WO1999061545A1 - Diesel engine antifreeze composition - Google Patents
Diesel engine antifreeze composition Download PDFInfo
- Publication number
- WO1999061545A1 WO1999061545A1 PCT/US1999/011324 US9911324W WO9961545A1 WO 1999061545 A1 WO1999061545 A1 WO 1999061545A1 US 9911324 W US9911324 W US 9911324W WO 9961545 A1 WO9961545 A1 WO 9961545A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- antifreeze
- sodium
- weight
- salt
- coolant
- Prior art date
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 108
- 230000002528 anti-freeze Effects 0.000 title claims description 70
- 238000005260 corrosion Methods 0.000 claims abstract description 91
- 230000007797 corrosion Effects 0.000 claims abstract description 83
- 239000002826 coolant Substances 0.000 claims abstract description 78
- 229920005646 polycarboxylate Polymers 0.000 claims abstract description 59
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 42
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 29
- 235000021317 phosphate Nutrition 0.000 claims abstract description 26
- 150000002823 nitrates Chemical class 0.000 claims abstract description 20
- 229910052751 metal Inorganic materials 0.000 claims abstract description 19
- 239000002184 metal Substances 0.000 claims abstract description 19
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims abstract description 13
- 150000003851 azoles Chemical class 0.000 claims abstract description 12
- 230000002401 inhibitory effect Effects 0.000 claims abstract description 11
- 150000003623 transition metal compounds Chemical class 0.000 claims abstract description 11
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 150000002739 metals Chemical class 0.000 claims abstract description 10
- 229910052500 inorganic mineral Inorganic materials 0.000 claims abstract description 4
- 239000011707 mineral Substances 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 49
- -1 azole compound Chemical class 0.000 claims description 44
- 150000003839 salts Chemical class 0.000 claims description 29
- 229920002125 Sokalan® Polymers 0.000 claims description 27
- 229920001577 copolymer Polymers 0.000 claims description 23
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 claims description 22
- 150000002826 nitrites Chemical class 0.000 claims description 17
- KAESVJOAVNADME-UHFFFAOYSA-N 1H-pyrrole Natural products C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 239000010452 phosphate Substances 0.000 claims description 16
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 15
- 239000004584 polyacrylic acid Substances 0.000 claims description 14
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 13
- LWIHDJKSTIGBAC-UHFFFAOYSA-K potassium phosphate Substances [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 claims description 13
- 159000000000 sodium salts Chemical class 0.000 claims description 13
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 12
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 12
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 11
- 239000011734 sodium Substances 0.000 claims description 11
- 229910052708 sodium Inorganic materials 0.000 claims description 11
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 10
- 239000013256 coordination polymer Substances 0.000 claims description 10
- 239000001488 sodium phosphate Substances 0.000 claims description 10
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 10
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 9
- CMGDVUCDZOBDNL-UHFFFAOYSA-N 4-methyl-2h-benzotriazole Chemical compound CC1=CC=CC2=NNN=C12 CMGDVUCDZOBDNL-UHFFFAOYSA-N 0.000 claims description 9
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 9
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 9
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 9
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 9
- 239000011591 potassium Substances 0.000 claims description 9
- 229910052700 potassium Inorganic materials 0.000 claims description 9
- 239000011976 maleic acid Substances 0.000 claims description 8
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 claims description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 7
- 150000003333 secondary alcohols Chemical class 0.000 claims description 7
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims description 6
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 claims description 6
- 229910000396 dipotassium phosphate Inorganic materials 0.000 claims description 6
- 235000019797 dipotassium phosphate Nutrition 0.000 claims description 6
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 6
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 6
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims description 6
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 claims description 6
- 229920001296 polysiloxane Polymers 0.000 claims description 6
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 6
- 239000011684 sodium molybdate Substances 0.000 claims description 6
- 235000015393 sodium molybdate Nutrition 0.000 claims description 6
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 6
- 239000004317 sodium nitrate Substances 0.000 claims description 6
- 235000010344 sodium nitrate Nutrition 0.000 claims description 6
- VLDHWMAJBNWALQ-UHFFFAOYSA-M sodium;1,3-benzothiazol-3-ide-2-thione Chemical compound [Na+].C1=CC=C2SC([S-])=NC2=C1 VLDHWMAJBNWALQ-UHFFFAOYSA-M 0.000 claims description 6
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 5
- 239000013530 defoamer Substances 0.000 claims description 5
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 4
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims description 4
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 4
- 229910000402 monopotassium phosphate Inorganic materials 0.000 claims description 4
- 235000019796 monopotassium phosphate Nutrition 0.000 claims description 4
- 235000010288 sodium nitrite Nutrition 0.000 claims description 4
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 4
- 229910000406 trisodium phosphate Inorganic materials 0.000 claims description 4
- 235000019801 trisodium phosphate Nutrition 0.000 claims description 4
- UCTUNCJCTXXXGJ-UHFFFAOYSA-N 1,3-dihydrobenzimidazole-2-thione;sodium Chemical compound [Na].C1=CC=C2NC(=S)NC2=C1 UCTUNCJCTXXXGJ-UHFFFAOYSA-N 0.000 claims description 3
- AZFNGPAYDKGCRB-XCPIVNJJSA-M [(1s,2s)-2-amino-1,2-diphenylethyl]-(4-methylphenyl)sulfonylazanide;chlororuthenium(1+);1-methyl-4-propan-2-ylbenzene Chemical compound [Ru+]Cl.CC(C)C1=CC=C(C)C=C1.C1=CC(C)=CC=C1S(=O)(=O)[N-][C@@H](C=1C=CC=CC=1)[C@@H](N)C1=CC=CC=C1 AZFNGPAYDKGCRB-XCPIVNJJSA-M 0.000 claims description 3
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 3
- 239000011609 ammonium molybdate Substances 0.000 claims description 3
- 229940010552 ammonium molybdate Drugs 0.000 claims description 3
- XUFUCDNVOXXQQC-UHFFFAOYSA-L azane;hydroxy-(hydroxy(dioxo)molybdenio)oxy-dioxomolybdenum Chemical compound N.N.O[Mo](=O)(=O)O[Mo](O)(=O)=O XUFUCDNVOXXQQC-UHFFFAOYSA-L 0.000 claims description 3
- 239000003139 biocide Substances 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 229910000397 disodium phosphate Inorganic materials 0.000 claims description 3
- 235000019800 disodium phosphate Nutrition 0.000 claims description 3
- 150000002460 imidazoles Chemical class 0.000 claims description 3
- 150000003854 isothiazoles Chemical class 0.000 claims description 3
- CTAPFRYPJLPFDF-UHFFFAOYSA-N isoxazole Chemical class C=1C=NOC=1 CTAPFRYPJLPFDF-UHFFFAOYSA-N 0.000 claims description 3
- NMHMDUCCVHOJQI-UHFFFAOYSA-N lithium molybdate Chemical compound [Li+].[Li+].[O-][Mo]([O-])(=O)=O NMHMDUCCVHOJQI-UHFFFAOYSA-N 0.000 claims description 3
- IDNHOWMYUQKKTI-UHFFFAOYSA-M lithium nitrite Chemical compound [Li+].[O-]N=O IDNHOWMYUQKKTI-UHFFFAOYSA-M 0.000 claims description 3
- AAJBNRZDTJPMTJ-UHFFFAOYSA-L magnesium;dinitrite Chemical compound [Mg+2].[O-]N=O.[O-]N=O AAJBNRZDTJPMTJ-UHFFFAOYSA-L 0.000 claims description 3
- 235000010755 mineral Nutrition 0.000 claims description 3
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims description 3
- 235000019799 monosodium phosphate Nutrition 0.000 claims description 3
- RAFRTSDUWORDLA-UHFFFAOYSA-N phenyl 3-chloropropanoate Chemical compound ClCCC(=O)OC1=CC=CC=C1 RAFRTSDUWORDLA-UHFFFAOYSA-N 0.000 claims description 3
- GNSKLFRGEWLPPA-UHFFFAOYSA-M potassium dihydrogen phosphate Chemical compound [K+].OP(O)([O-])=O GNSKLFRGEWLPPA-UHFFFAOYSA-M 0.000 claims description 3
- 239000004323 potassium nitrate Substances 0.000 claims description 3
- 235000010333 potassium nitrate Nutrition 0.000 claims description 3
- 239000004304 potassium nitrite Substances 0.000 claims description 3
- 235000010289 potassium nitrite Nutrition 0.000 claims description 3
- 150000003217 pyrazoles Chemical class 0.000 claims description 3
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 3
- 150000003557 thiazoles Chemical class 0.000 claims description 3
- QGAVSDVURUSLQK-UHFFFAOYSA-N ammonium heptamolybdate Chemical compound N.N.N.N.N.N.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Mo].[Mo].[Mo].[Mo].[Mo].[Mo].[Mo] QGAVSDVURUSLQK-UHFFFAOYSA-N 0.000 claims description 2
- 125000005625 siliconate group Chemical group 0.000 claims description 2
- 150000003852 triazoles Chemical class 0.000 claims description 2
- 229910000404 tripotassium phosphate Inorganic materials 0.000 claims description 2
- 235000019798 tripotassium phosphate Nutrition 0.000 claims description 2
- XMEKHKCRNHDFOW-UHFFFAOYSA-N O.O.[Na].[Na] Chemical compound O.O.[Na].[Na] XMEKHKCRNHDFOW-UHFFFAOYSA-N 0.000 claims 3
- 235000019441 ethanol Nutrition 0.000 claims 2
- VLLMWSRANPNYQX-UHFFFAOYSA-N thiadiazole Chemical compound C1=CSN=N1.C1=CSN=N1 VLLMWSRANPNYQX-UHFFFAOYSA-N 0.000 claims 2
- 230000003115 biocidal effect Effects 0.000 claims 1
- 238000009472 formulation Methods 0.000 abstract description 45
- 229910052782 aluminium Inorganic materials 0.000 abstract description 39
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract description 39
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical group [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 abstract description 31
- 239000000654 additive Substances 0.000 abstract description 22
- 239000007788 liquid Substances 0.000 abstract description 21
- 230000005764 inhibitory process Effects 0.000 abstract description 17
