EP1192296A1 - Corrosion inhibiting compositions for heat transfer fluids - Google Patents

Corrosion inhibiting compositions for heat transfer fluids

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Publication number
EP1192296A1
EP1192296A1 EP00949557A EP00949557A EP1192296A1 EP 1192296 A1 EP1192296 A1 EP 1192296A1 EP 00949557 A EP00949557 A EP 00949557A EP 00949557 A EP00949557 A EP 00949557A EP 1192296 A1 EP1192296 A1 EP 1192296A1
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weight
acid
formula
group
derivative
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German (de)
French (fr)
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Emeryc Valot
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Arkema SA
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Atofina SA
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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K5/00Heat-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
    • C09K5/20Antifreeze additives therefor, e.g. for radiator liquids
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23FNON-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
    • C23F11/00Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/08Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
    • C23F11/10Inhibiting 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

Definitions

  • the field of the invention is that of aqueous liquids which can be used as heat transfer fluids for cooling circuits, for example the cooling circuits of internal combustion engines, the corrosivity of which must be remedied.
  • Water and aqueous solutions are very widely used as cooling fluids in circuits constructed of various metals, copper, steel, aluminum, cast iron and their alloys, which they attack as soon as corrosion conditions are found.
  • the first consequence of corrosion is the loss of material from the walls of the circuits and their perforation. Added to this is the formation of corrosion products, the deposits of which disturb the heat transfers between the fluid and the walls of the circuit, and cause overheating in the hot walls with significant risks of rupture of sensitive mechanical parts.
  • the phosphates precipitate in contact with hard water, and therefore their concentration and their activity decreases (depletion), which we can fight against, but at the cost of an increase in the cost of protection, by using certain additives (JP -A-62205183); these phosphates are also harmful to the environment (eutrophication of water). Amines when combined with nitrites generate the risk of formation of nitrosamines, highly toxic products. Releases of fluids containing boron derivatives or molybdates are also harmful and require treatment before being returned to the environment. We therefore turned resolutely to other organic inhibitors, which has given rise to numerous publications and numerous patents, including for example:
  • compositions of the present invention provide an answer to this problem which is practically expressed in their compliance with the requirements of the so-called "cavitation” test at the same time as those of the conventional tests for evaluating the hot inhibitory efficacy vis-à-vis - screws of different metals in an antifreeze liquid.
  • the CEC C-05X-95 "cavitation" test is one which provides an evaluation of the performance of an inhibiting composition with regard to the corrosion of steel and aluminum by cavitation of a possibly antifreeze fluid. circulating in a loop under standardized conditions of flow, temperature and pressure. These tests are described in the examples.
  • the present invention is that of a method for inhibiting multimetal corrosion by heat transfer fluids, whether or not these fluids contain an organic compound lowering the freezing point, which consists in introducing into said fluids 3 to 6% by weight , and preferably 3.8 to 5%, of an organic inhibitor system consisting of:
  • (II) 40 to 70% by weight of at least one saturated carboxylic acid taken from the group comprising saturated monocarboxylic acids with 5-16 carbon atoms and saturated dicarboxylic acids with 4-12 carbon atoms, or a salt thereof alkali or amine or alkanolamine metal of these acids; - (III) 20 to 40% by weight of a tricarboxylic derivative of 1,3,5-triazine corresponding to the formula: NHR. -NOT. NHR
  • R is a carboxyalkyl group with 2-6 carbon atoms, or an alkali metal or amine or alkanolamine salt of this derivative - (IV) 1 to 5% by weight of an azole derivative taken from the group made up of:
  • R T is a hydrogen atom or a methyl radical
  • R 2 is a hydrogen atom or a mercapto radical
  • R 3 is a hydrogen atom or a radical of formula
  • R 4 and R 5 identical or different, representing a 2-ethylhexyl or hydroxyalkyl radical, in particular an ethanol residue.
  • the weight ratio of the constituents I and II (l / ll) will be between 5 and 15 and, preferably, between 8 and 12, and the weight ratio of the constituents I and II on the one hand and III (I + ll / lll) will be between 1.5 and 3 and, preferably, between 1.9 and 2.2.
  • C 5 -C 10 acids are preferred, in particular n-hexanoic acid, heptanoic acid, n-octanoic acid and nonanoic acid;
  • C 4 -C ⁇ 0 acids are preferred, in particular suberic acid, azelaic acid and sebacic acid.
  • undecylenic acid is preferred.
  • the preferred 1,3,5 triazine tricarboxylic derivative is the compound of formula:
  • RN 80584-91 -4 or its triethanolamine salt.
  • the inhibitor system according to the invention can be used in aqueous fluids with or without antifreeze for cooling circuits and in particular for cooling circuits of internal combustion engines. It can be implemented by introducing the various components of the inhibitor system directly into the transfer fluid. It is more convenient to use stock solutions which are aqueous solutions comprising from 10 to 60% by weight of the inhibitor system constituted by the components (I), (II), (III) and (IV) as described more high, and whose pH will be adjusted by neutralization, for example with sodium hydroxide in order to dissolve all of the components and so that the pH of the transfer fluid will be in the range 7-9, preferably 7.5- 8.5. These aqueous stock solutions are compositions of the invention. If it is desired to obtain both protection of the circuits against corrosion and freezing, use will be made of inhibiting anti-freeze compositions, also objects of the present invention, consisting of: 0.1 to 10% by weight of the composition inhibitor described above;
  • a hydroalcoholic solution having a freezing point below 0 ° C, preferably between -10 and - 40 ° C, the alcohol being taken from the group consisting of methanol, l ethanol, 2-propanol, glycerol, ethylene glycol, diethylene glycol, propylene glycol, 1-methoxy-2-propanol, methyl-, ethyl-, propyl-, butyl ethers of ethylene glycol. Ethylene glycol is preferred.
  • the inhibitor system according to the invention provides protection against multimetal corrosion under cavitation corrosion conditions (high temperature, high pressure), a fortiori under milder aggressiveness conditions.
  • the inhibitor system of the invention can be used in wide ranges of applications, using media of ferrous iron, cast iron, copper copper and aluminum in particular. We can cite surface treatment, metalworking, paint stripping, lubrication.
