WO2003054108A1 - Concentres de protection de radiateur et compositions de liquide de refroidissement offrant une meilleure protection contre la corrosion - Google Patents
Concentres de protection de radiateur et compositions de liquide de refroidissement offrant une meilleure protection contre la corrosion Download PDFInfo
- Publication number
- WO2003054108A1 WO2003054108A1 PCT/EP2002/014591 EP0214591W WO03054108A1 WO 2003054108 A1 WO2003054108 A1 WO 2003054108A1 EP 0214591 W EP0214591 W EP 0214591W WO 03054108 A1 WO03054108 A1 WO 03054108A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- acid
- coolant
- salt
- concentrate
- concentrate according
- Prior art date
Links
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
- C23F11/10—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 using organic inhibitors
- C23F11/12—Oxygen-containing compounds
-
- 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
- C09K5/08—Materials not undergoing a change of physical state when used
- C09K5/10—Liquid materials
-
- 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
-
- 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
Definitions
- the present invention relates to coolant concentrates or ready-to-use coolant compositions based on water and polyhydric alcohols, preferably alkylene glycols, derivatives thereof and / or glycerin.
- the compositions according to the invention contain, as minimum constituents, salts of 2-ethylhexanoic acid, 3,5,5-trimethylhexanoic acid (isononanoic acid) and of one or more aromatic monocarboxylic acids containing hydroxyl groups.
- the salts are preferably alkali metal, ammonium or substituted ammonium salts.
- the coolant concentrates are used for the production of aqueous coolant compositions for ner combustion engines.
- Antifreeze concentrates for the cooling circuits of ner combustion engines for example in automobiles, generally contain, in addition to water, polyhydric alcohols, preferably alkylene glycols, in particular ethylene glycol or propylene glycol and / or glycerin.
- polyhydric alcohols preferably alkylene glycols, in particular ethylene glycol or propylene glycol and / or glycerin.
- they are diluted with water and, in addition to frost protection (depending on the degree of dilution), should in particular ensure good heat dissipation.
- Water / alkylene glycol mixtures are very corrosive at the operating temperatures of internal combustion engines. Therefore, the various metals such as steel, cast iron (gray cast iron), copper, brass, aluminum, magnesium and their alloys as well as solder metals such as solder, which are used in the manufacture of the cooling system, must be adequately protected against the most varied types of corrosion, for example, by using corrosion inhibitors Pitting corrosion, crevice corrosion, erosion or cavitation are protected.
- EP-B 0 229 440 discloses glycol-containing protective agent concentrates which, in addition to mono- and dicarboxylic acids or their salts, contain 0.1 to 0.5% by weight of a triazole compound.
- EP-B 0 479 470 describes coolant compositions which, in addition to a suitable polyhydric alcohol to lower the freezing point as a corrosion inhibitor, contain at least one carboxylic acid with a branched aliphatic chain, in particular from the group consisting of neopentanoic acid, isononanoic acid, neoheptanoic acid, dimethylglutaric acid, diethylmalonic acid and 2-ethylvaleric acid.
- further corrosion inhibitors known per se can be added.
- Antifreeze agents are known from EP-B 0 564 721 which contain aliphatic C 5 -C 16 monocarboxylic acids or their salts in combination with triazoles and imidazoles in addition to a polyhydric alcohol for lowering the freeze, optionally further corrosion inhibitors such as dicarboxylic acid salts are used.
- EP-B 0 251 480 discloses coolant protection agents which, in addition to alcohol, contain an alkylbenzoic acid, one or more aliphatic C 8 -C 12 monocarboxylic acids, for example nonanoic acid or 2-ethylhexanoic acid, or their salts.
- WO 00/50532 describes coolants which, in addition to nitrite, nitrate, azoles, molybdates, silicates, and polyvinylpyrrolidone, contain one or more carboxylic acids, preferably aliphatic monobasic C 3 -C 16 -carboxylic acids, for example 2-ethylhexanoic acid or nonanoic acid or salts thereof, in addition an alcohol.
- carboxylic acids preferably aliphatic monobasic C 3 -C 16 -carboxylic acids, for example 2-ethylhexanoic acid or nonanoic acid or salts thereof, in addition an alcohol.
- WO 99/24524 describes silicate-free coolants which contain one or more aliphatic monobasic carboxylic acids, preferably Cs-C t o-carboxylic acids such as 2-ethylhexanoic acid or nonanoic acid or salts thereof, in combination with molybdate and azole derivatives.
- ES-A 21 24 195 describes glycol-containing coolants which contain a monocarboxylic acid or its salts in addition to triazoles, polysiloxanes and polyacrylates.
