Composition for cleaning metals

Abstract

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

Description

[Technical Field]

[0001] Alkaline cleaning solutions are commonly used as metal cleaners to remove various types of soils. These cleaners typically consist of an alkali, a wetting agent, a solvent, and a sequestering (chelating) agent. Such cleaners should be able to efficiently clean metal surfaces. Low foaming is an important criterion for cleaners, as excessive foam can lead to rinsing problems and / or overflow, resulting in spills and product waste. Rapid recovery of bath solution is another desirable characteristic of metal cleaners. The active substances present in the cleaner must be efficiently separated from the removed oil; otherwise, the cleaning power of the recirculating bath will be significantly reduced.

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

[0003] WO 2020 / 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] WO 2017 / 011216 discloses glycol ether solvents in liquid cleaning compositions for removing hydrophobic soils from hard surfaces and for the foaming properties of the compositions (see Abstract). The liquid cleaning compositions also contain surfactants, and the compositions have a pH of less than 10 (see Claim 1). The compositions may also contain chelates (see pages 13-14).

[0005] U.S. Patent Application Publication No. 2018 / 0127688 discloses cleaning compositions containing an ester solvent, preferably a fatty acid methyl ester, in combination with one or more linear alkylamines. The alkylamines are disclosed as acting to remove and suspend burned or thermally attached organic oils from surfaces, and these amines can be used alone as stain removers. Cleaning compositions are disclosed for use in cleaning distillation columns associated with biofuel and vegetable oil refining, as well as for use in cleaning and dry cleaning ovens and food preparation surfaces. See Abstract. The compositions may contain chelating agents (see, e.g., paragraph

[0043] ).

[0006] U.S. Patent Application Publication No. 2018 / 0291309 discloses a cleaning composition and process 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). Some organic amines are disclosed, for example, in paragraph

[0040] .

[0007] WO 93 / 16162 discloses an aqueous hard surface cleaner comprising: (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 surfactants, nonionic surfactants, and anionic surfactants, and mixtures thereof; (c) an effective amount of a buffer system comprising a nitrogen-containing buffer selected from ammonium or alkaline earth carbamates, guanidine derivatives, alkoxylalkylamines, and alkyleneamines; and (d) a residue substantially as water (see Abstract). Several nitrogen-containing buffers are listed on pages 10-11.

[0008] WO 2015 / 143034 discloses an in-situ staged steam extraction process for removing petroleum products from heavy oil or bitumen reservoirs from a subterranean location. The steam composition can consist essentially of steam or can include one or more enhanced oil recovery agents. See Abstract. Glycol ether amines can be used as enhanced oil recovery agents (see, e.g., p. 6, line 23 to p. 7, line 6).

[0009] U.S. Patent No. 9,574,126 discloses an aqueous drilling fluid composition comprising a shale hydration inhibitor of the formula H2N-CH(R)-R1-O-R2, where 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 aqueous drilling fluid at a concentration sufficient to reduce swelling of clay and shale when exposed to the water-based drilling fluid (see Abstract).

[0010] However, as noted 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, there is provided a process for cleaning a metal surface, the process 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,

[0012] [ka] In the formula, 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, x is 1 to 5, and when x≧2, the R2 groups in the —(CH2—CHR2—O)— portion may all be the same or some or all may be different, and when some or all are different, —(CH2—CHR2—O) x - moiety may contain any combination of hydrogen and / or methyl and / or ethyl as at least two different R2 groups,

[0013] [ka] at least one etheramine selected from formula 1A and / or at least one etheramine selected from formula 1B, wherein R4 is a monovalent carbon-containing group having 1 to 10 carbon atoms and R5 is hydrogen, methyl, or ethyl; b) applying to the metal surface a composition comprising:

[0014] In a second embodiment, the composition comprises 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,

[0015] [ka] In the formula, 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, x is 1 to 5, and when x≧2, the R2 groups in the —(CH2—CHR2—O)— portion may all be the same or some or all may be different, and when some or all are different, —(CH2—CHR2—O) x- moiety may contain any combination of hydrogen and / or methyl and / or ethyl as at least two different R2 groups,

[0016] [ka] at least one etheramine selected from formula 1A and / or at least one etheramine selected from formula 1B, wherein R4 is a monovalent carbon-containing group having 1 to 10 carbon atoms and R5 is hydrogen, methyl, or ethyl; b) at least one chelate. [Brief explanation of the drawings]

[0017] [Figure 1] 1 is a bar graph showing the percentage of oil removal for the compositions of the present invention and comparative compositions. [Figure 2] 1 is a bar graph showing the percentage of oil removal for the compositions described. [Figure 3] The figure shows a circulation type foaming tester. [Figure 4A] 1 shows the "foam height versus time" profile for the inventive and comparative compositions listed, respectively. [Figure 4B] 1 shows the "foam height versus time" profile for the inventive and comparative compositions listed, respectively. [Figure 5] 1 is a bar graph showing the time it takes for each of the compositions listed to separate from the oil and fill a volume of 5 mL or 10 mL. DETAILED DESCRIPTION OF THE INVENTION

[0018] A cleaning composition has been discovered that provides excellent oil removal performance, good foam control and rapid oil separation.

[0019] As noted above, in a first aspect, there is provided a process for cleaning a metal surface, the process comprising applying to the metal surface a composition comprising at least the following components a) and b), each as described herein. In a second aspect, there is provided a composition comprising at least the following components a) and b), each as described herein.

