Composition for cleaning metals

Abstract

A method for cleaning a metal surface, the method comprising applying to the metal surface a composition comprising at least the following component a) and component b) wherein component a is at least one ether amine selected from Formula 1A described herein, and / or at least one ether amine selected from Formula 1B described herein; and component b is at least one chelate. A composition comprising components a) and b) as described above.

Description

Background Art

[0001] Alkaline cleaning solutions are commonly used as metal cleaners to remove different types of dirt. These cleaners are usually composed of alkali, wetting agents, solvents and sequestering (chelating) agents. Such cleaners should be able to effectively clean metal surfaces. Low foaming is another key criterion for cleaners, because excessive foam causes rinsing problems and / or overflow, which can cause overflow and product waste. Rapid recovery of the bath is another desired characteristic of metal cleaners. The active substances present in the cleaner need to be effectively separated from the removed oil, otherwise, the cleaning ability of the recirculating bath is significantly reduced.

[0002] Inorganic bases (such as NaOH, KOH) and organic bases (such as monoethanolamine) are widely used ingredients in metal cleaning solutions. However, such chemicals only provide alkalinity and generally do not provide low foaming or fast separation from oil. There is a need for metal cleaning compositions that provide low foaming and fast oil separation in addition to excellent cleaning performance.

[0003] International publication WO2020 / 068481 discloses compositions containing alkyl ether amines for use as foam control compounds in food processing. The alkyl ether amines are used at various stages during the industrial processing of vegetables, fruits and plants such as potatoes and beets. See Abstract. Foam control compounds are described, for example, on pages 4-7.

[0004] International publication WO2017 / 011216 discloses glycol ether solvents in liquid cleaning compositions for removing hydrophobic stains from hard surfaces and also for the foaming characteristics of the composition (see abstract). The liquid cleaning composition also comprises a surfactant, and the composition has a pH of less than 10 (see claim 1). The composition may also contain a chelate (see pages 13-14).

[0005] U.S. Publication 2018 / 0127688 discloses a cleaning composition containing an ester solvent (preferably a fatty acid methyl ester) in combination with one or more linear alkylamines. Alkylamines are disclosed as being used to remove and suspend organic oils that have been burned or heated to adhere to surfaces, and these amines can be used alone as dirt removers. The disclosed cleaning composition is used to clean distillation towers associated with biofuel and vegetable oil refining, as well as for cleaning ovens, food cooking surfaces, and dry cleaning. See Abstract. The composition may contain a chelating agent (see, e.g., paragraph

[0043] ).

[0006] U.S. Publication No. 2018 / 0291309 discloses cleaning compositions and methods for cleaning post-chemical mechanical polishing (CMP) residues and contaminants from microelectronic devices (see Abstract). The composition contains at least one organic amine, water, at least one pH adjuster, at least one organic additive, and at least one metal corrosion inhibitor (see Claim 1). For example, some organic amines are disclosed in paragraph

[0040] .

[0007] International publication WO93 / 16162 discloses an aqueous, hard surface cleaner comprising the following: (a) an effective amount of a solvent selected from C1-C6 alkanols, C3-C24 alkylene glycol ethers and mixtures thereof; (b) an effective amount of a surfactant selected from amphoteric, nonionic and anionic surfactants and mixtures thereof; and (c) an effective amount of a buffer system comprising a nitrogen-containing buffer selected from ammonium carbamate or alkaline earth metal carbamate, guanidine derivatives, alkoxyalkylamines and alkyleneamines; and (d) the remainder is essentially water (see abstract). Some nitrogen-containing buffers are described on pages 10-11.

[0008] International Publication WO2015 / 143034 discloses an in-situ fractional steam extraction process for removing petroleum products from a heavy oil or bitumen reservoir at a subterranean location. The steam composition may consist essentially of steam or may include one or more oil recovery enhancing agents. See Abstract. Glycol ether amines may be used as oil recovery enhancing agents (see, e.g., page 6, line 23 to page 7, line 6).

[0009] U.S. Patent No. 9,574,126 discloses a water-based drilling fluid composition comprising a shale hydration inhibitor of the formula H2N-CH(R)-R1-O-R2, wherein R is hydrogen or an alkyl group having 1 to 12 carbons, R1 is an alkylene group having 1 to 12 carbons, and R2 is an alkyl group having 1 to 12 carbons (see abstract). The shale hydration inhibitor is present in the water-based drilling fluid in a sufficient concentration to reduce swelling of clay and shale when exposed to the water-based drilling fluid (see abstract).

[0010] However, as stated above, there remains a need for metal cleaning compositions that provide low foaming and rapid oil separation in addition to excellent cleaning performance. This need has been met by the following invention. Summary of the invention

[0011] In a first aspect, a method for cleaning a metal surface comprises applying to the metal surface a composition comprising at least the following components a) and b):

[0012] a) at least one etheramine selected from formula 1A and / or at least one etheramine selected from formula 1B:

[0013] wherein R1 is a monovalent carbon-containing group containing 1 to 10 carbon atoms; R2 is hydrogen, methyl or ethyl; R3 is hydrogen, methyl or ethyl; and x is 1 to 5; and when x ≥ 2, the R2 groups of the -(CH2-CHR2-O)- portion can all be the same, or some or all are different, and if some or all are different, then the -(CH2-CHR2-O)- x - the moiety can contain any combination of hydrogen and / or methyl and / or ethyl as at least two different R2 groups;

[0014] wherein R4 is a monovalent carbon-containing group containing 1 to 10 carbon atoms; and R5 is hydrogen, methyl or ethyl;

[0015] b) at least one chelate.

[0016] In a second aspect, a composition comprising at least the following components a) and b):

[0017] a) at least one etheramine selected from formula 1A and / or at least one etheramine selected from formula 1B:

[0018] wherein R1 is a monovalent carbon-containing group containing 1 to 10 carbon atoms; R2 is hydrogen, methyl or ethyl; R3 is hydrogen, methyl or ethyl; and x is 1 to 5; and when x ≥ 2, the R2 groups of the -(CH2-CHR2-O)- portion can all be the same, or some or all are different, and if some or all are different, then the -(CH2-CHR2-O)- x - the moiety can contain any combination of hydrogen and / or methyl and / or ethyl as at least two different R2 groups;

[0019] wherein R4 is a monovalent carbon-containing group containing 1 to 10 carbon atoms; and R5 is hydrogen, methyl or ethyl;

[0020] b) at least one chelate. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] Figure 1 is a bar graph showing the percent oil removal for the indicated compositions of the present invention and comparative compositions.

[0022] Figure 2 is a bar graph showing the percent oil removal for the indicated compositions.

[0023] Figure 3 A cyclic foam tester is depicted.

[0024] Figure 4A and Figure 4BThe "Foam Height vs. Time" curves are each plotted for the indicated inventive composition and a comparative composition.

[0025] Figure 5 is a bar graph showing the time it took for each indicated composition to separate from the oil and fill a 5 ml or 10 ml volume. DETAILED DESCRIPTION

[0026] Cleaning compositions have been found which provide excellent oil removal performance, good foam control and rapid oil separation.

[0027] As described above, in a first aspect, a method for cleaning a metal surface is provided, the method comprising applying to the metal surface a composition comprising at least the following components a) and b), each of which is as described herein. In a second aspect, a composition is provided, the composition comprising at least the following components a) and b), each of which is as described herein.

[0028] The above method may include a combination of two or more embodiments as described herein. The above composition may include a combination of two or more embodiments as described herein. Component a may include a combination of two or more embodiments as described herein. Component b may include a combination of two or more embodiments as described herein.

