EP0020042B1 - Inhibiteur de corrosion de métaux non basé sur du pétrole et objet métallique revêtu de cet inhibiteur - Google Patents

Inhibiteur de corrosion de métaux non basé sur du pétrole et objet métallique revêtu de cet inhibiteur Download PDF

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Publication number
EP0020042B1
EP0020042B1 EP19800301531 EP80301531A EP0020042B1 EP 0020042 B1 EP0020042 B1 EP 0020042B1 EP 19800301531 EP19800301531 EP 19800301531 EP 80301531 A EP80301531 A EP 80301531A EP 0020042 B1 EP0020042 B1 EP 0020042B1
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Prior art keywords
acid
weight
parts
composition
concentrate
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German (de)
English (en)
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EP0020042A3 (en
EP0020042A2 (fr
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Alvin J. Conner Sr.
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Priority claimed from US06/037,418 external-priority patent/US4233176A/en
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Priority to AT80301531T priority Critical patent/ATE6795T1/de
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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
    • C23F11/14—Nitrogen-containing compounds
    • C23F11/141—Amines; Quaternary ammonium compounds
    • C23F11/143—Salts of amines

Definitions

  • This invention relates to non-petroleum based metal corrosion inhibitors.
  • Inhibited petroleum based oils are widely used as coatings for inhibiting the corrosion of various steels.
  • This type of protection is becoming increasingly impractical due to cost, the hazardous conditions created by the use of the petroleum based coatings, difficulty in removing the coatings and difficulty in disposing of the oil following its removal from the steel. Additionally, so-called smudging is sometimes caused by the polymerization and oxidation of petroleum based inhibitor compositions. Since the surface of steel is microscopically porous, sufficient oil is absorbed into the surface to cause such smudging even after removal of the petroleum based inhibitor. In spite of these problems, these oil coatings continue to be used since they provide the required protection against corrosion and also serve to provide lubrication.
  • United States Patent No. 3573225 discloses a combination of an amine salt of a fatty acid, an alkali metal benzoate, and an alkanolamide in aqueous solution as a rust-preventing agent.
  • British Specification No. 1177873 discloses a solid composition comprising a higher carboxylic acid and an amine as a lubricant and rust preventative for sheet steel. According to British Specification No.
  • a lubricant may be emulsified in an aqueous solution of an anti-rust additive comprising an alkanolamine salt of a long chain fatty acid, an alkanolamine salt of an aromatic carboxylic acid, and excess alkanolamine.
  • the present invention provides a non-petroleum based metal corrosion inhibitor that will provide protection against oxidation and will provide lubricity equivalent or superior to that of petroleum-based inhibitors when applied to metal surfaces but which will not possess the undesirable characteristics of such inhibitors.
  • a metal corrosion inhibiting composition consisting essentially of a solution of one part by weight of an aqueous concentrate and 0 to five parts by weight of water, said aqueous concentrate being a clear solution comprising, per 100 parts by weight of the concentrate, the product of mixing
  • composition can be applied to the metals by spraying or rolling.
  • the composition according to the present invention is generally prepared as a concentrated aqueous solution containing from about 25 to about 65% by weight of the non-aqueous components.
  • this concentrate is generally diluted up to 5 times with water, i.e., 5 parts of water to 1 part of the concentrate.
  • the composition offers protection against oxidation to aluminium, zinc coated or galvanized steel, aluminum coated steel, tin plated steel, stainless steel, high carbon electrical grade steel, cold rolled carbon steel and the like.
  • the non-petroleum based corrosion inhibiting composition according to the present invention including a preferred composition which contains a minor amount of a petroleum oil as the lubricant, appears to be an aqueous solution of a reaction mixture of the various components. The exact mechanism of the formation of the solution, however, is not known.
  • Relatively high molecular weight aliphatic, monobasic acids are employed in preparing the non-petroleum based composition according to the present invention.
  • Aliphatic acids having from 8 to 20 carbon atoms have been found to be useful in preparing the composition. These acids include fatty acids, both saturated and unsaturated, such as caprylic acid, palmitic acid, stearic acid, oleic acid and linoleic acid and resin acids such as abietic acid and acids isomeric therewith. These acids can be used alone or in combination.
