US20140346404A1 - Corrosion inhibitor systems using environmentally friendly green solvents - Google Patents

Corrosion inhibitor systems using environmentally friendly green solvents Download PDF

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US20140346404A1
US20140346404A1 US14/030,602 US201314030602A US2014346404A1 US 20140346404 A1 US20140346404 A1 US 20140346404A1 US 201314030602 A US201314030602 A US 201314030602A US 2014346404 A1 US2014346404 A1 US 2014346404A1
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dispersant
weight
epoxy
curing agent
esters
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US14/030,602
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Gene H. Zaid
Stephen Philip Rivas
Thomas W. Burgoyne
David Jay Rose
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Jacam Chemical Co 2013 LLC
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Jacam Chemical Co 2013 LLC
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Priority claimed from US13/900,473 external-priority patent/US20140349015A1/en
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Priority to US14/030,602 priority Critical patent/US20140346404A1/en
Assigned to JACAM CHEMICAL COMPANY 2013, LLC reassignment JACAM CHEMICAL COMPANY 2013, LLC ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: BURGOYNE, THOMAS W., RIVAS, STEPHEN PHILIP, ROSE, DAVID JAY, ZAID, GENE H.
Publication of US20140346404A1 publication Critical patent/US20140346404A1/en
Abandoned legal-status Critical Current

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    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23FNON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F11/00Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/08Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
    • C23F11/10Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
    • C23F11/173Macromolecular compounds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/4007Curing agents not provided for by the groups C08G59/42 - C08G59/66
    • C08G59/4014Nitrogen containing compounds
    • C08G59/4042Imines; Imides
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D163/00Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins

