EP1041174B1 - Melamine containing corrosion inhibiting composition - Google Patents

Melamine containing corrosion inhibiting composition Download PDF

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Publication number
EP1041174B1
EP1041174B1 EP99106518A EP99106518A EP1041174B1 EP 1041174 B1 EP1041174 B1 EP 1041174B1 EP 99106518 A EP99106518 A EP 99106518A EP 99106518 A EP99106518 A EP 99106518A EP 1041174 B1 EP1041174 B1 EP 1041174B1
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Prior art keywords
acid
corrosion inhibitor
aqueous
corrosion
melamine
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German (de)
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EP1041174A1 (en
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Stefan Graichen
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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

Definitions

  • the invention relates to a melamine-containing anticorrosive and aqueous systems in which this anti-corrosion agent is used.
  • the free polycarboxylic acids are generally solid substances. During their manufacture, they are usually filtered out isolated from an aqueous phase. The filtered product is usually washed with water and then dried subjected. To the energy required for drying save, one has recently for use in aqueous Systems the moist filter cake, which is about 50% water contains, offered as a commercial form. The moist filter cake has the disadvantage, however, that it is not flowable. He can not to be poured or poured, but with the Bucket dosed or decanted manually. That's why too have already been proposed in the form of polycarboxylic acids use high-percentage aqueous dispersions.
  • Corrosion inhibitors also developed on the basis of melamine are already known. For example, US-A-2,485 309 methylolmelamine condensation products described but the high demands that are placed on an anti-corrosion agent today are not sufficient. About that from European patent application 0 846 690 already melamine polycarboxamides and their use as Anticorrosive known. It is for their manufacture however, the polycarboxylic acid or the like is required Polycarboxylic acid halide, the polycarboxylic anhydride or the polycarboxylic acid ester in a reaction vessel melt using heat and then, if necessary, also using an inert protective gas melamine in the Stir in the melt. This reaction generally a temperature between 120 and 180 ° C maintained.
  • the reaction product can then after cooling from the reaction vessel removed and in an aqueous alkaline solution to the anti-corrosion agent. Because this manufacture the melamine polycarboxylic acid amide was expensive the task of an equally good or better effective anti-corrosion agent to develop on the basis of melamine, in which the production of Acid amide bonds are not required.
  • a corrosion protection agent the melamine and an organic polycarboxylic acid of the formula I. in a molar ratio of 1: 1.5 to 1: 5, preferably in a molar ratio of 1: 3, where X is a straight-chain or branched alkylene or alkylidene radical having 1 to 20 carbon atoms, which carry one or more hydroxyl or carboxyl groups and a cyclopentylene , Cyclohexylene or phenylene group.
  • Suitable polycarboxylic acids are butanedioic acid, pentanedioic acid, hexanedioic acid, the heptanedioic acid, the nonanedioic acid and particularly preferably also as Decanedioic acid called sebacic acid.
  • the carbon chain of these dicarboxylic acids can also contain a cyclopentylene, cyclohexylene or phenylene radical.
  • Dicarboxylic acid can be combined in the anticorrosive agent according to the invention be included with melamine.
  • Polycarboxylic acids in particular mixtures of several dicarboxylic acids, can be used in the anti-corrosion agent according to the invention can be used.
  • polycarboxylic acids mentioned can also be monocarboxylic acids
  • Example the isononanoic acid may be present in the mixture.
  • the carboxylic acids mentioned react with melamine in aqueous solution Salt formation.
  • the resulting salts are characterized by sufficient solubility in water so that aqueous solutions can be prepared that these compounds in an amount of 0.1 to 10 percent by weight contain.
  • the anti-corrosion agent according to the invention is preferred used in aqueous systems.
