Galvanized metal corrosion inhibitor compositions and methods of use

Abstract

A method for preventing rust on a metal surface is provided. The 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. The compositions and methods disclosed herein can be used to inhibit corrosion of metal surfaces in contact with aqueous systems (Formula I).

Description

Background Art 1. Technical Field

[0002] The present disclosure generally relates to compositions and methods for inhibiting white rust on galvanized metal surfaces in industrial water systems. More specifically, the present disclosure relates to a composition comprising a 2-substituted benzimidazole, alone or in combination with a polyamine-based component, wherein the composition can be introduced onto the galvanized metal surface.

[0003] 2. Description of Related Technology

[0004] Galvanizing is a protective zinc coating that chemically bonds to a metal surface. The zinc coating protects the underlying metal from corrosion by providing a mechanical barrier to the environment as well as electrochemical resistance. Several galvanizing methods exist, including electroplating, continuous galvanizing, and hot-dip galvanizing. Many industrial water systems, such as cooling water circulation systems, feature this type of galvanized surface.

[0005] A common problem with galvanized coatings is white rust, a non-protective, porous deposit that appears as a white, waxy, fluffy, or powdery substance. It forms rapidly on galvanized surfaces when the surface is exposed to heat and / or humidity. White rust can cause considerable damage to the zinc coating and is also detrimental to the coating's appearance. If left untreated, white rust will continue to corrode the affected galvanized surface, eventually leading to premature failure of the coating. Due to the presence of this non-protective, porous deposit on the galvanized surface, the surface may develop more white rust and corrode rapidly.

[0006] Current white rust corrosion prevention programs involve combining cooling tower pre-passivation with ongoing water chemistry management to maintain the viability of the passivation layer. In addition to a protective layer of basic zinc carbonate, white rust prevention includes an inorganic phosphate pre-treatment and a chromate passivation. This inorganic solution has limited effectiveness and is inherently opposed by federal and local regulations due to environmental concerns. Summary of the Invention

[0007] Disclosed is a composition comprising a polyamine and a compound of formula (I) or a salt thereof,

[0008]

[0009] wherein X is independently hydrogen, halogen or substituted or unsubstituted C 1-5 Alkyl; m is 1, 2, 3 or 4; R 1 is hydrogen, substituted or unsubstituted C1-C 12 Alkyl or substituted or unsubstituted C4-C6 aryl; R 2 is absent, hydrogen, substituted or unsubstituted C1-C 12 Alkyl or substituted or unsubstituted C4-C6 aryl; R 3 Yes key or CHR4 ; R 4 For hydrogen, halogen, NR 5 R 6 OR 5 ; where R 5 and R 6 are each independently hydrogen, substituted or unsubstituted C1-C 12 alkyl or substituted or unsubstituted C4-C6 aryl; and Z is independently nitrogen, CX or N + R 5 .

[0010] In some aspects, X is independently hydrogen or halogen, R 1 is hydrogen, R 2 does not exist, and R 3 For CHR 4 .

[0011] In some aspects, the compound of formula (I) is

[0012]

[0013] In some aspects, the polyamine is poly[oxy(methyl)-1,2-ethanediyl],α-(2-aminomethylethyl)-ω-(2-aminomethyl-ethoxy)-) functionalized with 3-chloro-1,2-propanediol.

[0014] In other aspects, a method for preventing rust on a metal surface is provided. The method may comprise applying a polyamine to the metal surface and applying a compound of formula (I) or a salt thereof to the metal surface,

[0015]

[0016] wherein X is independently hydrogen, halogen or substituted or unsubstituted C 1-5 Alkyl; m is 1, 2, 3 or 4; R 1 is hydrogen, substituted or unsubstituted C1-C 12 Alkyl or substituted or unsubstituted C4-C6 aryl; R 2 is absent, hydrogen, substituted or unsubstituted C1-C 12 Alkyl or substituted or unsubstituted C4-C6 aryl; R 3 Yes key or CHR 4 ; R 4 For hydrogen, halogen, NR 5 R 6 OR 5 ; where R 5 and R 6 are each independently hydrogen, substituted or unsubstituted C1-C 12alkyl or substituted or unsubstituted C4-C6 aryl; and Z is independently nitrogen, CX or N + R 5 .