Definitions

  • the present invention is concerned with improved anti-corrosion systems or products for application to metal surfaces and including epoxy and curing agent fractions dispersed in an ester-containing dispersant. More particularly, the invention is concerned with such products and methods of use thereof, wherein the epoxy/curing agent materials are dispersed in relatively fast-drying carboxylic acid ester dispersants exhibiting low volatile organic compound (VOC) levels and which substantially prevent phase separation between the components of the products.
  • VOC volatile organic compound
  • a variety of anti-corrosion systems have been described in the past.
  • Many corrosion inhibitors are aqueous dispersions containing a variety of components, e.g., 2-mercaptobenzothiozole, benzotriozole, tolyltriozole, phosphates, polyphosphates, organic soluble polymers, silicates, dithiocarbamates, nitrites, oxazoles, imidazoles, imidazolines, lignands, lignosulfates, tannins, phosphoric acid esters and boric acid esters.
  • Many of these inhibitors are very prone to freezing during cold weather, making them very difficult to handle and maintain.
  • the useful life of many prior anti-corrosion treatments is very short, e.g., a week or less.
  • U.S. Pat. Nos. 5,936,059 and 5,945,164 describe highly useful anti-corrosion systems and methods particularly suited for oil and gas recovery and conveying equipment.
  • the systems of the invention include an epoxy component as well as an amine curing agent component, which are either mixed together at the introduction site, or are simultaneously injected into a well or pipeline.
  • a problem has arisen, however, when extremely long pipelines or deep wells require treatment. In such cases, the admixed epoxy and curing agent components tend to prematurely cure prior to application along the full length of the well or pipeline, meaning that certain portions of the equipment are not successfully treated. See also U.S. Pat. No. 4,526,813.
  • the present invention overcomes the problems outlined above, and provides improved anti-corrosion systems or products characterized by the use of low VOC ester-containing dispersants.
  • the products comprise a first component including an epoxy active ingredient in a first compatible dispersant, and a curing agent for the epoxy in a second compatible dispersant; the first and second dispersants each comprise selected esters containing —COO— ester groups or linkages.
  • the first and second dispersants are identical and each comprise a mixture of carboxylic acid esters.
  • the epoxy component may comprise any of the conventional epoxy resins dispersed in an ester-containing dispersant, with the epoxy being present at a level of from about 10-50% by volume, more preferably from about 15-40% by volume.
  • the curing agent component is preferably an imidazoline dispersed in an ester-containing dispersant, again at a level of from about 10-50% by volume, more preferably from about 15-40% by volume.
  • the first and second dispersants are identical and contain a plurality of polycarboxylic acid esters, and especially dicarboxylic acid alkyl esters selected from the group consisting of C5-C40 alkyl diesters. Dispersants containing respective quantities of glutaric, succinic, and adipic acid diesters are especially useful.
  • dispenser or “dispersion” is intended to mean all types of liquid mixtures, including suspensions, colloids, and solutions.
  • “Substituted” with respect to chemical compounds refers to any substituent or moiety (e.g., a metal atom or organic group) bound to the compounds and which does not substantially alter the characteristics of the compounds in the context of the disclosed uses thereof.
  • FIG. 1 is a photograph illustrating corresponding dispersions of a known epoxy/curing agent corrosion inhibitor in HAN solvent (right-hand beaker) and in an ester solvent in accordance with the invention (left-hand beaker), at a zero wait time;
  • FIG. 2 is a photograph similar to that of FIG. 1 , but illustrating the dispersions after 15 minutes wait time;
  • FIG. 3 is a photograph similar to that of FIG. 1 , but illustrating the dispersions after 30 minutes wait time;
  • FIG. 4 is a photograph similar to that of FIG. 1 , but illustrating the dispersions after 40 minutes wait time.
  • the anti-corrosion products or systems of the invention contain three principal ingredients or components, namely an epoxy component, a curing agent component, and an ester-containing dispersant or solvent. These components are individually described below.
  • a variety of epoxies can be used in the invention.
  • any epoxy resin having, on the average, more than one vicinal epoxy group per molecule can be used in the composition and process of the invention.
  • the epoxy resin may be saturated or unsaturated, aliphatic, cycloaliphatic, aromatic or heterocyclic, and may bear substituents which do not materially interfere with the curing reaction.
  • Suitable epoxy resins include glycidyl ethers prepared by the reaction of epichlorohydrin with a compound containing a hydroxyl group (e.g., bisphenol A) carried out under alkaline reaction conditions.
  • Other suitable epoxy resins can be prepared by the reaction of epichlorohydrin which mononuclear di- and tri-hydroxy phenolic compounds such as resorcinol and phloroglucinol, selected polynuclear polyhydroxy phenolic compounds such as bis(p-hydroxyphenyl)methane and 4,4′-dihydroxy biphenyl, or aliphatic polyols such as 1,4-butanediol and glycerol.
  • Epoxy resins suitable for use in the invention have molecular weights generally within the range of 50 to about 10,000, preferably about 1500 to about 2000.
  • Additional epoxy-containing materials suitable for use in the present invention include the epoxidized derivatives of natural oils such as the triesters of glycerol with mixed long-chain saturated and unsaturated acids which contain, e.g., 16, 18 and 20 carbon atoms.
  • Soybean oil is a typical triglyceride which can be converted to a polyepoxide suitable for use in the instant invention.
  • polyepoxides suitable for use in the present invention are derived from esters of polycarboxylic acids such as maleic acid, terephthalic acid, oxalic acid, succinic acid, azelaic acid, malonic acid, tartaric acid, adipic acid and the like, with unsaturated alcohols.
  • suitable polyepoxides can be derived from esters prepared from unsaturated alcohols and unsaturated carboxylic acids.
  • Representative epoxidized esters include the following: 2,3-epoxypentyl-3,4-epoxybutyrate; 2,3-epoxybutyl-3,4-epoxyhexanoate; 3,4-epoxyoctyl-2,3-epoxycyclohexane carboxylate; 2,3-epoxydodecyl-4,5-epoxyoctanoate; 2,3-epoxyisobutyl-4,5-epoxydodecanoate; 2,3-epoxycyclododedcyl-3,4-epoxypentanoate; 3,4-epoxyoctyl-2,3-epoxycyclododecane carboxylate and the like.
  • unsaturated materials which can be epoxidized to give resins suitable for use include butadiene based polymers such as butadiene-styrene copolymers, polyesters available as derivatives of polyols such as ethylene glycol with unsaturated acid anhydrides such as maleic anhydride and esters of unsaturated polycarboxylic acids.
  • polyepoxides derived from the latter include the following: dimethyl 3,4,7,8-diepoxydecanedioate; dibutyl 3,4,5,6-diepoxycyclohexane-1,2-carboxylate; dioctyl 3,4,7,8-diepoxyhexadecanedioate; diethyl 5,6,9,10-diepoxytetradecanedioate and the like.
  • Dimers of dienes such as 4-vinyl cyclohexene-1 from butadiene and dicyclopentadiene from cyclopentadiene can be converted to epoxidized derivatives which are suitable for use.
  • Imidazoline and various derivatives thereof are the preferred curing agent component. These preferred species are set forth in the following structural formula:
  • R 1 is hydrogen or an alkyl group having up to 18 carbon atoms therein
  • R 2 is hydrogen, or an alkyl or amine group having up to 18 carbon atoms therein.
  • the presently most preferred curing agent is imidazoline itself (C3H6N2), including the 2-, 3-, and 4-imidazoline isomers.
  • alkoxylated amine curing agents may also be used with or in lieu of the imidazoline curing agents.
  • Useful alkoxylated amines may be aliphatic, cycloaliphatic, aromatic or heterocyclic.
  • the alkoxylated polyamines, especially the alkoxylated N-alkyl- and N-alkylenyl-substituted 1,3-diaminopropanes and mixtures thereof may be used.
  • alkoxylated polyamines examples include alkoxylated N-hexadecyl-1,3-diaminopropane, N-tetradecyl-1,3-diaminopropane, N-octadecyl-1,3-diaminopropane, -pentadecyl-1,3-diaminopropane, N-heptadecyl-1,3-diaminopropane, N-nonadecyl-1,3-diaminopropane, and N-octadecenyl-1,3-diaminopropane.
  • ethoxylated-alkylated and N-alkenylated diamines can be used in the invention.
  • the presently preferred polyamine is a commercial product, ethoxylated-tallow-1,3-diaminopropane, where the degree of ethoxylation is approximately 10 moles ethoxylate per mole of tallow diamine.
  • the ester dispersants in accordance with the invention are dispersible in water at ambient temperature, and remain liquid at temperatures of from about ⁇ 20-200° F., more preferably from about 20-110° F.
  • the dispersants are substantially free of water (no more than about 5% by weight water, more preferably no more than about 2% by weight), and serve principally as a carrier for the epoxy and curing agent materials, and, as these materials react, the resulting epoxy/curing agent adducts.
  • the ester dispersants do not react with or modify to any significant extent either the epoxy materials, the curing agent materials, and/or the epoxy/curing agent adducts.
  • any chemical interactions between the ester dispersants and the other ingredients and reaction products of the mixtures of the invention would be minor and unintended side reactions, and would not fundamentally alter the chemical characteristics of the epoxy materials, the curing agent materials, or the epoxy/curing agent adducts.