  • a mixture of tall oil fatty acids and rosin is used as the high molecular weight aliphatic acid component of the composition.
  • Such mixtures are obtained as a byproduct of the paper industry from tall oil usually recovered from pine wood "black liquor”.
  • Oleic and linoleic acids are the major components of the tall oil fatty acids with acids such as palmitic acid, isostearic acid and stearic acid being present in relatively minor amounts.
  • oleic acid and linoleic acid comprise about 45% and 35% by weight, respectively, of the fatty acids.
  • Rosin is mainly comprised of isomeric forms of abietic acid.
  • the rosin can be present in amount of from 5 to 40% by weight, preferably 10 to 40% by weight, of the tall oil fatty acid/rosin mixture. Mixtures containing less than 5% by weight of rosin cannot be used because of problems relating to viscosity. Increased amounts of rosin appear to decrease the viscosity of the corrosion inhibiting composition. Mixtures containing more than 40% rosin are not economical.
  • aliphatic acids such as tallow fatty acids, the major constituents of which are oleic, palmitic, stearic, myristic and linoleic acids, can also be employed in preparing the non-petroleum based corrosion inhibiting compositions according to the present invention.
  • the high molecular weight aliphatic, monobasic acid component of the corrosion inhibiting composition is employed in an amount of 5 to 20 parts by weight based on 100 parts by weight of the concentrated solution.
  • the composition according to the present invention contains a minor amount of a lubricant which may be either a petroleum or a non-petroleum product.
  • a lubricant which may be either a petroleum or a non-petroleum product.
  • Any of the petroleum oils presently employed in petroleum based corrosion inhibiting compositions for steel are believed to be useful in the present composition. Good results have been obtained using a 100 SSU viscosity petroleum oil.
  • esters such as butyl stearate, dioctyl sebacate, butyl benzoate, or any of the light alkyl esters with boiling ranges above 350° (177°C) can be used as the lubricant.
  • a petroleum oil is used as the lubricant.
  • the amount of lubricant is limited by the amount of the high molecular weight aliphatic acid. More particularly, the lubricant is employed in an amount of from 10 to 20% of the aliphatic acid, i.e., 0.5 to 4 parts by weight per 100 parts by weight of the concentrated solution. Amounts of greater than 20% are not completely solubilized in the composition.
  • the aminoalkylalkanolamine of the metal corrosion inhibiting compositions according to this invention preferably has the following general structural formula: wherein R' and R 2 are independently alkylene of 1-4 carbon atoms and R 3 is hydrogen or alkyl of 1-4 carbon atoms.
  • R' and R 2 are independently alkylene of 1-4 carbon atoms and R 3 is hydrogen or alkyl of 1-4 carbon atoms.
  • R' and R 2 are independently alkylene of 1-4 carbon atoms and R 3 is hydrogen or alkyl of 1-4 carbon atoms.
  • R' and R 2 are independently alkylene of 1-4 carbon atoms
  • R 3 is hydrogen or alkyl of 1-4 carbon atoms.
  • One or more of these aminoalkylalkanolamines can be employed in the non-petroleum based inhibitor composition according to the present invention.
  • Aminoethylethanolamine is presently preferred because of its cost and the good results that it provides.
  • the metal corrosion inhibiting composition according to the present invention includes as a corrosion inhibitor a water-soluble amine salt of an aromatic acid.
  • an aromatic monocarboxylic acid such as benzoic acid or an aromatic polycarboxylic acid such as phthalic, isophthalic, terephthalic or trimellitic acid. Mixtures of the aromatic acids may also be employed. Although it has not been confirmed, it is believed that the aromatic acids may also contain other functional groups such as hydroxy and lower alkyl groups which do not inhibit the formation of the water-soluble salt. Good corrosion inhibiting effects have been obtained employing 10 to 35 parts and, particularly, 24 to 35 parts of the aromatic acid per 100 parts by weight of the concentrated solution.
  • any primary, secondary, tertiary or cyclic amine which forms the water-soluble salt with the aromatic acid can be used in the composition according to the present invention to provide corrosion inhibiting properties. Particularly good results have been obtained with the use of (lower C 2 -C 4 ) alkanolamines and, particularly, monoethanolamine and diethanolamine. Other suitable amines are triethanolamine, diisopropylamine, cyclohexylamine and morpholine. The amines can be used alone or in combination.
  • the amines employed in the metal-corrosion inhibiting composition according to the present invention also serve to neutralize the aliphatic acid and appear to assist in the solubilization of the lubricant component.
