TWI654293B - Additive compositions and industrial process fluids - Google Patents

Abstract

The present invention provides a treatment fluid containing no boron and a secondary amine, the treatment fluid comprising petroleum-based or non-petroleum based oils; water; and an additive composition comprising a long-chain primary amine, a cycloalkyl tertiary Amines and amino acids.

Description

Additive composition and industrial treatment fluid

The present technology is generally directed to additive compositions and industrial process fluids. In particular, the present technology relates to environmentally friendly metal processing, metal forming, forging, and mining fluids.

Metalworking fluids and metal forming fluids in the entire mechanical manufacturing or machining industry due to their cooling, lubrication and corrosion resistance properties such as metal cutting, grinding, boring, drilling, turning, forming, squeezing, embossing, It is widely used during stamping and drawing operations. Such fluids are typically made from a complex mixture of oils, detergents, surfactants, biocides, lubricants, corrosion inhibitors, and other potentially harmful ingredients. For example, commercially available fluids may incorporate additives such as boric acid, alkali metal borates, and borate esters for maintaining alkaline pH in metalworking fluids and metal forming fluids, and for neutralizing acidic functional components. A combination of alkanolamines.

Although these fluids are essential for metal forming and machining, they are currently being examined in an enhanced detailed review because of the risks associated with worker exposure, including but not limited to rash, potentially elevated cancer Rates, respiratory problems and other issues. These fluids can cause considerable environmental problems associated with their handling. It is now generally accepted that safer and more environmentally friendly functional fluids are needed.

In one aspect, an additive composition is provided. The additive composition includes a long chain primary amine, a cycloalkyl tertiary amine, and an amino acid; wherein the treatment fluid is boron free and free of secondary amines. The additive composition is suitable for use in water based industrial processing fluids to produce enhanced lubrication characteristics, corrosion protection, and cushioning capabilities. Furthermore, treatment fluids containing such additive compositions are less harmful to the environment and exhibit less negative health hazards to workers due to the absence of boron and the absence of secondary amines compared to conventional fluids. In any embodiment of the additive composition, the primary amine may be a long-chain C ₈ -C ₂₄ primary amine. For example, the long chain primary amine can include octylamine, decylamine, decylamine, undecylamine, dodecylamine, tridecylamine, tetradecylamine, pentaamine, hexadecylamine, heptadecylamine or octadecyl amine. In any embodiment of the additive composition, the cycloalkyl tertiary amine can be an ethoxylated cycloalkyl tertiary amine, including di(ethanol)cyclopentylamine, di(ethanol)cyclohexylamine, di( Ethanol) cycloheptylamine, dicyclopentyl (ethanol) amine or dicyclohexyl (ethanol) amine. In any embodiment of the additive composition, the amino acid can have the formula NH ₂ CHR ² CO ₂ H, wherein R ² is H, alkyl or aryl. For example, the amino acid may include alanine, arginine, aspartic acid, aspartic acid, cysteine, glutamic acid, glutamic acid, glycine, histidine, Isoleucine, leucine, lysine, methionine, phenylalanine, valine, serine, threonine, tryptophan, tyrosine or valine.

In another aspect, a treatment fluid is provided. The treatment fluid comprises petroleum-based or non-petroleum based oils; water; long chain primary amines; cycloalkyl tertiary amines; and amino acids; wherein the treatment fluid is boron free and free of secondary amines. In any embodiment of the process fluid, the primary amine may be a long chain C ₈ -C ₂₄ primary amine. For example, the long chain primary amine can include octylamine, decylamine, decylamine, undecylamine, dodecylamine, tridecylamine, tetradecylamine, pentaamine, hexadecylamine, heptadecylamine or octadecyl amine. In any embodiment of the treatment fluid, the cycloalkyl tertiary amine can be an ethoxylated cycloalkyl tertiary amine, including di(ethanol)cyclopentylamine, di(ethanol)cyclohexylamine, di(ethanol) a cycloheptylamine, a dicyclopentyl (ethanol) amine or a dicyclohexyl (ethanol) amine. In any embodiment of the process fluid, which may have the amino acid of formula NH ^₂ CHR ₂ CO ₂ H, wherein R ² is H, alkyl or aryl. For example, the amino acid may include alanine, arginine, aspartic acid, aspartic acid, cysteine, glutamic acid, glutamic acid, glycine, histidine, Isoleucine, leucine, lysine, methionine, phenylalanine, valine, serine, threonine, tryptophan, tyrosine or valine.

In some embodiments of the treatment fluid, it includes petroleum based oils. In other embodiments of the treatment fluid, it includes non-petroleum based oils. In a further embodiment of the treatment fluid, it comprises a mixture of petroleum and non-petroleum based oils.

In any embodiment of the treatment fluid, one or more of the following additives may be included: alkanolamines, polymeric fatty acids, phosphates, ethoxylated fatty amines, hydrocarbyl succinimides, sulfur-containing compounds, aliphatics A carboxylic acid, an aliphatic dicarboxylic acid, an antifoaming agent, a corrosion inhibitor or an olfactory agent.

