CN105073942B - 具有防腐功能的防冻浓缩物和由其制备的含水冷却剂组合物 - Google Patents
具有防腐功能的防冻浓缩物和由其制备的含水冷却剂组合物 Download PDFInfo
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- CN105073942B CN105073942B CN201480008793.XA CN201480008793A CN105073942B CN 105073942 B CN105073942 B CN 105073942B CN 201480008793 A CN201480008793 A CN 201480008793A CN 105073942 B CN105073942 B CN 105073942B
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- acid
- weight
- ammonium
- salt
- corrosion
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- 238000005260 corrosion Methods 0.000 title claims abstract description 77
- 239000012141 concentrate Substances 0.000 title claims abstract description 70
- 230000002528 anti-freeze Effects 0.000 title claims abstract description 48
- 239000000203 mixture Substances 0.000 title claims abstract description 41
- 239000002826 coolant Substances 0.000 title claims abstract description 36
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 23
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000001816 cooling Methods 0.000 claims abstract description 23
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 21
- 239000011593 sulfur Substances 0.000 claims abstract description 19
- 238000002485 combustion reaction Methods 0.000 claims abstract description 17
- 230000004907 flux Effects 0.000 claims abstract description 16
- 229910000679 solder Inorganic materials 0.000 claims abstract description 16
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 15
- 239000007788 liquid Substances 0.000 claims abstract description 15
- 239000004411 aluminium Substances 0.000 claims abstract description 12
- 125000002723 alicyclic group Chemical group 0.000 claims abstract description 10
- 150000002894 organic compounds Chemical class 0.000 claims abstract description 10
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 8
- 238000003466 welding Methods 0.000 claims abstract description 8
- 125000003118 aryl group Chemical group 0.000 claims abstract description 6
- 239000013529 heat transfer fluid Substances 0.000 claims abstract description 5
- 229910052816 inorganic phosphate Inorganic materials 0.000 claims abstract description 5
- 230000007797 corrosion Effects 0.000 claims description 60
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 36
- -1 carboxyalkyl sulphur Chemical compound 0.000 claims description 29
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 28
- 229910052783 alkali metal Inorganic materials 0.000 claims description 25
- 150000003839 salts Chemical class 0.000 claims description 25
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 22
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 22
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 21
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 18
- 150000001340 alkali metals Chemical class 0.000 claims description 18
- 239000002585 base Substances 0.000 claims description 14
- 239000005864 Sulphur Substances 0.000 claims description 13