[0017] In some aspects, the metal surface is a galvanized metal surface that is part of an industrial water system.

[0018] In some aspects, the compound of formula (I) and the polyamine are applied to the metal surface by spraying an effective amount thereof directly onto the metal surface.

[0019] In some aspects, the compound of formula (I) and the polyamine are applied to the metal surface by immersing the metal surface in a solution containing the compound of formula (I) and the polyamine.

[0020] In some aspects, the method may further comprise applying one or more compounds selected from the group consisting of: other corrosion inhibitors, scale inhibitors, fluorescent tracers, water treatment polymers, and combinations thereof.

[0021] In some aspects, the method can further include applying one or more additional 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.

[0022] In some aspects, the method can further comprise mixing the compound of formula (I) and the polyamine prior to applying to the metal surface.

[0023] In some aspects, the rust is white rust.

[0024] The above has been a fairly broad overview of the features and technical advantages of the present disclosure so that the following detailed description may be better understood. Other features and advantages of the present disclosure will be described below, which constitute the subject matter of the claims of this application. Those skilled in the art will appreciate that the concepts and specific aspects disclosed herein may be readily used as a basis for modifying or designing other aspects for achieving the same purposes of the present disclosure. Those skilled in the art will also recognize that such disclosures of equivalent aspects do not depart from the spirit and scope of the present disclosure as set forth in the appended claims. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] Figure 1 shows the average corrosion rates of galvanized pans exposed to various chemical treatments; and

[0026] Figure 2 Shown are the average corrosion rates for galvanized pans exposed to the lower dose chemical treatment. DETAILED DESCRIPTION

[0027] The various aspects are described below. The relationships and functions of the various aspects can be better understood by reference to the following detailed description. However, the various aspects are not limited to those described below. In some cases, details that are not necessary for understanding the aspects disclosed herein may be omitted.

[0028] "Alkyl" refers to a straight or branched chain alkyl substituent. Examples of such substituents include methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, isopentyl, hexyl, and the like.

[0029] "Aryl" refers to an unsubstituted or substituted aromatic carbocyclic substituent as generally understood in the art, and the term "C6-C 10 "Aryl" includes phenyl and naphthyl. It is understood that the term aryl applies to cyclic substituents that are planar and contain 4n+2n electrons according to Huckel's Rule.

[0030] "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, and more preferably about 4 to about 6 carbon atoms. Examples of such substituents include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, and the like. Cyclic alkyl groups can be unsubstituted or further substituted with alkyl groups, such as methyl, ethyl, and the like.

[0031] "Halogen" or "halo" refers to F, Cl, Br and I.

[0032] "Heteroaryl" refers to a monocyclic or bicyclic 5- or 6-membered ring system in which the heteroaryl group is unsaturated and satisfies Huckel's rule. Non-limiting examples of heteroaryl groups include furanyl, thienyl, pyrrolyl, pyrazolyl, imidazolyl, 1,2,3-triazolyl, 1,2,4-triazolyl, isoxazolyl, oxazolyl, isothiazolyl, thiazolyl, 1,3,4-oxadiazol-2-yl, 1,2,4-oxadiazol-2-yl, 5-methyl-1,3,4-oxadiazole, 3-methyl-1,2,4-oxadiazole, pyridyl, pyrimidinyl, pyrazinyl, triazinyl, benzofuranyl, benzothienyl, indolyl, quinolyl, isoquinolyl, benzimidazolyl, benzimidazolinyl, benzothiazolinyl, quinazolinyl, and the like.

[0033] "Oxo" refers to an oxygen atom double-bonded to a carbon atom.