- 150000004760 silicates Chemical class 0.000 abstract description 12
- 239000002244 precipitate Substances 0.000 abstract description 10
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 abstract description 8
- 239000008233 hard water Substances 0.000 abstract description 7
- 230000002195 synergetic effect Effects 0.000 abstract description 6
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 abstract description 5
- 230000006641 stabilisation Effects 0.000 abstract description 5
- 238000011105 stabilization Methods 0.000 abstract description 5
- 230000001681 protective effect Effects 0.000 abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 42
- 239000003112 inhibitor Substances 0.000 description 19
- 238000001816 cooling Methods 0.000 description 16
- 229910052783 alkali metal Inorganic materials 0.000 description 11
- 238000012360 testing method Methods 0.000 description 10
- 229910002651 NO3 Inorganic materials 0.000 description 9
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical class OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 8
- 238000006116 polymerization reaction Methods 0.000 description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 7
- 229910052802 copper Inorganic materials 0.000 description 7
- 239000010949 copper Substances 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 7
- 229910001369 Brass Inorganic materials 0.000 description 6
- 239000010951 brass Substances 0.000 description 6
- 239000012141 concentrate Substances 0.000 description 6
- 150000001340 alkali metals Chemical class 0.000 description 5
- 238000007710 freezing Methods 0.000 description 5
- 230000008014 freezing Effects 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
- 229920000058 polyacrylate Polymers 0.000 description 5
- 230000004580 weight loss Effects 0.000 description 5
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical class C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 4
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 230000003628 erosive effect Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
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- 239000007787 solid Substances 0.000 description 4
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- 229910000838 Al alloy Inorganic materials 0.000 description 3
- 229910001018 Cast iron Inorganic materials 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
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- 150000002763 monocarboxylic acids Chemical class 0.000 description 3
- QYHFIVBSNOWOCQ-UHFFFAOYSA-N selenic acid Chemical class O[Se](O)(=O)=O QYHFIVBSNOWOCQ-UHFFFAOYSA-N 0.000 description 3
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- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 description 3
- 125000001340 2-chloroethyl group Chemical group [H]C([H])(Cl)C([H])([H])* 0.000 description 2
- 238000012935 Averaging Methods 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical class [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 0.000 description 2
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- 239000004115 Sodium Silicate Substances 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 150000001447 alkali salts Chemical class 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
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- 125000003545 alkoxy group Chemical group 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 239000012964 benzotriazole Substances 0.000 description 2
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- 239000006172 buffering agent Substances 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
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- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical group 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
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- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
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- 229910052736 halogen Inorganic materials 0.000 description 2
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- 239000004615 ingredient Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
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- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
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- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 2
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 229910052911 sodium silicate Inorganic materials 0.000 description 2
- 239000004328 sodium tetraborate Substances 0.000 description 2
- 229910000679 solder Inorganic materials 0.000 description 2
- 238000007655 standard test method Methods 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000005691 triesters Chemical class 0.000 description 2
- LGJCFVYMIJLQJO-UHFFFAOYSA-N 1-dodecylperoxydodecane Chemical compound CCCCCCCCCCCCOOCCCCCCCCCCCC LGJCFVYMIJLQJO-UHFFFAOYSA-N 0.000 description 1
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- WROUWQQRXUBECT-UHFFFAOYSA-N 2-ethylacrylic acid Chemical compound CCC(=C)C(O)=O WROUWQQRXUBECT-UHFFFAOYSA-N 0.000 description 1
- 125000004777 2-fluoroethyl group Chemical group [H]C([H])(F)C([H])([H])* 0.000 description 1
- PSZAEHPBBUYICS-UHFFFAOYSA-N 2-methylidenepropanedioic acid Chemical compound OC(=O)C(=C)C(O)=O PSZAEHPBBUYICS-UHFFFAOYSA-N 0.000 description 1
- XQHCBHNLRWLGQS-UHFFFAOYSA-N 4-(3-methylphenyl)-2h-triazole Chemical compound CC1=CC=CC(C2=NNN=C2)=C1 XQHCBHNLRWLGQS-UHFFFAOYSA-N 0.000 description 1
- UZHQHNDRVITJPL-UHFFFAOYSA-N 5,6-dimethoxy-1h-indole-2-carboxylic acid Chemical compound C1=C(OC)C(OC)=CC2=C1NC(C(O)=O)=C2 UZHQHNDRVITJPL-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-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
- 239000004135 Bone phosphate Substances 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-N Metaphosphoric acid Chemical class OP(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-L Phosphate ion(2-) Chemical compound OP([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-L 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229920006243 acrylic copolymer Polymers 0.000 description 1
- 229910001963 alkali metal nitrate Inorganic materials 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- VZTDIZULWFCMLS-UHFFFAOYSA-N ammonium formate Chemical compound [NH4+].[O-]C=O VZTDIZULWFCMLS-UHFFFAOYSA-N 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 239000007853 buffer solution Substances 0.000 description 1
- PVEOYINWKBTPIZ-UHFFFAOYSA-N but-3-enoic acid Chemical compound OC(=O)CC=C PVEOYINWKBTPIZ-UHFFFAOYSA-N 0.000 description 1
- 125000006226 butoxyethyl group Chemical group 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 1
- 229940018557 citraconic acid Drugs 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 125000000853 cresyl group Chemical group C1(=CC=C(C=C1)C)* 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical class OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- VGYYSIDKAKXZEE-UHFFFAOYSA-L hydroxylammonium sulfate Chemical compound O[NH3+].O[NH3+].[O-]S([O-])(=O)=O VGYYSIDKAKXZEE-UHFFFAOYSA-L 0.000 description 1
- 229910000378 hydroxylammonium sulfate Inorganic materials 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 231100000647 material safety data sheet Toxicity 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- HNEGQIOMVPPMNR-NSCUHMNNSA-N mesaconic acid Chemical compound OC(=O)C(/C)=C/C(O)=O HNEGQIOMVPPMNR-NSCUHMNNSA-N 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- HNEGQIOMVPPMNR-UHFFFAOYSA-N methylfumaric acid Natural products OC(=O)C(C)=CC(O)=O HNEGQIOMVPPMNR-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 125000005375 organosiloxane group Chemical group 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- HVAMZGADVCBITI-UHFFFAOYSA-N pent-4-enoic acid Chemical compound OC(=O)CCC=C HVAMZGADVCBITI-UHFFFAOYSA-N 0.000 description 1
- 125000005385 peroxodisulfate group Chemical group 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 description 1
- PTMHPRAIXMAOOB-UHFFFAOYSA-L phosphoramidate Chemical class NP([O-])([O-])=O PTMHPRAIXMAOOB-UHFFFAOYSA-L 0.000 description 1
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical class [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920005996 polystyrene-poly(ethylene-butylene)-polystyrene Polymers 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 229940005657 pyrophosphoric acid Drugs 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- RBWSWDPRDBEWCR-RKJRWTFHSA-N sodium;(2r)-2-[(2r)-3,4-dihydroxy-5-oxo-2h-furan-2-yl]-2-hydroxyethanolate Chemical compound [Na+].[O-]C[C@@H](O)[C@H]1OC(=O)C(O)=C1O RBWSWDPRDBEWCR-RKJRWTFHSA-N 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 150000004867 thiadiazoles Chemical class 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- 230000004584 weight gain Effects 0.000 description 1
- 235000019786 weight gain Nutrition 0.000 description 1
- 125000005023 xylyl group Chemical group 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
-
- 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
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/20—Antifreeze additives therefor, e.g. for radiator liquids
Abstract
The present invention provides heavy duty long life corrosion inhibition formulations and compositions for inhibiting mineral scale and the corrosion of metals particularly the cavitation corrosion of aluminum in the presence of aqueous liquids. The combination of a mixture of polymeric polycarboxylates, azoles, a combination of nitrite and nitrate salts, phosphates, stabilized silicates and transition metal compounds provide a synergistic protective effect against the cavitation corrosion of aluminum in aqueous liquids reducing the corrosion rate and is effective at relatively low concentrations and varying pH ranges. The addition of selected polymeric polycarboxylates not only significantly reduces glycol based coolant cavitation erosion-corrosion, heat rejecting aluminum corrosion, and hard water precipitates and scale, it has been discovered that polymeric polycarboxylates in combination with siloxane stabilized silicates enhance secondary silicate stabilization leading to improvement in an aluminum corrosion protection and coolant life when utilized with selected amounts of the above-identified additives. The formulations are particularly suitable for automotive applications.
