Patent Application
20150299867
This invention relates to a novel mixture composition comprising various aliphatic dicarboxylic acids (diacids) in particular amounts. The invention further relates to a composition which comprises the novel mixture composition comprising various diacids in particular amounts, water and at least one water-soluble organic amine, and a method for use thereof.
Diacids are generally useful in polymer and corrosion inhibitor formulations, and can be esterified to produce diesters for use in solvent, cleaning, and lubricating oil formulations. These diesters can be reduced to the corresponding aliphatic dialcohols for use in polyurethane formulations. The composition of a mixture of various diacids can have a strong and unpredictable influence on the properties and effectiveness of final use formulations in specific applications. Therefore, a mixture composition comprising various diacids providing commercially desirable properties in final use formulations for specific applications is greatly needed.
WO 9502712 discloses generally that carboxylic acids or their salts may be used in agents for the treatment of metal surfaces. It also discloses generally a method for separating the agents from aqueous media after use for recovering the carboxylic acids or salts.
U.S. Pat. No. 4,941,925 discloses a method for high pressure detergent water cleaning of metal working compounds, swarf and chips from metal surfaces, using as the detergent a composition consisting essentially of C6 to C14 diacids and mixtures thereof. Exemplified in this disclosure is use of a mixture of C10 to C12 diacids, with the C12 diacid being 74% of the diacid mixture.
U.S. Pat. No. 4,946,616 discloses a coolant composition for use in a water cooled automotive engine comprising a freezing point depressant and an inhibitor consisting essentially of 2 to 5.5 weight percent of at least two C7 to C14 diacids or salts thereof, and a hydrocarbyl triazole or salt thereof. Exemplified in this disclosure is use of a mixture of C10 and C12 diacids.
U.S. Pat. No. 7,084,300 B2 discloses a method for synthesis of diacids, particularly diacids having from eight to sixteen carbon atoms, involving oxidation, separation, washing and recovering steps.
WO 2006/071996 discloses in general corrosion inhibitors useful in water-based heat transfer fluids. A corrosion inhibitor mentioned includes one or more C10 to C12 diacids or salts thereof, oxyalkylated carboxylate imidazoline, organophosphonic acid or amine salt thereof, and a secondary or tertiary alkanolamine organic acid salting agent.
EP 1418253 B1 discloses a composition said to inhibit boiler scale and corrosion containing a C7 to C14 diacid component and a fatty polyamine component.
Though each of the above publications discloses various compositions and uses of diacids, none teach the specific novel mixture composition comprising various diacids of the present invention. Opportunities exist for discovering novel mixture compositions which provide commercially desirable properties in final use formulations for specific applications. The present invention meets these and other needs.
It is an object of the present invention to provide a novel mixture composition comprising various diacids in specific amounts. Further objects of the present invention are to provide a composition which comprises the novel mixture composition comprising various diacids in specific amounts, water and at least one water-soluble organic amine, and a method for use thereof.
These and other objects are achieved by the present invention which provides as an embodiment a mixture composition comprising: 0.01 to 1 weight % of C4 diacid, 0.01 to 1 weight % of C5 diacid, 0.01 to 15 weight % of C6 diacid, 0.01 to 3 weight % of C7 diacid, 0.01 to 3 weight % of C8 diacid, 2 to 70 weight % of C9 diacid, 0.01 to 10 weight % of C10 diacid, 2 to 85 weight % of C11 diacid, 0.01 to 90 weight % of C12 diacid, 0.01 to 3 weight % of C13 diacid, 0.01 to 1 weight % of C14 diacid, 0.01 to 1 weight % of C15 diacid, and 0.01 to 1 weight % of C16 diacid. This mixture composition may comprise as little as 0.01 weight % of any one or number of the C4 to C8, C10, and C12 to C16 diacid components. For example, the mixture composition may comprise from 0.01 to 3 weight % of the C13 diacid. For example, the mixture composition may comprise a total amount of C4 to C7 diacids from 0.01 to 20 weight %. As a further example, the mixture composition may comprise a total amount of C13 to C16 diacids from 0.01 to 6 weight %. The mixture composition may also comprise a total amount of C4 to C7 diacids from 0.01 to 20 weight % and a total amount of C13 to C16 diacids from 0.01 to 6 weight %. In all preceding embodiments, the mixture composition can further comprise aliphatic, monocarboxylic acids (monoacids). The total amount of monoacids may comprise between 0.01 to 10 weight % of the mixture composition, for example, between 0.01 to 5 weight % or between 0.01 to 2 weight %.
