C(CH3)-X-S03H (lb), where X is an optionally present spacer group which can be selected from -(CH2)n- where n = 0 to 4, -C6H4-, -CH2-0-C6H4-, -C(0)-NH-C(C1-102-, -C(0)-NH-CH(CH2CH3)-, -C(0)NH-CH(CH3)CH2-, -C(0)NH-C(CH3)2CH2-, -C(0)NH-CH2CH(OH)CH2-, -C(0)NH-CH2-, -C(0)NH-CH2CH2- and -C(0)NH-CH2CH2CH2-.
Particularly preferred sulfonic acid group-comprising monomers are in this case 1-acrylamido-1-propanesulfonic acid (X = -C(0)NH-CH(CH2CH3)- in formula 11a), 2-acrylamido-
- 6 -propanesulfonic acid (X = -C(0)NH-CH(CH3)CH2- in formula Ha), 2-acrylamido-2-methylpropanesulfonic acid (AMPS, X = -C(0)NH-C(CH3)2CH2- in formula 11a), 2-methacrylamido-2-methylpropanesulfonic acid (X = -C(0)NH-C(CH3)2CH2- in formula 11b), 3-methacrylamido-2-hydroxypropanesulfonic acid (X = -C(0)NH-CH2CH(OH)CH2- in formula 11b), allylsulfonic acid (X = CH2 in formula 11a), methallylsulfonic acid (X = CH2 in formula 11b), allyloxybenzenesulfonic acid (X = -CH2-0-C6H4- in formula 11a), methallyloxybenzenesulfonic acid (X = -CH2-0-C6H4- in formula 11b), 2-hydroxy-3-(2-propenyloxy)propanesulfonic acid, 2-methyl-2-propene-1-sulfonic acid (X = CH2 in formula 11b), vinylsulfonic acid (X not present in formula 11a), 3-sulfopropyl acrylate (X = -C(0)0-CH2CH2CH2- in formula 11a), 2-sulfoethyl methacrylate (X = -C(0)0-CH2CH2- in formula 11b), 3-sulfopropyl methacrylate (X = -0(0)0-CH2CH2CH2- in formula 11b), sulfomethacrylamide (X = -C(0)NH- in formula 11b), sulfomethylmethacrylamide (X = -C(0)NH-CH2- in formula 11b), and also salts of said acids.
Suitable salts are generally water-soluble salts, preferably the sodium, potassium and ammonium salts of said acids.
Particular preference is given to 1-acrylamidopropanesulfonic acid, 2-acrylamido-2-propanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid (AMPS), 2-methacrylamido-2-methylpropanesulfonic acid, 3-methacrylamido-2-hydroxypropanesulfonic acid, 2-sulfoethyl methacrylate, sulfonic acid, vinylsulfonic acid, allylsulfonic acid (ALS) und methallylsulfonic acid, and also salts of said acids.
Very particularly preferred sulfonic acid group-comprising monomers are 2-acrylamido-2-methylpropanesulfonic acid (AMPS) and allylsulfonic acid, and also water-soluble salts thereof, in particular sodium, potassium and ammonium salts thereof. Particular preference is given to AMPS.
Generally, the weight-average molecular weight of the copolymers is 2000 to 20 000 g/mol, preferably 2500 to 15 000 g/mol, and particularly preferably 3000 to 13 000 g/mol.
The molecular weight is determined by means of gel permeation chromatography compared with polyacrylic acid standards.
Suitable salts are generally water-soluble salts, preferably the sodium, potassium and ammonium salts of said acids.
Particular preference is given to 1-acrylamidopropanesulfonic acid, 2-acrylamido-2-propanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid (AMPS), 2-methacrylamido-2-methylpropanesulfonic acid, 3-methacrylamido-2-hydroxypropanesulfonic acid, 2-sulfoethyl methacrylate, sulfonic acid, vinylsulfonic acid, allylsulfonic acid (ALS) und methallylsulfonic acid, and also salts of said acids.
Very particularly preferred sulfonic acid group-comprising monomers are 2-acrylamido-2-methylpropanesulfonic acid (AMPS) and allylsulfonic acid, and also water-soluble salts thereof, in particular sodium, potassium and ammonium salts thereof. Particular preference is given to AMPS.
Generally, the weight-average molecular weight of the copolymers is 2000 to 20 000 g/mol, preferably 2500 to 15 000 g/mol, and particularly preferably 3000 to 13 000 g/mol.
The molecular weight is determined by means of gel permeation chromatography compared with polyacrylic acid standards.
- 7 -Generally, the polydispersity index of the copolymers is Mw/Mn 5 2.5, preferably 5 2Ø
Generally, the copolymers according to the invention comprise 5 to 35% by weight of isoprenol (a), 30 to 80% by weight of the monoethylenically unsaturated C3 to 08 carboxylic acid (b) and 5 to 50% by weight of the sulfonic acid group-comprising monomer (c).
Particularly preferably, they comprise 5 to 30% by weight of isoprenol (a), 50 to 80% by weight of the monoethylenically unsaturated C3 to C8 carboxylic acid (b) and 10 to 30% by weight of the sulfonic acid group-comprising monomer (c).
The copolymers according to the invention are distinguished, in particular, in that they are obtained by a particularly mild polymerization method in which side reactions such as the isomerization from isoprenol to prenol or dimethylvinyl carbinol, the formation of 3-methyl-13-butanediol or isoprene or decarboxylation of maleic acid do not occur.
Known methods for producing isoprenol-comprising copolymers are based on free-radical polymerization at elevated temperatures around 100 C. It is known that, in particular, isoprenol under acidic conditions and high temperatures is rapidly subject to chemical degradation (F. Lynen, Liebigs Ann. Chem. 1960, 360, 58 to 70). In contrast, the method according to the invention makes possible a substantially milder polymerization reaction at temperatures between 10 to 80 C. Thus degradation of the isoprenol is effectively prevented. Preferably, the polymerization is carried out at 10 to 70 C, particularly preferably at 10 to 60 C.
The method according to the invention is generally carried out semi-continuously in the feed-stream procedure. The solvent used is generally water.
According to a preferred embodiment, the polymerization is carried out in aqueous solution with a monomer content of 25 to 50% by weight. In this case the free-radical polymerization is carried out under acidic conditions, generally at pH 0.5 to 6.5. It is preferably performed in such a manner that all monomers (a), (b) and (c) are added as feed, wherein the monoethylenically unsaturated 03-08 monocarboxylic acids (b), e.g. acrylic acid can also be partially neutralized. Isoprenol (a), monoethylenically unsaturated C3-C8 monocarboxylic acid (b), e.g. acrylic acid, and sulfonic acid group-comprising monomer (c), for example 2-acrylamido-2-methylpropanesulfonic acid, can also be charged initially in full or in part. For
Generally, the copolymers according to the invention comprise 5 to 35% by weight of isoprenol (a), 30 to 80% by weight of the monoethylenically unsaturated C3 to 08 carboxylic acid (b) and 5 to 50% by weight of the sulfonic acid group-comprising monomer (c).
Particularly preferably, they comprise 5 to 30% by weight of isoprenol (a), 50 to 80% by weight of the monoethylenically unsaturated C3 to C8 carboxylic acid (b) and 10 to 30% by weight of the sulfonic acid group-comprising monomer (c).
The copolymers according to the invention are distinguished, in particular, in that they are obtained by a particularly mild polymerization method in which side reactions such as the isomerization from isoprenol to prenol or dimethylvinyl carbinol, the formation of 3-methyl-13-butanediol or isoprene or decarboxylation of maleic acid do not occur.
Known methods for producing isoprenol-comprising copolymers are based on free-radical polymerization at elevated temperatures around 100 C. It is known that, in particular, isoprenol under acidic conditions and high temperatures is rapidly subject to chemical degradation (F. Lynen, Liebigs Ann. Chem. 1960, 360, 58 to 70). In contrast, the method according to the invention makes possible a substantially milder polymerization reaction at temperatures between 10 to 80 C. Thus degradation of the isoprenol is effectively prevented. Preferably, the polymerization is carried out at 10 to 70 C, particularly preferably at 10 to 60 C.
The method according to the invention is generally carried out semi-continuously in the feed-stream procedure. The solvent used is generally water.