  • aqueous system are water circuits, for example cooling water circuits, Circulations of aqueous machine fluids and coolants that are used during drilling, grinding, milling, Turning, cutting, sawing, grinding, thread cutting or used in rolling and drawing metals.
  • Antifreeze or hydraulic fluids Glycol water base as well as aqueous paints, for example Dispersion paints or aqueous powder coatings can be used with the Corrosion protection agent according to the invention anticorrosive be equipped.
  • the anti-corrosion agent according to the invention can be in aqueous Systems as a sole addition or in combination with others Additives are used.
  • Additives are used.
  • Known corrosion inhibitors such as Phosphonates, phosphonocarboxylic acids or phosphinocarboxylic acids, N-acyl sarcosines, imidazolines, triethanolamine or fatty amines.
  • Copper passivators such as water-soluble benzotriazoles, Methylene-bis-benzotriazoles or 2-mercaptobenzothiazoles can be added.
  • Dispersants and Carriers such as poly (meth) acrylic acid and its salts, hydrolyzed polyacrylonitrile, polyacrylamide and the like Copolymers, lignin sulfonic acid and its salts, starch and Starch derivatives, cellulose, alkylphosphonic acids, 1-aminoalkyl-1,1-diphosphonic acids and their salts, polymaleic acids and other polycarboxylic acids or alkali phosphates are added.
  • additives can be precipitants, such as alkali phosphates or alkali carbonates, oxygen scavengers such as Alkali sulfates or hydrazine, complexing agents such as Nitrilotriacetic acid or ethylenediamine tetraacetic acid and their salts or anti-foaming agents such as distearyl sebacic acid diamide, Distearyladipinklarediamid or ethylene oxide or Propylene oxide condensation products of such amides as well Fatty alcohols and their ethylene oxide condensation products.
  • precipitants such as alkali phosphates or alkali carbonates, oxygen scavengers such as Alkali sulfates or hydrazine
  • complexing agents such as Nitrilotriacetic acid or ethylenediamine tetraacetic acid and their salts or anti-foaming agents
  • the anti-corrosion agents according to the invention can also in Form of aqueous dispersions can be used.
  • Dispersants are suitable for all surface-active compounds, especially anionic and non-ionic surfactants.
  • Such dispersions can be thickened to be stabilized, with stabilizers in particular modified polysaccharides from xanthan, alginate, guar or Cellulose type used. This also includes cellulose ethers such as Methyl cellulose or carboxymethyl cellulose and heteropolysaccharides.
  • the dispersions according to the invention can still more Contain auxiliaries, for example hydrotropic agents such as Urea or sodium xylene sulfonate; Antifreeze like Ethylene or propylene glycol, diethylene glycol, glycerin or sorbitol; Biocides such as chloroacetamide, formalin or 1,2-benzisothiazolin-3-one or complexing agents.
  • hydrotropic agents such as Urea or sodium xylene sulfonate
  • Antifreeze like Ethylene or propylene glycol, diethylene glycol, glycerin or sorbitol
  • Biocides such as chloroacetamide, formalin or 1,2-benzisothiazolin-3-one or complexing agents.
  • the dispersions thus produced are at Room temperature as well as several at temperatures up to 40 ° C Stable for months. They keep their fluidity and segregate not yourself. That is for the storage and transportation of the Dispersions are an important property. For using the Dispersions have the advantage that they are like liquids can be handled and become very quickly in alkaline water Systems.
  • Corrosion protection agent was carried out according to the Regulation of DIN 51360 part II. Serve as a measure of corrosion the corrosion drawings on a round filter paper, which when exposed to artificially corrosive water on gray cast iron chips in the presence of the anti-corrosion agent arise. The test is carried out in the following way:
  • water with a total hardness of 3.58 mmol is made from CaCl 2 x 6 H 2 O and MgSO 4 x 7 H 2 O, mixed with 3% of the above-mentioned corrosion protection agent and with this Solution that wets gray cast iron chips distributed on round filters in a Petri dish. After a dwell time of 2 hours at room temperature, the gray cast iron chips are removed from the round filter, the round filter rinsed and dried, and the degree of corrosion is then determined visually in accordance with the table in DIN 51360, Part II. The results obtained are shown in the table above.

