Corrosion inhibited compositions and methods of using same

Abstract

New compositions, for example, corrosion inhibited compositions, and the like compositions and new methods of using such compositions are disclosed. Such compositions may be liquid solutions, for example, substantially without solid material formation and/or crystal formation, and may include different concentrations of organic acid components and/or different combinations of organic acid components relative to previous compositions. The present compositions may be used as antifreeze coolant compositions or formulations, for example, in the cooling systems of internal combustion engines.

Claims

1. A corrosion-inhibited composition comprising: a major amount of a liquid component selected from the group consisting of water, at least one freezing point depressant and mixtures thereof; a t-butyl benzoic acid component in an amount in a range of about 1000 to about 35000 mg per liter of the composition; a mixture of dicarboxylic acids comprising adipic acid, azelaic acid, sebacic acid, seberic acid, pimelic acid, and undecanoic acid, wherein the azelaic acid is present in an amount in a range of about 500 to about 12,500 mg per liter of the composition; and an aromatic triazole component in an amount in a range of about 100 to about 3500 mg per liter of the composition; and free of a C.sub.8-C.sub.12 aliphatic monobasic acid; wherein the composition causes less change in durometer, tensile strength, elongation and/or volume in at least one polymeric component of a cooling system in which the composition is employed relative to a reference composition which includes the C.sub.8-C.sub.12 aliphatic monobasic acid 2-ethyl hexanoic acid.

2. The composition of claim 1 which further comprises at least one additional C.sub.6-C.sub.12 hydrocarbonyl dibasic acid component present in an amount less than the amount of the azelaic acid component.

3. The composition of claim 2, wherein the additional C.sub.6-C.sub.12 hydrocarbonyl dibasic acid component is selected from the group consisting of pimelic acid, adipic acid, suberic acid, sebacic acid, undecanedioic acid, dodecanedioic acid and mixtures thereof.

4. The composition of claim 1, wherein the aromatic triazole component is selected from the group consisting of benzotriazole, mercaptobenzothiazole, tolyltriazole and mixtures thereof.

5. The composition of claim 1, wherein the aromatic triazole component is benzotriazole.

6. The composition of claim 1, which further comprises an effective amount of at least one metal-containing inhibitor component.

7. The composition of claim 6, wherein the at least one metal-containing inhibitor component is selected from the group consisting of Na.sub.2MoO.sub.4, NaNO.sub.3 and mixtures thereof.

8. The composition of claim 1, which further comprises at least one additional component selected from the group consisting of surfactant components, deformer components, dye components, scale inhibitor components and mixtures thereof.

9. The composition of claim 1, which further comprises an effective amount of at least one surfactant component.

10. The composition of claim 1, which further comprises an effective amount of at least one scale inhibitor component.

11. The composition of claim 1, wherein the composition is free of both a C.sub.8-C.sub.12 aliphatic monobasic acid and an alkali metal, ammonium, or amine salt thereof.

12. The composition of claim 1, wherein when the composition is included in a coolant in a cooling system, the coolant exhibits improved clarity, or, reduced turbidity, relative to a reference coolant which is the composition including a C.sub.6-C.sub.12 aliphatic monobasic acid.

13. The composition of claim 1, wherein the t-butyl benzoic acid component is selected from the group consisting of t-butyl benzoic acid, alkali metal salts thereof, ammonium salts thereof, amine salts thereof and mixtures thereof.

14. The composition of claim 1, wherein the azelaic acid component is selected from the group consisting of azelaic acid, alkali metal salts thereof, ammonium salts thereof, amine salts thereof and mixtures thereof.

15. The composition of claim 1, which causes no deleterious change in durometer, tensile strength, elongation and/or volume in hydrocarbon-containing elastomers and/or silicone-containing elastomers used in at least one component of a cooling system when such an elastomer is in sustained contact with the composition.

16. The composition of claim 1, which causes less change in durometer, tensile strength, elongation and/or volume in hydrocarbon-containing elastomers and silicone-containing elastomers used in at least one component of a cooling system when such an elastomer is in sustained contact with the composition relative to a substantially identical composition including, in addition, at least 100 mg per liter percent by weight of a C.sub.8-C.sub.12 aliphatic monobasic acid or the alkali metal, ammonium or amine salt thereof.