  • Hot plate test (ASTM D 4340: "Corrosion of cast aluminum alloys in Engine Coolants under Heat-rejecting Conditions"), by which follows the variations in weight of a cast aluminum sample simulating a piston, heated to 135 ° C, for 168 hours (7 days) and subjected to a pressure of 193 kPa in a corrosive solution (0.165 g / l of NaCl ) containing 25% antifreeze; - c) Cavitation test (CEC C-05X-95), by which we measure the mass variation of test bodies made up of cast iron and aluminum discs subjected to the action of flow in loop of a corrosive solution according to ASTM D 1384 (Na 2 S0 4 : 148 mg
  • the tests take into account three types of inhibitors: i) conventional mineral compositions based on nitrites, borax or sodium molybdate, ii) organic or mixed compositions of the prior art comprising sebacic acid, iii ) compositions according to the invention.
  • the inhibitor components were dissolved in ethylene glycol.
  • the pH of the concentrated solution was adjusted between 7 and 8 by adding sodium hydroxide.
  • the alkaline reserve (RA) of these compositions expressed in milliliters of 0.1N hydrochloric acid is determined according to standard ASTM D 1121-93.
  • These concentrated solutions constitute antifreezes. Coolants are obtained by dilution to 50% with deionized water.
  • the test solution consists of a corrosive solution to which this coolant has been added, at a rate of 33% by volume if the ASTM D 1384 standard is applied, 25% by volume for the ASTM D 4340 standard. , 20% by volume for the CEC C-05X-95 standard.
  • compositions To prepare the exemplified compositions, the following were used: - as monocarboxylic acid of type (I) heptanoic acid (C 7 ), - as type (II) monocarboxylic acid undecylenic acid
  • compositions V9 and V10 being preferred compositions according to the invention; the compositions V 2 , V 3 and V 6 emerging from the invention.
  • the ASTM D4340 hot plate test is passed if the weight loss is less than 1 mg / cm / week.
  • the CEC C-05X-95 test is considered accepted if the weight variation is between -50 and +10 mg for aluminum and between -10 and +5 mg for cast iron. TABLE 1
  • organic (O) or organic-mineral (M) compositions with diacids (adipic (H 2 C 6 ) and sebacic (H 2 C ⁇ 0 )), octanoic acid (C 8 ), sodium molybdate (Molyb.) , sodium nitrite (Nitrite) and tolyltriazole (TTZ) containing (in% by weight):
  • composition 03 has interesting performances except however in the test ASTM D 1384 for cast iron where it causes weight gain (instead of loss). This weight gain is a contraindication for a potential blockage of the circuits.
  • the use dose of these products is generally between 0.01 and 0.03% by weight relative to the total of the formulation of stock solutions.
  • a product well suited to the formulations is 1 - hydroxyethane-1, 1 diphosphonic acid and in particular the commercial product
  • DEQUEST 2010 from SOLUTIA This product may exhibit a certain activity with respect to corrosion tests which may require an adjustment of the overall composition according to the invention.

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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

The invention concerns compositions for inhibiting corrosion of various metals by heat transfer fluids consisting of a combination of an unsaturated monocarboxylic acid, a saturated monocarboxylic or dicarboxylic acid, a 1,3,5-triazine tricarboxylic derivative and an azole compound derivative. Said compositions inhibit corrosion by cavitation in particular.

Description

COMPOSITIONS INHIBITRICES DE LA CORROSION POUR FLUIDES DE CORROSION INHIBITOR COMPOSITIONS FOR FLUIDS
TRANSFERT DE CHALEURHEAT TRANSFER
Le domaine de l'invention est celui des liquides aqueux utilisables comme fluides de transfert de chaleur pour circuits de refroidissement, par exemple les circuits de refroidissement des moteurs à combustion interne, à la corrosivité desquels il s'agit de remédier.The field of the invention is that of aqueous liquids which can be used as heat transfer fluids for cooling circuits, for example the cooling circuits of internal combustion engines, the corrosivity of which must be remedied.
L'eau et les solutions aqueuses sont très largement utilisées comme fluides de refroidissement dans des circuits construits en métaux variés, cuivre, acier, aluminium, fonte et leurs alliages, qu'ils attaquent dès que des conditions de corrosion se trouvent réalisées. Les facteurs de corrosion sont nombreux : présence d'ions, températures importantes, pression, écoulement des fluides (corrosion par cavitation), couplage aux soudures. Une attention toute particulière devra être portée aux phénomènes de corrosion par cavitation. La première conséquence de la corrosion est la perte de matière des parois des circuits et leur perforation. S'y ajoute la formation de produits de corrosion dont les dépôts perturbent les transferts de chaleur entre le fluide et les parois du circuit, et engendrent des surchauffes au niveau des parois chaudes avec des risques importants de rupture des pièces mécaniques sensibles. Les produits utilisés pour abaisser le point de congélation de l'eau constituent un facteur particulièrement aggravant de la corrosivité des fluides de refroidissement. On a peu à peu renoncé à l'utilisation de saumures salines à l'agressivité desquelles, en particulier envers les soudures et l'aluminium, on n'a jamais vraiment trouvé de solution satisfaisante. L'industrie s'est ralliée aux antigels organiques de la classe des alcools, methanol, éthanol, 2-propanol, glycerol, éthyièneglycol, diéthylèneglycol, propylèneglycol, méthyl-, éthyl-, propyl-, butylé- ther de l'éthylènegiycol et 1-méthoxy-2-propanol. L'éthylèneglycol est de loin aujourd'hui l'antigel le plus utilisé. Le problème reste néanmoins posé de protéger contre la corrosion les circuits de refroidissement alimentés en fluides aqueux comportant ou non des antigels organiques, de développer des compositions inhibitrices de la corrosion dans de tels milieux, et si possible de formuler des compositions antigel elles-mêmes inhibitrices de la corrosion. Des contraintes particulières relatives à la protection de l'environnement pèsent sur ces compositions. Il est proscrit ou en tout cas fortement déconseillé, d'y faire entrer des