[0034] The compounds of the present disclosure can be substituted with suitable substituents. As used herein, the term "suitable substituents" refers to a chemically acceptable functional group, preferably a molecule that does not invalidate the activity of the compound. Such suitable substituents include but are not limited to halo, perfluoroalkyl, perfluoroalkoxy, alkyl, alkenyl, alkynyl, hydroxyl, oxo, sulfhydryl, alkylthio, alkoxy, aryl or heteroaryl, aryloxy or heteroaryloxy, aralkyl or heteroaralkyl, aralkyloxy or heteroaralkyloxy, HO-(C=O)-base, heterocyclic radical, cycloalkyl, amino, alkyl and dialkylamino, carbamoyl, alkylcarbonyl, alkoxycarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, arylcarbonyl, aryloxycarbonyl, alkylsulfonyl and arylsulfonyl. In some aspects, suitable substituents can include halogen, unsubstituted C1-C 12 Alkyl, unsubstituted C4-C6 aryl, or unsubstituted C1-C 10 Alkoxy. Those skilled in the art will appreciate that many substituents can be substituted with additional substituents.

[0035] In some aspects, a composition is disclosed that may include a polyamine and a compound of formula (I) or a salt thereof. The compound of formula (I) has the formula

[0036]

[0037] In some aspects, X is independently hydrogen, halogen, or substituted or unsubstituted C 1-5 alkyl, and m can be 1, 2, 3 or 4. In some aspects, R 1 It can be hydrogen, substituted or unsubstituted C1-C 12 alkyl or substituted or unsubstituted C4-C6 aryl. In some aspects, R 2 May be absent, hydrogen, substituted or unsubstituted C1-C 12 alkyl or substituted or unsubstituted C4-C6 aryl. In some aspects, R 3 Can be a key or CHR 4 In some aspects, R 4 Can be hydrogen, halogen, NR 5 R 6 OR 5 In some aspects, R 5 and R 6 are each independently hydrogen, substituted or unsubstituted C1-C 12 an alkyl group or a substituted or unsubstituted C4-C6 aryl group.

[0038] One or more X substituents can occupy any available position on the benzimidazole ring. Thus, in some aspects, one or more X substituents can be located at the 4, 5, 6, and / or 7 positions of the benzimidazole. In some aspects, the X substituent is at the 5 position.

[0039] The number m of X substituents can be 1, 2, 3 or 4. If m is 2, 3 or 4, the X substituents can occupy any open position and can be ortho, meta or para to each other.

[0040] In certain aspects, the salt of the compound of formula (I) can be any salt, such as chloride salts, bromide salts, iodide salts, sulfate salts, fluoride salts, perchlorate salts, acetate salts, trifluoroacetate salts, phosphate salts, nitrate salts, carbonate salts, bicarbonate salts, formates, chlorate salts, bromide salts, chlorite salts, thiosulfate salts, oxalate salts, cyanide salts, cyanate salts, tetrafluoroborate salts, etc. In certain aspects, the salt of the compound of formula (I) can be a hydrochloride salt or a sulfate salt.

[0041] In some aspects, Z is independently nitrogen, CX or N + R 5 .

[0042] In some ways, Z is CX.

[0043] In some aspects, X is hydrogen and m is 4. In some aspects, X is absent.

[0044] In some respects, R 1 It's hydrogen.

[0045] In some respects, R 2 Does not exist.

[0046] In some respects, R 3 is a key. In some aspects, R 3 It is CHR 4 .

[0047] In some respects, R 4 is hydrogen. In some aspects, R 4 It's a halogen.

[0048] In some respects, R 4 It is NR 5 R 6 In some aspects, R 4 is OR 5 .

[0049] In some respects, R 5 is substituted or unsubstituted C1-C 12 In some aspects, R 5 is hydrogen. In some aspects, R 5 It is a substituted or unsubstituted C4-C6 aryl group.

[0050] In some aspects, one Z is nitrogen and the rest are CX.

[0051] In some aspects, at least two Z are nitrogen, and the remainder are CX.

[0052] In some respects, R 3 is a bond, and at least one Z is nitrogen.

[0053] In some aspects, X is independently hydrogen or halogen, R 1 is hydrogen, R 2 does not exist, and R 3 For CHR 4 .