[0029] As used herein, with respect to Formula 1A or Formula 1B of component a, R1 = R1, R2 = R2, R3 = R3, R4 = R4 and R5 = R5. Unless otherwise indicated, the following embodiments apply to both the first and second aspects of the present invention.

[0030] In one embodiment or a combination of two or more embodiments described herein, the weight ratio of component a to component b is ≥0.40, or ≥0.50, or ≥0.60, or ≥0.70, or ≥0.80, or ≥0.90, or ≥1.0. In one embodiment or a combination of two or more embodiments described herein, the weight ratio of component a to component b is ≤200, or ≤150, or ≤100, or ≤50, or ≤20, or ≤10, or ≤8.0, or ≤7.0, or ≤6.0, or ≤5.0, or ≤4.0.

[0031] In one embodiment or a combination of two or more embodiments individually described herein, component b is a metal chelate.

[0032] In one embodiment or a combination of two or more embodiments each described herein, for Formula 1A, R1 is an alkyl group, further a C1-C5 alkyl group, further a C1-C4 alkyl group, further a C1-C3 alkyl group; and R2 is hydrogen or methyl and further a methyl; and R3 is hydrogen or methyl; and for Formula 1B, R4 is an alkyl group, further a C1-C5 alkyl group, further a C1-C4 alkyl group, further a C1-C3 alkyl group; and R5 is hydrogen or methyl.

[0033] In one embodiment or a combination of two or more embodiments individually described herein, component a is selected from the following structures (1a) to (1j):

[0034] In one embodiment or a combination of two or more embodiments each described herein, component a is selected from the following structures: (1a), (1b), (1c), (1d), (1e) or (1f), each as shown above.

[0035] In one embodiment or a combination of two or more embodiments individually described herein, component a is at least one etheramine selected from Formula 1A, and further is one etheramine selected from Formula 1A.

[0036] In one embodiment or a combination of two or more embodiments individually described herein, component a is at least one etheramine selected from Formula 1B, and further is one etheramine selected from Formula 1B.

[0037] In one embodiment or a combination of two or more embodiments individually described herein, the metal of the metal surface is selected from steel, stainless steel, brass, chromium, iron, aluminum, copper or gold.

[0038] In one embodiment or a combination of two or more embodiments individually described herein, the composition further comprises water.

[0039] In one embodiment or a combination of two or more embodiments described herein, the composition further comprises at least one surfactant as component c. In one embodiment or a combination of two or more embodiments described herein, component c is selected from at least one nonionic surfactant or at least one anionic surfactant or at least one cationic surfactant or at least one amphoteric surfactant, and further selected from at least one nonionic surfactant or at least one anionic surfactant, and further selected from at least one nonionic surfactant.

[0040] In one embodiment or a combination of two or more embodiments individually described herein, the composition further comprises at least one basic salt as component d.

[0041] In one embodiment or a combination of two or more embodiments described herein, the sum of component a and component b and water is present in an amount of ≥80 wt %, or ≥85 wt %, or ≥90 wt %, or ≥92 wt %, or ≥94 wt %, or ≥96 wt %, or ≥97 wt % or ≥98 wt %, based on the weight of the composition. In one embodiment or a combination of two or more embodiments described herein, the sum of component a and component b and water is present in an amount of ≤100 wt % or ≤99 wt %, based on the weight of the composition.

[0042] Component a-ether amine

[0043] Component a is described by Formula 1A or Formula 1B, each as shown above. For Formula 1A or Formula 1B, R1 or R4 each independently includes, but is not limited to, linear, branched, and cyclic alkyl groups such as methyl; ethyl; propyl, isopropyl; butyl; isobutyl; sec-butyl; tert-butyl; pentyl, hexyl; 1-methylbutyl; 2-methylbutyl; 3-methylbutyl; 1,1-dimethylpropyl; 1,2-dimethylpropyl; 2,2-dimethylpropyl; 1-ethyl-propyl; 1-methylpentyl; 2-methylpentyl; 3-methylpentyl; 4-methyl 1,2-dimethylbutyl; 1,3-dimethylbutyl; 2,2-dimethylbutyl; 2,3-dimethylbutyl; 3,3-dimethylbutyl; 1-ethylbutyl; 2-ethylbutyl; 1-ethyl-1-methylpropyl; 1,1,2-trimethylpropyl; 1,2,2-trimethylpropyl; heptyl; octyl; nonyl; decyl; cyclopentyl; methylcyclopentyl; cyclohexyl; methylcyclohexyl; ethylcyclohexyl; and propylcyclohexyl.

[0044] In one embodiment or a combination of two or more embodiments each described herein, for Formula 1A, R2 is methyl, R3 is methyl, and x = 1 or 2. In one embodiment or a combination of two or more embodiments each described herein, for Formula 1B, R5 is methyl.

[0045] In one embodiment or a combination of two or more embodiments individually described herein, component a is selected from any one of the following groups (a) to (g):

[0046] (a) 2-methoxyethylamine, 2-ethoxyethylamine, 2-propoxyethylamine, 2-butoxyethylamine, 2-pentyloxyethylamine, 2-hexyloxyethylamine, 2-heptyloxyethylamine and 2-octyloxyethylamine;

[0047] (b) 1-methoxypropan-2-amine, 1-ethoxypropan-2-amine, 1-propoxypropan-2-amine, 1-butoxypropan-2-amine, 1-pentyloxypropan-2-amine, 1-hexyloxypropan-2-amine, 1-heptyloxypropan-2-amine and 1-octyloxypropan-2-amine;

[0048] (c) 2-(2-methoxyethoxy)-1-aminoethane, 2-(2-ethoxyethoxy)-1-aminoethane, 2-(2-propoxyethoxy)-1-aminoethane, 2-(2-butoxyethoxy)-1-aminoethane, 2-(2-pentyloxyethoxy)-1-aminoethane and 2-(2-hexyloxyethoxy)-1-aminoethane;

[0049] (d) 1-(1-methoxyethoxy)-propan-2-amine, 1-(1-ethoxyethoxy)-propan-2-amine, 1-(1-propoxyethoxy)-propan-2-amine, 1-(1-butoxyethoxy)-propan-2-amine, 1-(1-pentyloxyethoxy)-propan-2-amine and 1-(1-hexyloxyethoxy)-propan-2-amine;

[0050] (e) 1-((1-methoxyprop-2-yl)oxy)-propan-2-amine, 1-((1-ethoxyprop-2-yl)oxy)-propan-2-amine, 1-((1-propoxyprop-2-yl)oxy)-propan-2-amine, 1-((1-butoxyprop-2-yl)oxy)-propan-2-amine, 1-((1-pentyloxyprop-2-yl)oxy)-propan-2-amine and 1-((1-hexyloxyprop-2-yl)oxy)-propan-2-amine;

[0051] (f) 2-[2-(2-methoxy-ethoxy)-ethoxy]-ethylamine, 2-[2-(2-ethoxy-ethoxy)-ethoxy]-ethylamine, 2-[2-(2-propoxy-ethoxy)-ethoxy]-ethylamine, 2-[2-(2-butoxy-ethoxy)-ethoxy]-ethylamine, 2-[2-(2-pentyloxy-ethoxy)-ethoxy]-ethylamine, 2-[2-(2-hexyloxy-ethoxy)-ethoxy]-ethylamine; and

[0052] (g) 1-(((1-methoxy(propan-2-yl)oxy)-propan-2-yl)oxy)-propan-2-amine, 1-(((1-ethoxy(propan-2-yl)oxy)-propan-2-yl)oxy)-propan-2-amine, 1-(((1-propoxy(propan-2-yl)oxy)-propan-2-yl)oxy)-propan-2-amine, 1-(((1-butoxy(propan-2-yl)oxy)-propan-2-yl)oxy)-propan-2-amine, 1-(((1-pentyloxy(propan-2-yl)oxy)-propan-2-yl)oxy)-propan-2-amine and 1-(((1-hexyloxy(propan-2-yl)oxy)-propan-2-yl)oxy)-propan-2-amine.