phosphates, des nitrites, des borates, des molybdates et des aminés associées à des nitrites, qui dans l'art antérieur avaient pourtant été préconisés et pour certains largement utilisés. Les phosphates précipitent au contact des eaux dures, et de ce fait leur concentration et leur activité diminue (déplétion), ce contre quoi on peut lutter, mais au prix d'une augmentation du coût de la protection, par utilisation de certains additifs (JP-A-62205183) ; ces phosphates sont en outre nuisibles pour l'environnement (eutrophisation de l'eau). Les aminés lorsqu'elles sont associées aux nitrites engendrent le risque de formation de nitrosamines, produits fortement toxiques. Les rejets de fluides addi- tivés de dérivés du bore ou de molybdates sont également nocifs et exigent un traitement avant leur renvoi dans l'environnement. On s'est donc orienté résolument vers d'autres inhibiteurs organiques, ce qui a donné lieu à de très nombreu- ses publications et de très nombreux brevets, dont par exemple :Water and aqueous solutions are very widely used as cooling fluids in circuits constructed of various metals, copper, steel, aluminum, cast iron and their alloys, which they attack as soon as corrosion conditions are found. There are many corrosion factors: presence of ions, high temperatures, pressure, flow of fluids (corrosion by cavitation), coupling to welds. Particular attention should be paid to the phenomena of cavitation corrosion. The first consequence of corrosion is the loss of material from the walls of the circuits and their perforation. Added to this is the formation of corrosion products, the deposits of which disturb the heat transfers between the fluid and the walls of the circuit, and cause overheating in the hot walls with significant risks of rupture of sensitive mechanical parts. The products used to lower the freezing point of water are a particularly aggravating factor in the corrosiveness of cooling fluids. Little by little, the use of saline brines was abandoned, the aggressiveness of which, in particular towards welds and aluminum, we never really found a satisfactory solution. The industry has rallied to organic antifreezes in the class of alcohols, methanol, ethanol, 2-propanol, glycerol, ethylene glycol, diethylene glycol, propylene glycol, methyl-, ethyl-, propyl-, butylether of ethylene glycol and 1 methoxy-2-propanol. Ethylene glycol is by far the most widely used antifreeze today. The problem remains posed, however, of protecting the cooling circuits supplied with aqueous fluids containing or not containing organic antifreezes against corrosion, of developing compositions which inhibit corrosion in such environments, and if possible formulating antifreeze compositions which themselves are inhibitors. corrosion. Particular constraints relating to the protection of the environment weigh on these compositions. It is prohibited or in any case strongly advised against bringing in phosphates, nitrites, borates, molybdates and amines associated with nitrites, which in the prior art had however been recommended and for some widely used. The phosphates precipitate in contact with hard water, and therefore their concentration and their activity decreases (depletion), which we can fight against, but at the cost of an increase in the cost of protection, by using certain additives (JP -A-62205183); these phosphates are also harmful to the environment (eutrophication of water). Amines when combined with nitrites generate the risk of formation of nitrosamines, highly toxic products. Releases of fluids containing boron derivatives or molybdates are also harmful and require treatment before being returned to the environment. We therefore turned resolutely to other organic inhibitors, which has given rise to numerous publications and numerous patents, including for example:
- la demande US n°819 321 , citée dans US 4,759,864, relative à un antigel basé sur l'association d'un acide alkylbenzoïque (ou alkylbenzoate) avec un acide monocarboxylique (ou carboxylate) en C8-Cι2 et du triazol, avec un dérivé d'acide aminophosphonique comme inhibiteur de précipitation et acide polyacryli- que (polyacrylate) comme stabilisant ;- US application No. 819,321, cited in US 4,759,864, relating to an antifreeze based on the association of an alkylbenzoic acid (or alkylbenzoate) with a C 8 -Cι 2 monocarboxylic acid (or carboxylate) and triazol, with an aminophosphonic acid derivative as a precipitation inhibitor and polyacrylic acid (polyacrylate) as a stabilizer;
- US 4,647,392 pour un antigel avec acide monocarboxylique (monocar- boxylate) en C5-C16, diacide (sel) en C5-Cι6 et dérivé du triazol ;- US 4,647,392 for an antifreeze with monocarboxylic acid (monocarboxylic boxylate) C 5 -C 16 dibasic acid (salt) C 5 -Cι 6 and derived from triazol;
- US 4,657,689 pour un antigel comportant un acide carboxylique (carboxylate) en C5-Cι6, un acide dicarboxylique (ou sel) en C5-C16, un dérivé du triazol et un sulfonate alcalin en C10-C20;- US 4,657,689 for an antifreeze comprising a C 5 -Cι 6 carboxylic acid (carboxylate), a C 5 -C 16 dicarboxylic acid (or salt), a triazol derivative and a C10-C20 alkali sulfonate;
- US 4,588,513 pour antigel avec acide dicarboxylique (ou un sel), un silicate alcalin et un dérivé du triazol ;- US 4,588,513 for antifreeze with dicarboxylic acid (or a salt), an alkali silicate and a triazol derivative;
- US 2,832,742 pour un inhibiteur comprenant un acide carboxylique en C7-C18 et l'acide p-terbutylbenzoïque ; - US 4,759,864 pour un antigel comportant un acide en CQ-C-\ 2 ou un sel, un dérivé alcalin du bore et un dérivé du triazol. L'article de G. T. Hefter et al. "Organic Corrosion Inhibitor in Neutral Solutions" paru dans "Corrosion-Vol. 53, n°8, 1997, NACE International" pages 657- 667, fait le point des problèmes rencontrés dans la corrosion multi-métaux.- US 2,832,742 for an inhibitor comprising a C 7 -C 18 carboxylic acid and p-terbutylbenzoic acid; - US 4,759,864 for an antifreeze comprising a CQ-C- \ 2 acid or a salt, an alkaline derivative of boron and a derivative of triazol. The article by GT Hefter et al. "Organic Corrosion Inhibitor in Neutral Solutions" published in "Corrosion-Vol. 53, n ° 8, 1997, NACE International" pages 657-667, takes stock of the problems encountered in multi-metal corrosion.