  • esters are quite broad, encompassing C8-C40 mono ester compounds each having one —COO— ester group, C4-C40 polycarboxylic ester compounds each containing 2 or more —COO— ester groups per molecule, and mixtures thereof.
  • Such esters are normally derived from the esterification of substituted or unsubstituted, saturated or unsaturated C7-C24 straight, branched chain, or cyclic alkyl, alkenyl, alkynyl, and aromatic monocarboxylic acids, C3-C24 straight, branched chain, or cyclic alkyl, alkenyl, alkynyl, and aromatic di-, tri-, or higher polycarboxylic acids, and mixtures thereof.
  • first and second dispersants respectively and individually comprise one or more dicarboxylic acid esters derived from the esterification of C3-C15 alkyl dicarboxylic acids, with the final diesters being C4-C40 diesters.
  • the carboxylic acids are normally esterified using one or more organic alcohols, and again the class of useable alcohols is quite broad, including straight, branched chain, or cyclic, saturated or unsaturated C1-C24 alkyl, alkenyl, alkynyl, and aryl alcohols containing one or more —OH alcohol groups.
  • the preferred alcohols used in the esterification of the carboxylic acids are the straight, branched chain, or cyclic C1-C15 mono-, di-, and tri-alcohols.
  • Particularly preferred dispersants comprise esters derived from C5-C15 alkyl dicarboxylic acids, and even more preferably C4-C8 alkyl dicarboxylic acids such as glutaric, succinic, and adipic acids, esterified using C1-C15 straight or branched chain organic alcohols.
  • a commercially available product RHODISOLV DIB may be used in the invention and is essentially completely an adipic acid diisobutyl ester (C14H26O4, CAS #141-04-8) having a molecular weight of 258.36.
  • RHODISOLV DIB adipic acid diisobutyl ester
  • the ESTASOL solvents may be used, which are essentially anhydrous mixtures containing from about 15-25% by weight dimethyl succinate (CAS #106-65-0), from about 12-23% by weight dimethyl adipate (CAS #627-93-0), and from about 55-65% by weight dimethyl glutarate. (CAS #1119-40-0).
  • the total of the ester groups (—COO—) in the complete dispersant ranges from about 15-50% by weight, more preferably from about 30-45% by weight, based upon the total weight of a given volume of the complete dispersant taken as 100% by weight.
  • the anti-corrosion systems of the invention comprising epoxy and curing agent components in compatible ester-containing dispersants, can be used as a pre-mixed composition containing all of the components combined in a single liquid, i.e., the epoxy, curing agent, and dispersant.
  • the pre-mixed composition is prepared at or near the time of application thereof by mixing together the individual epoxy and curing agent components. This is done so as to assure that there is no undue pre-reaction between the epoxy and curing agent prior to application thereof to surfaces to be protected.
  • the epoxy and curing agent components may be sequentially applied to surfaces to be protected, as described in U.S. Pat. No. 7,407,687.
  • each should have the active epoxy or curing agent present in the dispersant at a level of from about 10-50% by volume, more preferably from about 15-40% by volume, with the dispersant making up the balance of the individual compositions.
  • the epoxy fraction should be present at a level of from about 25-50% by volume, more preferably from about 30-40% by volume;
  • the curing agent fraction should be present at a level of from about 25-50% by volume, more preferably from about 30-40% by volume;
  • the dispersant should be present at a level of from about 5-50% by volume, more preferably from about 20-40% by volume.
  • the ratio of the curing agent to the epoxy fraction in the overall systems should be from about 1-4 parts by weight curing agent to each part by weight epoxy, more preferably from about 2-3 parts by weight curing agent to each part by weight epoxy.
  • the most preferred systems include Epon 828 epoxy resin, imidazoline curing agent, and with the first and second dispersants being identical and each containing quantities of C1-C6 alkyl esters of glutaric acid, succinic acid, and adipic acid.
  • the anti-corrosion systems of the invention find particular utility in the treatment of metal surfaces of oil and gas recovery or conveying equipment.
  • the individual epoxy and curing agent components may be sequentially applied to such surfaces in any order, or these components may be pre-mixed and applied together. In either case, the compositions provide significant protection against corrosion typically seen in such contexts.
  • the anti-corrosion systems of the invention can be used in a wide variety of other situations where corrosion problems exist.
  • the systems may be applied to the inner surfaces of liquid tanks forming a part of rail cars or tanker trucks.
  • the anti-corrosion systems may be applied by spraying, rolling, painting, or any other convenient method. Once the liquid system is applied to a metal surface, the epoxy and curing agent materials react and cure, with the ester dispersants substantially completely evaporating into ambient air, leaving the dried, reacted residue of the systems as thin anti-corrosion protective layers.
  • the systems of the invention can also be applied to downhole equipment in oil or gas wells. This is typically done by injecting the liquid system, or the individual components thereof in any sequential order, into a well. If formation water is present in the well, the active epoxy and curing agent components form a protective layer on the downhole equipment, while the dispersant is merely dissolved in the formation water.
  • a chief advantage of the anti-corrosion systems of the invention is that the VOC levels are drastically reduced, as compared with the prior systems making use of organic solvents, such as toluene or HAN solvents.
  • organic solvents such as toluene or HAN solvents.
  • the combined-component anti-corrosion systems of the invention resist phase separation to a much higher degree than the conventional systems.
  • Preferred dispersants in accordance with the invention may be prepared using the following ingredients:
  • PREFERRED COMPONENT RANGE AMOUNT glutaric acid ((C3H6(COOH)2) 10-60% 30% succinic acid (HOOC—(CH2)2—COOH) 2-25% 10% adipic acid ((CH2)4(COOH)2) 0-15% 4% isobutanol ((CH3)2CHCH2OH) 10-85% 50% phosphoric acid (H3PO4) 1-5% 2% sodium bicarbonate (NaHCO3) 1-5% 4%
  • the ester dispersant was prepared using the preferred amounts of acids, isobutanol, and phosphoric acid set forth above.
  • the reaction mixture was heated with stirring and refluxing to 237° F. (114° C.), and the reaction was allowed to proceed until the temperature dropped to 230° F. (110° C.).
  • the distillate was collected at a slightly higher temperature of approximately 240° F. Additional isobutanol was added to the reactor in a weight amount equal to that of the collected distillate.
  • the reaction was continued by collection of reflux at 10 minutes, 30 minutes, 1 hour, 2 hours, 3 hours, 4 hours, 5 hours, and 5.5 hours with further additions of isobutanol equaling the weight amounts of the collected distillate.
  • the reaction was monitored by IR to determine the loss of the 1711 cm ⁇ 1 carboxylic acid peak, and growth of the 1735 cm ⁇ 1 ester peak, and by gas chromatography.
  • the mixture was reflux cooled to 230° F. (110° C.).
  • the sodium bicarbonate was added slowly and carefully, because it created foaming and bubbling with a large amount of carbon dioxide being released from the reactor.
  • the mixture was heated to 248° F. (120° C.) for 2 hours.
  • the mixture was then purged with nitrogen to remove any remaining water and isobutanol.
  • the mixture was then cooled to room temperature and dried under a vacuum to remove any residual water and isobutanol.
  • the mixture was then checked by gas chromatography to ensure that all isobutanol had been removed, and filtered.
  • the acids used were essentially pure.
  • a waste stream from nylon manufacture may be used in lieu of the pure acids.
  • Such waste streams can differ from batch to batch, but all contain the preferred glutaric, succinic, and adipic acids, and may also contain other carboxylic acids and metal salts.
  • the water/isobutanol mixture can be distilled, followed by fractional distillation of the isobutanol and returning this isobutanol to the reaction vessel.
  • the distilled water/isobutanol mixture is passed through activated molecular sieves, followed by pumping the recovered isobutanol back into the reactor.
  • Solvents made in accordance with this Example can be used both the epoxy and curing agent components of the overall anti-corrosion systems of the invention.
  • a sample of a known anti-corrosion system was provided by mixing in a beaker one part by weight of an epoxy fraction A, made up of 35% by weight Epon 828 epoxy dispersed in 65% by weight HAN solvent, and one part by weight of a curing agent fraction B, made up of about 5% by weight ethoxylated tallow diamine and about 30% by weight imidazoline dispersed in 65% by weight HAN solvent. Three parts by weight of water were also added to the beaker.
  • a sample of an anti-corrosion system in accordance with the invention was prepared by mixing in another beaker one part by weight of an epoxy fraction A′, made up of 35% by weight Epon 828 epoxy in the previously described RHODISOLV DIB ester solvent, and one part by weight of a curing agent fraction B′, made up of 35% by weight imidazoline in 65% by weight RHODISOLV DIB ester solvent. Three parts by weight of water was also added in this beaker.
  • Photographs were taken at times 0, and at wait times of 15, 30, and 40 minutes, shown as FIGS. 1-4 , respectively. As is readily apparent, at time 0, the test systems were essentially the same in terms of color and separation of ingredients. However, as the test proceeded, the ingredients of the prior art system displayed a marked tendency to separate, whereas the system of the present invention displayed virtually no separation.

