Composition and method of use for corrosion inhibitors on zinc-plated metals

Abstract

A method for preventing rust formation on a metal surface is provided. The method may include applying a polyamine to a metal surface and applying a compound of formula (I) or a salt thereof to the metal surface. The compositions and methods disclosed herein may be used to inhibit corrosion of metal surfaces in contact with aqueous systems (Formula I).

Description

[Technical Field]

[0001] 1. Technical field This disclosure generally relates to compositions and methods for suppressing white rust on galvanized metal surfaces in industrial water systems. More specifically, this disclosure relates to compositions comprising a 2-substituted benzimidazole alone or in combination with a polyamine-based component, which can be introduced onto a galvanized metal surface. [Background technology]

[0002] 2.Background technology Zinc plating is a protective zinc coating chemically bonded to a metal surface. The zinc coating protects the underlying metal from corrosion by providing a mechanical barrier and electrochemical resistance to the environment. Several zinc plating methods exist, including electroplating, continuous galvanizing, and hot-dip galvanizing. Many industrial water systems, such as cooling water circulation systems, have such zinc-plated surfaces. [Overview of the project] [Problems that the invention aims to solve]

[0003] A common problem with galvanized coatings is white rust, which appears as a white, waxy, fuzzy, or powdery, unprotective, porous deposit that rapidly forms on galvanized surfaces when the surface is exposed to moisture and / or wet conditions. White rust can cause significant damage to the zinc coating and also negatively impacts the appearance of the coating. If left untreated, white rust will continuously corrode the affected galvanized surface, eventually leading to premature failure of the coating. The presence of such unprotective, porous deposits on a galvanized surface can cause the surface to form more white rust and corrode more rapidly.

[0004] Current white rust prevention programs include a combination of pre-passivation of cooling towers and continuous water chemistry management to support the viability of the passive layer. In addition to the basic zinc carbonate protective layer, pretreatment with inorganic phosphates and chromate passivation is listed as a white rust inhibitor. Such inorganic solutions have limited effectiveness and are increasingly subject to federal and local regulations due to environmental concerns.

Means for Solving the Problem

[0005] Compositions containing polyamines and compounds of formula (I) or salts thereof are disclosed,

Chemical Formula

[0006] In some embodiments, X is independently hydrogen or halogen, R 1 is hydrogen, R 2 is absent, R3 CHR 4 That is the case.

[0007] In some embodiments, the compound of formula (I) is [ka] That is the case.

[0008] In some embodiments, the polyamine is poly[oxy(methyl)-1,2-ethanediyl],alpha-(2-aminomethylethyl)-omega-(2-aminomethyl-ethoxy)-) functionalized with 1,2-propanediol,3-chloro.

[0009] In another embodiment, a method is provided for preventing rust formation on a metal surface. This method may include applying a polyamine to the metal surface and applying a compound of formula (I) or a salt thereof to the metal surface. [ka] In the formula, X is independently hydrogen, halogen, or substituted or unsubstituted C. 1~5 It is an alkyl group, where m is 1, 2, 3, or 4, and R 1 C1-C are hydrogen, substituted or unsubstituted C1-C 12 Alkyl group, or substituted or unsubstituted C4-C6 aryl group, R 2 It is either absent, or contains hydrogen, substituted or unsubstituted C1-C 12 Alkyl group, or substituted or unsubstituted C4-C6 aryl group, R 3 is a bond or CHR 4 And R 4 Hydrogen, halogen, NR 5 R 6 , or OR 5 And in the formula, R 5 and R 6 These are, independently, hydrogen, substituted or unsubstituted C1-C 12 The alkyl group is an alkyl group, or a substituted or unsubstituted C4-C6 aryl group, where Z is independently nitrogen, CX, or N + R5 That is the case.

[0010] In some embodiments, the metal surface is a galvanized metal surface that is part of an industrial water system.

[0011] In some embodiments, the compound of formula (I) and the polyamine are applied to a metal surface by directly spraying an effective amount onto the metal surface.

[0012] In some embodiments, the compound of formula (I) and the polyamine are applied to a metal surface by immersing the metal surface in a solution containing the compound of formula (I) and the polyamine.

[0013] In some embodiments, this method may further include applying one or more compounds selected from the group consisting of other corrosion inhibitors, scale inhibitors, fluorescent tracers, water treatment polymers, and combinations thereof.

[0014] In some embodiments, this method may further include applying one or more other corrosion inhibitors selected from the group consisting of phosphates, phosphonates, phosphinates, silicates, molybdates, tungstates, borates, zinc and its salts, vanadates, chromates, polycarboxylates, and combinations thereof.