17. A method of cooling an internal combustion engine having a cooling system, the method comprising employing a corrosion-inhibited composition of claim 1 in the cooling system of the internal combustion engine.

18. A method of cooling an industrial process having a cooling system employing a liquid coolant, the method comprising employing a corrosion-inhibited composition of claim 1 as the liquid coolant in the cooling system.

19. A method of transferring heat in a solar energy system employing a liquid to transfer heat, the method comprising employing a corrosion-inhibited composition of claim 1 as the liquid.

20. A corrosion-inhibited composition comprising: at least 50% by weight of a liquid component comprising water and/or a freezing point depressant component comprising at least one alcohol selected from the group consisting of methanol, ethanol, propanol, ethylene glycol, diethylene glycol, trimethylene glycol, propylene glycol, dipropylene glycol, butylene glycol, glycerol, the monoethylether of glycerol, the dimethylether of glycerol, alkoxy alkanols, and mixtures thereof; a t-butyl benzoic acid component in an amount in a range of about 1000 to about 35000 mg per liter of the composition; a C.sub.6-C.sub.12 hydrocarbonyl dibasic acid component in an amount in a range of about 500 to about 12,500 mg per liter of the composition, said dibasic acid component comprising adipic acid, azelaic acid, sebacic acid, seberic acid, pimelic acid, and undecanoic acid; and an aromatic triazole component, selected from the group consisting of benzotriazole, mercaptobenzothiazole, tolyltriazole and mixtures thereof, in an amount in a range of about 100 to about 3500 mg per liter of the composition; at least one metal-containing inhibitor component is selected from the group consisting of Na.sub.2MoO.sub.4, NaNO.sub.3 and mixtures thereof; at least one additional component selected from the group consisting of surfactant components, deformer components, dye components, scale inhibitor components and mixtures thereof; and said corrosion-inhibited composition lacking a C.sub.8-C.sub.12 aliphatic monobasic acid; and wherein said corrosion inhibiting composition causes less change in durometer, tensile strength, elongation and/or volume in at least one polymeric component of a cooling system in which the composition is employed relative to an otherwise substantially identical composition which includes at least 100 mg per liter of a C.sub.8-C.sub.12 aliphatic monobasic acid selected from the group consisting of neodecanoic acid, 2-ethyl hexanoic acid and the alkali metal, ammonium or amine salt thereof.

Description

DETAILED DESCRIPTION OF THE INVENTION

(1) The present invention relates to corrosion inhibited compositions including two or more organic acid components, which are effective for use as coolants to provide effective cooling and to provide prolonged corrosion protection in cooling systems, for example, such as found in, or coupled to, internal combustion engines.

(2) The present compositions may include organic acid components and other components useful to make an organic acid technology (OAT) coolant in soluble form which is easy or straightforward to use. For example, the present compositions may be soluble, that is may be solutions. The solubility characteristics of the present compositions, together with effective corrosion inhibition and other properties, for example, reduced aggressiveness toward polymeric components in cooling systems and reduced turbidity, for example, compared to other, prior art coolants, are highly advantageous.

(3) The present compositions may be used directly as a coolant or can be combined with an aqueous liquid to provide a final use composition that is an antifreeze formulation or actual coolant, for example, used in a cooling system, such as a cooling system associated with an internal combustion engine. The present compositions can be used in either heavy duty or light duty coolants, with the make-up of the composition being adjusted according to whether a heavy duty or a light duty application is involved.

(4) The mixing of the various components of the compositions in accordance with the present invention may occur, as evident to a person of skill in the art, in any suitable or appropriate mixing system, for example, including a vessel, such as a vat or a tank, with mixing/blending carried out by agitation and/or mixing, for example, using one or more mixers, e.g., overhead mixers.

(5) In one example, the present composition has a pH of greater than 7, or at least about 8 or in a range of about 8 to about 11, and provides increased solubility of the acid components and the aromatic triazole component in the composition relative to a substantially identical composition wherein the pH is less than 7.