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Abstract

Improved anti-corrosion systems or products are disclosed containing individual epoxy and curing agent fractions dispersed in low VOC ester-containing dispersants. Preferably, the epoxy fraction is a conventional epoxy resin, whereas the curing agent is an imidazoline. The dispersant advantageously includes a mixture of carboxylic acid esters, such as alkyl glutarate, succinate, and adipate esters.

Description

    CROSS-REFERENCE TO RELATED APPLICATION
  • This application is a continuation of identically-titled U.S. patent application Ser. No. 13/922,007, filed Jun. 19, 2013, which is a continuation-in-part of identically-titled U.S. patent application Ser. No. 13/900,473, filed May 22, 2013, both of which are incorporated herein by reference in their entirety.
  • BACKGROUND OF THE INVENTION
  • 1. Field of the Invention
  • The present invention is concerned with improved anti-corrosion systems or products for application to metal surfaces and including epoxy and curing agent fractions dispersed in an ester-containing dispersant. More particularly, the invention is concerned with such products and methods of use thereof, wherein the epoxy/curing agent materials are dispersed in relatively fast-drying carboxylic acid ester dispersants exhibiting low volatile organic compound (VOC) levels and which substantially prevent phase separation between the components of the products.
  • 2. Description of the Prior Art
  • It is well known that oil and gas wells are subject to extensive corrosion. Downhole equipment such as sucker rods, pump rods, tubing and casing are generally made of mild steel which is adversely affected by the production fluid of the well. The often high temperatures and acidic nature of the production fluids and formation waters magnifies these corrosion problems. Additionally, oil or gas-conveying pipelines are also prone to corrosion. Of course, a variety of other metal surfaces are subject to corrosion problems, in addition to oil and gas equipment.
  • A variety of anti-corrosion systems have been described in the past. Many corrosion inhibitors are aqueous dispersions containing a variety of components, e.g., 2-mercaptobenzothiozole, benzotriozole, tolyltriozole, phosphates, polyphosphates, organic soluble polymers, silicates, dithiocarbamates, nitrites, oxazoles, imidazoles, imidazolines, lignands, lignosulfates, tannins, phosphoric acid esters and boric acid esters. Many of these inhibitors are very prone to freezing during cold weather, making them very difficult to handle and maintain. Moreover, the useful life of many prior anti-corrosion treatments is very short, e.g., a week or less.
  • U.S. Pat. Nos. 5,936,059 and 5,945,164 describe highly useful anti-corrosion systems and methods particularly suited for oil and gas recovery and conveying equipment. The systems of the invention include an epoxy component as well as an amine curing agent component, which are either mixed together at the introduction site, or are simultaneously injected into a well or pipeline. A problem has arisen, however, when extremely long pipelines or deep wells require treatment. In such cases, the admixed epoxy and curing agent components tend to prematurely cure prior to application along the full length of the well or pipeline, meaning that certain portions of the equipment are not successfully treated. See also U.S. Pat. No. 4,526,813.
  • U.S. Pat. No. 7,407,687 describes an application technique wherein epoxy/curing agent anti-corrosion products are sequentially applied in overcome any issues of premature curing.
  • The prior anti-corrosion products described in the '059, '164, and '687 patents typically contain high VOC dispersants or solvents, such as xylene, toluene, or heavy aromatic naphthas (HAN), and these materials can thus present an environmental issue. Moreover, these compositions may suffer from undue phase separation prior to use thereof.
  • There is accordingly a need in the art for improved epoxy/curing agent anti-corrosion systems or products which make use of relatively fast-drying dispersants or solvents having low VOC characteristics and which inhibit phase separation.
  • SUMMARY OF THE INVENTION
  • The present invention overcomes the problems outlined above, and provides improved anti-corrosion systems or products characterized by the use of low VOC ester-containing dispersants. The products comprise a first component including an epoxy active ingredient in a first compatible dispersant, and a curing agent for the epoxy in a second compatible dispersant; the first and second dispersants each comprise selected esters containing —COO— ester groups or linkages. Preferably, the first and second dispersants are identical and each comprise a mixture of carboxylic acid esters.
  • Advantageously, the epoxy component may comprise any of the conventional epoxy resins dispersed in an ester-containing dispersant, with the epoxy being present at a level of from about 10-50% by volume, more preferably from about 15-40% by volume. Similarly, the curing agent component is preferably an imidazoline dispersed in an ester-containing dispersant, again at a level of from about 10-50% by volume, more preferably from about 15-40% by volume. Preferably, the first and second dispersants are identical and contain a plurality of polycarboxylic acid esters, and especially dicarboxylic acid alkyl esters selected from the group consisting of C5-C40 alkyl diesters. Dispersants containing respective quantities of glutaric, succinic, and adipic acid diesters are especially useful.
  • The preferred epoxy and curing agent components are described in the aforementioned U.S. Pat. Nos. 5,936,059, 5,945,164, and 7,407,687, and these patents are accordingly incorporated by reference herein in their entireties.
  • As used herein, “dispersant” or “dispersion” is intended to mean all types of liquid mixtures, including suspensions, colloids, and solutions. “Substituted” with respect to chemical compounds refers to any substituent or moiety (e.g., a metal atom or organic group) bound to the compounds and which does not substantially alter the characteristics of the compounds in the context of the disclosed uses thereof.
  • BRIEF DESCRIPTION OF THE DRAWINGS
  • The patent or application file contains at least one drawing executed in color. Copies of this patent or patent application publication with color drawing(s) will be provided by the Office upon request and payment of the necessary fee.
  • FIG. 1 is a photograph illustrating corresponding dispersions of a known epoxy/curing agent corrosion inhibitor in HAN solvent (right-hand beaker) and in an ester solvent in accordance with the invention (left-hand beaker), at a zero wait time;
  • FIG. 2 is a photograph similar to that of FIG. 1, but illustrating the dispersions after 15 minutes wait time;
  • FIG. 3 is a photograph similar to that of FIG. 1, but illustrating the dispersions after 30 minutes wait time; and
  • FIG. 4 is a photograph similar to that of FIG. 1, but illustrating the dispersions after 40 minutes wait time.
  • DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The Anti-Corrosion Systems of the Invention
  • As explained previously, the anti-corrosion products or systems of the invention contain three principal ingredients or components, namely an epoxy component, a curing agent component, and an ester-containing dispersant or solvent. These components are individually described below.
  • 1. The Epoxy Component
  • A variety of epoxies can be used in the invention. Generally, any epoxy resin having, on the average, more than one vicinal epoxy group per molecule can be used in the composition and process of the invention. The epoxy resin may be saturated or unsaturated, aliphatic, cycloaliphatic, aromatic or heterocyclic, and may bear substituents which do not materially interfere with the curing reaction.
  • Suitable epoxy resins include glycidyl ethers prepared by the reaction of epichlorohydrin with a compound containing a hydroxyl group (e.g., bisphenol A) carried out under alkaline reaction conditions. Other suitable epoxy resins can be prepared by the reaction of epichlorohydrin which mononuclear di- and tri-hydroxy phenolic compounds such as resorcinol and phloroglucinol, selected polynuclear polyhydroxy phenolic compounds such as bis(p-hydroxyphenyl)methane and 4,4′-dihydroxy biphenyl, or aliphatic polyols such as 1,4-butanediol and glycerol.
