WO2014031305A1 - Aliphatic dicarboxylic acid mixture formulation - Google Patents

Aliphatic dicarboxylic acid mixture formulation Download PDF

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Publication number
WO2014031305A1
WO2014031305A1 PCT/US2013/053247 US2013053247W WO2014031305A1 WO 2014031305 A1 WO2014031305 A1 WO 2014031305A1 US 2013053247 W US2013053247 W US 2013053247W WO 2014031305 A1 WO2014031305 A1 WO 2014031305A1
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WO
WIPO (PCT)
Prior art keywords
diacid
weight
diacids
composition
mixture
Prior art date
Application number
PCT/US2013/053247
Other languages
French (fr)
Inventor
James Michael Garner
Jian Shen
Denis John Smit
Edward A. SULLIVAN
Original Assignee
Invista North America S.A R.L.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Invista North America S.A R.L. filed Critical Invista North America S.A R.L.
Priority to US14/421,208 priority Critical patent/US20150299867A1/en
Priority to CN201380048055.3A priority patent/CN104718315A/en
Priority to EP13750431.2A priority patent/EP2888387A1/en
Priority to KR20157006847A priority patent/KR20150044943A/en
Priority to JP2015528499A priority patent/JP2015533932A/en
Publication of WO2014031305A1 publication Critical patent/WO2014031305A1/en

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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
    • C02F5/08—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents
    • C02F5/10—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C08K5/092—Polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/58—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M173/00—Lubricating compositions containing more than 10% water
    • C10M173/02—Lubricating compositions containing more than 10% water not containing mineral or fatty oils
    • C—CHEMISTRY; METALLURGY
    • C23—COATING 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
    • C23F—NON-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
    • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/04—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in markedly acid liquids
    • C—CHEMISTRY; METALLURGY
    • C23—COATING 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
    • C23F—NON-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
    • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/06—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in markedly alkaline liquids
    • C—CHEMISTRY; METALLURGY
    • C23—COATING 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
    • C23F—NON-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
    • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
    • C—CHEMISTRY; METALLURGY
    • C23—COATING 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
    • C23F—NON-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
    • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
    • C23F11/10—Inhibiting 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
    • C—CHEMISTRY; METALLURGY
    • C23—COATING 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
    • C23F—NON-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
    • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
    • C23F11/10—Inhibiting 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
    • C23F11/12—Oxygen-containing compounds
    • C23F11/124—Carboxylic acids
    • C23F11/126—Aliphatic acids
    • C—CHEMISTRY; METALLURGY
    • C23—COATING 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
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
    • C09K5/08—Materials not undergoing a change of physical state when used
    • C09K5/10—Liquid materials
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2207/121—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of seven or less carbon atoms
    • C10M2207/123—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of seven or less carbon atoms polycarboxylic
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2207/125—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids
    • C10M2207/127—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids polycarboxylic
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions
    • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/04—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2215/042—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Alkoxylated derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions
    • C10M2215/20—Containing nitrogen-to-oxygen bonds
    • C10M2215/202—Containing nitrogen-to-oxygen bonds containing nitro groups
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/12—Inhibition of corrosion, e.g. anti-rust agents or anti-corrosives