[0054] In some aspects, the compound of formula (I) or a salt thereof is

[0055]

[0056] In some aspects, the compound of formula (I) or a salt thereof is

[0057]

[0058] In some aspects, the compound of formula (I) or a salt thereof is

[0059]

[0060] In some aspects, the compound of formula (I) or a salt thereof is

[0061]

[0062] In some aspects, the compound of formula (I) or a salt thereof is

[0063]

[0064] In some aspects, the compound of formula (I) or a salt thereof is

[0065]

[0066] In some aspects, the compound of formula (I) or a salt thereof is

[0067]

[0068] In some aspects, the compound of formula (I) or a salt thereof is

[0069]

[0070] In some aspects, the compound of formula (I) or a salt thereof is

[0071]

[0072] In some aspects, the compound of formula (I) or a salt thereof is

[0073]

[0074] In some aspects, the compound of formula (I) or a salt thereof is

[0075]

[0076] In some aspects, the compound of formula (I) or a salt thereof is

[0077]

[0078] In some aspects, the composition may include a compound of formula (Ia) or a salt thereof,

[0079]

[0080] wherein X is independently hydrogen, halogen or substituted or unsubstituted C 1-5 alkyl, and m is 1, 2, 3 or 4; R 1 is hydrogen, substituted or unsubstituted C1-C 12 Alkyl or substituted or unsubstituted C4-C6 aryl; R 2 is absent, hydrogen, substituted or unsubstituted C1-C 12 alkyl or substituted or unsubstituted C4-C6 aryl; and R 3 For key or CHR 4 In some aspects, R 4 Can be hydrogen, halogen, NR 5 R 6 OR 5 In some aspects, R 5 and R 6 are each independently hydrogen, substituted or unsubstituted C1-C 12 an alkyl group or a substituted or unsubstituted C4-C6 aryl group.

[0081] In some aspects, the compound or its salt has formula (II),

[0082]

[0083] wherein X is independently hydrogen, halogen or substituted or unsubstituted C 1-5 Alkyl; m is 1, 2, 3 or 4; R 3 Yes key or CHR 4 ; Y is independently hydrogen, halogen or C 1-5 alkyl; and n is 1, 2, 3, 4 or 5. In some aspects, R 4 Can be hydrogen, halogen, NR 5 R 6 OR 5 In some aspects, R 5 and R6 are each independently hydrogen, substituted or unsubstituted C1-C 12 an alkyl group or a substituted or unsubstituted C4-C6 aryl group.

[0084] In some aspects, Y is hydrogen.

[0085] In some aspects, Y is independently hydrogen and halogen.

[0086] As described herein, m can be 1, 2, 3, or 4. If m is 2, 3, or 4, then the X substituents can occupy any open position and can be ortho, meta, or para to each other. The number of Y substituents, n, can be 1, 2, 3, or 4. If n is 2, 3, or 4, then the Y substituents can occupy any open position and can be ortho, meta, or para to each other.

[0087] In some aspects, the concentration of the compound of Formula (I), Formula (Ia) or Formula (II), or a salt thereof, in the composition can range from about 1 wt % to about 50 wt %, from about 5 wt % to about 50 wt %, from about 10 wt % to about 50 wt %, from about 15 wt % to about 50 wt %, from about 20 wt % to about 50 wt %, from about 20 wt % to about 45 wt %, from about 25 wt % to about 45 wt %, or from about 25 wt % to about 40 wt %.

[0088] In some aspects, the composition can include water.

[0089] In some aspects, the composition can be a homogeneous mixture. In some aspects, the composition can be a solution.

[0090] In some aspects, the polyamine is poly[oxy(methyl)-1,2-ethanediyl],α-(2-aminomethylethyl)-ω-(2-aminomethyl-ethoxy)-) functionalized with 3-chloro-1,2-propanediol.

[0091] In some aspects, the polyamine is formed from polyoxypropylene diamine. In some aspects, the polyamine has the formula [CH(OH)CH(OH)CH2]2N—[CH(CH3)CH2O] X -N[CH2CH(OH)CH(OH)]2. x is from 1 to about 20. In this aspect, the amine group of the compound is hydroxy-functionalized.

[0092] In some aspects, the polyamines are prepared by reacting a compound characterized by repeating oxypropylene units in the backbone, which has the formula H2N-(CH(CH3)CH2O) with glycidol (2,3-epoxy-1-propanol). Z -CH2CH(CH3)NH2, wherein Z is 1 to 3.

[0093] In some aspects, the composition can have a weight ratio of the compound of formula (I) to the polyamine of about 4: 1. In some aspects, the weight ratio ranges from about 2: 1 to 6: 1.

