EP0206311A2 - Process for preventing corrosion of metallic materials - Google Patents

Process for preventing corrosion of metallic materials Download PDF

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Publication number
EP0206311A2
EP0206311A2 EP86108576A EP86108576A EP0206311A2 EP 0206311 A2 EP0206311 A2 EP 0206311A2 EP 86108576 A EP86108576 A EP 86108576A EP 86108576 A EP86108576 A EP 86108576A EP 0206311 A2 EP0206311 A2 EP 0206311A2
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Prior art keywords
alkyl
formula
alkenyl
compounds
corrosion
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EP86108576A
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German (de)
French (fr)
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EP0206311B1 (en
EP0206311A3 (en
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Dieter Dr. Ohlendorf
Werner Dr. Interthal
Friedrich Dr. Stoll
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Hoechst AG
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Hoechst AG
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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
    • C23F11/149—Heterocyclic compounds containing nitrogen as hetero atom
    • 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
    • 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
    • C23F11/147—Nitrogen-containing compounds containing a nitrogen-to-oxygen bond

Definitions

  • additives to aqueous and non-aqueous solutions can reduce (inhibit) the rate of corrosion attack.
  • organic compounds such as amines, imines, quaternary ammonium salts, unsaturated alcohols and other substances act as inhibitors in media which attack metallic materials, especially unalloyed steels, by acid corrosion.
  • the group of amines including aliphatic and aromatic, saturated and unsaturated amine compounds, and the quaternary ammonium compounds, are known as adsorption inhibitors for acid corrosion. According to the protective mechanism, these substances only work in acidic aqueous media in the absence of oxidizing agents, especially atmospheric oxygen (Risch, K .: VDI report 365, 11 (1980).
  • the protective effect of inhibitors for corrosion in neutral and alkaline oxygen-containing water in particular phosphorus-containing products, for example phosphates and polyphosphates, depends on the formation of a film (film-forming inhibitors) or a barrier layer of precipitated solids, the corrosion protection effect of which strongly depends on the medium and the initial growth conditions, in particular in the case of heat transfer from metallic Material can get into the medium (heating elements, heat exchangers) Form ten that hinder the flow of heat and that lead to overheating or local corrosion under the top layer formed.
  • the invention thus relates to a process for avoiding corrosion of metallic materials in aqueous media, which is characterized in that the aqueous medium is given a compound of the formulas I or II R 1 - (C 2 H 4 O) n -K (+) A (-) (I) or admits, wherein R 1 is C 12 -C 26 alkyl or C 12 -C 26 alkenyl, n is a number from 0 to 5, K (+) is a group of the formulas or , R 2 C 1 -C 3 alkyl, R 3 C i -C 3 alkyl or a group of the formula - (C 2 H 4 O) x H, x a number from 1 to 3, A (-) an anion of the following formulas: SCN (-) , R 4 SO 3 (-) where R 4 is C 6 -C 9 alkyl or (C 6 -C 9 alkenyl and the sum of the C atoms in R 1 and R 4 at least Should be 21; where
  • Preferred amine oxides of the formula II are those in which R 9 is alkyl or alkenyl.
  • Aryl preferably means phenyl. Under the meaning of R 10 , methyl and hydroxyethyl are preferred.
  • the compounds described above show a pronounced anticorrosive effect on metallic materials of all kinds, preferably for copper and unalloyed steel. This anti-corrosive effect extends from the strongly acidic to the strongly alkaline pH range and is independent of the presence or absence of oxygen.
  • the use of these compounds in flowing aqueous media, for example in cooling and heating circuits, is of particular interest.
  • the use concentrations for the compounds of the formula 1 are 0.01 to 5% by weight, preferably 0.05 to 2% by weight and particularly preferably 0.1 to 1% by weight. In the case of the compounds of the formula II, this concentration is 0.075 to 3% by weight, preferably more than 0.4% by weight.
  • Some compounds of the formula I such as, for example, hexadecylpyridinium salicylate, are known (H. Hoffmann et al., Ber. Bunsenges. Phys. Chem. 85 (1981) 255) that they start from a very specific concentration which is characteristic of each surfactant and which Build CMC 11 , non-spherical, usually rod-shaped micelles from the individual surfactant ions and counterions.
  • Non-spherical, preferably rod-shaped micelles are present when the isotropic surfactant solution is examined using the electrical birefringence method with a pulsed, rectangular electrical field (E. Fredericq and C. Housier, Electric Dichroism and Electric Birefringence, Claredon Press, Oxford 1973 and H Hoffmann et al., Ber. Bunsenges. Phys. Chem.
  • the lower concentration limit above which a surfactant in aqueous solution is effective as a corrosion protection agent is therefore always determined by the CMC II , preferably by 1.5 to 3 times the concentration value of the CMC II .
  • the CMC II can be determined, for example, by measuring the electrical conductivity of the surfactant solution as a function of the surfactant concentration, as in H. Hoffmann et al. (Ber. Bunsenges. Phys. Chem. 85 (1981) 255). It was shown that the value of the CMC II is temperature-dependent and shifts to higher surfactant concentrations with increasing temperature.
  • the minimum concentration required to achieve a sufficient corrosion protection effect in a certain temperature range can be determined by determining the CMC II temperature can be determined using electrical conductivity.
  • the corrosion protection effect in the following examples was tested in the usual way by determining the loss of mass of samples of the metallic materials (sample coupons), in certain cases in which only acid corrosion predominated, also by determining the removal rates from the polarization resistance.
  • the effectiveness w of the individual inhibitor can be calculated by comparison with the removal rates in solutions without additives: where V is the removal rate without inhibitor, V I is the removal rate with inhibitor.

