US3770413A - Method of inhibiting corrosion - Google Patents

Method of inhibiting corrosion Download PDF

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Publication number
US3770413A
US3770413A US00059011A US3770413DA US3770413A US 3770413 A US3770413 A US 3770413A US 00059011 A US00059011 A US 00059011A US 3770413D A US3770413D A US 3770413DA US 3770413 A US3770413 A US 3770413A
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United States
Prior art keywords
acid
salt
corrosion
combination
halophenoxyalkanoic
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Expired - Lifetime
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US00059011A
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English (en)
Inventor
E Tabor
F French
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Dow Chemical Co
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Dow Chemical Co
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    • 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
    • C23F11/18—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 inorganic inhibitors
    • C23F11/182—Sulfur, boron or silicon containing compounds

Definitions

  • the inhibitory composition is particularly useful in i [58] Fielid of Search 71/83, 65, 84, 117, hibiting the corrosion of metal in Contact with herbi- 71 113 11 252 339 cidal compositions of which the active ingredient is halophenoxy-alkanoic acid or salt, especially when the [56] References Cit d composition also includes a corrosive chelating agent,
  • halophenoxyalkanoic acids and their salts have not heretofore been recognized as corrosion inhibitors and, in fact, exhibit little or no inhibitory action when used alone in the compositions described herein.
  • boric acid we mean to include all the common acids of boron, e.g., ortho-, meta-, tetraandpentaboric acid and the like.
  • halophenoxyalkanoic acids of special interest are thoseof the formula wherein R is H or alkyl, each R and R" independently is H, halogen or alkyl and n is an integer l6, at least one ofR and R" being H, and at least one of R and R" being halogen, the total number of carbon atoms in the group -CHR(C,,H ,,)-COOH being two to about 18.
  • acids are those of the above formula wherein at least two of R and R" are Cl, any others being H or CH R is H or CH and n is 0.
  • suitable acids include p-chlorophenoxyacetic, p-iodophenoxyacetic, 2(3,5-dichlorophenoxy)- propionic, 2,4,5-trichlorophenoxyacetic, 2(p-bromophenoxy)-valeric, 2-bromo-4-methylphenoxyacetic, 2(4,5-dichlorophenoxy)-butyric, 2(3- bromo-4-sec.
  • butylphenoxy)-caproic 2(3,5-difluoro-5- isopropylphenoxy)-butyric, 2-methyl-4-bromo-5- chlorophenoxyacetic and 2(2,3,4,5-tetrachloro phenoxy )-acetic acids and the like.
  • the inhibitor combination of the invention is of some value in acidic solutions, it is much more effective at higher pH values, i.e., in neutral or, preferably, alkaline solutions.
  • This means that both the boric acid and the halophenoxyalkanoic acid are usually used in the salt form rather than the free acid.
  • the identity of the cation of the salt is unimportant so long as the salt has adequate solubility in the aqueous medium to be inhibited.
  • the alkali metal, ammonium and amine salts are preferred, though others, particularly the alkaline earth metal salts, are also useful.
  • the amine salts are often preferred because of their high solubility, especially when the aqueous medium to be inhibited contains other amine salts.
  • Suitable amines include the primary, secondary and tertiary alkyland alkanolamines, such as mono-, diand trimethyl-, ethylbutyl-, ethanol-, propanoland butanolamines, dimethylethanolamine, butyl-diethanolamine and the like.
  • An area of special utility for the inhibitor composition of the invention is in the inhibition of the corrosiveness of herbicidal compositions based on the halophenoxyalkanoic acids and salts: of such acids.
  • Such compositions are often corrosive to metal containers in which they are prepared, shipped or stored or to the tanks, pumps,etc. of the equipment with which they are applied to the vegetation to be controlled.
  • This corrosiveness is often engendered or enhanced by the presence of chelating agents that are commonly used to sequester undesirable cations, thus reducing discoloration, precipitation or other undesirable effects of such ions.
  • the commonly used chelating agents are citric acid, tartaric acid, nitrilotriacetic acid, ethylenediaminetetracetic acid, etc., and the soluble salts of such acids. Since such herbicidal compositions consist essentially of one component of the present inhibitor combination, the combination can be conveniently formed in situ by adding thereto a small amount of the second component, i.e., the boric acid or salt. Effectively, the inhibitor combination is formed in and is present in a very large excess of the halophenoxyalk anoic acid component and thus inhibits the corrosiveness of the latter and of any corrosive chelating agent that is present. Such inhibition is particularly surprising because neither component of the inhibitor combination when used alone will effectively inhibit the corrosiveness of such chelating agents in aqueous media.
  • the amount of inhibitor used and the proportions of the two components therein are not critical and may be varied widely. Less than 1% by weight, based on the aqueous medium to be inhibited, of each component or of the combination is usually sufficient to markedly inhibit the corrosiveness of the medium. Ordinarily amounts in excess of about 5% contribute little additional inhibition, though larger amounts may be used if desired. For many purposes it is sufficient to use as little as about 0.1% of each component in the aqueous medium.
  • EXAMPLE 1 A 40 percent by weight aqueous solution of the dimethylamine salt of 2,4-dichlorlophenoxyacetic acid containing 3 percent, by weight, of citric acid was highly corrosive to ferrous metal tanks, drums and cans. The addition thereto of 2 percent, by weight, of H and adjustment of the pH to 7.4-7.8 by addition of dimethylamine substantially eliminated the discoloration of the material and the corrosion of ferrous metals in contact therewith.
  • cold rolled can stock, zinc phosphated steel and iron phosphated steel were also tested in contact with the inhibited composition and found not to be significantly corroded under normal storage conditions.
  • EXAMPLE 3 The corrosiveness of various solutions toward ordinary drum steel was estimated by applying a variable E.M.F. to the steel in contact with the solution and plotting the resultant current. The resulting graphs show little or no current at potentials of 0.7 volt or less (relative to a standard calomel electrode). Between 0.7 and about 0.4 the current went through a peak, the height of which was indicative of corrosive- I Inhibitor, Normality Current, m.a.
  • EXAMPLE 4 An aerosol window cleaner composition consisting essentially of a surfactant dissolved in aqueous isopropanol with small amounts of NH and glycol ethers and pressurized with isobutane was found to be corrosive to the steel aerosol container. Addition of various amounts of sodium nitrite, a widely used corrosion inhibitor, failed to inhibit the corrosion. Addition of 0.5 percent by weight of a l :1 molar complex of H and 2,4-dichloroph enoxyacetic acid resulted in substantially complete inhibition of corrosion throughout a test period of one month at F.
  • the inhibitor composition of the invention is of general utility in corrosive aqueous solutions.
  • inhibitor concentrates consisting essentially of a boric acid and a halophenoxyalkanoic acid, as
  • concentrates may vary in weight ratio of components from about 1:99 to about 99:1, though a ratio higher than about 10:1 of borate to phenoxy acid is not ordinarily preferred.