Another embodiment of the present invention is a mixture composition as above wherein at least one of the C8 to C12 diacids is manufactured by reaction of cyclododecanol, cyclododecanone, or a combination thereof with nitric acid, and at least one of the C9 to C13 diacids is manufactured by oxidative cleavage of unsaturated fatty acids or unsaturated fatty acid esters. In another embodiment, adipic acid, dodecanedioic acid, or a combination of adipic acid and dodecanedioic acid are combined with the at least one of the C8 to C12 diacids and the at least one of the C9 to C13 diacids of the preceding embodiment to obtain a mixture composition as above.
Another embodiment of the present invention is a mixture composition as above wherein at least one of the C8 to C12 diacids is manufactured by reaction of cyclododecanol, cyclododecanone, or a combination thereof with nitric acid. In another embodiment, adipic acid, dodecanedioic acid, or a combination of adipic acid and dodecanedioic acid are combined with the at least one of the C8 to C12 diacids of the preceding embodiment to obtain a mixture composition as above.
Another embodiment of the present invention is a mixture composition as above wherein at least one of the C9 to C13 diacids is manufactured by oxidative cleavage of unsaturated fatty acids or unsaturated fatty acid esters. In another embodiment, adipic acid, dodecanedioic acid, or a combination of adipic acid and dodecanedioic acid are combined with the at least one of the C9 to C13 diacids of the preceding embodiment to obtain a mixture composition as above.
Another embodiment of the present invention is a mixture composition as above comprising a total of from 1 to 90 weight % of C8 to C12 diacids that are manufactured by reaction of cyclododecanol, cyclododecanone, or a combination thereof with nitric acid; and another embodiment is a mixture composition as above comprising a total of from 1 to 90 weight % of C9 to C13 diacids that are manufactured by oxidative cleavage of unsaturated fatty acids or unsaturated fatty acid esters.
Another embodiment of the present invention is a mixture composition comprising: 0.01 to 1 weight % of C4 diacid, 0.01 to 1 weight % of C5 diacid, 0.01 to 2 weight % of C6 diacid, 0.01 to 3 weight % of C7 diacid, 1 to 3 weight % of C8 diacid, 5 to 70 weight % of C9 diacid, 4 to 7 weight % of C10 diacid, 12 to 45 weight % of C11 diacid, 3 to 45 weight % of C12 diacid, 0.01 to 3 weight % of C13 diacid, 0.01 to 1 weight % of C14 diacid, 0.01 to 1 weight % of C15 diacid, and 0.01 to 1 weight % of C16 diacid. The mixture composition may comprise as little as 0.01 weight % of any one or number of the C4 to C7 and C13 to C16 diacid components. For example, this mixture composition may comprise a total amount of C4 to C7 diacids from 0.01 to 7 weight %. As another example, this mixture composition may comprise a total amount of C13 to C16 diacids from 0.01 to 6 weight %. For example, the mixture composition may comprise a total amount of C4 to C7 diacids from 0.01 to 7 weight % and a total amount of C13 to C16 diacids from 0.01 to 6 weight %. In all preceding embodiments, the mixture composition can further comprise at least one monoacid. The total amount of monoacids may comprise between 0.01 to 10 weight % of the mixture composition, for example, between 0.01 to 5 weight % or between 0.01 to 2 weight %.
Another embodiment of the present invention is a composition, for example an aqueous composition, comprising the mixture composition of diacids as above, water and at least one water-soluble organic amine. Another embodiment of the present invention is a method for inhibiting corrosion of metal comprising contacting the metal with the composition comprising the mixture composition of diacids as above, water and at least one water-soluble organic amine.
The detailed description below is provided for the purpose of illustrating certain embodiments of the invention and should not be taken as limiting the present inventive concept to these specific embodiments. To the extent that this description is specific to a particular embodiment, this is for purposes of illustration only and should not be taken as limiting.
The present invention is directed to a specific novel mixture composition comprising various diacids in certain amounts which provide commercially desirable properties in final use formulations for specific applications, such as, for example, inhibiting the corrosion of metals. For clarity, diacid abbreviations, formulas, and names are provided in Table 1.