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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)

Abstract

Verwendung der Verbindungen der Formel <IMAGE> R1 C12-C26-Alkyl oder C12-C26-Alkenyl, n eine Zahl von 0 bis 5, <IMAGE> C1-C3-Alkyl, R3 C1-C3-Alkyl oder eine Gruppe der Formel -(C2H4O)xH, x eine Zahl von 1 bis 3, A<(-)> ein Anion, R9 eine Gruppe der Formel R1'-(OCH2CH2)n-, C8-C18-Alkylaryl oder Aryl-C8-C18-alkyl, R1' C14-C22-Alkyl oder C14-C22-Alkenyl, n eine Zahl von 0 bis 5 und die Reste R10 gleich sind und C1-C4-Alkyl oder C1-C4-Hydroxialkyl bedeuten, als Korrosionsschutzmittel für metallische Werkstoffe in wässrigen Medien.Use of the compounds of the formula <IMAGE> R1 C12-C26-alkyl or C12-C26-alkenyl, n is a number from 0 to 5, <IMAGE> C1-C3-alkyl, R3 C1-C3-alkyl or a group of the formula - (C2H4O) xH, x a number from 1 to 3, A <(-)> an anion, R9 a group of the formula R1 '- (OCH2CH2) n-, C8-C18-alkylaryl or aryl-C8-C18-alkyl, R1 'C14-C22-alkyl or C14-C22-alkenyl, n is a number from 0 to 5 and the radicals R10 are the same and are C1-C4-alkyl or C1-C4-hydroxyalkyl, as corrosion inhibitors for metallic materials in aqueous media.

Description

Bekannt ist, daß Zusätze zu wäßrigen und nichtwäßrigen Lösungen die Geschwindigkeit des Korrosionsangriffs verringern (inhibieren) können. Insbesondere organische Verbindungen wie Amine, Imine, quartäre Ammoniumsalze, ungesättigte Alkohole und andere Stoffe wirken als Inhibitoren in Medien, die metallische Werkstoffe, insbesondere unlegierte Stähle, durch Säurekorrosion angreifen. (vgl. Akstinat: Werkstoff und Korrosion 21, 273 (1970); Sanyal, B.: Progress in Organic Coatings 9, p 165 - 236 (1981); Rozenfeld, L.L.: Corrosion Inhibitors, McGraw Hill Inc., New York, 1981. Unterschieden werden Korrosionsinhibitoren nach ihrer Wirkungsweise als Adsorptionsinhibitoren, Passivatoren, Film- oder Deckschichtbildner, Neutralisatoren und andere (vgl. Dean, S.W. et al.: Materials Perfonnance, p. 47 - 51 (1981)).It is known that additives to aqueous and non-aqueous solutions can reduce (inhibit) the rate of corrosion attack. In particular, organic compounds such as amines, imines, quaternary ammonium salts, unsaturated alcohols and other substances act as inhibitors in media which attack metallic materials, especially unalloyed steels, by acid corrosion. (see Akstinat: Werkstoff und Korrosion 21, 273 (1970); Sanyal, B .: Progress in Organic Coatings 9, p 165 - 236 (1981); Rozenfeld, LL: Corrosion Inhibitors, McGraw Hill Inc., New York, 1981 A distinction is made between corrosion inhibitors according to their mode of action as adsorption inhibitors, passivators, film or top layer formers, neutralizers and others (cf. Dean, SW et al .: Materials Perfonnance, p. 47-51 (1981)).

Die Gruppe der Amine, umfassend aliphatische und aromatische, gesättigte und ungesättigte Aminverbindungen, sowie die quartären Ammoniumverbindungen, sind als Adsorptionsinhibitoren für die Säurekorrosion bekannt. Dem Schutzmechanismus entsprechend wirken diese Stoffe nur in sauren wäßrigen Medien in Abwesenheit von Oxidationsmitteln, insbesondere von Luftsauerstoff (Risch, K.: VDI Bericht 365, 11 (1980». Andererseits ist bekannt, daß die Schutzwirkung von Inhibitoren für die Korrosion in neutralen und alkalischen sauerstoffhaltigen Wässern, das sind insbesondere phosphorhaltige Produkte, beispielsweise Phosphate und Polyphosphate, von der Ausbildung eines Films (filmbildende Inhibitoren) oder einer Barriereschicht aus gefällten Feststoffen abhängig ist, deren Korrosionsschutzwirkung stark vom Medium und den anfänglichen Wachstumsbedingungen abhängt. Insbesondere im Fall der Wärmeübertragung von metallischen Werkstoff in das Medium (Heizelemente, Wärmeaustauscher) können sich Schichten bilden, die den Wärmestrom behindern und die zu Überhitzungen oder lokaler Korrosion unter der gebildeten Deckschicht führen.The group of amines, including aliphatic and aromatic, saturated and unsaturated amine compounds, and the quaternary ammonium compounds, are known as adsorption inhibitors for acid corrosion. According to the protective mechanism, these substances only work in acidic aqueous media in the absence of oxidizing agents, especially atmospheric oxygen (Risch, K .: VDI report 365, 11 (1980). On the other hand, it is known that the protective effect of inhibitors for corrosion in neutral and alkaline oxygen-containing water, in particular phosphorus-containing products, for example phosphates and polyphosphates, depends on the formation of a film (film-forming inhibitors) or a barrier layer of precipitated solids, the corrosion protection effect of which strongly depends on the medium and the initial growth conditions, in particular in the case of heat transfer from metallic Material can get into the medium (heating elements, heat exchangers) Form ten that hinder the flow of heat and that lead to overheating or local corrosion under the top layer formed.