Mais de toute façon, ces compositions laissent non résolu de façon satis- faisante le problème de la corrosion par cavitation, qui reste une préoccupation importante notamment des constructeurs de moteurs pour automobiles. Les compositions de la présente invention apportent une réponse à ce problème qui s'exprime pratiquement dans leur conformité aux exigences du test dit de "cavitation" en même temps que celles des tests classiques d'évaluation de l'efficacité inhibitrice à chaud vis-à-vis de différents métaux dans un liquide antigel. Le test de "cavitation" CEC C-05X-95, est celui qui fournit une évaluation des performances d'une composition inhibitrice à l'égard de la corrosion de l'acier et de l'aluminium par cavitation d'un fluide éventuellement antigel circulant en boucle dans des conditions normalisées de débit, de température et de pression. Ces tests sont décrits dans les exemples.However, in any case, these compositions leave the problem of cavitation corrosion, which remains a major concern in particular of automobile engine manufacturers, unsatisfactory. The compositions of the present invention provide an answer to this problem which is practically expressed in their compliance with the requirements of the so-called "cavitation" test at the same time as those of the conventional tests for evaluating the hot inhibitory efficacy vis-à-vis - screws of different metals in an antifreeze liquid. The CEC C-05X-95 "cavitation" test is one which provides an evaluation of the performance of an inhibiting composition with regard to the corrosion of steel and aluminum by cavitation of a possibly antifreeze fluid. circulating in a loop under standardized conditions of flow, temperature and pressure. These tests are described in the examples.
La présente invention est celle d'un procédé pour inhiber la corrosion multimétaux par les fluides de transfert de chaleur, que ces fluides contiennent ou non un composé organique abaissant le point de congélation, qui consiste à introduire dans lesdits fluides 3 à 6 % en poids, et de préférence 3,8 à 5 %, d'un système d'inhibiteurs organiques constitué de :The present invention is that of a method for inhibiting multimetal corrosion by heat transfer fluids, whether or not these fluids contain an organic compound lowering the freezing point, which consists in introducing into said fluids 3 to 6% by weight , and preferably 3.8 to 5%, of an organic inhibitor system consisting of:
(I) 5 à 15 % en poids d'au moins un acide monocarboxylique insaturé à 10-18 atomes de carbone ou d'un de ses sels de métal alcalin, d'aminé du groupe de la monoéthylamine, diéthylamine, triéthylamine ou d'alcanolamine du groupe de la monoéthanolamine, diéthanolamine, triéthanolamine ou méthyldié- thanolamine ;(I) 5 to 15% by weight of at least one monocarboxylic acid unsaturated with 10-18 carbon atoms or of an alkali metal salt thereof, of amine from the group of monoethylamine, diethylamine, triethylamine or alkanolamine from the monoethanolamine group, diethanolamine, triethanolamine or methyldiethanolamine;
(II) 40 à 70 % en poids d'au moins un acide carboxylique saturé pris dans le groupe comprenant les acides monocarboxyliques saturés à 5-16 atomes de carbone et les acides dicarboxyliques saturés à 4-12 atomes de carbone, ou un sel de métal alcalin ou d'aminé ou d'alcanolamine de ces acides ; - (III) 20 à 40 % en poids d'un dérivé tricarboxylique de la 1 ,3,5- triazine répondant à la formule : NHR. -N. ,NHR(II) 40 to 70% by weight of at least one saturated carboxylic acid taken from the group comprising saturated monocarboxylic acids with 5-16 carbon atoms and saturated dicarboxylic acids with 4-12 carbon atoms, or a salt thereof alkali or amine or alkanolamine metal of these acids; - (III) 20 to 40% by weight of a tricarboxylic derivative of 1,3,5-triazine corresponding to the formula: NHR. -NOT. NHR
N. ,NN., N
NHRNHR
dans laquelle R est un groupe carboxyalkyle à 2-6 atomes de carbone, ou un sel de métal alcalin ou d'aminé ou d'alcanolamine de ce dérivé - (IV) 1 à 5 % en poids d'un dérivé azole pris dans le groupe constitué par :in which R is a carboxyalkyl group with 2-6 carbon atoms, or an alkali metal or amine or alkanolamine salt of this derivative - (IV) 1 to 5% by weight of an azole derivative taken from the group made up of:
(a) les imidazoles de formule :(a) imidazoles of formula:
(b) les benzimidazoles de formule(b) the benzimidazoles of formula
(c) les triazoles de formule(c) the triazoles of formula
(d) les benzotriazoles de formule(d) the benzotriazoles of formula
(e) le tétrahydrobenzotriazole (e) tetrahydrobenzotriazole
(f) les thiazoles de formule(f) the thiazoles of formula
(g) les benzothiazoles de formule(g) the benzothiazoles of formula
(h) et les sels de métaux alcalins de ces dérivés azoles, formules dans lesquelles(h) and the alkali metal salts of these azole derivatives, formulas in which
RT est un atome d'hydrogène ou un radical méthyle R2 est un atome d'hydrogène ou un radical mercapto R3 est un atome d'hydrogène ou un radical de formuleR T is a hydrogen atom or a methyl radical R 2 is a hydrogen atom or a mercapto radical R 3 is a hydrogen atom or a radical of formula
avec R4 et R5, identiques ou différents, représentant un radical 2-éthylhexyle ou hydroxyalkyle, en particulier un reste éthanol.with R 4 and R 5 , identical or different, representing a 2-ethylhexyl or hydroxyalkyl radical, in particular an ethanol residue.
Dans une forme préférée de mise en œuvre du procédé de l'invention, le rapport pondéral des constituants I et II (l/ll) sera compris entre 5 et 15 et, de préférence, entre 8 et 12, et le rapport pondéral des constituants I et II d'une part et III (I + ll/lll) sera compris entre 1.5 et 3 et, de préférence, entre 1.9 et 2.2.In a preferred embodiment of the process of the invention, the weight ratio of the constituents I and II (l / ll) will be between 5 and 15 and, preferably, between 8 and 12, and the weight ratio of the constituents I and II on the one hand and III (I + ll / lll) will be between 1.5 and 3 and, preferably, between 1.9 and 2.2.