[0020] The above process may comprise a combination of two or more embodiments as described herein. The above composition may comprise a combination of two or more embodiments as described herein. Component a may comprise a combination of two or more embodiments as described herein. Component b may comprise a combination of two or more embodiments as described herein.

[0021] 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 stated, the following embodiments apply to both the first and second aspects of the invention.

[0022] In one embodiment or a combination of two or more embodiments, each 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, each 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.

[0023] In one embodiment or a combination of two or more embodiments, each described herein, component b is a metal chelate.

[0024] 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; R2 is hydrogen or methyl, further a methyl; 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.

[0025] In one embodiment or a combination of two or more embodiments, each described herein, component a has the following structures (1a)-(1j):

[0026] [ka] 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.

[0027] In one embodiment or a combination of two or more embodiments, each described herein, component a is at least one etheramine selected from Formula 1A, and further is one etheramine selected from Formula 1A.

[0028] In one embodiment or a combination of two or more embodiments, each described herein, component a is at least one etheramine selected from Formula 1B, and further is one etheramine selected from Formula 1B.

[0029] In one embodiment or a combination of two or more embodiments, each described herein, the metal of the metal surface is selected from steel, stainless steel, brass, chromium, iron, aluminum, copper, or gold.

[0030] In one embodiment or a combination of two or more embodiments, each described herein, the composition further comprises water.

[0031] In one embodiment or a combination of two or more embodiments, each described herein, the composition further comprises at least one surfactant as component c. In one embodiment or a combination of two or more embodiments, each 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, further from at least one nonionic surfactant, or at least one anionic surfactant, further from at least one nonionic surfactant.

[0032] In one embodiment or a combination of two or more embodiments, each described herein, the composition further comprises at least one alkali salt as component d.

[0033] In one embodiment or a combination of two or more embodiments, each described herein, the sum of component a, 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, each described herein, 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.

[0034] Constituent component: a-etheramine 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 represent linear, branched, and cyclic 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-ethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, These include, but are not limited to, alkyl groups such as 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.

[0035] 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.

[0036] In one embodiment or a combination of two or more embodiments, each described herein, component a is selected from any of the following groups (a) to (g): (a) 2-methoxyethylamine, 2-ethoxyethylamine, 2-propoxyethylamine, 2-butoxyethylamine, 2-pentyloxyethylamine, 2-hexyloxyethylamine, 2-septyloxyethylamine, and 2-octyloxyethylamine, (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-septyloxypropan-2-amine, and 1-octyloxypropan-2-amine; (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; (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; (e) 1-((1-methoxypropan-2-yl)oxy)-propan-2-amine, 1-((1-ethoxypropan-2-yl)-oxy)-propan-2-amine, 1-((1-propoxypropan-2-yl)oxy)-propan-2-amine, 1-((1-butoxy-propan-2-yl)oxy)-propan-2-amine, 1-((1-pentyloxypropan-2-yl)oxy)-propan-2-amine, and 1-((1-hexyloxypropan-2-yl)oxy)-propan-2-amine; (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 (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.

[0037] In one embodiment, or a combination of two or more embodiments, each described herein, component a has a boiling point from 80°C to 290°C, further from 85°C to 285°C, further from 90°C to 280°C.

[0038] The synthesis of ether amines is well known in the art, and various ether amines are commercially available. For example, 1-methoxypropan-2-amine is available from Sigma-Aldrich. One mode of synthesis involves the reductive amination of glycol ethers with ammonia using a NiCoCuReB catalyst, as described in U.S. Pat. No. 9,574,126. Glycol ether starting materials may be obtained from The Dow Chemical Company, such as those available under the trade names DOWANOL, CELLOSOLVE, and CARBITOL, including 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.

[0039] Component a can be in the form of a liquid composition that is added to the aqueous composition. The etheramine itself can be in liquid form at room temperature (23°C), and therefore a "stock" composition can be one in which the etheramine is in undiluted form (100% by weight). Stock compositions can 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 can also be in the form of a solid composition, such as a powder or granular form, that can be added to the aqueous composition.

[0040] Component b-chelate Chelates are well known in the art. Chelates typically contain at least two ligands bound to a central metal atom. Chelates include, but are not limited to, aminocarboxylate chelators such as salts of ethylenediaminetetraacetic acid and its derivatives, salts of glutamic acid-N,N-diacetic acid, and phosphonate chelators such as ethylenediaminetetramethylenephosphonate and diethylenetriaminepentamethylenephosphonate. These chelates may exist in either their acid form or as salts. Biodegradable chelators include, but are not limited to, ethylenediamine-N,N'-disuccinic acid, or its alkali metal or alkaline earth metal, ammonium, or substituted ammonium salts, or mixtures thereof, and L-glutamic acid-N,N-diacetic acid (GLDA), commercially available from Akzo Nobel under the trade name DISSOLVINE 47S.

