CA2087393A1 - Corrosion inhibiting compositions - Google Patents
Corrosion inhibiting compositionsInfo
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- CA2087393A1 CA2087393A1 CA 2087393 CA2087393A CA2087393A1 CA 2087393 A1 CA2087393 A1 CA 2087393A1 CA 2087393 CA2087393 CA 2087393 CA 2087393 A CA2087393 A CA 2087393A CA 2087393 A1 CA2087393 A1 CA 2087393A1
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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
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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
- C23F11/10—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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
- Anti-Oxidant Or Stabilizer Compositions (AREA)
Abstract
Abstract of the Disclosure Corrosion Inhibiting Compositions A corrosion inhibiting composition comprising:
A) 40-90% by weight of a carboxylic acid corrosion inhibitor, or a water-soluble salt thereof, comprising one or more of:
A1) a triazine-carboxylic acid of formula I:
I
in which Z is a C1-C11 alkylene group, Rl and R2, independently, are hydrogen ormethyl, and R3 is a group -NR4R5 in which R4 is C1-C12 alkyl or-Z-COOH in which Z
has its previous significance, and R5 is hydrogen or C1-Cl2 alkyl, or a water-soluble salt thereof;
A2) a sulphonamidocarboxylic acid of formula II:
II
in which R6 and R7, independently, are hydrogen or C1-C4 alkyl, and m is an integer ranging from 1 to 10 or a water-soluble salt thereof; and A3) a dicarboxylic acid, or mixture thereof, having the formula III:
HOOC-(CH2)n-COOH III
in which n is an integer ranging from 4 to 12, or a water-soluble salt thereof;
B) 10-60% by weight of one or more aminobenzoic acids having the formula IV:
IV
in which R8 is hydrogen or a group of formula V orVI:
V VI
or one or more water-soluble salts thereof; C) 0-10% by weight of an alkanolamine of formula VII:
in which R9, R10 and R11, independently, are hydrogen, a linear or branched C1-C12 alkyl group which is optionally interrupted by an oxygen atom, or R9, R10 and R11 are a group of formula VIII:
VIII
where R12 and R13, independently, are hydrogen or C1-C12 alkyl and p and q, independently, are 0 or an integer ranging from 1 to 10, provided that p and q are not simultaneously 0 and provided that at least one of R9, R10 and R11 is a group of formula VIII; and D) 0-10% by weight of an alkali metal borate;
the percentages by weight being based on the total weight of the corrosion inhibitor composition.
A) 40-90% by weight of a carboxylic acid corrosion inhibitor, or a water-soluble salt thereof, comprising one or more of:
A1) a triazine-carboxylic acid of formula I:
I
in which Z is a C1-C11 alkylene group, Rl and R2, independently, are hydrogen ormethyl, and R3 is a group -NR4R5 in which R4 is C1-C12 alkyl or-Z-COOH in which Z
has its previous significance, and R5 is hydrogen or C1-Cl2 alkyl, or a water-soluble salt thereof;
A2) a sulphonamidocarboxylic acid of formula II:
II
in which R6 and R7, independently, are hydrogen or C1-C4 alkyl, and m is an integer ranging from 1 to 10 or a water-soluble salt thereof; and A3) a dicarboxylic acid, or mixture thereof, having the formula III:
HOOC-(CH2)n-COOH III
in which n is an integer ranging from 4 to 12, or a water-soluble salt thereof;
B) 10-60% by weight of one or more aminobenzoic acids having the formula IV:
IV
in which R8 is hydrogen or a group of formula V orVI:
V VI
or one or more water-soluble salts thereof; C) 0-10% by weight of an alkanolamine of formula VII:
in which R9, R10 and R11, independently, are hydrogen, a linear or branched C1-C12 alkyl group which is optionally interrupted by an oxygen atom, or R9, R10 and R11 are a group of formula VIII:
VIII
where R12 and R13, independently, are hydrogen or C1-C12 alkyl and p and q, independently, are 0 or an integer ranging from 1 to 10, provided that p and q are not simultaneously 0 and provided that at least one of R9, R10 and R11 is a group of formula VIII; and D) 0-10% by weight of an alkali metal borate;
the percentages by weight being based on the total weight of the corrosion inhibitor composition.
Description
20~73~3 Corrosion Inhibiting Compositions The present invention relates to corrosion inhibiting compositions.
A wide variety of different chemical structures have found use as corrosion inhibitors for metals which come into operational contact with corrosive media.
One such group of chemical compounds is carboxylic acid compounds. One example of a group of carboxylic acid compounds, which are very effective corrosion inhibitors for ferrous metal in contact with aqueous systems, is that described in US 4402907 and comprising compounds of formula:
R3 Nq~ N(R~)-Z-COOH
N~fN
N(R2~Z-COOH
in which Z is e.g. a Cl-Cll alkylene group, Rl and R2, independently, are e.g. hydrogen or methyl; and R3 is e.g. a group -NR4R5 in which R4 is Cl-CI2 alkyl or -ZCOOH in which Z has its previous significance, and R5 is hydrogen or Cl-Cl2 alkyl; or water-soluble salts thereof.
Also known, as a corrosion inhibitor for, e.g. ferrous metal in aqueous systems is o-aminobenzoic acid (anthranilic acid) as well as derivatives thereof, c.f. e.g. Kriss et al.
Zh. Prikl. Chem., 1989, 62(8~, 1844-9.
These known carboxylic acid corrosion inhibitors have the disadvantage that they tend to be less effective when used in hard water systems.
EP 341 536 describes an attempt to improve the coIrosion protection and hard water sensitivity of anthranilic acid clerivatives by combining them with an alkenylsuccinic acid and an alkanolamine.
A wide variety of different chemical structures have found use as corrosion inhibitors for metals which come into operational contact with corrosive media.
One such group of chemical compounds is carboxylic acid compounds. One example of a group of carboxylic acid compounds, which are very effective corrosion inhibitors for ferrous metal in contact with aqueous systems, is that described in US 4402907 and comprising compounds of formula:
R3 Nq~ N(R~)-Z-COOH
N~fN
N(R2~Z-COOH
in which Z is e.g. a Cl-Cll alkylene group, Rl and R2, independently, are e.g. hydrogen or methyl; and R3 is e.g. a group -NR4R5 in which R4 is Cl-CI2 alkyl or -ZCOOH in which Z has its previous significance, and R5 is hydrogen or Cl-Cl2 alkyl; or water-soluble salts thereof.
Also known, as a corrosion inhibitor for, e.g. ferrous metal in aqueous systems is o-aminobenzoic acid (anthranilic acid) as well as derivatives thereof, c.f. e.g. Kriss et al.
Zh. Prikl. Chem., 1989, 62(8~, 1844-9.
These known carboxylic acid corrosion inhibitors have the disadvantage that they tend to be less effective when used in hard water systems.
EP 341 536 describes an attempt to improve the coIrosion protection and hard water sensitivity of anthranilic acid clerivatives by combining them with an alkenylsuccinic acid and an alkanolamine.
2~3~3 We have now found that by constructing a different cornbination of carboxylic acid corrosion inhibitors, the resulting combination has outstanding corrosion inhibiting properties which are much less sensitive to hard water environments.