Definitions

  • This invention relates to a novel mixture composition comprising various aliphatic dicarboxylic acids (diacids) in particular amounts.
  • the invention further relates to a composition which comprises the novel mixture composition comprising various diacids in particular amounts, water and at least one water-soluble organic amine, and a method for use thereof.
  • Diacids are generally useful in polymer and corrosion inhibitor formulations, and can be esterified to produce diesters for use in solvent, cleaning, and lubricating oil formulations. These diesters can be reduced to the corresponding aliphatic dialcohols for use in polyurethane formulations.
  • the composition of a mixture of various diacids can have a strong and unpredictable influence on the properties and effectiveness of final use formulations in specific applications. Therefore, a mixture composition comprising various diacids providing commercially desirable properties in final use formulations for specific applications is greatly needed.
  • WO 9502712 discloses generally that carboxylic acids or their salts may be used in agents for the treatment of metal surfaces, It also discloses generally a method for separating the agents from aqueous media after use for recovering the carboxylic acids or salts.
  • U.S. Patent No. 4,941,925 discloses a method for high pressure detergent water cleaning of metal working compounds, swarf and chips from metal surfaces, using as the detergent a composition consisting essentially of to C 14 diacids and mixtures thereof. Exemplified in this disclosure is use of a mixture of C 10 to C 12 diacids, with the C 12 diacid being 74 % of the diacid mixture.
  • U.S. Patent No. 4,946,616 discloses a coolant composition for use in a water cooled automotive engine comprising a freezing point depressant and an inhibitor consisting essentially of 2 to 5.5 weight percent of at least two C 7 to C 14 diacids or salts thereof, and a hydrocarbyl triazole or salt thereof. Exemplified in this disclosure is use of a mixture of C 10 and Ci2 diacids.
  • U.S. Patent No. 7,084,300 B2 discloses a method for synthesis of diacids, particularly diacids having from eight to sixteen carbon atoms, involving oxidation, separation, washing and recovering steps.
  • WO 2006/071996 discloses in general corrosion inhibitors useful in water-based heat transfer fluids.
  • a corrosion inhibitor mentioned includes one or more Qo to C 12 diacids or salts thereof, oxyalkylated carboxylate imidazoline, organophosphonic acid or amine salt thereof, and a secondary or tertiary alkanolamine organic acid salting agent.
  • EP 1418253 Bl discloses a composition said to inhibit boiler scale and corrosion containing a C 7 to C 14 diacid component and a fatty polyamine component.
  • the present invention meets these and other needs.
  • a mixture composition comprising: 0.01 to 1 weight % of C 4 diacid, 0.01 to 1 weight % of C5 diacid, 0.01 to 15 weight % of C & diacid, 0.01 to 3 weight % of C 7 diacid, 0.01 to 3 weight % of C g diacid, 2 to 70 weight % of C 9 diacid, 0.01 to 10 weight % of do diacid, 2 to 85 weight % of Cn diacid, 0.01 to 90 weight % of C n diacid, 0.01 to 3 weight % of Ci3 diacid, 0.01 to 1 weight % of C ]4 diacid, 0.01 to 1 weight % of Ci 5 diacid, and 0.01 to 1 weight % of Ci6 diacid.
  • This mixture composition may comprise as little as 0.01 weight % of any one or number of the C 4 to C 8 , o, and C 12 to C 16 diacid components.
  • the mixture composition may comprise from 0.01 to 3 weight % of the C 13 diacid.
  • the mixture composition may comprise a total amount of C 4 to C 7 diacids from 0.01 to 20 weight %.
  • the mixture composition may comprise a total amount of Ci3 to Ci6 diacids from 0.01 to 6 weight %.
  • the mixture composition may also comprise a total amount of C 4 to C 7 diacids from 0.01 to 20 weight % and a total amount of C 13 to C 16 diacids from 0.01 to 6 weight %.
  • the mixture composition can further comprise aliphatic, monocarboxylic acids (monoacids).
  • the total amount of monoacids may comprise between 0.01 to 10 weight % of the mixture composition, for example, between 0.01 to 5 weight % or between 0.01 to 2 weight %.
  • Another embodiment of the present invention is a mixture composition as above wherein at least one of the C 8 to C 12 diacids is manufactured by reaction of cyclododecanol, cyclododecanone, or a combination thereof with nitric acid, and at least one of the C to C 13 diacids is manufactured by oxidative cleavage of unsaturated fatty acids or unsaturated fatty acid esters.
  • adipic acid, dodecanedioic acid, or a combination of adipic acid and dodecanedioic acid are combined with the at least one of the C 8 to C 12 diacids and the at least one of the C9 to C 13 diacids of the preceding embodiment to obtain a mixture composition as above.
  • Another embodiment of the present invention is a mixture composition as above wherein at least one of the C 8 to C 12 diacids is manufactured by reaction of cyclododecanol, cyclododecanone, or a combination thereof with nitric acid.
  • adipic acid, dodecanedioic acid, or a combination of adipic acid and dodecanedioic acid are combined with the at least one of the C 8 to C 12 diacids of the preceding embodiment to obtain a mixture composition as above.
  • Another embodiment of the present invention is a mixture composition as above wherein at least one of the C9 to C 13 diacids is manufactured by oxidative cleavage of unsaturated fatty acids or unsaturated fatty acid esters.
  • adipic acid, dodecanedioic acid, or a combination of adipic acid and dodecanedioic acid are combined with the at least one of the C9 to C 13 diacids of the preceding embodiment to obtain a mixture composition as above.
  • Another embodiment of the present invention is a mixture composition as above comprising a total of from 1 to 90 weight % of C 8 to C 12 diacids that are manufactured by reaction of cyclododecanol, cyclododecanone, or a combination thereof with nitric acid; and another embodiment is a mixture composition as above comprising a total of from 1 to 90 weight % of C 9 to C 13 diacids that are manufactured by oxidative cleavage of unsaturated fatty acids or unsaturated fatty acid esters.
  • Another embodiment of the present invention is a mixture composition
  • a mixture composition comprising: 0.01 to 1 weight % of C 4 diacid, 0.01 to 1 weight % of C 5 diacid, 0.01 to 2 weight % of C 6 diacid, 0.01 to 3 weight % of C 7 diacid, 1 to 3 weight % of C 8 diacid, 5 to 70 weight % of C 9 diacid, 4 to 7 weight % of C 10 diacid, 12 to 45 weight % of C n diacid, 3 to 45 weight % of diacid, 0.01 to 3 weight % of C 13 diacid, 0.01 to 1 weight % of C 14 diacid, 0.01 to 1 weight % of C 15 diacid, and 0.01 to 1 weight % of C 16 diacid.