[0015] In some embodiments, this method may further include mixing the compound of formula (I) with a polyamine before applying it to a metal surface.

[0016] In some embodiments, the rust is white rust.

[0017] The foregoing outlines the features and technical advantages of this disclosure in order to provide a better understanding of the subsequent embodiments for carrying out the invention. Further features and advantages of this disclosure, which form the subject matter of the claims of this application, are described below. It should be understood by those skilled in the art that the concepts and specific embodiments disclosed can be readily used as a basis for modifying or designing other embodiments for carrying out the same purpose as this disclosure. It should also be recognized by those skilled in the art that such equivalent embodiments do not deviate from the spirit and scope of this disclosure as expressed in the appended claims. [Brief explanation of the drawing]

[0018] [Figure 1] This shows the average corrosion rate of zinc-plated discs exposed to various chemical treatments.

[0019] [Figure 2] This shows the average corrosion rate of zinc-plated discs exposed to low doses of chemical treatment. [Modes for carrying out the invention]

[0020] Various embodiments are described below. The relationships and functions of the various elements of the embodiments can be better understood by referring to the embodiments for carrying out the invention described below. However, the embodiments are not limited to those illustrated below. In certain examples, details that are not necessary for understanding the embodiments disclosed herein may be omitted.

[0021] "Alkyl" refers to linear or branched alkyl substituents. Examples of such substituents include methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, isoamyl, and hexyl.

[0022] "Aryl" refers to an unsubstituted or substituted aromatic carbocyclic substituent, as is commonly understood in this art, and "C6~C 10The term "aryl" includes phenyl and naphthyl. According to Huckel's law, the term "aryl" is understood to be used for cyclic substituents that are planar and contain 4n+2n electrons.

[0023] "Cycloalkyl" refers to a cyclic alkyl substituent containing, for example, about 3 to about 8 carbon atoms, preferably about 4 to about 7 carbon atoms, more preferably about 4 to about 6 carbon atoms. Examples of such substituents include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl. The cyclic alkyl group may be unsubstituted or may be further substituted with alkyl groups such as methyl or ethyl groups.

[0024] "Halogen" or "halo" refers to F, Cl, Br, and I.

[0025] A "heteroaryl" refers to a monocyclic or bicyclic 5- or 6-membered ring system. Heteroaryl groups are unsaturated and satisfy Hackel's law. Non-restrictive examples of heteroaryl groups include furanyl, thiophenyl, pyrrolyl, pyrazolyl, imidazolyl, 1,2,3-triazolyl, 1,2,4-triazolyl, isoxazolyl, oxazolyl, isothiazolyl, thiazolyl, 1,3,4-oxadiazole-2-yl, 1,2,4-oxadiazole-2-yl, 5-methyl-1,3,4-oxadiazole, 3-methyl-1,2,4-oxadiazole, pyridinyl, pyrimidinyl, pyrazinyl, triazinyl, benzofuranyl, benzothiophenyl, indolyl, quinolinyl, isoquinolinyl, benzimidazolyl, benzoxazolinyl, benzothiazolinyl, and quinazolinyl.

[0026] "Oxo" refers to an oxygen atom that is double-bonded to a carbon atom.

[0027] The compounds of this disclosure may be substituted with preferred substituents. As used herein, the term “preferred substituent” is intended to mean a chemically acceptable functional group, preferably a portion that does not negate the activity of the compound. Such preferred substituents include, but are not limited to, halo groups, perfluoroalkyl groups, perfluoroalkoxy groups, alkyl groups, alkenyl groups, alkynyl groups, hydroxy groups, oxo groups, mercapto groups, alkylthio groups, alkoxy groups, aryl or heteroaryl groups, aryloxy or heteroaryloxy groups, aralkyl or heteroaralkyl groups, aralkoxy or heteroaralkoxy groups, HO-(C=O)- groups, heterocyclic groups, cycloalkyl groups, amino groups, alkyl and dialkylamino groups, carbamoyl groups, alkylcarbonyl groups, alkoxycarbonyl groups, alkylaminocarbonyl groups, dialkylaminocarbonyl groups, arylcarbonyl groups, aryloxycarbonyl groups, alkylsulfonyl groups, and arylsulfonyl groups. In some embodiments, preferred substituents include halogens, unsubstituted C1-C1 12 Alkyl groups, unsubstituted C4-C6 aryl groups, or unsubstituted C1-C6 groups 10 Examples include alkoxy groups. Those skilled in the art will understand that many substituents can be substituted with further substituents.