In any embodiment of the treatment fluid, the fluid can have an alkaline pH. For example, the treatment fluid may have a pH of 9 or greater.

The treatment fluid can be used in a variety of applications including, but not limited to, metalworking fluids, metal forming fluids, forging fluids, and mining fluids. Thus, in some embodiments, the metalworking fluid comprises any of the treatment fluids described above. In other embodiments, the metal forming fluid comprises any of the treatment fluids described above. In other embodiments, the forging fluid comprises any of the treatment fluids described above. In other embodiments, the production fluid comprises any of the treatment fluids described above.

Various embodiments are described below. It should be noted that the specific embodiments are not intended to be exhaustive or to limit the scope of the invention. An aspect described in connection with a specific embodiment is not necessarily limited to the embodiment and may be implemented by any other embodiment or embodiments.

As used herein, "about" will be understood by a person of ordinary skill and will vary to some extent, depending on the context in which it is used. If the use of the term is not clear to the general practitioner, "about" will mean adding or subtracting 10% of the specific term at most, given its context.

In the context of describing elements, particularly in the context of the following claims, the terms "a" and "the" and "the" The use of a representative object should be understood to include both singular and plural forms. Recitation of ranges of values herein are merely intended to serve as an abbreviated description of each individual value within the range, and each individual value is incorporated in the specification as if it were otherwise indicated herein. The general description is described separately herein. All methods described herein can be performed in any suitable order unless otherwise indicated herein or otherwise clearly contradicted by the context. The use of any and all examples or exemplary language, such as "such as" or "an" No language in the specification should be construed as indicating any element that is not claimed.

In general, "substitution" refers to the replacement of one or more hydrogen atoms of a molecule by a non-hydrogen atom or a group of atoms. Substituents consisting of at least two or more atoms may contain multiple bonds, including double or para-bonds, and one or more heteroatoms, ie, atoms other than hydrogen and carbon atoms, such as, for example, nitrogen, oxygen, etc. . Examples of the substituent include: a hydroxyl group; an alkoxy group, an alkenyloxy group, an alkynyloxy group, an aryloxy group, an aralkyloxy group, a heterocyclic oxy group, and a heterocycloalkoxy group; a carbonyl group (a pendant oxy group); a carboxyl group; an ester; ; urethane; hydrazine; hydroxylamine; alkoxyamine; aralkyloxyamine; thiol; sulfide; hydrazine; hydrazine; sulfonyl; sulfonamide; amine; N-oxide;醯肼; 腙; azide; guanamine; urea; hydrazine; hydrazine; enamine; quinone imine; isocyanate; isothiocyanate; cyanate; thiocyanate; imine;

"Alkyl" as used herein includes both straight and branched chain alkyl groups having from 1 to about 20 carbon atoms, and usually from 1 to 12 carbons, or in some embodiments, from 1 to 8 carbon atoms. Such as As used herein, "alkyl" includes cycloalkyl as defined below. The alkyl group may be substituted or unsubstituted. Examples of linear alkyl groups include methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl and n-octyl. Examples of branched alkyl groups include, but are not limited to, isopropyl, t-butyl, t-butyl, neopentyl, and isopentyl. A representative substituted alkyl group may be substituted one or more times by, for example, an amine group, a thio group, a hydroxyl group or an alkoxy group.

The cycloalkyl group is a cyclic alkyl group such as, but not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl. The cycloalkyl group may be substituted or unsubstituted. Cycloalkyl further includes polycyclic cycloalkyl such as, but not limited to, norbornyl, adamantyl, borneol, decenyl, isodecenyl and decenyl; and fused rings such as, but not limited to, decalin Base. Cycloalkyl also includes rings substituted with straight or branched alkyl groups as defined above. Representative substituted cycloalkyl groups may be monosubstituted or substituted more than once, such as, but not limited to, 2,2-disubstituted cyclohexyl, 2,3-disubstituted cyclohexyl, 2,4-disubstituted Cyclohexyl, 2,5-disubstituted cyclohexyl or 2,6-disubstituted cyclohexyl, or monosubstituted, disubstituted or trisubstituted norbornyl or cycloheptyl, which may be, for example, alkyl, alkoxy Substituted with an amino group, an amine group, a thio group, a hydroxyl group, a cyano group and/or a halogen group.

As used herein, "boron free" or "boron free" means that only trace amounts of boron are present. This may include the case where the composition contains less than 0.5% by weight of boron. In some embodiments, this can include the case where the composition contains less than 0.1% by weight boron or less than 0.05% by weight boron. As used herein, "without secondary amines" or "without secondary amines" means that only trace amounts of secondary amines are present. This may include the case where the composition contains less than 0.5% by weight of the secondary amine. In some embodiments, this can include the case where the composition contains less than 0.1% by weight of a secondary amine or less than 0.05% by weight of a secondary amine.