- 239000002253 acid Substances 0.000 claims description 13
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 125000004432 carbon atom Chemical group C* 0.000 claims description 10
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 10
- 150000003863 ammonium salts Chemical class 0.000 claims description 8
- 235000006408 oxalic acid Nutrition 0.000 claims description 6
- 230000009467 reduction Effects 0.000 claims description 6
- 150000003628 tricarboxylic acids Chemical class 0.000 claims description 6
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 5
- 150000001991 dicarboxylic acids Chemical class 0.000 claims description 5
- 235000019260 propionic acid Nutrition 0.000 claims description 5
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 5
- IKZGBIJWNYQDPJ-UHFFFAOYSA-N C(C)(=O)O.C(C1=CC=CC=C1)(=S)[S] Chemical compound C(C)(=O)O.C(C1=CC=CC=C1)(=S)[S] IKZGBIJWNYQDPJ-UHFFFAOYSA-N 0.000 claims description 4
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 4
- 229910052910 alkali metal silicate Inorganic materials 0.000 claims description 4
- 238000007710 freezing Methods 0.000 claims description 4
- 230000001376 precipitating effect Effects 0.000 claims description 4
- OCVLSHAVSIYKLI-UHFFFAOYSA-N 3h-1,3-thiazole-2-thione Chemical compound SC1=NC=CS1 OCVLSHAVSIYKLI-UHFFFAOYSA-N 0.000 claims description 3
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 3
- 230000008014 freezing Effects 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 2
- 229910001515 alkali metal fluoride Inorganic materials 0.000 claims description 2
- 229910001618 alkaline earth metal fluoride Inorganic materials 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 239000011737 fluorine Substances 0.000 claims description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 2
- 239000010931 gold Substances 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 150000001735 carboxylic acids Chemical class 0.000 claims 2
- 241000605159 Nitrobacter Species 0.000 claims 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 abstract 3
- 238000012360 testing method Methods 0.000 description 26
- 235000019441 ethanol Nutrition 0.000 description 16
- 235000001508 sulfur Nutrition 0.000 description 15
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 11
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 230000008859 change Effects 0.000 description 9
- 125000000623 heterocyclic group Chemical group 0.000 description 9
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 8
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 8
- 238000005554 pickling Methods 0.000 description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 7
- 150000001412 amines Chemical class 0.000 description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- 239000013049 sediment Substances 0.000 description 6
- 229910020239 KAlF4 Inorganic materials 0.000 description 5
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 5
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 5