[0028] In some embodiments, compositions comprising a polyamine and a compound of formula (I) or a salt thereof are disclosed. The compound of formula (I) has the following formula: [ka]

[0029] In some embodiments, X is independently hydrogen, halogen, or substituted or unsubstituted C. 1~5 It is an alkyl group, and m can be 1, 2, 3, or 4. In some embodiments, R 1 C1-C are hydrogen, substituted or unsubstituted C1-C 12 It may be an alkyl group, or a substituted or unsubstituted C4-C6 aryl group. In some embodiments, R2 It is either absent, or contains hydrogen, substituted or unsubstituted C1-C 12 It may be an alkyl group, or a substituted or unsubstituted C4-C6 aryl group. In some embodiments, R 3 is a bond or CHR 4 It is possible. In some embodiments, R 4 Hydrogen, halogen, NR 5 R 6 , or OR 5 It is possible. In some embodiments, R 5 and R 6 These are, independently, hydrogen, substituted or unsubstituted C1-C 12 It is an alkyl group, or a substituted or unsubstituted C4-C6 aryl group.

[0030] The X substituent or multiple X substituents can occupy any available position on the benzimidazole ring. Therefore, in certain embodiments, the X substituent or multiple X substituents may be located at positions 4, 5, 6, and / or 7 of benzimidazole. In certain embodiments, the X substituent is located at position 5.

[0031] The number of substituents m on X can be 1, 2, 3, or 4. When m is 2, 3, or 4, the substituents on X can occupy any open position and can be arranged ortho, meta, or para relative to each other.

[0032] In certain embodiments, the salt of the compound of formula (I) may be any salt, such as a chloride salt, bromide salt, iodide salt, sulfate, fluoride salt, perchlorate, acetate, trifluoroacetate, phosphate, nitrate, carbonate, bicarbonate, formate, chlorate, bromate, chlorite, thiosulfate, oxalate, cyanide salt, cyanate, tetrafluoroborate, etc. In some embodiments, the salt of the compound of formula (I) may be a hydrochloride salt or a sulfate salt.

[0033] In some embodiments, Z is independently nitrogen, CX, or N + R 5 That is,

[0034] In some embodiments, Z is CX.

[0035] In some embodiments, X is hydrogen and m is 4. In some embodiments, X does not exist.

[0036] In some embodiments, R 1 It is hydrogen.

[0037] In some embodiments, R 2 It does not exist.

[0038] In some embodiments, R 3 is a combination. In some aspects, R 3 CHR 4 That is the case.

[0039] In some embodiments, R 4 is hydrogen. In some embodiments, R 4 It is a halogen.

[0040] In some embodiments, R 4 , NR 5 R 6 In some embodiments, R 4 is OR 5 That is the case.

[0041] In some embodiments, R 5 This is either substitution or non-substitution C1~C 12 It is an alkyl group. In some embodiments, R 5 is hydrogen. In some embodiments, R 5 These are substituted or unsubstituted C4-C6 alkyl groups.

[0042] In some embodiments, one Z is nitrogen and the rest are CX.

[0043] In some embodiments, at least two Zs are nitrogen atoms, and the rest are CX atoms.

[0044] In some embodiments, R3 This is a bond, and at least one Z is nitrogen.

[0045] In some embodiments, X is independently hydrogen or halogen, and R 1 is hydrogen, and R 2 It does not exist, R 3 CHR 4 That is the case.

[0046] In some embodiments, the compound of formula (I) or a salt thereof is [ka] That is the case.

[0047] In some embodiments, the compound of formula (I) or a salt thereof is [ka] That is the case.

[0048] In some embodiments, the compound of formula (I) or a salt thereof is [ka] That is the case.

[0049] In some embodiments, the compound of formula (I) or a salt thereof is [ka] That is the case.

[0050] In some embodiments, the compound of formula (I) or a salt thereof is [ka] That is the case.

[0051] In some embodiments, the compound of formula (I) or a salt thereof is [ka] That is the case.

[0052] In some embodiments, the compound of formula (I) or a salt thereof is [ka] That is the case.

[0053] In some embodiments, the compound of formula (I) or a salt thereof is [ka] That is the case.

[0054] In some embodiments, the compound of formula (I) or a salt thereof is [ka] That is the case.

[0055] In some embodiments, the compound of formula (I) or a salt thereof is [ka] That is the case.

[0056] In some embodiments, the compound of formula (I) or a salt thereof is [ka] That is the case.