[0053] In one embodiment or a combination of two or more embodiments individually described herein, component a has a boiling point of 80 to 290°C, further 85 to 285°C, further 90 to 280°C.

[0054] The synthesis of etheramines is known in the art, and various etheramines are also commercially available. For example, l-methoxypropane-2-amine is available from Sigma-Aldrich. One synthesis involves reductive amination of ethylene glycol ethers with ammonia using a NiCoCuReB catalyst as described in U.S. Pat. No. 9,574,126. Glycol ether starting materials can be obtained from The Dow Chemical Company, such as those available under the DOWANOL, CELLOSOLVE and CARBITOL trade names, such as propylene glycol n-butyl ether (DOWANOL PnB glycol ether), dipropylene glycol methyl ether (DOWANOL DPM glycol ether), dipropylene glycol n-propyl ether (DOWANOL DPnP glycol ether), propylene glycol n-propyl ether (DOWANOL PnP glycol ether), dipropylene glycol n-butyl ether (DOWANOL DPnB glycol ether), ethylene glycol monohexyl ether (hexyl CELLOSOLVE solvent), ethylene glycol mono-n-propyl ether (propyl CELLOSOLVE solvent), diethylene glycol monohexyl ether, ethylene glycol mono-n-propyl ether (propyl CELLOSOLVE solvent), diethylene glycol monohexyl ether (hexyl CARBITOL solvent, diethylene glycol monobutyl ether (butyl CARBITOL solvent), and triethylene glycol monobutyl ether.

[0055] Component a may be in the form of a liquid composition that is added to the aqueous composition. The etheramine itself may be in liquid form at room temperature (23° C.), so a “stock solution” composition may be one in which the etheramine is in pure form (100% by weight). Stock solutions may also be prepared with the etheramine in one or more compatible solvents, for example, where the etheramine is present in an amount ranging from about 30% by weight to about 99% by weight. The etheramine may be in the form of a solid composition, such as a powder or granules that may be added to the aqueous composition.

[0056] Component b - Chelate

[0057] Chelates are known in the art. Chelates typically contain at least two ligands bonded to a central metal atom. Chelates include, but are not limited to, salts of ethylenediaminetetraacetic acid and derivatives thereof; aminocarboxylate chelators such as glutamic acid-N,N-diacetate; phosphonate chelators such as ethylenediaminetetramethylenephosphonate and diethylenetriaminepentamethylenephosphonate. These chelates may be present in their acid form or as salts. Biodegradable chelators include, but are not limited to, ethylenediamine N,N'-disuccinic acid, or an alkali metal salt or alkaline earth metal salt, an ammonium salt or a substituted ammonium salt thereof, or a mixture thereof; and L-glutamic acid N,N-diacetic acid (GLDA) commercially available from Akzo Nobel under the trade name DISSOLVINE 47S.

[0058] Suitable aminocarboxylates include ethylenediaminetetraacetate, diethylenetriaminepentaacetate, diethylenetriaminepentaacetate (DTPA), N-hydroxyethylethylenediaminetriacetate, nitrilotriacetate, ethylenediaminetetrapropionate, triethylenetetraamine-hexaacetate, ethanol diglycine and methylglycine diacetic acid (MGDA), all in their acid form or in the form of their alkali metal, ammonium and substituted ammonium salts. Particularly suitable aminocarboxylates include, but are not limited to, salts of ethylenediaminetetraacetic acid (EDTA); EDTA; propylenediaminetetraacetic acid (PDTA), commercially available, for example, from BASF under the trade name TRILON FS; methylglycine diacetic acid (MGDA); and diethylenetriaminepentaacetate (DTPA) from BASF. Additional carboxylate chelating agents include salicylic acid, aspartic acid, glutamic acid, glycine, malonic acid or mixtures thereof.

[0059] In one embodiment or a combination of two or more embodiments individually described herein, component b is ethylenediaminetetraacetic acid or a salt thereof, such as EDTA-4Na·H2O.

[0060] Component c - Surfactant

[0061] Surfactants include, but are not limited to, anionic compounds, cationic compounds, amphoteric compounds, and nonionic compounds. Combinations of two or more of these surfactants may be used; for example, a cationic surfactant may be used together with a nonionic surfactant, or an anionic surfactant may be used together with a nonionic surfactant.

[0062] Cationic surfactants include, but are not limited to, salts of long-chain primary, secondary or tertiary amines, such as oleamide acetate, cetylamine acetate, stearylamine acetate, didodecylamine lactate, aminoethyl-aminoethyl stearamide acetate, dilauroyl triethylenetetramine diacetate, 1-aminoethyl-2-heptadecenyl imidazoline acetate; and quaternary ammonium salts, such as cetyl pyridinium bromide, hexadecyl ethyl morpholinium chloride and diethyl didodecyl ammonium chloride. Examples of cationic surfactants include alkyl trimethyl ammonium salts.

[0063] Anionic surfactants include, but are not limited to, alkali metal salts of alkyl-aryl sulfonic acids; sodium dialkyl sulfosuccinates, sulfated oils or sulfonated oils, such as sulfated castor oil; sulfonated tallow, and alkali metal salts of short-chain petroleum sulfonic acids; ammonium soaps and amine soaps; the fatty acid portion of such soaps preferably contains at least 16 carbon atoms. These soaps can also be formed "in situ"; in other words, fatty acids can be added to the oil phase, and alkaline substances can be added to the aqueous phase. Anionic surfactants also include, but are not limited to, alkyl sulfates, alkyl ether sulfates, sulfated alkanolamides, alpha olefin sulfonates, lignin sulfonates, sulfosuccinates, fatty acid salts, and phosphates. For example, anionic surfactants are DOWFAXC10L commercially available from Dow Chemical Company.

[0064] Examples of nonionic surfactants include, but are not limited to, alkoxylated alcohols, alkoxylated alkylphenols, fatty acid esters, amine and amide derivatives, alkyl polyglucosides, ethylene oxide / propylene oxide copolymers, polyols and alkoxylated polyols. For example, the nonionic surfactant is TERGITOL L-62 commercially available from The Dow Chemical Company. In general, nonionic surfactants include, but are not limited to, the following: a) condensation products of higher fatty alcohols and ethylene oxide; b) condensation products of alkylphenols and ethylene oxide; c) condensation products of higher fatty acid amides and five or more ethylene oxide units; d) polyethylene glycol esters of long-chain fatty acids, such as tetraethylene glycol monopalmitate, hexaethylene glycol monolaurate, nonaethylene glycol monostearate, nonaethylene glycol dioleate, tridecaethylene glycol monoarachidate, tricosyl glycol monoarachidate, tricosyl glycol monodibehenate; e) polyol partial higher fatty acid esters, such as sorbitan tristearate; f) ethylene oxide condensation products of polyol partial higher fatty acid esters, and their internal anhydrides; g) long-chain polyethylene glycols in which one hydroxyl group is esterified with a higher fatty acid and the other hydroxyl group is etherified with a low molecular weight alcohol, such as methoxypolyethylene glycol 550 monostearate (550 represents the average molecular weight of the polyethylene glycol ether).

[0065] Amphoteric surfactants include, but are not limited to, alkyl amidopropylamine N-oxides, alkyl dimethylamine N-oxides, alkyl betaines, alkyl amidopropyl betaines, cocoamidopropyl betaine, cocoamphoacetate and cocoamphodiacetate.