According to a preferred embodiment, the polymerization is carried out in aqueous solution with a monomer content of 25 to 50% by weight. In this case the free-radical polymerization is carried out under acidic conditions, generally at pH 0.5 to 6.5. It is preferably performed in such a manner that all monomers (a), (b) and (c) are added as feed, wherein the monoethylenically unsaturated 03-08 monocarboxylic acids (b), e.g. acrylic acid can also be partially neutralized. Isoprenol (a), monoethylenically unsaturated C3-C8 monocarboxylic acid (b), e.g. acrylic acid, and sulfonic acid group-comprising monomer (c), for example 2-acrylamido-2-methylpropanesulfonic acid, can also be charged initially in full or in part. For
- 8 -example, the monomer (c) can be situated in the receiver and the monomers (a) and (b) can be added as feed. (Meth)allylsulfonate as monomer (c) is preferably charged initially.
In a further embodiment, the polymerization is carried out in a water/methanol mixture having a monomer content of 25 to 50% by weight. In a special embodiment, isoprenol in methanol is added as feed. After the end of the polymerization, methanol can be removed under reduced pressure, wherein an aqueous polymer solution is obtained having a solids content of preferably 30 to 60% by weight.
The reducing agent is generally added separately as feed. This lowers the activation threshold of the peroxidic initiator, such that the copolymerization can be carried out at low temperatures.
Generally, the redox chemical initiator comprises a peroxide and a reducing agent.
Suitable peroxides are, for example, hydrogen peroxide, sodium, potassium or ammonium peroxodisulfate, tert-butyl hydroperoxide, dibenzoyl peroxide or cumyl hydroperoxide. In a preferred embodiment, the initiator comprises hydrogen peroxide. Hydrogen peroxide is generally used as aqueous solution, for example having a hydrogen peroxide content of 30%
by weight.
Hydrogen peroxide is preferably situated in the receiver, but can be also added as feed.
Suitable reducing agents are, for example, iron(II) salts, sodium hydroxymethanesulfinate (for example available as Rongalit or BrOggolit SFS), sodium-2-hydroxy-2-sulfinatoacetic acid (for example available as Bruggolit FF06), ascorbic acid, alkali metal sulfites and alkali metal metabisulfites, sodium hypophosphite and thiourea. In a preferred embodiment, the initiator, as reducing agent, comprises sodium hydroxymethanesulfinate or sodium 2-hydroxy-2-sulfinatoacetic acid.
In a further embodiment, the initiator, in addition to the peroxide and the reducing agent, comprises an iron salt.
In a further embodiment, the polymerization is carried out in a water/methanol mixture having a monomer content of 25 to 50% by weight. In a special embodiment, isoprenol in methanol is added as feed. After the end of the polymerization, methanol can be removed under reduced pressure, wherein an aqueous polymer solution is obtained having a solids content of preferably 30 to 60% by weight.
The reducing agent is generally added separately as feed. This lowers the activation threshold of the peroxidic initiator, such that the copolymerization can be carried out at low temperatures.
Generally, the redox chemical initiator comprises a peroxide and a reducing agent.
Suitable peroxides are, for example, hydrogen peroxide, sodium, potassium or ammonium peroxodisulfate, tert-butyl hydroperoxide, dibenzoyl peroxide or cumyl hydroperoxide. In a preferred embodiment, the initiator comprises hydrogen peroxide. Hydrogen peroxide is generally used as aqueous solution, for example having a hydrogen peroxide content of 30%
by weight.
Hydrogen peroxide is preferably situated in the receiver, but can be also added as feed.
Suitable reducing agents are, for example, iron(II) salts, sodium hydroxymethanesulfinate (for example available as Rongalit or BrOggolit SFS), sodium-2-hydroxy-2-sulfinatoacetic acid (for example available as Bruggolit FF06), ascorbic acid, alkali metal sulfites and alkali metal metabisulfites, sodium hypophosphite and thiourea. In a preferred embodiment, the initiator, as reducing agent, comprises sodium hydroxymethanesulfinate or sodium 2-hydroxy-2-sulfinatoacetic acid.
In a further embodiment, the initiator, in addition to the peroxide and the reducing agent, comprises an iron salt.
- 9 -In a particularly preferred embodiment, the redox chemical initiator comprises hydrogen peroxide, an iron salt and also a reducing agent.
Suitable chain-transfer agents are inorganic sulfur compounds such as hydrogen sulfites, disulfites and dithionites, organic sulfides, sulfoxides, sulfones and mercapto compounds such as mercaptoethanol, mercaptoacetic acid and also inorganic phosphorus compounds such as hypophosphorous acid (phosphinic acid) and salts thereof, e.g. sodium hypophosphite.
In a preferred embodiment, the chain-transfer agent comprises a mercapto compound, in particular mercaptoethanol.
The chain-transfer agent is generally added at least in part as feed. A
subquantity of the chain-transfer agent can also be situated in the receiver.
The present invention also relates to the use of the copolymers for inhibiting the precipitation and sedimentation of calcium salts in water-bearing systems, in particular for inhibiting the precipitation and sedimentation of calcium carbonate, calcium sulfate, calcium phosphate or calcium phosphonate. The copolymers according to the invention are distinguished in that they inhibit the precipitation of two or more of said calcium salts.
Water-bearing systems in which the isoprenol-comprising copolymers can be used are, in particular, cooling water systems and boiler feed water systems, and also seawater desalination plants.
Generally, the polymers according to the invention are added to the water-bearing systems in amounts of 0.1 mg/I to 100 mg/1. The optimum dosage depends on the requirements of the respective application and the operating conditions of the respective method.
For instance, in the thermal desalination of seawater the polymers are preferably used in concentrations from 0.5 mg/I to 10 mg/I. In industrial cooling circuits or boiler feed water systems, polymer concentrations up to 100 mg/I are employed. Frequently, water analyses are carried out in order to determine the proportion of deposit-forming salts and therefore the optimum dosage.
Suitable chain-transfer agents are inorganic sulfur compounds such as hydrogen sulfites, disulfites and dithionites, organic sulfides, sulfoxides, sulfones and mercapto compounds such as mercaptoethanol, mercaptoacetic acid and also inorganic phosphorus compounds such as hypophosphorous acid (phosphinic acid) and salts thereof, e.g. sodium hypophosphite.
In a preferred embodiment, the chain-transfer agent comprises a mercapto compound, in particular mercaptoethanol.
The chain-transfer agent is generally added at least in part as feed. A
subquantity of the chain-transfer agent can also be situated in the receiver.
The present invention also relates to the use of the copolymers for inhibiting the precipitation and sedimentation of calcium salts in water-bearing systems, in particular for inhibiting the precipitation and sedimentation of calcium carbonate, calcium sulfate, calcium phosphate or calcium phosphonate. The copolymers according to the invention are distinguished in that they inhibit the precipitation of two or more of said calcium salts.
Water-bearing systems in which the isoprenol-comprising copolymers can be used are, in particular, cooling water systems and boiler feed water systems, and also seawater desalination plants.
Generally, the polymers according to the invention are added to the water-bearing systems in amounts of 0.1 mg/I to 100 mg/1. The optimum dosage depends on the requirements of the respective application and the operating conditions of the respective method.
For instance, in the thermal desalination of seawater the polymers are preferably used in concentrations from 0.5 mg/I to 10 mg/I. In industrial cooling circuits or boiler feed water systems, polymer concentrations up to 100 mg/I are employed. Frequently, water analyses are carried out in order to determine the proportion of deposit-forming salts and therefore the optimum dosage.
- 10 -Formulations can also be added to the water-bearing systems, which formulations, in addition to the copolymers according to the invention, according to requirements, can comprise, inter alia, phosphonates, polyphosphates, zinc salts, molybdate salts, organic corrosion inhibitors such as benzotriazole, tolyltriazole, benzimidazole or ethynyl carbinol alkoxylates, biocides, complexing agents and/or surfactants. Examples of phosphonates are 1-hydroxyethane-1,1-diphosphonic acid (HEDP), 2-phosphonobutane-1,2,4-tricarboxylic acid (PBTC), aminotrimethylenephosphonic acid (ATMP), diethylenetriaminepenta(methylenephosphonic acid) (DTPMP) and ethylenediaminetetra(methylenephosphonic acid) (EDTMP), which are used in the acid form or in the form of sodium salts thereof.