[0057] In some embodiments, the compound of formula (I) or a salt thereof is [ka] That is the case.

[0058] In some embodiments, the composition may comprise a compound of formula (Ia) or a salt thereof. [ka] In the formula, X is independently hydrogen, halogen, or substituted or unsubstituted C.1~5 is an alkyl group, m is 1, 2, 3, or 4, and R 1 is hydrogen, a substituted or unsubstituted C1-C 12 alkyl group, or a substituted or unsubstituted C4-C6 aryl group, and R 2 is absent, hydrogen, a substituted or unsubstituted C1-C 12 alkyl group, or a substituted or unsubstituted C4-C6 aryl group, and R 3 is a bond or CHR 4 . In some embodiments, R 4 is hydrogen, halogen, NR 5 R 6 , or OR 5 . In some embodiments, R 5 and R 6 are each independently hydrogen, a substituted or unsubstituted C1-C 12 alkyl group, or a substituted or unsubstituted C4-C6 aryl group.

[0059] In some embodiments, the compound or its salt is of formula (II),

Chemical formula

[0060] In some embodiments, Y is hydrogen.

[0061] In some embodiments, Y is independently hydrogen and halogen.

[0062] As described herein, m may be 1, 2, 3, or 4. When m is 2, 3, or 4, the X substituents can occupy any open position and may be arranged ortho, meta, or para relative to each other. The number n of Y substituents may be 1, 2, 3, or 4. When n is 2, 3, or 4, the Y substituents can occupy any open position and may be arranged ortho, meta, or para relative to each other.

[0063] In some embodiments, the concentration of the compound of formula (I), formula (Ia), or formula (II) or a salt thereof in the composition may be in the range of about 1% to about 50% by weight, about 5% to about 50% by weight, about 10% to about 50% by weight, about 15% to about 50% by weight, about 20% to about 50% by weight, about 20% to about 45% by weight, about 25% to about 45% by weight, or about 25% to about 40% by weight.

[0064] In some embodiments, the composition may include water.

[0065] In some embodiments, the composition may be a homogeneous mixture. In some embodiments, the composition may be a solution.

[0066] In some embodiments, the polyamine is poly[oxy(methyl)-1,2-ethanediyl],alpha-(2-aminomethylethyl)-omega-(2-aminomethyl-ethoxy)-) functionalized with 1,2-propanediol,3-chloro.

[0067] In some embodiments, the polyamine is formed from polyoxypropylenediamine. In some embodiments, the polyamine is derived from the formula [CH(OH)CH(OH)CH2]2N-[CH(CH3)CH2O] XThe compound is -N[CH2CH(OH)CH(OH)]2, where X is between 1 and approximately 20. In this embodiment, the amine group of the compound is hydroxyl-functionalized.

[0068] In some embodiments, polyamines are characterized by repeating oxypropylene units in the main chain and are prepared by reacting a compound having the chemical formula H2N-(CH(CH3)CH2O)Z-CH2CH(CH3)NH2 with glycidol (2,3-epoxy-1-propanol), where Z is 1 to 3.

[0069] In some embodiments, the composition may have a weight ratio of the compound of formula (I) to the polyamine of about 4:1. In some embodiments, the weight ratio is in the range of about 2:1 to about 6:1.

[0070] In other embodiments, a method is provided for preventing the formation of rust on a metal surface. This method may include applying a polyamine to the metal surface and applying a compound of formula (I) or a salt thereof to the metal surface.

[0071] This disclosure provides methods for using heterocyclic compounds and formulations containing heterocyclic compounds, which are particularly useful for suppressing the corrosion of metal components in industrial aqueous systems. In addition to aqueous systems, benzimidazoles capable of chelating with metals provide excellent resistance to metal corrosion. In particular, the addition of benzimidazole substituted with 2-pyridyl or benzyl alcohol to aqueous systems in contact with metal surfaces results in excellent corrosion suppression for metals such as copper. Furthermore, while benzotriazoles and benzimidazoles are generally unstable in the presence of halogen oxide compounds, the compounds of this disclosure can 1,2-chelate with metals to provide exemplary protection for metals in the presence of halogen oxide compounds. In particular, 2-(2-pyridyl)benzimidazole provides better protection against corrosion than benzimidazole, 2-phenylbenzimidazole, and tolyltriazole in the presence of halogen oxide compounds. While we do not wish to be bound by any particular theory, the compounds of this disclosure are thought to form a protective film that is essentially impenetrable to common halogen oxide compounds through bidentate chelation with the metal surface of the corrosion inhibitor. Therefore, in certain embodiments, the methods of this disclosure provide protection against metal corrosion in aqueous systems using halogen oxide compounds as biocides.