The mixture composition of diacids comprises 0 to about 1 weight % of C4 diacid, 0.01 to 1 weight % of C5 diacid, 0.01 to 15 weight % of C6 diacid, 0.01 to 3 weight % of C7 diacid, 0.01 to 3 weight % of C8 diacid, 2 to 70 weight % of C9 diacid, 0.01 to 10 weight % of C10 diacid, 2 to 85 weight % of C11 diacid, 0.01 to 90 weight % of C12 diacid, 0.01 to 3 weight % of C13 diacid, 0.01 to 1 weight % of C14 diacid, 0.01 to 1 weight % of C15 diacid, and 0.01 to 1 weight % of C16 diacid. This mixture composition may comprise as little as 0.01 weight % of any one or number of the C4 to C8, C10, and C12 to C16 components. For example, the mixture composition may comprise from 0.01 to 3 weight % of the C13 diacid. For example, the mixture composition can comprise 1 to 15 weight % of C6 diacid. For another example, the mixture composition can comprise a total amount of C4 to C7 diacids from 0.01 to 20 weight %. The mixture composition may also comprise a total amount of C4 to C7 diacids from 0.01 to 20 weight % and a total amount of C13 to C16 diacids from 0.01 to 6 weight %. In all preceding embodiments, the mixture composition can further comprise at least one monoacid. The total amount of monoacids may comprise between 0.01 to 10 weight % of the mixture composition, for example, between 0.01 to 5 weight % or between 0.01 to 2 weight %. Monoacids may be selected from C4 to C16, aliphatic monocarboxylic acids where the aliphatic hydrocarbon chain of each monoacid may be linear or branched.
Another embodiment of the present invention is a mixture composition of diacids comprising 0.01 to 1 weight % of C4 diacid, 0.01 to 1 weight % of C5 diacid, 0.01 to 2 weight % of C6 diacid, 0.01 to 3 weight % of C7 diacid, 1 to 3 weight % of C8 diacid, 5 to 70 weight % of C9 diacid, 4 to 7 weight % of C10 diacid, 12 to 45 weight % of C11 diacid, 3 to 45 weight % of C12 diacid, 0.01 to 3 weight % of C13 diacid, 0.01 to 1 weight % of C14 diacid, 0.01 to 1 weight % of C15 diacid, and 0.01 to 1 weight % of C16 diacid. For example, this mixture composition can comprise 5 to 15 weight % of C12 diacid. This mixture composition may comprise as little as 0.01 weight % of any one or number of the C4 to C7, and C13 to C16 components. For example, the mixture composition may comprise from 0.01 to 3 weight % of C13 diacid. For another example, this mixture composition can comprise a total amount of C4 to C7 diacids from 0.01 to 7 weight % and a total amount of C13 to C16 diacids from 0.01 to 6 weight %. In all preceding embodiments, the mixture composition can further comprise at least one monoacid. The total amount of monoacids may comprise between 0.01 to 10 weight % of the mixture composition, for example, between 0.01 to 5 weight % or between 0.01 to 2 weight %. Monoacids may be selected from C4 to C16, aliphatic monocarboxylic acids where the aliphatic hydrocarbon chain of each monoacid may be linear or branched.
Features of the present mixture composition of diacids for commercially improved applications are the particular diacid and amount of each diacid in the mixture composition. Another feature is the source of certain diacids in the mixture composition.
A mixture of diacids can be manufactured, for example, by reaction of cyclododecanol, cyclododecanone, or a combination of cyclododecanol and cyclododecanone, with nitric acid. The major diacid in the reaction product is a C12 diacid, dodecanedioic acid, but it can also contain other shorter chain diacids, comprising a C8 diacid (suberic acid), a C9 diacid (azelaic acid), a C10 diacid (sebacic acid), and a C11 diacid (undecanedioic acid). With control of reaction conditions, the reaction product can further comprise a C4 diacid (succinic acid), a C5 diacid (glutaric acid), a C6 diacid (adipic acid), and a C7 diacid (pimelic acid), or any combination of these diacids.
A suitable method for recovering the diacids for the present invention is fractional crystallization. For example, a reaction of cyclododecanol, cyclododecanone, or a combination of cyclododecanol and cyclododecanone, with nitric acid can be carried out in the presence of water to produce an aqueous reaction product, comprising, for example, the C8 to C12 diacids. A fraction of the C12 diacid can be first crystallized from this aqueous reaction product in high purity (e.g. >90%). When the solid C12 diacid is separated from the aqueous mother liquor, for example by filtration or decantation, this liquor becomes enriched in the C8 to C11 diacids and depleted in the C12 diacid, relative to the aqueous reaction product. But this mother liquor can still comprise significant amounts of the C12 diacid.