  • the mixture composition may comprise as little as 0.01 weight % of any one or number of the C 4 to C 7 and C 13 to Ci 6 diacid components.
  • this mixture composition may comprise a total amount of C 4 to C diacids from 0.01 to 7 weight %.
  • this mixture composition may comprise a total amount of C 13 to C 16 diacids from 0.01 to 6 weight %.
  • the mixture composition may comprise a total amount of C 4 to C 7 diacids from 0.01 to 7 weight % and a total amount of C 13 to Ci 6 diacids from 0.01 to 6 weight %.
  • the mixture composition can further comprise at least one monoacid.
  • the total amount of monoacids may comprise between 0.01 to 10 weight % of the mixture composition, for example, between 0.01 to 5 weight % or between 0.01 to 2 weight %.
  • Another embodiment of the present invention is a composition, for example an aqueous composition, comprising the mixture composition of diacids as above, water and at least one water-soluble organic amine.
  • Another embodiment of the present invention is a method for inhibiting corrosion of metal comprising contacting the metal with the composition comprising the mixture composition of diacids as above, water and at least one water-soluble organic amine.
  • the present invention is directed to a specific novel mixture composition comprising various diacids in certain amounts which provide commercially desirable properties in final use formulations for specific applications, such as, for example, inhibiting the corrosion of metals.
  • diacid abbreviations, formulas, and names are provided in Table 1.
  • the mixture composition of diacids comprises 0 to about 1 weight % of C 4 diacid, 0.01 to 1 weight % of C 5 diacid, 0.01 to 15 weight % of C 6 diacid, 0.01 to 3 weight % of C 7 diacid, 0.01 to 3 weight % of C 8 diacid, 2 to 70 weight % of C 9 diacid, 0.01 to 10 weight % of Co diacid, 2 to 85 weight % of C n diacid, 0.01 to 90 weight % of C u diacid, 0.01 to 3 weight % of diacid, 0.01 to 1 weight % of C 1 diacid, 0.01 to 1 weight % of C15 diacid, and 0.01 to 1 weight % of Ci 6 diacid.
  • This mixture composition may comprise as little as 0.01 weight % of any one or number of the C 4 to C 8 , Cio, and Q 2 to Ci 6 components.
  • the mixture composition may comprise from 0.01 to 3 weight % of the (3 ⁇ 4 diacid.
  • the mixture composition can comprise 1 to 15 weight % of C 6 diacid.
  • the mixture composition can comprise a total amount of C 4 to C 7 diacids from 0.01 to 20 weight %.
  • the mixture composition may also comprise a total amount of C 4 to C 7 diacids from 0.01 to 20 weight % and a total amount of Q 3 to C e diacids from 0.01 to 6 weight %.
  • the mixture composition can further comprise at least one monoacid.
  • the total amount of monoacids may comprise between 0.01 to 10 weight % of the mixture composition, for example, between 0.01 to 5 weight % or between 0.01 to 2 weight %.
  • Monoacids may be selected from C 4 to Ci 6 , aliphatic monocarboxylic acids where the aliphatic hydrocarbon chain of each monoacid may be linear or branched.
  • Another embodiment of the present invention is a mixture composition of diacids comprising 0.01 to 1 weight % of C 4 diacid, 0.01 to 1 weight % of C 5 diacid, 0.01 to 2 weight % of C 6 diacid, 0.01 to 3 weight % of C 7 diacid, 1 to 3 weight % of Cg diacid, 5 to 70 weight % of C 9 diacid, 4 to 7 weight % of C 10 diacid, 12 to 45 weight % of Cn diacid, 3 to 45 weight % of C 12 diacid, 0.01 to 3 weight % of C 13 diacid, 0.01 to 1 weight % of C M diacid, 0.01 to 1 weight % of Ci5 diacid, and 0.01 to 1 weight % of C 16 diacid.
  • this mixture composition can comprise 5 to 15 weight % of Cu diacid.
  • This mixture composition may comprise as little as 0.01 weight % of any one or number of the C 4 to C 7 , and C 13 to C 16 components.
  • the mixture composition may comprise from 0.01 to 3 weight % of Cn diacid.
  • this mixture composition can comprise a total amount of C 4 to C 7 diacids from 0.01 to 7 weight % and a total amount of C13 to C16 diacids from 0.01 to 6 weight %.
  • the mixture composition can further comprise at least one monoacid.
  • the total amount of monoacids may comprise between 0.01 to 10 weight % of the mixture composition, for example, between 0.01 to 5 weight % or between 0.01 to 2 weight %.
  • Monoacids may be selected from C4 to CI 6, aliphatic monocarboxylic acids where the aliphatic hydrocarbon chain of each monoacid may be linear or branched.
  • a mixture of diacids can be manufactured, for example, by reaction of cyclododecanol, cyclododecanone, or a combination of cyclododecanol and
  • the major diacid in the reaction product is a Q 2 diacid, dodecanedioic acid, but it can also contain other shorter chain diacids, comprising a Cg diacid (suberic acid), a C9 diacid (azelaic acid), a C 10 diacid (sebacic acid), and a Cn diacid (undecanedioic acid).
  • the reaction product can further comprise a C 4 diacid (succinic acid), a C5 diacid (glutaric acid), a C 6 diacid (adipic acid), and a C 7 diacid (pimelic acid), or any combination of these diacids.
  • a suitable method for recovering the diacids for the present invention is fractional crystallization.
  • a reaction of cyclododecanol, cyclododecanone, or a combination of cyclododecanol and cyclododecanone, with nitric acid can be carried out in the presence of water to produce an aqueous reaction product, comprising, for example, the Cg to C12 diacids.
  • a fraction of the Co diacid can be first crystallized from this aqueous reaction product in high purity (e.g. > 90%).
  • this liquor becomes enriched in the C 8 to Cn diacids and depleted in the C ]2 diacid, relative to the aqueous reaction product. But this mother liquor can still comprise significant amounts of the 2 diacid.
  • the mixture of C 8 to Ci 2 diacids can then be recovered from this aqueous mother liquor by various methods.
  • recovery methods include (1) a second fractional crystallization of a solid mixture of C 8 to Ci 2 diacids from the aqueous mother liquor, or (2) partial or complete evaporation of water from the aqueous mother liquor to crystallize or precipitate a solid mixture of C 8 to Q 2 diacids.
  • filtration or decantation can be applied to separate the solid mixture of C 8 to Q 2 diacids from any resulting mother liquor.
  • the recovered mixture of C 8 to C 12 diacids comprises from 10 to 60 weight % of the Q 2 diacid in the recovered mixture of C 8 to C 12 diacids, for example from 30 to 50 weight % of the recovered mixture of C 8 to Ci 2 diacids.
  • the recovered mixture of C 8 to Q 2 diacids further comprises a mixture of the C 6 and C 7 diacids and the total amount of C 6 and C 7 diacids is from 0.1 to 10 weight % of the recovered mixture of C 8 to C 12 diacids, for example from 0.5 to 5 weight % of the recovered mixture of C 8 to Ci 2 diacids.