This article provides industrial treatment fluids that are miscible with water. As used herein, the term miscible with water refers to a fluid that can be mixed with water. Such treatment fluids are intended to replace current state of the art fluids in a variety of applications, including as metalworking fluids and metal forming fluids, in an environmentally compatible manner. The treatment fluid provided is free of boron and secondary amines and has no or low amounts Volatile organic component (VOC). Such treatment fluids should generally be non-toxic to metal workers and others who may be in contact with such fluids.

The treatment fluid is a base fluid that can be incorporated into a wide range of products used in industrial lubricants and processes, including but not limited to metalworking, cutting, grinding, and metal forming industries. Alternatively, the treatment fluid can be used as a process cleaner, a water based hydraulic fluid, and a production fluid. The water-miscible treatment fluid can be used in water-based lubricants such as, but not limited to, soluble oils containing greater than 50% by weight mineral oil and forming an emulsion having a particle size greater than 1 μm when diluted with water; having a thickness of 0.5 to 1 μm a semi-synthetic lubricant having a typical emulsion particle size and containing less than 50% by weight of mineral oil; a microemulsion containing less than 5% by weight of mineral oil and present in the form of minute droplets in water (ie having a particle size of less than 0.5 μm) Emulsion); vegetable oils, animal oils, animal fats, natural esters, synthetic esters, polyglycols containing no mineral oil but containing up to 30% by weight or more of water-insoluble substances in water as tiny droplets And/or a new synthetic lubricant for the synthesis of polyolefins; and a true solution synthetic oil in which all additives are soluble in water.

The water miscible treatment fluid is suitable for use as a lubricant in the machining and forming of metals such as, but not limited to, steel, aluminum, titanium and alloys thereof. The treatment fluid does not corrode, rust or discolor such metals, or only minimally corrodes, rusts or discolors such metals. The treatment fluid provides corrosion protection and cushions other aqueous industrial fluids. Moreover, when residual amounts are left on the surface of the metal being processed or formed, such residues do not interfere with or adversely affect additional processes such as heat treatment, welding, coating, and/or painting.

In one aspect, a treatment fluid is provided that is free of boron and a secondary amine. Such treatment fluids include petroleum-based or non-petroleum based oils; water; long-chain primary amines; cycloalkyl tertiary amines, particularly ethoxylated cycloalkyl tertiary amines; and amino acids. The treatment fluid can be water miscible.

In some embodiments, the treatment fluid comprises a petroleum based oil. Illustrative petroleum base oils include, but are not limited to, refined naphthenic oils and paraffinic oils. Any two types of treatment fluids can be used. A mixture of more or more such oils.

In some embodiments, the treatment fluid comprises a non-petroleum based oil. Illustrative non-petroleum based oils include, but are not limited to, vegetable oils, synthetic esters, polyalphaolefins, polyalkylene glycols, and fatty oils, such as triglycerides of vegetable or animal origin. Mixtures of any two or more such oils or mixtures with any petroleum-based oils may also be employed in the treatment fluid.

According to some embodiments, a long chain amine may be a C ₈ -C ₂₄ primary amine. Illustrative long chain primary amines include, but are not limited to, octylamine, decylamine, decylamine, undecylamine, dodecylamine, tridecylamine, tetradecylamine, pentaamine, hexadecylamine, heptadecylamine or stearylamine . The treatment fluid can include a mixture of any two or more such long chain primary amines.

Illustrative ethoxylated cycloalkyl tertiary amines include, but are not limited to, di(ethanol)cyclopentylamine, di(ethanol)cyclohexylamine, di(ethanol)cycloheptylamine, dicyclopentyl (ethanol)amine or two Cyclohexyl (ethanol) amine. In some embodiments, the ethoxylated cycloalkyl tertiary amine is di(ethanol)cyclohexylamine.

The long chain primary amine can be present in the treatment fluid in an amount from about 1% to about 5% by weight. In some embodiments, from about 2% to about 4% by weight of the long chain primary amine is present in the treatment fluid. The ethoxylated cycloalkyl tertiary amine can be present in the treatment fluid in an amount from about 1% to about 5% by weight. In some embodiments, from about 2% to about 4% by weight of the ethoxylated cycloalkyl tertiary amine is present in the treatment fluid.