The invention is described in more detail by the examples hereinafter.
Examples The medium molecular weights were determined by means of GPC.
Instrument: Waters Alliance 2690 with UV-detector (Waters 2487) and RI
detector (Waters 2410) Columns: Shodex 0Hpak SB 804HQ and 802.5HQ
(PHM gel, 8 x 300 mm, pH 4.0 to 7.5) Eluent: 0.05 M aqueous ammonium formate/methanol mixture = 80:20 (parts by volume) Flow rate: 0.5 ml/min Temperature: 50 C
Injection: 50 to 100 pl Detection: RI and UV
Molecular weights of the polymers were determined relative to polyacrylic acid standards from Varian Inc. The molecular weight distribution curves of the polyacrylic acid standards were determined by light scattering. The masses of the polyacrylic acid standards were 115 000, 47 500, 28 000, 16 000, 7500, 4500, 4100, 2925 and 1250 g/mol.
Synthesis examples
The invention is described in more detail by the examples hereinafter.
Examples The medium molecular weights were determined by means of GPC.
Instrument: Waters Alliance 2690 with UV-detector (Waters 2487) and RI
detector (Waters 2410) Columns: Shodex 0Hpak SB 804HQ and 802.5HQ
(PHM gel, 8 x 300 mm, pH 4.0 to 7.5) Eluent: 0.05 M aqueous ammonium formate/methanol mixture = 80:20 (parts by volume) Flow rate: 0.5 ml/min Temperature: 50 C
Injection: 50 to 100 pl Detection: RI and UV
Molecular weights of the polymers were determined relative to polyacrylic acid standards from Varian Inc. The molecular weight distribution curves of the polyacrylic acid standards were determined by light scattering. The masses of the polyacrylic acid standards were 115 000, 47 500, 28 000, 16 000, 7500, 4500, 4100, 2925 and 1250 g/mol.
Synthesis examples
-11 -Example 1 IP/AS/AMPS (10/70/20) -Terpolymer In a glass reactor equipped with stirrer, thermometer, pH electrode and a plurality of feed appliances, 125 g of deionized water, 0.5 g of 2-mercaptoethanol and 0.02 g of iron(II) sulfate heptahydrate were charged and brought to and maintained at a polymerization start temperature of 20 C (receiver). In a separate feed vessel, 81 g of 90%
strength by weight acrylic acid were provided (solution A). 10 g of isoprenol were charged (solution B) into a further separate feed vessel. In a further separate feed vessel, 45 g of a 50%
strength by weight aqueous AMPS solution were mixed with 4 g of 2-mercaptoethanol (solution C). In parallel thereto, a third solution of 5 g of sodium hydroxymethanesulfinate (Braggolit SFS from Bruggemann GmbH) in 45 g of water was produced (solution D). Then, 14 g of hydrogen peroxide (30% by weight in water) were added to the receiver mixture. The addition of solution A, solution B, solution C and solution D to the stirred receiver was started simultaneously.
Solution A was added over 60 minutes at a metering rate of 80 g/h.
Solution B was added over a period of 60 minutes in parallel at a metering rate of 10 g/h.
Solution C was added over a period of 60 minutes in parallel at a metering rate of 49 g/h.
Solution D was added over a period of 70 minutes in parallel at a metering rate of 20 g/h.
Then, the polymer solution obtained was adjusted to a pH of 2.6 using a 50%
strength by weight sodium hydroxide solution.
The copolymer obtained was produced in a colorless solution which had a solids content of 37%. The medium molecular weight of the copolymer was Mw 4900 g/mol.
strength by weight acrylic acid were provided (solution A). 10 g of isoprenol were charged (solution B) into a further separate feed vessel. In a further separate feed vessel, 45 g of a 50%
strength by weight aqueous AMPS solution were mixed with 4 g of 2-mercaptoethanol (solution C). In parallel thereto, a third solution of 5 g of sodium hydroxymethanesulfinate (Braggolit SFS from Bruggemann GmbH) in 45 g of water was produced (solution D). Then, 14 g of hydrogen peroxide (30% by weight in water) were added to the receiver mixture. The addition of solution A, solution B, solution C and solution D to the stirred receiver was started simultaneously.
Solution A was added over 60 minutes at a metering rate of 80 g/h.
Solution B was added over a period of 60 minutes in parallel at a metering rate of 10 g/h.
Solution C was added over a period of 60 minutes in parallel at a metering rate of 49 g/h.
Solution D was added over a period of 70 minutes in parallel at a metering rate of 20 g/h.
Then, the polymer solution obtained was adjusted to a pH of 2.6 using a 50%
strength by weight sodium hydroxide solution.
The copolymer obtained was produced in a colorless solution which had a solids content of 37%. The medium molecular weight of the copolymer was Mw 4900 g/mol.
- 12 -Example 2 IP/AS/AMPS (10/70/20) -Terpolymer In a glass reactor equipped with stirrer, thermometer, pH electrode and a plurality of feed appliances, 125 g of deionized water, 0.5 g of 2-mercaptoethanol and 0.02 g of iron(II) sulfate heptahydrate were charged and brought to and maintained at a polymerization start temperature of 20 C (receiver). In a separate feed vessel, 81 g of 90% by weight acrylic acid were provided (solution A). 10 g of isoprenol were charged (solution B) into a further separate feed vessel. In a further separate feed vessel, 45 g of a 50% by weight aqueous AMPS
solution were mixed with 2 g of 2-mercaptoethanol (solution C). In parallel thereto, a third solution of 5 g of sodium hydroxymethanesulfinate (Bruggolit SFS from Bruggemann GmbH) in 45 g of water was produced (solution D). Then, 14 g of hydrogen peroxide (30%
by weight in water) were added to the receiver mixture. The addition of solution A, solution B, solution C
and solution D to the stirred receiver was started simultaneously.
Solution A in this case was added over 60 minutes at a metering rate of 80 g/h.
Solution B was added over said period of 60 minutes in parallel at a metering rate of 10 g/h.
Solution C was added over said period of 60 minutes in parallel at a metering rate of 47 g/h.
Solution D was added over said period of 70 minutes in parallel at a metering rate of 20 g/h.
Then, the polymer solution obtained was adjusted to a pH of 2.6 using a 50%
strength by weight sodium hydroxide solution.
The copolymer obtained was produced as a colorless solution which had a solids content of 36% by weight. The medium molecular weight of the copolymer was Mw 10 000 g/mol.
Example 3
solution were mixed with 2 g of 2-mercaptoethanol (solution C). In parallel thereto, a third solution of 5 g of sodium hydroxymethanesulfinate (Bruggolit SFS from Bruggemann GmbH) in 45 g of water was produced (solution D). Then, 14 g of hydrogen peroxide (30%
by weight in water) were added to the receiver mixture. The addition of solution A, solution B, solution C
and solution D to the stirred receiver was started simultaneously.
Solution A in this case was added over 60 minutes at a metering rate of 80 g/h.
Solution B was added over said period of 60 minutes in parallel at a metering rate of 10 g/h.
Solution C was added over said period of 60 minutes in parallel at a metering rate of 47 g/h.
Solution D was added over said period of 70 minutes in parallel at a metering rate of 20 g/h.
Then, the polymer solution obtained was adjusted to a pH of 2.6 using a 50%
strength by weight sodium hydroxide solution.
The copolymer obtained was produced as a colorless solution which had a solids content of 36% by weight. The medium molecular weight of the copolymer was Mw 10 000 g/mol.