Pour les sels des acides organiques, les pourcentages poids sont ramenés à la fraction acide du sel concerné. Parmi les acides monocarboxyliques saturés en C5-Cι6, on préfère les acides en C5-C10, en particulier l'acide n-hexanoïque, l'acide heptanoïque, l'acide n-octanoïque et l'acide nonanoïque ;For the salts of organic acids, the weight percentages are reduced to the acid fraction of the salt concerned. Among the saturated C 5 -C 6 monocarboxylic acids, C 5 -C 10 acids are preferred, in particular n-hexanoic acid, heptanoic acid, n-octanoic acid and nonanoic acid;
Parmi les acides dicarboxyliques aliphatiques à chaînes saturées en C4- C12, on préfère les acides en C4-Cι0, en particulier l'acide subérique, l'acide azé- laïque et l'acide sébacique.Among the aliphatic dicarboxylic acids with saturated C 4 -C 12 chains, C 4 -Cι 0 acids are preferred, in particular suberic acid, azelaic acid and sebacic acid.
Parmi les acides monocarboxyliques insaturés en C10-C22, on préfère l'acide undécylénique.Among the unsaturated C 10 -C 22 monocarboxylic acids, undecylenic acid is preferred.
Quand on utilise ensemble un acide monocarboxylique et un acide dicar- boxylique saturés, il est avantageux de les associer dans un rapport massique diacide/monoacide de 0,1 :1 à 10:1 , de préférence 0,6:1 à 5:1.When a saturated monocarboxylic acid and a saturated dicarboxylic acid are used together, it is advantageous to combine them in a diacid / monoacid mass ratio of 0.1: 1 to 10: 1, preferably 0.6: 1 to 5: 1 .
Le dérivé tricarboxylique de la 1 ,3,5 triazine préféré est le composé de formule :The preferred 1,3,5 triazine tricarboxylic derivative is the compound of formula:
RN = 80584-91 -4 ou son sel de triéthanolamine.RN = 80584-91 -4 or its triethanolamine salt.
Le système inhibiteur selon l'invention peut être utilisé dans des fluides aqueux avec ou sans antigel pour circuits de refroidissement et en particulier pour circuits de refroidissement de moteurs à combustion interne. On peut le mettre en œuvre en introduisant directement dans le fluide de transfert les divers composants du système inhibiteur. Il est plus commode d'employer des solutions-mères qui sont des solutions aqueuses comportant de 10 à 60 % en poids du système inhibiteur constitué par les composants (I), (II), (III) et (IV) tels que décrits plus haut, et dont le pH sera ajusté par neutralisation, par exemple par la soude afin de solubiliser l'ensemble des composants et de telle sorte que le pH du fluide de transfert sera dans l'intervalle 7-9, de préférence 7,5-8,5. Ces solutions-mères aqueuses sont des compositions de l'invention. Si l'on veut obtenir à la fois une protection des circuits contre la corrosion et le gel, on utilisera plutôt des compositions antigels inhibitrices, également objets de la présente invention, constituées de : - 0,1 à 10 % en poids de la composition inhibitrice ci-dessus décrite ;The inhibitor system according to the invention can be used in aqueous fluids with or without antifreeze for cooling circuits and in particular for cooling circuits of internal combustion engines. It can be implemented by introducing the various components of the inhibitor system directly into the transfer fluid. It is more convenient to use stock solutions which are aqueous solutions comprising from 10 to 60% by weight of the inhibitor system constituted by the components (I), (II), (III) and (IV) as described more high, and whose pH will be adjusted by neutralization, for example with sodium hydroxide in order to dissolve all of the components and so that the pH of the transfer fluid will be in the range 7-9, preferably 7.5- 8.5. These aqueous stock solutions are compositions of the invention. If it is desired to obtain both protection of the circuits against corrosion and freezing, use will be made of inhibiting anti-freeze compositions, also objects of the present invention, consisting of: 0.1 to 10% by weight of the composition inhibitor described above;
90 à 99,9 % en poids d'une solution hydroalcoolique ayant un point de congélation inférieur à 0°C, de préférence compris entre -10 et — 40°C, l'alcool étant pris dans le groupe constitué par le methanol, l'éthanol, le 2-propanol, le glycerol, l'ethylèneglycol, le diéthylèneglycol, le propylèneglycol, le 1 -méthoxy-2- propanol, les méthyl-, éthyl-, propyl-, butylethers de l'ethylèneglycol. On préfère l'ethylèneglycol.90 to 99.9% by weight of a hydroalcoholic solution having a freezing point below 0 ° C, preferably between -10 and - 40 ° C, the alcohol being taken from the group consisting of methanol, l ethanol, 2-propanol, glycerol, ethylene glycol, diethylene glycol, propylene glycol, 1-methoxy-2-propanol, methyl-, ethyl-, propyl-, butyl ethers of ethylene glycol. Ethylene glycol is preferred.
Le système d'inhibiteurs selon l'invention assure une protection contre la corrosion multimétaux dans les conditions de corrosion par cavitation (haute température, haute pression), a fortiori dans des conditions d'agressivité plus douces.The inhibitor system according to the invention provides protection against multimetal corrosion under cavitation corrosion conditions (high temperature, high pressure), a fortiori under milder aggressiveness conditions.
Le système d'inhibiteurs de l'invention peut être utilisé dans de larges gammes d'applications, mettant en œuvre les milieux de type fer ferreux, fonte, cuivre cuivreux et aluminium notamment. On peut citer le traitement de surface, le travail des métaux, le décapage peinture, la lubrification.The inhibitor system of the invention can be used in wide ranges of applications, using media of ferrous iron, cast iron, copper copper and aluminum in particular. We can cite surface treatment, metalworking, paint stripping, lubrication.