As indicated, the treatment fluid includes an amino acid. It is believed that the amino acid provides good emulsifying properties to the fluid and contributes to the dispersibility and stability of the emulsion. For example, the amino acid can be a protein (alpha) amino acid. Illustrative amino acids can have any of the formula NH ₂ CHR ² CO ₂ H, NH ₂ CH ₂ CHR ² CO ₂ H or NH ₂ CHR ² CH ₂ CO ₂ H, wherein R ² is H or alkyl. In some embodiments, R ² is H or C ₁ -C ₄ alkyl. Illustrative amino acids can include, but are not limited to, alanine, arginine, aspartic acid, aspartic acid, cysteine, glutamic acid, glutamic acid, glycine, histidine, Isoleucine, leucine, lysine, methionine, phenylalanine, valine, serine, threonine, tryptophan, tyrosine or valine. Any two or more such amino acids may be used in the treatment fluid. In any of the above embodiments, the amino acid can be glycine, lysine, aspartic acid or a mixture of any two or more of such amino acids. The amino acid can be present in the treatment fluid in an amount from about 1% to about 5% by weight. In some embodiments, from about 2% to about 4% by weight of the amino acid is present in the treatment fluid.

In some embodiments, the treatment fluid comprises an alkanolamine. Illustrative alkanolamines include, but are not limited to, methanolamine, ethanolamine, propanolamine, trimethylolamine, triethanolamine, tripropanolamine, methyldimethanolamine, ethyldimethanolamine, propyldimethanolamine, cyclohexyl Dimethanolamine, methyldiethanolamine, ethyldiethanolamine or propyldiethanolamine. Mixtures of any two or more such alkanolamines can be used in the treatment fluid.

The alkanolamine can be present in the treatment fluid in an amount from about 1% to about 15% by weight. In some embodiments, from about 5% to about 10% by weight of the alkanolamine is present in the treatment fluid.

As indicated, the treatment fluid includes a polymeric fatty acid. The polymeric fatty acid can be a material such as, but not limited to, a polymeric ricinoleic acid derived from castor oil or a polymeric fatty acid derived from soybean oil or linseed oil.

Any of the above treatment fluids may also include a phosphate ester. Phosphates can be used as pressure agents, antiwear agents and/or corrosion inhibitors. In the case where the fluid comprises a phosphate, it is a compound of the formula [R ⁴ (CH ₂ CH ₂ O) _n ] _a P(O)[OX] _b . In the formula, R ⁴ is C ₆ -C ₃₀ alkyl, phenyl, (C ₁ -C ₁₀ alkyl)phenyl or (C ₁ -C ₁₀ dialkyl)phenyl; X is H, ammonium, Tetraalkylammonium, amine or metal, the metal is Li, Na, K, Rb, Cu, Ag, Au, Be, Mg, Ca, Sr, Ba, Zn, Cd and Hg. Further, in the formula, n is 0 to 50; a is 1, 2 or 3; and b is 0, 1, or 2 such that the sum of a and b is 3. In some embodiments, the phosphate ester is polyethylene glycol monooleyl ether phosphate, polyethylene glycol mono C ₁₂ -C ₁₅ alcohol ether phosphate or polyethylene glycol mono C ₁₀ -C ₁₄ alcohol ether phosphate .

In some embodiments, the fluid comprises an ethoxylated fatty amine which is the reaction product of ethylene oxide and a fatty amine having the formula R ³ N[(CH _{2 )} CH ₂ O) _m H][(CH ₂ CH ₂ O) _n H]. Ethoxylated fatty amines exhibit surfactant-like characteristics and are commonly used as emulsifiers and/or humectants. In the formula, R ³ is cocoalkyl (C ₁₂ , C ₁₄ saturated), tallow (C ₁₆ , C ₁₈ saturated, and C ₁₈ unsaturated), stearyl (C ₁₈ saturated), and oil based (C ₁₈ Monounsaturated); and m and n are from about 2 to about 20. In some embodiments, the ethoxylated fatty amine is polyoxyethylene cocoamine, bis-(2-hydroxyethyl)isotridecyloxypropylamine or N-tallow-poly(3) oxyethylene-1, 3-Diaminopropane.

Any of the above treatment fluids may also include a hydrocarbyl butylimine. Such additives can be used as dispersants and/or detergents in the treatment fluid. The hydrocarbyl butylimine may include a reaction product of polyisobutylene having a molecular weight of from about 500 to about 3000 Daltons with maleic anhydride.

Any of the above treatment fluids may also include a sulfur-containing compound. Sulfur-containing compounds in combination with the above phosphates can be used as high pressure agents, antiwear agents, and corrosion inhibitors. Illustrative sulfur-containing compounds can include, but are not limited to, elemental sulfur, sulfurized mineral oil, or a compound of the formula:

In such formulas, R ¹ is H, SO ₄ , NH ₂ , CH ₃ , COOH, OCH ₃ or OCH ₂ CH ₃ . In a treatment fluid containing both a sulfur-containing compound and a phosphate ester, the weight ratio of phosphate to sulfur in the sulfur-containing compound may range from about 25:1 to about 1:1.