(6) The source of alkalinity for the present compositions, if any, may be any source of alkalinity that is compatible with the other components of the composition and that provides the composition with the desired pH.

(7) Exemplary sources of alkalinity include, without limitation, alkali metal hydroxides, alkali metal salts, silicates, phosphates, amines, and mixtures thereof. Exemplary alkali metal hydroxides include, without limitation, sodium hydroxide, potassium hydroxide, and lithium hydroxide. The alkali metal hydroxides may be added to the composition in a variety of forms. Alkali metal hydroxides are commercially available as aqueous solutions, for example, as solutions including 45% by weight, 50% by weight or 73% by weight alkali metal hydroxide.

(8) Exemplary alkali metal salts include, without limitation, sodium carbonate, trisodium phosphate, potassium carbonate, and mixtures thereof. Exemplary silicates include, without limitation, sodium metasilicates, sesquisilicates, orthosilicates, potassium silicates, and mixtures thereof. Exemplary phosphates include, without limitation, sodium pyrophosphate, potassium pyrophosphate, and mixtures thereof. Exemplary amines include, without limitation, alkanolamine. Exemplary alkanolamines include, without limitation, triethanolamine, monoethanolamine, diethanolamine, and mixtures thereof.

(9) The source of alkalinity is provided in an amount sufficient to provide the composition with a pH of 7 or above, for example, at least about 8. The composition may have a pH in a range of about 8.0 and about 11, or in a range of between about 8.0 and about 9.5.

(10) The present compositions may comprise an effective amount of one or more additional components, such as anti-foaming agents, dyes, pH buffers, scale inhibitors, surfactants, sequestration agents, dispersion agents, and the like and mixtures thereof.

(11) In one example, the compositions of this invention may also include an effective amount of one or more additional corrosion inhibitors, such as thiazoles, alkali metal phosphates, borates, silicates, benzoates, nitrates, nitrites, molybdates and mixtures thereof.

(12) Examples of other components which may be included in the compositions include, without limitation, anti-foaming agents, e.g., polyglycol copolymers, such as Dow 112-2 from Dow Chemical Company, PM-5150 from Union Carbide Corp., Pluronic L-61 from BASF Corp., and Patco 492 and Patco 415 from American Ingredients Company; dyes, e.g., Alizarine Green, Uranine Yellow and Green AGS-liquid from Abbey Color Inc., and Orange II (Acid Orange 7) and Intracid Rhodamine WT (Acid Red 388) from Crompton & Knowles Corp.; pH buffers; scale inhibitors, such as the Aquatreat terpolymer products AR545, AR540, AR900A, AR980 and AR802, and Versaflex products from Akzo-Nobel; polyacrylate homopolymers, such as T5000N from Telomer Corporation; sequestration and dispersion agents, e.g., Dequest from Monsanto Chemical Company, Bayhibit from Miles Inc., NalPREP from Nalco Chemical Company; surfactants and coupling agents, such as TP4-LF from Dow Chemical Company; hydrotropes, such as xylene sulfonates, e.g., sodium xylene sulfonate, ammonium xylene sulfonate and sodium dimethylbenzenesulfonate; and the like and mixtures thereof.

(13) Other additives, for example, such as chelants, may also be added in order to stabilize the corrosion inhibitor components in the composition. The stabilization property of the chelant may be pH dependant. Examples of chelants include ethanol diglycide disodium salt (EDG), ethylene diamine tetraacetic acid (EDTA) and its salts or mixtures thereof, mono and dicarboxylic acids such as, for example, citric acid, tartaric acid, their salts and mixtures thereof, and mixtures thereof. The chelants can be provided in the composition in an amount sufficient or effective to stabilize the corrosion inhibitor components.

