[0002] Aqueous fluids are used extensively as metalworking fluids due to their lubricity and cooling capacity. Synthetic, or completely water-based fluids, have additional advantages of low misting, improved cleanliness and safety. However, most of these fluids are not waste-treatable using simple conventional methods. In large part, this is due to their lubricity and corrosion inhibiting additives. Suitable organic inhibitors include phosphate esters, fatty acids, amines and aromatic acids. Such compounds, however, tend to have high chemical oxygen demand levels (COD). As a result, it can be difficult to reduce the COD of fluids containing such inhibitors to acceptable levels, particularly when simple waste treatment techniques are employed. Although inorganic corrosion inhibitors, such as clay and metal borates, do not affect the COD levels of metalworking fluids, such inhibitors tend to form hard residues, especially when the water used to dilute the metalworking fluid contains high levels of naturally occurring elements such as calcium or magnesium. These hard residues have negative effects, particularly on the machine or parts.
[0003] It is among the objects of the present invention to provide an alternative composition for a metal-working fluid.
[0004] According to the present invention, there is provided an additive composition for a metalworking fluid, said additive composition comprising a reaction product obtainable by the reaction between a molar excess of an anhydride and an amine, wherein the amine is at least one amino alkyl mono- or di-alkanolamine.
[0005] Where a mixture of two different alkanolamines is employed, the mixture preferably comprises a primary alkanolamine and a secondary alkanolamine, and/or a primary alkanolamine and a tertiary alkanolamine.
[0006] Any suitable anhydride may be used to produce the additive composition of the present invention. Preferably, a polycarboxylic acid anhydride is employed. More preferably, the polycarboxylic acid anhydride is a dicarboxylic acid anhydride. Suitable dicarboxylic acid anhydrides include succinic, phthalic, glutaric, pimelic, suberic, azelaic and sebacic anhydrides. Such anhydrides may comprise up to 50 carbon atoms, for example, 4 to 30, preferably, 8 to 15 carbon atoms. Additionally, these anhydrides may further comprise aliphatic hydrocarbyl substituents, for example, saturated or unsaturated hydrocarbyl substituents. These substituents include C
[0007] Where an amino alkyl di-alkanolamine is employed, the amino alkyl di-alkanolamine preferably has an alkyl group of 1 to 12 carbon atoms, more preferably, 2 to 8 carbon atoms, and most preferably, 3 to 6 carbon atoms. For example, the alkyl group may be an ethyl, propyl, butyl, pentyl or hexyl group. The amino alkyl di-alkanolamine may have a di-alkanolamine group having 2 to 12 carbon atoms, preferably, 2 to 6 carbon atoms. For example, the di-alkanolamine may be derived from an unsubstituted and/or substituted diethanolaamine, dipropanolamine, di-t-butanolamine, diisopropanolamine, 2,2′-iminbutanol, 3,3′-iminodipentanol-2, and/or N-(hydroxyethyl)-propanolamine. For the avoidance of doubt, an amino alkyl di-alkanolamine is a secondary dialkanolamine: in this application, the terms have been used interchangeably.
[0008] Where a mixture of a primary alkanolamine and a secondary alkanolamine or tertiary alkanolamine is employed, the primary alkanolamine preferably has an alkyl group of 1 to 12 carbon atoms, more preferably 2 to 8 carbon atoms, and most preferably 3 to 6 carbon atoms. For example, the primary amine may be derived from an unsubstituted and/or substituted monoethanolamine, monoisopropanolamine, diglycolamine and/or 2-amino-2-methyl-1-propanol. The secondary or tertiary amine preferably has an alkyl group of 1 to 12 carbon atoms, more preferably 2 to 10 carbon atoms, and most preferably 4 to 8 carbon atoms. Suitable secondary amines are described above in the preceding paragraph. A preferred secondary amine is one derived from a di-isopropanolamine. Suitable tertiary amines include those derived from, 2-dimethylamino-2-methyl-1-propanol, and/or bis-hydroxylethylmethylamine.
[0009] In a preferred embodiment, the amine is amino propyl di-iso-propanolamine (APDIPA).
[0010] In a most preferred embodiment, the reaction product is a reaction product of aminopropyl di-iso-propanolamine (CAS#77355-06-7) and octenyl succinic anhydride.
[0011] The mole ratio of amine to anhydride employed may be in the range of 0.1 to less than 1:1, preferably, 0.2 to less than 1:1, more preferably, 0.4 to less than 1:1, for example, 0.6:1. In a most preferred embodiment, the reaction product is a reaction product of amino propyl di-iso-propanolamine and octenyl succinic anhydride, wherein the mole ratio of amine to anhydride employed is 0.5:1.