Überraschend war nun, daß spezielle Verbindungen aus den Gruppen der quartären Ammoniumverbindungen, der oxalkylierten quartären Ammoniumverbindungen und der Aminoxide die Korrosion metallischer Werkstoffe, insbesondere von unlegierten Stählen und von Kupfer, im sauren, neutralen und alkalischen pH-Bereich wirksam zu inhibieren vermögen, wobei die Schutzwirkung, insbesondere in strömenden und neutralen wäßrigen Medien unabhängig davon ist, ob gelöster Sauerstoff vorhanden ist oder nicht.It was surprising that special compounds from the groups of the quaternary ammonium compounds, the oxyalkylated quaternary ammonium compounds and the amine oxides are able to effectively inhibit the corrosion of metallic materials, especially unalloyed steels and copper, in the acidic, neutral and alkaline pH range, the Protective effect, especially in flowing and neutral aqueous media is independent of whether dissolved oxygen is present or not.

Gegenstand der Erfindung ist somit ein Verfahren zur Vermeidung der Korrosion metallischer Werkstoffe in wäßrigen Medien, das dadurch gekennzeichnet ist, daß man dem wäßrigen Medium eine Verbindung der Formeln I oder II R1-(C2H4O)n-K(+) A(-) (I) oder

Figure imgb0001
zugibt, wobei R1 C12-C26-Alkyl oder C12-C26-Alkenyl, n eine Zahl von 0 bis 5, K(+) eine Gruppe der Formeln
Figure imgb0002
oder
Figure imgb0003
, R2 C1-C3-Alkyl, R 3 Ci-C3-Alkyl oder eine Gruppe der Formel -(C2H4O)xH, x eine Zahl von 1 bis 3, A(-) ein Anion der folgenden Formeln: SCN(-), R4SO3 (-) wo R4 C6-C9-Alkyl oder (C6-C9-Alkenyl ist und die Summe der C-Atome in R1 und R4 mindestens 21 betragen soll;
Figure imgb0004
 wo Hal Fluor oder Chlor, Brom, Jod, R5 C1-C5-Alkyl, C2-C5-Alkenyl oder C1-C5-Alkoxy in den Stellungen 3, 4, 5 und 6 und R6 Wasserstoff oder Hydroxy in den Stellungen 2 und 3 zur Carboxyl-Gruppe und
Figure imgb0005
wo R7 COO- oder SO3 (-) und R8 Wasserstoff oder Methyl ist, R9 eine Gruppe der Formel R'1-(OCH2CH2)n-, C8-C18-Alkylaryl oder Aryl-C8-C18-alkyl, R'1 C14-C22-Alkyl oder C 14-C 22-Alkenyl, n eine Zahl von 0 bis 5 und die Reste R10 gleich sind und C1-C4-Alkyl oder C1-C4-Hydroxialkyl bedeuten.The invention thus relates to a process for avoiding corrosion of metallic materials in aqueous media, which is characterized in that the aqueous medium is given a compound of the formulas I or II R 1 - (C 2 H 4 O) n -K (+) A (-) (I) or
Figure imgb0001
 admits, wherein R 1 is C 12 -C 26 alkyl or C 12 -C 26 alkenyl, n is a number from 0 to 5, K (+) is a group of the formulas
Figure imgb0002
 or
Figure imgb0003
 , R 2 C 1 -C 3 alkyl, R 3 C i -C 3 alkyl or a group of the formula - (C 2 H 4 O) x H, x a number from 1 to 3, A (-) an anion of the following formulas: SCN (-) , R 4 SO 3 (-) where R 4 is C 6 -C 9 alkyl or (C 6 -C 9 alkenyl and the sum of the C atoms in R 1 and R 4 at least Should be 21;
Figure imgb0004
 where Hal is fluorine or chlorine, bromine, iodine, R 5 C 1 -C 5 alkyl, C 2 -C 5 alkenyl or C 1 -C 5 alkoxy in positions 3, 4, 5 and 6 and R 6 is hydrogen or Hydroxy in positions 2 and 3 to the carboxyl group and
Figure imgb0005
 where R 7 is COO - or SO 3 (-) and R 8 is hydrogen or methyl, R 9 is a group of the formula R'1- (OCH 2 CH 2 ) n -, C 8 -C 18 alkylaryl or aryl-C8- C18-alkyl, R ' 1 C 14 -C 22 alkyl or C 14 - C 22 alkenyl, n is a number from 0 to 5 and the radicals R 10 are the same and C 1 -C 4 alkyl or C 1 -C 4 -Hydroxialkyl mean.