EXEMPLESEXAMPLES
Les exemples qui suivent feront mieux comprendre l'invention. Ils font appel aux résultats de tests régulièrement pratiqués dans l'industrie automobile qu'on rappelle ici : - a) L'essai de corrosion en verrerie (ASTM D 1384 : "Corrosion test forThe following examples will better understand the invention. They call on the results of tests regularly carried out in the automobile industry which we recall here: - a) The corrosion test in glassware (ASTM D 1384: "Corrosion test for
Engine Coolants in Glassware"), qui permet de suivre les variations de poids de différents métaux (cuivre, soudure, laiton, acier, fonte d'acier, fonte d'aluminium) après une immersion de 336 heures (15 jours) à 88°C dans une eau corrosive additionnée d'antigel; - b) Test de la plaque chaude (ASTM D 4340 : "Corrosion of cast aluminium alloys in Engine Coolants under Heat-rejecting Conditions"), par lequel on suit les variations de poids d'un échantillon en fonte d'aluminium simulant un piston, chauffé à 135°C, pendant 168 heures (7 jours) et soumis à une pression de 193 kPa dans une solution corrosive (0,165 g/l de NaCI) comportant 25% d'antigel ; - c) Test de cavitation (CEC C-05X-95), par lequel on mesure la variation de masse de corps d'épreuves constituées de disques en fonte d'acier et d'aluminium soumis à l'action de l'écoulement en boucle d'une solution corrosive selon ASTM D 1384 (Na2S04 : 148 mg/l, NaCI : 165 mg/l, NaHC03 : 138 mg/l) dans des conditions d'essai générant des différences de vitesse et de pression locales et de température de nature à induire des phénomènes de cavitation et de corrosion. La température de l'essai est de 115°C, le débit du fluide de 300 l/h, la pression de 150 kPa. La durée de l'essai est de 72 heures.Engine Coolants in Glassware "), which tracks the weight variations of different metals (copper, solder, brass, steel, cast steel, cast aluminum) after immersion for 336 hours (15 days) at 88 ° C in corrosive water with antifreeze added; - b) Hot plate test (ASTM D 4340: "Corrosion of cast aluminum alloys in Engine Coolants under Heat-rejecting Conditions"), by which follows the variations in weight of a cast aluminum sample simulating a piston, heated to 135 ° C, for 168 hours (7 days) and subjected to a pressure of 193 kPa in a corrosive solution (0.165 g / l of NaCl ) containing 25% antifreeze; - c) Cavitation test (CEC C-05X-95), by which we measure the mass variation of test bodies made up of cast iron and aluminum discs subjected to the action of flow in loop of a corrosive solution according to ASTM D 1384 (Na 2 S0 4 : 148 mg / l, NaCI: 165 mg / l, NaHC0 3: 138 mg / l) under test conditions generating differences in speed and pressure local and temperature likely to induce cavitation and corrosion. The test temperature is 115 ° C, the fluid flow rate of 300 l / h, the pressure of 150 kPa. The duration of the test is 72 hours.
Les essais prennent en compte trois types d'inhibiteurs : i) des compositions classiques minérales à base de nitrites, de borax ou de molybdate de sodium, ii) des compositions organiques ou mixtes de l'art antérieur comportant de l'acide sébacique, iii) des compositions selon l'invention.The tests take into account three types of inhibitors: i) conventional mineral compositions based on nitrites, borax or sodium molybdate, ii) organic or mixed compositions of the prior art comprising sebacic acid, iii ) compositions according to the invention.
Pour toutes les compositions d'essai, les composants inhibiteurs ont été solubilisés dans l'ethylèneglycol. Le pH de la solution concentrée a été ajustée entre 7 et 8 par addition de soude. La réserve alcaline (RA) de ces compositions, exprimée en millilitres d'acide chlorhydrique 0,1 N est déterminée selon la norme ASTM D 1121-93. Ces solutions concentrées constituent les antigels. Les liquides de refroidissement sont obtenus par dilution à 50 % avec de l'eau désionisée. La solution d'essai est constituée d'une solution corrosive à laquelle on a ajouté ce liquide de refroidissement, à raison de 33 % en volume si l'on applique la norme ASTM D 1384, 25 % en volume pour la norme ASTM D 4340, 20 % en volume pour la norme CEC C-05X-95.For all test compositions, the inhibitor components were dissolved in ethylene glycol. The pH of the concentrated solution was adjusted between 7 and 8 by adding sodium hydroxide. The alkaline reserve (RA) of these compositions, expressed in milliliters of 0.1N hydrochloric acid is determined according to standard ASTM D 1121-93. These concentrated solutions constitute antifreezes. Coolants are obtained by dilution to 50% with deionized water. The test solution consists of a corrosive solution to which this coolant has been added, at a rate of 33% by volume if the ASTM D 1384 standard is applied, 25% by volume for the ASTM D 4340 standard. , 20% by volume for the CEC C-05X-95 standard.
Pour préparer les compositions exemplifiées, on a utilisé : - comme acide monocarboxylique de type (I) l'acide heptanoïque (C7), - comme acide monocarboxylique de type (II) l'acide undécyléniqueTo prepare the exemplified compositions, the following were used: - as monocarboxylic acid of type (I) heptanoic acid (C 7 ), - as type (II) monocarboxylic acid undecylenic acid
(C11 1),(C 11 1 ),
- comme dérivé tricarboxylique de la triazine, le composé IRGACOR®L190 commercialisé par CIBA (L190 ; RN=80584-91-4), - comme dérivé triazole, le tolyltriazole (TTZ)- as triicarboxylic derivative of triazine, the compound IRGACOR ® L190 marketed by CIBA (L190; RN = 80584-91-4), - as triazole derivative, tolyltriazole (TTZ)
EXEMPLE 1 :EXAMPLE 1:
On a réalisé les compositions suivantes, en % en poids par rapport à la composition dans l'ethylèneglycol, les compositions V9 et V10 étant des composi- tions préférées selon l'invention ; les compositions V2, V3 et V6 sortant de l'invention.The following compositions were produced, in% by weight relative to the composition in ethylene glycol, compositions V9 and V10 being preferred compositions according to the invention; the compositions V 2 , V 3 and V 6 emerging from the invention.
Les résultats aux divers tests selon les normes visées ci-dessous sont donnés dans le tableau 1.The results of the various tests according to the standards referred to below are given in Table 1.
Pour ASTM D1384 - corrosion en verrerie - le test est passé avec succès si la perte de poids est inférieure à 5 mg sur cuivre, 5 mg sur laiton, 5 mg sur soudure, 2,5 mg sur acier, 4 mg sur fonte et 10 mg sur aluminium.For ASTM D1384 - corrosion in glassware - the test is passed if the weight loss is less than 5 mg on copper, 5 mg on brass, 5 mg on welding, 2.5 mg on steel, 4 mg on cast iron and 10 mg on aluminum.
Le test ASTM D4340 - plaque chaude - est passé si la perte de poids est inférieure à 1 mg/cm/semaine.The ASTM D4340 hot plate test is passed if the weight loss is less than 1 mg / cm / week.