[0066] In one embodiment or a combination of two or more embodiments individually described herein, component c is an alcohol alkoxylate, such as an ethoxylated propoxylated alkanol, and further an ethoxylated propoxylated 2-ethyl-1-hexanol.

[0067] Component d - basic salt

[0068] Basic salts are the product of a strong base and a weak acid, and they can form a basic solution when dissolved in water. Basic salts include, but are not limited to, sodium carbonate, sodium acetate, sodium hydroxide, sodium bicarbonate, sodium chloride, and sodium sulfide.

[0069] In one embodiment or a combination of two or more embodiments individually described herein, component d is selected from metal bicarbonates, metal carbonates, metal chlorides, metal chlorates, metal nitrates, metal phosphates, metal sulfates, metal sulfides, or mixtures thereof.

[0070] Other additives

[0071] The compositions of the present invention may optionally include one or more additional additives. Examples of additives include, but are not limited to, block or random copolymers of ethylene oxide / propylene oxide, butylene oxide / propylene oxide, ethylene oxide / butylene oxide; waxes; silicone-based materials; foam control compounds such as those obtained by

[0072] Agents derived from the alkoxylation of alcohols, alkyl polyglucosides, ketal suds control agents and cellulose derivative suds control agents.

[0073] definition

[0074] Unless stated to the contrary, implicit from the context, or customary in the art, parts and percentages are based on weight and all test methods are current as of the filing date of this disclosure.

[0075] As used herein, the term "composition" includes mixtures of materials including the composition as well as reaction products and decomposition products formed from the composition materials. Any reaction products or decomposition products are typically present in trace or residual amounts.

[0076] The term "polymer" as used herein refers to a polymer compound prepared by polymerizing monomers of the same or different types. Thus, the generic term polymer includes the term homopolymer (used to refer to polymers prepared from only one type of monomer, it being understood that trace impurities may be incorporated into the polymer structure) and the term interpolymer as defined below. Trace impurities (such as catalyst residues) may be incorporated into and / or within the polymer. Typically, the polymer is stabilized with very low amounts ("ppm" amounts) of one or more stabilizers.

[0077] The term "interpolymer" as used herein refers to polymers prepared by the polymerization of at least two different types of monomers. The term interpolymer thus includes the term copolymer (used to refer to polymers prepared from two different types of monomers) and polymers prepared from more than two different types of monomers.

[0078] The phrase "applying to a metal surface" with respect to methods of cleaning metal surfaces with the compositions described herein refers to the act of contacting the metal surface with the composition. Such contact can be performed by wetting the metal surface with the composition using a spray, a brush, a roller, or by dipping the metal into the composition, or by any other means known in the art.

[0079] As used herein with respect to R1 of Formula 1A and R4 of Formula 1B, the phrase "a monovalent carbon-containing group comprising 1 to 10 carbon atoms" refers to a chemical group comprising 1 to 10 carbon atoms and which is bonded to the remainder of Formula 1A (for R1) or the remainder of Formula 1B (for R4) via a single bond (i.e., R1- or R4-). Such a chemical group can be, for example, a straight-chain aliphatic group, a branched-chain aliphatic group, a cyclic aliphatic group, an aromatic group (e.g. ), a combination of straight-chain aliphatic and cyclic aliphatic groups, a combination of branched aliphatic and cyclic aliphatic groups, a combination of straight-chain aliphatic and aromatic groups, a combination of branched aliphatic and aromatic groups, or other combinations known in the art. In addition, with respect to the number of carbon atoms in R1 of Formula 1A or in R4 of Formula 1B, for example, the notation "C1-C10" (wherein "1 to 10" represents a consecutive number from 1 to 10) refers to the numerical range of carbon atoms that may be present in each R group.

[0080] The terms "comprising," "including," "having," and derivatives thereof are not intended to exclude the presence of any additional components, steps, or procedures, whether or not the components, steps, or procedures are specifically disclosed. For the avoidance of any doubt, all compositions claimed through use of the term "comprising" may include any additional additives, adjuvants, or compounds, whether polymeric or otherwise, unless stated to the contrary. In contrast, the term "consisting essentially of excludes from the scope of any subsequently recited component, step, or procedure, except those that are not essential to operability. The term "consisting of excludes any component, step, or procedure not specifically recited or listed.

[0081] List of some method and composition features

[0082] A] A method for cleaning a metal surface, the method comprising applying to the metal surface a composition comprising at least the following components a) and b):

[0083] a) at least one etheramine selected from formula 1A and / or at least one etheramine selected from formula 1B:

[0084] wherein R1 is a monovalent carbon-containing group containing 1 to 10 carbon atoms; R2 is hydrogen, methyl or ethyl; R3 is hydrogen, methyl or ethyl; and x is 1 to 5; and when x ≥ 2, the R2 groups of the -(CH2-CHR2-O)- portion can all be the same, or some or all are different, and if some or all are different, then the -(CH2-CHR2-O)- x - the moiety can contain any combination of hydrogen and / or methyl and / or ethyl as at least two different R2 groups;

[0085] wherein R4 is a monovalent carbon-containing group containing 1 to 10 carbon atoms; and R5 is hydrogen, methyl or ethyl;

[0086] b) at least one chelate.

[0087] B] The method according to A] above, wherein the weight ratio of component a to component b is ≥0.40, or ≥0.50, or ≥0.60, or ≥0.70, or ≥0.80, or ≥0.90, or ≥1.0.

[0088] C] The method according to A] or B] above, wherein the weight ratio of component a to component b is ≤200, or ≤150, or ≤100, or ≤50, or ≤20, or ≤10, or ≤8.0, or ≤7.0, or ≤6.0, or ≤5.0, or ≤4.0.

[0089] D] The method according to any one of A]-C] (A] to C]) above, wherein for Formula 1A, when x ≥ 2, the R2 groups of the -(CH2-CHR2-O)- moiety are all the same.

[0090] E] A method according to any one of A] to C] above, wherein for Formula 1A, when x ≥ 2, some or all of the R2 groups of the -(CH2-CHR2-O)- moiety are different, and -(CH2-CHR2-O) x The - moiety may contain any combination of hydrogen and / or methyl and / or ethyl as at least two different R2 groups.

[0091] F] A method according to any one of A] to E] above, wherein component b is a metal chelate.

[0092] G] A method according to any one of A] to F] above, wherein component b comprises a metal salt of ethylenediaminetetraacetic acid.

[0093] H] The method according to any one of A]-G] above, wherein for Formula 1A, R1 is an alkyl group, further a C1-C5 alkyl group, further a C1-C4 alkyl group, further a C1-C3 alkyl group; and R2 is hydrogen or methyl and further a methyl; and R3 is hydrogen or methyl; and

[0094] For Formula 1B, R4 is an alkyl group, further a C1-C5 alkyl group, further a C1-C4 alkyl group, further a C1-C3 alkyl group; and R5 is hydrogen or methyl.

[0095] I] The method according to any one of A] to H] above, wherein for Formula 1A, x=1 or 2.

[0096] J] A method according to any one of A] to I] above, wherein for Formula 1A, x=1 or 2, and if x=2, R2 of each -(CH2-CHR2-O)- moiety is the same.

[0097] K] A method according to any one of A] to J] above, wherein component a is selected from the following structures (1a) to (1j):

[0098]

[0099] L] The method according to any one of A] to K] above, wherein component a is selected from the following structures: (1a), (1b), (1c), (1d), (1e) or (1f), each as shown above.

[0100] M] A method according to any one of A] to L] above, wherein component a is at least one etheramine selected from Formula 1A or at least one etheramine selected from Formula 1B.