Besonders bevorzugt sind die Salze aus den folgenden Kationen und Anionen:

  • 1. 1. [CnH2n+1N(CH3)3];
    Figure imgb0006
    oder CnH2n+1N(CH3)2-(CH2CH2O)xH mit x= 1-2
    • a) mit dem Anion C6H13SO3 (-) für n= 20 bis 26
    • b) mit dem Anion C7H15SO3 (-) für n= 14 bis 22
    • c) mit dem Anion C8H17SO3 (-) für n= 14 bis 20
    • d) mit dem Anion SCN(-) für n= 16 bis 26
  • 2. [CnH2n+1N(CH3)3] oder
    Figure imgb0007
    CnH2n+1N(CH3)2-(CH2CH2O)xH mit x= 1 - 2 für n= 12 bis 24 mit folgenden Benzoesäureanionen
    • a) Salicylat oder m-Halogenbenzoat,
      Figure imgb0008
    • mit R= Methyl oder Ethyl oder Propyl oder CnH2n+1O - mit n= 1 bis 4, vorzugsweise in den Stellungen 3 oder 4 oder 5 zur Carboxylgruppe,
      Figure imgb0009
    • mit R= Methyl oder Ethyl oder Propyl oder CnH2n+1O - mit n= 1 bis 4, vorzugsweise in den Stellungen 4 oder 5 zur Carboxylgruppe,
      Figure imgb0010
    • mit Hal= F, Cl, Br, J
      Figure imgb0011
  • 3. [CnH2n+1N(+)(CH3] oder für n= 12 bis 24
    Figure imgb0012
    mit den Anionen 2-hydroxy-l-naphthoat, 3-(oder 4)-hydroxy-2-naphthoat bzw. die entsprechenden Derivate der Naphthol-Sulfonsäuren.
The salts of the following cations and anions are particularly preferred:
  • 1. 1. [C n H 2n + 1 N (CH 3 ) 3 ];
    Figure imgb0006
     or C n H 2n + 1 N (CH 3 ) 2 - (CH 2 CH 2 O) x H with x = 1-2
    • a) with the anion C 6 H 13 SO 3 (-) for n = 20 to 26
    • b) with the anion C 7 H 15 SO 3 (-) for n = 14 to 22
    • c) with the anion C 8 H 17 SO 3 (-) for n = 14 to 20
    • d) with the anion SCN (-) for n = 16 to 26
  • 2. [C n H 2n + 1 N (CH 3 ) 3 ] or
    Figure imgb0007
     C n H 2n + 1 N (CH 3 ) 2 - (CH 2 CH 2 O) x H with x = 1 - 2 for n = 12 to 24 with the following benzoic acid anions
    • a) salicylate or m-halobenzoate,
      Figure imgb0008
    • with R = methyl or ethyl or propyl or C n H 2n + 1 O - with n = 1 to 4, preferably in positions 3 or 4 or 5 to the carboxyl group,
      Figure imgb0009
    • with R = methyl or ethyl or propyl or C n H 2n + 1 O - with n = 1 to 4, preferably in positions 4 or 5 to the carboxyl group,
      Figure imgb0010
    • with Hal = F, Cl, Br, J
      Figure imgb0011
  • 3. [C n H 2n + 1 N (+) (CH 3 ] or for n = 12 to 24
    Figure imgb0012
     with the anions 2-hydroxy-1-naphthoate, 3- (or 4) -hydroxy-2-naphthoate or the corresponding derivatives of naphthol sulfonic acids.

Bei den Aminoxiden der Formel II sind solche bevorzugt, worin R9 Alkyl oder Alkenyl bedeutet. Aryl bedeutet vorzugsweise Phenyl. Unter der Bedeutung von R10 sind Methyl und Hydroxiethyl bevorzugt.Preferred amine oxides of the formula II are those in which R 9 is alkyl or alkenyl. Aryl preferably means phenyl. Under the meaning of R 10 , methyl and hydroxyethyl are preferred.