Any of the above treatment fluids may also include an aliphatic carboxylic acid or an aliphatic dicarboxylic acid. These types of additives are commonly used as corrosion inhibitors, lubricants and/or emulsifiers when neutralized with a suitable alkanolamine. According to various embodiments, the aliphatic monocarboxylic acid or dicarboxylic acid may be a C ₆ -C ₂₅ monocarboxylic acid or a dicarboxylic acid. Illustrative monocarboxylic acids and dicarboxylic acids for use in treating fluids include, but are not limited to, caproic acid, heptanoic acid, octanoic acid, lanolinic acid, isodecanoic acid, neodecanoic acid, rhododendic acid, citric acid, undecanoic acid, Leucic acid, citric acid, dodecanoic acid, tetradecanoic acid, palmitic acid, octadecanoic acid, icosonic acid, dodecenoic acid, tetradecenoic acid, hexadecenoic acid, octadecenoic acid , eicosenoic acid, docosaenoic acid, octadecatrienoic acid, suberic acid, azelaic acid, ricinoleic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, ten Trioxanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecandioic acid, heptadecanedioic acid, octadecanedioic acid, nonadecanedioic acid, eicosanedioic acid, twenty-two Alkanoic acid, abietic acid, rosin acid or sinapic acid.

Any of the above treatment fluids may also include a variety of additional additives including, but not limited to, antifoaming agents, corrosion inhibitors, or odorants.

As will be noted, the treatment fluid is a water based fluid. The water content of the fluid can be in a wide range. In any of the above embodiments, from about 1% to about 50% by weight water may be present. In other embodiments, from about 1% to about 25% by weight water is present. In other embodiments, from about 25% to about 50% by weight water is present. In other embodiments, from about 20% to about 50% by weight water is present. In other embodiments, from about 25% to about 35% by weight water is present. The treatment fluid also has an alkaline pH. This may include a pH greater than 7. In any of the above embodiments, the treatment fluid has a pH of at least 9. For example, the pH of the treatment fluid can range from 9 to 12.

In an illustrative embodiment, the treatment fluid may comprise any one or more of the following and, when included (the material is not required), the substance may be present in an amount from about 1% to about 10% by weight of the industrial fluid. % by weight, in some embodiments, from about 3% by weight to about 5% by weight of hydrocarbyl butylimine; from about 1% to about 15% by weight, based on industrial fluids, and in some embodiments, about 5 wt% to about 10 wt% of the amount of alkanolamine; industrial fluid to from about 1% to about 10 wt%, in some embodiments, an amount of about 2% to about 7% by weight of the mixed C ₇ - C ₂₅ fatty acid; industrial fluid to about 1 wt.% to about 5 wt%, in some embodiments, from about 1% to about 3% by weight of the amount of units derived from C ₁₅ -C ₂₂ fatty acid is polymerized fatty acid; industrial The fluid is from about 0.5% by weight to about 5% by weight, and in some embodiments, from about 1% by weight to about 3% by weight, of monohydric and/or binary C ₇ -C ₂₅ acid; about 1 weight by weight of the industrial fluid % to about 10% by weight, in some embodiments, a phosphate ester in an amount of from about 2% by weight to about 4% by weight; from about 0.5% by weight to about 3% by weight, based on the industrial fluid, In some embodiments, the ethoxylated fatty amine is present in an amount from about 0.7% to about 1.5% by weight; from about 0.5% to about 3% by weight, based on the industrial fluid, and in some embodiments, from about 0.7% to about 1.5% by weight of glycerol; from about 0.5% to about 3% by weight of the industrial fluid, in some embodiments, from about 0.7% to about 1.5% by weight of the antifoaming agent; about 0.1% by industrial fluid From about 1% by weight to about 1% by weight, in some embodiments, from about 0.15% to about 0.5% by weight of the corrosion inhibitor; in some embodiments, from about 10% to about 15% by weight as water soluble lubrication Alkanolamine fatty acid soap, wherein the fatty acid moiety is derived from a C ₆ -C ₂₂ fatty acid; a sulfur-containing compound having a weight ratio of the phosphate to the sulfur-containing compound of about 25:1 by weight of sulfur in the sulfur-containing compound To a range of about 1:1; and an amount sufficient to make up the balance of the composition, that is, from about 20% by weight to about 60% by weight based on the industrial fluid, and in some embodiments, from about 30% by weight to about 40% by weight. The amount of base oil.

In an illustrative embodiment, the treatment fluid can include:

The invention as generally described herein will be more readily understood by reference to the accompanying claims,

Instance

Example 1: pH stability test. Based on the formulation presented in Table 1, the forming fluid was prepared by combining the materials.

In Table 1, the following definitions apply: DCHA is an abbreviation for dicyclohexylamine.

MDCHA is an abbreviation for methyl dicyclohexylamine.

The amine mixture 1 is a mixture of dicyclohexylamine and dibutylaminoethanol.

The amine mixture 2 is a mixture of methyl dicyclohexylamine, dibutylaminoethanol, and methyldiethanolamine.

The amine mixture 3 is a mixture of 3-amino-4-octanol and 2-amino-2-methyl-1-propanol.