  • the recovered mixture of C 8 to Ci2 diacids further comprises a mixture of C 4 , C 5 , C 6 and C 7 diacids and the total amount of C 4 to C 7 diacids is less than 10 weight % of the recovered mixture of C 8 to Ci 2 diacids, for example from 0.5 to 5 weight % of the recovered mixture of C 8 to C 12 diacids.
  • the mixture of Cg to Ci 3 diacids can be recovered from the resulting reaction product.
  • unsaturated fatty acids and unsaturated fatty acid esters include palmitoleic acid, oleic acid, asclepic acid, linoleic acid, a-linolenic acid, gondoic acid, erucic acid, methyl esters of the preceding unsaturated fatty acids, glyceryl esters of the preceding unsaturated fatty acids, and mixtures thereof.
  • Oxidative cleavage of unsaturated fatty acids or unsaturated fatty acid esters can be carried out using oxidants such as ozone and oxygen, ozone and hydrogen peroxide, or nitric acid.
  • the mixture composition of diacids as above can be obtained by combining diacid mixtures together, by combining at least one diacid mixture with at least one pure diacid, or by combining more than one pure diacid together, all in the proper proportions.
  • Another embodiment of the present invention is a mixture composition as above wherein at least one of the Cg to C 12 diacids is manufactured by reaction of cyclododecanol, cyclododecanone, or a combination thereof with nitric acid, and at least one of the C9 to C13 diacids is manufactured by oxidative cleavage of unsaturated fatty acids or unsaturated fatty acid esters.
  • the mixture composition of diacids as above is obtained by combining the at least one of the C 8 to C 12 diacids with the at least one of the C9 to C 13 diacids.
  • the mixture composition of diacids as above is obtained by combining the at least one of the C 8 to C 12 diacids, at least one of the C9 to C 13 diacids, and another diacid selected from the group of adipic acid and dodecanedioic acid.
  • Another embodiment of the present invention is a mixture composition as above wherein at least one of the C 8 to C 12 diacids is manufactured by reaction of cyclododecanol, cyclododecanone, or a combination thereof with nitric acid.
  • the mixture composition of diacids as above is obtained by combining the at least one of the C 8 to C 12 diacids with another diacid selected from the group of adipic acid and dodecanedioic acid.
  • Another embodiment of the present invention is a mixture composition as above wherein at least one of the C9 to C 13 diacids is manufactured by oxidative cleavage of unsaturated fatty acids or unsaturated fatty acid esters.
  • the mixture composition of diacids as above is obtained by combining the at least one of the C9 to C 13 diacids with another diacid selected from the group of adipic acid and dodecanedioic acid.
  • a composition comprising the diacid mixture composition as above, water and at least one water-soluble organic amine is very useful for inhibiting corrosion of metal surfaces.
  • the water-soluble organic amine is selected from the group consisting of monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, triisopropanolamine, diglycolamine, 2-amino-2-methyl-l-propanol, and mixtures thereof.
  • This composition comprises from about 0.1 to about 25 weight % of the diacid mixture composition as above, from about 15 to about 85 weight % water, and from about 10 to about 65 weight % water-soluble organic amine.
  • a molar ratio of nitrogen atoms in the water-soluble organic amine to carboxylic acid groups in the diacid mixture composition is equal to or greater than one.
  • more than one water- soluble organic amine is selected for the composition.
  • two different water-soluble organic amines are selected for the composition and a molar ratio of the two different water-soluble organic amines is from 0.01 to 100, preferably from 0.1 to 10, e.g. from 0.2 to 5.
  • a specific embodiment of this provides the ratio of nitrogen atoms in the amines to carboxylic acid groups in the diacid mixture of about 1.01 to 1.2.
  • compositions of diacid mixtures can be determined by esterification with a BF3/CH 3 OH reagent followed by analysis of the corresponding diester mixture by gas chromatography.
  • Sebacic acid and dodecanedioic acid are commercial diacids used as corrosion inhibitors in water-based, metal-working fluid formulations.
  • Oxzone diacid is a mixture of C9 to C 13 diacids recovered from the oxidative cleavage of unsaturated fatty acids or unsaturated fatty acid esters with ozone and oxidative workup.
  • Nitric diacid is a mixture of C $ to C 12 diacids recovered from the reaction of a mixture of cyclododecanol and cyclododecanone with nitric acid. A Cn diacid sample was prepared through oxidative cleavage of fatty acids or fatty acid esters.
  • Blends 1 and 2 were obtained by combining the ozone diacid mixture with DDDA.
  • Blend 3 was obtained by combining the ozone diacid mixture with DDDA and adipic acid.
  • Blends 4 and 5 were obtained by combining the ozone diacid mixture with the nitric diacid mixture.
  • Blend 6 was obtained by combining the ozone diacid mixture, the nitric diacid mixture, and DDDA together.
  • Blend 7 was obtained by combining the Cn diacid sample with DDDA. Table 2 presents particulars of the blends.
  • the same GC method can measure the amounts of monoacids in the adipic acid, DDDA, ozone diacid mixture, nitric diacid mixture and Cn diacid sample.
  • the total monoacids are less than 1 weight % meaning that all b lends of Table 2 are also less than 1 weight %.
  • the same GC method can measure the amounts of monoacids in the adipic acid, DDDA, ozone diacid mixture, nitric diacid mixture, and Cn diacid sample.
  • the total monoacids are less than 1 weight % meaning that all blends of Table 2 are also less than 1 weight %.
  • the ASTM standard test method for iron chip corrosion for water-dilutable metalworking fluids was utilized to compare the properties of Blends 1-7 with those of the commercial diacids, sebacic acid and DDDA.
  • the metalworking fluid concentrates were prepared by dissolving the diacid or diacid mixture in an aqueous solution containing water, monoethanolamine, and triethanolamine. Each metalworking fluid concentrate was then diluted with water at either a water hardness of 100 ppm or 500 ppm (as CaC0 3 ), according to the method. Then the breakpoints (concentration of the diacid or diacid mixture required to inhibit corrosion) were determined. A hard water stability test at 500 ppm was also performed for each metalworking fluid concentrate. The formation of a visible precipitate indicated hard water instability - an undesired result. The data from these tests are compiled in Table 3.