[0041] Suitable aminocarboxylates include ethylenediaminetetraacetate, diethylenetriaminepentaacetate, diethylenetriaminepentaacetate (DTPA), N-hydroxyethylethylenediaminetriacetate, nitrilotriacetate, ethylenediaminetetrapropionate, triethylenetetraminehexaacetate, ethanoldiglycine, and methylglycinediacetic acid (MGDA), both in the acid form or in the alkali metal, ammonium, and substituted ammonium salt form. Particularly suitable aminocarboxylates include, but are not limited to, salts of ethylenediaminetetraacetic acid (EDTA), EDTA, for example, propylenediaminetetraacetic acid (PDTA), methylglycinediacetic acid (MGDA), and diethylenetriaminepentaacetate (DTPA) from BASF, both of which are commercially available under the trade name TRILON FS. Additional carboxylate chelating agents include salicylic acid, aspartic acid, glutamic acid, glycine, malonic acid, or mixtures thereof.

[0042] In one embodiment, or a combination of two or more embodiments, each described herein, component b is ethylenediaminetetraacetic acid or a salt thereof, for example, EDTA-4Na HO.

[0043] Component c - surfactant 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, cationic surfactants may be used with nonionic surfactants, or anionic surfactants may be used with nonionic surfactants.

[0044] Cationic surfactants include, but are not limited to, salts of long-chain primary, secondary, or tertiary amines, such as oleylamide acetate, cetylamine acetate, stearatamine acetate, didodecylamine lactate, aminoethyl-aminoethylstearamide acetate, dilauroyltriethylenetetramine diacetate, 1-aminoethyl-2-heptadecenylimidazoline acetate, and quaternary salts, such as cetylpyridinium bromide, hexadecylethylmorpholinium chloride, and diethyldidodecylammonium chloride. Examples of cationic surfactants include alkyltrimethylammonium salts.

[0045] Anionic surfactants include, but are not limited to, alkali metal salts of alkyl-aryl sulfonic acids, sodium dialkyl sulfosuccinate, sulfated or sulfonated oils such as sulfated castor oil and sulfonated tallow, alkali salts of short-chain petroleum sulfonic acids, and ammonium and amine soaps (the fatty acid portion of such soaps preferably contains at least 16 carbon atoms). Soaps can also be formed "in situ," i.e., the fatty acid is added to the oil phase and the alkaline material is added to the aqueous phase. Anionic surfactants also include, but are not limited to, alkyl sulfates, alkyl ether sulfates, sulfated alkanolamides, alpha olefin sulfonates, lignosulfonates, sulfosuccinates, fatty acid salts, and phosphate esters. For example, an anionic surfactant is DOWFAX C10L, commercially available from The Dow Chemical Company.

[0046] 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, a nonionic surfactant is TERGITOL L-62, available from The Dow Chemical Company.Generally, nonionic surfactants include, but are not limited to: a) condensation products of higher fatty alcohols with ethylene oxide, b) condensation products of alkylphenols with ethylene oxide, c) condensation products of higher fatty acid amides with five or more ethylene oxide units, d) polyethylene glycol esters of long-chain fatty acids, for example, tetraethylene glycol monopalmitate, hexaethylene glycol monolaurate, nonaethylene glycol monostearate, nonaethylene glycol dioleate, tridecaethylene glycol monoarachidate, tricosaethylene glycol monobehenate, tricosaethylene glycol dibehenate, e) polyhydric alcohol moiety higher fatty acid esters such as sorbitan tristearate, f) ethylene oxide condensation products of polyhydric alcohol moiety higher fatty acid esters and their intramolecular anhydrides, g) long-chain polyglycols 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 refers to the average molecular weight of the polyglycol ether).

[0047] Amphoteric surfactants include, but are not limited to, alkylamidopropylamine N-oxides, alkyldimethylamine N-oxides, alkylbetaines, alkylamidopropylbetaines, cocamidopropylbetaine, cocoamphoacetate, and cocoamphodiacetate.

[0048] In one embodiment, or a combination of two or more embodiments, each described herein, component c is an alcohol alkoxylate such as, for example, an ethoxylated propoxylated alkanol, and also an ethoxylated propoxylated 2-ethyl-1-hexanol.

[0049] Constituent d-alkali salt Alkali salts are the product of a strong base and a weak acid and are capable of forming a basic solution when dissolved in water. Alkali salts include, but are not limited to, sodium carbonate, sodium acetate, sodium hydroxide, sodium bicarbonate, sodium chloride, and sodium sulfide.

[0050] In one embodiment, or a combination of two or more embodiments, each described herein, component d is selected from a metal bicarbonate, a metal carbonate, a metal chloride, a metal chlorate, a metal nitrate, a metal phosphate, a metal sulfate, a metal sulfide, or a mixture thereof.

[0051] Other additives The compositions of the present invention may optionally contain one or more additional additives, such as block or random copolymers of ethylene oxide / propylene oxide, butylene oxide / propylene oxide, ethylene oxide / butylene oxide, waxes, silicone-based materials, and the like. and foam control compounds such as those produced by the alkoxylation of alcohols, alkyl polyglucosides, ketal foam control agents, and cellulose derivative foam control agents.

[0052] definition Unless stated to the contrary, implicit from the context, or customary in the art, parts and percentages are by weight and all test methods are current as of the filing date of this disclosure.

[0053] As used herein, the term "composition" includes a mixture of materials, including the composition and reaction and decomposition products formed from the materials of the composition. Any reaction or decomposition products are typically present in trace or residual amounts.

[0054] As used herein, the term "polymer" refers to a polymeric compound prepared by polymerizing monomers of the same or different types. Thus, the generic term polymer includes the term homopolymer (used to refer to a polymer prepared from only one type of monomer, with the understanding that trace amounts of impurities may be incorporated into the polymer structure) and the term interpolymer, as defined below. Trace amounts of impurities, such as catalyst residues, may be incorporated into and / or within the polymer. Typically, polymers are stabilized with very small amounts ("ppm (parts per million)" amounts) of one or more stabilizers.