Description
TITLE: DIESEL ENGINE ANTIFREEZE COMPOSITION
TECHNICAL FIELD
This invention relates to extending diesel engine coolant lifetime through polymeric polycarboxylate secondary silicate stabilization. More particulary, this invention relates to an antifreeze formulation for inhibition and prevention erosion and corrosion of aluminum and the corrosion of other metals exposed to an aqueous liquid in automotive coolant systems. The formulation further inhibits mineral scale.
The novel antifreeze formulation comprises a mixture of polymeric polycarboxylates, azoles, nitrate and nitrite salts, phosphates, siloxane stabilized silicates and transition metal compounds which provide a synergistic protective effect against the cavitation corrosion of aluminum in aqueous liquids reducing the corrosion rate and is effective at relatively low concentrations and varying pH ranges . The addition of selected polymeric polycarboxylates not only significantly reduces glycol based coolant cavitation erosion-corrosion, heat rejecting aluminum corrosion, and hard water precipitates and scale, it has been discovered that selected polymeric polycarboxylates in combination with siloxane stabilized silicates enhance secondary silicate stabilization leading to improvement in aluminum corrosion protection and coolant life when utilized with selected amounts of the above- identified additives. The formulations are particularly suitable for automotive applications .
DESCRIPTION OF THE PRIOR ART
Antifreeze/coolant technology traditionally use silicate as a corrosion inhibitor. Silicates are particularly useful in protecting aluminum automotive cooling system components. The silicate corrosion
inhibitors generally also use a phosphate, usually in the form of an alkali metal salt, to help protect metal cooling system parts and also as a buffer to control the pH of the coolant. Often phosphate salts are used to help maintain a stable alkaline environment from which multiple corrosion inhibitors can most effectively function.
Traditionally antifreeze/coolant is sold at nearly one-hundred percent glycol content. This concentrated packaging allows for flexibility so that the user can dilute the antifreeze/coolant, as needed, with available water to obtain the required freeze/boil protection. However, corrosion protection is needed over the entire dilution range. In modern automotive engineering, many engine components are fabricated from aluminum. Engine coolants, primarily ethylene glycol or propylene glycol based solutions, must transfer heat from operating aluminum engines while inhibiting corrosion. Older automotive engines did not have aluminum components and thus, the traditional antifreeze/coolant compositions may produce corrosion in heat rejecting aluminum or aluminum alloy components. The cavitation erosion-corrosion of aluminum water pumps upon exposure to aqueous systems such as water-cooled internal combustion engine coolants is a relatively new development.
U.S. Patent 4,717,495 by Hercamp et al . , hereby incorporated by reference, teaches a sodium-free buffer solution. U.S. Patent No. 4,548,787 discloses the use of a combination water soluble phosphate with tungstae, selenate and molybdate for protection against cavitation erosion-corrosion on aluminum. U.S. Patent No. 4,404113 discloses the use of polyhydric alcohols as corrosion inhibiting and cavitation reducing additives for coolants.
Certain polycarboxylate type materials have been disclosed for prevention of precipitates in
antifreeze/coolant compositions. for example, U.S. Patent No. 3,663,448 discloses scale inhibition for industrial cooling waters using amino phosphonate and polyacrylic acid compounds, U.S. Patent No. 3,948,792 discloses an aqueous additive mixture to reduce and modify the amount of silicate scale formed in automotive cooling systems.
U.S. Patent No 4,487,712 discloses the use of polyacrylic acid as a silicate stabilizer to inhibit gelation which is a silicate depletion mechanism which can occur separately from hard water precipitates.
The addition of polymeric polycarboxylates has been shown to significantly reduce glycol based coolant cavitation erosion- corrosion as set forth in U.S. Patent Nos. 5,288,419 and 5,290,469; to reduce heat rejecting aluminum corrosion as set forth in U.S. Patent Nos. 5,320,670 and 5,290,467; and to reduce hard water precipitates and scale as set forth in U.S. Patent Nos. 5,330,670 and 5,290,468; all of which are hereby incorporated by reference.
U.S. Patent No. 4,440,721, hereby incorporated by reference, discloses the combination of a water-soluble phosphate with a water soluble molybdate, tungstate, or selenate for providing a protective effect against the cavitation corrosion of aluminum in aqueous liquids. While alkali metal molybdates and the soluble salts of tungstic and selenic acids have been used in antifreeze compositions to prevent the corrosion of metals, particularly cast iron, soluble salts of molybdic, tungstic and selenic acids act to retard the corrosion of aluminum, particularly the cavitation erosion-corrosion of aluminum water pumps .
None of the above references provide a means for obtaining a long life silicate based antifreeze composition as does Applicant's present invention. The combination of a selected polymeric polycarboxylates, azoles, nitrate and nitrite salts, molybdates,
phosphates, stabilized silicates and transition metal compounds provide a synergistic protective effect against the cavitation corrosion of aluminum in aqueous liquids reducing the corrosion rate and is effective at relatively low concentrations and varying pH ranges. The addition of selected polymeric polycarboxylates not only significantly reduces glycol based coolant cavitation erosion-corrosion, heat rejecting aluminum corrosion, and hard water precipitates and scale, it has been discovered that utilization of selected polymeric polycarboxylates in combination with certain additives enhance secondary silicate stabilization leading to improvement in aluminum corrosion protection and coolant life.
Moreover, such a formulation would be designed for modern aluminum engine based passenger car cooling systems. The formulation must be liquid, easily miscible with diluted antifreeze in the cooling system, protect all cooling system metals, have a useful shelf life, not harm automotive finishes or paint and not promote excessive cooling system foam.
SUMMARY OF THE INVENTION
The present invention has met the above-described need by providing an antifreeze/coolant composition using selected polymeric polycarboxylate additives which reduce corrosion over the entire dilution range without creating precipitates. This composition is soluble in water, alcohol, and alcohol/water mixtures, is compatible with other commonly used antifreeze/coolant components, does not corrode or damage automotive cooling systems and is effective at relatively low concentrations. In addition, the present corrosion inhibition formulations are effective in reducing corrosion in the entire range of cooling system metals, including heat rejecting aluminum, aluminum alloys, copper, steel, cast iron, brass, solder and the like.
It his been found that water-soluble salts of an acid elected from the group consisting or molybdic, tungstic and selenic acids or salts thereof, in combination with a water-soluble phosphate and a polymeric polycarboxylate provide a synergistic improvement in the retardation or the cavitation erosion- corrosion of aluminum water pumps and other metal engine components when used in contact with aqueous liquids, particularly aqueous antifreeze compositions containing a water-soluble alcohol freezing point depressant.
It is an object of the present invention to provide corrosion inhibition formulations for antifreeze/coolant compositions with selected polymeric polycarboxylate additives for reducing glycol based coolant cavitation erosion-corrosion.
It is another object of the present invention to provide corrosion inhibition formulations for antifreeze/coolant compositions with selected polymeric polycarboxylate additives for enhancing silicate stability providing an improvement in coolant life.
It is another object of the present invention to provide corrosion inhibition formulations which reduce corrosion over the entire dilution range of antifreeze/coolant compositions without creating precipitates.
It is an additional object of the present invention to provide corrosion inhibition formulations which are effective in reducing corrosion in the entire range of cooling system metals. It is an additional object of the present invention to provide corrosion inhibition formulations which are effective in reducing heat rejecting aluminum corrosion.
It is an additional object of the present invention to provide corrosion inhibition formulations which are effective in reducing hard water precipitates and scale.
It is a further object of the present invention to provide corrosion inhibition formulations which are soluble in alcohol, alcohol/water mixtures and water alone. It is an object of the present invention to provide corrosion inhibition formulations which are compatible with commonly used antifreeze/coolant components.
It is another object of the present invention to provide corrosion inhibition formulations which are effective at relatively low concentrations.
It is an additional object of the present invention to use polymeric polycarboxylates in the corrosion inhibition formulations to reduce the corrosion.
It is a further object of the present invention to utilize a combination of nitrites and nitrates to maximize the protection of ferrous metals and minimize pitting thereof .
It is a further object of the present invention to utilize molybdate to protect against erosion and cavitation of aluminum.
These and other objects of the present invention will be more fully understood from the following description of the invention.