The aliphatic primary amine is selected from one or more of the following: indoleamine, decylamine, undecylamine, dodecylamine, tridecylamine, tetradecylamine, pentaamine, hexadecylamine, heptadecylamine or ten Octamine.

The alpha amino acid is selected from one or more of the following: alanine, aspartic acid, cysteine, glutamic acid, glutamic acid, glycine, leucine, lysine, A Thiamine, phenylalanine, valine, tryptophan, tyrosine or valine.

The alkanolamine mixture is a mixture of monoethanolamine, monoisopropylamine and triethanolamine.

The fatty acid mixture 1 is a mixture of tall oil fatty acid, neodecanoic acid and dibasic acid.

The fatty acid mixture 2 is a mixture of polymerized ricinoleic acid, high erucic acid and ricinoleic acid.

For the results presented in Table 1, many conclusions can be drawn. First, when a working fluid sample of Example 7 containing a synergistic combination of a long chain aliphatic amine and a protein amino acid was used, the pH stability of the emulsion was excellent at the working concentration. In contrast, the pH stability of other emulsion samples tested under the same conditions appeared inferior.

Secondly, in the working fluid sample of Example 23 containing a synergistic combination of a long chain aliphatic amine, a protein amino acid and a cyclic amine, the tapping torque was low at the working concentration, thereby providing excellent lubricating characteristics on the aluminum alloy. In contrast, the lubrication characteristics of other emulsion samples as measured by the tapping torque test under the same test conditions were inferior.

Third, when the working fluid sample of Example 23 was tested, the tapping torque was low at the working concentration, thereby providing excellent lubrication characteristics on the titanium alloy. In contrast, as in The lubrication characteristics of other emulsion samples measured by the tapping torque test under the same test conditions were inferior.

Fourth, the working fluid sample of Example 23 exhibited excellent residue formation and subsequent washout characteristics at the working concentration. In contrast, the residue and washout characteristics of other emulsion samples tested under the same conditions were inferior.

For comparison, the formulation of Example 23 was compared to another lubricating fluid from Fuchs (ECOCOOL ^® 761B). The results are presented in Table 2.

Based on the data presented in Table 2, the formulations provided in Example 23 are comparable in some respects to prior art coolants, and are otherwise significantly superior to prior art coolants. Example For example, the formulation of Example 23 was superior to the prior art in terms of lubricity, titanium machining, residue, and Airbus performance.

In Table 2, the following are the parameters of the tests provided: ¹ pH stability: An emulsion of each fluid was prepared in duplicate at a concentration of 10% in the presence of agar sheets. A single inoculum of the microbial suspension was added and incubated at 25 °C for a period of 14 days. The stability of the emulsion was evaluated by measuring the difference in pH between the start and end of the test.

² TEWL: Transepidermal water loss rate (TEWL) is a term related to dermatology and related sciences. It is defined as a measure of the amount of water that reaches the surrounding atmosphere from the body through the epidermal layer (skin) via diffusion and evaporation processes. Measurements of TEWL can be used to identify skin damage caused by certain chemicals because the TEWL rate increases proportionally with the degree of damage.

³ FLC micro-hole tapping torque test: the lower the value, the better the lubricity. Machinability.

Aluminum: Microporous tapping test for each product diluted to a concentration of 10% by volume. All aluminum tests were performed on pre-drilled holes on 6061 aluminum strips.

Titanium: Microporous tapping tests were performed on each of the products diluted to a concentration of 20% by volume. All titanium tests were performed on pre-drilled holes on the titanium strip. All tests were performed on Megatap II (Micro-electronische Gerate GMBH).

⁴ machine tools - Fuchs UK. This test was performed on Fuchs UK's machine tool test equipment based on the OEM aerospace metalworking test program. The method is based on grinding a titanium alloy with an integral carbide end mill. The tool was worn under a stereomicroscope at a cutting time of 5 minutes until the tool reached a high degree of wear and the cutting edge of the tool broke. This gives the tool life and is listed in minutes of cutting. Tool information: Sandvik 16mm end mill R216.24 16050IAK32P1620. Substrate: Ti6AI-4V, grade 5 ASTM B348. Test conditions: RPM: 2337 rpm; feed rate: 972 mm/min; axial cutting depth: 10.0 mm; radial cutting depth: 1.0 mm; cutting length: 740 mm; introduction radius: 10.0 mm; extraction radius: 10.0 mm.

⁵ Airbus performance test in accordance with ABR 9-0204.

⁶ Emulsion stability: The product was mixed at 5% in the following items: (1) tap water (125 ppm Ca), (2) water containing 500 ppm Ca, (3) water containing 500 ppm Mg, and (4) containing 1,000 ppm Ca water and all samples were allowed to stand for 24 hours. When a precipitate formed at the bottom or scum was observed at the top, the product was considered to be unsuitable at the indicated water hardness. Performance evaluation: excellent (stable in all hardnesses (1), (2), (3), (4)); good (stable in (1), (2), and (3)); (1) and (2) stable).