Le test CEC C-05X-95 est considéré est accepté si la variation de poids est comprise entre -50 et +10 mg pour l'aluminium et entre -10 et +5 mg pour la fonte. TABLEAU 1The CEC C-05X-95 test is considered accepted if the weight variation is between -50 and +10 mg for aluminum and between -10 and +5 mg for cast iron. TABLE 1
On peut observer que passent l'ensemble des tests les seuls systèmes à quatre composants inhibiteurs et dans les limites des compositions revendiquées. On voit en particulier la difficulté à passer le test de cavitation.It can be observed that all of the tests pass the only systems with four inhibitor components and within the limits of the claimed compositions. We see in particular the difficulty in passing the cavitation test.
EXEMPLE 2 (comparatif) : compositions de l'art antérieurEXAMPLE 2 (comparative): compositions of the prior art
Ce sont des compositions organiques (O) ou organiques-minérales (M), avec diacides (adipique (H2C6) et sebacique (H20)), acide octanoïque (C8), molybdate de sodium (Molyb.), nitrite de sodium (Nitrite) et tolyltriazole (TTZ) contenant (en % en poids) : These are organic (O) or organic-mineral (M) compositions, with diacids (adipic (H 2 C 6 ) and sebacic (H 20 )), octanoic acid (C 8 ), sodium molybdate (Molyb.) , sodium nitrite (Nitrite) and tolyltriazole (TTZ) containing (in% by weight):
Les résultats des tests sont donnés dans le Tableau 2 ci-après.The results of the tests are given in Table 2 below.
TABLEAU 2TABLE 2
Seule de toutes ces formules selon l'art antérieur, la composition tout- minéral passe l'ensemble des tests, mais avec des composants prohibés ou fortement déconseillés. On peut également observer que la composition 03 présente des performances intéressantes sauf cependant dans le test ASTM D 1384 pour la fonte d'acier où elle entraîne une prise de poids (au lieu d'une perte). Cette prise de poids est une contre-indication sur un bouchage potentiel des circuits.Only of all these formulas according to the prior art, the all-mineral composition passes all of the tests, but with prohibited or strongly discouraged components. We can also observe that composition 03 has interesting performances except however in the test ASTM D 1384 for cast iron where it causes weight gain (instead of loss). This weight gain is a contraindication for a potential blockage of the circuits.
Il est bien connu de l'homme de l'art que certains additifs complémentai- res peuvent être incorporés dans ce type de formulation pour apporter des propriétés spécifiques. Parmi les produits les plus courants, on trouve des antimousses, des agents séquestrant et des colorants.It is well known to those skilled in the art that certain additional additives can be incorporated into this type of formulation to provide specific properties. Among the most common products are defoamers, sequestering agents and dyes.
Parmi les anti-mousses commerciaux, les produits suivants sont particulièrement adaptés à la composition revendiquée : - Wacker SE47 (tensioactif sur base silicone)Among the commercial anti-foaming agents, the following products are particularly suitable for the claimed composition: - Wacker SE47 (surfactant on silicone base)
- Pluronic PE6100 de BASF (tensioactif non ionique)- BASF Pluronic PE6100 (non-ionic surfactant)
- Ultra MS 455-3A (mélange d'un tensioactif silicone et d'un non ionique OP-OE)- Ultra MS 455-3A (mixture of a silicone surfactant and a non-ionic OP-OE)
La dose d'utilisation de ces produits est généralement comprise entre 0.01 et 0.03 % en poids par rapport au total de la formulation de solutions-mères.The use dose of these products is generally between 0.01 and 0.03% by weight relative to the total of the formulation of stock solutions.
Parmi les séquestrants, un produit bien adapté aux formulations est le 1 - hydroxyéthane-1 ,1 diphosphonique acide et en particulier le produit commercialAmong the sequestrants, a product well suited to the formulations is 1 - hydroxyethane-1, 1 diphosphonic acid and in particular the commercial product
DEQUEST 2010 de la Société SOLUTIA. Ce produit peut présenter une certaine activité vis-à-vis des tests de corrosion qui peut necesiter un ajustement de la composition globale selon l'invention. DEQUEST 2010 from SOLUTIA. This product may exhibit a certain activity with respect to corrosion tests which may require an adjustment of the overall composition according to the invention.

Claims

REVENDICATIONS
1. Procédé pour inhiber la corrosion multimétaux par les fluides de transfert de chaleur, que ces fluides contiennent ou non un composé organique abaissant le point de congélation, qui consiste à introduire dans lesdits fluides 3 à1. A method for inhibiting multimetal corrosion by heat transfer fluids, whether or not these fluids contain an organic compound lowering the freezing point, which consists in introducing into said fluids 3 to
6 % en poids, et de préférence 3,8 à 5 %, d'un système d'inhibiteurs organiques constitué de :6% by weight, and preferably 3.8 to 5%, of an organic inhibitor system consisting of:
(I) 5 à 15 % en poids d'au moins un acide monocarboxylique insaturé à 10-18 atomes de carbone ou d'un de ses sels de métal alcalins, d'aminé du groupe de la monoéthylamine, diethylamine, tnethylamine ou d'alcanolamine du groupe de la monoéthanolamine, diéthanolamine, triéthanolamine ou méthyldié- thanolamine ;(I) 5 to 15% by weight of at least one monocarboxylic acid unsaturated with 10-18 carbon atoms or of one of its alkali metal salts, of amine from the group of monoethylamine, diethylamine, tnethylamine or alkanolamine from the monoethanolamine group, diethanolamine, triethanolamine or methyldiethanolamine;
(II) 40 à 70 % en poids d'au moins un acide carboxylique saturé pris dans le groupe comprenant les acides monocarboxyliques saturés à 5-16 atomes de carbone et les acides dicarboxyliques saturés à 4-12 atomes de carbone, ou un sel de métal alcalin ou d'aminé ou d'alcanolamine de ces acides ;(II) 40 to 70% by weight of at least one saturated carboxylic acid taken from the group comprising saturated monocarboxylic acids with 5-16 carbon atoms and saturated dicarboxylic acids with 4-12 carbon atoms, or a salt thereof alkali or amine or alkanolamine metal of these acids;