[0101] N] A method according to any one of A] to L] above, wherein component a is at least one etheramine selected from Formula 1A and at least one etheramine selected from Formula 1B.

[0102] O] The method according to any one of A] to M] above, wherein component a is at least one etheramine selected from Formula 1A, and further is one etheramine selected from Formula 1A.

[0103] P] The method according to any one of A] to M] above, wherein component a is at least one etheramine selected from Formula 1B, and further is one etheramine selected from Formula 1B.

[0104] Q] The method according to any one of A] to P] above, wherein the metal of the metal surface is selected from steel, stainless steel, brass, chromium, iron, aluminum, copper or gold.

[0105] R] A method according to any one of A] to Q] above, wherein the temperature of the composition when applied to the metal surface is from 20°C to 30°C.

[0106] A2] A composition comprising at least the following components a) and b):

[0107] a) at least one etheramine selected from formula 1A and / or at least one etheramine selected from formula 1B:

[0108] wherein R1 is a monovalent carbon-containing group containing 1 to 10 carbon atoms; R2 is hydrogen, methyl or ethyl; R3 is hydrogen, methyl or ethyl; and x is 1 to 5; and when x ≥ 2, the R2 groups of the -(CH2-CHR2-O)- portion can all be the same, or some or all are different, and if some or all are different, then the -(CH2-CHR2-O)- x - the moiety can contain any combination of hydrogen and / or methyl and / or ethyl as at least two different R2 groups;

[0109] wherein R4 is a monovalent carbon-containing group containing 1 to 10 carbon atoms; and R5 is hydrogen, methyl or ethyl;

[0110] b) at least one chelate.

[0111] B2] The composition according to A2] above, wherein the weight ratio of component a to component b is ≥0.40, or ≥0.50, or ≥0.60, or ≥0.70, or ≥0.80, or ≥0.90, or ≥1.0.

[0112] C2] A composition according to A2] or B2] above, wherein the weight ratio of component a to component b is ≤200, or ≤150, or ≤100, or ≤50, or ≤20, or ≤10, or ≤8.0, or ≤7.0, or ≤6.0, or ≤5.0, or ≤4.0.

[0113] D2] A composition according to any one of A2] to C2] above, wherein for Formula 1A, when x ≥ 2, all R2 groups of the -(CH2-CHR2-O)- moiety are the same.

[0114] E2] A composition according to any one of A2] to C2] above, wherein for Formula 1A, when x ≥ 2, some or all of the R2 groups of the -(CH2-CHR2-O)- moiety are different, and -(CH2-CHR2-O) x The - moiety may contain any combination of hydrogen and / or methyl and / or ethyl as at least two different R2 groups.

[0115] F2] A composition according to any one of A2] to E2] above, wherein component b is a metal chelate.

[0116] G2] A composition according to any one of A2] to F2] above, wherein component b comprises a metal salt of ethylenediaminetetraacetic acid.

[0117] H2] A composition according to any one of A2]-G2] above, wherein for Formula 1A, R1 is an alkyl group, further a C1-C5 alkyl group, further a C1-C4 alkyl group, further a C1-C3 alkyl group; and R2 is hydrogen or methyl and further a methyl; and R3 is hydrogen or methyl; and for

[0118] In Formula 1B, R4 is an alkyl group, further a C1-C5 alkyl group, further a C1-C4 alkyl group, further a C1-C3 alkyl group; and R5 is hydrogen or methyl.

[0119] I2] A composition according to any one of A2] to H2] above, wherein for Formula 1A, x=1 or 2.

[0120] J2] A composition according to any one of A2] to I2] above, wherein for Formula 1A, x=1 or 2, and if x=2, then R2 of each -(CH2-CHR2-O)- moiety is the same.

[0121] K2] A composition according to any one of A2] to J2] above, wherein component a is selected from the following structures (1a) to (1j), each as shown above.

[0122] L2] A composition according to any one of A2] to K2] above, wherein component a is selected from the following structures: (1a), (1b), (1c), (1d), (1e) or (1f), each as shown above.

[0123] M2] A composition according to any one of A2] to L2] above, wherein component a is at least one etheramine selected from Formula 1A or at least one etheramine selected from Formula 1B.

[0124] N2] A composition according to any one of A2] to L2] above, wherein component a is at least one etheramine selected from Formula 1A and at least one etheramine selected from Formula 1B.

[0125] O2] A composition according to any one of A2] to M2] above, wherein component a is at least one etheramine selected from Formula 1A, and further is one etheramine selected from Formula 1A.

[0126] P2] A composition according to any one of A2] to M2] above, wherein component a is at least one etheramine selected from Formula 1B, and further is one etheramine selected from Formula 1B.

[0127] Q2] A composition according to any one of A2] to P2] above, wherein the composition is used for cleaning metal surfaces.

[0128] R2] The composition according to Q2] above, wherein the metal of the metal surface is selected from steel, stainless steel, brass, chromium, iron, aluminum, copper or gold.

[0129] A3] A method according to any one of A] to R] above, or a composition according to any one of A2] to R2] above, wherein the composition further comprises water.

[0130] B3] A method according to any one of A] to R] or A3] above or a composition according to any one of A2] to R2] or A3] above, wherein the composition further comprises at least one surfactant as component c.

[0131] C3] The method according to B3] above, or the composition according to B3] above, wherein the component c is present in an amount of ≥0.01 wt.%, or ≥0.02 wt.%, or ≥0.04 wt.%, or ≥0.06 wt.%, or ≥0.08 wt.%, based on the weight of the composition.

[0132] D3] The method according to B3] or C3] above or the composition according to B3] or C3] above, wherein the component c is present in an amount of ≤5.0 wt%, or ≤4.0 wt%, or ≤3.0 wt%, or ≤2.0 wt%, or ≤1.0 wt%, or ≤0.8 wt%, or ≤0.6 wt%, or ≤0.4 wt%, or ≤0.2 wt%, or ≤0.1 wt%, based on the weight of the composition.

[0133] E3] A method according to any one of B3] to D3] above, or a composition according to any one of B3] to D3] above, wherein the component c is selected from at least one nonionic surfactant or at least one anionic surfactant or at least one cationic surfactant or at least one amphoteric surfactant, and is further selected from at least one nonionic surfactant or at least one anionic surfactant, and is further selected from at least one nonionic surfactant.

[0134] F3] A method according to any one of A]-R] or A3]-E3] above or a composition according to any one of A2]-R2] or A3]-E3] above, wherein the composition further comprises at least one basic salt as component d.

[0135] G3] The method according to F3] above, or the composition according to F3] above, wherein the component d is present in an amount of ≥0.05 wt%, or ≥0.10 wt%, or ≥0.20 wt%, or ≥0.30 wt%, or ≥0.40 wt%, or ≥0.50 wt%, based on the weight of the composition.

[0136] H3] The method according to F3] or G3] above or the composition according to F3] or G3] above, wherein the component d is present in an amount of ≤20 wt%, or ≤10 wt%, or ≤5.0 wt%, or ≤4.0 wt%, or ≤3.0 wt%, or ≤2.0 wt%, or ≤1.0 wt%, based on the weight of the composition.

[0137] I3] A method according to any one of A]-R] or A3]-H3] above, or a composition according to any one of A2]-R2] or A3]-H3] above, wherein each etheramine of component a independently has a molecular weight of ≥60, or ≥65, or ≥70, or ≥75, or ≥80, or ≥85 g / mol.

[0138] J3] A method according to any one of A]-R] or A3]-I3] above, or a composition according to any one of A2]-R2] or A3]-I3] above, wherein each etheramine of component a independently has a molecular weight of ≤500, or ≤450, or ≤400, or ≤350, or ≤300, or ≤250 g / mol.