[0055] As used herein, the term "interpolymer" refers to a polymer prepared by the polymerization of at least two different types of monomers. Thus, the term interpolymer includes the term copolymer (used to refer to a polymer prepared from two different types of monomers) and polymers prepared from three or more different types of monomers.

[0056] With respect to the process of cleaning a metal surface with the compositions described herein, the phrase "applying to the metal surface" refers to the act of contacting the metal surface with the composition. This contacting may be done by wetting the metal surface with the composition using a spray, brush, roller, or by immersing the metal in the composition, or by any other means known in the art.

[0057] As used herein, the phrase "monovalent carbon-containing group containing 1 to 10 carbon atoms" with respect to R1 of Formula 1A and R4 of Formula 1B refers to a chemical group containing 1 to 10 carbon atoms, which is attached 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-). The chemical group can be, for example, a linear aliphatic group, a branched aliphatic group, a cyclic aliphatic group, an aromatic group (e.g.,

[0058] [ka] The combinations may be combinations of straight-chain aliphatic groups and cyclic aliphatic groups, combinations of branched-chain aliphatic groups and cyclic aliphatic groups, combinations of straight-chain aliphatic groups and aromatic groups, combinations of branched-chain aliphatic groups and aromatic groups, or other combinations known in the art. Also, with respect to the number of carbon atoms in R1 of Formula 1A or R4 of Formula 1B, the notation "C1-C10" (e.g., "1-10" represents the sequential numbers from 1 to 10) refers to the range of the number of carbon atoms that may be present in each R group.

[0059] The terms "comprising," "including," "having," and their derivatives are not intended to exclude the presence of any additional component, step, or procedure, whether or not it is specifically disclosed. For the avoidance of doubt, all compositions claimed through the use of the term "comprising" may include any additional additive, adjuvant, or compound, whether polymeric or not, unless stated to the contrary. In contrast, the term "consisting essentially of" excludes from the scope of any succeeding recitation any other component, step, or procedure, except those that are not essential to operability. The term "consisting of" excludes any component, step, or procedure not specifically defined or listed.

[0060] Listing of Some Process and Composition Features A] A process for cleaning a metal surface, said process 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,

[0061] [ka] In the formula, 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, x is 1 to 5, and when x≧2, the R2 groups in the —(CH2—CHR2—O)— portion may all be the same or some or all may be different, and when some or all are different, —(CH2—CHR2—O) x - moiety may contain any combination of hydrogen and / or methyl and / or ethyl as at least two different R2 groups,

[0062] [ka] at least one etheramine selected from formula 1A and / or at least one etheramine selected from formula 1B, wherein R4 is a monovalent carbon-containing group having 1 to 10 carbon atoms and R5 is hydrogen, methyl, or ethyl; b) applying to a metal surface a composition comprising:

[0063] B] The process described in 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.

[0064] C] The process described in 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.

[0065] D] A process described in any one of A] to C] above, wherein for formula 1A, when x≧2, the R2 groups in the —(CH2—CHR2—O)— moieties are all the same.

[0066] E] For Formula 1A, when x≧2, some or all of the R groups in the —(CH—CHR—O)— moiety are different, and —(CH—CHR—O) x The process according to any one of A] to C] above, wherein the - moiety may contain any combination of hydrogen and / or methyl and / or ethyl as at least two different R2 groups.

[0067] F] The process described in any one of A] to E] above, wherein component b is a metal chelate.

[0068] G] The process described in any one of A] to F] above, wherein component b comprises a metal salt of ethylenediaminetetraacetic acid.

[0069] H] 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; R2 is hydrogen or methyl, further methyl; and R3 is hydrogen or methyl; The process of any one of A] to G] above, wherein for Formula 1B, R4 is an alkyl group, further a C1 to C5 alkyl group, further a C1 to C4 alkyl group, further a C1 to C3 alkyl group, and R5 is hydrogen or methyl.

[0070] I] The process described in any one of A] to H] above, wherein for formula 1A, x=1 or 2.

[0071] J] The process described in any one of A] to I] above, wherein for formula 1A, x=1 or 2, and when x=2, R2 of each -(CH2-CHR2-O)- moiety is the same.

[0072] K] Component b has the following structures (1a) to (1j):

[0073] [ka] The process according to any one of A] to J] above, wherein the process is selected from the following:

[0074] L] The process described in 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.

[0075] M] The process 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.

[0076] N] The process described in 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.

[0077] O] The process described in 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.

[0078] P] The process described in 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.

[0079] Q] The process 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.

[0080] R] The process described in any one of A] to Q] above, wherein the temperature of the composition when applied to the metal surface is 20°C to 30°C.

[0081] A2] 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,

[0082] [ka] In the formula, 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, x is 1 to 5, and when x≧2, the R2 groups in the —(CH2—CHR2—O)— portion may all be the same or some or all may be different, and when some or all are different, —(CH2—CHR2—O) x - moiety may contain any combination of hydrogen and / or methyl and / or ethyl as at least two different R2 groups,

[0083] [ka] at least one etheramine selected from formula 1A and / or at least one etheramine selected from formula 1B, wherein R4 is a monovalent carbon-containing group having 1 to 10 carbon atoms and R5 is hydrogen, methyl, or ethyl; b) at least one chelate.