Die oben beschriebenen Verbindungen zeigen eine ausgeprägte antikorrosive Wirkung an metallischen Werkstoffen aller Art, vorzugsweise bei Kupfer und unlegiertem Stahl. Diese antikorrosive Wirkung erstreckt sich vom stark sauren bis zum stark alkalischen pH Bereich und ist unabhängig von der Anwesenheit oder Abwesenheit von Sauerstoff. Von besonderem Interesse ist die Verwendung dieser Verbindungen in strömenden wäßrigen Medien wie zum Beispiel in Kühl- und Heizkreisläufen. Die Einsatzkonzentrationen betragen für die Verbindungen der Formel 1 0,01 bis 5 Gew.-% bevorzugt 0,05 bis 2 Gew.-% und besonders bevorzugt 0,1 bis 1 Gew.-%. Bei den Verbindungen der Formel II beträgt diese Konzentration 0,075 bis 3 Gew.-%, vorzugsweise mehr als 0,4 Gew.-%. Für die Herstellung der Verbindungen der Formeln I und II wird verwiesen auf die deutschen Offenlegungsschriften 32 24 148 und 33 36 198.The compounds described above show a pronounced anticorrosive effect on metallic materials of all kinds, preferably for copper and unalloyed steel. This anti-corrosive effect extends from the strongly acidic to the strongly alkaline pH range and is independent of the presence or absence of oxygen. The use of these compounds in flowing aqueous media, for example in cooling and heating circuits, is of particular interest. The use concentrations for the compounds of the formula 1 are 0.01 to 5% by weight, preferably 0.05 to 2% by weight and particularly preferably 0.1 to 1% by weight. In the case of the compounds of the formula II, this concentration is 0.075 to 3% by weight, preferably more than 0.4% by weight. For the preparation of the compounds of the formulas I and II, reference is made to German Offenlegungsschriften 32 24 148 and 33 36 198.

Für jede der Verbindungen der Formel I und II existiert in Abhängigkeit von der Temperatur eine andere untere kritische Konzentrationsgrenze für eine ausreichende Korrosionsschutzwirkung, die jedoch, wie weiter hinten beschrieben, durch einen einfachen Vorversuch bestimmt werden kann. Die Wirkung ist abhängig von der Temperatur. Die genannten Verbindungen wirken insgesamt in einem Temperaturbereich von 0°C bis 145°C; eine einzelne Verbindung zeigt eine Wirksamkeit jedoch nur über ein Temperaturintervall von ca. 45°C (±25°C). Die untere Temperaturgrenze ist bei allen Verbindungen die Löslichkeitstemperatur (isotrope Lösung) oder besser der Krafft-Punkt. Ist das Tensid jedoch in Lösung, so kann die Löslichkeitstemperatur in den meisten Fällen für einige Stunden bis Wochen um 5 bis 25°C unterschritten werden, ohne daß ein Verlust der Wirksamkeit auftritt. Eine Verwendung derjenigen Tenside, die bis zum Schmelzpunkt des Wassers in Lösung bleiben, ist bei Temperaturen unter 0°C möglich, wenn der Schmelzpunkt des Wassers durch Zumischung organischer Lösungsmittel, wie z.B. Ethylenglykol oder Isopropanol, erniedrigt wird. Eine Absenkung der Schmelztemperatur des Wassers durch Elektrolytzugabe, wie z.B. NaCl, ohne Verlust der Wirksamkeit ist nur bedingt möglich.For each of the compounds of the formulas I and II, depending on the temperature, there is a different lower critical concentration limit for a sufficient corrosion protection effect, which, however, as described further below, can be determined by a simple preliminary test. The effect depends on the temperature. The compounds mentioned act overall in a temperature range from 0 ° C to 145 ° C; however, a single compound shows effectiveness only over a temperature interval of approx. 45 ° C (± 25 ° C). The lower temperature limit for all compounds is the solubility temperature (isotropic solution) or better the Krafft point. However, if the surfactant is in solution, the solubility temperature can in most cases fall below 5 to 25 ° C. for a few hours to weeks without loss of effectiveness. The use of those surfactants which remain in solution up to the melting point of the water is possible at temperatures below 0 ° C if the melting point of the water is admixed with organic solvents, e.g. Ethylene glycol or isopropanol, is lowered. Lowering the melting temperature of the water by adding electrolyte, e.g. NaCl, without loss of effectiveness is only possible to a limited extent.

Von einigen Verbindungen der Formel I, wie z.B. dem Hexadecylpyridiniumsalicylat ist bekannt (H. Hoffmann et al., Ber. Bunsenges. Phys. Chem. 85 (1981) 255), daß sie ab einer ganz bestimmten, für jedes Tensid charakteristischen Konzentration, der CMC11, nichtkugelförmige, meist stäbchenförmige Mizellen aus den einzelnen Tensidionen und Gegenionen aufbauen.Some compounds of the formula I, such as, for example, hexadecylpyridinium salicylate, are known (H. Hoffmann et al., Ber. Bunsenges. Phys. Chem. 85 (1981) 255) that they start from a very specific concentration which is characteristic of each surfactant and which Build CMC 11 , non-spherical, usually rod-shaped micelles from the individual surfactant ions and counterions.