DESCRIPTION OF THE PREFERRED EMBODIMENT
The present invention provides long life corrosion inhibition antifreeze/coolant compositions by using certain polymeric polycarboxylate additives in a synergistic combination with stabilized silicate
("siloxane") , and other selected compounds, primarily the combination of nitrates and nitrates and an increased amount of molybdate which reduces coolant cavitation erosion-corrosion, heat rejecting aluminum corrosion, and hard water precipitates and scale. Moreover, it has been discovered that polymeric polycarboxylates enhance secondary silicate stabilization leading to improvement
in aluminum corrosion protection and prolonged coolant life as compared to conventional silicon based coolants. In addition, the present corrosion inhibition formulations are effective in reducing corrosion in the entire range of cooling system metals, including heat rejecting aluminum, aluminum alloys, copper, steel, cast iron, brass, solder and the like. This formulation is soluble in alcohol, alcohol/water mixtures and in water alone and exhibits excellent stability characteristics. The most preferred antifreeze/coolant composition is a silicate-phosphate type having a pH of about 10.5 and having about 94% antifreeze grade glycols and about 3% corrosion inhibitors, with the balance being water.
The freezing point depressant utilized in the antifreeze compositions of the invention can be any suitable water-soluble liquid alcohol used heretofore in formulating antifreeze compositions. The water-soluble alcohol contains 1 to about 4 carbon atoms and 1 to about 3 hydroxy groups . Ethylene glycol is preferred as the freezing point depressant and especially the commercially available mixtures containing largely ethylene glycol and a small amount of diethylene glycol . The commercial mixture generally contains at least 85 to 95 percent by weight of ethylene glycol with the remainder being diethylene glycol and small amounts of substances which are incidentally present such as water. Other water- soluble liquid alcohol can be admixed with ethylene glycol but such mixtures usually are not preferred. Inexpensive commercially available water soluble alcohols can also be used such as methyl, ethyl, propyl, and isopropyl alcohol alone or in mixtures .
The concentrated corrosion inhibitor formulations of the present invention is a water-based mixture of polymeric polycarboxylates, nitrate and nitrite salts, molybdates, phosphate, azoles, stabilized silicates and transition metal compounds . Optionally, other components including defoamers, dyes, buffering agents, biocides,
detergents, and the like may be added to the present formulation. Although a water soluble phosphate level is given on the basis of hydrogen phosphate, alkali metal salts are typically used. Alkaline earth or ammonium slats are also possible alone or in combination therewith. Nitrates and nitrites are typically introduced as an alkali salt although acid, alkaline earth or ammonium salts could be utilized including potassium, sodium or salts alone or in combinations therewith. The azoles include tolytriazole, benzotriazole, mercaptobenzothizole including mixtures and other substituted azoles. Stabilized silicate, typically referred to as siloxane compounds, are of the type described in U.S. Patent Nos. 4,354,002, 4,362,644, and/or 4,370,255, hereby incorporated by reference. Suitable defoamers include PLURONIC® L-61, PATCOTE® 415 and other surfactants including silicone types. The synergistic combination of phosphate, molybdate and stabilized silicate is described in U.S. Patent Nos. 4,548,787, 4,707,286, and 4 , 440 , 721 , hereby incorporated by reference.
It is contemplated that in addition to silicate- phosphate type coolants, these additives are useful in silicate-borax, silicate phosphate and borax coolants, organic acid, and organic acid silicate hybrid type coolants, and the like. The corrosion inhibitor formulations are compatible with other commonly used antifreeze/coolant components and are effective at relatively low concentrations. Each of the preferred ingredients of the synergistic antifreeze formulation, whether mandatory or optional, is discussed below:
POLYCARBOXYLATES
The preferred class of stabilizing polymeric polycarboxylates are based on polyacrylic acid (PAA)
and/or polymaleic acid (PMA) . These polymeric polycarboxylates are compatible with other components in the typical antifreeze/coolant composition, and present no additional toxicity or disposal concerns . The molecular weight distribution of useful materials may average about one hundred grams/mole to about three million grams/mole. Chemically, the materials should be based on polymers and copolymers of acrylic acid and/or maleic acid, including any modifiers, such as alcohols. The polycarboxylates used in the present invention have a molecular weight range of from about 1,200 to about 250,000, with a preferred range of from 500 to 12,000. More specifically, the most preferred additives have average molecular weights in the range of about 500 to about 4,000, and more specifically about 1300 to about 1800 and about 300 to about 4600.
When reference is made to polycarboxylates within the context of the present invention it is understood to encompass those watersoluble homo- and copolymers having at least one monomeric unit containing C3-6 monoethylenically unsaturated mono- or dicarboxylic acids or their salts. Suitable monocarboxylic acids of this type are for example, acrylic acid, methacrylic acid, ethacrylic acid, vinylacetic acid, allylacetic acid, and crotonic acid. The preferable monocarboxylic acids from this group are acrylic acid and methacrylic acid. A further component of the polycarboxylate comprises monoethylenically unsaturated C4-s dicarboxylic acids, for example, maleic acid, itaconic acid, citraconic acid, mesaconic acid, fumaric acid, or methylenemalonic acid. The preferred acid is maleic acid.
Other organic substituents may be used as co- monomers or as modifiers added along the polymer chain. Examples of such are shown as Formula I . H R
C-C (I)
H X n
where R=H or a secondary alcohol such as isopropanol, X=COOH, COONa÷, ethylvinylether, isobutylene, vinyl acetate, acrylamide, or styrene, with the proviso that when R= a secondary alcohol, X=COOH or COO-Na+, and when X= any other above referenced group, R=H. The preferred polycarboxylates are a copolymer of acrylic acid and maleic acid, or their sodium salts, said copolymer having a molecular weight of 3000, and a sodium salt of polyacrylic acid modified with a secondary alcohol such as isopropanol, said polymer having a molecular weight of 4000.
The polycarboxylates used in the present invention are obtained by methods well known to those skilled in the art. The general method of synthesis is via free acid radical polymerization. The polymerization may be carried out in an aqueous medium, in the presence of polymerization initiators, with or without regulants. The polymerization can take various forms,- for example, the monomer (s) can be polymerized batchwise in the form of aqueous solutions. It is also possible to introduce into the polymerization reactor a portion of the monomer (s) and a portion of the initiator, to heat the mixture in an inert atmosphere to the polymerization temperature and then to add the remaining monomer (s) and initiator to the reactor at the rate of polymerization.
Polymerization temperatures range from 20°C to 200°C. At temperatures above 100°C, pressure vessels are employed.
The carboxyl containing monomers can be polymerized in the free carboxylic acid form, in the partial neutralized form, or completely neutralized. The neutralization is preferably effected with alkali metal or ammonium base .
The polymerization initiators used are preferably water soluble free radical formers such as hydrogen peroxide, peroxodisulfates and mixtures of the two. The polymerization may also be started with water insoluble initiators such as dibenzoyl peroxide, dilaurylperoxide,
or azodiisobutyronitrile . The polymerization may be carried out in the presence of regulants . Examples of such regulants include water soluble mercaptans, ammonium formate, and hydroxylammonium sulfate. Polymeric polycarboxylate materials which are useful in the present invention include Belclene water treatment additives from CIBA-GEIGY®, Colloid additives from COLLOIDS®, Inc., GOOD-RITE® polyacrylates and CARBOPOL® resins from BF GOODRICH® and the like. Examples of the polycarboxylates which may be used in the present invention are those marketed by BASF® under the trademark SOKALAN® polycarboxylates, which are available in aqueous polymer solutions . More particularly, the SOKALAN® polyacrylic dispersants are copolymer carboxylate dispersants. These SOKALAN® polycarboxylates are acrylic/maleic copolymers and other copolymers of either maleic or acrylic acid. These polycarboxylates are generally fully neutralized. The suffix "S" is a designation used to indicate free acids in the SOKALAN® range.
While particularly preferred additive, SOKALAN® CP10, CPlOs, or CP12s, has been shown to be particularly effective at about 0.05 to about 0.20 weight percent in one inhibitor concentrate, other levels of additive and different polycarboxylates may also be used. SOKALAN® 10 has an average relative molecular weight of about 4,000, and comprises a secondary alcohol modified polyacrylic acids; whereas SOKALAN® 12 has an average relative molecular weight of about 3,000 and comprises a sodium salt of a copolymer of acrylic acid and maleic acid. The polymeric polycarboxylate is preferably present in the formulation in an amount of about 0.001 to about 10.0 percent by weight, and more preferably in an amount of about 0.01 to about 0.1 percent by weight. The polymeric polycarboxylate is effective at enhancing stability at relatively low concentrations, generally about 100 to about 1000 ppm per total volume of inhibitor concentrate.
The most preferred polycarboxylates are the K-700 polyacrylate polymers from BF GOODRICH® which include the GOOD-RITE® K-732 AND GOOD-RITE® K-752 polyacrylate polymers . Both are mixtures of sodium polyacrylate and polyacrylic acid in water as set forth and described in the copies of the Material Safety Data sheets as set forth in the Information Disclosure Document and incorporated by reference herewith. These polymers are similar, while differentiated by their molecular weight.