[0084] 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.

[0085] C2] The 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.

[0086] D2] The composition according to any one of the above A2] to C2], wherein, in formula 1A, when x≧2, all R2 groups in the —(CH2—CHR2—O)— moieties are the same.

[0087] E2] For Formula 1A, when x≧2, some or all of the R2 groups in the —(CH2—CHR2—O)— moiety are different, and —(CH2—CHR2—O) x The composition according to any one of A2] to C2] above, wherein the - moiety may contain any combination of hydrogen and / or methyl and / or ethyl as at least two different R2 groups.

[0088] F2] The composition according to any one of A2] to E2] above, wherein component b is a metal chelate.

[0089] G2] The composition according to any one of A2] to F2] above, wherein component b includes a metal salt of ethylenediaminetetraacetic acid.

[0090] H2] 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; R2 is hydrogen or methyl, further methyl; and R3 is hydrogen or methyl; The composition according to any one of A2] to G2] above, wherein in formula 1B, R4 is an alkyl group, further a C1 to C5 alkyl group, further a C1 to C4 alkyl group, further a C1 to C3 alkyl group, and R5 is hydrogen or methyl.

[0091] I2] The composition according to any one of A2] to H2] above, wherein, in formula 1A, x=1 or 2.

[0092] J2] A composition according to any one of A2] to I2] above, wherein for formula 1A, x=1 or 2, and when x=2, R2 in each -(CH2-CHR2-O)- moiety is the same.

[0093] K2] The 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:

[0094] L2] The composition described in 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.

[0095] M2] The 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.

[0096] N2] The 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.

[0097] O2] The 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.

[0098] P2] The 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.

[0099] Q2] The composition according to any one of A2] to P2] above, wherein the composition is used to clean a metal surface.

[0100] 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.

[0101] A3] The process described in any one of A] to R] above, or the composition described in any one of A2] to R2] above, wherein the composition further comprises water.

[0102] B3] The process described in any one of A] to R] or A3] above, or the composition described in any one of A2] to R2] or A3] above, wherein the composition further comprises at least one surfactant as component c.

[0103] C3] The process described in B3] above, or the composition described in B3] above, wherein 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.

[0104] D3] The process of B3] or C3] above, or the composition of B3] or C3] above, wherein 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.

[0105] E3] The process according to any one of B3] to D3] above, or the composition according to any one of B3] to D3] above, wherein 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, further from at least one nonionic surfactant or at least one anionic surfactant, further from at least one nonionic surfactant.

[0106] F3] The process described in any one of A] to R] or A3] to E3] above, or the composition described in any one of A2] to R2] or A3] to E3] above, wherein the composition further comprises at least one alkali salt as component d.

[0107] G3] The process of F3] above, or the composition of F3] above, wherein 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.

[0108] H3] The process of F3] or G3] above, or the composition of F3] or G3] above, wherein 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.

[0109] I3] The process described in any one of A] to R] or A3] to H3] above, or the composition described in any one of A2] to R2] or A3] to H3] above, wherein each etheramine of component a independently has a molecular weight of ≧60, or ≧65, or ≧70 wt%, or ≧75, or ≧80, or ≧85 g / mol.

[0110] J3] The process described in any one of A] to R] or A3] to I3] above, or the composition described in any one of A2] to R2] or A3] to 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.

[0111] K3] The process of any one of A] to R] or A3] to J3] above, or the composition of any one of A2] to R2] or A3] to J3] above, wherein the sum of components a and 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.

[0112] L3] The process of any one of A] to R] or A3] to K3] above, or the composition of any one of A2] to R2] or A3] to K3] above, wherein the sum of components a and 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.

[0113] M3] The process of any one of B3] to L3] above, or the composition of any one of B3] to L3] above, wherein the sum of components a and 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.

[0114] N3] The process described in any one of B3] to M3] above, or the composition described in any one of B3] to M3] above, wherein the sum of components a and 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.

[0115] O3] The process of any one of A] to R] or A3] to N3] above, or the composition of any one of A2] to R2] or A3] to N3] above, wherein the sum of component a, 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.

[0116] P3] The process described in any one of A] to R] or A3] to O3] above, or the composition described in any one of A2] to R2] or A3] to 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.

[0117] Q3] The process described in any one of B3] to P3] above, or the composition described in any one of B3] to P3] above, wherein the sum of components a, b, c, and water is present in an amount of ≧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.

[0118] R3] The process described in any one of B3] to Q3] above, or the composition described in any one of B3] to Q3] above, wherein the sum of components a, b, c, and water is present in an amount of ≦100 wt. % or ≦99 wt. % based on the weight of the composition.

[0119] S3] The composition has a "% oil removal" determined from the formula [(W2-W3) / (W2-W1)] x 100 of ≥ 40%, or ≥ 45%, or ≥ 50%, or ≥ 52%, or ≥ 54%, or ≥ 56%, or ≥ 58%, or ≥ 60%, where each of W1, W2, and W3 is defined herein (see Experimental Section), a process described in any one of A]-R] or A3]-R3] above, or a composition described in any one of A2]-R2] or A3]-R3] above.

[0120] T3] The process described in any one of A]-R] or A3]-S3] above, or the composition described in any one of A2]-R2] or A3]-S3] above, wherein the composition has a "% Oil Removal" of ≦100%.