überraschenderweise wurde nun gefunden, daß Tenside in wäßriger Lösung immer dann als Korrosionsschutzmittel wirksam sind, wenn sie für Konzentrationen größer der CMCII nichtkugelförmige, vorzugsweise stäbchenförmige Mizellen ausbilden. Nichtkugelförmige, vorzugsweise stäbchenförmige Mizellen liegen vor, wenn bei der Untersuchung der isotropen Tensidlösung mit Hilfe der Methode der elektrischen Doppelbrechung mit gepulstem, rechteckförmigen elektrischen Feld (E. Fredericq und C. Housier, Electric Dichroism and Electric Birefringence, Claredon Press, Oxford 1973 und H. Hoffmann et al., Ber. Bunsenges. Phys. Chem. 85 (1981) 255) ein Meßsignal gefunden wird, aus dessen Abfall sich eine Relaxationszeit von >0,5 µs bestimmen läßt. Die untere Konzentrationsgrenze, ab der ein Tensid in wäßriger Lösung als Korrosionsschutzmittel wirksam ist, wird daher immer durch die CMCII, vorzugsweise durch den 1,5 bis 3-fachen Konzentrationswert der CMCII, festgelegt. Die Bestimmung der CMCII ist z.B. durch Messung der elektrischen Leitfähigkeit der Tensidlösung in Abhängigkeit von der Tensidkonzentration möglich, wie bei H. Hoffmann et al. (Ber. Bunsenges. Phys. Chem. 85 (1981) 255) beschrieben. Es zeigte sich, daß der Wert der CMCII temperaturabhängig ist und sich mit zunehmender Temperatur zu höheren Tensidkonzentrationen verschiebt.Surprisingly, it has now been found that surfactants in aqueous solution are always effective as corrosion inhibitors if they form non-spherical, preferably rod-shaped micelles for concentrations greater than the CMC II . Non-spherical, preferably rod-shaped micelles are present when the isotropic surfactant solution is examined using the electrical birefringence method with a pulsed, rectangular electrical field (E. Fredericq and C. Housier, Electric Dichroism and Electric Birefringence, Claredon Press, Oxford 1973 and H Hoffmann et al., Ber. Bunsenges. Phys. Chem. 85 (1981) 255), a measurement signal is found, from the drop of which a relaxation time of> 0.5 μs can be determined. The lower concentration limit above which a surfactant in aqueous solution is effective as a corrosion protection agent is therefore always determined by the CMC II , preferably by 1.5 to 3 times the concentration value of the CMC II . The CMC II can be determined, for example, by measuring the electrical conductivity of the surfactant solution as a function of the surfactant concentration, as in H. Hoffmann et al. (Ber. Bunsenges. Phys. Chem. 85 (1981) 255). It was shown that the value of the CMC II is temperature-dependent and shifts to higher surfactant concentrations with increasing temperature.

Auch bei den Salzen der Formel I kann die Konzentration, die minimal notwendig ist, um eine ausreichende Korrosionsschutzwirkung in einem bestimmten Temperaturbereich zu erzielen, durch die Bestimmung der CMCII bei der Anwen- dungstemperatur mit Hilfe der elektrischen Leitfähigkeit ermittelt werden.In the case of the salts of the formula I as well, the minimum concentration required to achieve a sufficient corrosion protection effect in a certain temperature range can be determined by determining the CMC II temperature can be determined using electrical conductivity.

Die Prüfung der Korrosionsschutzwirkung in den folgenden Beispielen erfolgte auf die übliche Weise durch Bestimmung des Masseverlustes von Proben der metallischen Werkstoffe (Probecoupons), in bestimmten Fällen, in denen ausschließlich Säurekorrosion vorherrscht, auch durch Bestimmung der Abtragsraten aus dem Polarisationswiderstand. Durch Vergleich mit den Abtragsraten in Lösungen ohne Zusätze kann die Wirksamkeit w des einzelnen Inhibitors berechnet werden:

Figure imgb0013
wobei V die Abtragsrate ohne Inhibitor, VI die Abtragsrate mit Inhibitor bedeutet.The corrosion protection effect in the following examples was tested in the usual way by determining the loss of mass of samples of the metallic materials (sample coupons), in certain cases in which only acid corrosion predominated, also by determining the removal rates from the polarization resistance. The effectiveness w of the individual inhibitor can be calculated by comparison with the removal rates in solutions without additives:
Figure imgb0013
 where V is the removal rate without inhibitor, V I is the removal rate with inhibitor.

Beispiel 1example 1

Die Abtragsraten und die Inhibitorwirksamkeit der Verbindung Hexadecyltrimethylammonium Salicylat, C16TA-Sal, wurde in den Konzentrationen 0,075 Gew.-% und 0,1 Gew.-% in Lösungen mit vollentsalztem Wasser (VE Wasser) durch Messung des Polarisationswiderstandes bestimmt. Dazu wurde ein Meßgerät der Firma Magnachem (Corrater-Modell 1136) verwendet. Die Ergebnisse sind in Tabelle 1 zusammengefaßt. Untersucht wurden unlegierter Stahl (ST 37) und Kupfer.

Figure imgb0014
The removal rates and the inhibitory activity of the compound hexadecyltrimethylammonium salicylate, C 16 TA-Sal, were determined in concentrations of 0.075% by weight and 0.1% by weight in solutions with deionized water (DI water) by measuring the polarization resistance. A measuring device from Magnachem (Corrater model 1136) was used for this. The results are summarized in Table 1. Unalloyed steel (ST 37) and copper were examined.
Figure imgb0014

Beispiel 2Example 2

Wie in Beispiel 1 beschrieben, wurden Lösungen von Hexadecyltrimethylammonium-3-hydroxi-2-naphthoat (C16TA-Bons) in VE-Wasser auf ihre Inhibitorwirksamkeit für Kupfer und unlegierten Stahl (ST 37) untersucht. Bei einer Meßtemperatur von 50°C wurden die folgenden Konzentrationen untersucht:

  • 0,01; 0,025; 0,05; 0,075 und 0,1 Gew.-%
  • Tabelle 2 faßt die Ergebnisse zusammen.
    Figure imgb0015
As described in Example 1, solutions of hexadecyltrimethylammonium-3-hydroxy-2-naphthoate (C 16 TA-Bons) in demineralized water were tested for their inhibitory activity for copper and unalloyed steel (ST 37). The following concentrations were examined at a measuring temperature of 50 ° C:
  • 0.01; 0.025; 0.05; 0.075 and 0.1% by weight
  • Table 2 summarizes the results.
    Figure imgb0015

Beispiel 3Example 3

Die Abtragsraten von unlegiertem Stahl und Kupfer in belüftetem und unbelüftetem VE-Wasser mit Zusatz von 0,04, 0,05 und 0,075 Gew.-% C16TA-Bons wurden in einer Durchströmungsapparatur durch Einbringen von Probecoupons und Rohrproben bestimmt. Die Ergebnisse enthält Tabelle 3.The removal rates of unalloyed steel and copper in aerated and non-aerated demineralized water with the addition of 0.04, 0.05 and 0.075% by weight of C 16 TA vouchers were determined in a flow-through apparatus by introducing test coupons and pipe samples. The results are shown in Table 3.

Figure imgb0016
Figure imgb0016

Beispiel 4Example 4

Wie in Beispiel 3 beschrieben, wurden Lösungen von Docosyl- trimethylammonium-3-hydroxi-2-naphthoat in VE-Wasser von 100 bzw. 120°C auf ihre Abtragsraten für unlegierten Stahl (ST37) untersucht. Bei einer Konzentration von 0,125 Gew.-% wurden Werte kleiner 0,01 mm/Jahr gemessen.As described in Example 3, solutions of docosyltrimethylammonium-3-hydroxy-2-naphthoate in demineralized water at 100 or 120 ° C. were examined for their removal rates for unalloyed steel (ST37). At a concentration of 0.125% by weight, values less than 0.01 mm / year were measured.

Beispiel 5Example 5

Wie in Beispiel 3 beschrieben, wurden Lösungen von Octadecyl- di(hydroxiethyl)aminoxid in belüftetem VE-Wasser von 65°C auf ihre Abtragsraten für unlegierten Stahl (ST37) untersucht. Ohne Zusatz beträgt die Abtragsrate 0,3 mm/Jahr, mit 2 Gew.-% der Substanz weniger als 0,01 mm/Jahr.As described in Example 3, solutions of octadecyldi (hydroxiethyl) amine oxide in aerated demineralized water at 65 ° C. were examined for their removal rates for unalloyed steel (ST37). Without additive, the removal rate is 0.3 mm / year, with 2% by weight of the substance less than 0.01 mm / year.

Beispiel 6Example 6

Wie in Beispiel 1 beschrieben, wurden Lösungen von C16TA-BONS in 0,1 n Salzsäure von 65°C auf ihre Abtragsraten für unlegierten Stahl (ST37) untersucht. Der Wert für die Konzentration 0 beträgt 6,3 mm/Jahr, für 0,0075 Gew.-% 1,5 mm/Jahr und 0,075 Gew.-% 1,2 mm/Jahr, entsprechend 76 % und 81 % Inhibitorwirksamkeit.As described in Example 1, solutions of C 16 TA-BONS in 0.1 N hydrochloric acid at 65 ° C. were examined for their removal rates for unalloyed steel (ST37). The value for the concentration 0 is 6.3 mm / year, for 0.0075% by weight 1.5 mm / year and 0.075% by weight 1.2 mm / year, corresponding to 76% and 81% inhibitor activity.

Beispiel 7Example 7

Wie in Beispiel 3 beschrieben, wurden Lösungen von C16TA-BONS in 0,1 n Salzsäure von 65°C auf Abtragsrate für unlegierten Stahl (ST37) untersucht. Der Wert für die Konzentration 0 beträgt 16,2 mm/Jahrfür 0,075 Gew.-% 0,9 mm/Jahr entsprechend 94 % Inhibitorwirksamkeit.As described in Example 3, solutions of C 16 TA-BONS in 0.1 N hydrochloric acid at 65 ° C. were examined for the removal rate for unalloyed steel (ST37). The value for concentration 0 is 16.2 mm / year for 0.075% by weight 0.9 mm / year corresponding to 94% inhibitor activity.

