EP0029529B1 - Produits de réaction d'acides sulfone ou carboxamido carboxyliques avec des alcanolamines et leur utilisation comme inhibiteurs de corrosion pauvres en mousse - Google Patents

Produits de réaction d'acides sulfone ou carboxamido carboxyliques avec des alcanolamines et leur utilisation comme inhibiteurs de corrosion pauvres en mousse Download PDF

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Publication number
EP0029529B1
EP0029529B1 EP80106805A EP80106805A EP0029529B1 EP 0029529 B1 EP0029529 B1 EP 0029529B1 EP 80106805 A EP80106805 A EP 80106805A EP 80106805 A EP80106805 A EP 80106805A EP 0029529 B1 EP0029529 B1 EP 0029529B1
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Prior art keywords
carbon atoms
hydrogen
alkyl
acid
diphenyl
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EP80106805A
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German (de)
English (en)
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EP0029529A1 (fr
Inventor
Rudi Dr. Widder
Elmar Getto
Albert Dr. Hettche
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BASF SE
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BASF SE
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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
    • C23F11/16—Sulfur-containing compounds
    • C23F11/164—Sulfur-containing compounds containing a -SO2-N group
    • 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
    • C23F11/145—Amides; N-substituted amides
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S507/00—Earth boring, well treating, and oil field chemistry
    • Y10S507/939—Corrosion inhibitor