The GOOD-RITE® K-752 polyacrylate is a water soluble acrylic acid polymer supplied as a clear to hazy, colorless to amber colored, and ranging from about 62% to about 64% total solids solution in water averaging about 63%, with the active solids being about 62.5% having a specific gravity of about 1.23. The molecular weight (GPC Mκ) is about 2100. The pH ranges from about 2.2 to 3.0 and averages about 2.6. Viscosity (CP at 25°C) ranges from between about 400 to about 1,400, and averages about 950. The GOOD-RITE® K-732 polyacrylate is a water soluble acrylic acid polymer supplied as a clear to hazy, colorless to amber colored, and ranging from about 49% to about 51% total solids solution in water and averaging about 50%, with the active solids being about 49.5% having a specific gravity of about 1.2. The molecular weight (GPC Mw) is about 5,100. The pH ranges from about 2.2 to 3.0 and averages about 2.6. Viscosity (CP at 25°C) ranges from between about 250 to about 500, and averages about 350. Combinations of the polycarboxylates may also be utilized in the present invention such as a mixture of a secondary alcohol modified polyacrylic acid, a sodium salt of a copolymer of acrylic acid and maleic acid and/or mixtures of sodium polyacrylate and polyacrylic acid in water. These combinations having a molecular weight of less than 10,000 are deemed to be suitable
polycarboxylate additives .
SALT CORROSION INHIBITORS (Nitrates and Nitrites)
Where the aqueous liquids contact other metals in addition to aluminum, including aluminum water pumps, metal salt corrosion inhibitors, preferably alkali metal salts known in the prior art can be usefully added to the aqueous liquids or the invention. Such known corrosion inhibitors include the water-soluble: nitrates, nitrites, silicates, carbonates, sodium silicate, sodium nitrate, potassium carbonate, ammonium silicate.
Preferably, a nitrate in combination with a nitrite is used in the preferred composition in a higher concentration for heavy duty applications in diesel engines than typically used in gasoline engines. The source of the nitrate and nitrite ions can be any water- soluble nitrate or nitrite such as the alkali metal nitrates and nitrites . Nitrate salts suitable in the present invention include, sodium nitrate, potassium nitrate, magnesium nitrate, calcium nitrate, lithium nitrate, mixtures thereof and the like. Nitrite salts suitable in the present invention include, sodium nitrite, potassium nitrite, magnesium nitrite, calcium nitrite, lithium nitrite, mixtures thereof and the like. Any compatible salt may be used including sodium, potassium, lithium, magnesium, calcium and the like. The most preferred nitrate salt is sodium nitrate and the preferred nitrite is sodium nitrite.
Other equivalent methods of supplying nitrate may be used. For example, the pH of the total composition may be adjusted by addition of nitric acid ions. The reaction of nitrate acid and basic salts contained in the composition will result in liberation of free carboxylic
acid and the formation of nitrate salts .
Nitrate salts serve to inhibit corrosion in the formulations of the present invention and aids in the protection of aluminum. The nitrate salt is preferably present in the formulation in an amount of about 0.01 to about 10.0 percent by weight, more preferably in an amount of about 0.1 to about 3.0 percent by weight, and most preferably in an amount of about 0.1 to about 1.0 percent by weight . Nitrite salts are especially good for preventing heavy duty cylinder linings from pitting. They are good oxidizers when used with ferrous metals for protecting surfaces such as cylinder liner sleeves and other ferrous components of diesel engines. The nitrites have a higher oxidation state than the nitrates and are ions are depleted at a higher rate making them more expensive than the nitrate salts,- however, the nitrites are especially good in reducing pitting by forming a coating on the ferrous surface. Of course, the nitrates form nitrites upon oxidation. The nitrite salt is preferably present in the formulation in an amount of about 0.01 to about 10.0 percent by weight, more preferably in an amount of about 0.1 to about 3.0 percent by weight, and more preferably in an amount of about 0.1 to about 1.0 percent by weight.
The preferred embodiment of the present formulation utilizes a greater amount of water soluble nitrite than water soluble nitrates. More specifically, one preferred formula utilizes water soluble nitrates in a range of from about 0.05 to about 0.30 percent by weight, and water soluble nitrites in a range of from about 0.30 to about 0.60 percent by weight, representing about a 2:1 ratio.
AZOLE ADDITIVES
Azoles are present in the formulation to inhibit corrosion of yellow metal like copper and brass. Brass thermostats and radiator caps are common as well as copper and brass radiators. The azole compound providing protection for copper and brass from corrosion is selected from among the water- soluble triazoles, pyrazoles, imidazoles, isooxazoles, isothiazoles, thiazoles, thiadiazole salts, and the like. Generally, the alkali metal salts are used. Specific preferred azole compounds include 1, 2, 3 -benzotriazole; 1, 2, 3 -tolyltriazole,- sodium 2 -mercaptobenzothiazole; and sodium 2-mercaptobenzimidazole . Azole compounds suitable in the present invention include, salts of mercaptobenzothiazole, salts of tolytriazole, benzotriazole, mixtures thereof and the like. Typically, these azoles are preferably present in a fifty percent concentration. However, one preferred azole compound consists of the salts of mercaptobenzothiazole and salts of tolytriazole. More particularly, one preferred azole compound is a mixture of sodium mercaptobenzothiazole and sodium tolytriazole which may be used in about a 3 to 1 ratio.
The azoles are preferably present in the ormulation in an amount of about 0.01 to about 10.0 percent by weight, and more preferably in an amount of about 0.05 to about 1.0 percent by weight. Generally, the azole compound is used in amounts of about 0.1 parts to about 0.5 parts by weight, preferably about 0.1 to about 0.4 parts by weight, based on 100 parts by weight of the aqueous liquid.
MOLYBDATE ADDITIVES
The water-soluble molybdate which is preferred for use in the aqueous systems of the present invention can be any salt of molybdic acid which is readily soluble in water. These include both alkali metal and alkaline earth metal molybdates as well as ammonium molybdate, the term "alkali molybdate" being used in a broad sense so as to include alkali metal, alkaline earth metal and ammonium molybdates . Examples of useful molybdates are sodium molybdate . potassium molybdate, lithium molybdate and ammonium molybdates including ammonium dimolybdate and ammonium heptamolybdate . Alkali molybdate compounds, sodium molybdate and potassium molybdate are preferred because of their availability and compatibility with the aqueous system as well as for economic reasons . The specific concentration of the molybdate ion will vary depending upon the degree of hardness of the aqueous system, the temperature, and the amount of dissolved oxygen in the aqueous system. While concentrations of the molybdate ion above about 0.5 parts by weight per 100 parts by weight of aqueous liquid can be employed, in most instances concentrations of molybdate ion above this limit normally do not provide significant improvements in the inhibitive characteristics or the aqueous system and are undesirable for economic reasons.
Transition metal compounds suitable for use in the present invention include, disodium salt dehydrate of molybdic acid, sodium molybdate 2H20, molybdenum trioxide, silicoheteropolymolybdates, phosphoroheteropolymolybdates, mixtures thereof and the like. Any compatible transition metal may be used, including for example, molybdate, cobalt, cerium,
mixtures thereof and the like. In addition, any acid salt may be used including sodium, potassium, lithium, calcium, magnesium and the like. The most preferred transition metal compound is the disodium salt dehydrate of molybdic acid or sodium molybdate 2H20.
Transition metal acids are used to inhibit corrosion in formulations of the present invention. The transition metal compound is preferably present in the formulation in an amount of about 0.001 to about 10.0 percent by weight, and more preferably in an amount of about 0.1 to about 0.5 percent by weight. The molybdate ion is employed in amounts so as to provide a concentration in the aqueous system of at least about 0.01 parts by weight per 100 parts by weight of aqueous liquid. Preferably about 0.15 to about 0.2 parts by weight per 100 parts by weight of molybdate based upon said aqueous liquid are employed. More molybdate is utilized in the present diesel engine formulation than typically used in automotive engine coolants.
PHOSPHORUS ADDITIVES
Both inorganic and organic water-soluble phosphorus compounds are useful in inhibiting the cavitation erosion corrosion of aluminum in contact with aqueous liquids. The water-soluble phosphates are used generally in amounts so as to provide a concentration of about 0.5 to about 2 parts by weight per 100 parts by weight of the aqueous liquid. These compounds include the preferred water-soluble alkali metal salts of orthophosphoric acid, pyrophosphoric acid, and metaphosphoric acid. Orthophosphoric acid being tri-basic forms three series of salts, potassium dihydrogen phosphate, disodium
hydrogen phosphate, and trisodium phosphate. Useful organic phosphates include the oxyesters of phosphoric acid, as well as the amides and triesters thereof. The most common phosphorus acid esters which are useful are the mono-, di-, and tri-esters of orthophosphoric acid. These can be alkyl phosphates , aryl phosphates and mixed alkyl-aryl phosphates. Representative alkyl groups having 1 to about 18 carbon atoms which can be present in the alkyl phosphates include methyl, ethyl, propyl, isopropyl and n-butyl, isobutyl, etc. Representative substituted alkyl groups which can be present in the phosphorus esters include said alkyl groups substituted with halogen, especially chlorine and fluorine, and with alkoxy groups. Examples of substituted alkyl groups include butoxyethyl, 2-chloroethyl, 2-nuoroethyl, etc. Examples or other groups which can be present in the phosphorus esters include alkyl groups substituted with halogen, especially chlorine and fluorine, and with alkoxy groups. Examples of substituted alkyl groups include butyoxycthyl, 2-chloroethyl. 2-fluoroethyl, etc. Examples of aryl groups which can be present in the phosphorus esters include phenyl, xylyl, cresyl and halogenated phenyl .