- EP-A 0 816 647 discloses silicate-free, borate-free and nitrate-free coolant concentrates containing glycol, which in addition to 0.05 to 10% by weight of a salt of at least a carboxylic acid 0.01 to 3 wt .-% of a hydrocarbon triazole and / or hydrocarbon ethiazole.
- the object of the present invention is to provide improved coolant concentrates or coolant compositions derived therefrom. This object is achieved by a coolant concentrate containing, in addition to water and a conventional polyhydric alcohol, the following components:
- the aromatic carboxylic acids containing hydroxyl groups are carboxylic acids which are derived from benzoic acid. They have one or two hydroxyl groups.
- Preferred hydroxyl-containing aromatic monocarboxylic acids which are used in the present invention are 2-, 3- or 4-hydroxybenzoic acid or 2-, 3- or 4- (hydroxymethyl) benzoic acid.
- 4-hydroxybenzoic acid as the aromatic monocarboxylic acid containing hydroxyl groups.
- the carboxylic acids used according to the invention are present as salts in the coolant concentrates according to the invention.
- the acids are preferably present as alkali metal salts, ammonium salts or substituted ammonium salts (amine salts), that is to say for example as salts of ammonia, triallcylamines or trialkanolamines.
- amine salts substituted ammonium salts
- sodium or potassium salts are used.
- the coolant concentrates according to the invention additionally contain 0.05 to 5% by weight, based on the total amount of the concentrate, of a salt of one or more aliphatic dicarboxylic acids having 3 to 21 carbon atoms.
- dicarboxylic acids are also preferably in the form of an alkali metal, ammonium or substituted ammonium salt, in particular a sodium or potassium salt.
- a dicarboxylic acid malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedicarboxylic acid or dodecanedicarboxylic acid are preferably used.
- 1,12-dodecanedicarboxylic acid is used.
- the coolant concentrates according to the invention may contain further, known corrosion-inhibiting substances.
- these can be heterocycles, for example mononuclear 5- or 6-membered systems with one, two or three nitrogen atoms or with one nitrogen atom and one sulfur atom. These heterocycles can be benzanellated. Binuclear systems of 5- and / or 6-membered partial rings with two, three or four nitrogen atoms can also be used.
- the heterocyclic backbone can be substituted with alkyl groups, preferably Ci-Gralkyl groups.
- the substituted or unsubstituted heterocycles can have functional groups, preferably CrC 4 - alkoxy, amino and / or mercapto groups.
- heterocycles mentioned are benzotriazole and tolutriazole
- Tolyltriazole hydrogenated tolutriazole, lH-l, 2,4-triazole, benzirnidazole, benzthiazole, adenine, purine, 6-methoxypurine, indole, isoindole, isoindoline, pyridine, pyrimidine, 3,4-
- Diaminopyridine, 2-aninopyrimidine and 2-mercaptopyrimidine are Usually used in doses of 0.05 to 5 wt .-%, based on the total amount of the concentrate.
- Examples of other corrosion inhibitors optionally present are sodium tetraborate (borax), disodium hydrogen phosphate, trisodium phosphate, sodium metasilicate, sodium nitrite, sodium nitrate, magnesium nitrate and sodium molybdate.
- alkali metal silicates are also used, these are expediently stabilized in customary amounts by conventional organosilicophosphates or organosilicon sulfonates.
- the coolant concentrates contain, in addition to the inventive combination of alcohols, a triazole from the group of triazoles listed above and a silicate from the group of silicates listed above.
- soluble salts of magnesium from organic acids for example magnesium benzene sulfonate, magnesium methane sulfonate, magnesium acetate or magnesium propionate, and hydrocarbazoles or quaternized imidazoles, as described in DE-A 196 05 509, can also advantageously be used in many cases in customary amounts Inhibitors are added.
- one or more hard water stabilizers based on polyacrylic acid, polymaleic acid, acrylic acid-maleic acid copolymers, polyvinylpyrrolidone, polyvinylimidazole, Vmylpyrrolidon-Vmylimidazol copolymers and / or copolymers of unsaturated carboxylic acids and olefins are present.
- the pH of the radiator protection concentrates according to the invention is usually in the range from 6 to 11, preferably 6 to 10, in particular 6.5 to 8.5.
- the desired pH can optionally also be adjusted by adding alkali metal hydroxide, ammonia or the corresponding amine to the formulation. Solid sodium or potassium hydroxide and aqueous sodium or potassium hydroxide are particularly suitable for this.
- the carboxylic acids used are expediently added directly in the form of the corresponding alkali metal salts in order to automatically obtain the desired pH range. However, the carboxylic acids can also be added as free acids and then neutralize with alkali metal hydroxide, ammonia or amine and adjust the desired pH range.