- 125000004433 nitrogen atom Chemical group N* 0.000 description 5
- 229910052700 potassium Inorganic materials 0.000 description 5
- 239000011591 potassium Substances 0.000 description 5
- 229960004063 propylene glycol Drugs 0.000 description 5
- 239000005711 Benzoic acid Substances 0.000 description 4
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- 235000010233 benzoic acid Nutrition 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- HEBKCHPVOIAQTA-UHFFFAOYSA-N meso ribitol Natural products OCC(O)C(O)C(O)CO HEBKCHPVOIAQTA-UHFFFAOYSA-N 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 238000010186 staining Methods 0.000 description 4
- 125000001424 substituent group Chemical group 0.000 description 4
- 229910000838 Al alloy Inorganic materials 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229910002651 NO3 Inorganic materials 0.000 description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 3
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 3
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical group C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 125000000217 alkyl group Chemical class 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 239000002518 antifoaming agent Substances 0.000 description 3
- 229910021538 borax Inorganic materials 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000000975 dye Substances 0.000 description 3
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 description 3
- 239000008233 hard water Substances 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 235000011007 phosphoric acid Nutrition 0.000 description 3
- 229910000077 silane Inorganic materials 0.000 description 3
- 239000004328 sodium tetraborate Substances 0.000 description 3
- 235000010339 sodium tetraborate Nutrition 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- 229940124530 sulfonamide Drugs 0.000 description 3
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 2
- KDSNLYIMUZNERS-UHFFFAOYSA-N 2-methylpropanamine Chemical compound CC(C)CN KDSNLYIMUZNERS-UHFFFAOYSA-N 0.000 description 2
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 2
- KDCGOANMDULRCW-UHFFFAOYSA-N 7H-purine Chemical compound N1=CNC2=NC=NC2=C1 KDCGOANMDULRCW-UHFFFAOYSA-N 0.000 description 2
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- KXDAEFPNCMNJSK-UHFFFAOYSA-N Benzamide Chemical compound NC(=O)C1=CC=CC=C1 KXDAEFPNCMNJSK-UHFFFAOYSA-N 0.000 description 2
- HEBKCHPVOIAQTA-QWWZWVQMSA-N D-arabinitol Chemical compound OC[C@@H](O)C(O)[C@H](O)CO HEBKCHPVOIAQTA-QWWZWVQMSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- PWLXTFFHCFWCGG-UHFFFAOYSA-N Heneicosanedioic acid Chemical compound OC(=O)CCCCCCCCCCCCCCCCCCCC(O)=O PWLXTFFHCFWCGG-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 2
- 230000003260 anti-sepsis Effects 0.000 description 2
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical compound C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 2
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 description 2