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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)
  • Treatment And Processing Of Natural Fur Or Leather (AREA)
  • Chemical And Physical Treatments For Wood And The Like (AREA)

Abstract

Corrosion inhibitor composition comprises melamine and a polycarboxylic acid (I) in a molar ratio of 1:1.5-5, preferably 1:3 Corrosion inhibitor composition comprises melamine and a polycarboxylic acid of formula (I) in a molar ratio of 1:1.5-5, preferably 1:3. HOOC-X-COOH (I) X = 1-20C alkylene or alkylidene, optionally substituted by OH or COOH and optionally interrupted by cyclopentylene, cyclohexylene or phenylene. An Independent claim is also included for an aqueous system containing the corrosion inhibitor composition in an amount of 0.1-10 wt.%.

Description

Gegenstand der Erfindung ist ein Melamin enthaltendes Korrosionsschutzmittel und wässrige Systeme, in denen dieses Korrosionsschutzmittel eingesetzt wird.The invention relates to a melamine-containing anticorrosive and aqueous systems in which this anti-corrosion agent is used.

Es ist bekannt, dass erhebliche Anstrengungen unternommen werden, um die Korrosion von Metallen zu vermindern. So ist in der europäischen Patentschrift 46 139 die Verwendung von Triazincarbonsäuren als Korrosionsinhibitoren für wässrige Systeme, die in Kontakt mit Eisen oder eisenhaltigen Metallen stehen, vorgeschlagen worden.It is known that considerable efforts are being made to achieve this Reduce corrosion of metals. So in European patent specification 46 139 the use of triazine carboxylic acids as corrosion inhibitors for aqueous Systems in contact with iron or ferrous metals have been proposed Service.

Aus der US-Patentschrift US-A-3 976 588 ist bereits die Verwendung von Melamin als Korrosionsschutzmittel in Textilreinigungsmitteln erwähnt; in der US-Patentschrift US-A-4 647 392 wird ein Korrosionsschutzmittel für wässrige und alkoholische Frostschutzmittel, dass aus einer Kombination aus aliphatischen Monocarbonsäuren oder Dicarbonsäuren und Hydroxycarboxyl-Triazolen besteht. Des weiteren sind aus der europäischen Patentschrift 511 163 fließfähige wässrige Dispersionen bekannt, die einen festen Polycarbonsäuretriazin-Korrosionsinhibitor enthalten. Weiterhin ist aus US-A-4 402 907 und der EP-A-129 506 bekannt, dass bestimmte heterozyklische Polycarbonsäuren als Korrosionsinhibitoren für wässrige Systeme, die mit Metallen in Kontakt stehen, gut geeignet sind. Sie können in wässrigen Systemen, zum Beispiel in Kühlwassersystemen, in Dampferzeugungsanlagen, in Metallbearbeitungsmitteln und wässrigen Hydraulikflüssigkeiten verwendet werden. Da die meisten Polycarbonsäuren in Wasser nur eine geringe Löslichkeit haben, verwendet man die Polycarbonsäuren in Form ihrer wasserlöslichen Salze, d.h., man neutralisiert sie vor dem Gebrauch oder man setzt sie einem basischen Wassersystem zu. Lager- und Handelsform sind jedoch im allgemeinen die freien Polycarbonsäuren. The use of melamine is already known from US Pat. No. 3,976,588 mentioned as an anti-corrosion agent in textile cleaning agents; in the U.S. patent US-A-4 647 392 becomes an anti-corrosion agent for aqueous and alcoholic Antifreeze that is made from a combination of aliphatic monocarboxylic acids or dicarboxylic acids and hydroxycarboxyl triazoles. Furthermore are out European patent 511 163 known as flowable aqueous dispersions, which contain a solid polycarboxylic acid triazine corrosion inhibitor. Furthermore is known from US-A-4 402 907 and EP-A-129 506 that certain heterocyclic polycarboxylic acids as corrosion inhibitors for aqueous systems, that are in contact with metals are well suited. You can in watery Systems, for example in cooling water systems, in steam generating plants, in Metalworking agents and aqueous hydraulic fluids are used. Since most polycarboxylic acids are only slightly soluble in water, the polycarboxylic acids are used in the form of their water-soluble salts, i.e. man neutralize them before use or put them in a basic Water system too. Storage and trading forms are, however, generally the free ones Polycarboxylic acids.