[0139] K3] A method according to any one of A]-R] or A3]-J3] above, or a composition according to any one of A2]-R2] or A3]-J3] above, wherein the sum of component a and component b is present in an amount of ≥0.50 wt.%, or ≥1.0 wt.%, or ≥1.5 wt.%, or ≥2.0 wt.%, based on the weight of the composition.

[0140] L3] A method according to any one of A]-R] or A3]-K3] above, or a composition according to any one of A2]-R2] or A3]-K3] above, wherein the sum of component a and component b is present in an amount of ≤10 wt%, or ≤9.0 wt%, or ≤8.0 wt%, or ≤7.0 wt%, or ≤6.0 wt%, or ≤5.0 wt%, or ≤4.0 wt%, or ≤3.0 wt%, based on the weight of the composition.

[0141] M3] A method according to any one of B3] to L3] above, or a composition according to any one of B3] to L3] above, wherein the sum of component a and component c is present in an amount of ≥0.50 wt%, or ≥1.0 wt%, or ≥1.5 wt%, or ≥2.0 wt%, based on the weight of the composition.

[0142] N3] A method according to any one of B3] to M3] above, or a composition according to any one of B3] to M3] above, wherein the sum of component a and component c is present in an amount of ≤10 wt.%, or ≤8.0 wt.%, or ≤6.0 wt.%, or ≤4.0 wt.%, or ≤3.0 wt.%, based on the weight of the composition.

[0143] O3] According to the method described in any one of A]-R] or A3]-N3] above, or according to the composition described in any one of A2]-R2] or A3]-N3] above, wherein the sum of component a, component b and water is present in an amount of ≥80 weight %, or ≥85 weight %, or ≥90 weight %, or ≥92 weight %, or ≥94 weight %, or ≥96 weight %, or ≥97 weight %, or ≥98 weight % based on the weight of the composition.

[0144] P3] A method according to any one of A]-R] or A3]-O3] above, or a composition according to any one of A2]-R2] or A3]-O3] above, wherein the sum of component a, component b and water is present in an amount of ≤100 wt.% or ≤99 wt.%, based on the weight of the composition.

[0145] Q3] A method according to any one of B3] to P3] above, or a composition according to any one of B3] to P3] above, wherein the sum of component a, component b, component c and water is present in an amount of ≥85 wt%, ≥90 wt%, ≥92 wt%, ≥94 wt%, ≥96 wt%, ≥97 wt%, or ≥98 wt%, based on the weight of the composition.

[0146] R3] A method according to any one of B3] to Q3] above, or a composition according to any one of B3] to Q3] above, wherein the sum of component a, component b, component c and water is present in an amount of ≤100 wt. %, or ≤99 wt. %, based on the weight of the composition.

[0147] S3] According to the method described in any one of A]-R] or A3]-R3] above, or according to the composition described in any one of A2]-R2] or A3]-R3] above, wherein the "oil removal %" of the composition is ≥40%, or ≥45%, or ≥50%, or ≥52%, or ≥54%, or ≥56%, or ≥58%, or ≥60%, as defined by the equation [(W2-W3) / (W2-W1)]×100, wherein W1, W2 and W3 are each as defined herein (see Experimental section).

[0148] T3] A method according to any one of A]-R] or A3]-S3] above, or a composition according to any one of A2]-R2] or A3]-S3] above, wherein the "oil removal %" of the composition is ≤100%.

[0149] U3] A method according to any one of A]-R] or A3]-T3] above, or a composition according to any one of A2]-R2] or A3]-T3] above, wherein the composition produces a foam height of ≤20 cm, or ≤18 cm, or ≤16 cm after circulating for 60 seconds as described herein (see the experimental part).

[0150] V3] A method according to any one of A]-R] or A3]-U3] above, or a composition according to any one of A2]-R2] or A3]-U3] above, wherein the composition produces a foam height of ≥5.0 cm after circulating for 60 seconds as described herein.

[0151] W3] according to the method described in any one of A]-R] or A3]-V3] above, or according to the composition described in any one of A2]-R2] or A3]-V3] above, wherein the composition is separated from the oil and fills a "10 ml" volume in a time of ≤65, or ≤62, or ≤60, or ≤58, or ≤55, or ≤52, or ≤50, or ≤48, or ≤46, or ≤44, or ≤42, or ≤40 seconds as determined by the emulsification evaluation described herein (see the experimental part).

[0152] X3] A method according to any one of A]-R] or A3]-W3] above, or a composition according to any one of A2]-R2] or A3]-W3] above, wherein the composition separates from the oil and fills a "10 ml" volume in ≥2 seconds.

[0153] Y3] A method according to any one of A]-R] or A3]-X3] above, or a composition according to any one of A2]-R2] or A3]-X3] above, wherein the composition is separated from the oil and fills a "5 ml" volume in ≤30, or ≤28, or ≤25, or ≤22, or ≤20, or ≤18, or ≤16, or ≤14, or ≤12 seconds as determined by the emulsification evaluation described herein (see Experimental Section).

[0154] Z3] A method according to any one of A]-R] or A3]-Y3] above, or a composition according to any one of A2]-R2] or A3]-Y3] above, wherein the composition separates from the oil and fills a "5 ml" volume in ≥1 second.

[0155] experiment

[0156] Synthesis of etheramines

[0157] Reductive Amination Catalyst

[0158] Each etheramine (Formula 1A and Formula 1B) as described herein is produced using a glycol ether starting material and then subjecting the glycol ether to a reductive amination reaction. A solution containing "236 g Ni(NO3)·6H2O, 69 g Co(NO3)2·6H2O, 51 g Cu(NO3)2·2.5H2O, 20.4 g NH4ReO4 and 59 g H3BO3" was prepared in 700 ml of boiling deionized water. The boiling solution was poured into a 1-L beaker containing 150 g of a catalyst support (1 / 16" spherical alumina support available from UOP under the trade name SAB-17). The support mixture was mixed thoroughly to ensure complete and uniform wetting of the support. The impregnated support was dried in a crucible at 120°C for 3 hours with frequent stirring, then calcined in a wind furnace at 300°C for 3 hours, and then stored in a 120°C oven until activated.

[0159] The NiCoCuReB catalyst prepared in this way is reduced in an activation chamber. The temperature of the chamber is slowly heated to 350°C over 2 hours, while a stream of pure hydrogen flows through the chamber at about 30 ml / min. After the temperature reaches 350°C, activation is continued for 4 hours. The heating is then turned off, but the hydrogen stream is maintained until the chamber cools to room temperature. The activated catalyst (pyrophoric) is carefully transferred to a bottle in a nitrogen-filled drying oven and stored therein until use. The resulting catalyst has a total metal loading of 40 wt%. It contains a Ni / Co / Cu / Re / B metal weight ratio of 48 / 14 / 14 / 14 / 10, a Ni / Co weight ratio of 3.4, and a Ni / Cu weight ratio of 3.4.

[0160] The catalyst was loaded into the reactor in a nitrogen-filled dry box (oxygen <10 ppm) to prevent deactivation. Ceramic ball packing (1 / 8") was used above and below the catalyst so that the catalyst bed was located in the constant temperature zone of the reactor.