The mixture of C8 to C12 diacids can then be recovered from this aqueous mother liquor by various methods. Non-limiting examples of recovery methods include (1) a second fractional crystallization of a solid mixture of C8 to C12 diacids from the aqueous mother liquor, or (2) partial or complete evaporation of water from the aqueous mother liquor to crystallize or precipitate a solid mixture of C8 to C12 diacids. In recovery methods (1) and (2), filtration or decantation can be applied to separate the solid mixture of C8 to C12 diacids from any resulting mother liquor.
According to any preceding embodiment, the recovered mixture of C8 to C12 diacids comprises from 10 to 60 weight % of the C12 diacid in the recovered mixture of C8 to C12 diacids, for example from 30 to 50 weight % of the recovered mixture of C8 to C12 diacids. In another embodiment, the recovered mixture of C8 to C12 diacids further comprises a mixture of the C6 and C7 diacids and the total amount of C6 and C7 diacids is from 0.1 to 10 weight % of the recovered mixture of C8 to C12 diacids, for example from 0.5 to 5 weight % of the recovered mixture of C8 to C12 diacids. In another embodiment, the recovered mixture of C8 to C12 diacids further comprises a mixture of C4, C5, C6 and C7 diacids and the total amount of C4 to C7 diacids is less than 10 weight % of the recovered mixture of C8 to C12 diacids, for example from 0.5 to 5 weight % of the recovered mixture of C8 to C12 diacids.
In yet another embodiment, a mixture of C9 to C13 diacids can be manufactured by a reaction involving oxidative cleavage at C═C bonds in unsaturated fatty acids or unsaturated fatty acid esters. The mixture of C9 to C13 diacids can be recovered from the resulting reaction product. Examples of such unsaturated fatty acids and unsaturated fatty acid esters include palmitoleic acid, oleic acid, asclepic acid, linoleic acid, α-linolenic acid, gondoic acid, erucic acid, methyl esters of the preceding unsaturated fatty acids, glyceryl esters of the preceding unsaturated fatty acids, and mixtures thereof. Oxidative cleavage of unsaturated fatty acids or unsaturated fatty acid esters can be carried out using oxidants such as ozone and oxygen, ozone and hydrogen peroxide, or nitric acid.
The mixture composition of diacids as above can be obtained by combining diacid mixtures together, by combining at least one diacid mixture with at least one pure diacid, or by combining more than one pure diacid together, all in the proper proportions.
Another embodiment of the present invention is a mixture composition as above wherein at least one of the C8 to C12 diacids is manufactured by reaction of cyclododecanol, cyclododecanone, or a combination thereof with nitric acid, and at least one of the C9 to C13 diacids is manufactured by oxidative cleavage of unsaturated fatty acids or unsaturated fatty acid esters. In another embodiment, the mixture composition of diacids as above is obtained by combining the at least one of the C8 to C12 diacids with the at least one of the C9 to C13 diacids. In another embodiment, the mixture composition of diacids as above is obtained by combining the at least one of the C8 to C12 diacids, at least one of the C9 to C13 diacids, and another diacid selected from the group of adipic acid and dodecanedioic acid.
Another embodiment of the present invention is a mixture composition as above wherein at least one of the C8 to C12 diacids is manufactured by reaction of cyclododecanol, cyclododecanone, or a combination thereof with nitric acid. In another embodiment, the mixture composition of diacids as above is obtained by combining the at least one of the C8 to C12 diacids with another diacid selected from the group of adipic acid and dodecanedioic acid.
Another embodiment of the present invention is a mixture composition as above wherein at least one of the C9 to C13 diacids is manufactured by oxidative cleavage of unsaturated fatty acids or unsaturated fatty acid esters. In another embodiment, the mixture composition of diacids as above is obtained by combining the at least one of the C9 to C13 diacids with another diacid selected from the group of adipic acid and dodecanedioic acid.