  • Epoxy resins suitable for use in the invention have molecular weights generally within the range of 50 to about 10,000, preferably about 1500 to about 2000. The commercially available Epon 828 epoxy resin, a reaction product of epichlorohydrin and 2,2-bis(4-hydroxyphenyl)propane (bisphenol A) and having a molecular weight of about 400, an epoxide equivalent (ASTM D-1652) of about 185-192, is presently preferred.
  • Additional epoxy-containing materials suitable for use in the present invention include the epoxidized derivatives of natural oils such as the triesters of glycerol with mixed long-chain saturated and unsaturated acids which contain, e.g., 16, 18 and 20 carbon atoms. Soybean oil is a typical triglyceride which can be converted to a polyepoxide suitable for use in the instant invention.
  • Other polyepoxides suitable for use in the present invention are derived from esters of polycarboxylic acids such as maleic acid, terephthalic acid, oxalic acid, succinic acid, azelaic acid, malonic acid, tartaric acid, adipic acid and the like, with unsaturated alcohols.
  • In addition to the foregoing, it is contemplated that suitable polyepoxides can be derived from esters prepared from unsaturated alcohols and unsaturated carboxylic acids. Representative epoxidized esters include the following: 2,3-epoxypentyl-3,4-epoxybutyrate; 2,3-epoxybutyl-3,4-epoxyhexanoate; 3,4-epoxyoctyl-2,3-epoxycyclohexane carboxylate; 2,3-epoxydodecyl-4,5-epoxyoctanoate; 2,3-epoxyisobutyl-4,5-epoxydodecanoate; 2,3-epoxycyclododedcyl-3,4-epoxypentanoate; 3,4-epoxyoctyl-2,3-epoxycyclododecane carboxylate and the like.
  • Other unsaturated materials which can be epoxidized to give resins suitable for use include butadiene based polymers such as butadiene-styrene copolymers, polyesters available as derivatives of polyols such as ethylene glycol with unsaturated acid anhydrides such as maleic anhydride and esters of unsaturated polycarboxylic acids. Representative polyepoxides derived from the latter include the following: dimethyl 3,4,7,8-diepoxydecanedioate; dibutyl 3,4,5,6-diepoxycyclohexane-1,2-carboxylate; dioctyl 3,4,7,8-diepoxyhexadecanedioate; diethyl 5,6,9,10-diepoxytetradecanedioate and the like.
  • Dimers of dienes such as 4-vinyl cyclohexene-1 from butadiene and dicyclopentadiene from cyclopentadiene can be converted to epoxidized derivatives which are suitable for use.
  • 2. The Curing Agent Component
  • Imidazoline and various derivatives thereof are the preferred curing agent component. These preferred species are set forth in the following structural formula:
  • Figure US20140346404A1-20141127-C00001
  • wherein R1 is hydrogen or an alkyl group having up to 18 carbon atoms therein, and R2 is hydrogen, or an alkyl or amine group having up to 18 carbon atoms therein. The presently most preferred curing agent is imidazoline itself (C3H6N2), including the 2-, 3-, and 4-imidazoline isomers.
  • The alkoxylated amine curing agents may also be used with or in lieu of the imidazoline curing agents. Useful alkoxylated amines may be aliphatic, cycloaliphatic, aromatic or heterocyclic. The alkoxylated polyamines, especially the alkoxylated N-alkyl- and N-alkylenyl-substituted 1,3-diaminopropanes and mixtures thereof may be used. Examples of such alkoxylated polyamines include alkoxylated N-hexadecyl-1,3-diaminopropane, N-tetradecyl-1,3-diaminopropane, N-octadecyl-1,3-diaminopropane, -pentadecyl-1,3-diaminopropane, N-heptadecyl-1,3-diaminopropane, N-nonadecyl-1,3-diaminopropane, and N-octadecenyl-1,3-diaminopropane. Various commercially available mixtures of ethoxylated-alkylated and N-alkenylated diamines can be used in the invention. The presently preferred polyamine is a commercial product, ethoxylated-tallow-1,3-diaminopropane, where the degree of ethoxylation is approximately 10 moles ethoxylate per mole of tallow diamine.
  • 3. The Ester Dispersants
  • The ester dispersants in accordance with the invention, for both the epoxy and curing agent components, are dispersible in water at ambient temperature, and remain liquid at temperatures of from about −20-200° F., more preferably from about 20-110° F. The dispersants are substantially free of water (no more than about 5% by weight water, more preferably no more than about 2% by weight), and serve principally as a carrier for the epoxy and curing agent materials, and, as these materials react, the resulting epoxy/curing agent adducts. Thus, the ester dispersants do not react with or modify to any significant extent either the epoxy materials, the curing agent materials, and/or the epoxy/curing agent adducts. That is, any chemical interactions between the ester dispersants and the other ingredients and reaction products of the mixtures of the invention would be minor and unintended side reactions, and would not fundamentally alter the chemical characteristics of the epoxy materials, the curing agent materials, or the epoxy/curing agent adducts.
  • The types of useable esters are quite broad, encompassing C8-C40 mono ester compounds each having one —COO— ester group, C4-C40 polycarboxylic ester compounds each containing 2 or more —COO— ester groups per molecule, and mixtures thereof. Such esters are normally derived from the esterification of substituted or unsubstituted, saturated or unsaturated C7-C24 straight, branched chain, or cyclic alkyl, alkenyl, alkynyl, and aromatic monocarboxylic acids, C3-C24 straight, branched chain, or cyclic alkyl, alkenyl, alkynyl, and aromatic di-, tri-, or higher polycarboxylic acids, and mixtures thereof. In many instances, it is preferred that the first and second dispersants respectively and individually comprise one or more dicarboxylic acid esters derived from the esterification of C3-C15 alkyl dicarboxylic acids, with the final diesters being C4-C40 diesters.
  • Useful carboxylic acids which may be esterified and used as dispersants in accordance with the invention include: C7-C24 monocarboxylic acids, such as heptanoic, octanoic, nonanoic, decanoic, lauric, myristic, palmitic, stearic, palmitoleic, oleic, linoleic, linolenic, and benzoic; C3-C24 dicarboxylic acids, such as propanedioic (malonic), butanedioic (succinic), pentanedioic (glutaric), hexanedioic (adipic), heptanedioic (pinelic), octanedioic (suberic), nonanedioic (azelaic), decanedioic (sebacic), undecanedioic, dodecanedioic, maleic, glutaconic, traumatic, muconic, itaconic, phthalic, isophthalic, terephthalic; and tricaroboxylic acids, such as citric, isocitric, aconoicic, carballyic, and trimesic.
  • The carboxylic acids are normally esterified using one or more organic alcohols, and again the class of useable alcohols is quite broad, including straight, branched chain, or cyclic, saturated or unsaturated C1-C24 alkyl, alkenyl, alkynyl, and aryl alcohols containing one or more —OH alcohol groups. The preferred alcohols used in the esterification of the carboxylic acids are the straight, branched chain, or cyclic C1-C15 mono-, di-, and tri-alcohols.
  • Particularly preferred dispersants comprise esters derived from C5-C15 alkyl dicarboxylic acids, and even more preferably C4-C8 alkyl dicarboxylic acids such as glutaric, succinic, and adipic acids, esterified using C1-C15 straight or branched chain organic alcohols. A commercially available product RHODISOLV DIB may be used in the invention and is essentially completely an adipic acid diisobutyl ester (C14H26O4, CAS #141-04-8) having a molecular weight of 258.36. However, for reasons of cost and ready availability, it is preferred to use mixtures of esters derived form the manufacturing waste generated during nylon manufacturing. For example, the ESTASOL solvents may be used, which are essentially anhydrous mixtures containing from about 15-25% by weight dimethyl succinate (CAS #106-65-0), from about 12-23% by weight dimethyl adipate (CAS #627-93-0), and from about 55-65% by weight dimethyl glutarate. (CAS #1119-40-0).
  • Whatever ester-containing dispersant(s) are employed, it is preferred that the total of the ester groups (—COO—) in the complete dispersant (i.e., the complete dispersant whether made up of 1 ester species or a plurality thereof and any other dispersant components) ranges from about 15-50% by weight, more preferably from about 30-45% by weight, based upon the total weight of a given volume of the complete dispersant taken as 100% by weight.
  • The Complete Anti-Corrosion Systems
  • The anti-corrosion systems of the invention, comprising epoxy and curing agent components in compatible ester-containing dispersants, can be used as a pre-mixed composition containing all of the components combined in a single liquid, i.e., the epoxy, curing agent, and dispersant. In such uses, the pre-mixed composition is prepared at or near the time of application thereof by mixing together the individual epoxy and curing agent components. This is done so as to assure that there is no undue pre-reaction between the epoxy and curing agent prior to application thereof to surfaces to be protected. In alternate uses, the epoxy and curing agent components may be sequentially applied to surfaces to be protected, as described in U.S. Pat. No. 7,407,687.