[0072] In some embodiments, the Disclosure provides methods for inhibiting or preventing corrosion of metal surfaces in contact with aqueous systems. These methods may include adding any of the compositions described herein to an aqueous system. For example, the compositions may include compounds of formula (I) and polyamines.

[0073] "Industrial water systems" refers to any system that circulates water. Non-exclusive examples of "industrial water systems" include cooling systems, boiler systems, heating systems, membrane systems, papermaking systems, or any other system that circulates water.

[0074] Compositions comprising polyamines and compounds of formula (I), (Ia), and / or (II) may provide corrosion protection for galvanized metals. These compositions may prevent the formation of rust. In some embodiments, the rust is white rust.

[0075] The term "white rust" refers to a type of corrosion product affecting galvanized surfaces, characterized by the accumulation of white, fuzzy, or waxy, unprotective zinc corrosion products that adhere to the zinc surface of galvanized steel.

[0076] One way to passivate a surface is to allow the zinc coating to develop a natural, non-porous surface of basic zinc carbonate during the initial startup of the cooling tower. This natural chemical barrier helps prevent or slow further rapid corrosion of the zinc coating from the environment and normal cooling tower operation. White rust is also a form of zinc carbonate that has a different porous structure, formation rate, and density compared to the protective zinc carbonate barrier described above.

[0077] The compounds of formulas (I), (Ia), and (II) can be added to an aqueous system at any dosage rate, but they are generally added to aqueous systems at dosage rates of about 0.01 ppm to about 500 ppm. In certain embodiments, the compounds of formulas (I), (Ia), or (II) are added to aqueous systems at dosage rates of about 0.01 ppm to about 100 ppm. In certain embodiments, compounds of formula (I), (Ia), or (II) are present in concentrations of approximately 0.01 ppm to 100 ppm, approximately 0.01 ppm to 75 ppm, approximately 0.01 ppm to 50 ppm, approximately 0.01 ppm to 25 ppm, approximately 0.01 ppm to 10 ppm, approximately 0.01 ppm to 5 ppm, approximately 0.1 ppm to 100 ppm, approximately 0.1 ppm to 75 ppm, approximately 0.1 ppm to 50 ppm, and approximately 0.1 ppm to 25 ppm. It is added to an aqueous system at a dosage rate of approximately 0.1 ppm to 10 ppm, approximately 0.1 ppm to 5 ppm, approximately 1 ppm to 100 ppm, approximately 1 ppm to 75 ppm, approximately 1 ppm to 50 ppm, approximately 1 ppm to 25 ppm, approximately 1 ppm to 10 ppm, approximately 5 ppm to 100 ppm, approximately 10 ppm to 100 ppm, approximately 25 ppm to 100 ppm, approximately 50 ppm to 100 ppm, or approximately 80 ppm to 100 ppm.

[0078] In certain embodiments, the aqueous system is a cooling system. The cooling system may be a closed-loop or open-loop cooling system. In certain embodiments, the compound of formula (I), (Ia), or (II) is added to a closed-loop cooling system at a dosing rate of about 0.01 ppm to about 200 ppm. In certain embodiments, the compound of formula (I), (Ia), or (II) is added to an open-loop cooling system at a dosing rate of about 0.01 ppm to about 20 ppm.

[0079] The compounds of formulas (I), (Ia), and (II) are brought into contact with a metal surface by any suitable method. In certain embodiments, a solution of the compound of formula (I), (Ia), or (II) is brought into contact with a metal surface by immersion, spraying, or other coating techniques. In certain embodiments, a solution of the compound of formula (I), (Ia), or (II) is introduced into water in an aqueous system by any conventional method and supplied to the aqueous system either periodically or on a continuous basis.

[0080] In one embodiment, introducing a composition onto a galvanized surface involves incorporating this method into a hot-dip manufacturing process. For example, the metal is first immersed in molten zinc at 450°C (a temperature at which iron / steel and zinc share a great affinity), where the metal is protected by a zinc coating. The next step in the manufacturing process is to immerse the zinc-coated metal in a composition comprising a compound of formula (I), (Ia), or (II) and a polyamine.