Definitions

  • the invention relates to reaction products of sulfonic or carbonamido carboxylic acids with alkanolamines. It also relates to the use of these reaction products as water-soluble, low-foaming corrosion inhibitors for the weakly acidic to alkaline range. Finally, it relates to the use of these substances together with reaction products of orthoboric acid with alkanolamines for the technical field mentioned.
  • inhibitors have been proposed for this, especially organic compounds, such as acyl sarcosides, amines, alkanolamines or amides of longer-chain fatty acids (see also “Soaps, Oils, Fats, Waxes” 103, No. 6, pages 167 to 168 (1977)).
  • the subject of DE-C-900 041 includes Salts of sulfonamidocarboxylic acids or carbonamidocarboxylic acids which are obtained by reacting aliphatic carboxylic acid chlorides or sulfonic acid chlorides with aliphatic aminocarboxylic acids or aromatic aminocarboxylic acids, such as anthranilic acid. They are recommended as anti-corrosion agents.
  • US-A-2 578 725 teaches such reaction products of, for example, anthranilic acid or preferably aliphatic amino acids with aliphatic sulfonic acid chlorides.
  • DE-A-1 298 672 specifically describes reaction products of arylsulfonyl halides with aliphatic aminocarboxylic acids. The same reaction products are also taught in DE-A-2 840 112, but in a mixture with boric acid and diethanolamine.
  • X represents -CO- or (mostly) -SO 2 -, R 'is hydrogen or alkyl and Y is hydrogen, a metal or optionally substituted one Ammonium ion.
  • the substances described have good corrosion-inhibiting properties and are also partially low-foaming; However, they are still not fully satisfactory, especially with regard to corrosion protection in saline water.
  • the aim of the invention was to find substances that optimally guarantee corrosion protection and low foam in processes in which iron, iron alloys, aluminum or aluminum alloys as well as copper, zinc or their alloys come into contact with water and especially hard and saline water.
  • R 'and R 2 are hydrogen, fluorine, chlorine, bromine, an alkyl or alkoxy radical having 1 to 4 carbon atoms, the sum of the carbon atoms of the radicals R' and R 2 not exceeding the number seven, preferably 3,
  • A is a benzene, naphthalene or anthracene radical or a biphenyl system such as the diphenyl, diphenylmethane, diphenyloxide, diphenylsulfide, diphenylsulfoxide or diphenylsulfone radical
  • R 3 is hydrogen, an alkyl radical with not more than 4 carbon atoms, the ⁇ -cyanoethyl radical or a hydroxyalkyl radical having 2 to 4 carbon atoms and R 4 being hydrogen, fluorine, chlorine, bromine, an alkyl or alkoxy radical having 1 to 4 carbon atoms, the hydroxyl radical or the carboxyl
  • the acids of the formula can be obtained by known methods - for example, reference is made to the literature cited in Beilstein. From a technical point of view, however, it is mainly the reaction of aromatic acid halides, preferably the chlorides, with aromatic amino carboxylic acids.
  • the starting products are acid chlorides of the formula III in which R 1 , R 2 , A and X are defined according to the formula and Hal represents a chlorine, bromine or iodine atom.
  • Aromatics from which the carboxylic acid and (preferably) sulfochlorides are derived, are e.g. As benzene, fluorine, chlorine, bromobenzene, toluene, xylene, naphthalene, methyl, dimethylnaphthalenes, anthracene, biphenyl, diphenylmethane, diphenyl oxide, diphenyl sulfoxide or diphenyl sulfone.
  • benzene fluorine, chlorine, bromobenzene, toluene, xylene, naphthalene, methyl, dimethylnaphthalenes, anthracene, biphenyl, diphenylmethane, diphenyl oxide, diphenyl sulfoxide or diphenyl sulfone.
  • Preferred acid chlorides are benzenesulfonyl chloride, o- and p-toluenesulfochloride, p-xylenesulfochloride and, of the carboxylic acid chlorides, especially benzoyl chloride, naphthoyl chloride or p-toluenesulfonic acid chloride.
  • R 3 and R 4 are preferably hydrogen atoms, and R 4 is also a carboxyl group, and anthranilic acid (o-aminobenzoic acid), p-aminobenzoic acid and aminobenzene dicarboxylic acids may be mentioned as representatives of the aminocarboxylic acids.
  • Preferred alkanolamines are especially triethanolamine, triisopropanol- or -n-propanolamine, methyl-diethanol- or -isopropanolamine, then simply ethoxylated or propoxylated ethylenediamine per active H atom.
  • the equivalent ratio of amidocarboxylic acid to alkanolamine should be 1: 1 to 1: 4, preferably 1: 1.4 to 1: 2.
  • the reaction which can be carried out by simply combining the reactants with stirring, optionally with cooling of the reaction vessel, produces salts (equivalent ratio 1: 1) and mixtures of the salts with free alkanolamine, which can be used directly as inhibitors.
  • reaction products of orthoboric acid and alkanolamine can be present in the inhibitors.
  • the starting point for their preparation is mono-, di- or trialkanolamines with 2 or 4 carbon atoms per alkanol group or mixtures thereof.
  • the dialkanolamines are preferably chosen from the individual alkanolamines. Mixtures of the type which arise from the alkoxylation of ammonia in the production of alkanolamines are technically particularly valuable. Such a mixture contains dialkanolamine as the main component in addition to smaller proportions of mono- and trialkanolamine.
  • Preferred individual compounds are diethanolamine and diisopropanolamine and mixtures which are formed by ethoxylation or propoxylation of ammonia and which largely contain diethanolamine or diisopropanolamine.
  • alkanolamines are those which are simply substituted on the nitrogen atom by methyl, ethyl or n or isopropyl groups, for.
  • the corrosion inhibitors according to the invention can be used in all aqueous systems which come into contact with iron, its alloys (steels), aluminum, its alloys, zinc or copper and their alloys.
  • concentrations of the inhibitors according to the invention vary depending on the area of use and the type of aqueous medium and the metals to be protected. In general, based on the aqueous preparation, 0.01 to 5% by weight is used. Falling below this limit reduces the protective effect, exceeding this does not result in any additional advantages.
  • the concentration should preferably be 0.1 to 3% by weight.
  • the corrosion test was carried out as follows:
  • the corrosion test consists of the gray cast iron filter sample.
  • a petri dish with an inner diameter of approx. 10 cm is used with a suitable lid dish. Place in the petri dish Black band round filter.
  • a suitable spoon is used to distribute 5 to 10 g of coarse cast iron GG-20 shavings onto the filter in such a way that a uniform heap is formed in the middle, which is around 1.5 cm away from the edge.
  • the chips have a length of approx. 5 to 8 mm and must be obtained from clean gray cast iron GG-20 material without the use of drilling oil or other cooling lubricants. All fine components must be screened off.
  • the impact method was used based on DIN 53 902.
  • the simple test procedure was sufficient, in which the punch with the perforated plate 30 ml was evenly drawn in and out in 30 s and then carefully pulled out (IG impact method).
  • the foam volume is read on the graduated foam cylinder after 1, 5 and 10 min in ml. Information about temperature, concentration and water hardness are also important.

Landscapes

  • 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)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Claims (3)