[0094] In other aspects, a method for preventing rust on a metal surface is provided. The method may include applying a polyamine and applying a compound of formula (I) or a salt thereof to the metal surface.

[0095] The present disclosure provides methods for using heterocyclic compounds and formulations containing heterocyclic compounds that are particularly useful for inhibiting corrosion of metal components in industrial water systems. Adding metal-chelating benzimidazoles to aqueous systems can provide excellent metal corrosion resistance. In particular, adding 2-pyridyl- or benzylalcohol-substituted benzimidazoles to aqueous systems in contact with metal surfaces results in excellent corrosion inhibition of metals such as copper. Furthermore, while benzotriazole and benzimidazole are generally unstable in the presence of oxidizing halogen compounds, the compounds of the present disclosure are capable of 1,2-chelating with metals to provide exemplary protection in the presence of oxidizing halogen compounds. In particular, 2-(2-pyridyl)benzimidazole exhibits superior corrosion protection compared to benzimidazole, 2-phenylbenzimidazole, and tolyltriazole in the presence of oxidizing halogen compounds. While not wishing to be bound by any particular theory, it is believed that the compounds of the present disclosure, due to the bidentate chelation of the corrosion inhibitors with the metal surface, form a protective film that is substantially impenetrable by common oxidizing halogen compounds. Thus, in certain aspects, the methods of the present disclosure provide protection against metal corrosion in aqueous systems using oxidizing halogen compounds as biocides.

[0096] In some aspects, the present disclosure provides a method for inhibiting corrosion of a metal surface in contact with an aqueous system. The method may include adding any composition described in the present disclosure to the aqueous system. For example, the composition may include a compound of formula (I) and a polyamine.

[0097] An "industrial water system" refers to any system that circulates water. Non-limiting examples of an "industrial water system" include a cooling system, a boiler system, a heating system, a membrane filtration system, a papermaking system, or any other system that circulates water.

[0098] Compositions comprising a polyamine and a compound of formula (I), (Ia) and / or (II) can provide corrosion protection for galvanized metals. The compositions can prevent rust. In some aspects, the rust is white rust.

[0099] The term "white rust" refers to a type of corrosion product that affects galvanized surfaces and is characterized by the accumulation of white, fluffy or waxy non-protective zinc corrosion products attached to the zinc surface of galvanized steel.

[0100] One method of passivating the surface is to allow the zinc coating to form 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 than the protective zinc carbonate barrier described above.

[0101] Although the compounds of formula (I), (Ia), and (II) can be added to the aqueous system at any dosage rate, the compounds of formula (I), (Ia), and (II) are typically added to the aqueous system at a dosage rate of about 0.01 ppm to about 500 ppm. In certain aspects, the compounds of formula (I), (Ia), or (II) are added to the aqueous system at a dosage rate of about 0.01 ppm to about 100 ppm. In certain aspects, the compound of Formula (I), (la) or (II) is added to an aqueous system at a dosage rate of about 0.01 ppm to about 100 ppm, about 0.01 ppm to about 75 ppm, about 0.01 ppm to about 50 ppm, about 0.01 ppm to about 25 ppm, about 0.01 ppm to about 10 ppm, about 0.01 ppm to about 5 ppm, about 0.1 ppm to about 100 ppm, about 0.1 ppm to about 75 ppm, about 0.1 ppm to about 50 ppm, about 0.1 ppm to about 25 ppm, about 0.1 ppm to about 10 ppm, about 0.1 ppm to about 5 ppm, about 1 ppm to about 100 ppm, about 1 ppm to about 75 ppm, about 1 ppm to about 50 ppm, about 1 ppm to about 25 ppm, about 1 ppm to about 10 ppm, about 5 ppm to about 100 ppm, about 10 ppm to about 100 ppm, about 25 ppm to about 100 ppm, about 50 ppm to about 100 ppm, or about 80 ppm to about 100 ppm.

[0102] In some aspects, the aqueous system is a cooling water system. The cooling water system can be a closed-loop cooling water system or an open-loop cooling water system. In some aspects, formula (I), (Ia) or (II) compound is added to the closed-loop cooling water system at a dosage rate of about 0.01ppm to about 200ppm. In some aspects, formula (I), (Ia) or (II) compound is added to the open-loop cooling water system at a dosage rate of about 0.01ppm to about 20ppm.