- polyhydric alcohols known to the person skilled in the art are suitable as liquid alcohol freezing agents.
- Alkylene glycols and their derivatives and glycerol are preferred.
- Examples are ethylene glycol and propylene glycol, higher glycols and glycol ethers, for example diethylene glycol and dipropylene glycol, monoethers of glycols, for example methyl, ethyl, propyl and butyl ether of ethylene glycol, propylene glycol, diethylene glycol and dipropylene glycol.
- the use of propylene glycol and ethylene glycol is more preferred, and ethylene glycol is particularly preferred.
- the abovementioned alcohols can be used alone or as a mixture, mixtures of glycols and glycol ethers with glycerol also being able to be used.
- the coolant concentrates according to the invention contain water
- the concentrates according to the invention contain a total of at least 20% by weight of one of the abovementioned polyhydric alcohols or mixtures of the polyhydric alcohols.
- the coolant concentrates according to the invention can also contain defoamers in customary small amounts as a further customary aid, generally in amounts of 0.003 to 0.008% by weight, and for reasons of hygiene and safety they contain bitter substances, for example of the denatonium benzoate type, in order to prevent swallowing prevent.
- Other common auxiliaries are dyes in amounts of 0.0005 to 0.1% by weight, based on the total amount of the concentrate, for example the dyes CI Reactive Violet 5 (Color Index No. 18097), Direct Blue 199 (CI 74190), Direct Blue 86 (CI 74180), Acid Green 25 (CI 61570), Acid Yellow 73 (CI 45350), Uranine (sodium fluorescein), Acid Green 25, Acid Yellow 221 and Basic Violet 10 (CI 45170), alone or in combination.
- Reactive Violet 5 is described in German application Az. 101 22 769.8 dated May 10, 2001.
- the present invention furthermore relates to ready-to-use aqueous coolant compositions, in particular for the cooler protection of internal combustion engines, which contain water and 8 to 90% by weight of the coolant concentrates according to the invention.
- the ready-to-use mixtures are generally obtained by diluting the coolant concentrates according to the invention with water.
- Formulation A according to the invention was prepared by simply mixing the following components with stirring:
- a commercially available aqueous coolant concentrate which is marketed by BASF AG under the name Glysacorr ® G 93, was used as a comparison.
- This product is the only aliphatic monocarboxylic acid containing 2-ethylhexanoic acid in the form of an alkali salt.
- Tables 1 to 3 show corrosion results of the Formulation A according to the invention compared to Glysacorr ® G 93 in Glassware Corrosion Test in accordance with ASTM D 1384-97, in the static hot corrosion test according to ASTM D 4340 and in the iron corrosion test according to DIN 51360-81 (part 2).
- formulation A according to the invention which contains a combination of 2-ethylhexanoic acid, isononanoic acid and 4-hydroxybenzoic acid, good corrosion rates on different metals are achieved.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Combustion & Propulsion (AREA)
- Thermal Sciences (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
Abstract
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AU2002358168A AU2002358168A1 (en) | 2001-12-21 | 2002-12-19 | Radiator protective agent concentrates and coolant compositions having an improved protection against corrosion |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE10163337.8 | 2001-12-21 | ||
DE2001163337 DE10163337A1 (de) | 2001-12-21 | 2001-12-21 | Kühlerschutzmittel-Konzentrate und Kühlmittelzusammensetzungen mit verbessertem Korrosionsschutz |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2003054108A1 true WO2003054108A1 (fr) | 2003-07-03 |
Family
ID=7710417
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP2002/014591 WO2003054108A1 (fr) | 2001-12-21 | 2002-12-19 | Concentres de protection de radiateur et compositions de liquide de refroidissement offrant une meilleure protection contre la corrosion |
Country Status (4)
Country | Link |
---|---|
AR (1) | AR038043A1 (fr) |
AU (1) | AU2002358168A1 (fr) |
DE (1) | DE10163337A1 (fr) |