Example 3
- 13 -IP/AS/AMPS (15/60/25) -Terpolymer In a glass reactor equipped with stirrer, thermometer, pH electrode and a plurality of feed appliances, 125 g of deionized water, 0.5 g of 2-mercaptoethanol and 0.02 g of iron(II) sulfate heptahydrate were charged and brought to and maintained at a polymerization start temperature of 20 C. In a separate feed vessel, 81 g of 90% strength by weight acrylic acid were provided (solution A). 18 g of isoprenol were charged (solution B) into a further separate feed vessel. In a further separate feed vessel, 66 g of a 50% strength by weight aqueous AMPS solution were mixed with 4 g of 2-mercaptoethanol (solution C). In parallel thereto, a third solution of 5 g of sodium hydroxymethanesulfinate (BrOggolit SFS from Bruggemann GmbH) in 45 g of water was produced (solution D). Then, 14 g of hydrogen peroxide (30% by weight in water) were added to the receiver mixture. The addition of solution A, solution B, solution C and solution D to the stirred receiver was started simultaneously.
Solution A was added over a period of 60 minutes at a metering rate of 80 g/h.
Solution B was added over a period of 60 minutes in parallel at a metering rate of 18 g/h.
Solution C was added over a period of 60 minutes in parallel at a metering rate of 70 g/h.
Solution D was added over a period of 70 minutes in parallel at a metering rate of 20 g/h.
Then, the polymer solution obtained was adjusted to a pH of 2.6 using a 50%
strength by weight sodium hydroxide solution.
The copolymer obtained was produced as a colorless solution which had a solids content of 39% by weight. The medium molecular weight of the copolymer was Mw 6500 g/mol.
Example 4 IP/AS/AMPS (20/60/20) -Terpolymer = CA 02844514 2014-02-06
Solution A was added over a period of 60 minutes at a metering rate of 80 g/h.
Solution B was added over a period of 60 minutes in parallel at a metering rate of 18 g/h.
Solution C was added over a period of 60 minutes in parallel at a metering rate of 70 g/h.
Solution D was added over a period of 70 minutes in parallel at a metering rate of 20 g/h.
Then, the polymer solution obtained was adjusted to a pH of 2.6 using a 50%
strength by weight sodium hydroxide solution.
The copolymer obtained was produced as a colorless solution which had a solids content of 39% by weight. The medium molecular weight of the copolymer was Mw 6500 g/mol.
Example 4 IP/AS/AMPS (20/60/20) -Terpolymer = CA 02844514 2014-02-06
- 14 -In a glass reactor equipped with stirrer, thermometer, pH electrode and a plurality of feed appliances, 125 g of deionized water, 0.5 g of 2-mercaptoethanol and 0.02 g of iron(II) sulfate heptahydrate were charged and brought to and maintained at a polymerization start temperature of 20 C. In a separate feed vessel, 81 g of 90% strength by weight acrylic acid were provided (solution A). 24 g of isoprenol were charged (solution B) into a further separate feed vessel. In a further separate feed vessel, 53 g of a 50% strength by weight aqueous AMPS solution were mixed with 2 g of 2-mercaptoethanol (solution C). In parallel thereto, a third solution of 5 g of sodium hydroxymethanesulfinate (Bruggolit SFS from BrOggemann GmbH) in 45 g of water was produced (solution D). Then, 14 g of hydrogen peroxide (30% by weight in water) were added to the receiver mixture. The addition of solution A, solution B, solution C and solution D to the stirred receiver was started simultaneously.
Solution A in this case was added over a period of 60 minutes at a metering rate of 80 g/h.
Solution B was added over said period of 60 minutes in parallel at a metering rate of 24 g/h.
Solution C was added over said period of 60 minutes in parallel at a metering rate of 55 g/h.
Solution D was added over said period of 70 minutes in parallel at a metering rate of 20 g/h.
Then, the polymer solution obtained was adjusted to a pH of 2.6 using a 50%
strength by weight sodium hydroxide solution.
The copolymer obtained was produced in a colorless solution which had a solids content of 39%. The medium molecular weight of the copolymer was Mw 11 000 g/mol.
Example 5 IP/AS/ALS (10/70/20) -Terpolymer In a glass reactor equipped with stirrer, thermometer, pH electrode and a plurality of feed appliances, 140 g of deionized water, 20 g of sodium allylsulfonate, 0.5 g of 2-mercaptoethanol
Solution A in this case was added over a period of 60 minutes at a metering rate of 80 g/h.
Solution B was added over said period of 60 minutes in parallel at a metering rate of 24 g/h.
Solution C was added over said period of 60 minutes in parallel at a metering rate of 55 g/h.
Solution D was added over said period of 70 minutes in parallel at a metering rate of 20 g/h.
Then, the polymer solution obtained was adjusted to a pH of 2.6 using a 50%
strength by weight sodium hydroxide solution.
The copolymer obtained was produced in a colorless solution which had a solids content of 39%. The medium molecular weight of the copolymer was Mw 11 000 g/mol.
Example 5 IP/AS/ALS (10/70/20) -Terpolymer In a glass reactor equipped with stirrer, thermometer, pH electrode and a plurality of feed appliances, 140 g of deionized water, 20 g of sodium allylsulfonate, 0.5 g of 2-mercaptoethanol
- 15 -and 0.02 g of iron(II) sulfate heptahydrate were charged and brought to and maintained at a polymerization start temperature of 20 C. In a separate feed vessel, 81 g of 90% strength by weight acrylic acid were provided (solution A). 10 g of isoprenol were charged (solution B) into a further separate feed vessel. In a further separate feed vessel, 15 g of water were mixed with 4 g of 2-mercaptoethanol (solution C). In parallel thereto, a third solution of 5 g of sodium hydroxymethanesulfinate (Bruggolit SFS from Bruggemann GmbH) in 45 g of water was produced (solution D). Then, 14 g of hydrogen peroxide (30% by weight in water) were added to the receiver mixture. The addition of solution A, solution B, solution C
and solution D to the stirred receiver was started simultaneously.
Solution A was added over a period of 60 minutes at a metering rate of 80 g/h.
Solution B was added over a period of 60 minutes in parallel at a metering rate of 10 g/h.
Solution C was added over a period of 60 minutes in parallel at a metering rate of 19 g/h.
Solution D was added over a period of 60 minutes in parallel at a metering rate of 20 g/h.
Then, the polymer solution obtained was adjusted to a pH of 2.6 using a 50%
strength by weight sodium hydroxide solution.
The copolymer obtained was produced in a colorless solution which had a solids content of 38% by weight. The medium molecular weight of the copolymer was Mw 5400 g/mol.
Example 6 IP/AS/ALS (10/75/15) -Terpolymer In a glass reactor equipped with stirrer, thermometer, pH electrode and a plurality of feed appliances, 27 g of deionized water, 14 g of sodium allylsulfonate, 40 g of methanol, 0.5 g of 2-mercaptoethanol and 0.01 g of iron(II) sulfate heptahydrate were charged and brought to and maintained at a polymerization start temperature of 20 C. In a separate feed vessel, 81 g of
and solution D to the stirred receiver was started simultaneously.
Solution A was added over a period of 60 minutes at a metering rate of 80 g/h.
Solution B was added over a period of 60 minutes in parallel at a metering rate of 10 g/h.
Solution C was added over a period of 60 minutes in parallel at a metering rate of 19 g/h.
Solution D was added over a period of 60 minutes in parallel at a metering rate of 20 g/h.
Then, the polymer solution obtained was adjusted to a pH of 2.6 using a 50%
strength by weight sodium hydroxide solution.
The copolymer obtained was produced in a colorless solution which had a solids content of 38% by weight. The medium molecular weight of the copolymer was Mw 5400 g/mol.
Example 6 IP/AS/ALS (10/75/15) -Terpolymer In a glass reactor equipped with stirrer, thermometer, pH electrode and a plurality of feed appliances, 27 g of deionized water, 14 g of sodium allylsulfonate, 40 g of methanol, 0.5 g of 2-mercaptoethanol and 0.01 g of iron(II) sulfate heptahydrate were charged and brought to and maintained at a polymerization start temperature of 20 C. In a separate feed vessel, 81 g of
- 16 -90% strength by weight acrylic acid were provided (solution A). In a further separate feed vessel, 9 g of isoprenol were mixed with 32 g of methanol (solution B). In a further separate feed vessel, 10 g of water were mixed with 3.5 g of 2-mercaptoethanol (solution C). In parallel thereto, a third solution of 5 g of sodium hydroxymethanesulfinate (BrOggolit SFS from Bruggemann GmbH) in 45 g of water was produced (solution D). Then, 6 g of hydrogen peroxide (30% by weight in water) were added to the receiver mixture. The addition of solution A, solution B, solution C and solution D to the stirred receiver was started simultaneously.