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000012809 cooling fluid Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- LJOODBDWMQKMFB-UHFFFAOYSA-N cyclohexylacetic acid Chemical compound OC(=O)CC1CCCCC1 LJOODBDWMQKMFB-UHFFFAOYSA-N 0.000 description 2
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 2
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 2
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 2
- LVTYICIALWPMFW-UHFFFAOYSA-N diisopropanolamine Chemical compound CC(O)CNCC(C)O LVTYICIALWPMFW-UHFFFAOYSA-N 0.000 description 2
- 229940043276 diisopropanolamine Drugs 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 2
- FBPFZTCFMRRESA-GUCUJZIJSA-N galactitol Chemical compound OC[C@H](O)[C@@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-GUCUJZIJSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- FJDUDHYHRVPMJZ-UHFFFAOYSA-N nonan-1-amine Chemical compound CCCCCCCCCN FJDUDHYHRVPMJZ-UHFFFAOYSA-N 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- FBUKVWPVBMHYJY-UHFFFAOYSA-N nonanoic acid Chemical compound CCCCCCCCC(O)=O FBUKVWPVBMHYJY-UHFFFAOYSA-N 0.000 description 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 2
- LPNBBFKOUUSUDB-UHFFFAOYSA-N p-toluic acid Chemical compound CC1=CC=C(C(O)=O)C=C1 LPNBBFKOUUSUDB-UHFFFAOYSA-N 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 description 2
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- HEBKCHPVOIAQTA-ZXFHETKHSA-N ribitol Chemical compound OC[C@H](O)[C@H](O)[C@H](O)CO HEBKCHPVOIAQTA-ZXFHETKHSA-N 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 description 2
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 150000003456 sulfonamides Chemical class 0.000 description 2
- 150000003462 sulfoxides Chemical class 0.000 description 2
- 125000004434 sulfur atom Chemical group 0.000 description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 2
- OBETXYAYXDNJHR-SSDOTTSWSA-M (2r)-2-ethylhexanoate Chemical compound CCCC[C@@H](CC)C([O-])=O OBETXYAYXDNJHR-SSDOTTSWSA-M 0.000 description 1
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 description 1
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
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- 235000010288 sodium nitrite Nutrition 0.000 description 1
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- 229940005605 valeric acid Drugs 0.000 description 1
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Abstract
本发明涉及具有防腐功能的防冻浓缩物,其适用于冷却剂和传热流体并且包含降低凝固点的液体和含硫有机化合物、无机钼酸盐、无机磷酸盐以及脂族、脂环族和芳族一元碳酸、二元碳酸或三元碳酸。可由其得到适合用于冷却内燃机的含水冷却剂组合物,所述内燃机的冷却设备由铝通过使用包含氟铝酸盐焊剂的焊接方法制成。
Description
本发明涉及一种新型防冻浓缩物,所述防冻浓缩物基于作为主要成分的降低凝固点的液体、作为缓蚀剂的特定的含硫有机化合物以及其他的与其不相同的缓蚀剂。此防冻浓缩物适用于冷却剂,例如用于内燃机,以及适用于传热流体。本发明还涉及由其制备的含水冷却剂组合物。本发明还涉及此含水冷却剂组合物用于冷却内燃机的用途,所述内燃机的冷却设备由铝使用氟铝酸盐焊剂通过焊接制成。本发明还涉及特定的含硫有机化合物通常在此类防冻浓缩物和含水冷却剂组合物中作为缓蚀剂的用途。
用于例如汽车的内燃机冷却设备(其通常配置成为冷却回路)的冷却剂组合物通常包含亚烷基二醇如单乙二醇或单丙二醇(任选地与甘油混合)来作为降低冷却剂组合物凝固点的防冻成分。除了其他的成分如消泡剂、染料或苦味物之外,还特别包含缓蚀剂。