⁷ Foam Control: Test One 300 ml emulsion was prepared at 5% in tap water (125 ppm Ca) and blended for 1 minute at high speed in a Waring Blender. The fluid was immediately poured into a 1000 ml graduated cylinder and the foam height was measured. The foam height was measured again 2 minutes after the blending was stopped. Performance evaluation: excellent foam control (<20 ml foam); good (<50 ml foam); and acceptable (<100 ml).

⁸ Cast iron corrosion: The product was mixed in tap water (<25 ppm chloride) at the indicated concentrations (1%, 2%, 3% and 4%). The mixture was then applied to ASTM cast iron sheets and placed on filter paper for 2 hours, then the cover was removed and the mixture allowed to dry overnight. Performance evaluation: Excellent (no rust at 2%); good (no rust at 3%); and acceptable (no rust at 4%).

⁹ Non-ferrous rust: Non-ferrous samples were mechanically sanded, stored in acetone, and then soaked for 20 hours in a product mixed with 10% in tap water (about 120 ppm hardness).

¹⁰ Resistant oil capacity: 95 mL of the product was mixed with 5 mL of hydraulic fluid (Renolin AW 68) in tap water (125 ppm Ca) at 5% and then blended at high speed for 1 minute in a Waring blender. The fluid was immediately poured into a 100 ml graduated cylinder and allowed to stand for 24 hours. The reading consists of oil and paste on top of the fluid. Performance evaluation: excellent soil-repellent performance (3 ml oil layer and 1 ml cream layer); good (2 ml oil layer and 1 ml cream layer).

¹¹ Residue wash-off test: 50 ml of the product in tap water (Ca 125 ppm) was placed in an oven at 48.8 ° C in a petri dish for 24 hours. The appearance of the residue after 24 hours was recorded and then washed off with cold water under a tap. Performance evaluation: excellent (soft/partial fluid, quick washout, no residue); good (soft/partial fluid, slowly washed away, but no residue after washing); and acceptable (partial fluid/viscous, Slow, not completely washed off).

¹² FLC Test #: Recycling Test: This is a test to determine how the product will perform in a recirculating machining tank. A 10% dilution of the product in deionized water (2 L) was placed in a 4 liter beaker. The pump and hose are then used to recirculate the product. Every 30 minutes, a hardness of 100 ppm was added up to a total hardness of 300 ppm (in the form of calcium). The fluid is then recirculated daily (closed at night) for 3 weeks. Performance evaluation: Excellent (the emulsion remained stable throughout the test, low foam. No unstable or no insoluble soap formation); good (some emulsion instability, moderate foam and insoluble soap formation); still acceptable (moderately unstable, Increased foam and insoluble soap formation; and poor (demulsified, high foam and heavy insoluble soap formation).

¹³ Concentrate stability: 20 ml of product was placed in 3 separate vials, then different vials were inserted a) set in an oven at 48.8 °C and b) set in a 4.4 °C freezer and c) set at -18 °C In the freezer. Check the stability of the vial concentrate daily. The sample in the freezer was taken out daily and allowed to warm to room temperature, after which stability was recorded. Stability testing is usually carried out for 5 days. Any visual separation, precipitation or turbidity is considered an unstable problem. Result: The product exhibited excellent concentrate stability with very slight color darkening in the oven. The product will freeze hard but will become clear and clear without the need for agitation after returning to room temperature.

Although certain embodiments have been illustrated and described, it is understood that the invention may be modified and modified in accordance with the ordinary skill of the art without departing from the scope of the invention.

Embodiments illustratively described herein may be suitably implemented in the absence of any one or more of the elements, one or more limitations not specifically disclosed herein. Therefore, for example, the terms "including", "including", "including" and the like should be interpreted broadly and without limitation. In addition, the terms and expressions used herein have been used as descriptive terms and not as a limiting term, and are not intended to exclude any equivalents of the features and parts shown and described in the use of such terms and expressions, but should It is recognized that various modifications are possible within the scope of the claimed technology. In addition, the phrase "consisting essentially of" will be understood to include the elements of the specific description and the additional elements that do not substantially affect the basic and novel characteristics of the claimed technology. The phrase "consisting of" does not include any unspecified elements.

The invention is not limited to the specific embodiments described in the application. Many modifications and variations can be made without departing from the spirit and scope of the invention, as apparent to those skilled in the art. Functionally equivalent methods and compositions within the scope of the present invention will be apparent to those skilled in the art in light of the <RTIgt; Such modifications and variations are intended to fall within the scope of the appended claims. The invention is to be limited only by the scope of the appended claims and the scope of the equivalents. It will be understood that the invention is not limited to specific methods, reagents, compounds, compositions or biological systems, which may of course vary. It is also understood that the terminology used herein is for the purpose of describing particular embodiments, and is not intended to be limiting.