Phosphates suitable in the present invention include, dipotassium phosphate, disodium phosphate, monopotassium phosphate, tripotassium phosphate, monosodium phosphate, trisodium phosphate, mixtures thereof and the like. Any compatible salt may be used including sodium, potassium, lithium, and the like. The most preferred phosphate is a dipotassium phosphate. The phosphates are preferably present in a fifty percent solution.
Phosphates serve to buffer and inhibit corrosion in
the formulations of the present invention. The phosphate is preferably present in the formulation as fifty percent dipotassium phosphate in an amount of about 0.1 to about 10.0 percent by weight, and more preferably in an amount of about 1.0 to about 4.0 percent by weight.
SILOXANE-SILICATE COPOLYMERS
The phosphonate and sulfonate siloxane-silicate copolymers can be formed in situ upon combination of a water-soluble silicate and a water-soluble siloxane. In the preferred composition, the silicone-silicate copolymer is selected from the group comprising alkali siliconate silylalkylphosphonates and salts thereof, arylalkyl silicone sulfonate-silicates and salts thereof, and sulfosiloxane-silicates and salts thereof and/or mixtures thereof. These copolymers are believed to provide improved metal corrosion inhibition over the use of the water-soluble silicates. The stabilized silicate,
("siloxane copolymers"), substantially inhibit the gelation tendency of a water-soluble silicate at a pH of about 7 to about 11. The anticorrosive activity of the soluble silicate is maintained in the copolymer as compared to an ordinary unstabilized soluble silicate such as sodium silicate. The stabilized silicone/silicate technology is disclosed in U.S. Patents 4,370,255; 4,362,644; and 4,354,002, all hereby incorporated by reference. Other siloxane-silicate copolymers can be utilized in combination with the water- soluble molybdates and the water-soluble salts and esters of phosphorus acids. These are disclosed in U.S. Patent Nos. 3,341,469; 3,337,496; 3,312,622; 3,198,820; 3,203,969; 3,248,329; and 4,093,641 all incorporated
herein by reference.
Silicone/silicates are used to inhibit corrosion in the formulation of the present invention. The silicone silicates are preferably present in the formulation in an amount of about 0.1 to about 10.0 percent by weight, and more preferably in an amount of about 0.2 to about 1.0 percent by weight .
DEFOAMERS
Any suitable defoamer, well known in the art, is suitable for the present formulations . Suitable defoamers include, for example, PLURONIC® L-61 non-ionic surfactant (commercially available from BASF®
Corporation) or PATCOTE® 415 liquid defoamer
(commercially available from Patco Specialty Chemicals Division, American Ingredients Company) . The defoamer may be present in an amount up to about 10.0 percent by weight and more preferably present in an amount of about
0.001 to about 10.0 percent by weight, and most preferably, in an amount of about 0.01 to about 0.05 percent by weight.
ADDITIVES
Other additives such as bittering agents, dyes, buffering agents, or biocides may be added to the antifreeze/coolant solution.
Synergistic Effect
The above synergistic combination of selected polycarboxylates and stabilized silicates ("siloxane"),
in combination with inhibitors is particularly suited for the corrosion protection of aluminum in contact with an aqueous system so as to provide protection against cavitation-erosion corrosion or aluminum water pumps in a long life antifreeze composition providing additional protection as compared to other silicate and stabilized silicate based compositions without the addition of polycarboxylates . Other corrosion inhibitors are optionally added to the aqueous liquid exhibiting synergy together and in combination with the siloxane polycarboxylate components.
The synergistic combination of corrosion inhibitors useful in inhibiting the cavitation-erosion corrosion of aluminum water pumps is generally effective in a basic aqueous corrosive media. For instance, the corrosion inhibitors of the invention are useful in aqueous alcohol based antifreeze compositions which are generally maintained at a pH of at least 6, and preferably about 7 to about 11. The corrosion inhibitors of the invention are also useful in best transfer media utilized in cooling towers.
The antifreeze concentrates of the invention are prepared by first dissolving in a water-alcohol blend
(preferably ethylene glycol in combination with diethylene glycol) a water-soluble silicate, an organosiloxane, preferably a phosphonate siloxane, or a sulfonate siloxane, and an alkali metal molybdate, tungstate or selenate. Subsequently the composition is rendered basic by the addition of sodium or potassium hydroxide. Where protection against the corrosion of copper and copper-containing alloys is also required in addition to aluminum in contact with the aqueous antifreeze concentrates of the invention, an alkali metal
azole such as potassium mercaptobenozthiozole or sodium tolyltriazole is then generally added as a 50 percent aqueous solution. Optionally, an antifoam agent is used which can be a low-foaming polyoxyethylene adduct of a polyoxypropylene hydrophobic base having a molecular weight of about 1750 wherein the oxycthylene content is about 10 weight percent of the molecule. Additional low- foaming nonionic surface active agents can be used which are disclosed in U.S. Pat. Nos. 3,340,309; 3,504,041; 3,770,701; and 2.425,755. The disclosures of low-foaming nonionic surface active agents in the above-mentioned U.S. patents are incorporated herein by reference. The resultant antifreeze concentrate composition can be diluted with water in accordance with prior a practice to produce an antifreeze fluid or heat transfer medium having be desired freezing point. As a general rule, the antifreeze concentrate used to prepare the coolant can be diluted with about 1 to about 3 volume of water to arrive at the coolant fluid which is circulated in the engine cooling system or in a cooling tower. Smaller or larger quantities of water can be added as necessary to void the freezing of the coolant.
In order to obtain the desired resistance to cavitation erosion corrosion of aluminum water pumps in contact with aqueous liquids containing a siloxane- silicate co-polymer metal corrosion inhibitor, it is necessary to provide the required amounts of phosphate and at least one of a molybdate, tungstate, or selenate in the amounts specified above.
EXPERIMENTAL EVALUATION
The ASTM D-1384-87 test was used to evaluate the
corrosion inhibitor formulations of the present invention. ASTM D-1384-87 is the standard test method for corrosion testing of engine coolants in glassware and simulates the some world operating conditions of cooling systems. The ASTM D-2570 test was used to evaluate the corrosion inhibitor formulations of the present invention. ASTM D-2570 is the standard test method for simulated service testing of engine coolants in glassware and better simulates the real world operating conditions of cooling systems than the D-1384-87 test.
A typical formulation utilizing GOODRITE K-752® polycarboxylate as compared to a conventional formula are presented in Table 1. Similar results would be expected substituting SOKALAN® CP-12s polycarboxylate for the GOODRITE K-752®.
TABLE 1
(Formulations)
Composition A (without polycarboxylate) Composition B (with GOOD-RITE® K752 polycarboxylate)
TABLE 2
(ASTM D-1384 Weight Loss in Mg/Specimen)
The results from Table 2 show that Formulations A and B passed the ASTM D-1384 weight loss tests.