[0161] Reductive Amination of Glycol Ethers

[0162] A continuous plug flow reactor system was used for all reductive amination reactions. An ISCO 500D continuous supply syringe pump system (maximum pressure of 3750 psi) with TEFLON seals was used for glycol ether solvent supply. A second ISCO 500D syringe pump system was used to supply ammonia at a constant flow rate. A Brooks 5850TR mass flow controller (maximum pressure of 4500 psi) was used with a 5896 digital readout box to control the flow of hydrogen from a 6000 psig cylinder. A differential pressure regulator (AP = 50 psig) from VERIFLO was used to adjust the inlet / outlet bias of the flow sensor. The three supply streams were combined and supplied to the tubular packed bed reactor through a spiral preheater (1 / 8" OD, 316 stainless steel tubing, total length 15 feet). This 316 stainless steel Kuentzel type reactor (1.25" ID, 250 ml capacity) manufactured by Autoclave Engineers was rated at 9,500 psi / 500°F and was loaded with 200 ml of catalyst. A 1 / 16" diameter thermocouple inserted from the top of the reactor into the center of the catalyst bed was used to monitor the catalyst temperature. The reactor volume not filled with catalyst was filled with glass wool. The reactor pressure was maintained by a back pressure control valve (BPCV, maximum pressure = 6000 psi) manufactured by TESCOM. From the BPCV, the product solution was collected in a sample bottle.

[0163] The plug flow reactor system is equipped with several automatic shutoff features to ensure continuous unattended operation. The reactor controller has a high temperature cutoff sensor, and both ISCO feed pumps have high pressure cutoff capability. Whenever the high pressure sensor or high temperature sensor detects any excessive reactor pressure or temperature, respectively, the hydrogen supply line is blocked by an actuator driven by two solenoid valves.

[0164] The aminated glycol ethers are isolated as a crude reaction mixture containing residual ammonia, water and some glycol ether starting material. Ammonia is removed by bubbling nitrogen through the crude mixture or by using a low pressure evaporator (e.g., a Büchi rotary evaporator). Further purification of each product is achieved by distillation.

[0165] Typical reaction conditions

[0166] The reactor conditions for the reductive amination of glycol ethers are as follows: reactor temperature = 170°C-215°C, reactor pressure = 1200 psig, glycol ether solvent feed rate = 0.5-1.5 ml / min, liquid hourly space velocity (LHSV) = 0.15-0.45, NH3 / OH molar ratio = 20-25, hydrogen content 3 mol%-5 mol%,

[0167] purification

[0168] For purification, 1-methoxy-2-aminopropane (or 1-methoxypropan-2-amine) is first treated with NaOH pellets to produce a separate aqueous layer, which is decanted prior to distillation to improve recovery. Purity analysis is performed by acid titration, Karl-Fisher water titration, gas chromatography, and / or nuclear magnetic resonance spectroscopy.

[0169] Most of the water in 1-methoxy-2-aminopropane is removed by adding NaOH pellets, thereby inducing the formation of an alkaline water layer. In a typical experiment, 1-methoxy-2-aminopropane (2000 g) is added to a 3L three-necked flask, which is shaped as having an elongated bottom and equipped with an overhead stirrer and a bottom stopcock. The stirrer is turned on, and NaOH pellets (273 g) are added to the flask spoon by spoon in an amount of NaOH to produce a concentration of about "12% by weight", added to the combined 1-methoxy-2-aminopropane / NaOH mixture. The mixture is stirred overnight for at least 12 hours. Stirring is stopped, and each phase is separated. The bottom "water layer containing about 31% by weight NaOH" is separated from the top "organic layer containing 1-methoxy-2-aminopropane". The resulting 1-methoxy-2-aminopropane contains about 5% by weight of water. The remaining etheramine is not dried using NaOH.

[0170] Each etheramine was distilled in a "6 foot x 1.5 inch inner diameter" glass column or a "2 foot x 1 inch diameter" glass column (see Table 1). Both columns were equipped with an overhead reflux distributor and filled with 0.25 inch ceramic saddles and were identical in form and function except for scale. The etheramines were charged into flasks of appropriate size to obtain a certain amount of usable material and attached to the bottom of the distillation column. For 2-butoxy-1-aminoethane and 1-butoxy-2-aminopropane, the column was flushed with nitrogen, placed under vacuum, and then heated. 1-methoxy-2-amino-propane was flushed with nitrogen, but distilled at atmospheric pressure. Light impurities were removed from the top of the column first, followed by the desired etheramine. The sample was distilled until the sample level in the bottom flask was no longer sufficient to ensure adequate coverage of the built-in thermowell. Sections were removed periodically, analyzed, and recombined based on purity. Information on the distillation parameters is provided in Table 1.

[0171] The analysis of "0.15 g aliquots" of (purified) etheramine diluted in 60 ml of deionized water (DI water) was performed in triplicate using a Mettler Toledo DL67 titrator equipped with a DG115-SC sensor and a standardized 0.1 M HCl titrant. The standardization of the HCl titrant was performed by titrating a known amount of potassium hydrogen phthalate with a NaOH solution and then titrating the HCl with a standardized NaOH solution.

[0172] The purity of the etheramines (aminated glycol ethers) was determined using the following formula and the purity is reported in Table 1 (purity determined by acid titration):

[0173] {[(ml "0.1M HCl" to reach equivalence point) / 10 / gram of titrated sample] / [1000 / molecular weight of aminated glycol ether]}×100.

[0174] Table 1: Example distillation conditions and purities

[0175]

[0176]

[0177] The etheramines shown in Table 2 were prepared as discussed above. The crude reaction mixture, after removal of ammonia, was purified by distillation. Two comparative amines are also shown in Table 2.

[0178] Table 2: Etheramines

[0179]

[0180]

[0181] Reagents and samples

[0182] The reagents and test samples are listed in Table 3 below.

[0183] Table 3: Reagents and test samples

[0184]

[0185] Composition

[0186] The compositions of the present invention and comparative compositions are shown in Table 4A and Table 4B below. Each composition was prepared by mixing the indicated reagents at room temperature. The required amount of EDTA-4Na·4H2O was added to DI water and mixed until dissolved. Then, the etheramine and LFE-635 were added to the solution and the final solution was mixed until a uniform suspension was formed or completely dissolved.

[0187] Table 4A: Cleaning Composition*

[0188]

[0189]

[0190] *Each weight % is based on the weight of the composition.

[0191] Table 4B: Cleaning Composition*

[0192]

[0193] *Each weight % is based on the weight of the composition.

[0194] Testing and Results

[0195] Metal Cleaning Performance Evaluation

[0196] A stainless steel (ss) sample was washed under running DI water for about 10 seconds and then rinsed by spraying acetone from a squeeze bottle onto the sample until all surfaces on the sample were covered. The washed and rinsed sample was blown dry at room temperature and then weighed. The weight of the dried ss sample was recorded as W1.

[0197] The cleaning composition (45 g, see Table 4A or Table 4B) was added to a 50 mL PP bottle. The dried ss sample was tared on a scale and stamping oil (0.20 g + / - 0.01 g) was applied to the upper surface of the sample using a dropper. The sample was carefully rotated to ensure that the oil was evenly spread on the sample surface. The weight of the contaminated sample was recorded as W2.

[0198] Using tweezers, place the contaminated coupon in the cleaning composition (50 ml bottle) and immediately start the timer. After 5 minutes, remove the coupon from the composition and rinse by placing the coupon in 200 mL DI water (in a 250 mL beaker) for about 3 to 5 seconds.

[0199] The rinsed samples were placed in a metal tray on a laboratory bench ("top" facing up) and air dried at room temperature for one day. The weight of the dried sample was recorded as W3. The percentage of oil removed by the cleaning composition (or "% oil removal") was calculated using the following formula: [(W2-W3) / (W2-W1)]×100. The results are shown in Figure 1 and Figure 2 For Figure 1 Three test samples were examined for each composition and the average value is reported (relative standard deviation (RSD) = 2.7%).