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Abstract

A novel mixture composition comprising various aliphatic dicarboxylic acids is provided. Further, a composition comprising the aliphatic dicarboxylic acid mixture composition, water and at least one water-soluble organic amine is provided. Further, a method for inhibiting corrosion of metal surfaces comprising contacting the metal with the composition comprising the aliphatic dicarboxylic acid mixture composition as above, water and at least one water-soluble organic amine is provided.

Description

ALIPHATIC DICARBOXYLIC ACID MIXTURE FORMULATION
CROSS-REFERENCE TO RELATED APPLICATION
[0001] This application claims benefit of priority from U.S. Provisional Application No. 61/692,042 filed August 22, 2012, U.S. Provisional Application No. 61/728,529 filed on November 20, 2012 and U.S. Provisional Application No. 61/731,148 filed on November 29, 2012, These applications hereby incorporate by reference these applications in their entirety.
FIELD OF THE INVENTION
[0002] This invention relates to a novel mixture composition comprising various aliphatic dicarboxylic acids (diacids) in particular amounts. The invention further relates to a composition which comprises the novel mixture composition comprising various diacids in particular amounts, water and at least one water-soluble organic amine, and a method for use thereof.
BACKGROUND OF THE INVENTION
[0003] Diacids are generally useful in polymer and corrosion inhibitor formulations, and can be esterified to produce diesters for use in solvent, cleaning, and lubricating oil formulations. These diesters can be reduced to the corresponding aliphatic dialcohols for use in polyurethane formulations. The composition of a mixture of various diacids can have a strong and unpredictable influence on the properties and effectiveness of final use formulations in specific applications. Therefore, a mixture composition comprising various diacids providing commercially desirable properties in final use formulations for specific applications is greatly needed.
[0004] WO 9502712 discloses generally that carboxylic acids or their salts may be used in agents for the treatment of metal surfaces, It also discloses generally a method for separating the agents from aqueous media after use for recovering the carboxylic acids or salts.
[0005] U.S. Patent No. 4,941,925 discloses a method for high pressure detergent water cleaning of metal working compounds, swarf and chips from metal surfaces, using as the detergent a composition consisting essentially of to C14 diacids and mixtures thereof. Exemplified in this disclosure is use of a mixture of C10 to C12 diacids, with the C12 diacid being 74 % of the diacid mixture.
[0006] U.S. Patent No. 4,946,616 discloses a coolant composition for use in a water cooled automotive engine comprising a freezing point depressant and an inhibitor consisting essentially of 2 to 5.5 weight percent of at least two C7 to C14 diacids or salts thereof, and a hydrocarbyl triazole or salt thereof. Exemplified in this disclosure is use of a mixture of C10 and Ci2 diacids.
[0007] U.S. Patent No. 7,084,300 B2 discloses a method for synthesis of diacids, particularly diacids having from eight to sixteen carbon atoms, involving oxidation, separation, washing and recovering steps.
[0008] WO 2006/071996 discloses in general corrosion inhibitors useful in water-based heat transfer fluids. A corrosion inhibitor mentioned includes one or more Qo to C12 diacids or salts thereof, oxyalkylated carboxylate imidazoline, organophosphonic acid or amine salt thereof, and a secondary or tertiary alkanolamine organic acid salting agent.
[0009] EP 1418253 Bl discloses a composition said to inhibit boiler scale and corrosion containing a C7 to C14 diacid component and a fatty polyamine component.
[0010] Though each of the above publications discloses various compositions and uses of diacids, none teach the specific novel mixture composition comprising various diacids of the present invention. Opportunities exist for discovering novel mixture compositions which provide commercially desirable properties in final use formulations for specific applications.
The present invention meets these and other needs.
SUMMARY OF THE INVENTION
[0011] It is an object of the present invention to provide a novel mixture composition comprising various diacids in specific amounts. Further objects of the present invention are to provide a composition which comprises the novel mixture composition comprising various diacids in specific amounts, water and at least one water-soluble organic amine, and a method for use thereof.
[0012] These and other objects are achieved by the present invention which provides as an embodiment a mixture composition comprising: 0.01 to 1 weight % of C4 diacid, 0.01 to 1 weight % of C5 diacid, 0.01 to 15 weight % of C& diacid, 0.01 to 3 weight % of C7 diacid, 0.01 to 3 weight % of Cg diacid, 2 to 70 weight % of C9 diacid, 0.01 to 10 weight % of do diacid, 2 to 85 weight % of Cn diacid, 0.01 to 90 weight % of Cn diacid, 0.01 to 3 weight % of Ci3 diacid, 0.01 to 1 weight % of C]4 diacid, 0.01 to 1 weight % of Ci5 diacid, and 0.01 to 1 weight % of Ci6 diacid. This mixture composition may comprise as little as 0.01 weight % of any one or number of the C4 to C8, o, and C12 to C16 diacid components. For example, the mixture composition may comprise from 0.01 to 3 weight % of the C13 diacid. For example, the mixture composition may comprise a total amount of C4 to C7 diacids from 0.01 to 20 weight %. As a further example, the mixture composition may comprise a total amount of Ci3 to Ci6 diacids from 0.01 to 6 weight %. The mixture composition may also comprise a total amount of C4to C7 diacids from 0.01 to 20 weight % and a total amount of C13 to C16 diacids from 0.01 to 6 weight %. In all preceding embodiments, the mixture composition can further comprise aliphatic, monocarboxylic acids (monoacids). The total amount of monoacids may comprise between 0.01 to 10 weight % of the mixture composition, for example, between 0.01 to 5 weight % or between 0.01 to 2 weight %.
[0013] Another embodiment of the present invention is a mixture composition as above wherein at least one of the C8 to C12 diacids is manufactured by reaction of cyclododecanol, cyclododecanone, or a combination thereof with nitric acid, and at least one of the C to C13 diacids is manufactured by oxidative cleavage of unsaturated fatty acids or unsaturated fatty acid esters. In another embodiment, adipic acid, dodecanedioic acid, or a combination of adipic acid and dodecanedioic acid are combined with the at least one of the C8 to C12 diacids and the at least one of the C9 to C13 diacids of the preceding embodiment to obtain a mixture composition as above.
[0014] Another embodiment of the present invention is a mixture composition as above wherein at least one of the C8 to C12 diacids is manufactured by reaction of cyclododecanol, cyclododecanone, or a combination thereof with nitric acid. In another embodiment, adipic acid, dodecanedioic acid, or a combination of adipic acid and dodecanedioic acid are combined with the at least one of the C8 to C12 diacids of the preceding embodiment to obtain a mixture composition as above.
[0015] Another embodiment of the present invention is a mixture composition as above wherein at least one of the C9 to C13 diacids is manufactured by oxidative cleavage of unsaturated fatty acids or unsaturated fatty acid esters. In another embodiment, adipic acid, dodecanedioic acid, or a combination of adipic acid and dodecanedioic acid are combined with the at least one of the C9 to C13 diacids of the preceding embodiment to obtain a mixture composition as above. [0016] Another embodiment of the present invention is a mixture composition as above comprising a total of from 1 to 90 weight % of C8 to C12 diacids that are manufactured by reaction of cyclododecanol, cyclododecanone, or a combination thereof with nitric acid; and another embodiment is a mixture composition as above comprising a total of from 1 to 90 weight % of C9 to C13 diacids that are manufactured by oxidative cleavage of unsaturated fatty acids or unsaturated fatty acid esters.