Die freien Polycarbonsäuren sind im allgemeinen feste Stoffe. Bei ihrer Herstellung werden sie meist durch Filtration aus einer wässrigen Phase isoliert. Das filtrierte Produkt wird üblicherweise mit Wasser gewaschen und dann einer Trocknung unterzogen. Um die für die Trocknung benötigte Energie zu sparen, hat man neuerdings für die Verwendung in wässrigen Systemen den feuchten Filterkuchen, der etwa 50% Wasser enthält, als Handelsform angeboten. Der feuchte Filterkuchen hat jedoch den Nachteil, dass er nicht fließfähig ist. Er kann nicht geschüttet oder gegossen werden, sondern wird mit der Schaufel manuell dosiert oder umgefüllt. Deshalb ist auch schon vorgeschlagen worden, Polycarbonsäuren in Form von hochprozentigen wässrigen Dispersionen einzusetzen.The free polycarboxylic acids are generally solid substances. During their manufacture, they are usually filtered out isolated from an aqueous phase. The filtered product is usually washed with water and then dried subjected. To the energy required for drying save, one has recently for use in aqueous Systems the moist filter cake, which is about 50% water contains, offered as a commercial form. The moist filter cake has the disadvantage, however, that it is not flowable. He can not to be poured or poured, but with the Bucket dosed or decanted manually. That's why too have already been proposed in the form of polycarboxylic acids use high-percentage aqueous dispersions.

Auch auf der Basis von Melamin entwickelte Korrosionsinhibitoren sind bereits bekannt. So werden in der US-A-2 485 309 Methylolmelamin-Kondensationsprodukte beschrieben, die aber den hohen Anforderung, welche heute an ein Korrosionsschutzmittel gestellt werden, keinesfalls genügen. Darüber hinaus sind aus der europäischen Patentanmeldung 0 846 690 bereits Melaminpolycarbonsäureamide und ihre Verwendung als Korrosionsschutzmittel bekannt. Zu deren Herstellung ist es jedoch erforderlich, die Polycarbonsäure oder das entsprechende Polycarbonsäurehalogenid, das Polycarbonsäureanhydrid oder den Polycarbonsäureester in einem Reaktionsgefäß unter Anwendung von Hitze aufzuschmelzen und dann, ggf. auch unter Anwendung eines inerten Schutzgases Melamin in die Schmelze einzurühren. Bei dieser Reaktion wird im Allgemeinen eine Temperatur zwischen 120 und 180°C eingehalten. Nach etwa 30 Minuten ist die Reaktion im wesentlichen beendet. Das Reaktionsprodukt kann dann nach dem Erkalten aus dem Reaktionsgefäß entnommen und in einer wässrig alkalischen Lösung zum Korrosionsschutzmittel gelöst werden. Da diese Herstellung der Melaminpoly-carbonsäureamide aufwendig ist, stellte sich die Aufgabe, ein gleich gut oder besser wirksames Korrosionsschutzmittel auf Melaminbasis zu entwickeln, bei dem die Herstellung von Säureamidbindungen nicht erforderlich ist.Corrosion inhibitors also developed on the basis of melamine are already known. For example, US-A-2,485 309 methylolmelamine condensation products described but the high demands that are placed on an anti-corrosion agent today are not sufficient. About that from European patent application 0 846 690 already melamine polycarboxamides and their use as Anticorrosive known. It is for their manufacture however, the polycarboxylic acid or the like is required Polycarboxylic acid halide, the polycarboxylic anhydride or the polycarboxylic acid ester in a reaction vessel melt using heat and then, if necessary, also using an inert protective gas melamine in the Stir in the melt. This reaction generally a temperature between 120 and 180 ° C maintained. After about The reaction is essentially complete in 30 minutes. The The reaction product can then after cooling from the reaction vessel removed and in an aqueous alkaline solution to the anti-corrosion agent. Because this manufacture the melamine polycarboxylic acid amide was expensive the task of an equally good or better effective anti-corrosion agent to develop on the basis of melamine, in which the production of Acid amide bonds are not required.