TABLE 3
The results from Table 3 show that Formulations A and B passed the ASTM D-2570 simulated service weight loss tests
Moreover, an ASTM D-4340 test was conducted which showed the corrosion rate of compositions A and B in mg/cm-cm/week as follows
TABLE 4
Tables 1-4 show the percent silicate in solution for Composition A (without the polycarboxylate) vs Composition B (with GOOD-RITE® 752 polycarboxylate) as a function of the addition of the polycarboxylate, specifically the GOOD-RITE® K752 in combination with the stabilized siloxane silicate and other synergistically acting components including the water soluble nitrate and nitrites, water soluble phosphates, azole compound, water soluble molybdate,
sodiu hydroxide in the glycol solution The silicate level drops precipitously for Composition A without the selected polycarboxylate additive
It is expected that Composition B containing the selected GOOD RITE® K752 polycarboxylate and stabilized silicate "siloxane" compound would show a relatively constant rate of depletion for silicate, yet a sufficient amount of silicate s maintained in solution for the duration of the test
The foregoing detailed description is given primarily for clearness of understanding and no unnecessary limitations are to be understood therefrom, for modification will become obvious to those skilled in the art upon reading this disclosure and may be made upon departing from the spirit of the invention and scope of the appended claims Accordingly, this invention is not intended to be limited by the specific exemplifications presented hereinabove Rather, what is intended to be covered is within the spirit and scope of the appended claims
Claims
We claim:
Claim 1 An antifreeze/coolant solution for inhibiting the corrosion of metals and inhibiting mineral scale based on 100 parts by weight of said glycol -based solution, comprising: a polymeric polycarboxylate in the amount of from about 0001 to about 10.0 percent by weight, a salt which is at least one selected from the group consisting of sodium nitrate, potassium nitrate, magnesium nitrate, calcium nitrate, lithium nitrate and combinations thereof in an amount of about 0.01 to about 100 percent by weight; a salt which is at least one selected from the group consisting of sodium nitrite, potassium nitrite, magnesium nitrite, calcium nitrite, lithium nitrite and combinations thereof in an amount of about 0.01 to about 100 percent by weight; an azole compound which is selected from the group consisting essentially of sodium mercaptobenzoth azole, sodium tolytriazole, water-soluble tπ azoles, pyrazoles, imidazoles, isooxazoles, isothiazoles, thiazoles, thiadiazole, 1, 2, 3-benzotπazole, 1,2,3- tolyltπazole, sodium -mercaptobenzothiazole, and sodium 2- mercaptobenzimidazole in an amount of about 0.01 to about 10.0 percent by weight, a silicone-silicate copolymer in an amount of about 0.1 to about 100 percent by weight,; a phosphate compound which is selected from the group consisting essentially of dipotassium phosphate, disodium phosphate, monopotassium phosphate, tπpotassium phosphate, monosodium
phosphate, trisodium phosphate, and mixtures thereof in an amount of about 0.1 to about 10.0 percent by weight; a transition metal compound selected from the group consisting essentially of disodium salt dihydrate of molybdic acid, molybdenum trioxide, silicoheteropolymolybdates and/or phosphoroheteropolymolybdates, sodium molybdate, potassium molybdate, lithium molybdate, ammonium molybdate, ammonium dimolybdate, and ammonium heptamolybdate in an amount of about 0.001 to about 10.0 percent by weight; and a glycol compound selected from the group consisting essentially of ethylene glycol , diethylene glycol , propylene glycol , methyl alcohol, ethyl alcohol, propyl alcohol, isopropyl alcohol and combinations thereof making up the balance of the solution.
2. The antifreeze/coolant solution of claim 1, wherein said polymeric polycarboxylate has a molecular weight in a range of between about 500 to 12,000.
3. The antifreeze/coolant solution of claim 1, wherein said polymeric polycarboxylate has a molecular weight in a range of between about 500 to 4,000.
4. The antifreeze/coolant solution of claim 1, wherein said polymeric polycarboxylate has a molecular weight in a range of between about 500 to 1,800.
5. The antifreeze/coolant solution of claim 1, wherein said azole compound is a mixture of sodium mercaptobenzothiazole and
sodium tolytriazole.
6. The antifreeze/coolant solution of claim 5, wherein said sodium mercaptobenzothiazole and sodium tolytriazole are present in a about a 3 to 1 ratio.
7. The antifreeze/coolant solution of claim 1, wherein said azole compound is present in a about a 50% concentration.
8. The antifreeze/coolant solution of claim 1, wherein said nitrate salt is sodium nitrate.
9. The antifreeze/coolant solution of claim 8, wherein said nitrate salt is present in an amount between about 1 wtt to about 3 wtr
10. The antifreeze/coolant solution of claim 1, wherein said phosphate salt is a dipotassium phosphate.
11. The antifreeze/coolant solution of claim 1, wherein said phosphate salt is present in about a 50% solution.
12. The antifreeze/coolant solution of claim 1, wherein said transition metal compound is the disodium salt dihydrate of molybdic acid.
13. The antifreeze/coolant solution of claim 1, including a defoamer.
14. The antifreeze/coolant solution of claim 13, wherein said defoamer is present in an amount between about 0.001 to about 10.0 wt.r
15. The antifreeze/coolant solution of claim 1 , including a bittering agent .
16. The antifreeze/coolant sol ution of cl aim 1 , incl uding a dye.
17. The antifreeze/coolant solution of claim 1 , including a biocide.
18. The antifreeze/coolant solution of claim 1 , wherein said silicone-silicate copolymer is present in an amount between about 0.1 to about 6.0 wt.r
19. The antifreeze/coolant solution of claim 1 , wherein said si l icone-silicate copolymer is selected from the group consi sting of alkali siliconate silylalkylphosphonates and salts thereof, aryl alkyl sil icone sulfonate-silicates and salts thereof, and sulfosiloxane-silicates and salts thereof.
Claim 20. The antifreeze/coolant solution of claim 1, wherein said polymeric polycarboxylate is selected from the group consisting of a secondary alcohol modified polyacrylic acid, a sodium salt of a copolymer of acrylic acid and maleic acid , a polyacryl ic acid or sodium salt thereof having a molecular weight (GPC M of about 2100
and a viscosity (CP at 25°C) ranging from between about 400 to about 1,400, a polyacrylic acid or sodium salt thereof having a molecular weight (GPC M of about 5,100 and a viscosity (CP at 25°C) ranging from between about 250 to about 500, and combinations thereof.
Claim 21. The antifreeze/coolant solution of claim 20, wherein said polyacrylic acid or sodium salt thereof having a molecular weight (GPC M of about 2100 and a viscosity (CP at 25°C) ranging from between about 400 to about 1,400 is GOODRITE® K-752.
Claim 22. The antifreeze/coolant solution of claim 20, wherein said polyacrylic acid or sodium salt thereof having a molecular weight (GPC of about 5,100 and a viscosity (CP at 25°C) ranging from between about 250 to about 500 is GOODRITE® K-732.
Claim 23. An antifreeze/coolant solution for inhibiting the corrosion of metals and inhibiting mineral scale said solution comprising a corrosion inhibiting effective amount of: a polymeric polycarboxylate; a salt which is at least one selected from the group consisting of sodium nitrate, potassium nitrate, magnesium nitrate, calcium nitrate, lithium nitrate and combinations thereof; a salt selected from the group consisting of sodium nitrite, potassium nitrite, magnesium nitrite, calcium nitrite, lithium nitrite and combinations thereof; an azole compound which is selected from the group consisting of sodium mercaptobenzothiazole, sodium tolytriazole, water-soluble triazoles, pyrazoles, imidazoles, isooxazoles, isothiazoles,
thiazoles, thiadiazole, 1, 2, 3-benzotriazole, 1,2,3-tolyltriazole, sodium 2-mercaptobenzothiazole, and sodium 2-mercaptobenzimidazole; a silicone-silicate copolymer; a phosphate compound which is selected from the group consisting of dipotassium phosphate, disodium phosphate, monopotassium phosphate, tripotassium phosphate, monosodium phosphate, trisodium phosphate, and mixtures thereof; a transition metal compound selected from the group consisting of disodium salt dihydrate of molybdic acid, molybdenum trioxide, silicoheteropolymolybdates and/or phosphoroheteropolymolybdates, sodium molybdate, potassium molybdate, lithium molybdate, ammonium molybdate, ammonium dimolybdate, and ammonium heptaolybdate; and a glycol compound selected from the group consisting of ethylene glycol, diethylene glycol, propylene glycol, methyl alcohol, ethyl alcohol, propyl alcohol, isopropyl alcohol and combinations thereof making up the balance of the solution.
Claim 24. The antifreeze/coolant solution of claim 23, wherein said polymeric polycarboxylate is selected from the group consisting of a secondary alcohol modified polyacrylic acid, a sodium salt of a copolymer of acrylic acid and maleic acid, a polyacrylic acid or sodium salt thereof having a molecular weight (GPC Mw) of about 2100 and a viscosity (CP at 25°C) ranging from between about 400 to about 1,400, a polyacrylic acid or sodium salt thereof having a molecular weight (GPC M„) of about 5,100 and a viscosity (CP at 25°C) ranging from between about 250 to about 500, and combinations thereof.
Claim 25. The antifreeze/coolant solution of claim 24, wherein said polyacryl ic acid or sodi um salt thereof having a molecular weight (GPC M„) of about 2100 and a viscosity (CP at 25°C) ranging from between about 400 to about 1,400 is GOODRITE® K-752.
Claim 26. The antifreeze/cool ant sol ution of cl aim 24, wherein said polyacrylic acid or sodium salt thereof having a molecular weight (GPC
of about 5, 100 and a vi scosity (CP at 25°C) ranging from between about 250 to about 500 i s GOODRITE® K-732
Claim 27. The antifreeze/coolant solution of claim 23, wherein said polymeric polycarboxylate comprises from about 0.001 to about 10 0 percent by weight.
Claim 28. The antifreeze/coolant sol ution of claim 23, wherein said nitrate salt compri ses an amount of about 0.1 to about 10 0 percent by weight.
Claim 29. The antifreeze/cool ant sol ution of claim 23, wherein said nitrate salt comprises an amount of about 0.01 to about 1.0 percent by weight
Claim 30. The antifreeze/coolant sol ution of claim 23, wherein said nitrite salt comprises an amount of about 0.01 to about 10.0 percent by weight.