[0103] The compounds of formula (I), (Ia) and (II) are contacted with the metal surface by any suitable method. In some aspects, a solution of the compound of formula (I), (Ia) or (II) is contacted with the metal surface by dipping, spraying or other coating techniques. In some aspects, a solution of the compound of formula (I), (Ia) or (II) is introduced into water of an aqueous system by any conventional method and periodically or continuously injected into the aqueous system.

[0104] In one aspect, introducing the composition to a galvanized surface involves incorporating the 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 have a strong affinity), in which case the metal will be protected by the zinc coating. The next step in the manufacturing process is to immerse the galvanized metal in a composition comprising a compound of formula (I), (Ia), or (II) and a polyamine.

[0105] In another aspect, the composition is directed onto a metal surface, including spraying a solution of the composition directly onto the surface, including surfaces in industrial water systems. In one aspect, the composition is mixed with a foaming agent to form a mixture, which is then sprayed onto the galvanized metal surface using any suitable spraying device. The foaming agent may include a surfactant, such as an alkoxylated alcohol, polyethylene glycol, or any other suitable surfactant. In alternative embodiments, the composition may be physically applied to the surface by rolling it on with a paint roller or similar tool, applying it with a paint brush or similar tool, wiping it with a mop or similar tool, or using any other suitable method or technique.

[0106] In some aspects, the compound of formula (I), (Ia), or (II) and the polyamine can be applied to the metal surface independently and in any order.

[0107] In another aspect, the composition is reintroduced onto the surface one or more times after one or more time intervals to "cap" the barrier or "repassivate" the surface. An ongoing capping step is also contemplated to renew the corrosion barrier and / or repassivate the galvanized surface. Depending on the circumstances, the method may include a variety of different compositions and capping the barrier may include introducing a different corrosion inhibiting composition or compositions onto the galvanized metal surface.

[0108] In some aspects, the compositions disclosed herein may include fluorescent organic compounds. In some aspects, the fluorescent organic compounds may be selected from rhodamine or its derivatives, acridine dyes, fluorescein or its derivatives, and combinations thereof. In some aspects, the compositions disclosed herein may include fluorescently labeled polymers.

[0109] Those skilled in the art will appreciate that the polyamine and the compound of formula (I), (Ia) or (II) can be added to an aqueous system or applied to a metal surface alone or in combination with other corrosion inhibitors or treatment chemicals. A plurality of corrosion inhibitors can be administered as a combined corrosion inhibitor formulation, or each corrosion inhibitor can be added individually, including two or more compounds of formula (I), (Ia) and / or formula (II) in a combined corrosion inhibitor formulation. In addition, the compound of formula (I), (Ia) or (II) can be added to an aqueous system in combination with a variety of additional corrosion inhibitors, including but not limited to triazoles, benzotriazoles (e.g., benzotriazole or tolyltriazole), benzimidazoles, orthophosphates, polyphosphates, phosphonates, molybdates, silicates, oximes, and nitrites. The compounds of formula (I), (Ia) and (II) may also be added to aqueous systems in combination with a variety of additional additives such as treating polymers, antimicrobials, antifouling agents, colorants, fillers, buffers, surfactants, viscosity modifiers, chelating agents, dispersants, deodorants, sequestering agents, oxygen scavengers and indicator dyes.

[0110] Composition of the present disclosure can comprise the polyamine of about 0 to 10 weight percent and the formula (I) compound of about 10 to about 100 weight percent, and all the other are auxiliary components and water.More preferably, the amount of polyamine is about 2 to 10 weight percent by weight, and the amount of formula (I) compound is about 20 to about 100 weight percent by weight by weight, and all the other are auxiliary components and water.Preferred blend comprises the polyamine of about 10 weight percent and the formula (I) compound of about 90 weight percent.More preferably, blend comprises the polyamine of about 40 weight percent and the formula (I) compound of about 60 weight percent.Most preferably, blend is made up of the polyamine of about 60 weight percent and the formula (I) compound of about 40 weight percent.

