EP0142627B1 - Corrosion inhibitors - Google Patents
Corrosion inhibitors Download PDFInfo
- Publication number
- EP0142627B1 EP0142627B1 EP84109614A EP84109614A EP0142627B1 EP 0142627 B1 EP0142627 B1 EP 0142627B1 EP 84109614 A EP84109614 A EP 84109614A EP 84109614 A EP84109614 A EP 84109614A EP 0142627 B1 EP0142627 B1 EP 0142627B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- corrosion inhibitors
- radical
- compounds
- hydrogen atom
- corrosion
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
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Classifications
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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
Definitions
- the invention relates to the use of special sulfonamide derivatives as corrosion inhibitors in aqueous systems. Corrosion protection in aqueous systems is a major problem in technical processes. The use of corrosion inhibitors is associated with considerable difficulties. Foam formation, for example, is undesirable. The water solubility or the water hardness sensitivity is essential for the usability of the agents. Furthermore, the toxicity and degradability of the substances and their storage stability play an important role.
- FR-A-2 249 181 describes a method for corrosion inhibition of metals using sulfonylated glycine compounds.
- the metal surface is first pretreated with an aqueous solution of a chemical compound which passivates the metal surface and forms a monomolecular layer thereon.
- a chemical compound which passivates the metal surface and forms a monomolecular layer thereon.
- Compounds of hexavalent chromium for example Na 2 Cr0 4 or Na 2 Cr0 4 / polyphosphate, are suitable for this purpose.
- the benzene sulfonyl-N-methyl-a-aminoacetic acid in the form of the triethanolammonium salt (Compose 2) is mentioned.
- This compound shows in the test, for example, in comparison to benzenesulfonyl-N-methyl- E- aminocaproic acid (Compose 5) - no corrosion protection at all.
- alkali metal or ammonium salts of compounds of the formula are used as corrosion inhibitors in aqueous systems where R, an alkyl radical having 1 to 6 carbon atoms and R 2 is a methyl radical or a hydrogen atom used.
- R in the above formula is a hexyl radical and R 2 is a hydrogen atom.
- alkali metal salts such as sodium or potassium salts
- organic bases such as ammonia, mono-, di- or trialkanolamines
- the anti-corrosion agents according to the invention can be used individually or as a mixture in aqueous solutions, dispersions or emulsions. They are highly effective even at low concentrations. It has been shown that a sufficient effect is sometimes achieved at 0.05 percent by weight. The agents used have a pronounced low foam and have good water hardness stability.
- para-alkyl-aryl-sulfonamidoacetic acids and their water-soluble salts are prepared by methods known per se and are not the subject of the invention.
- the corrosion protection properties were determined by determining the mass removal.
- test strips Three carefully pretreated and weighed test strips (unalloyed steel, 80 x 15 x 1 mm) were hung in a 1 l vessel containing 800 ml test water, 50 ml buffer solution and a defined amount of the substance to be examined, and added for 3 hours Leave room temperature and 80 revolutions per minute in it.
- test water used as a corrosive medium was prepared according to DIN 51360/2 and buffered to pH 9 with ammonia / ammonium chloride.
- Tables 2 to 4 below show the results obtained in the form of the diethanolamine salt in comparison with benzenesulfonamidocaproic acid.
- Table 1 shows which compounds the products labeled A to M are.
- the data R, and R 2 refer to the formula.
- Table 4 also contains mixtures of several compounds of the claimed type.
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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)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
Gegenstand der Erfindung ist die Verwendung von speziellen Sulfonamidderivaten als Korrosionsinhibitoren in wäßrigen Systemen. Der Korrosionsschutz in wäßrigen Systemen ist ein wesentliches Problem bei technischen Prozessen. Die Verwendung von Korrosionsinhibitoren ist dabei mit erheblichen Schwierigkeiten verbunden. Es ist beispielsweise die Schaumbildung unerwünscht. Die Wasserlöslichkeit oder auch die Wasserhärteempfindlichkeit ist für die Brauchbarkeit der Mittel von wesentlicher Bedeutung. Weiterhin spielt die Toxizität und die Abbaubarkeit der Substanzen sowie ihre Lagerstabilität eine erhebliehe Rolle.The invention relates to the use of special sulfonamide derivatives as corrosion inhibitors in aqueous systems. Corrosion protection in aqueous systems is a major problem in technical processes. The use of corrosion inhibitors is associated with considerable difficulties. Foam formation, for example, is undesirable. The water solubility or the water hardness sensitivity is essential for the usability of the agents. Furthermore, the toxicity and degradability of the substances and their storage stability play an important role.