  • the total amount of amines employed in the composition is generally in slight excess of the amount required to neutralize, i.e., form salts with, the aliphatic and aromatic acids.
  • this amount of the amine component is typically within the range of 5 to 25 parts by weight per 100 parts by weight of the concentrated solution. In preferred embodiments the amount is within the range of 15 to 20 parts by weight per 100 parts by weight of the concentrate.
  • the non-aqueous components of the compositions are employed in an amount of from 25 to 65 parts per 100 parts by weight of the concentrate.
  • the non-aqueous components are employed in an amount of from 55 to 65 parts per 100 parts by weight of the concentrate; the remainder of the concentrate being water.
  • the concentrated solutions are diluted up to 5 times, preferably about 4 times, with water, i.e., up to 500 parts of water per 100 parts of the concentrate.
  • the mixture of the above-described aliphatic, monobasic acid component and lubricant are added to water with stirring in a suitable mixing device. This is followed by the addition of the aminoalkylalkanolamine which causes the formation of a cloudy emulsion. An amount of the amine (which forms the water-soluble salt with the aromatic acid) in excess of that required to form a clear solution from the cloudy emulsion is then added followed by the aromatic acid and the remainder of the salt-forming amine. In another variation, a solution of the aromatic acid and salt-forming amine can be added to a solution of the aliphatic acid-lubricant-aminoalkylalkanolamine.
  • a unique characteristic of the present invention is that following these procedures, a lubricant, either natural or synthetic, can be completely solubilized in water when the amounts of the components of the non-petroleum based inhibitor concentration are maintained within the ranges described above.
  • composition prepared as described above is diluted with up to 5 parts of water and applied as either a rust preventative and/or lubricant.
  • the recommended dilution ratio is 1 part concentrate to about 4 parts water.
  • compositions according to the present invention are formed by the sequential addition of the following compounds to 250 Ibs (about 30 gallons: 113 kg, 114 litres) of water with stirring (weights are approximate).
  • composition according to the present invention does not have to be removed from the surface of metals prior to painting in most cases. However, when it must be removed, water will remove it from the surface. The water can be discharged into drains since the solution is biodegradable.
  • the inhibitor composition of the present invention When employed in a steel making operation, the inhibitor composition of the present invention should be applied after pickling and hot roll reduction operations, and prior to cold reduction, because the cleaned pickled sheet is very susceptible to rusting. Reapplication of the composition after the final reduction protects the coils during storage prior to annealing.
  • the composition can be reapplied at the temper mill operation, either on the entry or exit side of the temper mill. When the composition is applied at the entry side, a very fine mist application is desirable so as not to cause problems on the temper mill rolls.
  • the composition is applied at the exit side of the temper mill either as a light or heavy spray. This also applies when the solution is applied at the stretch or shear line.
  • compositions were prepared according to the general procedures described above.
  • percentages are by weight and the tall oil fatty acids/rosin mixtures employed are commercially available compositions in which the fatty acids are composed primarily of a mixture of oleic and linoleic acids:
  • compositions were evaluated for corrosion inhibiting properties according to the testing procedures described below. Data for other corrosion inhibiting compositions are presented for comparative purposes.
  • Cold roll dry strips (1 1/4", 3.2 cm. wide by 4", 10.2 cm. long, dry, clean and rust-free) were used as test specimens.
  • a 1/16" (1.6 mm.) hole was punched 1/8" (3.2 mm.) from the top and bottom, and 5/8" (1.6 cm.) from one side.
  • a hook, fabricated from galvanized wire, was used to hang the strips in a humidity cabinet. Each strip was marked for identification by embossing a number with a metal stamp about 1/4" (6.4 mm.) below the punched hole.
  • a strip as described above was dipped 2" (5 cm.) in the solution to be tested and suspended by a metal hook with the dipped or coated portion of the strip at the bottom.
  • the strip was allowed to dry or drain for one hour, and the hook transferred to the opposite end of the strip, which was then suspended on a rack in the humidity cabinet.
  • the coated or dipped end was now on top, and the lower, uncoated end of the strip on the bottom.
  • the conditions in the humidity cabinet were maintained at 100°F (38°C) and 100% humidity.