[0111] The dosage range of adding or applying the polyamine can be 0.01ppm to about 200ppm. In some aspects, the polyamine dosage can be in the range of about 0.01ppm to about 50ppm, about 0.01ppm to about 10ppm, or about 0.01ppm to about 5ppm. In some aspects, the polyamine dosage can be about 0.5ppm.

[0112] The dosage range of adding or applying the compound of formula (I) can be 0.01ppm to about 200ppm. In some aspects, the dosage can be in the range of about 0.01ppm to about 50ppm, about 0.01ppm to about 10ppm, or about 0.01ppm to about 5ppm. In some aspects, the dosage can be about 2ppm.

[0113] Example

[0114] A three-electrode electrochemical cell is used in which the working electrode is a galvanized disk. Two steel electrodes serve as one reference electrode and the other as a counter electrode. The test solution is a mixture of corrosive water and the candidate inhibitor to be evaluated. The corrosive water generally includes 200 ppm of calcium (calculated as CaCO3); 200 ppm of magnesium (calculated as CaCO3); 500 ppm of chloride; and 150 ppm of bicarbonate. 190 ml of test solution is used in each test and is continuously stirred using a magnetic stirrer while being maintained at 80 + / - 2°F. Measurements are taken every 5 hours until the high corrosion rate damages the galvanized surface of the working electrode.

[0115] The efficacy of the corrosion inhibitor composition was determined by measuring the electrochemical corrosion rate from the polarization resistance. Cathodic and anodic slopes were determined by Tafel scans prior to the polarization run. Scans were performed using a Gamry potentiostat / galvanostat set to 0.1 mV / s.

[0116] Example 1

[0117] The total chemical content (corrosion inhibitor + polyamine) added in this experiment was approximately 10 ppm. The weight ratio of corrosion inhibitor to polyamine was approximately 1:1. Figure 1 The average corrosion rates for the various treatments are shown in mpy. Compound YMI refers to Compound 1 shown in the figure below. TT refers to toluenetriazole, and H0680 is poly[oxy(methyl)-1,2-ethanediyl],α-(2-aminomethylethyl)-ω-(2-aminomethyl-ethoxy)-) functionalized with 3-chloro-1,2-propanediol.

[0118]

[0119] Example 2

[0120] The total chemical content (corrosion inhibitor + polyamine) added in this experiment was approximately 2.5 ppm. The weight ratio of corrosion inhibitor to polyamine was approximately 4:1. Figure 2 The average corrosion rate for each treatment is shown in mpy.

[0121] Any composition disclosed herein may comprise, consist of, or consist essentially of any compound / component disclosed herein. According to the present disclosure, the phrases "consist essentially of, consists essentially of, consisting essentially of," and the like limit the scope of a claim to the specified materials or steps and those materials or steps that do not materially affect one or more basic and novel characteristics of the claimed invention.

[0122] As used herein, the term "about" means that the stated value is within the error range caused by the standard deviation found in its respective testing measurements, and if such error cannot be determined, "about" means within 10% of the stated value.

[0123] All compositions and methods disclosed and claimed herein can be prepared and executed without undue experimentation in light of the present disclosure. Although the present invention can be embodied in many different forms, specific preferred embodiments of the invention are described in detail herein. The present disclosure is illustrative of the principles of the invention and is not intended to limit the invention to the specific embodiments shown. In addition, unless expressly stated to the contrary, the use of the term "a / an" is intended to include "at least one / at least one" or "one or more / one or more". For example, "a compound" is intended to include "at least one compound" or "one or more compounds."

[0124] Any range given in absolute terms or approximate terms is intended to encompass both, and any definition used herein is intended to illustrate rather than to limit. Although the numerical ranges and parameters setting forth the broad scope of the present invention are approximate, the numerical values ​​set forth in the specific embodiments are reported as accurately as possible. However, any numerical value inherently contains certain errors, which are necessarily caused by the standard deviation found in their respective test measurements. In addition, all ranges disclosed herein are understood to encompass any and all subranges (including all fractional values ​​and entire values) contained therein.