Solution A in this case was added over 40 minutes at a metering rate of 120 g/h.
Solution B was added over said period of 40 minutes in parallel at a metering rate of 61 g/h.
Solution C was added over said period of 40 minutes in parallel at a metering rate of 21 g/h.
Solution D was added over said period of 60 minutes in parallel at a metering rate of 10 g/h.
Then, the methanol was removed at reduced pressure. The remaining aqueous polymer solution was adjusted to a pH of 2.6 using a 50% strength by weight sodium hydroxide solution.
The resultant copolymer was produced in a colorless solution which had a solids content of 49%. The medium molecular weight of the copolymer was Mw 4000 g/mol.
Example 7 IP/AS/ALS (15/65/20) -Terpolymer In a glass reactor equipped with stirrer, thermometer, pH electrode and a plurality of feed appliances, 115 g of deionized water, 21 g of sodium allylsulfonate, 0.5 g of 2-mercaptoethanol and 0.01 g of iron(II) sulfate heptahydrate were charged and brought to and maintained at a polymerization start temperature of 20 C. In a separate feed vessel, 81 g of 90% strength by weight acrylic acid were mixed with 64 g of water (solution A). 16.5 g of isoprenol were
Solution A in this case was added over 40 minutes at a metering rate of 120 g/h.
Solution B was added over said period of 40 minutes in parallel at a metering rate of 61 g/h.
Solution C was added over said period of 40 minutes in parallel at a metering rate of 21 g/h.
Solution D was added over said period of 60 minutes in parallel at a metering rate of 10 g/h.
Then, the methanol was removed at reduced pressure. The remaining aqueous polymer solution was adjusted to a pH of 2.6 using a 50% strength by weight sodium hydroxide solution.
The resultant copolymer was produced in a colorless solution which had a solids content of 49%. The medium molecular weight of the copolymer was Mw 4000 g/mol.
Example 7 IP/AS/ALS (15/65/20) -Terpolymer In a glass reactor equipped with stirrer, thermometer, pH electrode and a plurality of feed appliances, 115 g of deionized water, 21 g of sodium allylsulfonate, 0.5 g of 2-mercaptoethanol and 0.01 g of iron(II) sulfate heptahydrate were charged and brought to and maintained at a polymerization start temperature of 20 C. In a separate feed vessel, 81 g of 90% strength by weight acrylic acid were mixed with 64 g of water (solution A). 16.5 g of isoprenol were
- 17 -charged (solution B) into a further separate feed vessel. In a further separate feed vessel, 10 g of water were mixed with 3.5 g of 2-mercaptoethanol (solution C). In parallel thereto, a third solution of 5 g of sodium hydroxymethanesulfinate (Bruggolit SFS from Bruggemann GmbH) in 45 g of water was produced (solution D). Then, 6 g of hydrogen peroxide (30%
by weight in water) were added to the receiver mixture. The addition of solution A, solution B, solution C
and solution D to the stirred receiver was started simultaneously.
Solution A was added in this case over 60 minutes at a metering rate of 145 g/h.
Solution B was added over said period of 60 minutes in parallel at a metering rate of 16.5 g/h.
Solution C was added over said period of 60 minutes in parallel at a metering rate of 13.5 g/h.
Solution D was added over said period of 60 minutes in parallel at a metering rate of 12 g/h.
Then, methanol was removed under reduced pressure. The remaining aqueous polymer solution was adjusted to a pH of 2.6 using a roughly 50% strength by weight sodium hydroxide solution.
The copolymer obtained was produced in a colorless solution which had a solids content of 38% by weight. The medium molecular weight of the copolymer was Mw 6200 g/mol.
Example 8 IP/AS/ALS (20/60/20) -Terpolymer In a glass reactor equipped with stirrer, thermometer, pH electrode and a plurality of feed appliances, 140 g of deionized water, 31 g of sodium allylsulfonate, 0.5 g of 2-mercaptoethanol and 0.02 g of iron(II) sulfate heptahydrate were charged and brought to and maintained at a polymerization start temperature of 20 C. In a separate feed vessel, 81 g of 90% strength by weight acrylic acid were provided (solution A). 24 g of isoprenol were charged (solution B) into a further separate feed vessel. In a further separate feed vessel, 15 g of water were mixed with
by weight in water) were added to the receiver mixture. The addition of solution A, solution B, solution C
and solution D to the stirred receiver was started simultaneously.
Solution A was added in this case over 60 minutes at a metering rate of 145 g/h.
Solution B was added over said period of 60 minutes in parallel at a metering rate of 16.5 g/h.
Solution C was added over said period of 60 minutes in parallel at a metering rate of 13.5 g/h.
Solution D was added over said period of 60 minutes in parallel at a metering rate of 12 g/h.
Then, methanol was removed under reduced pressure. The remaining aqueous polymer solution was adjusted to a pH of 2.6 using a roughly 50% strength by weight sodium hydroxide solution.
The copolymer obtained was produced in a colorless solution which had a solids content of 38% by weight. The medium molecular weight of the copolymer was Mw 6200 g/mol.
Example 8 IP/AS/ALS (20/60/20) -Terpolymer In a glass reactor equipped with stirrer, thermometer, pH electrode and a plurality of feed appliances, 140 g of deionized water, 31 g of sodium allylsulfonate, 0.5 g of 2-mercaptoethanol and 0.02 g of iron(II) sulfate heptahydrate were charged and brought to and maintained at a polymerization start temperature of 20 C. In a separate feed vessel, 81 g of 90% strength by weight acrylic acid were provided (solution A). 24 g of isoprenol were charged (solution B) into a further separate feed vessel. In a further separate feed vessel, 15 g of water were mixed with
- 18-3 g of 2-mercaptoethanol (solution C). In parallel thereto, a third solution of 5 g of sodium hydroxymethanesulfinate (Bruggolit SFS from Bruggemann GmbH) in 45 g of water was produced (solution D). Then, 14 g of hydrogen peroxide (30% by weight in water) were added to the receiver mixture. The addition of solution A, solution B, solution C
and solution D to the stirred receiver was started simultaneously.
Solution A was added over a period of 60 minutes at a metering rate of 80 g/h.
Solution B was added over said period of 60 minutes in parallel at a metering rate of 24 g/h.
Solution C was added over said period of 60 minutes in parallel at a metering rate of 18 g/h.
Solution D was added over said period of 70 minutes in parallel at a metering rate of 20 g/h.
Then, the polymer solution obtained was adjusted to a pH of 2.6 using a roughly 50% strength by weight sodium hydroxide solution.
The copolymer obtained was produced in a colorless solution which had a solids content of 41%. The medium molecular weight of the copolymer was Mw 8100 g/mol.
Comparative example A
Polyacrylic acid A
In a reactor, 304.0 g of deionized water were charged together with 1.84 g of a 50% strength by weight aqueous solution of phosphorous acid and heated under a nitrogen atmosphere to 98 C internal temperature. At this temperature, simultaneously, 461.0 g of a distilled acrylic acid, 132.0 g of a 7% strength by weight sodium peroxodisulfate solution and 196.0 g of a 40%
strength by weight aqueous sodium bisulfite solution were added separately and in parallel with stirring. Acrylic acid was added in the course of 4 hours, sodium peroxodisulfate in the course of 4.25 hours and sodium bisulfite in the course of 3.75 hours. After completion of the acrylic acid feed, 496.0 g of a 50% strength by weight aqueous sodium hydroxide solution were added in the course of 1 hour at 98 C internal temperature, and polymerization was
and solution D to the stirred receiver was started simultaneously.
Solution A was added over a period of 60 minutes at a metering rate of 80 g/h.
Solution B was added over said period of 60 minutes in parallel at a metering rate of 24 g/h.
Solution C was added over said period of 60 minutes in parallel at a metering rate of 18 g/h.
Solution D was added over said period of 70 minutes in parallel at a metering rate of 20 g/h.
Then, the polymer solution obtained was adjusted to a pH of 2.6 using a roughly 50% strength by weight sodium hydroxide solution.