特别是在现代内燃机中,达到的温度对所使用的材料提出严格的要求。任意类型和任意程度的腐蚀均代表着潜在的危险因素,其可导致发动机的寿命的缩短和可靠性的降低。此外,各种不同的材料,例如铸铁、铜、黄铜、软焊料、钢以及铝、铝合金和镁合金,被越来越多地用于现代发动机。金属材料的这种多元化还导致潜在的腐蚀问题,特别是在不同金属互相接触的位置。特别是在这些地方能相对较容易地发生各种类型的腐蚀如点蚀、裂隙腐蚀、侵蚀或空化腐蚀。冷却剂组合物同样必须与冷却设备中的非金属成分例如软管连接或密封体的弹性体和塑料相容,且必须不得改变它们。此外,冷却剂组合物的类型对于现代内燃机中的热交换至关重要。
在一段时间内,用于通常在车辆和汽车制造中使用的内燃机以及用于固定式发动机的冷却设备或冷却回路主要由或仅由铝或铝合金制成。此处使用特定的焊接方法,例如在保护气体气氛下焊接。在此焊接方法中,必须伴随使用焊剂。此处,通常使用氟铝酸钾作为焊剂,例如KAlF4、K2AlF5和K3AlF6的混合物(例如可以名称商购)。
上述焊剂在焊接操作后部分保留在了冷却设备的表面。在引入含水冷却剂组合物并运行发动机之后,由于与水和含水冷却剂组合物的成分的一连串的化学反应(其互相处于平衡),冷却设备中的这些残留焊剂或快或慢地导致氢氧化铝凝胶的沉淀并因此导致在冷却回路中形成油泥。这极大地限制了从发动机中散热的效率并因此还限制了加热***的热交换、空气供给的冷却和变速箱油的冷却的功能。此外,氢氧化铝凝胶的存在对由冷却剂提供的防腐功能具有不利效应,因为缓蚀剂在氢氧化铝凝胶上吸附,从而防腐作用显著降低。
WO 2009/111443 A2公开了基于醇类的传热流体,其可用于含有使用氟铝酸钾焊接的铝成分的热交换设备。对于此传热流体,推荐整个系列的可能的单独的缓蚀剂,其本质上为无机或有机的,例如钼酸盐、钨酸盐、钒酸盐、磷酸盐、锑酸盐、硝酸盐、亚硝酸盐、硼酸盐、唑类或羧酸盐。作为可使用的含硫唑类,提及了2-巯基苯并噻唑(MTB)。表1示出了,作为基本的冷却剂浓缩物的,基于单乙二醇的剂型(I),其包含>94重量%的乙二醇、0.1-0.3重量%的甲苯基***、0.2-0.5重量%的硝酸盐、0.04-0.1重量%的钼酸盐、0.1-2.0重量%的硼砂、0.1-0.5重量%的磷酸、<0.3重量%的MBT、0.1-0.5重量%的硅酸盐和0.4-2.0重量%的NaOH/KOH,其中MBT可以但不一定是巯基苯并噻唑,因为没有给出MBT的解释。
然而,迄今为止还没有发现足够胜任用于内燃机的具有防腐功能的冷却剂组合物,所述冷却剂组合物在用于使用上述焊剂所焊接的铝冷却设备时,能实际上满足在提高焊剂耐受性方面的要求。因此本发明的目的是提供一种具有防腐功能的防冻浓缩物,由所述防冻浓缩物可得到含水冷却剂组合物,该含水冷却剂组合物对焊接的铝散热器中的氟铝酸盐的残留物具有高度耐受性,即其不再趋向于,或明显较低程度地趋向于,形成氢氧化铝凝胶沉淀和在冷却回路中形成油泥,由此使更有效的防腐成为可能。
因此我们发现了一种具有防腐功能的防冻浓缩物,其包含
(A)至少一种选自一元醇、二元醇和三元醇、多羟基醇、它们的醚及其混合物的降低凝固点的液体作为主要成分;
(B)至少一种选自以下的含硫有机化合物作为缓蚀剂;
(B1)包含下式结构要素的化合物
(B2)具有至少一个环硫原子、至少一个环外硫原子和至少一个环氮原子的杂环化合物以及
(B3)含硫脂族羧酸
(C)至少一种无机钼酸盐作为其他的缓蚀剂;
(D)至少一种无机磷酸盐作为其他的缓蚀剂;
(E)至少一种以碱金属盐、铵盐或取代铵盐的形式存在的脂族、脂环族或芳族一元羧酸、二元羧酸或三元羧酸,其在酸部分具有3至21个碳原子。
防冻组分(A),其代表着本发明的防冻浓缩物的主要成分并因此通常构成多于50重量%的浓缩物,确保了当具有由其制备的冷却剂组合物的内燃机在明显低于0℃的环境中启动时发动机的无故障启动,并确保了随后在发动机运行期间的良好的流动性能和良好的散热性。用于组分(A)的合适的一元醇、二元醇和三元醇、多羟基醇及其醚为,例如,甲醇、乙醇、正丙醇和异丙醇、正丁醇、异丁醇和仲丁醇、糠醛、四氢糠醇、乙氧基化糠醇、烷氧基烷醇如甲氧基乙醇、单乙二醇、单丙二醇、二乙二醇、二丙二醇、三乙二醇、三丙二醇、四乙二醇、四丙二醇、五乙二醇、五丙二醇、六乙二醇、六丙二醇、甘油、山梨醇、甘露醇、双甘油、苏糖醇、赤藓醇、阿东糖醇(核糖醇)、阿糖醇(lyxitol)、木糖醇、卫矛醇(半乳糖醇)、麦芽糖醇、异麦芽糖醇、1,2,6-己三醇、三羟甲基丙烷、三羟甲基乙烷、季戊四醇以及二醇的单醚如单乙二醇、单丙二醇、二乙二醇和二丙二醇的甲基醚、乙基醚、丙基醚和丁基醚(其中优选正丁基醚)。当然,也可使用所提及的醇、多羟基醇和醚的混合物。就本发明而言,术语丙二醇包含1,2-丙二醇和1,3-丙二醇。
在一个优选实施方案中,本发明的具有防腐功能的防冻浓缩物包含,作为降低凝固点的液体(A)的,单乙二醇、单丙二醇或者单乙二醇或单丙二醇与最高达35重量%的甘油的混合物,各自均基于降低凝固点的液体的总量计。非常特别优选使用单乙二醇而不添加其他的醇或醚。
在缓蚀剂(B)的实施方案(B1)中,所述至少一种含硫有机化合物包含下式结构要素
其中氮原子或硫原子上的自由键可连接至杂环,特别是五元或六元杂环,则其也可归入实施方案(B2)的定义下。
在缓蚀剂(B)的实施方案(B2)中,环硫原子和环氮原子优选形成具有噻唑结构的五元环,其在2位带有以巯基(-SH)或硫醚基(-S-烃基)形式存在的含硫取代基。然而,其他的杂环,通常的五元或六元环体系,例如在4或5位具有此含硫取代基的3H-1,2,3-二噻唑、在2、3、5或6位具有此含硫取代基的4H-1,4-噻嗪或在2、4或6位具有此含硫取代基的2H-1,3,5-噻二嗪,也可用于(B2)。
在一个特别优选的实施方案中,本发明的具有防腐功能的防冻浓缩物包含至少一种通式I的2-硫代噻唑作为缓蚀剂(B1)或(B2)
其中变量R1为式-(CmH2m)-COOX的羧基烷基基团,其中m为1至4且X为氢、碱金属阳离子、铵阳离子或取代的铵阳离子,而变量R2和R3各自,相互独立地,为氢或C1-C4-烷基基团,其中R2和R3与其连接的两个噻唑环环碳原子一起还可形成五元或六元饱和或不饱和环。
在变量R1中的C1-C4-亚烷基基团可为支链基团如1,2-亚丙基、1,2-亚丁基或2,3-亚丁基或直链多亚甲基基团。R1优选为式-(CH2)m-COOX的基团,其中m为1、2、3或4,优选2或3。
如果变量R2和R3中的一个或两个为C1-C4-烷基基团,则此烷基基团通常选自甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基和叔丁基。特别地,R2和R3均为氢或这些变量的一个为氢而另一个为甲基或乙基或两个变量R2和R3与其连接的两个噻唑环环碳原子一起形成苯环(苯并稠环体系)。
如果变量X为碱金属阳离子,则其为,例如,锂或优选钠或钾。如果变量X为未取代的铵阳离子,则其衍生自氨(NH3)。如果变量X为取代的铵阳离子,则其衍生自,例如,单烷基胺、二烷基胺或三烷基胺如单乙胺、二乙胺或三乙胺或衍生自三烷醇胺如三乙醇胺或三异丙醇胺。
实施方案(B1)或(B2)的某些特别优选的缓蚀剂为(2-苯并噻唑基硫)乙酸、3-(2-苯并噻唑基硫)丙酸或其碱金属、铵或取代铵的盐。所提及的两种缓蚀剂可以名称ABT和PBT商购(制造商:Sanshin Chemical Industry)。此外,同样市售可得的2-巯基苯并噻唑也特别优选作为实施方案(B1)或(B2)的缓蚀剂。