Es wurde nun gefunden, dass diese Aufgabe durch ein Korrosionsschutzmittel gelöst wird, das Melamin und eine organische Polycarbonsäure der Formel I

Figure 00040001
im Molverhältnis 1 : 1,5 bis 1 : 5 vorzugsweise im Molverhältnis 1 : 3, enthält, wobei X ein geradkettiger oder verzweigter Alkylen- oder Alkylidenrest mit 1 bis 20 Kohlenstoffatomen ist, der eine oder mehrere Hydroxyl- oder Carboxylgruppen tragen und eine Cyclopentylen-, Cyclohexylen- oder Phenylengruppe enthalten kann.It has now been found that this problem is solved by a corrosion protection agent, the melamine and an organic polycarboxylic acid of the formula I.
Figure 00040001
in a molar ratio of 1: 1.5 to 1: 5, preferably in a molar ratio of 1: 3, where X is a straight-chain or branched alkylene or alkylidene radical having 1 to 20 carbon atoms, which carry one or more hydroxyl or carboxyl groups and a cyclopentylene , Cyclohexylene or phenylene group.

Geeignete Polycarbonsäuren sind die Butandisäure, die Pentandisäure, die Hexandisäure, die Heptandisäure, die Nonandisäure und besonders bevorzugt die auch als Sebacinsäure bezeichnete Decandisäure. Die Kohlenstoffkette dieser Dicarbonsäuren kann auch einen Cyclopentylen-, Cyclohexylen- oder Phenylenrest enthalten. Auch Zitronensäure oder eine Ethylenoxid- oder Propylenoxid-Einheiten enthaltende Dicarbonsäure kann in dem erfindungsgemäßen Korrosionsschutzmittel zusammen mit Melamin enthalten sein. Auch Gemische mehrerer unterschiedlicher Polycarbonsäuren, insbesondere Gemische mehrerer Dicarbonsäuren können in dem erfindungsgemäßen Korrosionsschutzmittel verwendet werden. Zusätzlich zu den genannten Polycarbonsäuren können auch noch Monocarbonsäuren, zum Beispiel die Isononansäure in dem Gemisch vorhanden sein.Suitable polycarboxylic acids are butanedioic acid, pentanedioic acid, hexanedioic acid, the heptanedioic acid, the nonanedioic acid and particularly preferably also as Decanedioic acid called sebacic acid. The carbon chain of these dicarboxylic acids can also contain a cyclopentylene, cyclohexylene or phenylene radical. Also citric acid or one containing ethylene oxide or propylene oxide units Dicarboxylic acid can be combined in the anticorrosive agent according to the invention be included with melamine. Mixtures of several different ones Polycarboxylic acids, in particular mixtures of several dicarboxylic acids, can be used in the anti-corrosion agent according to the invention can be used. In addition to the polycarboxylic acids mentioned can also be monocarboxylic acids Example the isononanoic acid may be present in the mixture.