[0121] U3] The process of any one of A]-R] or A3]-T3] above, or the composition of 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 60 seconds of circulation as described herein (see Experimental Section).

[0122] V3] The process of any one of A]-R] or A3]-U3] above, or the composition of any one of A2]-R2] or A3]-U3] above, wherein the composition, as described herein, produces a foam height of ≥ 5.0 cm after 60 seconds of circulation.

[0123] W3] The process of any one of A]-R] or A3]-V3] above, or the composition of any one of A2]-R2] or A3]-V3] above, wherein the composition separates 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 emulsification evaluation as described herein (see experimental section).

[0124] X3] The process described in any one of A] to R] or A3] to W3] above, or the composition described in any one of A2] to R2] or A3] to W3] above, wherein the composition separates from the oil and fills a volume of "10 mL" within a time of ≧2 seconds.

[0125] Y3] The process of any one of A]-R] or A3]-X3] above, or the composition of any one of A2]-R2] or A3]-X3] above, wherein the composition separates from the oil and fills a "5 mL" volume in a time of ≦30, or ≦28, or ≦25, or ≦22, or ≦20, or ≦18, or ≦16, or ≦14, or ≦12 seconds as determined by emulsification evaluation as described herein (see Experimental Section).

[0126] Z3] The process described in any one of A] to R] or A3] to Y3] above, or the composition described in any one of A2] to R2] or A3] to Y3] above, wherein the composition separates from the oil and fills a volume of "5 mL" within a time of ≧1 second.

[0127] experiment Synthesis of etheramines Reductive Amination Catalyst Each etheramine (Formula 1A and Formula 1B) described herein was produced using a glycol ether starting material followed by a reductive amination reaction on the glycol ether. A solution containing 236 g of Ni(NO)6H2O, 69 g of Co(NO)26H2O, 51 g of Cu(NO)22.5H2O, 20.4 g of NH4ReO4, and 59 g of H3BO3 was prepared in 700 mL of boiling deionized water. This boiling solution was poured into a 1 L beaker containing 150 g of catalyst support (1 / 16 inch spherical alumina support available from Universal Oil Products (UOP) under the trade name SAB-17). The support mixture was thoroughly mixed to ensure complete and uniform wetting of the support. The impregnated support is dried in a crucible at 120° C. for 3 hours with frequent stirring, then calcined in an air furnace at 300° C. for 3 hours, and then stored in an oven at 120° C. until activation.

[0128] The NiCoCuReB catalyst thus prepared is reduced in an activation chamber. The chamber temperature is slowly heated to 350°C over 2 hours while a pure hydrogen gas flow is passed through the chamber at approximately 30 mL / min. After the temperature reaches 350°C, activation is continued for 4 hours. Heating is then stopped, but the hydrogen flow is maintained until the chamber cools to room temperature. The activated catalyst (pyrophoric) is carefully transferred to a bottle in a nitrogen-filled dry box and stored there until use. The total metal loading of the resulting catalyst is 40 wt%. It contains a Ni / Co / Cu / Re / B metal weight ratio of 48 / 14 / 14 / 14 / 10, as well as Ni / Co and Ni / Cu weight ratios of 3.4.

[0129] The catalyst is loaded into the reactor in a nitrogen-filled dry box (oxygen <10 ppm) to prevent deactivation. Ceramic ball packing (1 / 8 inch) is used above and below the catalyst to position the catalyst bed in the constant temperature zone of the reactor.

[0130] Reductive amination of glycol ethers A continuous plug-flow reactor system is used for all reductive amination reactions. An ISCO Model 500D continuous-feed syringe pump system (maximum pressure 3750 psi) with TEFLON seals is used for the glycol ether solvent feed. A second ISCO Model 500D syringe pump system is used to provide a constant flow of ammonia. A Brooks Model 5850TR mass flow controller (maximum pressure 4500 psi) is used in conjunction with a Model 5896 digital readout box to control the hydrogen flow from a 6000 psig cylinder. A VERIFLO differential pressure regulator (AP = 50 psig) is used to adjust the inlet / outlet bias pressure of the flow transducer. The three feed streams are mixed and fed through a coiled preheater (1 / 8 inch OD, 316 stainless steel tubing, 15 feet long) into the tubular packed-bed reactor. This 316 stainless steel Kuentzel-type reactor (1.25 inch internal diameter, 250 mL capacity) manufactured by Autoclave Engineers is rated at 9,500 psi / 500°F and contains 200 mL of catalyst. Catalyst temperature is monitored using a 1 / 16 inch diameter thermocouple inserted from the top of the reactor into the center of the catalyst bed. The reactor volume not filled with catalyst is packed with glass wool. Reactor pressure is maintained by a back-pressure control valve (BPCV, maximum pressure = 6000 psi) manufactured by TESCOM Corporation. From the BPCV, product solution is collected in a sample bottle.

[0131] The plug flow reactor system is equipped with several automatic shutdown features to ensure 24-hour unattended operation. The reactor controller has a high-temperature shut-off sensor, and both ISCO feed pumps have high-pressure shut-off capability. The hydrogen supply line is shut off by an actuator driven by two electric solenoid valves whenever the high-pressure or high-temperature sensors detect reactor pressure or temperature exceeding their respective limits.