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
US00059011A 1970-07-28 1970-07-28 Method of inhibiting corrosion Expired - Lifetime US3770413A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US5901170A 1970-07-28 1970-07-28

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US3770413A true US3770413A (en) 1973-11-06

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Country Status (8)

Country Link
US (1) US3770413A (OSRAM)
AU (1) AU456210B2 (OSRAM)
CA (1) CA965977A (OSRAM)
DE (1) DE2137783A1 (OSRAM)
FR (1) FR2103752A5 (OSRAM)
GB (1) GB1350274A (OSRAM)
IT (1) IT939339B (OSRAM)
NL (1) NL7110338A (OSRAM)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4532047A (en) * 1984-06-29 1985-07-30 Nalco Chemical Company Silica inhibition: prevention of silica deposition by addition of low molecular weight organic compounds
US4584104A (en) * 1984-06-29 1986-04-22 Nalco Chemical Company Silica inhibition: prevention of silica deposition by boric acid/orthorborate ion
AU741048B2 (en) * 1994-04-22 2001-11-22 Buckman Laboratories International, Inc. Borates useful for the prevention/mitigation of microbiologically influenced corrosion and staining
US20080032892A1 (en) * 2006-08-02 2008-02-07 Mark Richard Linton High-strength, low-temperature stable herbicidal formulations of 2,4-dichlorophenoxy acetic acid salts
AU2006201766B2 (en) * 2006-04-27 2010-10-21 Corteva Agriscience Llc High-strength, low-temperature stable herbicidal formulations of 2,4-dichlorophenoxy acetic acid salts

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB9201642D0 (en) * 1992-01-25 1992-03-11 Ciba Geigy Corrosion inhibitors
US5654012A (en) * 1994-04-22 1997-08-05 Buckman Laboratories International, Inc. Borates useful for the prevention/mitigation of microbiologically influenced corrosion and staining

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2904423A (en) * 1954-12-07 1959-09-15 United States Borax Chem Herbicidal granular composition and method of preparing the same
US3004844A (en) * 1953-11-27 1961-10-17 United States Borax Chem Composition and method for control of vegetation
US3340041A (en) * 1963-01-31 1967-09-05 Ici Ltd Herbicidal composition and method employing 4, 4'-bipyridylium quaternary salts
US3464810A (en) * 1965-10-22 1969-09-02 United States Borax Chem Process for producing flaked sodium metaborate compositions

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3004844A (en) * 1953-11-27 1961-10-17 United States Borax Chem Composition and method for control of vegetation
US2904423A (en) * 1954-12-07 1959-09-15 United States Borax Chem Herbicidal granular composition and method of preparing the same
US3340041A (en) * 1963-01-31 1967-09-05 Ici Ltd Herbicidal composition and method employing 4, 4'-bipyridylium quaternary salts
US3464810A (en) * 1965-10-22 1969-09-02 United States Borax Chem Process for producing flaked sodium metaborate compositions

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4532047A (en) * 1984-06-29 1985-07-30 Nalco Chemical Company Silica inhibition: prevention of silica deposition by addition of low molecular weight organic compounds
US4584104A (en) * 1984-06-29 1986-04-22 Nalco Chemical Company Silica inhibition: prevention of silica deposition by boric acid/orthorborate ion
AU741048B2 (en) * 1994-04-22 2001-11-22 Buckman Laboratories International, Inc. Borates useful for the prevention/mitigation of microbiologically influenced corrosion and staining
AU2006201766B2 (en) * 2006-04-27 2010-10-21 Corteva Agriscience Llc High-strength, low-temperature stable herbicidal formulations of 2,4-dichlorophenoxy acetic acid salts
US20080032892A1 (en) * 2006-08-02 2008-02-07 Mark Richard Linton High-strength, low-temperature stable herbicidal formulations of 2,4-dichlorophenoxy acetic acid salts
US7683008B2 (en) * 2006-08-02 2010-03-23 Dow Agrosciences Llc High-strength, low-temperature stable herbicidal formulations of 2,4-dichlorophenoxy acetic acid salts

Also Published As

Publication number Publication date
DE2137783A1 (de) 1972-02-03
FR2103752A5 (OSRAM) 1972-04-14
NL7110338A (OSRAM) 1972-02-01
CA965977A (en) 1975-04-15
AU456210B2 (en) 1974-12-12
IT939339B (it) 1973-02-10
AU3168271A (en) 1973-02-01
GB1350274A (en) 1974-04-18

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