Die genannten Carbonsäuren reagieren mit Melamin in wässriger Lösung unter Salzbildung. Die dabei entstehenden Salze zeichnen sich durch eine ausreichende Löslichkeit in Wasser aus, so dass wässrige Lösungen hergestellt werden können, die diese Verbindungen in einer Menge von 0,1 bis 10 Gewichtsprozent enthalten. Insbesondere empfiehlt es sich zur Erhöhung der Löslichkeit die freien Carboxylgruppen durch Alkali-, Ammonium- oder insbesondere Triethanolammonium-Kationen zu neutralisieren.The carboxylic acids mentioned react with melamine in aqueous solution Salt formation. The resulting salts are characterized by sufficient solubility in water so that aqueous solutions can be prepared that these compounds in an amount of 0.1 to 10 percent by weight contain. In particular, it is recommended to increase the solubility of the free carboxyl groups by alkali, Ammonium or in particular triethanolammonium cations neutralize.

Das erfindungsgemäße Korrosionsschutzmittel wird vorzugsweise in wässrigen Systemen verwendet. Bei dem wässrigen System handelt es sich um Wasserkreisläufe, beispielsweise Kühlwasserkreisläufe, Kreisläufe von wässrigen Maschinenflüssigkeiten und Kühlflüssigkeiten, die beim Bohren, Mahlen, Fräsen, Drehen, Schneiden, Sägen, Schleifen, Gewindeschneiden oder beim Walzen und Ziehen von Metallen eingesetzt werden. Auch Gefrierschutzmittel oder hydraulische Flüssigkeiten auf Glykol-Wasserbasis sowie wässrige Anstrichmittel, zum Beispiel Dispersionsfarben oder wässrige Pulverlacke, können mit dem erfindungsgemäßen Korrosionsschutzmittel antikorrosiv ausgerüstet werden.The anti-corrosion agent according to the invention is preferred used in aqueous systems. With the aqueous system are water circuits, for example cooling water circuits, Circulations of aqueous machine fluids and coolants that are used during drilling, grinding, milling, Turning, cutting, sawing, grinding, thread cutting or used in rolling and drawing metals. Also Antifreeze or hydraulic fluids Glycol water base as well as aqueous paints, for example Dispersion paints or aqueous powder coatings can be used with the Corrosion protection agent according to the invention anticorrosive be equipped.

Das erfindungsgemäße Korrosionsschutzmittel kann in wässrigen Systemen als alleiniger Zusatz oder in Kombination mit anderen Zusätzen verwendet werden. Beispiele für solche Zusatzstoffe in Wasserkreisläufen sind bekannte Korrosionsinhibitoren wie Phosphonate, Phosphonocarbonsäuren oder Phosphinocarbonsäuren, N-Acylsarcosine, Imidazoline, Triethanolamin oder Fettamine. Auch Kupfer-Passivatoren wie wasserlösliche Benztriazole, Methylen-bis-benztriazole oder 2-Mercaptobenzthiazole können zugesetzt werden. Weiterhin können Dispersionsmittel und Trägerstoffe wie Poly(meth)acrylsäure und ihre Salze, hydrolisiertes Polyacrylnitril, Polyacrylamid und dessen Copolymere, Ligninsulfonsäure und deren Salze, Stärke und Stärkederivate, Cellulose, Alkylphosphonsäuren, 1-Aminoalkyl-1,1-Diphosphonsäuren und ihre Salze, Polymaleinsäuren und andere Polycarbonsäuren oder Alkaliphosphate zugegeben werden. The anti-corrosion agent according to the invention can be in aqueous Systems as a sole addition or in combination with others Additives are used. Examples of such additives Known corrosion inhibitors such as Phosphonates, phosphonocarboxylic acids or phosphinocarboxylic acids, N-acyl sarcosines, imidazolines, triethanolamine or fatty amines. Copper passivators such as water-soluble benzotriazoles, Methylene-bis-benzotriazoles or 2-mercaptobenzothiazoles can be added. Dispersants and Carriers such as poly (meth) acrylic acid and its salts, hydrolyzed polyacrylonitrile, polyacrylamide and the like Copolymers, lignin sulfonic acid and its salts, starch and Starch derivatives, cellulose, alkylphosphonic acids, 1-aminoalkyl-1,1-diphosphonic acids and their salts, polymaleic acids and other polycarboxylic acids or alkali phosphates are added.