在缓蚀剂(B)的实施方案(B3)中,所述至少一种含硫有机化合物包含含硫脂族羧酸。化合物(B3)可包含一个或多个,特别是1、2或3个,羧基官能团。其中所含的硫可例如作为硫醚、亚砜或砜官能团而存在。化合物(B3)可额外地包含本质上为脂族、脂环族和/或芳脂族的烃基基团以及任选地包含位于分子中的其他杂原子和/或官能团。
在一个优选实施方案中,本发明的具有防腐功能的防冻浓缩物包含至少一种选自2,2-巯基二乙酸、(硫代苯甲酰基硫)乙酸、2-羟烷基羧基烷基硫醚、2-羟烷基羧基烷基亚砜以及其碱金属、铵和取代铵的盐的含硫脂族羧酸作为缓蚀剂(B3)。2,2-巯基二乙酸(也称为硫二乙酸:
HOOC-CH2-S-CH2-COOH)和(硫代苯甲酰基硫)乙酸
(Ph-CS-S-CH2-COOH)为市售可得的。分子式为烷基
-CH(OH)-CH2-S(=O)n-亚烷基-COOH的2-羟烷基羧基烷基硫醚和2-羟烷基羧基烷基亚砜记载于EP 0 025 125 A1,作为用于处理水输送***如蒸气产生设备、加热***、冷却水回路和水管道***的缓蚀剂。
作为缓蚀剂(C),通常使用钼酸H2MoO4的碱金属、铵或取代铵的盐或酸本身,其中碱金属、铵或取代铵的盐具有如以上所说明的意义。然而,组分(C)通常完全或主要以盐的形式存在于通常pH值为4至11的本发明的浓缩物中。也可使用其混合物。此钼酸盐(C)的典型的代表物是钼酸钠和钼酸钾。
作为缓蚀剂(D),通常使用正磷酸H3PO4的碱金属、铵或取代铵的盐或酸本身,其中碱金属、铵或取代铵的盐具有如以上所说明的意义。然而,组分(D)通常完全或主要以盐的形式存在于本发明的浓缩物中,其通常的pH值为4至11,特别是7至11。当使用游离的正磷酸时,通常通过氢氧化钠或氢氧化钾、氨或合适的胺将其转化为所需的盐。其他的合适的组分(D)为二磷酸、偏磷酸、焦磷酸和/或多聚磷酸的碱金属、铵或取代铵的盐或酸本身,其中碱金属、铵或取代铵的盐具有如以上所说明的意义。还可使用所提及的盐和/或酸的混合物。此磷酸盐(D)的典型的代表物是磷酸二氢钠、磷酸氢二钠、磷酸钠、二磷酸钠、焦磷酸钠、三聚磷酸钠、六偏磷酸钠以及类似的钾盐。
可能的缓蚀剂(E)特别为选自以下羧酸的单独的代表物或这些代表物的混合物:
(E1)以碱金属、铵或取代铵的盐的形式存在的各自具有3至16个碳原子的脂族、脂环族或芳族一元羧酸;
(E2)以碱金属、铵或取代铵的盐的形式存在的各自具有3至21个碳原子的脂族或芳族二元羧酸或三元羧酸。
(E1)组的可能的直链或支链的脂族或脂环族一元羧酸为,例如,丙酸、戊酸、己酸、环己基乙酸、辛酸、2-乙基己酸、壬酸、异壬酸、癸酸、新癸酸、十一烷酸或十二烷酸。(E1)组的合适的芳族一元羧酸特别为苯甲酸以及,例如,C1-C8-烷基苯甲酸如邻甲基苯甲酸、间甲基苯甲酸或对甲基苯甲酸或对叔丁基苯甲酸;含羟基的芳族一元酸如邻羟基苯甲酸、间羟基苯甲酸或对羟基苯甲酸或对(羟甲基)苯甲酸或卤代苯甲酸如邻氟苯甲酸、间氟苯甲酸或对氟苯甲酸。
(E2)组的二元羧酸或三元羧酸的典型实例为丙二酸、丁二酸、戊二酸、庚二酸、辛二酸、壬二酸、癸二酸、十一烷二酸、十二烷二酸、环戊二烯二羧酸、对苯二甲酸、邻苯二甲酸以及三嗪三亚氨基羧酸如6,6’,6”-(1,3,5-三嗪-2,4,6-三基三亚氨基)三己酸。
上述羧酸(E)通常完全或主要以如上所定义的碱金属、铵或取代铵的盐的形式存在,即使当其在本发明的防冻浓缩物的制备过程中是作为游离酸加入时,因为该浓缩物通常的pH值为4至11,特别是7至11。通常通过氢氧化钠或氢氧化钾、氨或合适的胺将作为游离羧酸使用的组分(E)转化为所需的盐。
在降低凝固点的液体(A)中的缓蚀剂(B)至(E)之间的相互作用是实现开篇所述目的的关键。此外,本发明的具有防腐功能的防冻浓缩物还可包含其他的缓蚀剂和/或其他的添加剂组分,以各自单独的形式或以混合物的形式并且以为此目的的常规量。
其他可能的缓蚀剂(F)至(K)为:
(F)作为无机盐的,碱金属硼酸盐、碱金属硅酸盐、碱金属亚硝酸盐、碱金属或碱土金属硝酸盐和/或碱金属或碱土金属氟化物;
(G)具有2至15个碳原子并且还可含有醚氧原子或羟基基团的脂族、脂环族或芳族胺;
(H)具有4至10个碳原子并且可为苯并稠合的和/或带有其他的官能团的单环或双环不饱和或部分不饱和杂环;
(J)四(C1-C8-烷氧基)硅烷(四-C1-C8-烷基原硅酸酯);
(K)羧酰胺或磺酰胺。
除了所提及的缓蚀剂(B)至(K)外,还可以以常规量使用例如镁与有机酸的可溶性盐,例如苯磺酸镁、甲磺酸镁、乙酸镁或丙酸镁、氢化咔唑或记载于DE-A 196 05 509中的季铵化咪唑作为其他的抑制剂。
无机盐(F)的典型的实例为四硼酸钠(硼砂)、偏硅酸钠、亚硝酸钠、硝酸钠、硝酸镁、氟化钠、氟化钾和氟化镁。当同时使用碱金属硅酸盐和碱金属偏硅酸盐时,其有利地用常规的有机硅膦酸盐或有机硅磺酸盐以常规量稳定。
胺(G)优选具有2至9,特别是4至8个碳原子。胺(G)优选叔胺。胺(G)优选包含0至3个醚氧原子或0至3个羟基基团。胺(G)的典型实例为乙胺、丙胺、异丙胺、正丁胺、异丁胺、仲丁胺、叔丁胺、正戊胺、正己胺、正庚胺、正辛胺、2-乙基己胺、正壬胺、异壬胺、二正丙胺、二异丙胺、二正丁胺、单乙醇胺、二乙醇胺和三乙醇胺、单异丙醇胺、二异丙醇胺和三异丙醇胺、哌啶、吗啉、环己胺、苯胺和苄胺。脂族和脂环族(G)通常为饱和的。
杂环(H)为,特别是具有1、2或3个氮原子并且可为苯并稠合的单环五元或六元体系。然而,还可使用具有五元和/或六元杂环部分环的双环体系,该杂环部分环通常具有总共2、3或4个氮原子。杂环(H)还可带有官能团如C1-C4-烷氧基,任选取代的氨基或巯基。杂环骨架当然还可带有烷基基团,特别是C1-C4-烷基基团。杂环(H)的典型实例为苯并***、甲苯***(甲苯基***)、氢化甲苯***、1H-1,2,4-***、苯并咪唑、苯并噻唑、腺嘌呤、嘌呤、6-甲氧基嘌呤、吲哚、异吲哚、异二氢吲哚、吡啶、嘧啶、3,4-二氨基吡啶、2-氨基嘧啶和2-巯基嘧啶。
可能的硅烷(J)为,例如四甲氧基硅烷、四乙氧基硅烷、四正丙氧基硅烷或四正丁氧基硅烷。
在DE-A 100 36 031中给出了可用于此处的芳族、杂芳族、脂族和脂环族(具有酰胺基团作为环的一部分)羧酰胺以及可用于此处的脂族和芳族磺酰胺(K)的典型实例。作为其中所提及的所有酰胺的代表物,此处可提及的仅是以下实例:己二酰二胺、苯甲酰胺、邻氨基苯甲酰胺、3-氨基苯甲酰胺和4-氨基苯甲酰胺、N-甲基-2-吡咯烷酮、吡啶酰胺、烟酰胺、苯磺酰胺、邻甲苯磺酰胺和对甲苯磺酰胺以及2-氨基苯磺酰胺。
其他的添加剂组分(L)至(O)可为:
(L)基于聚丙烯酸、聚马来酸、丙烯酸-马来酸共聚物、聚乙烯吡咯烷酮、聚乙烯咪唑、乙烯吡咯烷酮-乙烯咪唑共聚物和/或不饱和羧酸与烯烃的共聚物的硬水稳定剂;此处合适的市售可得的硬水稳定剂为CP 42;
(M)消泡剂;
(N)染料;