Accordingly, the present invention provides a corrosion inhibiting composition comprising:
A) 40-90% by weight of a carboxylic acid corrosion inhibitor or a wa~er-soluble, salt thereof, comprising one or more of:
Al) a triazino- carboxylic acid of formula I as hereinbefore defined;
A2) a sulphonamidocarboxylic acid formula II:
R6~ S--1-- (CH2)mCOOH
in which R6 and R7, independently, are hydrogen or Cl-C4 alkyl, and m is an integer ranging from I to 10; and A3) a dicarboxylic acid, or mixture thereof, having the formula III:
HOOC-(CH2)n-COOH III
in which n is an integer ranging from 4 to 12;
B) 10 to 60% by weight of one or more aminobenzoic acids or water-soluble salts thereof having the forrnula IV:
COOH
~`~ IV
in which R8 is hydrogen or a group of formula V or VI:
7~9~
Accordingly, the present invention provides a corrosion inhibiting composition comprising:
A) 40-90% by weight of a carboxylic acid corrosion inhibitor or a wa~er-soluble, salt thereof, comprising one or more of:
Al) a triazino- carboxylic acid of formula I as hereinbefore defined;
A2) a sulphonamidocarboxylic acid formula II:
R6~ S--1-- (CH2)mCOOH
in which R6 and R7, independently, are hydrogen or Cl-C4 alkyl, and m is an integer ranging from I to 10; and A3) a dicarboxylic acid, or mixture thereof, having the formula III:
HOOC-(CH2)n-COOH III
in which n is an integer ranging from 4 to 12;
B) 10 to 60% by weight of one or more aminobenzoic acids or water-soluble salts thereof having the forrnula IV:
COOH
~`~ IV
in which R8 is hydrogen or a group of formula V or VI:
7~9~
COOH
--CH2~ V --~CH2)2 N~[~3 optionally, C) 0 to 10% by weight of an alkanolamine of forrnula VII:
NRgRIoRll VII
in which Rg, Rlo and Rl 1, independently, are hydrogen, a linear or branched Cl-C12 alkyl group which is optionally interrupted by an oxygen atom, or Rg, Rlo and Rll aIe a group of formula VIII:
(CH)p (CH)q--OH
Rl2 Rl3 in which Rl2 and Rl3, independently, are hydrogen or linear or branched Cl-Cl2 alkyl and p and q, independently, are 0 or an integer ranging from I to 10, provided that p and q are not simultaneously 0; and provided that at least one of Rg, Rlo and Rll is a group of formula VIII; and, optionally, D) 0 to 10% by weight of an alkali metal borate; the percentages by weight being based on the total weight of the corrosion inhibitorcomposition.
Cl-CII Alkylene groups 2: are, e.g., methylene, ethylene, n-propylene, n-butylene, n-pentylene, n-hexylene, n-heptylene, n-octylene, n-decylene and n-undecylene. Preferred such groups are Cl-C5 alkylene groups, especially n-pentylene.
Cl-C4 Alkyl groups R6 and/or R7 are, e.g., methyl, ethyl, n-propyl, isopropyl or n-butyl.
Preferably, R6 and R7 are independently hydrogen or methyl, R6 being methyl and R7 being hydrogen in especially preferred embodiments.
Cl-Cl2 Alkyl groups R4, Rs, Rg, Rlo, R1l, R12 and R13 are e.g. methyl, ethyl, n-propyl, isopropyl, n-butyl, n-hexyl, n-octyl, n-decyl or n-dodecyl.
C1-Cl2 Alkyl groups Rg, Rlo and R1l interrupted by an oxygen atom are, e.g., methoxymethyl, ethoxymethyl, 2-methoxyethyl, 2-ethoxyethyl, 3-methoxypropyl, I-or 2-methoxybutyl, I-methoxyoctyl, l-methoxydecyl or l-methoxydodecyl.
2~7~93 In forrnula III n is preferably 11 and/or 12.
Preferably, R4 is Cl-C8 alkyl or -Z-COOH where ~ is a Cl-C5 alkylene group; Rs is hydrogen or Cl-C4 alkyl; Rg and Rlo are independently hydrogen, Cl-C4 aLlcyl or a group of formula VIII where Rl2 and Rl3 are independently hydrogen or ~l-C4 aL~cyl, while Rll is a group of forrnula VIII where Rl2 and Rl3 are independently hydrogen or Cl-C4 aL~cyl.
Thus, preferred compounds A1) are of formula I where Rl and R2 are independentlyhydrogen or rnèthyl, R3 is -NR4R5 where R4 is Cl-C8 alkyl or -Z-COOH, R5 is hydrogen or Cl-C4 alkyl, and Z is Cl-C5 alkylene and their water soluble salts; preferred compounds A2) are of forrnula II where R6 and R7 are independently hydrogen or methyl and their water-soluble salts; and preferred compounds A3) are of forrnula III where n is 11 or 12, mixtures of an acid where n is 11 with an acid where n is 12, and water-soluble salts of such acids and mixtures of acids.
Exarnples of specific compounds of formula I are as follows:
2,4,6-Tris(5'-carboxypenlylamino)-1,3,5-triazine, 2,4,6-Tris(carboxymethylamino)- 1 ,3,5-triazine, 2,4,6-Tris(3'-carboxypropylamino)-1,3,5-triazine, 2,4,6-Tris(4'-carboxybutylamino)-1,3,5-triazine, 2,4,6-Tris(ll'-carboxyundecylamino)- 1,3 ,S-triazine, 2,4,6-Tris(S'-carboxypentyl-N-methylamino)- 1 ,3,5-triazine, 2,4,6-Tris(carboxymethyl-N-methylamino)- 1 ,3,5-triazine, 2,4,6-Tris(3'-carboxypropyl-N-methylamino)- 1 ,3,5-triazine, 2,4-Bis(S'-carboxypentylamino)-6-n-octylamino)- 1,3 ,S-triazine, 2,4-Bis(2'-carboxyethylamino)-6-n-octylamino)- 1,3 ,S-triazine, 2,4-Bis(2'-carboxyethylamino)-6-diethylamino)- 1 ,3,5-triazine, 2,4-Bis(2'-carboxyethylamino)-6-butylamino)- 1 ,3,5-triazine, 2,4-Bis(2'-carboxyethylamino)-6-ethylamino)-1,3,5-triazine, 2,4-Bis(3'-carboxypropylamino)-6-ethylamino)-1,3,5-triazine, 2,4-Bis(3'-carboxypropylamino)-6-n-octylamino)- 1 ,3,5-triazine 2,4-Bis(3'-carboxypropylamino)-6-n-propylamino)- 1 ,3,5-triazine 2,4-Bis(carboxymethylamino)-6-n-octylamino)- 1 ,3,5-triazine, 2,4,-Bis(carboxymethylamino)-6-dodecylamino)- 1 ,3,5-triazine, 2,4-Bis(3'-carboxypropyl-N-methylamino)-6-n-octylamino)-1 ,3,5-triazine, 2,4-Bis(carboxymethyl-N-methylamino)-6-n-octylamino)- 1 ,3,5-triazine, ~.
2~739~
2,4-Bis(2'-carboxyethyl-N-methylamino)-6-n-octylamino)- 1 ,3,5-tria~ine, 2,4-Bis(5'-carboxypentylamino)-6-(2"-carboxyethylam ino)- 1 ,3,5-triazine, 2,4-Bis(5'-carboxypentylamino)-6-(carboxymethylamino)- 1 ,3,5-triazine, 2,4-Bis(3'-carboxypropylarnino)-6-(2"-carboxyethylamino)- 1 ,3,5-triazine, 2,4-Bis(2'-carboxyethylamino)-6-(5 "-carboxypentylamino)- 1 ,3,5-triazine, 2,4-Bis(3'-carboxypropylamino)-6-(5 "-carboxypentylamino)-1,3,5-triazine, The compounds of foIInula I are not new. These compounds and their production are described e.g. in Zhurnal Analiticheskoi Khimii 15, 419-423 (1960), in DE-OS 1935010, in DE-OS 2819796, in US Patent Specification 3697520 and in J. Prakt Chemie 23 173-85 (1963). ~specially preferred compounds are 2,4,~tris(5-carboxypentylamino)-1,3,5-triazine and water-soluble salts thereof.
Examples of compounds of formula II include benzenesulphonamidoacetic acid, benzenesulphonamido-2-propionic acid, benzenesulphonamido-4-butyric acid, benzenesulphonamido-6-n-hexanoic acid, benzenesulphonamido-8-n-octanoic acid, benzenesulphonamido-10-n-decanoic acid, N-methylbenzenesulphonamido acetic acid,4-toluene sulphonamidoacetic acid and N-methyl-4-toluene sulphonamidoacetic acid.
Especially preferred compounds are p-toluenesulphonamidocaproic acid and water-soluble salts thereof.
Compounds of formula III include, e.g. adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, nonane-1,9-dioic acid, decane-1,10-dioic acid, undecane-l,ll-dioic acid and dodecane-1,12-dioic acid, as well as mixtures of these e.g. the commercially -available mixture of undecane-l,ll-dioic acid and dodecane-1,12-dioic acid sold as "Alox 232", the last-named being especially preferred.
Specific examples of aminobenzoic acids of formula IV include anthranilic acid and N-(2-carboxy benzyl)-2-aminobenzoic acid.