  • Considering first the respective epoxy and curing agent components as individual compositions, each should have the active epoxy or curing agent present in the dispersant at a level of from about 10-50% by volume, more preferably from about 15-40% by volume, with the dispersant making up the balance of the individual compositions. When the epoxy and curing agent components are combined as a single composition, the epoxy fraction should be present at a level of from about 25-50% by volume, more preferably from about 30-40% by volume; the curing agent fraction should be present at a level of from about 25-50% by volume, more preferably from about 30-40% by volume; and the dispersant should be present at a level of from about 5-50% by volume, more preferably from about 20-40% by volume. The ratio of the curing agent to the epoxy fraction in the overall systems should be from about 1-4 parts by weight curing agent to each part by weight epoxy, more preferably from about 2-3 parts by weight curing agent to each part by weight epoxy. The most preferred systems include Epon 828 epoxy resin, imidazoline curing agent, and with the first and second dispersants being identical and each containing quantities of C1-C6 alkyl esters of glutaric acid, succinic acid, and adipic acid.
  • The anti-corrosion systems of the invention find particular utility in the treatment of metal surfaces of oil and gas recovery or conveying equipment. In such situations, the individual epoxy and curing agent components may be sequentially applied to such surfaces in any order, or these components may be pre-mixed and applied together. In either case, the compositions provide significant protection against corrosion typically seen in such contexts. The anti-corrosion systems of the invention can be used in a wide variety of other situations where corrosion problems exist. To give one example, the systems may be applied to the inner surfaces of liquid tanks forming a part of rail cars or tanker trucks. In these contexts, the anti-corrosion systems may be applied by spraying, rolling, painting, or any other convenient method. Once the liquid system is applied to a metal surface, the epoxy and curing agent materials react and cure, with the ester dispersants substantially completely evaporating into ambient air, leaving the dried, reacted residue of the systems as thin anti-corrosion protective layers.
  • The systems of the invention can also be applied to downhole equipment in oil or gas wells. This is typically done by injecting the liquid system, or the individual components thereof in any sequential order, into a well. If formation water is present in the well, the active epoxy and curing agent components form a protective layer on the downhole equipment, while the dispersant is merely dissolved in the formation water.
  • A chief advantage of the anti-corrosion systems of the invention is that the VOC levels are drastically reduced, as compared with the prior systems making use of organic solvents, such as toluene or HAN solvents. In addition, it has been discovered that the combined-component anti-corrosion systems of the invention resist phase separation to a much higher degree than the conventional systems.
  • Example 1
  • Preferred dispersants in accordance with the invention may be prepared using the following ingredients:
  • PREFERRED
    COMPONENT RANGE AMOUNT
    glutaric acid ((C3H6(COOH)2) 10-60% 30%
    succinic acid (HOOC—(CH2)2—COOH)  2-25% 10%
    adipic acid ((CH2)4(COOH)2)  0-15% 4%
    isobutanol ((CH3)2CHCH2OH) 10-85% 50%
    phosphoric acid (H3PO4) 1-5% 2%
    sodium bicarbonate (NaHCO3) 1-5% 4%
  • The ester dispersant was prepared using the preferred amounts of acids, isobutanol, and phosphoric acid set forth above. The glutaric, succinic, and adipic acids, together with isobutanol and phosphoric acid, were first charged into a reactor with stirring. The reaction mixture was heated with stirring and refluxing to 237° F. (114° C.), and the reaction was allowed to proceed until the temperature dropped to 230° F. (110° C.). The distillate was collected at a slightly higher temperature of approximately 240° F. Additional isobutanol was added to the reactor in a weight amount equal to that of the collected distillate. The reaction was continued by collection of reflux at 10 minutes, 30 minutes, 1 hour, 2 hours, 3 hours, 4 hours, 5 hours, and 5.5 hours with further additions of isobutanol equaling the weight amounts of the collected distillate. The reaction was monitored by IR to determine the loss of the 1711 cm−1 carboxylic acid peak, and growth of the 1735 cm−1 ester peak, and by gas chromatography. At the end of 6 hours reaction time, the mixture was reflux cooled to 230° F. (110° C.). At that point, the sodium bicarbonate was added slowly and carefully, because it created foaming and bubbling with a large amount of carbon dioxide being released from the reactor. In the final step, the mixture was heated to 248° F. (120° C.) for 2 hours. The mixture was then purged with nitrogen to remove any remaining water and isobutanol. The mixture was then cooled to room temperature and dried under a vacuum to remove any residual water and isobutanol. The mixture was then checked by gas chromatography to ensure that all isobutanol had been removed, and filtered.
  • In the foregoing method, the acids used were essentially pure. However, as noted previously, a waste stream from nylon manufacture may be used in lieu of the pure acids. Such waste streams can differ from batch to batch, but all contain the preferred glutaric, succinic, and adipic acids, and may also contain other carboxylic acids and metal salts. In the use of these waste mixtures, it may be appropriate to initially load the reactor with the waste stream acid blend, and heat to 220° C. for 3 hours and/or add 1000 ppm copper metal. These steps are reported to reduce the color of the final product (U.S. Pat. No. 3,991,100, incorporated by reference herein).
  • It is desirable to remove the water produced during the esterification reaction, which may be accomplished by the above-described technique of distilling water/isobutanol mixtures, followed by adding back isobutanol in a weight amount equal to the distillate. Alternately, the water/isobutanol mixture can be distilled, followed by fractional distillation of the isobutanol and returning this isobutanol to the reaction vessel. As a further option, the distilled water/isobutanol mixture is passed through activated molecular sieves, followed by pumping the recovered isobutanol back into the reactor.
  • Solvents made in accordance with this Example can be used both the epoxy and curing agent components of the overall anti-corrosion systems of the invention.
  • Example 2
  • In order to determine the relative degree of phase separation of components between a prior art anti-corrosion system using HAN solvent, versus an anti-corrosion system using an ester dispersant in accordance with the invention, the following test was conducted. First, a sample of a known anti-corrosion system was provided by mixing in a beaker one part by weight of an epoxy fraction A, made up of 35% by weight Epon 828 epoxy dispersed in 65% by weight HAN solvent, and one part by weight of a curing agent fraction B, made up of about 5% by weight ethoxylated tallow diamine and about 30% by weight imidazoline dispersed in 65% by weight HAN solvent. Three parts by weight of water were also added to the beaker.
  • Second, a sample of an anti-corrosion system in accordance with the invention was prepared by mixing in another beaker one part by weight of an epoxy fraction A′, made up of 35% by weight Epon 828 epoxy in the previously described RHODISOLV DIB ester solvent, and one part by weight of a curing agent fraction B′, made up of 35% by weight imidazoline in 65% by weight RHODISOLV DIB ester solvent. Three parts by weight of water was also added in this beaker.
  • Photographs were taken at times 0, and at wait times of 15, 30, and 40 minutes, shown as FIGS. 1-4, respectively. As is readily apparent, at time 0, the test systems were essentially the same in terms of color and separation of ingredients. However, as the test proceeded, the ingredients of the prior art system displayed a marked tendency to separate, whereas the system of the present invention displayed virtually no separation.