The copolymer obtained was produced in a colorless solution which had a solids content of 41%. The medium molecular weight of the copolymer was Mw 8100 g/mol.
Comparative example A
Polyacrylic acid A
In a reactor, 304.0 g of deionized water were charged together with 1.84 g of a 50% strength by weight aqueous solution of phosphorous acid and heated under a nitrogen atmosphere to 98 C internal temperature. At this temperature, simultaneously, 461.0 g of a distilled acrylic acid, 132.0 g of a 7% strength by weight sodium peroxodisulfate solution and 196.0 g of a 40%
strength by weight aqueous sodium bisulfite solution were added separately and in parallel with stirring. Acrylic acid was added in the course of 4 hours, sodium peroxodisulfate in the course of 4.25 hours and sodium bisulfite in the course of 3.75 hours. After completion of the acrylic acid feed, 496.0 g of a 50% strength by weight aqueous sodium hydroxide solution were added in the course of 1 hour at 98 C internal temperature, and polymerization was
- 19 -continued for a further 1 hour at 98 C. Thereafter, the polymer solution was cooled to room temperature. A slightly viscose clear polymer solution was obtained having a pH of 6.9 and a solids content of 43.5%. The weight average molecular weight (Mw) is 4450 g/mol Comparative example B
AS/AMPS (80/20) ¨Copolymer In a glass reactor equipped with stirrer, thermometer, pH electrode and a plurality of feed appliances, 100 g of deionized water, 0.5 g of 2-mercaptoethanol and 0.01 g of iron(II) sulfate heptahydrate were charged and brought to and maintained at a polymerization start temperature of 20 C. In a separate feed vessel, 88 g of 90% strength by weight acrylic acid (solution A) were provided. In a further separate feed vessel, 40 g of a 50%
strength by weight aqueous AMPS solution were mixed with 3.5 g of 2-mercaptoethanol (solution B).
In parallel thereto, a third solution of 5 g of sodium hydroxymethanesulfinate (Bruggolit SFS from Bruggemann GmbH) in 45 g of water was produced (solution C). Then, 6 g of hydrogen peroxide (30% by weight in water) were added to the receiver mixture. The addition of solution A, solution B and solution C to the stirred receiver was started simultaneously.
Solution A was added over a period of 60 minutes at a metering rate of 88 g/h.
Solution B was added over a period of 60 minutes in parallel at a metering rate of 44 g/h.
Solution C was added over said period of 60 minutes in parallel at a metering rate of 10 g/h.
Then, the polymer solution obtained was adjusted to a pH of 2.6 using an about 50% strength by weight sodium hydroxide solution.
The copolymer obtained was produced in a colorless solution which had a solids content of 39% by weight. The medium molecular weight of the copolymer was Mw 6500 g/mol.
AS/AMPS (80/20) ¨Copolymer In a glass reactor equipped with stirrer, thermometer, pH electrode and a plurality of feed appliances, 100 g of deionized water, 0.5 g of 2-mercaptoethanol and 0.01 g of iron(II) sulfate heptahydrate were charged and brought to and maintained at a polymerization start temperature of 20 C. In a separate feed vessel, 88 g of 90% strength by weight acrylic acid (solution A) were provided. In a further separate feed vessel, 40 g of a 50%
strength by weight aqueous AMPS solution were mixed with 3.5 g of 2-mercaptoethanol (solution B).
In parallel thereto, a third solution of 5 g of sodium hydroxymethanesulfinate (Bruggolit SFS from Bruggemann GmbH) in 45 g of water was produced (solution C). Then, 6 g of hydrogen peroxide (30% by weight in water) were added to the receiver mixture. The addition of solution A, solution B and solution C to the stirred receiver was started simultaneously.
Solution A was added over a period of 60 minutes at a metering rate of 88 g/h.
Solution B was added over a period of 60 minutes in parallel at a metering rate of 44 g/h.
Solution C was added over said period of 60 minutes in parallel at a metering rate of 10 g/h.
Then, the polymer solution obtained was adjusted to a pH of 2.6 using an about 50% strength by weight sodium hydroxide solution.
The copolymer obtained was produced in a colorless solution which had a solids content of 39% by weight. The medium molecular weight of the copolymer was Mw 6500 g/mol.
- 20 -Comparative example C
AS/AMPS/tBAM (70:20:10) -Terpolymer In a glass reactor equipped with stirrer, thermometer, pH electrode and a plurality of feed appliances, 70 g of deionized water, 0.25 g of 2-mercaptoethanol and 0.02 g of iron(II) sulfate heptahydrate were charged and brought to and maintained at a polymerization start temperature of 20 C (receiver). In a separate feed vessel, 80 g of 90%
strength by weight acrylic acid were neutralized with 62 g of 50% sodium hydroxide solution (solution A). In a further separate feed vessel, 41 g of a 50% strength by weight aqueous AMPS
solution were mixed with 4 g of 2-mercaptoethanol (solution B). In a further feed solution, 12 g of tert-butylacrylamide were mixed with 45 g of methanol (solution C).
In parallel thereto, a solution of 5 g of sodium hydroxymethanesulfinate (Bruggolit SFS from Bruggemann GmbH) in 45 g of water was produced (solution D). Then, 6 g of hydrogen peroxide (30% by weight in water) were added to the receiver mixture. The addition of solution A, solution B, solution C and solution D to the stirred receiver was started simultaneously.
Solution A was added in this case over 60 minutes at a metering rate of 80 g/h.
Solution B was added over said period of 60 minutes in parallel at a metering rate of 45 g/h.
Solution C was added over said period of 60 minutes in parallel at a metering rate of 47 g/h.
Solution D was added over said period of 70 minutes in parallel at a metering rate of 15 g/h.
Then, the methanol was removed under reduced pressure. The remaining aqueous polymer solution was adjusted to a pH of 2.6 using a 50% strength by weight sodium hydroxide solution.
. CA 02844514 2014-02-06
AS/AMPS/tBAM (70:20:10) -Terpolymer In a glass reactor equipped with stirrer, thermometer, pH electrode and a plurality of feed appliances, 70 g of deionized water, 0.25 g of 2-mercaptoethanol and 0.02 g of iron(II) sulfate heptahydrate were charged and brought to and maintained at a polymerization start temperature of 20 C (receiver). In a separate feed vessel, 80 g of 90%
strength by weight acrylic acid were neutralized with 62 g of 50% sodium hydroxide solution (solution A). In a further separate feed vessel, 41 g of a 50% strength by weight aqueous AMPS
solution were mixed with 4 g of 2-mercaptoethanol (solution B). In a further feed solution, 12 g of tert-butylacrylamide were mixed with 45 g of methanol (solution C).
In parallel thereto, a solution of 5 g of sodium hydroxymethanesulfinate (Bruggolit SFS from Bruggemann GmbH) in 45 g of water was produced (solution D). Then, 6 g of hydrogen peroxide (30% by weight in water) were added to the receiver mixture. The addition of solution A, solution B, solution C and solution D to the stirred receiver was started simultaneously.
Solution A was added in this case over 60 minutes at a metering rate of 80 g/h.
Solution B was added over said period of 60 minutes in parallel at a metering rate of 45 g/h.
Solution C was added over said period of 60 minutes in parallel at a metering rate of 47 g/h.
Solution D was added over said period of 70 minutes in parallel at a metering rate of 15 g/h.
Then, the methanol was removed under reduced pressure. The remaining aqueous polymer solution was adjusted to a pH of 2.6 using a 50% strength by weight sodium hydroxide solution.
. CA 02844514 2014-02-06
- 21 -The copolymer obtained was produced in a colorless solution which had a solids content of 40% by weight. The medium molecular weight of the copolymer was Mw 5800 g/mol.
Calcium carbonate inhibition test A solution of NaHCO3, Mg2SO4, CaCl2 and polymer is shaken for 2 h at 70 C in waterbath.
After filtration of the still warm solution through a 0.45 pm Milex filter, the Ca content of the filtrate is determined by optical emission spectrometry using inductively coupled plasma (ICP-OES) and determined in accordance with the formula I hereinafter by comparing before/after the CaCO3 inhibition in %.