[0017] Another embodiment of the present invention is a mixture composition comprising: 0.01 to 1 weight % of C4 diacid, 0.01 to 1 weight % of C5 diacid, 0.01 to 2 weight % of C6 diacid, 0.01 to 3 weight % of C7 diacid, 1 to 3 weight % of C8 diacid, 5 to 70 weight % of C9 diacid, 4 to 7 weight % of C10 diacid, 12 to 45 weight % of Cn diacid, 3 to 45 weight % of diacid, 0.01 to 3 weight % of C13 diacid, 0.01 to 1 weight % of C14 diacid, 0.01 to 1 weight % of C15 diacid, and 0.01 to 1 weight % of C16 diacid. The mixture composition may comprise as little as 0.01 weight % of any one or number of the C4 to C7 and C13 to Ci6 diacid components. For example, this mixture composition may comprise a total amount of C4 to C diacids from 0.01 to 7 weight %. As another example, this mixture composition may comprise a total amount of C13 to C16 diacids from 0.01 to 6 weight %. For example, the mixture composition may comprise a total amount of C4to C7 diacids from 0.01 to 7 weight % and a total amount of C13 to Ci6 diacids from 0.01 to 6 weight %. In all preceding embodiments, the mixture composition can further comprise at least one monoacid. The total amount of monoacids may comprise between 0.01 to 10 weight % of the mixture composition, for example, between 0.01 to 5 weight % or between 0.01 to 2 weight %.
[0018] Another embodiment of the present invention is a composition, for example an aqueous composition, comprising the mixture composition of diacids as above, water and at least one water-soluble organic amine. Another embodiment of the present invention is a method for inhibiting corrosion of metal comprising contacting the metal with the composition comprising the mixture composition of diacids as above, water and at least one water-soluble organic amine.
DETAILED DESCRIPTION OF THE INVENTION
[0019] The detailed description below is provided for the purpose of illustrating certain embodiments of the invention and should not be taken as limiting the present inventive concept to these specific embodiments. To the extent that this description is specific to a particular embodiment, this is for purposes of illustration only and should not be taken as limiting.
[0020] The present invention is directed to a specific novel mixture composition comprising various diacids in certain amounts which provide commercially desirable properties in final use formulations for specific applications, such as, for example, inhibiting the corrosion of metals. For clarity, diacid abbreviations, formulas, and names are provided in Table 1.
Table 1
Figure imgf000007_0001
[0021] The mixture composition of diacids comprises 0 to about 1 weight % of C4 diacid, 0.01 to 1 weight % of C5 diacid, 0.01 to 15 weight % of C6 diacid, 0.01 to 3 weight % of C7 diacid, 0.01 to 3 weight % of C8 diacid, 2 to 70 weight % of C9 diacid, 0.01 to 10 weight % of Co diacid, 2 to 85 weight % of Cn diacid, 0.01 to 90 weight % of Cu diacid, 0.01 to 3 weight % of diacid, 0.01 to 1 weight % of C1 diacid, 0.01 to 1 weight % of C15 diacid, and 0.01 to 1 weight % of Ci6 diacid. This mixture composition may comprise as little as 0.01 weight % of any one or number of the C4 to C8, Cio, and Q2 to Ci6 components. For example, the mixture composition may comprise from 0.01 to 3 weight % of the (¾ diacid. For example, the mixture composition can comprise 1 to 15 weight % of C6 diacid. For another example, the mixture composition can comprise a total amount of C4 to C7 diacids from 0.01 to 20 weight %. The mixture composition may also comprise a total amount of C4 to C7 diacids from 0.01 to 20 weight % and a total amount of Q3 to C e diacids from 0.01 to 6 weight %. In all preceding embodiments, the mixture composition can further comprise at least one monoacid. The total amount of monoacids may comprise between 0.01 to 10 weight % of the mixture composition, for example, between 0.01 to 5 weight % or between 0.01 to 2 weight %. Monoacids may be selected from C4 to Ci6, aliphatic monocarboxylic acids where the aliphatic hydrocarbon chain of each monoacid may be linear or branched. [0022] Another embodiment of the present invention is a mixture composition of diacids comprising 0.01 to 1 weight % of C4 diacid, 0.01 to 1 weight % of C5 diacid, 0.01 to 2 weight % of C6 diacid, 0.01 to 3 weight % of C7 diacid, 1 to 3 weight % of Cg diacid, 5 to 70 weight % of C9 diacid, 4 to 7 weight % of C10 diacid, 12 to 45 weight % of Cn diacid, 3 to 45 weight % of C12 diacid, 0.01 to 3 weight % of C13 diacid, 0.01 to 1 weight % of CM diacid, 0.01 to 1 weight % of Ci5 diacid, and 0.01 to 1 weight % of C16 diacid. For example, this mixture composition can comprise 5 to 15 weight % of Cu diacid. This mixture composition may comprise as little as 0.01 weight % of any one or number of the C4 to C7, and C13 to C16 components. For example, the mixture composition may comprise from 0.01 to 3 weight % of Cn diacid. For another example, this mixture composition can comprise a total amount of C4 to C7 diacids from 0.01 to 7 weight % and a total amount of C13 to C16 diacids from 0.01 to 6 weight %. In all preceding embodiments, the mixture composition can further comprise at least one monoacid. The total amount of monoacids may comprise between 0.01 to 10 weight % of the mixture composition, for example, between 0.01 to 5 weight % or between 0.01 to 2 weight %. Monoacids may be selected from C4 to CI 6, aliphatic monocarboxylic acids where the aliphatic hydrocarbon chain of each monoacid may be linear or branched.
[0023] Features of the present mixture composition of diacids for commercially improved applications are the particular diacid and amount of each diacid in the mixture composition. Another feature is the source of certain diacids in the mixture composition.
[0024] A mixture of diacids can be manufactured, for example, by reaction of cyclododecanol, cyclododecanone, or a combination of cyclododecanol and
cyclododecanone, with nitric acid. The major diacid in the reaction product is a Q2 diacid, dodecanedioic acid, but it can also contain other shorter chain diacids, comprising a Cg diacid (suberic acid), a C9 diacid (azelaic acid), a C10 diacid (sebacic acid), and a Cn diacid (undecanedioic acid). With control of reaction conditions, the reaction product can further comprise a C4 diacid (succinic acid), a C5 diacid (glutaric acid), a C6 diacid (adipic acid), and a C7 diacid (pimelic acid), or any combination of these diacids.
[0025] A suitable method for recovering the diacids for the present invention is fractional crystallization. For example, a reaction of cyclododecanol, cyclododecanone, or a combination of cyclododecanol and cyclododecanone, with nitric acid can be carried out in the presence of water to produce an aqueous reaction product, comprising, for example, the Cg to C12 diacids. A fraction of the Co diacid can be first crystallized from this aqueous reaction product in high purity (e.g. > 90%). When the solid C12 diacid is separated from the aqueous mother liquor, for example by filtration or decantation, this liquor becomes enriched in the C8 to Cn diacids and depleted in the C]2 diacid, relative to the aqueous reaction product. But this mother liquor can still comprise significant amounts of the 2 diacid.
[0026] The mixture of C8 to Ci2 diacids can then be recovered from this aqueous mother liquor by various methods. Non-limiting examples of recovery methods include (1) a second fractional crystallization of a solid mixture of C8 to Ci2 diacids from the aqueous mother liquor, or (2) partial or complete evaporation of water from the aqueous mother liquor to crystallize or precipitate a solid mixture of C8 to Q2 diacids. In recovery methods (1) and (2), filtration or decantation can be applied to separate the solid mixture of C8 to Q2 diacids from any resulting mother liquor.
[0027] According to any preceding embodiment, the recovered mixture of C8 to C12 diacids comprises from 10 to 60 weight % of the Q2 diacid in the recovered mixture of C8 to C12 diacids, for example from 30 to 50 weight % of the recovered mixture of C8 to Ci2 diacids. In another embodiment, the recovered mixture of C8 to Q2 diacids further comprises a mixture of the C6 and C7 diacids and the total amount of C6 and C7 diacids is from 0.1 to 10 weight % of the recovered mixture of C8 to C12 diacids, for example from 0.5 to 5 weight % of the recovered mixture of C8 to Ci2 diacids. In another embodiment, the recovered mixture of C8 to Ci2 diacids further comprises a mixture of C4, C5, C6 and C7 diacids and the total amount of C4 to C7 diacids is less than 10 weight % of the recovered mixture of C8 to Ci2 diacids, for example from 0.5 to 5 weight % of the recovered mixture of C8 to C12 diacids.