(O)出于卫生和摄入安全原因的苦味物,例如地那铵苯甲酸盐型苦味物;
降低凝固点的液体(A)在本发明的防冻浓缩物中的量通常为至少75重量%、优选至少80重量%、特别为至少85重量%、尤其为至少90重量%,每种情况下均基于浓缩物的总量计。
缓蚀剂(B)至(K)在本发明的防冻浓缩物中的总量通常为1至70重量%、优选2至35重量%、特别为2.5至15重量%、尤其为3至10重量%,每种情况下均基于浓缩物的总量计。
含硫有机化合物(B1)、(B2)和/或(B3)在本发明的防冻浓缩物中的量通常为0.01至5重量%、优选0.03至3重量%、尤其为0.07至1重量%,每种情况下均基于浓缩物的总量计。
无机钼酸盐(C)在本发明的防冻浓缩物中的量通常为0.001至2重量%、特别为0.003至1重量%、尤其为0.007至0.5重量%,每种情况下均基于浓缩物的总量计。
无机磷酸盐(D)在本发明的防冻浓缩物中的量通常为0.1至8重量%、特别为0.1至5重量%、尤其为0.1至3重量%,每种情况下均基于浓缩物的总量计。
脂族、脂环族或芳族一元羧酸、二元羧酸和/或三元羧酸(E)在本发明的防冻浓缩物中的量通常为0.1至10重量%、特别为0.5至8重量%、尤其为1至5重量%,每种情况下均基于浓缩物的总量计。
无机硼酸盐、硅酸盐、亚硝酸盐、硝酸盐和/或氟化物盐(F)在本发明的防冻浓缩物中的量通常为0至2重量%、特别为0.01至2重量%、尤其为0.1至1重量%,每种情况下均基于浓缩物的总量计。
脂族、脂环族和/或芳族胺(G)在本发明的防冻浓缩物中的量通常为0至5重量%、特别为0.01至5重量%、尤其为0.1至3重量%,每种情况下均基于浓缩物的总量计。
单环或双环杂环(H)在本发明的防冻浓缩物中的量通常为0至5重量%、特别为0.01至5重量%、尤其为0.05至2重量%,每种情况下均基于浓缩物的总量计。
四(C1-C8-烷氧基)硅烷(J)在本发明的防冻浓缩物中的量通常为0至5重量%、特别为0.01至5重量%、尤其为0.1至2重量%,每种情况下均基于浓缩物的总量计。
羧酰胺和/或磺酰胺(K)在本发明的防冻浓缩物中的量通常为0至10重量%、特别为0.01至10重量%、尤其为0.1至5重量%,每种情况下均基于浓缩物的总量计。
硬水稳定剂(L)在本发明的防冻浓缩物中的量通常为0至1重量%、特别为0.01至1重量%、尤其为0.05至0.5重量%,每种情况下均基于浓缩物的总量计。
消泡剂(M)在本发明的防冻浓缩物中的量通常为0至0.5重量%、特别为0.001至0.05重量%、尤其为0.002至0.02重量%,每种情况下均基于浓缩物的总量计。
染料(N)在本发明的防冻浓缩物中的量通常为0至0.05重量%、特别为0.001至0.05重量%,每种情况下均基于浓缩物的总量计。
苦味物(O)在本发明的防冻浓缩物中的量通常为0至0.05重量%、特别为0.001至0.05重量%,每种情况下均基于浓缩物的总量计。
本发明的防冻浓缩物还可包含少量的水,通常为0至10重量%、特别为0至5重量%,每种情况下均基于浓缩物的总量计。本发明的防冻浓缩物所包含的所有组分的总量(包括水)在所有情况下均为100.0重量%。
在一个优选实施方案中,本发明的防冻浓缩物包含75至99.5重量%的降低凝固点的液体(A)、总和为0.5至25重量%的缓蚀剂(B)至(E)、0至10重量%的不同于(B)至(E)并且通常选自上述组(F)至(K)的其他的缓蚀剂以及0至10重量%的水。
可通过将各个组分简单地混合来制备本发明的防冻浓缩物。然而,还可通过将合适的超浓缩物与起到防冻组分作用的降低凝固点的液体(A)和任选的一些水稀释来制备本发明的防冻浓缩物,所述超浓缩物中活性组分(B)至(O)以较高的浓度存在。浓缩物中超浓缩物的比例通常为3至60重量%。超浓缩物(通常为了运输目的)由具有正常浓度的浓缩物通过移除使其他的组分仍恰好以溶解的形式存在的量的防冻组分来制备。
本发明还提供含水冷却剂组合物,其包含10至90重量%、特别是20至60重量%的本发明的防冻浓缩物。本发明的含水冷却剂组合物通常由本发明的防冻浓缩物通过用适量的水稀释来制备。
本专利申请还提供上述本发明的含水冷却剂组合物用于冷却内燃机的用途,所述内燃机的冷却设备主要由或仅仅由铝使用氟铝酸盐焊剂通过焊接方法制成。这样,如开篇所指明的在此冷却设备中氢氧化铝凝胶的沉淀和冷却回路中油泥的形成的问题以非常有利的方式得以解决。因此本发明的含水冷却剂组合物对氟铝酸盐焊剂的残留物具有明显更高的耐受性并因此提供更有效的腐蚀防护。
上述系列的含硫有机化合物(B),还通常甚至在不含任何使用氟铝酸盐焊剂所焊接的铝散热器的冷却设备和传热回路中适合用作防冻浓缩物中的特别有效的缓蚀剂。因此本发明还提供(2-苯并噻唑基硫)乙酸、3-(2-苯并噻唑基硫)丙酸、2,2-巯基二乙酸、(硫代苯甲酰基硫)乙酸、2-羟烷基羧基烷基硫醚、2-羟烷基羧基烷基亚砜以及其碱金属、铵和取代铵的盐在防冻浓缩物中以及在由其制备的含水冷却剂组合物中用作缓蚀剂的用途,所述防冻浓缩物基于作为主要成分的选自单价醇、二价醇和三价醇、多羟基醇、它们的醚及其混合物的降低凝固点的液体。
以下实施例说明本发明而不限制本发明。
实施例
以下腐蚀实验根据ASTM D 4340来进行。此标准测试用来测定内燃机的冷却设备中的铝或铝合金的腐蚀敏感性。用于此目的的标准设备模拟了内燃机的冷却回路的热的含铝内表面。从下面加热铝测试板,而上表面与待测试的冷却流体接触。测试温度为135℃。在168小时的设定测试时间的测试结束后,用目测评估板的腐蚀并通过称重测定重量变化(酸洗前或酸洗后)。
所用的冷却剂组合物KM1至KM6[组分以重量%表示]:
冷却剂组合物KM1至KM7各自用去离子水以50:50的体积比稀释以进行测试。
在KAlF4下使用KM1和KM2根据ASTM D 4340进行的腐蚀测试(酸洗后):
在测试前将KM1(用于比较)、KM2(本发明)和KM3(本发明)各自与600mg的四氟铝酸钾/升冷却剂组合物混合从而模拟焊剂的污染。在KM1的情况下,铝测试板在测试之后获得黑色锈斑并且显示出严重的腐蚀;重量变化为+2.90mg/cm2。在KM2和KM3的情况下,铝测试板无变化且无沉淀物并且未显示出腐蚀现象;重量变化非常微小且均为-0.19mg/cm2。
在KAlF4下使用KM4至KM7根据ASTM D 4340进行的腐蚀测试(未酸洗):
在测试前将KM4(用于比较)、KM5(本发明)、KM6(本发明)和KM7(本发明)各自与300mg的四氟铝酸钾/升冷却剂组合物混合从而模拟焊剂的污染;将KM7,在第二次测试中(KM7a,本发明),事先与双倍量的KAlF4(600mg/每升)混合。在KM4的情况下,铝测试板在测试之后显示出明显的腐蚀痕迹;重量变化为-0.34mg/cm2。在KM5、KM6、KM7和KM7a的情况下,铝测试板均轻微变色并显示出沉淀物;重量变化微小且在KM5的情况下为-0.12mg/cm2、在KM6的情况下为+0.06mg/cm2、在KM7的情况下为+0.04mg/cm2以及在KM7a的情况下为+0.07mg/cm2。
无KAlF4下使用KM4、KM5和KM7根据ASTM D 4340进行的腐蚀测试(未酸洗):