(14) Chelants include, for example, sodium gluconate, pentasodium salt of diethylenetriamine pentaacetic acid (available under the name Versenex 80), sodium glucoheptonate, ethylene diamine tetraacetic acid (EDTA), salts of ethylene diamine tetraacetic acid, hydroxyethyl ethylene diamine triacetic acid (HEDTA), salts of hydroxyethyl ethylene diamine triacetic acid, nitrilotriacetic acid (NTA), salts of nitrilotriacetic acid, diethanolglycine sodium salt (DEG), ethanoldiglycine disodium salt (EDG), and mixtures thereof and the like. Exemplary salts of ethylene diamine tetraacetic acid include disodium salts, tetrasodium salts, diammonium salts, and trisodium salts. An exemplary salt of hydroxyethyl ethylene diamine triacetic acid is the trisodium salt.

(15) Examples of acid chelants include, but are not limited to, citric acid; propionic acid; gluconic acid; glycolic acid; glucoheptanoic acid; succinic acid; lactic acid; methyllactic acid; 2-hydroxybutanoic acid; mandelic acid; atrolactic acid; phenyllactic acid; glyeric acid; 2,3,4-trihydroxybutanoic acid; alpha hydroxylauric acid; benzillic acid; isocitric acid; citramalic acid; agaricic acid; quinic acid; uronic acids, including glucuronic acid, glucuronolactonic acid, galaturonic acid, and galacturonolactonic acid; hydroxypyruvic acid; ascorbic acid; and tropic acid. Salts of such acids may be useful as chelants.

(16) Care is to be exercised in choosing a chelant for use in the present compositions. Some chelants, such as citric acid, may be aggressive towards metals, such as iron, and may become corrosive when used.

(17) In one example, the present compositions are free or substantially free of chelant components which have one or more detrimental effects, for example, are aggressive toward, for example, may cause unacceptable corrosion and/or other deterioration, of one or more components, e.g., metal components, in a system in which a composition including such a chelant component is used.

(18) The present compositions are particularly well-suited for use in antifreeze coolant formulations for use in internal combustion engines.

(19) In one example, the liquid freezing point depressant comprises at least one alcohol. Suitable alcohols, for example, liquid alcohols, for use in the present freezing point depressants include any alcohol effective as a freezing point depressant. Among the useful alcohols are those selected from the group consisting of methanol, ethanol, propanol, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, butylene glycol, glycerol, the monethylether of glycerol, the dimethylether of glycerol, alkoxy alkanols (such as, for example, methoxyethanol and the like) and mixtures thereof.

(20) Examples of highly useful alcohols are those selected from the group consisting of ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol and mixtures thereof.

(21) Methods of making or producing antifreeze compositions are provided in accordance with the present invention. In one example, the individual components of the present compositions are selected. Such components are combined, for example, added together one at a time or in any other convenient manner. The resulting combination of components may be mixed to obtain a uniform final composition.

(22) The present invention also provides methods for inhibiting corrosion of metal components in internal combustion engines. Such methods may comprise contacting the metals to be protected, against corrosion, with an antifreeze composition and/or coolant composition, as described elsewhere herein.

(23) The present invention further provides methods of cooling industrial processes having a cooling system employing a liquid coolant. Such methods may comprise employing a composition, for example, a corrosion-inhibited composition, in accordance with the present invention as the liquid coolant in the cooling system.

(24) The present invention still further provides methods of transferring heat in a system, for example, a solar energy system, employing a liquid to transfer heat. Such methods may comprise employing a composition, for example, a corrosion-inhibited composition, in accordance with the present invention, as the liquid.

(25) The following non-limiting examples are provided to illustrate certain aspects and features of the present invention.

Examples 1 and 2

(26) Two different corrosion inhibited compositions were prepared. The components of these formulations are described in Table 1 below. These compositions are prepared by first placing the liquid component (water and ethylene glycol) in a vessel equipped with a mixer. The other ingredients are added to the vessel, with stirring (mixing), at room temperature (about 22 C.).

(27) In each of the two Examples, a liquid solution is obtained.