Moreover, where features or aspects of the invention are described in the Markush group, those skilled in the art will recognize that the invention is therefore also a child of any individual member or member of the Markush group. Group to describe.

Combinations of any and all possible sub-ranges and sub-ranges are also contemplated by the scope of the disclosure. It is readily recognized that any of the ranges listed fully describe the same range and such that the range can be divided into at least two equal parts, three equal parts, four equal parts, five equal parts, ten equal parts, and the like. As a non-limiting example, each of the ranges discussed herein can be readily divided into the lower third, the middle third, the upper third, and the like. As will be appreciated by those skilled in the art, all terms such as "maximum", "at least", "greater than", "less than" and the like may include the recited number and the meaning The scope of the range. Ultimately, as will be appreciated by those skilled in the art, the scope includes each individual member.

All publications, patent applications, issued patents, and other documents mentioned in this specification are herein incorporated by reference as if individually and individually The text is generally incorporated herein by reference in its entirety. In the case where the definition contained in the text portion incorporated by reference is contradictory to the definition in the present invention, it is excluded.

Other embodiments are set forth in the scope of the following claims.

Claims (21)

An additive composition comprising: a C ₈ -C ₂₄ long chain primary amine; an ethoxylated cycloalkyl tertiary amine; and an amino acid; wherein the additive composition is boron free and free of secondary amine. The additive composition of claim 1, wherein the ethoxylated cycloalkyl tertiary amine is selected from the group consisting of bis(ethanol)cyclopentylamine, di(ethanol)cyclohexylamine, di(ethanol)cycloheptylamine, and bicyclic ring. A group of amyl (ethanol) amines and/or dicyclohexyl (ethanol) amines. The additive composition of claim 1, wherein the amino acid has the formula NH ₂ CHR ² CO ₂ H, wherein R ² is H or an alkyl group. The additive composition of claim 1, wherein the amino acid is alanine, arginine, aspartic acid, aspartic acid, cysteine, glutamic acid, glutamic acid, glycine , histidine, isoleucine, leucine, lysine, methionine, phenylalanine, serine, threonine, tryptophan, tyrosine or valine. A treatment fluid comprising: petroleum-based or non-petroleum based oils; water; C ₈ -C ₂₄ long-chain primary amine; ethoxylated cycloalkyl tertiary amine; and amino acid; wherein the treatment fluid is free Boron and no secondary amines. The treatment fluid of claim 5, wherein the C ₈ -C ₂₄ long chain primary amine comprises octylamine, decylamine, decylamine, undecylamine, dodecylamine, tridecylamine, tetradecylamine, pentaamine, ten Hexamine, heptadecyl or octadecylamine. The treatment fluid of claim 5, wherein the ethoxylated cycloalkyl tertiary amine is selected from the group consisting of di(ethanol)cyclopentylamine, di(ethanol)cyclohexylamine, di(ethanol)cycloheptylamine, dicyclopentyl (Ethanol) amine or dicyclohexyl (ethanol) amine. The treatment fluid of claim 5, wherein the amino acid has the formula NH ₂ CHR ² CO ₂ H, wherein R ² is H, alkyl or aryl. The treatment fluid of claim 5, wherein the amino acid is alanine, arginine, aspartic acid, aspartic acid, cysteine, glutamic acid, glutamic acid, glycine, Histamine, isoleucine, leucine, lysine, methionine, phenylalanine, serine, threonine, tryptophan, tyrosine or valine. The treatment fluid of claim 5, which further comprises an alkanolamine comprising methanolamine, ethanolamine, propanolamine, trimethylolamine, triethanolamine, tripropanolamine, methyldimethanolamine, ethyldi Methanolamine, propyldimethanolamine, cyclohexyldimethanolamine, methyldiethanolamine, ethyldiethanolamine or propyldiethanolamine. The treatment fluid of claim 5, which further comprises a polymeric fatty acid which is a polymeric ricinoleic acid derived from castor oil or a polymeric fatty acid derived from soybean oil or linseed oil. The treatment fluid of claim 5, which comprises the petroleum-based oil. The treatment fluid of claim 5, which comprises the non-petroleum based oil. The treatment fluid of claim 5, which further comprises a phosphate ester and/or an ethoxylated fatty amine. The treatment fluid of claim 5, wherein from about 1% to about 50% by weight of the water is present. The treatment fluid of claim 5, which further comprises a hydrocarbyl butylimine. The treatment fluid of claim 5, which further comprises a sulfur-containing compound. The treatment fluid of claim 5, comprising a sulfur-containing compound and a phosphate, wherein the weight ratio of the phosphate to the sulfur in the sulfur-containing compound is from about 25:1 to about 1:1. The treatment fluid of claim 5, which further comprises an aliphatic carboxylic acid or an aliphatic dicarboxylic acid. The treatment fluid of claim 5, further comprising an additive comprising an antifoaming agent, a corrosion inhibitor or an olfactory agent. The treatment fluid of claim 5 which has a pH of at least 9.