[0200] like Figure 1 As seen in the Figures 1-6, Examples 1-6 show equal or better degreasing than Comparative Examples 1 and 2. Note that Comparative Example 1 (MEA) is widely used in industrial cleaning applications, including metal cleaning. The results of this study indicate that the compositions of the present invention containing the indicated etheramines are good replacements for existing amine products in metal cleaners.

[0201] like Figure 2As can be seen in the Figures 1 and 2 (one test sample for each additional composition), for the same etheramine, compositions having a weight ratio of etheramine to chelate falling within the range of 0.40 to 200 (Example 3, a / b = 4.0) outperform corresponding compositions falling below this range (Example 7, a / b = 0.36) and above this range (Example 8, a / b = 250).

[0202] Foaming evaluation

[0203] The cleaning composition (750 ml, see Table 4A and Table 4B) was poured into a circular foam tester (see Figure 3 , Golden Chemical Co., Ltd. (Golden Chemical, Model: GT-2) in a glass tube. When no additional foam is observed on the surface of the composition in the tube, turn on the tester (voltage = 27.8V), which circulates the cleaning composition to generate foam. Generate foam for one minute, and record the foam height at the following times: 15 seconds, 30 seconds, 60 seconds. After 60 seconds, turn off the tester (circulation), and record the foam height at the following times: 75 seconds, 90 seconds, 120 seconds, 180 seconds, 240 seconds and 300 seconds. Compare Example 1 and Examples 3-6 with Comparative Examples 1 and 2. See Figure 4A and Figure 4B .

[0204] like Figure 4A As can be seen from the table, Example 1 and Example 3 are each superior to Comparative Example 1. Figure 4B , Examples 4-6 are each superior to Comparative Example 2. As shown in the various figures, during the foam generation phase, the foam height of each of the inventive compositions did not increase as much as the foam height of the comparative composition. In addition, after stopping the cycle, the residual foam level of the inventive compositions was lower than that of the comparative composition. The ability of a cleaning composition to generate a small amount of foam is an important consideration for metal cleaning compositions, especially those used in large-scale metal cleaning processes. Excessive foaming can result in insufficient rinsing of the metal surface and / or overflow and spillage in the bath, resulting in product waste. Moreover, as seen in each of the inventive compositions, good foam control reduces or eliminates the need for additional foam control agents.

[0205] Emulsification evaluation

[0206] Liquid paraffin was used as the oil phase. The cleaning composition (20 ml, see Table 4A and Table 4B) was added to a graduated cylinder (100 ml), and 20 ml of oil was added after this addition. The cylinder was shaken up and down 10 times as one cycle. The "up and down" shaking was repeated for 5 cycles with an interval of one minute between each cycle. After completing 5 cycles, the time required for the aqueous phase to separate from the oil and reach the 5 ml and then 10 ml calibration marks was recorded. The longer the separation time, the stronger the emulsification of the cleaning composition and the oil. Example 1 was compared with Comparative Example 2. See Figure 5 (5ml and 10ml markings).

[0207] like Figure 5 As seen in the , Example 1 has a lower emulsification strength for oil than Comparative Example 2. Emulsification is generally related to chemical structure. Example 1 (PM amine) and Comparative Example 2 (MPA) have the same molecular formula. PM amine has a branched methyl group, but MPA has a linear structure, which leads to differences in the emulsification of oil. Example 1 (PM amine) shows faster oil separation, which is beneficial for a long-lasting cleaning bath life. This feature is advantageous in metal cleaning processes because the cleaning solution is expected to separate from the oil quickly after cleaning the metal. Strong binding with oil can lead to a significant reduction in the efficacy of the cleaning bath and therefore a shorter bath life. The results herein show that Example 1 is the best cleaning composition for effective oil separation and longer bath life.

Claims

1. A method for cleaning a metal surface, the method comprising applying to the metal surface a composition comprising at least the following components a) and b): a) at least one etheramine selected from formula 1A and / or at least one etheramine selected from formula 1B: wherein R1 is a monovalent carbon-containing group containing 1 to 10 carbon atoms; R2 is hydrogen, methyl or ethyl; R3 is hydrogen, methyl or ethyl; and x is 1 to 5; and when x ≥ 2, the R2 groups of the -(CH2-CHR2-O)- portion may all be the same, or some or all may be different, and if some or all are different, then the -(CH2-CHR2-O)- x - the moiety may contain any combination of hydrogen and / or methyl and / or ethyl as at least two different R2 groups; wherein R4 is a monovalent carbon-containing group containing 1 to 10 carbon atoms; and R5 is hydrogen, methyl or ethyl; b) at least one chelate.

2. The method according to claim 1, wherein the weight ratio of component a to component b is 0.40 to 200.

3. The method according to claim 1 or claim 2, wherein component b is a metal chelate.

4. The method according to any one of claims 1 to 3, wherein for Formula 1A, R1 is an alkyl group; R2 is hydrogen or methyl; and R3 is hydrogen or methyl; and for Formula 1B, R4 is an alkyl group; and R5 is hydrogen or methyl.

5. The method according to any one of claims 1 to 4, wherein component a is selected from the following structures (1a) to (1j):

6. The method according to any one of claims 1 to 5, wherein component a is selected from the following structures: (1a), (1b), (1c), (1d), (1e) or (1f), each as shown above.

7. The process according to any one of claims 1 to 6, wherein component a is at least one etheramine selected from formula 1A.

8. The process according to any one of claims 1 to 6, wherein component a is at least one etheramine selected from formula 1B.

9. The method according to any one of claims 1 to 8, wherein the metal of the metal surface is selected from steel, stainless steel, brass, chromium, iron, aluminum, copper or gold.

10. A composition comprising at least the following components a) and b): a) at least one etheramine selected from formula 1A and / or at least one etheramine selected from formula 1B: wherein R1 is a monovalent carbon-containing group containing 1 to 10 carbon atoms; R2 is hydrogen, methyl or ethyl; R3 is hydrogen, methyl or ethyl; and x is 1 to 5; and when x ≥ 2, the R2 groups of the -(CH2-CHR2-O)- portion may all be the same, or some or all may be different, and if some or all are different, then the -(CH2-CHR2-O)- x - the moiety may contain any combination of hydrogen and / or methyl and / or ethyl as at least two different R2 groups; wherein R4 is a monovalent carbon-containing group containing 1 to 10 carbon atoms; and R5 is hydrogen, methyl or ethyl; b) at least one chelate.

11. The composition according to claim 10, wherein the weight ratio of component a to component b is 0.40 to 200.

12. A composition according to claim 10 or claim 11, wherein for Formula 1A, R1 is an alkyl group; R2 is hydrogen or methyl; and R3 is hydrogen or methyl; and for Formula 1B, R4 is an alkyl group; and R5 is hydrogen or methyl.

13. The composition according to any one of claims 10 to 12, wherein component a is selected from the following structures (1a) to (1j), each as shown above.

14. The composition according to any one of claims 10 to 13, wherein component a is selected from the following structures: (1a), (1b), (1c), (1d), (1e) or (1f), each as shown above.

15. The composition according to any one of claims 10 to 14, wherein component a is at least one etheramine selected from formula 1A.

16. The composition according to any one of claims 10 to 14, wherein component a is at least one etheramine selected from formula 1B.

17. The composition according to any one of claims 10 to 16, wherein the composition further comprises water.

18. The composition according to any one of claims 10 to 17, wherein the composition further comprises at least one surfactant as component c.

19. The composition according to any one of claims 10 to 18, wherein the composition further comprises at least one basic salt as component d.

20. The composition of any one of claims 17 to 19, wherein the sum of component a and component b and water is present in an amount of 80% to 100% by weight, based on the weight of the composition.

Images