The optional alkanolamine of formula VII may be, e.g., ethanolamine, diethanolamine, triethanolamine, methylelthanolamine, dimethylethanolamine, diethylethanolamine,butylethanolamine, dibutylethanolamine, di-isopropylethanolamine, methyldiethanolamine, ethyldiethanolamine, isopropanolamine, di-isopropanolamine, tri-isopropanolamine, sec.butanolamine, di-sec.butanolamine, tri-sec.butanolarrline, or dimethylisopropanolamine. An especially preferred alkanolamine is triethanolamine.
20~73~
The alkali metal borate may be e.g. sodium borate or potassium borate.
The water-soluble salts of carboxylic acid compounds of formula I andlor II may be alkali metal salts such as sodium or potassium salts; alkaline e:arth metal salts such as calcium or magnesium salts; or Cl-Cl2 alkyl amine salts such as methylamine, ethylarnine, isopropylamine, dibutylarnine, tributylamine, octylarnine or dodecylamine salts. The Cl-CI2 amine salt may be hydroxy-substituted and may be, e.g., a mono-, di- or tri-ethanolamine salt.
As already indicated, the corrosion inhibiting composition according to the present invention provide excellent inhibition against corrosion of ferrous metals in contact with an aqueous medium.
Accordingly, the present invention also provides a method of inhibiting the corrosion of a ferrous metal in contact with an aqueous system, comprising incorporating into the aqueous system an effective, corrosion-inhibiting amount, preferably 0.001 to 5% by weight, based on the weight of the aqueous system, of a corrosion inhibiting composition as hereinbefore defined.
The aqueous system which is treated according to the method of the present invention may be a totally aqueous or a partly aqueous medium.
Aqueous systems which may be effectively treated according to the present invention include e.g. cooling water systems, steam generating systems, sea-water evaporators, reverse osmosis equipment, bottle washing plants, paper manufacturing equipment, sugar evaporator equipment, soil irrigation systems, hydrostatic cookers, gas scrubbing systems, closed circuit heating systems, aqueous - based refrigeration systems, down-well systems, aqueous machining fluid formations (e.g. for use in boring, milling, reaming, broaching, drawing, turning, cutting, sawing, grinding, and in thread-cutting operations, or in non-cutting shaping, spinning, drawing or rolling operations), aqueous scouring systems, aqueous glycol anti-freeze systems, water/glycol hydraulic fluids; and aqueous - based polymer surface coating systems.
The corrosion-inhibiting composition of the present invention may be used in the method of the present invention either alone or in conjunction with other materials known to be useful in water treatment.
7 2~ 7~ ~
In the treatment of systerns which are completely aqueous, e.g. cocling water systems, steam-generating systems, sea water evaporator systems, hydrostatic cookers and closed circuit heating systems, examples of further water treatrnent additives include one or more of further corrosion inhibitors; metal deactivators; further scale inhibitors/dispersing agents;
threshold agents; precipitating agents; oxygen scavengers; sequestering agents; antifoaming agents; and biocides.
Further corrosion inhibitors which may be used include water-soluble zinc salts;phosphates; polyphosphates; phosphonic acids or their salts, e.g. hydroxyethyl diphosphonic acid (HEDP), nitrilotris methylene phosphonic acid, methylamino dimethylene phosphonocarboxylic acids and their salts (e.g. those described in DE-OS 2632774), hydroxyphosphonoacetic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid and those described in GB-PS 1572406; nitrates e.g. sodium nitrate; nitrites e.g. sodium nitrite;
tungstates and molybdates e.g. sodium tungstate or molybdate; silicates e.g. sodium silicate;
N-acylsarcosines; N-acylimino diacetic acids; ethanolamines; ~atty amines; and polycarboxylic acids, e.g. polymaleic acid and polyacrylic acid (and their respective alkali metal salts), copolymers of maleic anhydride e.g. with sulphonated styrene, copolymers of acrylic acid e.g. with hydroxyalkylated acrylic acid, and substituted derivatives of polymaleic and polyacrylic acids and their copolymers.
Metal deactivators espècially for copper, include benzotriazole,5,5'-methylene bis-benzotriazole or copper - deactivating derivatives of benzotriazole or tolutriazole, or their Mannich base derivatives, or mercaptobenzothiazole.
Scale inhibitors/dispersing agents include polymerized acrylic acid (or its salts), phosphino-polycarboxylic acids (e.g. those described in GB-PS 1458235), the cotelomers described in EP-PS 0150706, hydrolyzed polyacrylonitrile, polymerized methacrylic acid and its salts, polyacrylamide and copolymers of acrylamide with acrylic and methacrylic acids, lignin sulphonic acid and its salts, tannin naphthalene sulphonic acid/formaldehyde condensation products, starch and its derivatives, cellulose, acrylic acid / lower alkyl hydroxy-acrylate copolymers (e.g. those described in US-PS 402g577) styrene/maleic anhydride copolymers and sulphonated styrene homopolymers (e.g. those described in US-PS 4374733, and combinations of these).
Specific threshold agents, include 2-phosphonobutane-1,2,4-tri-carboxylic acid, HEDP, 2~8~3~
hydrolyzed polymaleic anhydride and its salts, alkyl phosphonic acids, hydroxyphosphonoacetic acid, l-aminoalkyl~ diphosplhonic acids and their salts, and alkali metal polyphosphates.
It will be clear from the above lists that certain additive compounds, e.g.
phosphonocarboxylic acids, ~unction both as scale inhibitors and as corrosion inhibitors.
Precipitating agent co-additives which may be used are alkali metal orthophosphates or carbonates; oxygen scavengers include allcali metal sulphites and hydrazines; sequestering agents are nitrilotriacetic acid and its salts; antifoaming agents are silicones, e.g.
polydimethylsiloxanes, distearyl sebacimide, distearyl adipamide, and lelated products derived from ethylene oxide and/or propylene oxide condensations, in addition to fatty alcohols such as capryl alcohol and its ethylene oxide condensates. Biocides which may be used are, e.g. amines, quaternary ammonium compounds, m-chlorophenols, sulphur-containing compounds such as sulphones, methylene bis thiocyanates and carbonates, isothiazolines, brominated propionamides, triazines, phosphonium compounds, chlorine and chlorine-release agents, bromine and bromine release agents, and organometallic compounds such as tributyl tin oxide.
If the system to be treated according to the invention is not completely aqueous e.g. an aqueous machining fluid formulation, it may be e.g. a water dilutable cutting or grinding fluid.
The aqueous machining fluid formulations of the invention may be e.g. metal working formulations. By "metal working" we mean "reaming, broaching, drawing, spinning,cutting, grinding, boring, milling, turning, sawing, non-cutting shaping or rolling".
Examples of water-dilutable cutting or grinding fluids into which the corrosion inhibiting compound of formula I may be incorporated include:
a) Aqueous concentrates of one or more corrosion inhibitors, and optionally one or more anti-wear additives, used at dilutions of 1:50 to 1:100, which are usually employed as grinding fluids;
b) Polyglycols containing biocides, corrosion inhibitors and anti-wear additives which are used at dilutions of 1:20 to 1:40 for cutting operations and 1:60 to 1:80 for grinding;
~73~
c) Semi-synthetic cutting :fluids similar to b) but containing in addition 10 to 25% oil with sufficient emulsifier to Tender the water diluted product translucent;
d) An emulsifiable mineral oil concentrate containing, for example, emulsifiers, corrosion inhibitors, extreme press~lre/anti-wear additives, biocides, antifoaming agents, coupling agents etc; they are generally diluted from 1:10 to 1:~0 with water to a white opaque emulsion;
e) A product similar to d) containing less oil and more emulsifier which, on dilution to the range 1:50 to 1:100, gives a translucent emulsion for cutting or grinding operations.
Mixtures of sodium nitrite and triethanolamine have been used to inhibit corrosion in metal working but, because of related toxicity problems, due e.g. to the danger of forming N-nitrosamines, and because of legal regulations in some countries relating to effluents, alternatives to the use of sodium nitrite are being sought.
For those partly-aqueous systems in which the aqueous system component is an aqueous machining fluid formulation, the corrosion inhibitor composition of the present invention may be used singly, or in admixture with other additives e.g. known further corrosion inhibitors and/or extreme pressure additives.