[0081] In another embodiment, such introduction onto a metal surface involves directly spraying a solution of the composition onto the surface, including the surface, in an industrial water system. In one embodiment, the composition is mixed with a foaming agent to form a mixture, which is then sprayed onto a galvanized metal surface using any suitable spraying device. Examples of foaming agents include surfactants such as alkoxylated alcohols, polyethylene glycol, or any other suitable surfactant. In an alternative embodiment, the composition may be applied physically to the surface by rolling with a paint roller or the like, brushing with a paintbrush or the like, wiping with a mop or the like, or by any other suitable method or technique.

[0082] In some embodiments, the compounds of formula (I), (Ia), or (II) and the polyamines can be applied to a metal surface independently and in any order.

[0083] In another embodiment, the composition is reintroduced onto the surface one or more times after one or more time intervals to “overlay” the barrier or “repassivate” the surface. Continuous overlay steps are also contemplated to renew the corrosion-inhibiting barrier and / or repassivate the galvanized surface. As determined on a case-by-case basis, this method may comprise several different compositions, and overlaying the barrier may involve introducing one or more different corrosion-reducing compositions onto the galvanized metal surface.

[0084] In some embodiments, the compositions disclosed herein may include fluorescent organic compounds. In certain embodiments, the fluorescent organic compounds may be selected from rhodamine or its derivatives, acridine dyes, fluorescein or its derivatives, and combinations thereof. In certain embodiments, the compositions disclosed herein may include fluorescently tagged polymers.

[0085] Those skilled in the art will understand that polyamines and compounds of formula (I), (Ia), or (II) can be added to aqueous systems alone or in combination with other corrosion inhibitors or treatment chemicals. Numerous corrosion inhibitors comprising two or more compounds of formula (I), (Ia), and / or formula (II) can be administered as combined corrosion inhibitor formulations, or each corrosion inhibitor can be added individually. Furthermore, compounds of formula (I), (Ia), or (II) can be added to aqueous systems in combination with a variety of additional corrosion inhibitors, including but not limited to triazoles, benzotriazoles (e.g., benzotriazole or toltriazole), benzimidazoles, orthophosphates, polyphosphates, phosphonates, molybdates, silicates, oximes, and nitrites. The compounds of formulas (I), (Ia), and (II) can also be added to aqueous systems in combination with various additional additives such as treatment polymers, antimicrobial agents, anti-scaling agents, colorants, fillers, buffers, surfactants, viscosity modifiers, chelating agents, dispersants, deodorants, masking agents, oxygen absorbers, and indicator dyes.

[0086] The compositions of this disclosure may comprise about 0 to 10 weight percent of a polyamine and about 10 to about 100 weight percent of a compound of formula (I), with the remainder being auxiliary components and water. More preferably, the polyamine is present in about 2 to 10 weight percent, the compound of formula (I) is present in about 20 to about 100 weight percent, with the remainder being auxiliary components and water. A preferred blend comprises about 10 weight percent of a polyamine and about 90 weight percent of a compound of formula (I). More preferably, the blend comprises about 40 weight percent of a polyamine and about 60 weight percent of a compound of formula (I). Most preferably, the blend consists of about 60 weight percent of a polyamine and about 40 weight percent of a compound of formula (I).

[0087] The dosage range for adding or applying polyamines may be in the range of 0.01 ppm to about 200 ppm. In some embodiments, the polyamine dosage may be in the range of about 0.01 ppm to about 50 ppm, about 0.01 ppm to about 10 ppm, or about 0.01 ppm to about 5 ppm. In some embodiments, the polyamine dosage may be about 0.5 ppm.

[0088] The dosage range for adding or applying the compound of formula (I) may be in the range of 0.01 ppm to about 200 ppm. In some embodiments, the dosage may be in the range of about 0.01 ppm to about 50 ppm, about 0.01 ppm to about 10 ppm, or about 0.01 ppm to about 5 ppm. In some embodiments, the dosage may be about 2 ppm. [Examples]

[0089] When the working electrode was a galvanized disk, a three-electrode electrochemical cell was used. Two steel electrodes functioned as one reference electrode and the other as the counter electrode. The test solution was a mixture of corrosive water and the candidate inhibitor to be evaluated. The corrosive water generally contained 200 ppm calcium (as CaCO3), 200 ppm magnesium (as CaCO3), 500 ppm chloride, and 150 ppm bicarbonate. 190 ml of the test solution was used in each test and continuously stirred using a magnetic stirrer while maintaining a temperature of 80 ± 2°F. Measurements were taken at 5-hour intervals until the galvanized surface of the working electrode was damaged at a high corrosion rate.