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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)
  • Lubricants (AREA)

Claims (14)

1. Composition inhibitrice de corrosion métallique à base de produits non pétroliers caractérisée par le fait qu'elle comprend essentiellement une solution d'une partie en poids d'un concentrat aqueux et de 0 à 5 parties en poids d'eau, ledit concentrat aqueux étant une solution limpide comprenant, pour 100 parties en poids de concentrat, le produit résultant du mélange de:
(a) 5 à 20 parties en poids d'un acide aliphatique monobasique ayant de 8 à 20 atomes de carbone;
(b) un lubrifiant dans une proportion de 10 à 20% en poids de l'acide aliphatique (a);
(c) 10 à 35 parties en poids d'un acide mono ou polycarboxylique aromatique; et
(d) une quantité suffisante d'une amine, comprenant une aminoalkylalcanolamine, qui forme un sel soluble dans l'eau avec les acides aliphatique et aromatique en fournissant une solution limpide, les conditions de mélange étant telles que lesdits acides forment des sels avec ladite amine ou lesdites amines.
2. Composition inhibitrice de corrosion métallique à base de produits non pétroliers selon la revendication 1, caractérisée par le fait que ladite amine (d) comprend
(di) une aminoalkylalcanolamine de formule:
Figure imgb0010
dans laquelle R' et R2 sont indépendamment un alkylène de 1-4 atomes de carbone, et R3 est l'hydrogène ou un alkyle de 1-4 atomes de carbone; et
(dii) une seconde amine qui forme un sel soluble dans l'eau avec ledit acide aromatique.
3. Composition selon la revendication 2, caractérisée par le fait que la quantité de l'aminoalkylalcanolamine (di) du concentrat est de 0,5 à 4 parties en poids.
4. Composition selon la revendication 2 ou 3, caractérisée par le fait que ladite aminoalkylalcanolamine (di) est l'aminoéthyléthanolamine.
5. Composition selon l'une des revendications 2 à 4, caractérisée par le fait que l'amine (dii) est une alcanolamine dans laquelle le groupe alcanol à 2-4 atomes de carbone, la cyclohexylamine, la diisopropylamine ou la morpholine.
6. Composition selon l'une des revendications 2 à 5, caractérisée par le fait que le lubrifiant (b) est une huile de pétrole ou un ester.
7. Composition selon la revendication 6, caractérisée par le fait que le lubrifiant est une huile de pétrole de viscosité 100 SSU.
8. Composition selon l'une des revendications 2 à 7, caractérisée par le fait que les quantités des composants dudit concentrat aqueux, pour 100 parties en poids du concentrat, sont:
(a) 5 à 20 parties en poids,
(b) 0,5 à 4 parties en poids,
(c) 24 à 35 parties en poids,
(di) 0,5 à 4 parties en poids, et
(dii) 15 à 20 parties en poids.
9. Composition selon l'une des revendications 2 à 8, caractérisée par le fait que la quantité totale des composants (a), (b), (c), (di) et (dii) dudit concentrat aqueux est de 25 à 65 parties pour 100 parties en poids du concentrat, le restant étant de l'eau.
10. Composition selon la revendication 9, caractérisée par le fait que la quantité totale des composants (a), (b), (c), (di) et (dii) dudit concentrat aqueux est de 55 à 65 parties pour 100 parties en poids du concentrat, le restant étant de l'eau.
11. Composition selon l'une des revendications 1 à 10, caractérisée par le fait que l'acide aliphatique monobasique est l'acide oléique, l'acide linoléique, l'acide caprylique, l'acide palmitique, l'acide stéarique, l'acide myristique, l'acide abiétique ou un mélange de ceux-ci.
12. Composition selon l'une des revendications 1 à 10, caractérisée par le fait que l'acide aliphatique monobasique est un mélange d'acides gras de tall oil (huile de pin) et d'au moins 5% de colophane ou est constitué par des acides gras de suif.
13. Composition selon l'une des revendications 1 à 12, caractérisée par le fait que l'acide aromatique est l'acide benzoîque, l'acide phtalique, l'acide téréphtalique, l'acide isophtalique ou l'acide tri- mellitique.
14. Objet métallique revêtu de la composition inhibitrice de corrosion selon l'une des revendications 1 à 13.
EP19800301531 1979-05-09 1980-05-09 Inhibiteur de corrosion de métaux non basé sur du pétrole et objet métallique revêtu de cet inhibiteur Expired EP0020042B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT80301531T ATE6795T1 (de) 1979-05-09 1980-05-09 Nicht auf erdoel basierendes korrosionsschutzmittel fuer metalle und hiermit ueberzogener metallgegenstand.