Examples of other corrosion inhibitors which may be used in these aqueous systems, in addition to the corrosion inhibitor composition of the present invention include the following groups:
a) Further organic acids, their esters or ammonium, amine, alkanolamine and metal salts, for example, benzoic acid, p-tert-butyl benzoic acid, triethanolamine laurate, iso-nonanoic acid, sodium N-lauroyl sarcosinate or nonyl phenoxy acetic acid;
b) Nitrogen containing materials such as the following types: fatty acid alkanolamides;
imidazolines, for example, I-hydroxyethyl-2-oleyl-imidazolines; oxazolines; triazoles, for example, benzotriazoles, triethanolamines; fatty amines; and inorganic salts, for example sodium nitrate;
c) Phosphorus containing materials such as the following types: amine phosphates, phosphonic acids or inorganic salts, for example, sodium dihydrogen phosphate or zinc 3 9 ~
phosphate;
d) Sulphur containing compounds such as the following types: sodium, calcium or barium petroleum sulphonates, or heterocyclics, for example, sodium mercaptobenzothiazole.
Nitrogen containing materials, particularly triethanolamine, are preferred.
Examples of extreme pressure additives which may be present in the systems of the present invention include sulphur and/or phosphorus andlor halogen containing materials, for instarice, sulphurised sperm oil, sulphurised fats, tritolyl phosphate, chlorinated paraffins or ethoxylated phosphate esters.
When triethanolamine is present in the aqueous systems treated according to the present invention, it is preferably present in an amount such that the ratio of the corrosion inhibitor composition of the present invention to triethanolamine is from 2:1 to 1:~0.
The partly-aqueous systems treated by the method of the present invendon may also be aqueous surface-coating compositions e.g. primer emulsion paints and aqueous powder coatings for metallic substrates.
The aqueous surface-coating composition may be e.g. a paint such as styrene-acrylic copolymer emulsion paint, a resin, latex, or other aqueous based polymer surface-coating systems.
Sodium nitrite and sodium benzoate have been used to inhibit flash rusting of aqueous based primer paints but, because of related toxiciy problems and problems of emulsion stability at the high ionic concentrations used, industry is moving away from sodium nitrite and sodium benzoate.
In aqueous surface-coating compositions treated according to the invention the corrosion inhibitor composition of the present invention may be used singly, or in admixture with other additives e.g. known corrosion inhibitors, biocides, emulsifiers and/or pigments.
The further known corrosion inhibitors which may be used are e.g. those of classes a), b), c) and d) hereinbefore defined.
2~
Examples of biocides which may be used in these aqueous systems, in addition to the corrosion inhibitor composition of the present invention, include the following:
Phenols and aLlcyl- and halogenated phenols, for example pentachlorophenol, o-phenyl phenol, o-phenoxyphenol and chlorinated ~phenoxyphenol, and salicylanilides, diamines, triazines and organometallic compounds such as organomercury compounds and organotin compounds.
Examples of pigments which may be used in these aqueous systems, in addition to the corrosion inhibitor composition of che present invention, include titanium dioxide, zinc chromate, iron oxide and organic pigments such as the phthalocyanines.
The following Examples f~Jrther illustrate the present invention.
Examples 1 and 2 A) A corrosion inhibitor composition is formed by mixing 30 parts by weight o~
2,4,6-tris(5-carboxypentylamino)-1,3,5-triazine and 20 parts by weight of anthranilic acid.
B) The corrosion-inhibiting performance of this composition A) is then evaluated in the DIN 51360 test ("Filter Chip Test"). The composition A) is dissolved in DIN 51360 water, with triethanolamine and/or borax added, to adjust the resulting solution to a pH
of 8.0 or ~.5. The concentration of the corrosion inhibitor A) in the solution is 1.0% or 1.5% by weight, respectively.
Staining by cast iron "chips", that lie on a filter paper and which are wetted by a small volume of the test solution, is evaluated according to the following rating scale:
0 no staining traces of staining 2 slight staining 3 moderate staining 4 heavy staining The results obtained, as well as tne corresponding results obtained with each of ~7~3 2,4,6-tris(S-carboxypentylamino)-1,3,5-triazine or anthranilic acid, respectively used alone, are set out in the following Tables 1 and 2:
Table 1 , _ _ _ Concentraîion Example Fonnulation % by weight Rating at pH 8.5 2,4,6-tris(5-carboxypentylamino~l ,3,5-triazine 1.0 2 anthranilic acid l.O __ Product of Exa~nple l(A) 1.0 O
Table 2 Conccntration Example Fonnulation % by weight Rating at pH 8.0 _ 2,4,6-tris(5-carboxy,oentyla nino~l,3,5-triazine1.5 3 anthranilic acid 1.5 2 2 Product of Ex~unple l(A) 1.5 Example 3 A) A corrosion inhibitor composition is made up by mixing 10 parts by weight of p-toluene sulphonamidocaproic acid and 10 parts by weight of anthranilic acid.
B) Using the procedure described in Example l(B~, at pH 8.5, the following results are obtained.
2~7~93 Table 3 Concen~adon Radng Example Fonnuladon % by weight .
~toluene sulphonamido-caproic acid0.9 3 antl~anilic acid 0.9 3 3 Producl of Example 0.9 O
Example 4 A) A corrosion inhibitor composition comprising 10 parts by weight of Alox 232 (a commerically - available mixture of Cll/Cl2 dicarboxylic acids) and 10 parts by weight of anthranilic acid is prepared.
B) Using the procedure described in Example l(B), at pH 8.5, the following results:
Table 4 Concen~ation Raling E; :nple Formulation % by weigh~ .
Alox 232 1.2 3 anthranilic acid 1.2 2 4 P~oducl of Example ~ j9) Example 5 A) A corrosion inhibitor composition is prepared comprising 30 parts by weight of 2,4,6-tris(5-carboxypentylamino)-1,3,5-triazine and 10 parts by weight of N'-(2-carboxybenzyl)-2-aminobenzoic acid.
B) Using the procedure described in Example l(B), at pH 9.0, the following results are obtained:
~0873~3 Table 5 -_ . ConcentrationRating E~: plc Fonnulatlono by weight . _ .
2,4,6-tris(5-carboxypentylamino)-1 .3,5-triazin~ 0.6 4 N -(2-carboxybenzyl)-2-aminobenzoic acid 0.6 . , S P~oductofExample~ S~) 0.6 O
The results in Tables 1, 2, 3, 4 and 5 demonstrate the striking improvement in corrosion inhi~itor performance of the compositions of the invention, in aLkaline pH ranges.
--CH2~ V --~CH2)2 N~[~3 optionally, C) 0 to 10% by weight of an alkanolamine of forrnula VII:
NRgRIoRll VII
in which Rg, Rlo and Rl 1, independently, are hydrogen, a linear or branched Cl-C12 alkyl group which is optionally interrupted by an oxygen atom, or Rg, Rlo and Rll aIe a group of formula VIII:
(CH)p (CH)q--OH
Rl2 Rl3 in which Rl2 and Rl3, independently, are hydrogen or linear or branched Cl-Cl2 alkyl and p and q, independently, are 0 or an integer ranging from I to 10, provided that p and q are not simultaneously 0; and provided that at least one of Rg, Rlo and Rll is a group of formula VIII; and, optionally, D) 0 to 10% by weight of an alkali metal borate; the percentages by weight being based on the total weight of the corrosion inhibitorcomposition.
Cl-CII Alkylene groups 2: are, e.g., methylene, ethylene, n-propylene, n-butylene, n-pentylene, n-hexylene, n-heptylene, n-octylene, n-decylene and n-undecylene. Preferred such groups are Cl-C5 alkylene groups, especially n-pentylene.
Cl-C4 Alkyl groups R6 and/or R7 are, e.g., methyl, ethyl, n-propyl, isopropyl or n-butyl.
Preferably, R6 and R7 are independently hydrogen or methyl, R6 being methyl and R7 being hydrogen in especially preferred embodiments.
Cl-Cl2 Alkyl groups R4, Rs, Rg, Rlo, R1l, R12 and R13 are e.g. methyl, ethyl, n-propyl, isopropyl, n-butyl, n-hexyl, n-octyl, n-decyl or n-dodecyl.