Weitere Zusatzstoffe können Fällungsmittel sein, wie Alkaliphosphate oder Alkalicarbonate, Sauerstoffabfänger wie Alkalisulfate oder Hydrazin, Komplexierungsmittel wie Nitrilotriessigsäure oder Ethylendiamin-Tetraessigsäure und deren Salze oder schaumverhütende Mittel wie Distearylsebacinsäurediamid, Distearyladipinsäurediamid oder Ethylenoxid- oder Propylenoxid-Kondensationsprodukte solcher Amide sowie Fettalkohole und ihre Ethylenoxid-Kondensationsprodukte.Other additives can be precipitants, such as alkali phosphates or alkali carbonates, oxygen scavengers such as Alkali sulfates or hydrazine, complexing agents such as Nitrilotriacetic acid or ethylenediamine tetraacetic acid and their salts or anti-foaming agents such as distearyl sebacic acid diamide, Distearyladipinsäurediamid or ethylene oxide or Propylene oxide condensation products of such amides as well Fatty alcohols and their ethylene oxide condensation products.

Wässrige Systeme, die als Maschinenflüssigkeiten verwendet werden und als ein wasserverdünnbares Schneid- oder Schleiföl eingesetzt werden, können folgende Zusammensetzungen haben:

  • a) Wässrige Lösungen des erfindungsgemäßen Korrosionsschutzmittels mit oder ohne einen Antiverschleißzusatz, die dann in einer Verdünnung von 1:50 bis 1:100 als Schleifflüssigkeit verwendet werden können;
  • b) Polyglykole, die ein erfindungsgemäßes Korrosionsschutzmittel, Biocide und ein Antiverschleißmittel enthalten und die als Schneidflüssigkeit in einer Verdünnung von 1:20 bis 1:40 und als Schleifflüssigkeit in einer Verdünnung von 1:60 bis 1:80 verwendet werden können;
  • c) Halbsynthetische Schneidöle auf ähnlicher Basis wie b), die jedoch zusätzlich 10 bis 25% eines Öls enthalten sowie genügend Emulgator, um die Flüssigkeit beim Verdünnen transparent zu halten;
  • d) Emulgierbare Mineralöl-Konzentrate, die außer dem Emulgator das erfindungsgemäße Korrosionsschutzmittel, Antiverschleißmittel, Biocide, Antischaummittel enthalten und die üblicherweise im Verhältnis 1:20 bis 1:50 mit Wasser zu einer opaken Emulsion verdünnt werden;
  • e) Produkte ähnlich d), die jedoch weniger Öl und mehr Emulgator enthalten und bei einer Verdünnung von 1:50 bis 1:100 durchscheinende Emulsionen ergeben.
    • Aqueous systems used as machine fluids and used as a water-dilutable cutting or grinding oil can have the following compositions:
  • a) aqueous solutions of the anti-corrosion agent according to the invention with or without an antiwear additive, which can then be used in a dilution of 1:50 to 1: 100 as grinding fluid;
  • b) polyglycols which contain an anti-corrosion agent according to the invention, biocides and an antiwear agent and which can be used as cutting fluid in a dilution of 1:20 to 1:40 and as grinding fluid in a dilution of 1:60 to 1:80;
  • c) Semi-synthetic cutting oils on a similar basis to b), but which additionally contain 10 to 25% of an oil and sufficient emulsifier to keep the liquid transparent when diluted;
  • d) emulsifiable mineral oil concentrates which, in addition to the emulsifier, contain the anticorrosive agent, antiwear agent, biocide, antifoam agent and which are usually diluted 1:20 to 1:50 with water to give an opaque emulsion;
  • e) Products similar to d), but which contain less oil and more emulsifier and give translucent emulsions when diluted 1:50 to 1: 100.