Claims (19)

We claim:
1. A liquid composition comprising an epoxy curing agent in a compatible dispersant, said dispersant selected from the group consisting of C8-C40 monocarboxylic acid esters, C4-C40 polycarboxylic acid esters, and mixtures thereof, the total of the ester groups (—COO—) in said dispersant is from about 15-50% by weight, based upon the total weight of a given volume of the complete dispersant taken as 100% by weight.
2. The composition of claim 1, the total of the ester groups (—COO—) in said dispersant is from about 30-45% by weight, based upon the total weight of a given volume of the complete dispersant taken as 100% by weight.
3. The composition of claim 1, said dispersant including at least one C4-C40 polycarboxylic acid ester.
4. The composition of claim 1, said dispersant comprising a plurality of said esters.
5. The composition of claim 4, said dispersant comprising a plurality of C4-C40 of dicarboxylic acid esters.
6. The composition of claim 5, said dicarboxylic acid esters selected from the group consisting of isobutyl esters of dicarboxylic acids selected from the group consisting of glutaric, succinic, and adipic acids, and mixtures thereof.
7. A liquid composition comprising an epoxy in a compatible dispersant, said dispersant selected from the group consisting of C8-C40 monocarboxylic acid esters, C4-C40 polycarboxylic acid esters, and mixtures thereof, the total of the ester groups (—COO—) in said dispersant is from about 15-50% by weight, based upon the total weight of a given volume of the complete dispersant taken as 100% by weight.
8. The composition of claim 7, the total of the ester groups (—COO—) in said dispersant is from about 30-45% by weight, based upon the total weight of a given volume of the complete dispersant taken as 100% by weight.
9. The composition of claim 7, said dispersant including at least one C4-C40 polycarboxylic acid ester.
10. The composition of claim 7, said dispersant comprising a plurality of said esters.
11. The composition of claim 10, said dispersant comprising a plurality of C4-C40 of dicarboxylic acid esters.
12. The composition of claim 11, said dicarboxylic acid esters selected from the group consisting of isobutyl esters of dicarboxylic acids selected from the group consisting of glutaric, succinic, and adipic acids, and mixtures thereof.
13. An anti-corrosion product comprising a liquid composition including an epoxy, a curing agent for the epoxy, and dispersants for the epoxy and curing agent, said dispersants each comprising at least one ester selected from the group consisting of C8-C40 monocarboxylic acid esters, C4-C40 polycarboxylic acid esters, and mixtures thereof, the total of the ester groups (—COO—) in each of said dispersants ranging from about 15-50% by weight, based upon the total weight of a given volume of the complete dispersants taken as 100% by weight.
14. The product of claim 13, the total of the ester groups (—COO—) in said dispersants being from about 30-45% by weight, based upon the total weight of a given volume of the complete dispersant taken as 100% by weight.
15. The product of claim 13, said dispersant including at least one C4-C40 polycarboxylic acid ester.
16. The product of claim 13, said dispersant comprising a plurality of said esters.
17. The product of claim 16, said dispersant comprising a plurality of C4-C40 of dicarboxylic acid esters.
18. The product of claim 17, said dicarboxylic acid esters selected from the group consisting of isobutyl esters of dicarboxylic acids selected from the group consisting of glutaric, succinic, and adipic acids, and mixtures thereof.
19. A method of treating a metallic surface comprising the step of applying the product of claim 18 to the surface.
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8575237B1 (en) * 2013-05-22 2013-11-05 Jacam Chemical Company 2013, Llc Corrosion inhibitor systems using environmentally friendly green solvents
US20140349015A1 (en) * 2013-05-22 2014-11-27 Jacam Chemical Company 2013, Llc Corrosion inhibitor systems using environmentally friendly green solvents
US9617645B1 (en) 2015-04-24 2017-04-11 MicroCor Technologies, Inc. Anti-corrosion and water-repellent substance and method
US11911790B2 (en) 2022-02-25 2024-02-27 Saudi Arabian Oil Company Applying corrosion inhibitor within tubulars

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5859095A (en) * 1987-05-11 1999-01-12 Morton International, Inc. Epoxy corrosion-inhibiting coating composition
US20110126980A1 (en) * 2008-07-23 2011-06-02 Campbell Christopher J Two-part epoxy-based structural adhesives
WO2011093474A1 (en) * 2010-01-29 2011-08-04 日本化薬株式会社 Phenolic compound, epoxy resin, epoxy resin composition, prepreg, and cured product thereof
US20120309897A1 (en) * 2009-06-30 2012-12-06 Lanxess Deutschland Gmbh Polymers containing heterocyclic 3-ring compounds and iodine-containing compounds
US8575237B1 (en) * 2013-05-22 2013-11-05 Jacam Chemical Company 2013, Llc Corrosion inhibitor systems using environmentally friendly green solvents