[0090] The effectiveness of the corrosion inhibitor composition was determined by the electrochemical corrosion rate measured by polarization resistance. The cathode and anode gradients were determined by a Tafel scan before performing polarization. The scan was performed using a Gamry Potentiostat / Galvanostat set to 0.1 mV / sec.

[0091] Example 1

[0092] The total amount of chemicals (corrosion inhibitor + polyamine) administered in this experiment was approximately 10 ppm. The weight ratio of corrosion inhibitor to polyamine was approximately 1:1. Figure 1 shows the average corrosion rate in mpy for various treatments. Compound YMI refers to Compound 1 shown below. TT refers to tritriazole, and H0680 is poly[oxy(methyl)-1,2-ethanediyl],alpha-(2-aminomethylethyl)-omega-(2-aminomethyl-ethoxy)-) functionalized with 1,2-propanediol,3-chloro. [ka]

[0093] Example 2

[0094] The total amount of chemicals (corrosion inhibitor + polyamine) administered in this experiment was approximately 2.5 ppm. The weight ratio of corrosion inhibitor to polyamine was approximately 4:1. Figure 2 shows the average corrosion rate in mpy for various treatments.

[0095] Any composition disclosed herein may contain, consist of, or essentially consist of any of the compounds / components disclosed herein. According to this disclosure, phrases such as “consist essentially of,” “consists essentially of,” and “consisting essentially of” limit the scope of the claims to specific materials or steps and materials or steps that do not substantially affect the basic and novel features of the claimed invention.

[0096] As used herein, the term “approximately” means a cited value that is within the error resulting from the standard deviation observed in each of those test measurements, and if those errors cannot be determined, “approximately” means within 10% of the cited value.

[0097] All compositions and methods disclosed and claimed herein can be prepared and performed without undue experimentation, taking into consideration this disclosure. The present invention can be embodied in many different forms, and certain preferred embodiments of the invention are described in detail herein. This disclosure is illustrative of the principles of the invention and is not intended to limit the invention to the specific embodiments illustrated. Furthermore, unless expressly stated otherwise, the use of the term “one (a)” is intended to include “at least one” or “one or more.” For example, “a certain compound” is intended to include “at least one compound” or “one or more compounds.”

[0098] Any range given by either an absolute or approximate term is intended to encompass both, and any definitions used herein are intended to clarify, not limit. Numerical ranges and parameters that specify the broad scope of the invention are approximate, but the numerical values ​​specified in specific examples are reported as accurately as possible. However, any numerical value inherently contains a certain error that inevitably results from the standard deviation observed in their respective test measurements. Furthermore, all ranges disclosed herein should be understood to encompass all subranges contained therein (including all decimal and whole values).

[0099] Furthermore, the present invention encompasses any possible combination of some or all of the various embodiments described herein. It should also be understood that various changes and modifications to the preferred embodiments of the present invention described herein will be obvious to those skilled in the art. Such changes and modifications may be made without departing from the spirit and scope of the invention and without diminishing its intended advantages. Accordingly, such changes and modifications are intended to be covered by the appended claims. Examples of embodiments of the present disclosure are listed in the following items [1] to

[15] . [1] A method for preventing the formation of rust on a metal surface, Applying the compound of formula (I) to the aforementioned metal surface,

change

change

[10] The method according to any one of claims 1 to 9, wherein the rust is white rust.

[11] The method according to any one of claims 1 to 10, further comprising mixing the compound of formula (I) with the polyamine before applying it to the metal surface.

[12] A composition for inhibiting corrosion, Polyamines and, The compound of formula (I) and,

change

[13] X is independently either hydrogen or a halogen. R 1 However, it is hydrogen, R 2 However, it does not exist. R 3 However, CHR 4 The composition according to claim 12.

[14] The compound of formula (I) above,

change

[15] The composition according to any one of claims 12 to 14, wherein the polyamine is poly[oxy(methyl)-1,2-ethanediyl],alpha-(2-aminomethylethyl)-omega-(2-aminomethyl-ethoxy)-) functionalized with 1,2-propanediol,3-chloro.