用KM4(用于比较)、KM5(本发明)和KM7(本发明)进行腐蚀测试而事先不添加KAlF4。在KM4的情况下,铝测试板在测试之后同样显示出明显的腐蚀痕迹;重量变化再次为-0.34mg/cm2。在KM5和KM7的情况下,铝测试板具有彩虹色的锈斑;重量变化微小且在KM5的情况下为-0.08mg/cm2以及在KM7的情况下为0mg/cm2。
铝测试板的酸洗的影响和锈蚀的显著性:
为了解释实验结果,应指出在酸洗过程中,在测试进行期间通过从测试板上腐蚀性除去以及从冷却流体中再沉淀而形成的沉淀物被完全或至少大部分地再次除去。这导致了仅仅略微正(当通过酸洗除去沉淀物不完全时)或略微负(当通过酸洗除去沉淀物完全且从板上的腐蚀性除去在重量上变得可识别时)的重量变化。在测试期间沉淀物形成的程度以及在酸洗后仍保留的沉淀物层是腐蚀敏感性的量度。因此,相比于在KM2和KM3情况下的-0.19mg/cm2的值,在KM1情况下的+2.90mg/cm2的残留沉淀物表明了高的腐蚀敏感性。
在KM1情况下的铝测试板上的黑色锈斑(通常与可见的腐蚀损害有关)表明了高的腐蚀敏感性。另一方面,在KM5和KM7情况下的在无酸洗的测试过程中的彩虹色的锈斑通常象征着形成了非常薄的保护层并且表明了良好的防腐作用。
Claims (9)
1.一种具有防腐功能的防冻浓缩物,适用于冷却剂和传热流体,其特征在于包含
(A)至少一种选自一元醇、二元醇和三元醇、多羟基醇、它们的醚及其混合物的降低凝固点的液体作为主要成分;
(B)至少一种选自以下的含硫有机化合物作为缓蚀剂;
至少一种2-硫代噻唑,其选自(2-苯并噻唑基硫)乙酸、3-(2-苯并噻唑基硫)丙酸或其碱金属、铵或取代铵的盐
以及
含硫脂族羧酸,其选自2,2-巯基二乙酸、(硫代苯甲酰基硫)乙酸、2-羟烷基羧基烷基硫醚、2-羟烷基羧基烷基亚砜以及其碱金属、铵和取代铵的盐;
(C)至少一种无机钼酸盐作为其他的缓蚀剂;
(D)至少一种无机磷酸盐作为其他的缓蚀剂;
(E)至少一种以碱金属盐、铵盐或取代铵盐的形式存在的脂族、脂环族或芳族一元羧酸、二元羧酸或三元羧酸,其在酸部分具有3至21个碳原子。
2.权利要求1的具有防腐功能的防冻浓缩物,其特征在于包含单乙二醇、单丙二醇或者单乙二醇或单丙二醇与最高达35重量%的甘油的混合物作为降低凝固点的液体(A),各自均基于降低凝固点的液体的总量计。
3.权利要求1的具有防腐功能的防冻浓缩物,其特征在于包含75至99.5重量%的降低凝固点的液体(A)、总和为0.5至25重量%的缓蚀剂(B)至(E)、0至10重量%的不同于(B)至(E)的其他缓蚀剂以及0至10重量%的水。
4.权利要求3的具有防腐功能的防冻浓缩物,其特征在于还包含0.01至2重量%的无机盐,其中所述无机盐选自碱金属硼酸盐、碱金属硅酸盐、碱金属亚硝酸盐、碱金属或碱土金属硝酸盐和/或碱金属或碱土金属氟化物。
5.一种含水冷却剂组合物,其特征在于包含10至90重量%的权利要求1至3中任一项的具有防腐功能的防冻浓缩物。
6.权利要求5的含水冷却剂组合物用于冷却内燃机的用途,其特征在于所述内燃机的冷却设备主要由或仅仅由铝使用氟铝酸盐焊剂通过焊接方法制成。
7.权利要求5的含水冷却剂组合物用于降低冷却回路中的来自氟铝酸盐焊剂的氢氧化铝凝胶沉淀的用途。
8.(2-苯并噻唑基硫)乙酸、3-(2-苯并噻唑基硫)丙酸、2,2-巯基二乙酸、(硫代苯甲酰基硫)乙酸、2-羟烷基羧基烷基硫醚、2-羟烷基羧基烷基亚砜以及其碱金属、铵和取代铵的盐在防冻浓缩物中以及在由其制备的含水冷却剂组合物中用作缓蚀剂的用途,其特征在于所述防冻浓缩物包含
(A)至少一种选自一元醇、二元醇和三元醇、多羟基醇、它们的醚及其混合物的降低凝固点的液体作为主要成分;
(B)至少一种选自以下的含硫有机化合物作为缓蚀剂;
至少一种2-硫代噻唑,其选自(2-苯并噻唑基硫)乙酸、3-(2-苯并噻唑基硫)丙酸或其碱金属、铵或取代铵的盐
以及
含硫脂族羧酸,其选自2,2-巯基二乙酸、(硫代苯甲酰基硫)乙酸、2-羟烷基羧基烷基硫醚、2-羟烷基羧基烷基亚砜以及其碱金属、铵和取代铵的盐;
(C)至少一种无机钼酸盐作为其他的缓蚀剂;
(D)至少一种无机磷酸盐作为其他的缓蚀剂;
(E)至少一种以碱金属盐、铵盐或取代铵盐的形式存在的脂族、脂环族或芳族一元羧酸、二元羧酸或三元羧酸,其在酸部分具有3至21个碳原子。
9.通过在冷却回路中使用权利要求5的含水冷却剂组合物降低冷却回路中的来自氟铝酸盐焊剂的氢氧化铝凝胶沉淀的方法。
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PCT/EP2014/051988 WO2014124826A1 (de) | 2013-02-13 | 2014-02-03 | Gefrierschutzmittel-konzentrat mit korrosionsschutz und daraus hergestellte wässrige kühlmittelzusammensetzung |
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CN107987802B (zh) * | 2016-10-26 | 2020-06-09 | 中国石油化工股份有限公司 | 一种耐高温的发动机冷却液 |
KR20190127739A (ko) | 2017-03-21 | 2019-11-13 | 바스프 에스이 | 동결방지 부식방지 농축물 |
JP6364149B1 (ja) * | 2017-08-03 | 2018-07-25 | 加藤 行平 | 自動車用クーラント基材、クーラント添加剤、クーラント及びクーラント試験装置 |
CN107779176A (zh) * | 2017-12-07 | 2018-03-09 | 陈星朴 | 一种汽车发动机有机冷却液及其制备方法 |
KR102529534B1 (ko) * | 2017-12-26 | 2023-05-08 | 현대자동차주식회사 | 차량용 냉각액 |
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JP2023538744A (ja) | 2020-08-26 | 2023-09-11 | ビーエーエスエフ ソシエタス・ヨーロピア | 貯蔵安定性の改善を示す新規冷却剤 |
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CA3240404A1 (en) | 2021-12-09 | 2023-06-15 | Masayuki Hirosue | Antifreeze concentrate with corrosion protection and aqueous coolant composition produced therefrom |
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