[0125] In addition, the present invention encompasses any and all possible combinations of some or all of the various aspects described herein. It should also be understood that various changes and modifications made to the presently preferred aspects described herein will be apparent to those skilled in the art. Such changes and modifications may be made without departing from the spirit and scope of the present invention and without diminishing its intended advantages. Therefore, the appended claims are intended to cover such changes and modifications.

Claims

1. A method for preventing rust on a galvanized metal surface, comprising: applying a compound of formula (I) to the galvanized metal surface, and applying a polyamine to the metal surface, wherein the polyamine is poly[oxy(methyl)-1,2-ethanediyl],α-(2-aminomethylethyl)-ω-(2-aminomethyl-ethoxy)-functionalized with 3-chloro-1,2-propanediol; in Each X is independently hydrogen, halogen or substituted or unsubstituted C 1-5 alkyl; m is 1, 2, 3, or 4; R 1 is hydrogen, substituted or unsubstituted C1-C 12 Alkyl or substituted or unsubstituted C6 aryl; R 2 for non-existence; R 3 Yes key or CHR 4 ; R 4 It is hydrogen, halogen, NR 5 R 6 OR 5 ; where R 5 and R 6 are each independently hydrogen, substituted or unsubstituted C1-C 12 alkyl, or substituted or unsubstituted C6 aryl; and Each Z is independently nitrogen or CX; When substituted, R 1 、R 5 and R 6 The substituents are selected from the group consisting of halo, perfluoroalkyl, perfluoroalkoxy, alkyl, hydroxy, oxo, mercapto, alkylthio, alkoxy, cycloalkyl, amino, alkylamino, and dialkylamino.

2. The method according to claim 1, wherein Each X is independently hydrogen or halogen; R 1 is hydrogen; R 2 does not exist; and R 3 For CHR 4 .

3. The method according to claim 1, wherein the compound of formula (I) is 4. The method according to any one of claims 1 to 3, wherein the metal surface is a galvanized metal surface which is part of an industrial water system.

5. The method according to any one of claims 1 to 3, wherein the compound of formula (I) and the polyamine are applied to the metal surface by spraying an effective amount thereof directly onto the metal surface; wherein the dosage range of the compound of formula (I) is 0.01 ppm to 200 ppm, and the dosage range of the polyamine is 0.01 ppm to 200 ppm.

6. The method according to any one of claims 1 to 3, wherein the compound of formula (I) and the polyamine are applied to the metal surface by immersing the metal surface in a solution containing the compound of formula (I) and the polyamine.

7. The method of any one of claims 1-3, 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.

8. The method of any one of claims 1-3, further comprising applying one or more additional 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.

9. The method according to any one of claims 1 to 3, wherein the rust is white rust.

10. The method according to any one of claims 1 to 3, further comprising applying the compound of formula (I) and the polyamine to the metal surface after mixing.

11. A composition for inhibiting corrosion, comprising: Polyamines, wherein the polyamine is poly[oxy(methyl)-1,2-ethanediyl],α-(2-aminomethylethyl)-ω-(2-aminomethyl-ethoxy)-functionalized with 3-chloro-1,2-propanediol; and A compound of formula (I), in Each X is independently hydrogen, halogen or substituted or unsubstituted C 1-5 alkyl; m is 1, 2, 3, or 4; R 1 is hydrogen, substituted or unsubstituted C1-C 12 Alkyl or substituted or unsubstituted C6 aryl; R 2 for non-existence; R 3 Yes key or CHR 4 ; R 4 It is hydrogen, halogen, NR 5 R 6 OR 5 ; where R 5 and R 6 are each independently hydrogen, substituted or unsubstituted C1-C 12 alkyl, or substituted or unsubstituted C6 aryl; and Each Z is independently nitrogen or CX; When substituted, R 1 、R 5 and R 6 The substituents are selected from the group consisting of halo, perfluoroalkyl, perfluoroalkoxy, alkyl, hydroxy, oxo, mercapto, alkylthio, alkoxy, cycloalkyl, amino, alkylamino, and dialkylamino.

12. The composition according to claim 11, wherein Each X is independently hydrogen or halogen; R 1 is hydrogen; R 2 does not exist; and R 3 For CHR 4 .

13. The composition according to any one of claims 11-12, wherein the compound of formula (I) is

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