A composition comprising the diacid mixture composition as above, water and at least one water-soluble organic amine is very useful for inhibiting corrosion of metal surfaces. For this use, the water-soluble organic amine is selected from the group consisting of monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, triisopropanolamine, diglycolamine, 2-amino-2-methyl-1-propanol, and mixtures thereof. This composition comprises from about 0.1 to about 25 weight % of the diacid mixture composition as above, from about 15 to about 85 weight % water, and from about 10 to about 65 weight % water-soluble organic amine. According to any preceding embodiment, of the composition, a molar ratio of nitrogen atoms in the water-soluble organic amine to carboxylic acid groups in the diacid mixture composition is equal to or greater than one. According to any preceding embodiment of the composition, more than one water-soluble organic amine is selected for the composition. And in another embodiment, two different water-soluble organic amines are selected for the composition and a molar ratio of the two different water-soluble organic amines is from 0.01 to 100, preferably from 0.1 to 10, e.g. from 0.2 to 5. For example, a composition formed by contacting ethanolamine and triethanolamine, in approximately an equimolar ratio, with the diacid mixture composition as above, and water; wherein the molar ratio of nitrogen atoms in both of these water-soluble organic amines to carboxylic acid groups in the diacid mixture composition is equal to or greater than one, such as from 1 to 25, e.g. from 1 to 5. For example, a specific embodiment of this provides the ratio of nitrogen atoms in the amines to carboxylic acid groups in the diacid mixture of about 1.01 to 1.2.
The present invention is further described with reference to the following non-limiting examples. All percentages are by weight. The compositions of diacid mixtures can be determined by esterification with a BF3/CH3OH reagent followed by analysis of the corresponding diester mixture by gas chromatography.
Sebacic acid and dodecanedioic acid (DDDA) are commercial diacids used as corrosion inhibitors in water-based, metal-working fluid formulations. “Ozone diacid” is a mixture of C9 to C13 diacids recovered from the oxidative cleavage of unsaturated fatty acids or unsaturated fatty acid esters with ozone and oxidative workup. “Nitric diacid” is a mixture of C8 to C12 diacids recovered from the reaction of a mixture of cyclododecanol and cyclododecanone with nitric acid. A C11 diacid sample was prepared through oxidative cleavage of fatty acids or fatty acid esters.
Blends 1 and 2 were obtained by combining the ozone diacid mixture with DDDA. Blend 3 was obtained by combining the ozone diacid mixture with DDDA and adipic acid. Blends 4 and 5 were obtained by combining the ozone diacid mixture with the nitric diacid mixture. Blend 6 was obtained by combining the ozone diacid mixture, the nitric diacid mixture, and DDDA together. Blend 7 was obtained by combining the C11 diacid sample with DDDA. Table 2 presents particulars of the blends. The same GC method can measure the amounts of monoacids in the adipic acid, DDDA, ozone diacid mixture, nitric diacid mixture and C11 diacid sample. The total monoacids are less than 1 weight % meaning that all blends of Table 2 are also less than 1 weight %. The same GC method can measure the amounts of monoacids in the adipic acid, DDDA, ozone diacid mixture, nitric diacid mixture, and C11 diacid sample. The total monoacids are less than 1 weight % meaning that all blends of Table 2 are also less than 1 weight %.
The ASTM standard test method for iron chip corrosion for water-dilutable metalworking fluids, D4627-92, was utilized to compare the properties of Blends 1-7 with those of the commercial diacids, sebacic acid and DDDA. The metalworking fluid concentrates were prepared by dissolving the diacid or diacid mixture in an aqueous solution containing water, monoethanolamine, and triethanolamine. Each metalworking fluid concentrate was then diluted with water at either a water hardness of 100 ppm or 500 ppm (as CaCO3), according to the method. Then the breakpoints (concentration of the diacid or diacid mixture required to inhibit corrosion) were determined. A hard water stability test at 500 ppm was also performed for each metalworking fluid concentrate. The formation of a visible precipitate indicated hard water instability—an undesired result. The data from these tests are compiled in Table 3.
While the invention has been described in terms of specific embodiments, those skilled in the art will appreciate that various modifications and variations to these embodiments can be made without departing from the spirit and scope of this invention. For example, while certain embodiments are exemplified, other mixture compositions are also contemplated. Additionally, while compositions comprising the mixture composition embodiments and their use for inhibiting corrosion of metal are discussed, other uses, such as in polymer formulations, and use in solvent, cleaning, and lubricating oil formulations, are also contemplated.
This application claims benefit of priority from U.S. Provisional Application No. 61/692,042 filed Aug. 22, 2012, U.S. Provisional Application No. 61/728,529 filed on Nov. 20, 2012 and U.S. Provisional Application No. 61/731,148 filed on Nov. 29, 2012. These applications hereby incorporate by reference these applications in their entirety.
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/US13/53247 | 8/1/2013 | WO | 00 |
| Number | Date | Country | |
|---|---|---|---|
| 61692042 | Aug 2012 | US | |
| 61728529 | Nov 2012 | US | |
| 61731148 | Nov 2012 | US |