Claim 31. The antifreeze/coolant sol ution of claim 23, wherein said nitrite salt comprises an amount of about 0.1 to about
1.0 percent by weight.
Claim 32. The antifreeze/coolant solution of claim 23, wherein said azole compound comprises an amount of about 0.01 to about 1.0 percent by weight.
Claim 33. The antifreeze/coolant solution of claim 23, wherein said silicone-silicate copolymer comprises an amount of about 0.1 to about 10.0 percent by weight.
Claim 34. The antifreeze/coolant solution of claim 23, wherein said phosphate salt comprises an amount providing a concentration of about 0.5 to about 2 parts by weight per 100 parts by weight.
Claim 35. The antifreeze/coolant solution of claim 23, wherein said transition metal compound an amount of from about 0.001 to about 10.0 percent by weight.
Priority Applications (12)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AU40943/99A AU743301B2 (en) | 1998-05-22 | 1999-05-21 | Diesel engine antifreeze composition |
| CA002333046A CA2333046C (en) | 1998-05-22 | 1999-05-21 | Diesel engine antifreeze composition |
| BRPI0010276-8B1A BR0010276B1 (en) | 1999-02-26 | 2000-02-25 | antifreeze composition based on monocarboxylic acid |
| EP00913616A EP1159372B1 (en) | 1999-02-26 | 2000-02-25 | Monocarboxylic acid based antifreeze composition for diesel engines |
| DE60045442T DE60045442D1 (en) | 1999-02-26 | 2000-02-25 | ANTIFREEZE FOR DIESEL ENGINES BASED ON MONOCARBONIC ACIDS |
| AT00913616T ATE493481T1 (en) | 1999-02-26 | 2000-02-25 | ANTIFREEZE FOR DIESEL ENGINES BASED ON MONOCARBOXYLIC ACIDS |
| PCT/US2000/004850 WO2000050532A1 (en) | 1999-02-26 | 2000-02-25 | Monocarboxylic acid based antifreeze composition for diesel engines |
| DK00913616.9T DK1159372T3 (en) | 1999-02-26 | 2000-02-25 | Monocarboxylic acid-based coolant composition for diesel engines |
| CNB008059918A CN1200990C (en) | 1999-02-26 | 2000-02-25 | Monocarboxylic acid based antifreeze composition for diesel engines |
| CA002363660A CA2363660C (en) | 1999-02-26 | 2000-02-25 | Monocarboxylic acid based antifreeze composition for diesel engines |
| MXPA01008616A MXPA01008616A (en) | 1999-02-26 | 2000-02-25 | Monocarboxylic acid based antifreeze composition for diesel engines. |
| AU35029/00A AU772428B2 (en) | 1999-02-26 | 2000-02-25 | Monocarboxylic acid based antifreeze composition for diesel engines |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US8382198A | 1998-05-22 | 1998-05-22 | |
| US09/083,821 | 1998-05-22 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO1999061545A1 true WO1999061545A1 (en) | 1999-12-02 |
Family
ID=22180917
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/US1999/011324 WO1999061545A1 (en) | 1998-05-22 | 1999-05-21 | Diesel engine antifreeze composition |
Country Status (4)
| Country | Link |
|---|---|
| CN (1) | CN1246415C (en) |
| AU (1) | AU743301B2 (en) |
| CA (1) | CA2333046C (en) |
| WO (1) | WO1999061545A1 (en) |
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| WO2007021961A1 (en) | 2005-08-12 | 2007-02-22 | Honeywell International Inc. | Method for stabilizing an engine coolant concentrate and preventing hard water salt formation upon dilution |
| WO2007050568A2 (en) * | 2005-10-25 | 2007-05-03 | Honeywell International Inc. | Heat transfer fluid compositions for cooling systems containing magnesium or magnesium alloys |
| CN100441657C (en) * | 2006-06-12 | 2008-12-10 | 蓝星环境工程有限公司 | Cooling fluid of engine |
| CN103666389A (en) * | 2013-09-30 | 2014-03-26 | 安阳化学工业集团有限责任公司 | Engine cooling liquid prepared by utilizing coal ethylene glycol waste |
| CN103694966A (en) * | 2013-09-30 | 2014-04-02 | 安阳化学工业集团有限责任公司 | Production apparatus for preparing engine liquid coolant from coal glycol waste material and technology thereof |
| WO2014124826A1 (en) * | 2013-02-13 | 2014-08-21 | Basf Se | Anti-freeze concentrate having corrosion protection and aqueous coolant composition produced therefrom |
| US9080093B2 (en) | 2013-02-13 | 2015-07-14 | Basf Se | Antifreeze concentrate with corrosion protection and aqueous coolant composition produced therefrom |
| CN104893687A (en) * | 2015-06-03 | 2015-09-09 | 辽宁石油化工大学 | Method for directly preparing anti-freezing solution by quickly treating coal-to-ethylene glycol technology waste liquid by inorganic base |
| US10307344B2 (en) * | 2016-02-15 | 2019-06-04 | Shofu Inc. | Two-paste type sealer composition for root canal filling |
| CN113930221A (en) * | 2021-10-27 | 2022-01-14 | 常州市鑫光化工科技有限公司 | Special cooling liquid for diesel locomotive |
| CN114672287A (en) * | 2022-04-01 | 2022-06-28 | 陶普斯化学科技(北京)有限公司 | High-corrosion-inhibition low-conductivity heat transfer medium and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2007021961A1 (en) | 2005-08-12 | 2007-02-22 | Honeywell International Inc. | Method for stabilizing an engine coolant concentrate and preventing hard water salt formation upon dilution |
| US7754097B2 (en) | 2005-08-12 | 2010-07-13 | Honeywell International Inc. | Method for stabilizing an engine coolant concentrate and preventing hard water salt formation upon dilution |
| WO2007050568A2 (en) * | 2005-10-25 | 2007-05-03 | Honeywell International Inc. | Heat transfer fluid compositions for cooling systems containing magnesium or magnesium alloys |
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| US9080093B2 (en) | 2013-02-13 | 2015-07-14 | Basf Se | Antifreeze concentrate with corrosion protection and aqueous coolant composition produced therefrom |
| US9458369B2 (en) | 2013-02-13 | 2016-10-04 | Basf Se | Antifreeze concentrate with corrosion protection and aqueous coolant composition produced therefrom |
| WO2014124826A1 (en) * | 2013-02-13 | 2014-08-21 | Basf Se | Anti-freeze concentrate having corrosion protection and aqueous coolant composition produced therefrom |
| CN103666389A (en) * | 2013-09-30 | 2014-03-26 | 安阳化学工业集团有限责任公司 | Engine cooling liquid prepared by utilizing coal ethylene glycol waste |
| CN103694966A (en) * | 2013-09-30 | 2014-04-02 | 安阳化学工业集团有限责任公司 | Production apparatus for preparing engine liquid coolant from coal glycol waste material and technology thereof |
| CN103666389B (en) * | 2013-09-30 | 2016-08-24 | 安阳化学工业集团有限责任公司 | The engine coolant prepared with coal-ethylene glycol waste material |
| CN103694966B (en) * | 2013-09-30 | 2016-08-24 | 安阳化学工业集团有限责任公司 | Process units and the technique thereof of engine coolant is prepared with coal-ethylene glycol waste material |
| CN104893687A (en) * | 2015-06-03 | 2015-09-09 | 辽宁石油化工大学 | Method for directly preparing anti-freezing solution by quickly treating coal-to-ethylene glycol technology waste liquid by inorganic base |
| CN104893687B (en) * | 2015-06-03 | 2018-05-29 | 辽宁石油化工大学 | A kind of method that coal-ethylene glycol process waste liquor anti-icing fluid directly processed is quickly handled using inorganic base |
| US10307344B2 (en) * | 2016-02-15 | 2019-06-04 | Shofu Inc. | Two-paste type sealer composition for root canal filling |
| CN113930221A (en) * | 2021-10-27 | 2022-01-14 | 常州市鑫光化工科技有限公司 | Special cooling liquid for diesel locomotive |
| CN113930221B (en) * | 2021-10-27 | 2023-12-26 | 常州市鑫光新材料科技有限公司 | Special coolant for diesel locomotive |
| CN114672287A (en) * | 2022-04-01 | 2022-06-28 | 陶普斯化学科技(北京)有限公司 | High-corrosion-inhibition low-conductivity heat transfer medium and preparation method and application thereof |
| CN114672287B (en) * | 2022-04-01 | 2023-08-18 | 陶普斯化学科技(北京)有限公司 | High corrosion inhibition low conductivity heat transfer medium and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CA2333046C (en) | 2007-02-06 |
| CN1308663A (en) | 2001-08-15 |
| AU4094399A (en) | 1999-12-13 |
| CA2333046A1 (en) | 1999-12-02 |
| CN1246415C (en) | 2006-03-22 |
| AU743301B2 (en) | 2002-01-24 |
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