In letzter Zeit sind als Korrosionsinhibitoren Verbindungen wie Halbamide der Maleinsäure oder Alkenylbernsteinsäure sowie Arylsulfonamidocarbonsäuren mit mebr als 3 Kohlenstoffatomen im Carbonsäurerest vorgeschlagen worden. Diese Inhibitoren zeigen jedoch nur bei hohen Konzentrationen einen guten Korrosionsschutz und werden häufig den oben genannten anwendungstechnischen Erfordernissen nicht gerecht.Recently, compounds such as half-amides of maleic acid or alkenylsuccinic acid and arylsulfonamidocarboxylic acids with mebr as 3 carbon atoms in the carboxylic acid residue have been proposed as corrosion inhibitors. However, these inhibitors show good corrosion protection only at high concentrations and often do not meet the above-mentioned application requirements.
Ferner wird in der FR-A-2 249 181 ein Verfahren zur Korrosionsinhibierung von Metallen unter Verwendung von sulfonylierten Glycinverbindungen beschrieben. Bei diesem Verfahren wird die Metalloberfläche zunächst mit einer wäßrigen Lösung einer chemischen Verbindung vorbehandelt, welche die Metalloberfläche passiviert und auf dieser eine monomolekulare Schicht ausbildet. Hierzu kommen Verbindungen des sechswertigen Chroms, beispielsweise Na2Cr04 oder Na2Cr04/Polyphosphat in Frage. Anschließend wird zu dieser wäßrigen Lösung eine Glycinverbindung der allgemeinen Formel
Gegenstand der FR-A-1 576 681 ist ein wäßriges Metallbearbeitungs- und Korrosionsschutzmittel, enthaltend Alkali- oder Aminsalze von Sulfonamido-carbonsäuren der allgemeinen Formel
Es wurde nun gefunden, daß man überraschenderweise zu ausgezeichneten Ergebnissen gelangt, wenn man als Korrosionsinhibitoren in wäßrigen Systemen Alkali- beziehungsweise Ammoniumsalze von Verbindungen der Formel
Insbesondere sind solche Verbindungen geeignet, bei denen in der oben angeführten Formel R, einen Hexylrest und R2 ein Wasserstoffatom bedeuten.Particularly suitable are those compounds in which R in the above formula is a hexyl radical and R 2 is a hydrogen atom.
Es wurde weiterhin gefunden, daß neben Alkalisalzen, wie Natrium- oder Kaliumsalze, vorzugsweise Ammoniumsalze mit organischen Basen, wie Ammoniak, Mono-, Di- oder Trialkanolamine geeignet sind.It has also been found that, in addition to alkali metal salts, such as sodium or potassium salts, preferably ammonium salts with organic bases, such as ammonia, mono-, di- or trialkanolamines, are suitable.
Die erfindungsgemäßen Korrosionsschutzmittel können einzeln oder im Gemisch in wäßrigen Lösungen, Dispersionen oder Emulsionen verwendet werden. Sie zeigen bereits bei geringen Konzentrationen eine hohe Wirksamkeit. Es hat sich gezeigt, daß teilweise bei 0,05 Gewichtsprozent noch eine ausreichende Wirkung erzielt wird. Die zur Anwendung gelangenden Mittel besitzen eine ausgeprägte Schaumarmut und haben eine gute Wasserhärtestabilität.The anti-corrosion agents according to the invention can be used individually or as a mixture in aqueous solutions, dispersions or emulsions. They are highly effective even at low concentrations. It has been shown that a sufficient effect is sometimes achieved at 0.05 percent by weight. The agents used have a pronounced low foam and have good water hardness stability.
Die Herstellung der Para-alkyl-aryl-sulfonamidoessigsäuren und deren wasserlösliche Salze erfolgt nach an sich bekannten Methoden und ist nicht Gegenstand der Erfindung.The para-alkyl-aryl-sulfonamidoacetic acids and their water-soluble salts are prepared by methods known per se and are not the subject of the invention.
Der Anmeldungsgegenstand wird noch durch die nachstehenden Beispiele erläutert, ohne daß er hierauf beschränkt ist.The subject of the application is illustrated by the examples below, without being limited thereto.
Die Bestimmung der Korrosionsschutzeigenschaften erfolgte durch Ermittlung des Massenabtrags.The corrosion protection properties were determined by determining the mass removal.