Family Cites Families (48)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3282836A (en) 1963-03-22 1966-11-01 Shell Oil Co Corrosion resistant liquid hydrocarbons containing mixture of alkyl succinic acid and polyamine salt thereof
BE615628A (en) 1963-11-05 1900-01-01
DE2217331C3 (en) * 1971-04-23 1978-07-20 Hoechst Ag, 6000 Frankfurt Process for the production of moldings and coatings
GB1460999A (en) 1973-11-07 1977-01-06 Lubrizol Corp Salts of mannich bases or derivatives thereof and liquid hydrocarbon fuels containing them
JPS5241767B2 (en) 1974-03-15 1977-10-20
JPS56109261A (en) 1980-02-04 1981-08-29 Nippon Zeon Co Ltd Expansion type rust-inhibiting material
US5079041A (en) 1980-08-27 1992-01-07 Phillips Petroleum Company Composition and method for corrosion inhibition utilizing an epoxy resin, an amine curing agent, an alcohol and optionally a hydrocarbon diluent
US5045359A (en) 1980-08-27 1991-09-03 Phillips Petroleum Company Composition and method for corrosion inhibition of metal surface with epoxy resin and an N-tallow-1,3-diaminopropane curing agent
US5344674A (en) 1980-08-27 1994-09-06 Phillips Petroleum Company Composition and method for corrosion inhibition utilizing an epoxy resin, an amine curing agent, an alcohol and optionally a hydrocarbon diluent
EP0158128B1 (en) 1984-03-16 1987-11-25 Vianova Kunstharz Aktiengesellschaft Process for producing cathodically depositable electro-dipping paint binders
US4608405A (en) 1985-05-06 1986-08-26 Celanese Corporation Aqueous based epoxy resin curing agents
US4749728A (en) * 1986-06-06 1988-06-07 The Glidden Company Epoxy/nucleophile transesterification catalysts and thermoset coatings
US4863525A (en) * 1986-11-13 1989-09-05 Ashland Oil, Inc Flush solvents for epoxy adhesives
US5082698A (en) * 1987-05-11 1992-01-21 Morton Coatings, Inc. Aqueous epoxy resin compositions and metal substrates coated therewith
US4808441A (en) 1987-05-15 1989-02-28 Ford Motor Company Metal articles having corrosion-resistant epoxy coatings
JPS63301271A (en) 1987-05-30 1988-12-08 Nippon Oil & Fats Co Ltd Water-soluble rust-preventive paint composition
US5085788A (en) * 1987-11-19 1992-02-04 Exxon Chemical Patents Inc. Oil soluble dispersant additives useful in oleaginous compositions
JP2651223B2 (en) * 1988-11-29 1997-09-10 サンスター技研株式会社 Two-pack primer
JP2778183B2 (en) 1990-02-17 1998-07-23 東亞合成株式会社 Epoxy powder coating composition
US5252363A (en) * 1992-06-29 1993-10-12 Morton International, Inc. Method to produce universally paintable passivated galvanized steel
JPH07216057A (en) 1994-01-27 1995-08-15 Bridgestone Corp Epoxy resin composition
US5576416A (en) 1994-12-13 1996-11-19 Air Products And Chemicals, Inc. Amide-containing self-emulsifying epoxy curing agent
JPH08311392A (en) 1995-05-23 1996-11-26 Abc Trading Co Ltd Epoxy resin coating material
US5962629A (en) 1995-11-16 1999-10-05 Shell Oil Company Amine-terminated polyamide in oil-in-water emulsion
US6071436A (en) 1995-12-01 2000-06-06 Geo Specialty Chemicals, Inc. Corrosion inhibitors for cement compositions
JP3747294B2 (en) 1996-02-06 2006-02-22 出光興産株式会社 Fuel oil composition and method for producing the same
US5851311A (en) 1996-03-29 1998-12-22 Sophia Systems Co., Ltd. Polymerizable flux composition for encapsulating the solder in situ
JP3679563B2 (en) 1996-08-26 2005-08-03 謙一 安田 Epoxy resin-based composition
JPH1067995A (en) 1996-08-28 1998-03-10 Yachiyo Res Kk Load-bearing lubricating oil composition
JPH10120973A (en) 1996-10-17 1998-05-12 Toray Ind Inc Thermosetting coating composition
US5936059A (en) 1997-08-29 1999-08-10 Jacam Chemical Partners, Ltd. Epoxy corrosion inhibition systems including ethoxylated curing agents
US6059991A (en) * 1997-12-12 2000-05-09 Troy Technology Corporation, Inc. Stabilized composition containing halopropynyl compounds
US6258920B1 (en) 1999-01-27 2001-07-10 Air Products And Chemicals, Inc. Polyamidoamine curing agents based on mixtures of fatty and aromatic carboxylic acids
US20030054173A1 (en) * 2001-09-11 2003-03-20 Ruddy Larry R. Flexible epoxy sound damping coatings
US8058493B2 (en) 2003-05-21 2011-11-15 Baker Hughes Incorporated Removing amines from hydrocarbon streams
JP4882217B2 (en) 2004-10-13 2012-02-22 Jfeスチール株式会社 Resin coated heavy duty steel
ATE430788T1 (en) * 2005-05-19 2009-05-15 Lord Corp ROOM TEMPERATURE CURED, PROTECTIVE SEALANT
DE102005026523A1 (en) * 2005-06-08 2006-12-14 Eckart Gmbh & Co. Kg Two-component anticorrosion paint, its use and process for its preparation
US7682526B2 (en) 2005-12-22 2010-03-23 Afton Chemical Corporation Stable imidazoline solutions
US7407687B2 (en) * 2006-01-12 2008-08-05 Jacam Chemicals, Llc Method of sequentially forming anti-corrosive coatings
CN101821333A (en) * 2007-07-26 2010-09-01 汉高公司 Curable epoxy resin-based adhesive compositions
US8053031B2 (en) 2007-07-26 2011-11-08 Raven Lining Systems Inc. Two-part epoxy composition
EP2028244A1 (en) 2007-08-02 2009-02-25 Cytec Surface Specialties Austria GmbH Water-borne paints based on epoxy resins
EP2265657A2 (en) * 2008-04-07 2010-12-29 Dow Global Technologies Inc. Epoxy resin compositions having improved low temperature cure properties and processes and intermediates for making the same
JP5155723B2 (en) 2008-04-14 2013-03-06 株式会社四国総合研究所 Method of coating galvanized steel structure
EP2135909B1 (en) * 2008-06-12 2018-01-10 Henkel IP & Holding GmbH Next generation, highly toughened two part structural epoxy adhesive compositions
US8486873B2 (en) 2010-03-31 2013-07-16 Chevron Oronite Company Llc Lubricating oil compositions containing epoxide antiwear agents
JP5800699B2 (en) 2011-03-28 2015-10-28 株式会社イオックス Anti-corrosion coating composition

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5859095A (en) * 1987-05-11 1999-01-12 Morton International, Inc. Epoxy corrosion-inhibiting coating composition
US20110126980A1 (en) * 2008-07-23 2011-06-02 Campbell Christopher J Two-part epoxy-based structural adhesives
US20120309897A1 (en) * 2009-06-30 2012-12-06 Lanxess Deutschland Gmbh Polymers containing heterocyclic 3-ring compounds and iodine-containing compounds
WO2011093474A1 (en) * 2010-01-29 2011-08-04 日本化薬株式会社 Phenolic compound, epoxy resin, epoxy resin composition, prepreg, and cured product thereof
US20120296011A1 (en) * 2010-01-29 2012-11-22 Nipponkayaku Kabushikikaisha Phenolic compound, epoxy resin, epoxy resin composition, prepreg, and cured product thereof
US8575237B1 (en) * 2013-05-22 2013-11-05 Jacam Chemical Company 2013, Llc Corrosion inhibitor systems using environmentally friendly green solvents

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