C1-Cl2 Alkyl groups Rg, Rlo and R1l interrupted by an oxygen atom are, e.g., methoxymethyl, ethoxymethyl, 2-methoxyethyl, 2-ethoxyethyl, 3-methoxypropyl, I-or 2-methoxybutyl, I-methoxyoctyl, l-methoxydecyl or l-methoxydodecyl.
2~7~93 In forrnula III n is preferably 11 and/or 12.
Preferably, R4 is Cl-C8 alkyl or -Z-COOH where ~ is a Cl-C5 alkylene group; Rs is hydrogen or Cl-C4 alkyl; Rg and Rlo are independently hydrogen, Cl-C4 aLlcyl or a group of formula VIII where Rl2 and Rl3 are independently hydrogen or ~l-C4 aL~cyl, while Rll is a group of forrnula VIII where Rl2 and Rl3 are independently hydrogen or Cl-C4 aL~cyl.
Thus, preferred compounds A1) are of formula I where Rl and R2 are independentlyhydrogen or rnèthyl, R3 is -NR4R5 where R4 is Cl-C8 alkyl or -Z-COOH, R5 is hydrogen or Cl-C4 alkyl, and Z is Cl-C5 alkylene and their water soluble salts; preferred compounds A2) are of forrnula II where R6 and R7 are independently hydrogen or methyl and their water-soluble salts; and preferred compounds A3) are of forrnula III where n is 11 or 12, mixtures of an acid where n is 11 with an acid where n is 12, and water-soluble salts of such acids and mixtures of acids.
Exarnples of specific compounds of formula I are as follows:
2,4,6-Tris(5'-carboxypenlylamino)-1,3,5-triazine, 2,4,6-Tris(carboxymethylamino)- 1 ,3,5-triazine, 2,4,6-Tris(3'-carboxypropylamino)-1,3,5-triazine, 2,4,6-Tris(4'-carboxybutylamino)-1,3,5-triazine, 2,4,6-Tris(ll'-carboxyundecylamino)- 1,3 ,S-triazine, 2,4,6-Tris(S'-carboxypentyl-N-methylamino)- 1 ,3,5-triazine, 2,4,6-Tris(carboxymethyl-N-methylamino)- 1 ,3,5-triazine, 2,4,6-Tris(3'-carboxypropyl-N-methylamino)- 1 ,3,5-triazine, 2,4-Bis(S'-carboxypentylamino)-6-n-octylamino)- 1,3 ,S-triazine, 2,4-Bis(2'-carboxyethylamino)-6-n-octylamino)- 1,3 ,S-triazine, 2,4-Bis(2'-carboxyethylamino)-6-diethylamino)- 1 ,3,5-triazine, 2,4-Bis(2'-carboxyethylamino)-6-butylamino)- 1 ,3,5-triazine, 2,4-Bis(2'-carboxyethylamino)-6-ethylamino)-1,3,5-triazine, 2,4-Bis(3'-carboxypropylamino)-6-ethylamino)-1,3,5-triazine, 2,4-Bis(3'-carboxypropylamino)-6-n-octylamino)- 1 ,3,5-triazine 2,4-Bis(3'-carboxypropylamino)-6-n-propylamino)- 1 ,3,5-triazine 2,4-Bis(carboxymethylamino)-6-n-octylamino)- 1 ,3,5-triazine, 2,4,-Bis(carboxymethylamino)-6-dodecylamino)- 1 ,3,5-triazine, 2,4-Bis(3'-carboxypropyl-N-methylamino)-6-n-octylamino)-1 ,3,5-triazine, 2,4-Bis(carboxymethyl-N-methylamino)-6-n-octylamino)- 1 ,3,5-triazine, ~.
2~739~
2,4-Bis(2'-carboxyethyl-N-methylamino)-6-n-octylamino)- 1 ,3,5-tria~ine, 2,4-Bis(5'-carboxypentylamino)-6-(2"-carboxyethylam ino)- 1 ,3,5-triazine, 2,4-Bis(5'-carboxypentylamino)-6-(carboxymethylamino)- 1 ,3,5-triazine, 2,4-Bis(3'-carboxypropylarnino)-6-(2"-carboxyethylamino)- 1 ,3,5-triazine, 2,4-Bis(2'-carboxyethylamino)-6-(5 "-carboxypentylamino)- 1 ,3,5-triazine, 2,4-Bis(3'-carboxypropylamino)-6-(5 "-carboxypentylamino)-1,3,5-triazine, The compounds of foIInula I are not new. These compounds and their production are described e.g. in Zhurnal Analiticheskoi Khimii 15, 419-423 (1960), in DE-OS 1935010, in DE-OS 2819796, in US Patent Specification 3697520 and in J. Prakt Chemie 23 173-85 (1963). ~specially preferred compounds are 2,4,~tris(5-carboxypentylamino)-1,3,5-triazine and water-soluble salts thereof.
Examples of compounds of formula II include benzenesulphonamidoacetic acid, benzenesulphonamido-2-propionic acid, benzenesulphonamido-4-butyric acid, benzenesulphonamido-6-n-hexanoic acid, benzenesulphonamido-8-n-octanoic acid, benzenesulphonamido-10-n-decanoic acid, N-methylbenzenesulphonamido acetic acid,4-toluene sulphonamidoacetic acid and N-methyl-4-toluene sulphonamidoacetic acid.
Especially preferred compounds are p-toluenesulphonamidocaproic acid and water-soluble salts thereof.
Compounds of formula III include, e.g. adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, nonane-1,9-dioic acid, decane-1,10-dioic acid, undecane-l,ll-dioic acid and dodecane-1,12-dioic acid, as well as mixtures of these e.g. the commercially -available mixture of undecane-l,ll-dioic acid and dodecane-1,12-dioic acid sold as "Alox 232", the last-named being especially preferred.
Specific examples of aminobenzoic acids of formula IV include anthranilic acid and N-(2-carboxy benzyl)-2-aminobenzoic acid.
The optional alkanolamine of formula VII may be, e.g., ethanolamine, diethanolamine, triethanolamine, methylelthanolamine, dimethylethanolamine, diethylethanolamine,butylethanolamine, dibutylethanolamine, di-isopropylethanolamine, methyldiethanolamine, ethyldiethanolamine, isopropanolamine, di-isopropanolamine, tri-isopropanolamine, sec.butanolamine, di-sec.butanolamine, tri-sec.butanolarrline, or dimethylisopropanolamine. An especially preferred alkanolamine is triethanolamine.
20~73~
The alkali metal borate may be e.g. sodium borate or potassium borate.
The water-soluble salts of carboxylic acid compounds of formula I andlor II may be alkali metal salts such as sodium or potassium salts; alkaline e:arth metal salts such as calcium or magnesium salts; or Cl-Cl2 alkyl amine salts such as methylamine, ethylarnine, isopropylamine, dibutylarnine, tributylamine, octylarnine or dodecylamine salts. The Cl-CI2 amine salt may be hydroxy-substituted and may be, e.g., a mono-, di- or tri-ethanolamine salt.
As already indicated, the corrosion inhibiting composition according to the present invention provide excellent inhibition against corrosion of ferrous metals in contact with an aqueous medium.
Accordingly, the present invention also provides a method of inhibiting the corrosion of a ferrous metal in contact with an aqueous system, comprising incorporating into the aqueous system an effective, corrosion-inhibiting amount, preferably 0.001 to 5% by weight, based on the weight of the aqueous system, of a corrosion inhibiting composition as hereinbefore defined.
The aqueous system which is treated according to the method of the present invention may be a totally aqueous or a partly aqueous medium.
Aqueous systems which may be effectively treated according to the present invention include e.g. cooling water systems, steam generating systems, sea-water evaporators, reverse osmosis equipment, bottle washing plants, paper manufacturing equipment, sugar evaporator equipment, soil irrigation systems, hydrostatic cookers, gas scrubbing systems, closed circuit heating systems, aqueous - based refrigeration systems, down-well systems, aqueous machining fluid formations (e.g. for use in boring, milling, reaming, broaching, drawing, turning, cutting, sawing, grinding, and in thread-cutting operations, or in non-cutting shaping, spinning, drawing or rolling operations), aqueous scouring systems, aqueous glycol anti-freeze systems, water/glycol hydraulic fluids; and aqueous - based polymer surface coating systems.
The corrosion-inhibiting composition of the present invention may be used in the method of the present invention either alone or in conjunction with other materials known to be useful in water treatment.