Je drei sorgfältig vorbehandelte und gewogene Teststreifen (unlegierter Stahl, 80 x 15 x 1 mm) wurden in ein 1-1-Gefäß, das 800 ml Testwasser, 50 ml Pufferlösung sowie eine definierte Menge an zu untersuchender Substanz enthält, gehängt und 3 Stunden bei Raumtemperatur und 80 Umdrehungen pro Minute darin belassen.Three carefully pretreated and weighed test strips (unalloyed steel, 80 x 15 x 1 mm) were hung in a 1 l vessel containing 800 ml test water, 50 ml buffer solution and a defined amount of the substance to be examined, and added for 3 hours Leave room temperature and 80 revolutions per minute in it.
Aus dem Gewichtsverlust wurde der Korrosionsschutzwert S, bezogen auf eine Blindprobe, berechnet.
- S=100 (1 -
- a = Gewichtsverlust Probe
- b = Gewichtsverlust Blindwert
- S = 100 (1 -
- a = weight loss sample
- b = blank weight loss
Das als korrosives Medium benutzte Versuchswasser wurde nach DIN 51360/2 hergestellt und mit Ammoniak/Ammoniumchlorid auf pH 9 gepuffert.The test water used as a corrosive medium was prepared according to DIN 51360/2 and buffered to pH 9 with ammonia / ammonium chloride.
In den nachstehenden Tabellen 2 bis 4 sind die Ergebnisse angegeben, die im Vergleich mit Benzolsulfonamidocapronsäure in Form des Diethanolaminsalzes erhalten wurden. Aus Tabelle 1 ist ersichtlich, um welche Verbindungen es sich bei den mit A bis M bezeichneten Produkten handelt. Die Angaben R, und R2 beziehen sich dabei auf die Formel. Die Tabelle 4 enthält im übrigen Gemische von mehreren Verbindungen der beanspruchten Art.
Vergleichbare Ergebnisse werden mit Alkalisalzen der angeführten Formel erhalten.Comparable results are obtained with alkali salts of the formula given.
Claims (4)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AT84109614T ATE30603T1 (en) | 1983-08-22 | 1984-08-13 | CORROSION INHIBITORS. |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE3330223 | 1983-08-22 | ||
DE19833330223 DE3330223A1 (en) | 1983-08-22 | 1983-08-22 | CORROSION INHIBITORS |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0142627A1 EP0142627A1 (en) | 1985-05-29 |
EP0142627B1 true EP0142627B1 (en) | 1987-11-04 |
Family
ID=6207116
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP84109614A Expired EP0142627B1 (en) | 1983-08-22 | 1984-08-13 | Corrosion inhibitors |
Country Status (4)
Country | Link |
---|---|
EP (1) | EP0142627B1 (en) |
JP (1) | JPS6070190A (en) |
AT (1) | ATE30603T1 (en) |
DE (2) | DE3330223A1 (en) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3719046A1 (en) * | 1987-06-06 | 1988-12-15 | Basf Ag | USE OF SALTS OF SULFONAMIDE CARBONIC ACIDS AS CORROSION INHIBITORS IN AQUEOUS SYSTEMS |
JPH05320957A (en) * | 1992-05-15 | 1993-12-07 | Union Chem Kk | Rust preventing material |
DE4323907A1 (en) * | 1993-07-16 | 1995-01-19 | Henkel Kgaa | Use of carboxylic acids in agents for treating metal surfaces |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE1298672B (en) * | 1967-07-15 | 1969-07-03 | Hoechst Ag | Corrosion-preventing metalworking agent |
BE810115A (en) * | 1973-10-30 | 1974-05-16 | CORROSION INHIBITION METHOD USING CULFONYL GLYCINE COMPOUNDS | |
DE2947418A1 (en) * | 1979-11-24 | 1981-06-04 | BASF Corp., New York, N.Y. | IMPLEMENTATION PRODUCTS OF SULPHONE OR CARBONAMIDOCARBONIC ACIDS WITH ALKANOLAMINES AND THEIR USE AS LOW-FOAM CORROSION INHIBITORS |
-
1983
- 1983-08-22 DE DE19833330223 patent/DE3330223A1/en not_active Withdrawn
-
1984
- 1984-08-13 AT AT84109614T patent/ATE30603T1/en not_active IP Right Cessation
- 1984-08-13 EP EP84109614A patent/EP0142627B1/en not_active Expired
- 1984-08-13 DE DE8484109614T patent/DE3467190D1/en not_active Expired
- 1984-08-22 JP JP59175812A patent/JPS6070190A/en active Pending
Also Published As
Publication number | Publication date |
---|---|
JPS6070190A (en) | 1985-04-20 |
ATE30603T1 (en) | 1987-11-15 |
DE3330223A1 (en) | 1985-03-14 |
EP0142627A1 (en) | 1985-05-29 |
DE3467190D1 (en) | 1987-12-10 |
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