(III) 20 à 40 %) en poids d'un dérivé tricarboxylique de la 1 ,3,5- triazine répondant à la formule(III) 20 to 40%) by weight of a tricarboxylic derivative of 1,3,5-triazine corresponding to the formula
dans laquelle R est un groupe carboxyalkyle à 2-6 atomes de carbone, ou un sel de métal alcalin ou d'aminé ou d'alcanolamine de ce dérivé wherein R is a carboxyalkyl group with 2-6 carbon atoms, or an alkali metal or amine or alkanolamine salt of this derivative
(IV) 1 à 5 % en poids d'un dérivé azole pris dans le groupe constitué par : (h) les imidazoles de formule : (IV) 1 to 5% by weight of an azole derivative taken from the group consisting of: (h) imidazoles of formula:
(i) les benzimidazoles de formule(i) the benzimidazoles of formula
(j) les triazoles de formule(j) the triazoles of formula
(k) les benzotriazoles de formule(k) the benzotriazoles of formula
(I) le tétrahydrobenzotriazole (m)les thiazoles de formule(I) tetrahydrobenzotriazole (m) thiazoles of formula
(n) les benzothiazoles de formule (n) the benzothiazoles of formula
(h) et les sels de métaux alcalins de ces dérivés azoles, formules dans lesquelles(h) and the alkali metal salts of these azole derivatives, formulas in which
R est un atome d'hydrogène ou un radical méthyle R2 est un atome d'hydrogène ou un radical mercaptoR is a hydrogen atom or a methyl radical R 2 is a hydrogen atom or a mercapto radical
R3 est un atome d'hydrogène ou un radical de formuleR 3 is a hydrogen atom or a radical of formula
avec R4 et R5, identiques ou différents, représentant un radical 2-éthylhexyle ou hydroxyalkyle, en particulier un reste éthanol.with R 4 and R 5 , identical or different, representing a 2-ethylhexyl or hydroxyalkyl radical, in particular an ethanol residue.
2. Procédé selon la revendication 1 , caractérisé en ce que le rapport pondéral l/ll est compris entre 5 et 15, et de préférence entre 8 et 12, et le rapport pondéral I + ll/lll est compris entre 1 ,5 et 3 et de préférence entre 1 ,9 et 2,2.2. Method according to claim 1, characterized in that the weight ratio l / ll is between 5 and 15, and preferably between 8 and 12, and the weight ratio I + ll / lll is between 1, 5 and 3 and preferably between 1, 9 and 2.2.
3. Procédé selon l'une des revendications 1 ou 2, dans lequel le système d'inhibiteurs organiques est constitué de :3. Method according to one of claims 1 or 2, in which the system of organic inhibitors consists of:
6 à 8 % en poids du constituant (I) ; 55 à 65 % en poids du constituant (II) ; - 25 à 35 % en poids du constituant (III) ;6 to 8% by weight of the constituent (I); 55 to 65% by weight of the constituent (II); - 25 to 35% by weight of the constituent (III);
2 à 3 % du constituant (IV).2 to 3% of the constituent (IV).
4. Procédé selon l'une des revendications 1 à 3, dans lequel l'acide carboxylique saturé est l'acide n-hexanoïque, l'acide heptanoïque, l'acide n-octa- noïque ou l'acide nonanoïque. 4. Method according to one of claims 1 to 3, wherein the saturated carboxylic acid is n-hexanoic acid, heptanoic acid, n-octanoic acid or nonanoic acid.
5. Procédé selon l'une des revendications 1 à 3, dans lequel l'acide dicarboxylique est l'acide subérique, l'acide azélaïque ou l'acide sebacique.5. Method according to one of claims 1 to 3, wherein the dicarboxylic acid is suberic acid, azelaic acid or sebacic acid.
6. Procédé selon l'une des revendications 1 à 3, caractérisé en ce que l'acide monocarboxylique insaturé est l'acide undécylénique.6. Method according to one of claims 1 to 3, characterized in that the unsaturated monocarboxylic acid is undecylenic acid.
7. Procédé selon l'une des revendications 1 à 3, dans lequel le dérivé tricarboxylique de la 1 ,3,5 triazine est le composé de formule :7. Method according to one of claims 1 to 3, in which the tricarboxylic derivative of 1,3,5 triazine is the compound of formula:
8. Composition inhibitrice de la corrosion multimétaux constituée par une solution aqueuse titrant de 10 à 60 %> en poids d'un système inhibiteur tel que décrit dans les revendications 1 à 5.8. A multimetal corrosion inhibitor composition consisting of an aqueous solution titrating from 10 to 60%> by weight of an inhibitor system as described in claims 1 to 5.
9. Composition antigel inhibitrice de la corrosion multimétaux compre- nant :9. Multi-metal corrosion inhibitor antifreeze composition comprising:
0,1 à 10 % en poids de la composition inhibitrice selon la revendication 8 ;0.1 to 10% by weight of the inhibitor composition according to claim 8;
90 à 99,9 % en poids d'une solution hydroalcoolique ayant un point de congélation inférieur à 0°C, de préférence compris entre -10 et -40°C, l'alcool étant pris dans le groupe constitué par le methanol, l'éthanol, le 2-propanol, le glycerol, l'ethylèneglycol, le diéthylèneglycol, le propylèneglycol, le 1 -méthoxy-2- propanol, les méthyl-, éthyl-, propyl-, butylethers de l'ethylèneglycol.90 to 99.9% by weight of a hydroalcoholic solution having a freezing point below 0 ° C, preferably between -10 and -40 ° C, the alcohol being taken from the group consisting of methanol, l ethanol, 2-propanol, glycerol, ethylene glycol, diethylene glycol, propylene glycol, 1-methoxy-2-propanol, methyl-, ethyl-, propyl-, butyl ethers of ethylene glycol.
10. Composition antigel inhibitrice selon la revendication 7, dont l'alcool est l'ethylèneglycol. 10. An inhibitory antifreeze composition according to claim 7, the alcohol of which is ethylene glycol.
EP00949557A 1999-06-28 2000-06-23 Corrosion inhibiting compositions for heat transfer fluids Withdrawn EP1192296A1 (en)

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MXPA01013315A (en) 2002-07-30
WO2001000902A1 (en) 2001-01-04
AU6287700A (en) 2001-01-31

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