[0132] The aminated glycol ethers are isolated as a crude reaction mixture containing residual ammonia, water, and some glycol ether starting material. The ammonia is removed by bubbling nitrogen through the crude mixture or by using an evaporator (e.g., a Buchi rotary evaporator) at low pressure. Further purification of each product is achieved by distillation.

[0133] Typical reaction conditions The reactor conditions used for the reductive amination of glycol ethers are as follows: reactor temperature = 170-215°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, and hydrogen level = 3-5 mole percent.

[0134] purification To purify, 1-methoxy-2-aminopropane (or 1-methoxypropan-2-amine) is first treated with NaOH pellets to create a separate aqueous layer, which is decanted before distillation to improve recovery. Analysis of purity is performed by acidimetric titration, Karl Fischer water titration, gas chromatography, and / or nuclear magnetic resonance spectroscopy.

[0135] Most of the water in 1-methoxy-2-aminopropane is removed by adding NaOH pellets, which induces the formation of an aqueous caustic layer. In a typical experiment, 1-methoxy-2-aminopropane (2000 g) is added to a 3-L, three-necked flask with a narrow base, equipped with an overhead stirrer and a bottom stopper. With the stirrer running, NaOH pellets (273 g) are added portionwise to the flask in an amount that results in an NaOH concentration of approximately 12 weight percent relative to the combined 1-methoxy-2-aminopropane / NaOH mixture. The mixture is stirred overnight for a minimum of 12 hours. The stirring is stopped, and the phases are allowed to separate. The bottom aqueous layer, containing approximately 31 weight percent NaOH, is separated from the top organic layer, containing 1-methoxy-2-aminopropane. The resulting 1-methoxy-2-aminopropane contains approximately 5 weight percent water. The remaining ether amine is not dried using NaOH.

[0136] Each etheramine is distilled in either a 6 ft x 1.5 inch ID glass column or a 2 ft x 1 inch diameter glass column (see Table 1). Both columns are equipped with an overhead reflux splitter, packed with 0.25 inch ceramic saddles, and, apart from the scale, are identical in form and function. The etheramine is loaded into a flask of appropriate size for the amount of material available and attached to the bottom of the distillation column. For 2-butoxy-1-aminoethane and 1-butoxy-2-aminopropane, the column is flushed with nitrogen, placed under vacuum, and then heated. 1-Methoxy-2-aminopropane is flushed with nitrogen but distilled at atmospheric pressure. Light impurities are removed overhead first, followed by the desired etheramine. The sample is distilled until the sample level in the bottom flask is no longer sufficient to ensure adequate coverage of the built-in thermocouple well. Cuttings are removed at regular intervals, analyzed, and recombined based on purity. Information on the distillation parameters is provided in Table 1.

[0137] Triplicate analyses of 0.15 g aliquots of purified etheramine diluted in 60 mL of deionized water (DI water) are performed using a Mettler Toledo DL67 titrator equipped with a DG115-SC sensor and a standardized 0.1 M HCl titrant. Standardization of the HCl titrant is performed by titrating a known amount of potassium hydrogen phthalate with NaOH solution, followed by titrating the HCl using the standardized NaOH solution.

[0138] The purity of the ether amines (aminated glycol ethers) was determined using the following formula and the purity is reported in Table 1 (purity by acidimetric titration): {[(mL 0.1 M HCl to equivalence point) / 10 / gram of titrated sample)] / [1000 / molecular weight of aminated glycol ether]} x 100.

[0139] [Table 1]

[0140] The etheramines shown in Table 2 were prepared as described above. After removing the ammonia, the crude reaction mixture was purified by distillation. Two comparative amines are also shown in Table 2.

[0141] [Table 2]

[0142] Reagents and test strips The reagents and test strips are listed in Table 3 below.

[0143] [Table 3]

[0144] composition The compositions of the present invention and comparative compositions are shown in Tables 4A and 4B below. Each composition was prepared by mixing the listed reagents at room temperature. The required EDTA-4Na 4H2O was added to DI water and mixed until dissolved. The etheramine and LFE-635 were then added to the solution, and the final solution was mixed until a homogeneous suspension or complete dissolution was formed.

[0145] [Table 4] * Each weight percent is based on the weight of the composition.

[0146] [Table 5] * Each weight percent is based on the weight of the composition.

[0147] Tests and Results Metal cleaning performance evaluation A stainless steel (ss) specimen was washed under flowing DI water for approximately 10 seconds and then rinsed by spraying acetone onto the specimen from a squeeze bottle until all surfaces on the specimen were covered. The washed and rinsed specimen was blown dry at room temperature and then weighed. The weight of the dried ss specimen was recorded as W1.

[0148] The cleaning composition (45 g, see Table 4A or Table 4B) was added to a 50 mL PP bottle. The dried ss specimen was weighed, and stamping oil (0.20 g + / - 0.01 g) was applied to the top surface of the specimen with a dropper tube. The specimen was carefully rotated to ensure that the oil was evenly spread over the specimen surface. The weight of the soiled specimen was recorded as W2.

[0149] Using tweezers, the soiled test specimen was placed into the cleaning composition (50 mL bottle) and the timer was immediately started. After 5 minutes, the test specimen was removed from the composition and rinsed by placing the specimen in 200 mL of DI water (in a 250 mL beaker) for approximately 3-5 seconds.