(28) TABLE-US-00001 TABLE 1 Composition 1 Composition 2 Component (Heavy Duty) (Light Duty) Water Balance Balance to 100% to 100% Ethylene glycol, % by weight 50 50 Potassium Hydroxide, % by weight 1.9 0.8 t-Butyl Benzoic Acid, mg/l 25,000 18,000 Pimelic acid, mg/l 100 50 Suberic acid, mg/l 100 50 Azelaic acid, mg/l 10,000 5000 Sebacic acid, mg/l 150 75 Undecanedioic acid, mg/l 400 200 Benzotriazole, mg/l 1500 750 Na.sub.2MoO.sub.4, mg/l 1500 750 NaNO.sub.3, mg/l 1000 500 Scale inhibitor, mg/l 150 75 Defoamer, mg/l 65 65

(29) Composition 1 is identified as Heavy Duty, while Composition 2 is identified as Light Duty. Thus, Composition 1 is useful as an antifreeze/coolant composition in heavy duty diesel engine applications such as large (heavy) trucks/engines and in other large (heavy) applications. For example, Composition 1 may be useful; in providing a heavy duty engine coolant, for example, an ASTM D-6210 engine coolant.

(30) Composition 2 is useful as an antifreeze/coolant composition in light duty applications such as automobiles, small (light) trucks and in other relatively small (light) applications. For example, Composition 2 may be useful in providing a light duty ASTM D3306 engine coolant.

(31) Composition 1 was tested with polymeric specimens to determine the effects on (changes in) durometer, tensile strength, elongation and volume (change) of each of the polymers caused by immersion of a polymeric specimen in the composition for 168 hours at 212 F. Such tests were conducted in accordance with ASTM D471-12a.

(32) Specimens of four different polymeric materials were tested in this manner. These polymeric materials were Nitrile Sulfur Cured (NBR-1); NBR HNBR, VMQ (Silicone) and FKM (Viton).

(33) HNBRhydrogenated nitrile-butadiene-rubber

(34) NBR-1a specific type of sulfur cured nitrile rubber (Acrylonitrile-butadiene copolymer)

(35) VMQ1a type of silicone rubber (polydimethylsiloxane)

(36) FKMa class of fluorine-containing polymers containing vinylidene fluoride as monomer

(37) All of these tests using Composition 1 resulted in Composition 1 passing the limits set by Detroit Diesel Engine Company in specification 93K217 and using ASTM D-471-12 methodology.

(38) That is, changes in the durometer, tensile strength, elongation and volume of each of the polymeric specimens as the result of immersion of the specimen in Composition 1 was within the acceptable range using ASTM D471-12a.

(39) Since Composition 1 included higher concentrations of acids and other components relative to Composition 2, it is believed that running all the above-noted tests using Composition 2 would result in Composition 2 passing all the tests.

(40) The heavy duty engine coolant (Composition 1), which is preferably nitrite (NO.sub.2) free, provides beneficial cylinder liner cavitation and pitting corrosion inhibition, as shown in testing according to ASTM D-7583, which is the standard test method for the John Deere Coolant Cavitation Test.

(41) Such results demonstrate that the present compositions are compatible with, or not aggressive toward, polymeric, or elastomeric, components of cooling systems in which the compositions are employed.

(42) Similar tests using other compositions including C.sub.8 aliphatic monobasic acids, such as 2-ethyl hexanoic acid, caused unacceptable results, for example, unacceptable changes in the durometer of silicone polymeric specimens.

(43) These results indicate that the present compositions are more compatible with, or less aggressive to, polymeric, or elastomeric components of cooling systems in which the present compositions are employed relative to a composition including a C.sub.8-C.sub.12 aliphatic monobasic acid. In other words, the present compositions are advantageously substantially free of one or more C.sub.8-C.sub.12 aliphatic monobasic acids.

(44) All of the components identified in the Examples can be obtained commercially.

(45) One skilled in the art will appreciate that the present invention can be practiced by other than the above-described embodiments, which are presented herein for the purpose of illustration and not of limitation, and that the present invention is limited only by the claims that follow.

(46) Each and every publication, patent and published patent application cited herein is individually incorporated herein by reference in its entirety.

(47) While this invention has been described with respect to various specific examples and embodiments, it is to be understood that the invention is not limited thereto and that it can be variously practiced within the scope of the following claims. For example, any feature disclosed herein may be combined with any other component or feature and will be deemed to fall within the description of this patent application.