[0028] In yet another embodiment, a mixture of C9 to Ci3 diacids can be manufactured by a reaction involving oxidative cleavage at C=C bonds in unsaturated fatty acids or unsaturated fatty acid esters. The mixture of Cg to Ci3 diacids can be recovered from the resulting reaction product. Examples of such unsaturated fatty acids and unsaturated fatty acid esters include palmitoleic acid, oleic acid, asclepic acid, linoleic acid, a-linolenic acid, gondoic acid, erucic acid, methyl esters of the preceding unsaturated fatty acids, glyceryl esters of the preceding unsaturated fatty acids, and mixtures thereof. Oxidative cleavage of unsaturated fatty acids or unsaturated fatty acid esters can be carried out using oxidants such as ozone and oxygen, ozone and hydrogen peroxide, or nitric acid.
[0029] The mixture composition of diacids as above can be obtained by combining diacid mixtures together, by combining at least one diacid mixture with at least one pure diacid, or by combining more than one pure diacid together, all in the proper proportions. [0030] Another embodiment of the present invention is a mixture composition as above wherein at least one of the Cg to C12 diacids is manufactured by reaction of cyclododecanol, cyclododecanone, or a combination thereof with nitric acid, and at least one of the C9 to C13 diacids is manufactured by oxidative cleavage of unsaturated fatty acids or unsaturated fatty acid esters. In another embodiment, the mixture composition of diacids as above is obtained by combining the at least one of the C8 to C12 diacids with the at least one of the C9 to C13 diacids. In another embodiment, the mixture composition of diacids as above is obtained by combining the at least one of the C8 to C12 diacids, at least one of the C9 to C13 diacids, and another diacid selected from the group of adipic acid and dodecanedioic acid.
[0031] Another embodiment of the present invention is a mixture composition as above wherein at least one of the C8 to C12 diacids is manufactured by reaction of cyclododecanol, cyclododecanone, or a combination thereof with nitric acid. In another embodiment, the mixture composition of diacids as above is obtained by combining the at least one of the C8 to C12 diacids with another diacid selected from the group of adipic acid and dodecanedioic acid.
[0032] Another embodiment of the present invention is a mixture composition as above wherein at least one of the C9 to C13 diacids is manufactured by oxidative cleavage of unsaturated fatty acids or unsaturated fatty acid esters. In another embodiment, the mixture composition of diacids as above is obtained by combining the at least one of the C9 to C13 diacids with another diacid selected from the group of adipic acid and dodecanedioic acid.
[0033] A composition comprising the diacid mixture composition as above, water and at least one water-soluble organic amine is very useful for inhibiting corrosion of metal surfaces. For this use, the water-soluble organic amine is selected from the group consisting of monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, triisopropanolamine, diglycolamine, 2-amino-2-methyl-l-propanol, and mixtures thereof. This composition comprises from about 0.1 to about 25 weight % of the diacid mixture composition as above, from about 15 to about 85 weight % water, and from about 10 to about 65 weight % water-soluble organic amine. According to any preceding embodiment, of the composition, a molar ratio of nitrogen atoms in the water-soluble organic amine to carboxylic acid groups in the diacid mixture composition is equal to or greater than one. According to any preceding embodiment of the composition, more than one water- soluble organic amine is selected for the composition. And in another embodiment, two different water-soluble organic amines are selected for the composition and a molar ratio of the two different water-soluble organic amines is from 0.01 to 100, preferably from 0.1 to 10, e.g. from 0.2 to 5. For example, a composition formed by contacting ethanolamine and triethanolamine, in approximately an equimolar ratio, with the diacid mixture composition as above, and water; wherein the molar ratio of nitrogen atoms in both of these water-soluble organic amines to carboxylic acid groups in the diacid mixture composition is equal to or greater than one, such as from 1 to 25, e.g. from 1 to 5. For example, a specific embodiment of this provides the ratio of nitrogen atoms in the amines to carboxylic acid groups in the diacid mixture of about 1.01 to 1.2.
EXAMPLES
[0034] The present invention is further described with reference to the following non- limiting examples. All percentages are by weight. The compositions of diacid mixtures can be determined by esterification with a BF3/CH3OH reagent followed by analysis of the corresponding diester mixture by gas chromatography.
Example 1
[0035] Sebacic acid and dodecanedioic acid (DDDA) are commercial diacids used as corrosion inhibitors in water-based, metal-working fluid formulations. "Ozone diacid" is a mixture of C9 to C13 diacids recovered from the oxidative cleavage of unsaturated fatty acids or unsaturated fatty acid esters with ozone and oxidative workup. "Nitric diacid" is a mixture of C$ to C12 diacids recovered from the reaction of a mixture of cyclododecanol and cyclododecanone with nitric acid. A Cn diacid sample was prepared through oxidative cleavage of fatty acids or fatty acid esters.
[0036] Blends 1 and 2 were obtained by combining the ozone diacid mixture with DDDA. Blend 3 was obtained by combining the ozone diacid mixture with DDDA and adipic acid. Blends 4 and 5 were obtained by combining the ozone diacid mixture with the nitric diacid mixture. Blend 6 was obtained by combining the ozone diacid mixture, the nitric diacid mixture, and DDDA together. Blend 7 was obtained by combining the Cn diacid sample with DDDA. Table 2 presents particulars of the blends. The same GC method can measure the amounts of monoacids in the adipic acid, DDDA, ozone diacid mixture, nitric diacid mixture and Cn diacid sample. The total monoacids are less than 1 weight % meaning that all b lends of Table 2 are also less than 1 weight %. The same GC method can measure the amounts of monoacids in the adipic acid, DDDA, ozone diacid mixture, nitric diacid mixture, and Cn diacid sample. The total monoacids are less than 1 weight % meaning that all blends of Table 2 are also less than 1 weight %.
Figure imgf000013_0001
Example 2
[0037] The ASTM standard test method for iron chip corrosion for water-dilutable metalworking fluids, D4627-92, was utilized to compare the properties of Blends 1-7 with those of the commercial diacids, sebacic acid and DDDA. The metalworking fluid concentrates were prepared by dissolving the diacid or diacid mixture in an aqueous solution containing water, monoethanolamine, and triethanolamine. Each metalworking fluid concentrate was then diluted with water at either a water hardness of 100 ppm or 500 ppm (as CaC03), according to the method. Then the breakpoints (concentration of the diacid or diacid mixture required to inhibit corrosion) were determined. A hard water stability test at 500 ppm was also performed for each metalworking fluid concentrate. The formation of a visible precipitate indicated hard water instability - an undesired result. The data from these tests are compiled in Table 3.
Table 3
Figure imgf000015_0001
[0038] While the invention has been described in terms of specific embodiments, those skilled in the art will appreciate that various modifications and variations to these embodiments can be made without departing from the spirit and scope of this invention. For example, while certain embodiments are exemplified, other mixture compositions are also contemplated. Additionally, while compositions comprising the mixture composition embodiments and their use for inhibiting corrosion of metal are discussed, other uses, such as in polymer formulations, and use in solvent, cleaning, and lubricating oil formulations, are also contemplated.