Conditions:
Ca2+ 215 mg/I
mg2+ 43 mg/I
HCO3- 1220 mg/I
Na + 460 mg/I
Cl- 380 mg/I
S042" 170 mg/I
Polymer 100% pure 3 mg/I
Temperature 70 C
Time 2 hours pH 8.0-8.5 Formula I:
CaCO3- inhibition (%) = mg (Ca2+) after 24 h ¨ mg (Ca2+) blank value after 24 h/mg (Ca2+) zero value ¨ mg (Ca2+) blank value after 24 h x 100 = CA 02844514 2014-02-06
Calcium carbonate inhibition test A solution of NaHCO3, Mg2SO4, CaCl2 and polymer is shaken for 2 h at 70 C in waterbath.
After filtration of the still warm solution through a 0.45 pm Milex filter, the Ca content of the filtrate is determined by optical emission spectrometry using inductively coupled plasma (ICP-OES) and determined in accordance with the formula I hereinafter by comparing before/after the CaCO3 inhibition in %.
Conditions:
Ca2+ 215 mg/I
mg2+ 43 mg/I
HCO3- 1220 mg/I
Na + 460 mg/I
Cl- 380 mg/I
S042" 170 mg/I
Polymer 100% pure 3 mg/I
Temperature 70 C
Time 2 hours pH 8.0-8.5 Formula I:
CaCO3- inhibition (%) = mg (Ca2+) after 24 h ¨ mg (Ca2+) blank value after 24 h/mg (Ca2+) zero value ¨ mg (Ca2+) blank value after 24 h x 100 = CA 02844514 2014-02-06
- 22 -Calcium sulfate inhibition test A solution of NaCI, Na2SO4, CaCl2 and polymer was shaken for 24 h at 70 C in a waterbath.
After filtration of the still warm solution through a 0.45 pm Milex filter, the Ca content of the filtrate is determined by optical emission spectrometry using inductively coupled plasma (ICP-OES) and determined by comparison of before/after the CaSO4 inhibition in %
according to the formula II hereinafter.
Conditions:
Ca2+ 2940 mg/I
S042- 7200 mg/I
Na + 6400 mg/I
CI- 9700 mg/I
Polymer 100% pure 5 mg/I (100% pure) Temperature 90 C
Time 24 hours pH 8.0-8.5 Formula II:
CaSO4- inhibition (%) = mg (Ca2+) after 24 h ¨ mg (Ca2+) blank value after 24 h/mg (Ca2+) zero value - mg (Ca2+) blank value after 24 h x 100 Calcium phosphate inhibition test A solution of H3PO4, CaCl2, NaHCO3, MgSO4 and polymer was shaken for 24 h at 70 C in a waterbath. After filtration of the still warm solution through a 0.45 pm Milex filter, the phosphate content of the filtrate is determined by optical emission spectrometry using inductively coupled plasma (ICP-OES) and by comparison of before/after the Ca3(PO4)2 inhibition in % according to formula III hereinafter:
= CA 02844514 2014-02-06
After filtration of the still warm solution through a 0.45 pm Milex filter, the Ca content of the filtrate is determined by optical emission spectrometry using inductively coupled plasma (ICP-OES) and determined by comparison of before/after the CaSO4 inhibition in %
according to the formula II hereinafter.
Conditions:
Ca2+ 2940 mg/I
S042- 7200 mg/I
Na + 6400 mg/I
CI- 9700 mg/I
Polymer 100% pure 5 mg/I (100% pure) Temperature 90 C
Time 24 hours pH 8.0-8.5 Formula II:
CaSO4- inhibition (%) = mg (Ca2+) after 24 h ¨ mg (Ca2+) blank value after 24 h/mg (Ca2+) zero value - mg (Ca2+) blank value after 24 h x 100 Calcium phosphate inhibition test A solution of H3PO4, CaCl2, NaHCO3, MgSO4 and polymer was shaken for 24 h at 70 C in a waterbath. After filtration of the still warm solution through a 0.45 pm Milex filter, the phosphate content of the filtrate is determined by optical emission spectrometry using inductively coupled plasma (ICP-OES) and by comparison of before/after the Ca3(PO4)2 inhibition in % according to formula III hereinafter:
= CA 02844514 2014-02-06
- 23 -Conditions:
Ca2+ 148 mg/I
38 mg/I
P043- 10 mg/I
S042- 157 mg/I
Cl- 263 mg/I
Na + 146 mg/I
HCO3- 388 mg/I
Polymer 100% pure 15 mg/I
Temperature 70 C
Time 24 hours pH 8.0 to 8.5 Formula III:
Ca3(PO4)2- inhibition (%) = mg (P043-) after 24 h ¨ mg (P043") blank value after 24 h/mg (P043-) zero value - mg (P043") blank value after 24 h x 100 The results of the tests are summarized in the table hereinafter.
Table No. Monomer Weight M, Inhibition Inhibition Inhibition g/mol CaSO4 in Ca3(PO4)2 CaCO3 in %
in %
Ca2+ 148 mg/I
38 mg/I
P043- 10 mg/I
S042- 157 mg/I
Cl- 263 mg/I
Na + 146 mg/I
HCO3- 388 mg/I
Polymer 100% pure 15 mg/I
Temperature 70 C
Time 24 hours pH 8.0 to 8.5 Formula III:
Ca3(PO4)2- inhibition (%) = mg (P043-) after 24 h ¨ mg (P043") blank value after 24 h/mg (P043-) zero value - mg (P043") blank value after 24 h x 100 The results of the tests are summarized in the table hereinafter.
Table No. Monomer Weight M, Inhibition Inhibition Inhibition g/mol CaSO4 in Ca3(PO4)2 CaCO3 in %
in %
- 24 -A Polyacrylic acid A 4500 60 15 3 - C AS/AMPS/tBAM 70/20/10 5800 45 29 72 Abbreviations:
IP = Isoprenol AS = Acrylic acid ALS = Allylsulfonic acid sodium salt AMPS = 2-Acrylamido-2-methylpropanesulfonic acid tBAM = tert-Butylacrylamide
IP = Isoprenol AS = Acrylic acid ALS = Allylsulfonic acid sodium salt AMPS = 2-Acrylamido-2-methylpropanesulfonic acid tBAM = tert-Butylacrylamide
Claims (17)
1. A copolymer of (a) 5 to 40% by weight of isoprenol, (b) 5 to 93% by weight of at least one monoethylenically unsaturated C3 to C8 monocarboxylic acid, an anhydride or salt of same, (c) 2 to 90% by weight of one or more sulfonic acid group-comprising monomers.
2. The copolymer according to claim 1, wherein the monoethylenically unsaturated C3-C8 monocarboxylic acid (b) is selected from the group consisting of acrylic acid, methacrylic acid, ethacrylic acid, vinylacetic acid, allylacetic acid and crotonic acid.
3. The copolymer according to claim 2, wherein the monoethylenically unsaturated C3-C8 monocarboxylic acid (b) is acrylic acid or methacrylic acid.
4. The copolymer according to any one of claims 1 to 3, wherein the sulfonic acid group-comprising monomer (c) is selected from the group consisting of 1-acrylamidopropanesulfonic acid, 2-acrylamido-2-propanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid (AMPS), 2-methacrylamido-2-methylpropanesulfonic acid, 3-methacrylamido-2-hydroxypropanesulfonic acid, 2-sulfoethyl methacrylate, styrenesulfonic acid, vinylsulfonic acid, allylsulfonic acid (ALS) and methallylsulfonic acid.
5. The copolymer according to claim 4, wherein the sulfonic acid group-comprising monomer (c) is 2-acrylamido-2-methylpropanesulfonic acid (AMPS) or allylsulfonic acid.
6. The copolymer according to any one of claims 1 to 5, wherein the weight-average molecular weight thereof is 2000 to 20 000 g/mol.
7. The copolymer according to claim 6, wherein 5 to 30% by weight of isoprenol (a), 50 to 80% by weight of the monoethylenically unsaturated C3 to C8 carboxylic acid (b) and 10 to 30% by weight of the sulfonic acid group-comprising monomer (c) are present.