Beispiel 8Example 8

In einem Versuchsstand zur Untersuchung des Berstverhaltens von Kunststoffmembranen, der aus Messing, unlegiertem Stahl und verzinkten Stahrohren besteht mit einem Gesamtvolumen von 200 1 belüftetem VE-Wasser (T= 80°C), wurde eine starke abtragende Korrosion festgestellt. Der Zusatz von kommerziellen Inhibitoren auf Phosphatbasis (DIANODIC II, Fa. Betz, Düsseldorf) brachte nur einen unbefriedigenden Korrosionsschutz, erkennbar an der Bildung und dem Austrag von Korrosionsprodukten. Der Zusatz an 0,1 Gew.-% C16TA-BONS verhinderte die Ausbildung von Korrosionsprodukten vollständig. An zusätzlich eingehängten Probecoupons aus unlegiertem Stahl (ST37) bestimmte Abtragsraten (Versuchszeit 140 h) waren kleiner als 0,01 mm/Jahr.In a test stand to investigate the bursting behavior of plastic membranes, which consists of brass, unalloyed steel and galvanized steel pipes with a total volume of 200 liters of aerated demineralized water (T = 80 ° C), strong abrasive corrosion was found. The addition of commercial phosphate-based inhibitors (DIANODIC II, Betz, Düsseldorf) only provided unsatisfactory corrosion protection, recognizable by the formation and discharge of corrosion products. The addition of 0.1% by weight of C 16 TA-BONS completely prevented the formation of corrosion products. The removal rates (test time 140 h) on additional coupons made of unalloyed steel (ST37) were less than 0.01 mm / year.

Claims (3)

1. Verfahren zur Vermeidung der Korrosion metallischer Werkstoffe in wäßrigen Medien, dadurch gekennzeichnet, daß man dem wäßrigen Medium eine Verbindung der Formeln I oder II R1-(C2H40)n-K(+) A(-) (I) oder
Figure imgb0017
zugibt, wobei R1 C 12-C 26-Alkyl oder C12-C26-Alkenyl, n eine Zahl von 0 bis 5, K(+) eine Gruppe der Formeln
Figure imgb0018
 R 2 C1-C3-Alkyl, R 3 C1-C3-Alkyl oder eine Gruppe der Formel -(C2H4O)xH, x eine Zahl von 1 bis 3. A(-) ein Anion der folgenden Formeln: SCN(-), R4SO3 (-) wo R4 C6-C9-Alkyl oder C6-C9-Alkenyl ist und die Summe der C-Atome in R1 und R4 mindestens 21 betragen soll;
Figure imgb0019
wo Hal Fluor, Chlor, Brom oder Jod, R5 C1-C5-Alkyl, C2-C5-Alkenyl oder C1-C5-Alkoxy in den Stellungen 3, 4, 5 und 6 und R6 Wasserstoff oder Hydroxy in den Stellungen 2 und 3 zur Carboxyl-Gruppe und
Figure imgb0020
 wo R7 COO- oder SO3 (-) und R8 Wasserstoff oder Methyl ist, R9 eine Gruppe der Formel R'1-(OCH2CH2)n-, C8-C18-Alkylaryl oder Aryl-C8-C18-alkyl, Ri C14-C22-Alkyl oder C 14-C 22-Alkenyl, n eine Zahl von 0 bis 5 und die Reste R10 gleich sind und C1-C4-Alkyl oder C1-C4-Hydroxialkyl bedeuten. 1. A method for avoiding corrosion of metallic materials in aqueous media, characterized in that the aqueous medium is a compound of the formula I or II R 1 - (C 2 H 4 0) n -K (+) A (-) (I ) or
Figure imgb0017
 admits where R 1 is C 12 - C 26 alkyl or C 12 -C 26 -alkenyl, n is a number from 0 to 5, K (+) a group of the formulas
Figure imgb0018
 R 2 C 1 -C 3 alkyl, R 3 C 1 -C 3 alkyl or a group of the formula - (C 2 H 4 O) x H, x is a number from 1 to 3. A ( - ) is an anion of following formulas: SCN (-) , R 4 SO 3 (-) where R 4 is C 6 -C 9 alkyl or C 6 -C 9 alkenyl and the sum of the C atoms in R 1 and R 4 is at least 21 should;
Figure imgb0019
 where Hal is fluorine, chlorine, bromine or iodine, R 5 is C 1 -C 5 alkyl, C 2 -C 5 alkenyl or C 1 -C 5 alkoxy in positions 3, 4, 5 and 6 and R 6 is hydrogen or Hydroxy in positions 2 and 3 to the carboxyl group and
Figure imgb0020
 where R 7 is COO - or SO 3 (-) and R 8 is hydrogen or methyl, R 9 is a group of the formula R ' 1 - (OCH 2 CH 2 ) n - , C 8 -C 18 alkylaryl or aryl-C 8 -C 18 alkyl, R 1 C 14 -C 22 alkyl or C 14 - C 22 alkenyl, n is a number from 0 to 5 and the radicals R 10 are the same and C 1 -C 4 alkyl or C 1 -C 4 -Hydroxialkyl mean. 2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß man die Verbindungen der Formel I in einer Menge von 0,01 bis 5 Gew.-% und die Verbindungen der Formel II in einer Menge von 0,075 bis 3 Gew.-% einsetzt.2. The method according to claim 1, characterized in that the compounds of formula I in an amount of 0.01 to 5 wt .-% and the compounds of formula II in an amount of 0.075 to 3 wt .-%. 3. Korrosionsschutzmittel enthaltend eine Verbindung der Formel I oder II nach Anspruch 1.3. Corrosion protection agent containing a compound of formula I or II according to claim 1.
EP86108576A 1985-06-28 1986-06-24 Process for preventing corrosion of metallic materials Expired - Lifetime EP0206311B1 (en)

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