Claims

CLAIMS What is claimed is:
1. A mixture composition comprising:
0 to about 1 weight % of C4 diacid,
0 to about 1 weight % of C¾ diacid,
0 to about 15 weight % of C diacid,
0 to about 3 weight % of C7 diacid,
0 to about 3 weight % of Cg diacid,
2 to about 70 weight % of C9 diacid,
0 to about 10 weight % of o diacid,
2 to about 85 weight % of Cn diacid,
0 to about 90 weight % of Ci2 diacid,
0 to about 3 weight % of C13 diacid,
0 to about 1 weight % of Ci4 diacid,
0 to about 1 weight % of C15 diacid, and
0 to about 1 weight % of Ci6 diacid.
2. The mixture composition of claim 1 wherein the C8 to C12 diacids are manufactured by reaction of cyclododecanol, cyclododecanone, or a combination thereof with nitric acid, and at least one of the C9 to C13 diacids is manufactured by oxidative cleavage of unsaturated fatty acids or unsaturated fatty acid esters, and at least one of the other mixture components is selected from dodecanedioic acid, adipic acid and mixtures thereof.
3. The mixture composition of claim 1 wherein the C9 to C13 diacids are manufactured by oxidative cleavage of unsaturated fatty acids or unsaturated fatty acid esters, and at least one of the other mixture components is selected from dodecanedioic acid, adipic acid and mixtures thereof.
4. The mixture composition of claim 1 comprising from 1 to about 90 weight % C8 to Cn diacids.
5. The mixture composition of claim 1 comprising from 1 to about 90 weight % Cg to Ci3 diacids manufactured by oxidative cleavage of unsaturated fatty acids or unsaturated fatty acid esters.
6. The mixture composition of claim 1 comprising from 5 to about 15 weight % Ci2 diacid.
7. The mixture composition of claim 1 comprising from 1 to about 15 weight % C diacid.
8. The mixture composition of claim 1 comprising:
0 to about 1 weight % of C4 diacid,
0 to about 1 weight % of C5 diacid,
0 to about 2 weight % of C6 diacid,
0 to about 3 weight % of C7 diacid,
1 to about 3 weight % of Cg diacid,
5 to about 70 weight % of C9 diacid,
4 to about 7 weight % of C10 diacid,
12 to about 45 weight % of Cn diacid,
3 to about 45 weight % of Q2 diacid,
0 to about 3 weight % of C13 diacid,
0 to about 1 weight % of C14 diacid,
0 to about 1 weight % of C15 diacid, and
0 to about 1 weight % of C]6 diacid.
9. A composition comprising the mixture composition of claim 1, water and at least one water-soluble organic amine.
10. The composition of claim 9 wherein the water-soluble organic amine is selected from the group consisting of monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, triisopropanolamine, diglycolamine, 2-amino-2-methyl-l-propanol, and mixtures thereof.
11. A method for inhibiting corrosion of metal comprising contacting the metal with the composition of claim 9.
12. A method for inhibiting corrosion of metal comprising contacting the metal with the composition of claim 10.
13. A composition comprising the mixture composition of claim 8, water and at least one water-soluble organic amine.
14. The composition of claim 13 wherein the water-soluble organic amine is selected from the group consisting of monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, triisopropanolamine, diglycolamine, 2-amino-2-methyl-l-propanol, and mixtures thereof.
15. A method for inhibiting corrosion of metal comprising contacting the metal with the composition of claim 13.
16. A method for inhibiting corrosion of metal comprising contacting the metal with the composition of claim 14.
PCT/US2013/053247 2012-08-22 2013-08-01 Aliphatic dicarboxylic acid mixture formulation WO2014031305A1 (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019204687A1 (en) * 2018-04-19 2019-10-24 Biocellection Inc. Methods for the decomposition of contaminated plastic waste
US11220586B2 (en) 2018-04-19 2022-01-11 Novoloop, Inc. Methods for the decomposition of contaminated plastic waste
WO2023039387A1 (en) * 2021-09-10 2023-03-16 Bl Technologies, Inc. Method and composition for treating dilution steam generator systems
US11840610B2 (en) 2019-12-11 2023-12-12 Novoloop, Inc. Compositions and methods for the degradation of waste polypropylene

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6460536B2 (en) * 2016-02-24 2019-01-30 大同化学工業株式会社 Water-soluble rust preventive additive and water-soluble metalworking fluid
KR101879137B1 (en) 2017-09-25 2018-07-16 오길식 LED lamp protection tunnel light fixture

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1984004323A1 (en) * 1983-04-20 1984-11-08 Lubrizol Corp Polycarboxylic acid/boric acid/amine salts and aqueous systems containing same
US4941925A (en) 1988-02-26 1990-07-17 Nalco Chemical Company Cleaner for high pressure cleaning of ferrous and non-ferrous material
US4946616A (en) 1988-11-14 1990-08-07 The Dow Chemical Company Heat transfer fluids containing dicarboxylic acid mixtures as corrosion inhibitors
WO1995002712A2 (en) 1993-07-16 1995-01-26 Henkel Kommanditgesellschaft Auf Aktien Use of carboxylic acids in agents for the treatment of metal surfaces
US20030195374A1 (en) * 2002-04-11 2003-10-16 Degussa Ag Work-up of residues in the preparation of carboxylic acids
US20050000387A1 (en) * 2003-07-02 2005-01-06 Ying Wang Wood preservative with alkaline copper quaternary
WO2006071996A2 (en) 2004-12-29 2006-07-06 Trahan David O Corrosion inhibitors
EP1418253B1 (en) 2002-11-06 2010-07-07 BK Giulini GmbH Scale and corrosion inhibitor composition and process for water circuits
CA2809150A1 (en) * 2010-08-25 2012-03-01 Panolin Holding Ag Ester oils

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4903745B2 (en) * 2007-05-08 2012-03-28 ローム アンド ハース カンパニー Stabilized fluid
US8173581B2 (en) * 2008-05-19 2012-05-08 Baker Hughes Incorporated Mutual solvent-soluble and/or alcohol blends-soluble particles for viscoelastic surfactant fluids

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1984004323A1 (en) * 1983-04-20 1984-11-08 Lubrizol Corp Polycarboxylic acid/boric acid/amine salts and aqueous systems containing same
US4941925A (en) 1988-02-26 1990-07-17 Nalco Chemical Company Cleaner for high pressure cleaning of ferrous and non-ferrous material
US4946616A (en) 1988-11-14 1990-08-07 The Dow Chemical Company Heat transfer fluids containing dicarboxylic acid mixtures as corrosion inhibitors
WO1995002712A2 (en) 1993-07-16 1995-01-26 Henkel Kommanditgesellschaft Auf Aktien Use of carboxylic acids in agents for the treatment of metal surfaces
US20030195374A1 (en) * 2002-04-11 2003-10-16 Degussa Ag Work-up of residues in the preparation of carboxylic acids
US7084300B2 (en) 2002-04-11 2006-08-01 Degussa Ag Work-up of residues in the preparation of carboxylic acids
EP1418253B1 (en) 2002-11-06 2010-07-07 BK Giulini GmbH Scale and corrosion inhibitor composition and process for water circuits
US20050000387A1 (en) * 2003-07-02 2005-01-06 Ying Wang Wood preservative with alkaline copper quaternary
WO2006071996A2 (en) 2004-12-29 2006-07-06 Trahan David O Corrosion inhibitors
CA2809150A1 (en) * 2010-08-25 2012-03-01 Panolin Holding Ag Ester oils

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
INVISTA SPECIAL INTERMEDIATES: "CORFREE M1 dibasic acid mixture", 10 October 2008 (2008-10-10), XP002715167, Retrieved from the Internet <URL:http://c12.invista.com/doc/files/314/Corfree%20M1%20Technical%20and%20Corrosion%20Inhibitor%20Application.pdf> [retrieved on 20131021] *

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019204687A1 (en) * 2018-04-19 2019-10-24 Biocellection Inc. Methods for the decomposition of contaminated plastic waste
US10519292B2 (en) 2018-04-19 2019-12-31 Biocellection Inc. Products from the decomposition of plastic waste
US10557011B2 (en) 2018-04-19 2020-02-11 Biocellection Inc. Methods for the decomposition of contaminated plastic waste
US11192999B2 (en) 2018-04-19 2021-12-07 Novoloop, Inc. Products from the decomposition of plastic waste
US11220586B2 (en) 2018-04-19 2022-01-11 Novoloop, Inc. Methods for the decomposition of contaminated plastic waste
US11945918B2 (en) 2018-04-19 2024-04-02 Novoloop, Inc. Methods for the decomposition of contaminated plastic waste
US11840610B2 (en) 2019-12-11 2023-12-12 Novoloop, Inc. Compositions and methods for the degradation of waste polypropylene
WO2023039387A1 (en) * 2021-09-10 2023-03-16 Bl Technologies, Inc. Method and composition for treating dilution steam generator systems

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