7 2~ 7~ ~
In the treatment of systerns which are completely aqueous, e.g. cocling water systems, steam-generating systems, sea water evaporator systems, hydrostatic cookers and closed circuit heating systems, examples of further water treatrnent additives include one or more of further corrosion inhibitors; metal deactivators; further scale inhibitors/dispersing agents;
threshold agents; precipitating agents; oxygen scavengers; sequestering agents; antifoaming agents; and biocides.
Further corrosion inhibitors which may be used include water-soluble zinc salts;phosphates; polyphosphates; phosphonic acids or their salts, e.g. hydroxyethyl diphosphonic acid (HEDP), nitrilotris methylene phosphonic acid, methylamino dimethylene phosphonocarboxylic acids and their salts (e.g. those described in DE-OS 2632774), hydroxyphosphonoacetic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid and those described in GB-PS 1572406; nitrates e.g. sodium nitrate; nitrites e.g. sodium nitrite;
tungstates and molybdates e.g. sodium tungstate or molybdate; silicates e.g. sodium silicate;
N-acylsarcosines; N-acylimino diacetic acids; ethanolamines; ~atty amines; and polycarboxylic acids, e.g. polymaleic acid and polyacrylic acid (and their respective alkali metal salts), copolymers of maleic anhydride e.g. with sulphonated styrene, copolymers of acrylic acid e.g. with hydroxyalkylated acrylic acid, and substituted derivatives of polymaleic and polyacrylic acids and their copolymers.
Metal deactivators espècially for copper, include benzotriazole,5,5'-methylene bis-benzotriazole or copper - deactivating derivatives of benzotriazole or tolutriazole, or their Mannich base derivatives, or mercaptobenzothiazole.
Scale inhibitors/dispersing agents include polymerized acrylic acid (or its salts), phosphino-polycarboxylic acids (e.g. those described in GB-PS 1458235), the cotelomers described in EP-PS 0150706, hydrolyzed polyacrylonitrile, polymerized methacrylic acid and its salts, polyacrylamide and copolymers of acrylamide with acrylic and methacrylic acids, lignin sulphonic acid and its salts, tannin naphthalene sulphonic acid/formaldehyde condensation products, starch and its derivatives, cellulose, acrylic acid / lower alkyl hydroxy-acrylate copolymers (e.g. those described in US-PS 402g577) styrene/maleic anhydride copolymers and sulphonated styrene homopolymers (e.g. those described in US-PS 4374733, and combinations of these).
Specific threshold agents, include 2-phosphonobutane-1,2,4-tri-carboxylic acid, HEDP, 2~8~3~
hydrolyzed polymaleic anhydride and its salts, alkyl phosphonic acids, hydroxyphosphonoacetic acid, l-aminoalkyl~ diphosplhonic acids and their salts, and alkali metal polyphosphates.
It will be clear from the above lists that certain additive compounds, e.g.
phosphonocarboxylic acids, ~unction both as scale inhibitors and as corrosion inhibitors.
Precipitating agent co-additives which may be used are alkali metal orthophosphates or carbonates; oxygen scavengers include allcali metal sulphites and hydrazines; sequestering agents are nitrilotriacetic acid and its salts; antifoaming agents are silicones, e.g.
polydimethylsiloxanes, distearyl sebacimide, distearyl adipamide, and lelated products derived from ethylene oxide and/or propylene oxide condensations, in addition to fatty alcohols such as capryl alcohol and its ethylene oxide condensates. Biocides which may be used are, e.g. amines, quaternary ammonium compounds, m-chlorophenols, sulphur-containing compounds such as sulphones, methylene bis thiocyanates and carbonates, isothiazolines, brominated propionamides, triazines, phosphonium compounds, chlorine and chlorine-release agents, bromine and bromine release agents, and organometallic compounds such as tributyl tin oxide.
If the system to be treated according to the invention is not completely aqueous e.g. an aqueous machining fluid formulation, it may be e.g. a water dilutable cutting or grinding fluid.
The aqueous machining fluid formulations of the invention may be e.g. metal working formulations. By "metal working" we mean "reaming, broaching, drawing, spinning,cutting, grinding, boring, milling, turning, sawing, non-cutting shaping or rolling".
Examples of water-dilutable cutting or grinding fluids into which the corrosion inhibiting compound of formula I may be incorporated include:
a) Aqueous concentrates of one or more corrosion inhibitors, and optionally one or more anti-wear additives, used at dilutions of 1:50 to 1:100, which are usually employed as grinding fluids;
b) Polyglycols containing biocides, corrosion inhibitors and anti-wear additives which are used at dilutions of 1:20 to 1:40 for cutting operations and 1:60 to 1:80 for grinding;
~73~
c) Semi-synthetic cutting :fluids similar to b) but containing in addition 10 to 25% oil with sufficient emulsifier to Tender the water diluted product translucent;
d) An emulsifiable mineral oil concentrate containing, for example, emulsifiers, corrosion inhibitors, extreme press~lre/anti-wear additives, biocides, antifoaming agents, coupling agents etc; they are generally diluted from 1:10 to 1:~0 with water to a white opaque emulsion;
e) A product similar to d) containing less oil and more emulsifier which, on dilution to the range 1:50 to 1:100, gives a translucent emulsion for cutting or grinding operations.
Mixtures of sodium nitrite and triethanolamine have been used to inhibit corrosion in metal working but, because of related toxicity problems, due e.g. to the danger of forming N-nitrosamines, and because of legal regulations in some countries relating to effluents, alternatives to the use of sodium nitrite are being sought.
For those partly-aqueous systems in which the aqueous system component is an aqueous machining fluid formulation, the corrosion inhibitor composition of the present invention may be used singly, or in admixture with other additives e.g. known further corrosion inhibitors and/or extreme pressure additives.
Examples of other corrosion inhibitors which may be used in these aqueous systems, in addition to the corrosion inhibitor composition of the present invention include the following groups:
a) Further organic acids, their esters or ammonium, amine, alkanolamine and metal salts, for example, benzoic acid, p-tert-butyl benzoic acid, triethanolamine laurate, iso-nonanoic acid, sodium N-lauroyl sarcosinate or nonyl phenoxy acetic acid;
b) Nitrogen containing materials such as the following types: fatty acid alkanolamides;
imidazolines, for example, I-hydroxyethyl-2-oleyl-imidazolines; oxazolines; triazoles, for example, benzotriazoles, triethanolamines; fatty amines; and inorganic salts, for example sodium nitrate;
c) Phosphorus containing materials such as the following types: amine phosphates, phosphonic acids or inorganic salts, for example, sodium dihydrogen phosphate or zinc 3 9 ~
phosphate;
d) Sulphur containing compounds such as the following types: sodium, calcium or barium petroleum sulphonates, or heterocyclics, for example, sodium mercaptobenzothiazole.
Nitrogen containing materials, particularly triethanolamine, are preferred.
Examples of extreme pressure additives which may be present in the systems of the present invention include sulphur and/or phosphorus andlor halogen containing materials, for instarice, sulphurised sperm oil, sulphurised fats, tritolyl phosphate, chlorinated paraffins or ethoxylated phosphate esters.
When triethanolamine is present in the aqueous systems treated according to the present invention, it is preferably present in an amount such that the ratio of the corrosion inhibitor composition of the present invention to triethanolamine is from 2:1 to 1:~0.
The partly-aqueous systems treated by the method of the present invendon may also be aqueous surface-coating compositions e.g. primer emulsion paints and aqueous powder coatings for metallic substrates.
The aqueous surface-coating composition may be e.g. a paint such as styrene-acrylic copolymer emulsion paint, a resin, latex, or other aqueous based polymer surface-coating systems.
Sodium nitrite and sodium benzoate have been used to inhibit flash rusting of aqueous based primer paints but, because of related toxiciy problems and problems of emulsion stability at the high ionic concentrations used, industry is moving away from sodium nitrite and sodium benzoate.
In aqueous surface-coating compositions treated according to the invention the corrosion inhibitor composition of the present invention may be used singly, or in admixture with other additives e.g. known corrosion inhibitors, biocides, emulsifiers and/or pigments.
The further known corrosion inhibitors which may be used are e.g. those of classes a), b), c) and d) hereinbefore defined.