8. A method for producing copolymers of (a) 5 to 40% by weight of isoprenol, (b) 5 to 93% by weight of at least one monoethylenically unsaturated C3 to C8 monocarboxylic acid, an anhydride or salt of same, (c) 2 to 90% by weight of one or more sulfonic acid group-comprising monomers, in which the monomers (a), (b) and (c) are polymerized in the presence of a redox chemical initiator and a chain-transfer agent at a temperature in the range from 10 to 80°C.
9. The method according to claim 8, wherein the redox chemical initiator comprises a peroxide and a reducing agent.
10. The method according to claim 9, wherein the redox chemical initiator additionally comprises an iron salt.
11. The method according to claim 9 or 10, wherein the redox chemical initiator, as peroxide, comprises hydrogen peroxide.
12. The method according to any one of claims 9 to 11, wherein the redox chemical initiator as reducing agent, comprises sodium hydroxymethanesulfinate or sodium-2-hydroxy-2-sulfinatoacetic acid.
13. The method according to any one of claims 8 to 12, wherein the chain-transfer agent comprises a mercapto compound.
14. The use of the copolymer according to any one of claims 1 to 7 as deposit inhibitor in water-bearing systems.
15. The use of the copolymer according to any one of claims 1 to 7 for inhibiting the precipitation and sedimentation of calcium salts or magnesium salts in water-bearing systems.
16. The use according to claim 15 for inhibiting the precipitation and sedimentation of calcium carbonate, calcium sulfate, calcium phosphate or calcium phosphonate.
17. The use according to claim 15 or 16 in seawater desalination plants, brackish water desalination plants, cooling water systems and boiler feed water
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
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| EP11177170 | 2011-08-10 | ||
| EP11177170.5 | 2011-08-10 | ||
| PCT/EP2012/064406 WO2013020799A1 (en) | 2011-08-10 | 2012-07-23 | Copolymers made of isoprenol, monoethylenically unsaturated monocarboxylic acids and sulphonic acids, process for producing same and use of same as deposit inhibitors in systems conveying water |
Publications (2)
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| CA2844514A1 true CA2844514A1 (en) | 2013-02-14 |
| CA2844514C CA2844514C (en) | 2019-07-16 |
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| CA2844514A Expired - Fee Related CA2844514C (en) | 2011-08-10 | 2012-07-23 | Copolymers of isoprenol, monoethylenically unsaturated monocarboxylic acids and sulphonic acids, methods for production thereof and use thereof as deposit inhibitors in water-bearing systems |
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| EP (1) | EP2742075B1 (en) |
| JP (1) | JP6120847B2 (en) |
| KR (1) | KR101879183B1 (en) |
| CN (1) | CN103890022B (en) |
| AU (1) | AU2012292468B2 (en) |
| BR (1) | BR112014002935B1 (en) |
| CA (1) | CA2844514C (en) |
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| RU (1) | RU2632991C2 (en) |
| TN (1) | TN2014000053A1 (en) |
| WO (1) | WO2013020799A1 (en) |
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| CN105647678B (en) * | 2016-01-14 | 2018-05-15 | 广州立白企业集团有限公司 | Lift method and detergent composition of the cleaning compositions to albumen soil removal capabilities |
| CN114671982A (en) * | 2022-02-24 | 2022-06-28 | 浙江鑫月新材料科技有限公司 | A kind of shrinkage-reducing polycarboxylate water-reducing agent and preparation method thereof |
| FR3150808A1 (en) * | 2023-07-07 | 2025-01-10 | Snf Sa | Polymer, its preparation and use as a scale inhibitor |
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| JPS59102496A (en) * | 1982-12-06 | 1984-06-13 | Nippon Shokubai Kagaku Kogyo Co Ltd | Scale inhibitor |
| JPS59108010A (en) * | 1982-12-10 | 1984-06-22 | Nippon Shokubai Kagaku Kogyo Co Ltd | Dispersing agent for inorganic pigment |
| US4711725A (en) | 1985-06-26 | 1987-12-08 | Rohm And Haas Co. | Method of stabilizing aqueous systems |
| US4952327A (en) | 1986-12-08 | 1990-08-28 | The B. F. Goodrich Company | Scale control with terpolymers containing styrene sulfonic acid |
| US5135677A (en) * | 1988-04-11 | 1992-08-04 | Nippon Shokubai Co., Ltd. | Process for producing acid-type maleic acid polymer and water-treating agent and detergent additive containing said polymer |
| EP0337694B1 (en) * | 1988-04-11 | 1993-12-29 | Nippon Shokubai Co., Ltd. | Process for producing acid-type maleic acid polymer and water-treating agent and detergent additive containing said polymer |
| DE69015424T2 (en) * | 1989-04-28 | 1995-08-17 | Nippon Catalytic Chem Ind | Process for the preparation and use of salts of polymers of maleic acid with improved biodegradability. |
| CA2236605A1 (en) * | 1997-05-09 | 1998-11-09 | Yves Duccini | Scale inhibitors |
| US6756460B2 (en) * | 2000-08-22 | 2004-06-29 | Nippon Shokubai Co., Ltd. | Water-soluble copolymer and its production process and use |
| JP4739657B2 (en) * | 2002-08-29 | 2011-08-03 | 株式会社日本触媒 | Method for producing sulfur-containing unsaturated carboxylic acid polymer |
| ATE459655T1 (en) * | 2005-08-31 | 2010-03-15 | Nippon Catalytic Chem Ind | CONTINUOUS MANUFACTURING PROCESS FOR WATER SOLUBLE POLYMER AND WATER SOLUBLE POLYMER |
| ES2502524T3 (en) * | 2008-03-19 | 2014-10-03 | Construction Research & Technology Gmbh | Semi-continuously operated method for the production of copolymers |
| US7973110B2 (en) * | 2008-06-16 | 2011-07-05 | Construction Research & Technology Gmbh | Copolymer synthesis process |
| EP2373705B1 (en) * | 2008-12-08 | 2013-03-27 | Construction Research & Technology GmbH | Copolymer containing acid building blocks and various types of polyether building blocks |
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2012
- 2012-07-23 BR BR112014002935-0A patent/BR112014002935B1/en active IP Right Grant
- 2012-07-23 MX MX2014001453A patent/MX353846B/en active IP Right Grant
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- 2012-07-23 AU AU2012292468A patent/AU2012292468B2/en active Active
- 2012-07-23 RU RU2014108708A patent/RU2632991C2/en not_active IP Right Cessation
- 2012-07-23 CA CA2844514A patent/CA2844514C/en not_active Expired - Fee Related
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- 2012-07-23 JP JP2014524323A patent/JP6120847B2/en not_active Expired - Fee Related
- 2012-07-23 WO PCT/EP2012/064406 patent/WO2013020799A1/en not_active Ceased
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- 2012-07-23 CN CN201280049579.XA patent/CN103890022B/en active Active
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- 2014-02-09 IL IL230885A patent/IL230885A/en active IP Right Grant
- 2014-02-10 CL CL2014000335A patent/CL2014000335A1/en unknown
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| BR112014002935A2 (en) | 2017-04-04 |
| JP6120847B2 (en) | 2017-04-26 |
| AU2012292468B2 (en) | 2015-11-05 |
| RU2014108708A (en) | 2015-09-20 |
| ES2568912T3 (en) | 2016-05-05 |
| TN2014000053A1 (en) | 2015-07-01 |
| WO2013020799A1 (en) | 2013-02-14 |
| IL230885A0 (en) | 2014-03-31 |
| EP2742075A1 (en) | 2014-06-18 |
| KR101879183B1 (en) | 2018-08-17 |
| MX2014001453A (en) | 2014-02-27 |
| KR20140045554A (en) | 2014-04-16 |
| CL2014000335A1 (en) | 2014-08-01 |
| IL230885A (en) | 2017-02-28 |
| CN103890022B (en) | 2016-10-12 |
| RU2632991C2 (en) | 2017-10-12 |
| BR112014002935B1 (en) | 2020-10-13 |
| MA35339B1 (en) | 2014-08-01 |
| AU2012292468A1 (en) | 2014-02-27 |
| JP2014528977A (en) | 2014-10-30 |
| EP2742075B1 (en) | 2016-03-02 |
| CA2844514C (en) | 2019-07-16 |
| CN103890022A (en) | 2014-06-25 |
| MX353846B (en) | 2018-01-31 |
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