[0150] The rinsed specimens were placed in a metal tray (with the "top" side facing up) on a laboratory benchtop, and the specimens were allowed to air dry at room temperature for one day. The weight of the dried specimens was recorded as W3. The percentage of oil removed by the cleaning compositions (or "% oil removal") was calculated using the formula [(W2-W3) / (W2-W1)] x 100. The results are shown in Figures 1 and 2. For Figure 1, three specimens were examined per composition, and the average was reported (Relative Standard Deviation (RSD) = 2.7%).

[0151] As can be seen in Figure 1, Examples 1-6 show comparable or better oil removal compared to 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 demonstrate that compositions of the present invention containing the described ether amines are good replacements for current amine products in metal cleaning agents.

[0152] As can be seen in Figure 2 (one specimen per additional composition), for the same etheramine, the composition having an etheramine to chelate weight ratio falling within the range of 0.40 to 200 (Example 3, a / b = 4.0) outperforms the respective compositions below (Example 7, a / b = 0.36) and above (Example 8, a / b = 250) this range.

[0153] Foaming evaluation The cleaning composition (750 mL, see Tables 4A and 4B) was poured into a glass tube of a circulation type foaming tester (see Figure 3, manufactured by Golden Chemical, Model GT-2). When no additional foam was observed on the surface of the composition in the tube, the tester was turned on (voltage = 27.8 V) and the cleaning composition was circulated to generate foam. Foam was generated for 1 minute, and the foam height was recorded at 15, 30, and 60 seconds. After 60 seconds, the tester (circulation) was stopped, and the foam height was recorded at 75, 90, 120, 180, 240, and 300 seconds. Examples 1 and 3-6 were compared with Comparative Examples 1 and 2. See Figures 4A and 4B.

[0154] As seen in FIG. 4A, Examples 1 and 3 each outperformed Comparative Example 1. In FIG. 4B, Examples 4 through 6 each outperformed Comparative Example 2. As shown in each figure, during the foam generation phase, the foam height of each of the compositions of the present invention did not increase as much as that of the comparative composition. Furthermore, after circulation was stopped, the residual foam level of the compositions of the present invention was lower than that of the comparative composition. The ability of a cleaning composition to generate a low 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 inadequate rinsing of the metal surface and / or bath overflow and spillage, leading to product waste. Furthermore, good foam control, as seen in each of the compositions of the present invention, reduces or eliminates the need for additional foam control agents.

[0155] Emulsification evaluation Paraffin liquid was used as the oil phase. The cleaning composition (20 mL, see Tables 4A and 4B) was added to a measuring cylinder (100 mL), followed by the addition of 20 mL of oil. The cylinder was shaken up and down 10 times, which constitutes one cycle. The "up and down" shaking was repeated for 5 cycles, with a 1-minute interval between cycles. After the 5 cycles were completed, 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. A longer separation time indicated stronger emulsification of the cleaning composition and oil. Example 1 was compared with Comparative Example 2. See Figure 5 (5 mL and 10 mL marks).

[0156] As can be seen in Figure 5, Example 1 had lower emulsification strength for oil compared to Comparative Example 2. Emulsification is usually related to chemical structure. Example 1 (PM Amine) and Comparative Example 2 (MPA) share the same molecular formula. PM Amine has a branched methyl group, while MPA has a linear structure, resulting in differences in oil emulsification. Example 1 (PM Amine) showed faster oil separation, which is beneficial for a long-lasting cleaning bath life. This characteristic is advantageous in metal cleaning processes, as the cleaning solution is expected to quickly separate from the oil after cleaning the metal. Strong binding with oil can result in a significant decrease in the effectiveness of the cleaning bath and therefore a shorter bath life. The results herein indicate that Example 1 is an optimal cleaning composition for efficient oil separation and longer bath life.

Claims

1. 1. A process for cleaning a metal surface, said process 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, 【Chemical 1】 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, x is 1 to 5, and when x≧2, is —(CH ２ The R2 groups in the —CHR2—O)— moiety may all be the same, or some or all may be different. When some or all are different, —(CH ２ —CHR2-O) ｘ - the moiety may contain any combination of hydrogen and / or methyl and / or ethyl as at least two different R2 groups, 【Chemistry 2】 at least one etheramine selected from formula 1A and / or at least one etheramine selected from formula 1B, wherein R4 is a monovalent carbon-containing group having 1 to 10 carbon atoms and R5 is hydrogen, methyl, or ethyl; b) at least one chelate.

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

3. 3. The process of claim 1 or 2, wherein component b is a metal chelate.

4. 4. The process of 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. Component a has the following structures (1a) to (1j): 【Chemistry 3】 The process according to any one of claims 1 to 4, wherein the process is selected from

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

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

9. The process 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, aluminium, copper or gold.

10. 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, 【Chemistry 4】 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, x is 1 to 5, and when x≧2, is —(CH ２ The R2 groups in the —CHR2—O)— moiety may all be the same, or some or all may be different. When some or all are different, —(CH ２ —CHR2-O) ｘ - the moiety may contain any combination of hydrogen and / or methyl and / or ethyl as at least two different R2 groups, 【Chemistry 5】 at least one etheramine selected from formula 1A and / or at least one etheramine selected from formula 1B, wherein R4 is a monovalent carbon-containing group having 1 to 10 carbon atoms and R5 is hydrogen, methyl, or ethyl; b) at least one chelate.

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

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

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

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

16. The composition of 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, further comprising water.

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

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

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

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