2~
Examples of biocides which may be used in these aqueous systems, in addition to the corrosion inhibitor composition of the present invention, include the following:
Phenols and aLlcyl- and halogenated phenols, for example pentachlorophenol, o-phenyl phenol, o-phenoxyphenol and chlorinated ~phenoxyphenol, and salicylanilides, diamines, triazines and organometallic compounds such as organomercury compounds and organotin compounds.
Examples of pigments which may be used in these aqueous systems, in addition to the corrosion inhibitor composition of che present invention, include titanium dioxide, zinc chromate, iron oxide and organic pigments such as the phthalocyanines.
The following Examples f~Jrther illustrate the present invention.
Examples 1 and 2 A) A corrosion inhibitor composition is formed by mixing 30 parts by weight o~
2,4,6-tris(5-carboxypentylamino)-1,3,5-triazine and 20 parts by weight of anthranilic acid.
B) The corrosion-inhibiting performance of this composition A) is then evaluated in the DIN 51360 test ("Filter Chip Test"). The composition A) is dissolved in DIN 51360 water, with triethanolamine and/or borax added, to adjust the resulting solution to a pH
of 8.0 or ~.5. The concentration of the corrosion inhibitor A) in the solution is 1.0% or 1.5% by weight, respectively.
Staining by cast iron "chips", that lie on a filter paper and which are wetted by a small volume of the test solution, is evaluated according to the following rating scale:
0 no staining traces of staining 2 slight staining 3 moderate staining 4 heavy staining The results obtained, as well as tne corresponding results obtained with each of ~7~3 2,4,6-tris(S-carboxypentylamino)-1,3,5-triazine or anthranilic acid, respectively used alone, are set out in the following Tables 1 and 2:
Table 1 , _ _ _ Concentraîion Example Fonnulation % by weight Rating at pH 8.5 2,4,6-tris(5-carboxypentylamino~l ,3,5-triazine 1.0 2 anthranilic acid l.O __ Product of Exa~nple l(A) 1.0 O
Table 2 Conccntration Example Fonnulation % by weight Rating at pH 8.0 _ 2,4,6-tris(5-carboxy,oentyla nino~l,3,5-triazine1.5 3 anthranilic acid 1.5 2 2 Product of Ex~unple l(A) 1.5 Example 3 A) A corrosion inhibitor composition is made up by mixing 10 parts by weight of p-toluene sulphonamidocaproic acid and 10 parts by weight of anthranilic acid.
B) Using the procedure described in Example l(B~, at pH 8.5, the following results are obtained.
2~7~93 Table 3 Concen~adon Radng Example Fonnuladon % by weight .
~toluene sulphonamido-caproic acid0.9 3 antl~anilic acid 0.9 3 3 Producl of Example 0.9 O
Example 4 A) A corrosion inhibitor composition comprising 10 parts by weight of Alox 232 (a commerically - available mixture of Cll/Cl2 dicarboxylic acids) and 10 parts by weight of anthranilic acid is prepared.
B) Using the procedure described in Example l(B), at pH 8.5, the following results:
Table 4 Concen~ation Raling E; :nple Formulation % by weigh~ .
Alox 232 1.2 3 anthranilic acid 1.2 2 4 P~oducl of Example ~ j9) Example 5 A) A corrosion inhibitor composition is prepared comprising 30 parts by weight of 2,4,6-tris(5-carboxypentylamino)-1,3,5-triazine and 10 parts by weight of N'-(2-carboxybenzyl)-2-aminobenzoic acid.
B) Using the procedure described in Example l(B), at pH 9.0, the following results are obtained:
~0873~3 Table 5 -_ . ConcentrationRating E~: plc Fonnulatlono by weight . _ .
2,4,6-tris(5-carboxypentylamino)-1 .3,5-triazin~ 0.6 4 N -(2-carboxybenzyl)-2-aminobenzoic acid 0.6 . , S P~oductofExample~ S~) 0.6 O
The results in Tables 1, 2, 3, 4 and 5 demonstrate the striking improvement in corrosion inhi~itor performance of the compositions of the invention, in aLkaline pH ranges.
Claims (20)
1. A corrosion inhibiting composition comprising:
A) 40-90% by weight of a carboxylic acid corrosion inhibitor, or a water-soluble salt thereof, comprising one or more of:
Al) a triazine-carboxylic acid of formula I:
I
in which Z is a Cl-C1 1 alkylene group, R1 and R2, independently, are hydrogen or methyl, and R3 is a group -NR4R5 in which R4 is Cl-C12 alkyl or -Z-COOH in whichZ has its previous significance, and R5 is hydrogen or Cl-C12 alkyl, or a water-soluble salt thereof;
A2) a sulphonamidocarboxylic acid of formula II:
II
in which R6 and R7, independently, are hydrogen or Cl-C4 alkyl, and m is an integer ranging from 1 to 10 or a water-soluble salt thereof; and A3) a dicarboxylic acid, or mixture thereof, having the formula III:
HOOC-(CH2)n-COOH III
in which n is an integer ranging from 4 to 12, or a water-soluble salt thereof;
B) 10-60% by weight of one or more aminobenzoic acids having the formula IV:
IV
in which R8 is hydrogen or a group of formula V or VI:
VI
V or one or more water-soluble salts thereof;
C) 0-10% by weight of an alkanolamine of formula VII:
in which R9,R10 and R11, independently, are hydrogen, a linear or branched Cl-C12 alkyl group which is optionally interrupted by an oxygen atom, or R9,R10 and R11 are a group of formula VIII:
VIII
where Rl2 and Rl3, independently, are hydrogen or Cl-Cl2 alkyl and p and q, independently, are 0 or an integer ranging from 1 to 10, provided that p and q are not simultaneously 0 and provided that at least one of Rg,Rlo and Rll is a group of formula VIII; and D) 0-10% by weight of an alkali metal borate;
the percentages by weight being based on the total weight of the corrosion inhibitor composition.
A) 40-90% by weight of a carboxylic acid corrosion inhibitor, or a water-soluble salt thereof, comprising one or more of:
Al) a triazine-carboxylic acid of formula I:
I
in which Z is a Cl-C1 1 alkylene group, R1 and R2, independently, are hydrogen or methyl, and R3 is a group -NR4R5 in which R4 is Cl-C12 alkyl or -Z-COOH in whichZ has its previous significance, and R5 is hydrogen or Cl-C12 alkyl, or a water-soluble salt thereof;
A2) a sulphonamidocarboxylic acid of formula II:
II
in which R6 and R7, independently, are hydrogen or Cl-C4 alkyl, and m is an integer ranging from 1 to 10 or a water-soluble salt thereof; and A3) a dicarboxylic acid, or mixture thereof, having the formula III:
HOOC-(CH2)n-COOH III
in which n is an integer ranging from 4 to 12, or a water-soluble salt thereof;
B) 10-60% by weight of one or more aminobenzoic acids having the formula IV:
IV
in which R8 is hydrogen or a group of formula V or VI:
VI
V or one or more water-soluble salts thereof;
C) 0-10% by weight of an alkanolamine of formula VII:
in which R9,R10 and R11, independently, are hydrogen, a linear or branched Cl-C12 alkyl group which is optionally interrupted by an oxygen atom, or R9,R10 and R11 are a group of formula VIII:
VIII
where Rl2 and Rl3, independently, are hydrogen or Cl-Cl2 alkyl and p and q, independently, are 0 or an integer ranging from 1 to 10, provided that p and q are not simultaneously 0 and provided that at least one of Rg,Rlo and Rll is a group of formula VIII; and D) 0-10% by weight of an alkali metal borate;
the percentages by weight being based on the total weight of the corrosion inhibitor composition.
2. A composition according to claim 1, in which Al) is of formula I where Rl and R2 are independently hydogen or methyl, R3 is -NR4R5 where R4 is Cl-C8 alkyl or -Z-COOH, R5 is hydrogen or Cl-C4 alkyl and Z
is Cl-C5 alkylene, or a water-soluble salt thereof;
A2) is of formula II where R6 and R7 are independently hydrogen or methyl, or a water-soluble salt thereof; and A3) is an acid of formula III where n is 11 or 12, a mixture of an acid of formula III
where n is 11 with an acid of formula III where n is 12, or a water-soluble salt thereof.
is Cl-C5 alkylene, or a water-soluble salt thereof;
A2) is of formula II where R6 and R7 are independently hydrogen or methyl, or a water-soluble salt thereof; and A3) is an acid of formula III where n is 11 or 12, a mixture of an acid of formula III
where n is 11 with an acid of formula III where n is 12, or a water-soluble salt thereof.