1. Produits obtenus par la réaction d'acides de la formule 1
Figure imgb0015
dans laquelle R1 et R2 peuvent représenter chacun un atome d'hydrogène, de fluor, de chlore ou de brome ou un radical alcoyle ou alcoxy en Ci à C4, la somme des atomes de carbone des radicaux R1 et R2 étant au plus égale à sept et de préférence à trois; A désigne un groupe benzène, naphtalène ou anthracène ou un système biphényle tel qu'un groupe diphényle, diphényl-méthane, diphényl-oxyde, diphényl-sulfure, diphényl-sulfoxyde ou diphényl-sulfone; R3 représente un atome d'hydrogène, un radical alcoyle avec au plus 4 atomes de carbone, un groupe β-cyan-éthyle ou un groupe hydroxy-alcoyle en C2 à C4 et R4 un atome d'hydrogène, de fluor, de chlore ou de brome, un radical alcoyle ou alcoxy en Ci à C4 ou un radical hydroxyle ou carboxyle et X désigne un groupe -SO2- ou -CO-, avec une amine de la formule Il
Figure imgb0016
dans laquelle R5 et R6 peuvent désigner chacun un atome d'hydrogène, un radical alcoyle en C1 à C4, un groupe hydroxy-alcoyle en C2 à C4 ou un groupe
Figure imgb0017
dans lequel R7 et R8 représentent chacun un atome d'hydrogène, un radical alcoyle en Ci à C4 ou hydroxy-alcoyle en C2 à C4 et n est un nombre valant de 2 à 4, avec un rapport des équivalents compris entre 1 : 1 et 1 : 4.
2. Utilisation des produits selon la revendication 1 comme inhibiteurs de corrosion pauvres en mousse pour le fer, les alliages du fer, l'aluminium, les alliages de l'aluminium, le cuivre et le zinc et leurs alliages.
3. Utilisation suivant la revendication 2, caractérisée en ce que l'on emploie en outre jusqu'à 85% en poids, rapportés aux produits réactionnels définis dans la revendication 1, d'au moins un produit de la réaction de l'acide ortho-borique et d'au moins une alcanolamine avec 2 à 4 atomes de carbone par groupe alcanol dans un rapport molaire de 1 : 1 à 1 : 4.
EP80106805A 1979-11-24 1980-11-05 Produits de réaction d'acides sulfone ou carboxamido carboxyliques avec des alcanolamines et leur utilisation comme inhibiteurs de corrosion pauvres en mousse Expired EP0029529B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19792947418 DE2947418A1 (de) 1979-11-24 1979-11-24 Umsetzprodukte aus sulfon- oder carbonamidocarbonsaeuren mit alkanolaminen und ihre verwendung als schaumarme korrosionsinhibitoren
DE2947418 1979-11-24

Publications (2)

Publication Number Publication Date
EP0029529A1 EP0029529A1 (fr) 1981-06-03
EP0029529B1 true EP0029529B1 (fr) 1983-05-25

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EP (1) EP0029529B1 (fr)
DE (2) DE2947418A1 (fr)

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3119376A1 (de) 1981-05-15 1982-12-02 Basf Ag, 6700 Ludwigshafen Inhibitoren gegen die korrosion von h(pfeil abwaerts)2(pfeil abwaerts)s und co(pfeil abwaerts)2(pfeil abwaerts) in wasser-in-oel-emulsionen
US4473491A (en) * 1981-06-22 1984-09-25 Basf Aktiengesellschaft Alkanolamine salts of cyclic amide acids and their use as metal corrosion inhibitors in aqueous systems
DE3330223A1 (de) * 1983-08-22 1985-03-14 Henkel KGaA, 4000 Düsseldorf Korrosionsinhibitoren
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
DE3616721A1 (de) * 1986-05-17 1987-11-19 Basf Lacke & Farben Zink- und/oder bleisalze von carbonsaeuren und deren verwendung als korrosionsschutzmittel
US4683081A (en) * 1986-06-27 1987-07-28 Ferro Corporation Aqueous corrosion inhibitor compositions of a half-amide and a dicarboxylic acid amine salt
US5250725A (en) * 1986-11-20 1993-10-05 Elf Sanofi Aromatic acid intermediates
DE3719046A1 (de) * 1987-06-06 1988-12-15 Basf Ag Verwendung von salzen von sulfonamidcarbonsaeuren als korrosionsinhibitoren in waessrigen systemen
DE3732374A1 (de) * 1987-09-25 1989-04-06 Basf Lacke & Farben Zink-, blei- und/oder calciumsalze von carbonsaeuren und deren verwendung als korrosionsschutzmittel
DE3815884A1 (de) * 1988-05-10 1989-11-23 Basf Ag Mischungen aus alkanolaminsalzen von alkenylbernsteinsaeuren und arylsulfonylanthranilsaeuren zur verwendung als korrosionsschutzmittel fuer waessrige systeme

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE900041C (de) 1943-04-22 1953-12-17 Hoechst Ag Korrosionsschutzmittel
US2578725A (en) * 1949-10-20 1951-12-18 Josef M Michel Process of protecting metals against corrosion
GB765018A (en) * 1954-03-11 1957-01-02 Wander Ag Dr A Novel salts of n-benzoyl-ªÐ-amino-salicylic acid and their production
BE542184A (fr) * 1954-10-21
DE1298672B (de) * 1967-07-15 1969-07-03 Hoechst Ag Korrosionsverhinderndes Metallbearbeitungsmittel
DE2511400C2 (de) * 1975-03-15 1982-09-23 Basf Ag, 6700 Ludwigshafen Amidosulfocarbonsäuren und deren Salze, Verfahren zu deren Herstellung und deren Verwendung als Korrosionsschutzmittel
CH629540A5 (de) * 1977-09-19 1982-04-30 Hoechst Ag Wassermischbare korrosionsschutzmittel.

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US4344862A (en) 1982-08-17
DE3063538D1 (en) 1983-07-07
EP0029529A1 (fr) 1981-06-03
DE2947418A1 (de) 1981-06-04

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