WO (1) | WO2003054108A1 (fr) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2009035741A1 (fr) * | 2007-06-28 | 2009-03-19 | Chevron U.S.A Inc. | Compositions de concentré d'antigel et de liquide de refroidissement et leur préparation |
DE102011004765A1 (de) | 2010-02-25 | 2011-08-25 | Behr GmbH & Co. KG, 70469 | Zusätze für silikathaltige Heiz- und Kühlmittel |
DE102010002349A1 (de) | 2010-02-25 | 2011-08-25 | Behr GmbH & Co. KG, 70469 | Zusätze für Heiz- und Kühlmittel |
DE102010002341A1 (de) | 2010-02-25 | 2011-08-25 | Behr GmbH & Co. KG, 70469 | Wärmeübertrager und Bauteile für Kfz-Kühlkreisläufe |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2005047419A1 (fr) * | 2003-11-13 | 2005-05-26 | Vladisav Milovanovic | Solution aqueuse non toxique antigel et anticorrosion et dispositif de regeneration de l'antigel utilise |
KR101437690B1 (ko) | 2005-02-28 | 2014-09-03 | 바스프 에스이 | 부식 방지 특성을 갖는 글리세롤 함유 동결방지 농축물 |
DE102017206940A1 (de) * | 2017-04-25 | 2018-10-25 | Mahle International Gmbh | Verfahren zur Herstellung eines Wärmetauschers |
EP4056664A1 (fr) * | 2021-03-10 | 2022-09-14 | Basf Se | Concentrés solides de liquide de refroidissement et leur fabrication |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0229440B1 (fr) * | 1985-12-27 | 1990-06-06 | Texaco Development Corporation | Inhibiteur de corrosion pour antigel à base d'acide/sel monobasique/dibasique |
EP0487194A1 (fr) * | 1990-11-19 | 1992-05-27 | Texaco Development Corporation | Composition antigel/de refroidissement inhibée contre la corrosion et contenant un acide carboxylique aromatique |
EP0479470B1 (fr) * | 1990-10-01 | 1995-05-17 | Texaco Development Corporation | Composition d'antigel/de refroidissement inhibié contre la corrosion |
EP0863960B1 (fr) * | 1995-12-13 | 1999-10-13 | Henkel Kommanditgesellschaft auf Aktien | Concentre antigel |
DE19962757A1 (de) * | 1999-12-23 | 2001-06-28 | Basf Ag | Wässrige Motoreinlauf-Kühlflüssigkeit mit Dampfraumkorrosionsschutz |
-
2001
- 2001-12-21 DE DE2001163337 patent/DE10163337A1/de not_active Withdrawn
-
2002
- 2002-12-19 WO PCT/EP2002/014591 patent/WO2003054108A1/fr not_active Application Discontinuation
- 2002-12-19 AU AU2002358168A patent/AU2002358168A1/en not_active Abandoned
- 2002-12-19 AR ARP020104999 patent/AR038043A1/es not_active Application Discontinuation
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0229440B1 (fr) * | 1985-12-27 | 1990-06-06 | Texaco Development Corporation | Inhibiteur de corrosion pour antigel à base d'acide/sel monobasique/dibasique |
EP0479470B1 (fr) * | 1990-10-01 | 1995-05-17 | Texaco Development Corporation | Composition d'antigel/de refroidissement inhibié contre la corrosion |
EP0487194A1 (fr) * | 1990-11-19 | 1992-05-27 | Texaco Development Corporation | Composition antigel/de refroidissement inhibée contre la corrosion et contenant un acide carboxylique aromatique |
EP0863960B1 (fr) * | 1995-12-13 | 1999-10-13 | Henkel Kommanditgesellschaft auf Aktien | Concentre antigel |
DE19962757A1 (de) * | 1999-12-23 | 2001-06-28 | Basf Ag | Wässrige Motoreinlauf-Kühlflüssigkeit mit Dampfraumkorrosionsschutz |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2009035741A1 (fr) * | 2007-06-28 | 2009-03-19 | Chevron U.S.A Inc. | Compositions de concentré d'antigel et de liquide de refroidissement et leur préparation |
US7790054B2 (en) | 2007-06-28 | 2010-09-07 | Chevron U.S.A. Inc. | Antifreeze concentrate and coolant compositions and preparation thereof |
DE102011004765A1 (de) | 2010-02-25 | 2011-08-25 | Behr GmbH & Co. KG, 70469 | Zusätze für silikathaltige Heiz- und Kühlmittel |
DE102010002349A1 (de) | 2010-02-25 | 2011-08-25 | Behr GmbH & Co. KG, 70469 | Zusätze für Heiz- und Kühlmittel |
DE102010002341A1 (de) | 2010-02-25 | 2011-08-25 | Behr GmbH & Co. KG, 70469 | Wärmeübertrager und Bauteile für Kfz-Kühlkreisläufe |
WO2011104355A2 (fr) | 2010-02-25 | 2011-09-01 | Behr Gmbh & Co. Kg | Adjuvants pour fluides caloporteurs de chauffe et de refroidissement |
Also Published As
Publication number | Publication date |
---|---|
AR038043A1 (es) | 2004-12-22 |
DE10163337A1 (de) | 2003-07-03 |
AU2002358168A1 (en) | 2003-07-09 |
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