Claims

1. A method for preventing rust formation on a galvanized metal surface, Applying the compound of formula (I) to the aforementioned zinc-plated metal surface, 【Chemistry 1】 The method includes applying a polyamine having a polyoxypropylene main chain onto the galvanized metal surface, wherein the polyamine comprises alpha-(2-aminomethylethyl)-omega-(2-aminomethyl-ethoxy)-poly[oxy(methyl)-1,2-ethanediyl] functionalized with 3-chloro-1,2-propanediol. During the ceremony, X is independently hydrogen, halogen, or substituted or unsubstituted C. １～５ It is an alkyl group, m is 1, 2, 3, or 4, R １ However, hydrogen, substituted or unsubstituted C １ ~C １２ Alkyl alkyl groups, or substituted or unsubstituted C ４ ~C ６ It is an aryl group, R ２ is absent, hydrogen, substituted or unsubstituted C １ to C １２ alkyl group, or substituted or unsubstituted C ４ to C ６ aryl group, and R ３ However, binding or CHR ４ And, R ４ However, hydrogen, halogen, NR ５ R ６ , or OR ５ And in the formula, R ５ and R ６ However, each is independent of hydrogen, substituted or unsubstituted carbon. １ ~C １２ Alkyl alkyl groups, or substituted or unsubstituted C ４ ~C ６ It is an aryl group, Z is independently nitrogen, CX, or N ＋ R ５ The method.

2. Each of X is independently either hydrogen or a halogen. R １ However, it is hydrogen, R ２ However, it does not exist. R ３ However, CHR ４ The method according to claim 1.

3. The compound of formula (I) above, 【Chemistry 2】 The method according to claim 1 or 2.

4. The method according to any one of claims 1 to 3, wherein the polyamine is alpha-(2-aminomethylethyl)-omega-(2-aminomethyl-ethoxy)-poly[oxy(methyl)-1,2-ethanediyl] functionalized with 3-chloro-1,2-propanediol.

5. The method according to any one of claims 1 to 4, wherein the galvanized metal surface is part of an industrial water system.

6. The method according to any one of claims 1 to 5, wherein the compound of formula (I) and the polyamine are applied to the galvanized metal surface by spraying them directly onto the galvanized metal surface.

7. The method according to any one of claims 1 to 5, wherein the compound of formula (I) and the polyamine are applied to the galvanized metal surface by immersing the galvanized metal surface in a solution containing the compound of formula (I) and the polyamine.

8. The method according to any one of claims 1 to 7, further comprising applying one or more compounds selected from the group consisting of other corrosion inhibitors, scale inhibitors, fluorescent tracers, water treatment polymers, and combinations thereof.

9. The method according to any one of claims 1 to 7, further comprising applying one or more other corrosion inhibitors selected from the group consisting of phosphates, phosphonates, phosphinates, silicates, molybdates, tungstates, borates, zinc and its salts, vanadates, chromates, polycarboxylates, and combinations thereof.

10. The method according to any one of claims 1 to 9, wherein the rust is white rust.

11. The method according to any one of claims 1 to 10, further comprising mixing the compound of formula (I) with the polyamine before applying it to the galvanized metal surface.

12. A composition for suppressing corrosion of a galvanized metal surface, wherein the composition is Polyamines having a polyoxypropylene main chain, The compound of formula (I) comprises, wherein the polyamine comprises alpha-(2-aminomethylethyl)-omega-(2-aminomethyl-ethoxy)-poly[oxy(methyl)-1,2-ethanediyl] functionalized with 3-chloro-1,2-propanediol, 【Transformation 3】 During the ceremony, X is independently hydrogen, halogen, or substituted or unsubstituted C. １～５ It is an alkyl group, m is 1, 2, 3, or 4, R １ However, hydrogen, substituted or unsubstituted C １ ~C １２ Alkyl alkyl groups, or substituted or unsubstituted C ４ ~C ６ It is an aryl group, R ２ However, it is either absent, or is hydrogen, substituted or unsubstituted C １ ~C １２ Alkyl alkyl groups, or substituted or unsubstituted C ４ ~C ６ It is an aryl group, R ３ However, binding or CHR ４ And, R ４ However, hydrogen, halogen, NR ５ R ６ , or OR ５ And in the formula, R ５ and R ６ However, each is independent of hydrogen, substituted or unsubstituted carbon. １ ~C １２ Alkyl alkyl groups, or substituted or unsubstituted C ４ ~C ６ It is an aryl group, Z is independently nitrogen, CX, or N ＋ R ５ A composition.

13. Each of X is independently either hydrogen or a halogen. R １ However, it is hydrogen, R ２ However, it does not exist. R ３ However, CHR ４ The composition according to claim 12.

14. The compound of formula (I) above, 【Chemistry 4】 The composition according to claim 12 or 13.

15. The composition according to any one of claims 12 to 14, wherein the polyamine is alpha-(2-aminomethylethyl)-omega-(2-aminomethyl-ethoxy)-poly[oxy(methyl)-1,2-ethanediyl] functionalized with 3-chloro-1,2-propanediol.

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