3. A composition according to claim 1, in which A1) is 2,4,6-tris(5-carboxypentylamino)-1,3,5-triazine or a water-soluble salt thereof;
A2) is p-toluenesulphonamidocaproic acid or a water-soluble salt thereof; and A3) is a mixture of an acid of formula III where n is 11 with an acid of formula III
where n is 12, or a water-soluble salt thereof.
A2) is p-toluenesulphonamidocaproic acid or a water-soluble salt thereof; and A3) is a mixture of an acid of formula III where n is 11 with an acid of formula III
where n is 12, or a water-soluble salt thereof.
4. A composition according to claim 2, in which A) is A1).
5. A composition according to claim 2, in which A) is A2).
6. A composition according to claim 2, in which A) is A3).
7. A composition according to claim 3, in which A) is A1).
8. A composition according to claim 3, in which A) is A2).
9. A composition according to claim 3, in which A) is A3).
10. A composition according to claim 1, in which B) is anthranilic acid, N-(2-carboxybenzyl)-21aminobenzoic acid, or a water-soluble salt thereof.
11. A composition according to claim 2, in which B) is anthranilic acid, N-(2-carboxybenzyl)-21aminobenzoic acid, or a water-soluble salt thereof.
12. A composition according to claim 3, in which B) is anthranilic acid, N-(2-carboxybenzyl)-21aminobenzoic acid, or a water-soluble salt thereof.
13. A composition according to claim 1, in which the alkanolamine C) is present and is triethanolamine.
14. A composition according to claim 2, in which the alkanolamine C) is present and is triethanolamine.
15. A composition according to claim 3, in which the alkanolamine C) is present and is triethanolamine.
16. A composition according to claim 1, in which the borate D) is present and is sodium borate or potassium borate.
17. A composition according to claim 2, in which the borate D) is present and is sodium borate or potassium borate.
18. A composition according to claim 3, in which the borate D) is present and is sodium borate or potassium borate.
19. A method of inhibiting corrosion of a ferrous metal in contact with an aqueous system, comprising incorporating into the aqueous system an effective, corrosioninhibiting amount of a composition according to claim 1.
20. A method according to claim l9, in which in the composition A) is 2,4,6-tris(5-carboxypentylamino)-1,3,5-triazine or a water-soluble salt thereof, or p-toluenesulphonamidocaproic acid or a water-soluble salt thereof, or a mixture of acids of formula HOOC-(CH2)n-COOH where n is 11 and 12 or a water-soluble salt thereof; and B) is anthranilic acid, N-(2-carboxybenzyl)-21-aminobenzoic acid or a water-soluble salt thereof.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB929201165A GB9201165D0 (en) | 1992-01-18 | 1992-01-18 | Corrosion inhibiting compositions |
| GB9201165.9 | 1992-01-18 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2087393A1 true CA2087393A1 (en) | 1993-07-19 |
Family
ID=10708898
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2087393 Abandoned CA2087393A1 (en) | 1992-01-18 | 1993-01-15 | Corrosion inhibiting compositions |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP0553962A1 (en) |
| JP (1) | JPH05255873A (en) |
| CA (1) | CA2087393A1 (en) |
| GB (1) | GB9201165D0 (en) |
Families Citing this family (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1996039549A1 (en) * | 1995-06-05 | 1996-12-12 | Betzdearborn Inc. | Method for inhibiting metal corrosion in large scale water systems |
| US5665688A (en) * | 1996-01-23 | 1997-09-09 | Olin Microelectronics Chemicals, Inc. | Photoresist stripping composition |
| DE19648843C2 (en) * | 1996-11-26 | 1998-09-17 | Zts Chemie Gmbh | Melamine polycarboxamides and their use as anti-corrosion agents |
| DE59909853D1 (en) * | 1999-03-30 | 2004-08-05 | Stefan Graichen | Corrosion protection agent containing melamine |
| FR2795432B1 (en) * | 1999-06-28 | 2001-08-24 | Atofina | CORROSION INHIBITOR COMPOSITIONS FOR HEAT TRANSFER FLUIDS |
| AU2003220376A1 (en) * | 2002-03-18 | 2003-10-08 | The Lubrizol Corporation | Corrosion inhibiting salts, concentrates and metal working fluids containing same |
| US20060225605A1 (en) * | 2005-04-11 | 2006-10-12 | Kloeckener James R | Aqueous coating compositions and process for treating metal plated substrates |
| JP2007016167A (en) * | 2005-07-08 | 2007-01-25 | Taiyu Kk | Water soluble metal-working oil agent |
| WO2008006855A2 (en) * | 2006-07-11 | 2008-01-17 | Taminco | Inhibition of corrosion in cooling water system |
| RU2514962C2 (en) * | 2007-11-26 | 2014-05-10 | Дублин Инститьют Оф Текнолоджи Интеллекчуал Проперти Лимитед | Organosilane compositions for coatings and their application |
| CN102660745A (en) * | 2011-11-08 | 2012-09-12 | 中国石油大学(华东) | Green corrosion inhibitor for hot-dip zinc-aluminium alloy steel, and application thereof |
| CN102659700B (en) * | 2012-03-05 | 2014-04-09 | 浙江金科过氧化物股份有限公司 | Production process of granular 2,4,6-tri(amino caproyl)-1,3,5-triazine having low chlorine content |
| CN104271682B (en) * | 2012-03-08 | 2017-09-12 | 路博润公司 | Water paint, composition and its method for improving corrosion protection are provided |
| WO2014005861A1 (en) | 2012-07-03 | 2014-01-09 | Basf Se | 1,3,5-triazine derivatives as corrosion inhibitors for metallic surfaces |
| ES2537602B1 (en) * | 2015-02-17 | 2016-03-23 | Universitat Politècnica De València | Corrosion inhibitor solution in steel elements |
| RU2725249C1 (en) * | 2019-11-28 | 2020-06-30 | Публичное акционерное общество "Газпром" | Inhibited primer |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CH629540A5 (en) * | 1977-09-19 | 1982-04-30 | Hoechst Ag | WATER-MIXABLE ANTI-CORROSIVE AGENT. |
| US4402907A (en) * | 1980-08-13 | 1983-09-06 | Ciba-Geigy Corporation | Triazine carboxylic acids as corrosion inhibitors for aqueous systems |
| JPS5831086A (en) * | 1981-08-19 | 1983-02-23 | Otsuka Chem Co Ltd | Treatment for surface of metallic material |
| JPS591686A (en) * | 1982-06-28 | 1984-01-07 | Kawasaki Steel Corp | Tempering liquid for cold rolled steel sheet |
| DE3304164A1 (en) * | 1983-02-08 | 1984-08-09 | Hoechst Ag, 6230 Frankfurt | REACTION PRODUCTS FROM BORSAEURE, DIETHANOLAMINE AND MONOETHANOLAMINES AND THEIR USE AS A CORROSION PROTECTANT |
| GB2194782B (en) * | 1985-11-09 | 1989-10-04 | Ciba Geigy Ag | Additives for aqueous functional fluids |
| GB2204864A (en) * | 1987-04-29 | 1988-11-23 | Ciba Geigy Ag | Corrosion inhibition |
| EP0511163B1 (en) * | 1991-04-24 | 1995-07-26 | Ciba-Geigy Ag | Pourable aqueous dispersions of polycarboxylic acid corrosion inhibitors |
-
1992
- 1992-01-18 GB GB929201165A patent/GB9201165D0/en active Pending
-
1993
- 1993-01-12 EP EP93300175A patent/EP0553962A1/en not_active Withdrawn
- 1993-01-14 JP JP2181593A patent/JPH05255873A/en active Pending
- 1993-01-15 CA CA 2087393 patent/CA2087393A1/en not_active Abandoned
Also Published As
| Publication number | Publication date |
|---|---|
| JPH05255873A (en) | 1993-10-05 |
| GB9201165D0 (en) | 1992-03-11 |
| EP0553962A1 (en) | 1993-08-04 |
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