[0012] The reaction product may be produced by reacting the anhydride and the amine at a reaction temperature of 80 to 200° C., preferably, 100 to 180° C., more preferably, 130 to 160° C.
[0013] According to a further embodiment of the present invention there is provided a compound having a structural formula (I):
[0014] wherein:
[0015] X represents an alkyl group having 1 to 12 carbon atoms, preferably, 2 to 8 carbon atoms and more preferably 3 to 6 carbon atoms;
[0016] Y represents a hydrocarbyl group having 2 to 12 carbon atoms, preferably 2 to 6 carbon atoms;
[0017] R′ represents an alkyl or alkanol group having 2 to 12 carbon atoms; and
[0018] R and R″ independently represent hydrocarbyl groups which have up to 48 carbon atoms, preferably 2 to 28, more preferably 6 to 13 carbon atoms.
[0019] R and R′ may independently comprise aliphatic hydrocarbyl substituents, preferably C
[0020] A preferred compound according to formula I is butanedioic acid, octenyl-, mono(2-((3-((3-carboxyoctenyl-1-oxopropyl)amino)propyl)(2-hydroxypropyl)amino-1-methylethyl) ester CAS number: 384370-64-3 and represented by the formula II
[0021] In addition to the reaction product, the additive composition may also comprise water and other conventional additives for metal-working fluids. Suitable additives include lubricity additives, such as polyalkylene oxides, phosphate esters, fatty acids, fatty acid esters and derivatives thereof. Suitable polyalkylene oxides and polyoxyalkylene derivatives include polyoxyethylene, polyoxypropylene, oxyethylene oxypropylene (block) polymer, ethylene oxide propylene oxide (block) additive of ethylenediamine. Suitable phosphate ester derivatives include polyoxyethylene octadecenyl ether phosphates, polyoxyethylene hexyl ether phosphates and polyoxyethylene laural ether phosphates. Suitable fatty acids include fatty acids of 4 to 40 carbon atoms, preferably, 6 to 24 carbon atoms, more preferably, 8 to 20 carbon atoms. Specific examples of suitable fatty acids include stearic acid, palmitic acid, myristic acid, lauric acid, arachic acid, behenic acid, myristoleic acid, palmitoleic acid, oleic acid, linolic acid, linoleic acid, eleostearic acid, hydroxystearic acid and ricinolic acid. Salts, for example, metal salts of such acids may be employed. Alkali metal salts are preferred; examples include potassium and sodium salts. Suitable fatty acid esters include fatty acid polyglycol esters, such as 9-octadecanoic acid (Z)-, 1-methylethyl ester. De-foamers, biocides and/or additional corrosion inhibitors, such as benzotriazole may also be present in the additive composition.
[0022] The additive composition of the present invention may be added to a metalworking fluid, for example, as a corrosion inhibitor. Thus, according to a further aspect of the present invention, there is provided a metalworking fluid composition comprising a metalworking fluid and the reaction product of the additive composition described above. The metalworking fluid typically comprises greater than 50 wt % water, preferably, greater than 70 wt % water, preferably, between 70 and 99 wt % water. Examples of suitable metal-working fluids include those from the Castrol Syntilo® range, such as Castrol Syntilo® 9902, Castrol Syntilo® 9904, Castrol Syntilo® 9913, Castrol Syntilo® 9930, Castrol Syntilo® 9951, Castrol Syntilo® 9954 and Castrol Syntilo® E-55.
[0023] Preferably, the reaction product forms 1 to 50 wt %, more preferably, 10 to 30 wt %, most preferably, 15 to 20 wt % of the overall metalworking fluid composition.
[0024] The metal-working fluid composition may further comprise lubricity additives, such as polyalkylene oxides, phosphate esters, fatty acids, fatty acid esters and derivatives thereof. Suitable polyalkylene oxides and polyoxyalkylene derivatives include polyoxyethylene, polyoxypropylene, oxyethylene oxypropylene (block) polymer, ethylene oxide propylene oxide (block) additive of ethylenediamine. Suitable phosphate ester derivatives include polyoxyethylene octadecenyl ether phosphates, polyoxyethylene hexyl ether phosphates and polyoxyethylene laural ether phosphates. Suitable fatty acids include fatty acids of 4 to 40 carbon atoms, preferably, 6 to 24 carbon atoms, more preferably, 8 to 20 carbon atoms. Specific examples of suitable fatty acids include stearic acid, palmitic acid, myristic acid, lauric acid, arachic acid, behenic acid, myristoleic acid, palmitoleic acid, oleic acid, linolic acid, linoleic acid, eleostearic acid, hydroxystearic acid and ricinolic acid. Salts, for example, metal salts of such acids may be employed. Alkali metal salts are preferred; examples include potassium and sodium salts. Suitable fatty acid esters include fatty acid polyglycol esters, such as 9-octadecanoic acid (Z)-, 1-methylethyl ester. De-foamers, biocides and/or additional corrosion inhibitors, such as benzotriazole may also be present in the metalworking fluid composition.