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US37418 1979-05-09
US06/037,418 US4233176A (en) 1979-05-09 1979-05-09 Non-petroleum based metal corrosion inhibitor
US13875880A 1980-04-10 1980-04-10
US138758 1980-04-10

Publications (3)

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EP0020042A2 EP0020042A2 (fr) 1980-12-10
EP0020042A3 EP0020042A3 (en) 1981-01-07
EP0020042B1 true EP0020042B1 (fr) 1984-03-21

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EP19800301531 Expired EP0020042B1 (fr) 1979-05-09 1980-05-09 Inhibiteur de corrosion de métaux non basé sur du pétrole et objet métallique revêtu de cet inhibiteur

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EP (1) EP0020042B1 (fr)
DE (1) DE3067103D1 (fr)
PL (1) PL131859B1 (fr)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS61230772A (ja) * 1985-04-04 1986-10-15 Nippon Parkerizing Co Ltd 金属の被覆法
DE3521952A1 (de) * 1985-06-20 1987-01-02 Henkel Kgaa Waessrige zusammensetzungen fuer den hilite- und flux-prozess und ihre verwendung
WO1996039549A1 (fr) * 1995-06-05 1996-12-12 Betzdearborn Inc. Procede d'inhibition de la corrosion de metaux dans des systemes d'alimentation en eau a grande echelle
DE19747895A1 (de) * 1997-10-30 1999-05-06 Henkel Kgaa Metallbehandlungsflüssigkeit für den neutralen pH-Bereich
US5997763A (en) * 1998-04-27 1999-12-07 Shell Oil Company Corrosion inhibiting antifreeze compositions containing various carboxylic acids
US7306663B2 (en) 2003-08-05 2007-12-11 Halox, Division Of Hammond Group, Inc. Corrosion inhibitor

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3573225A (en) * 1968-02-01 1971-03-30 Masahiko Kondo Rust-proofing composite solutions
DE1769769B2 (de) * 1968-06-15 1973-05-03 Fuji Iron & Steel Co Ltd , Tokio Schmier- und korrosionsschutzmittel fuer die spanlose stahlbearbeitung, insbesondere fuer tiefziehbleche
FR2231739B1 (fr) * 1973-05-29 1980-04-04 Exxon Research Engineering Co

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Publication number Publication date
EP0020042A3 (en) 1981-01-07
PL224108A1 (fr) 1981-02-13
PL131859B1 (en) 1985-01-31
EP0020042A2 (fr) 1980-12-10
DE3067103D1 (en) 1984-04-26

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