[0025] According to a preferred embodiment, the metalworking fluid composition comprises independently by weight:
Water 40-90% e.g. 45-90% Reaction Product 2-50% e.g. 5-40% C6-C12 Fatty acids/potassium salts 5-15% e.g. 5-10% Benzotriazole 0-5% e.g. 0-1% Defoamer 0-1% Biocides 0-1%
[0026] The metalworking fluid composition of the present invention may be employed in any metal-working application, for example, in cutting and/or grinding. The metal-working fluid composition may be used to work a range of metals, including for example, iron, steel and aluminium.
[0027] An advantage of the metal-working fluid composition of the present invention is that it is waste-treatable, particularly, using conventional waste-treatment methods. Thus, the COD level of the composition may be reduced to acceptable values of 10,000 mg/l or less, preferably, to 2000 mg/l or less, more preferably, to 1500 mg/l or less using conventional waste-treatment techniques. The COD may not be reduced to zero and may be at least 200, 500 or 600 mg/l. Preferably, such conventional waste-treatment techniques may be used to reduce the initial COD levels of the metal-working fluid composition by more than 20%, preferably, more than 50%.
[0028] Conventional waste-treatment methods for metalworking fluids are described in detail in “Waste Minimization and Wastewater Treatment of Metalworking Fluids” by Jean C Childers, Shu-Jen Huang and Michael Romba; @1990 Independent Lubricant Manufactures Association. Such methods include evaporation, ultra-filtration and chemical treatment using, for example, polymer or acid/alum methods. Of these methods, acid/alum splits are particularly useful for reducing the COD of the metalworking fluid compositions of the present invention to acceptable levels. This form of chemical treatment is based on the principle of neutralization of surface charges. Typically, the pH of the solution to be waste treated is lowered with a strong acid (sulfuric acid) to a pH of 2.5. At this point, aluminum sulfate is added to the solution. Then, slowly raising the pH with the addition of sodium hydroxide will facilitate the formation of aluminum hydroxide which will attract the anionic particles and form an insoluble floc, causing separation from the aqueous phase.
[0029] Yet another aspect of the present invention provides the use of the additive composition described above, as a corrosion inhibitor for a metal-working fluid.
[0030] These and other aspects of the invention will now be described, by way of illustration, with reference to the following examples.
[0031] APDIPA and octenyl succinic anhydride were reacted together at a molar ratio of 0.5:1 to form a mixture of anhydride and amide, at approximately 150° C. for 4 hours. The reaction product was isolated for further use.
[0032] In this Example, the solution produced in Example 1 was incorporated into an experimental metalworking fluid formulation to test its corrosion inhibiting properties. More specifically, 4 grams of cast iron chips were placed in a petri dish and partially covered with 6 mls of diluted product (product diluted to 5% in 600 ppm CaCl
[0033] In this Example, Example 2 was repeated using a product consisting of a blend of APDIPA and Bis-hydroxylethylmethylamine reacted with Octenyl Succinic Anhydride at a 0.7:1.0 molar ratio. In this example, 40% of the filter paper showed signs of corrosion.
[0034] The COD level of the solution of Example 2 was tested using EPA Method 410.1. The COD level of the solution was found to be 4800 mg/l.
[0035] Example 3 was repeated using a solution of APDIPA reacted-with Phthalic Anhydride at a 1:1 molar ratio. The COD level of this solution was found to be 4400 mg/l.
[0036] The solution of Example 2 was treated using a conventional acid/alum split. The COD of the treated solution was found to have reduced to 800 mg/l.
[0037] Example 4 was repeated using the solution of Comparative Example B. The COD level of this solution was found to be 4000 mg/l.
[0038] Example 4 was repeated using the solution of Comparative Example A. The COD level of this solution was found to be 1000 mg/l.
[0039] Example 4 was repeated using a solution of Aminopropyl Diethanolamine ( APDEA) reacted with Tetrapropenyl Succinic Anhydride (TPSA) at a 1:1 molar ratio. The COD level of this solution was found to be 1600 mg/l.
[0040] Example 4 was repeated using a solution of APDIPA reacted with Methyl Nadic Anhydride at a 1:1 molar ratio. The COD level of this solution was found to be 4800 mg/l.
[0041] Example 4 was repeated using a solution of APDIPA reacted with Dodecyl Succinic Anhydride at a 1:1 molar ratio. The COD level of this solution was found to be 1800 mg/l.