    • Auch in Gefrierschutzmitteln oder Hydraulikflüssigkeiten können die erfindungsgemäßen Korrosionsschutzmittel entweder allein oder in Kombination mit anderen Zusätzen verwendet werden. Zusätzlich können darin auch andere Korrosionsinhibitoren enthalten sein wie

  • a) organische Säuren, deren Salze und Ester, zum Beispiel Benzoesäure, p-tert.Butylbenzoesäure, Dinatrium-sebacat, Triethanolamin-laurat, Isononansäure, das Triethanolaminsalz der p-Toluolsulfonamido-capronsäure, Natrium-N-lauroylsarcosinat oder Nonylphenoxyessigsäure;
  • b) stickstoffhaltige Substanzen, wie Fettsäurealkanolamide, Imidazoline, Oxazoline, Triazole oder anorganische Nitrite oder Nitrate;
  • c) phosphorhaltige Substanzen, beispielsweise Aminphosphate, Phosphonsäuren oder anorganische Phosphate, wie NaH2PO4;
  • d) schwefelhaltige Substanzen, beispielsweise Salze von Petroleumsulfonaten, oder heterocyclische Verbindungen wie Natrium-mercaptobenzthiazol.
    • The anticorrosive agents according to the invention can also be used either alone or in combination with other additives in antifreeze agents or hydraulic fluids. In addition, other corrosion inhibitors can also be included, such as
  • a) organic acids, their salts and esters, for example benzoic acid, p-tert-butylbenzoic acid, disodium sebacate, triethanolamine laurate, isononanoic acid, the triethanolamine salt of p-toluenesulfonamido-caproic acid, sodium N-lauroylsarcosinate or nonylphenoxyacetic acid;
  • b) nitrogenous substances, such as fatty acid alkanolamides, imidazolines, oxazolines, triazoles or inorganic nitrites or nitrates;
  • c) phosphorus-containing substances, for example amine phosphates, phosphonic acids or inorganic phosphates, such as NaH 2 PO 4 ;
  • d) sulfur-containing substances, for example salts of petroleum sulfonates, or heterocyclic compounds such as sodium mercaptobenzothiazole.

    • Die erfindungsgemäßen Korrosionsschutzmittel können auch in Form von wässrigen Dispersionen eingesetzt werden. Als Dispergiermittel eignen sich alle oberflächenaktiven Verbindungen, insbesondere anionische und nicht ionische Tenside. Derartige Dispersionen können durch Verdickungsmittel stabilisiert werden, wobei man als Stabilisatoren vor allem modifizierte Polysaccharide vom Xanthan-, Alginat-, Guar- oder Cellulosetyp verwendet. Dazu gehören auch Celluloseäther wie Methylcellulose oder Carboxymethylcellulose und Heteropolysaccharide. Außer dem Dispergiermittel und dem Verdickungsmittel können die erfindungsgemäßen Dispersionen noch weitere Hilfsmittel enthalten, beispielsweise hydrotrope Mittel wie Harnstoff oder Natriumxylolsulfonat; Gefrierschutzmittel wie Ethylen- oder Propylenglykol, Diethylenglykol, Glycerin oder Sorbit; Biocide wie Chlorazetamid, Formalin oder 1,2-Benzisothiazolin-3-on oder Komplexbildner. Zur Herstellung der Dispersionen setzt man der wässrigen Lösung des erfindungsgemäßen Korrosionsschutzmittel das Dispergiermittel und das Verdickungsmittel sowie weitere Zusätze zu und rührt das Gemisch so lange, bis eine gleichmäßige, homogene Dispersion entstanden ist. Die so hergestellten Dispersionen sind bei Raumtemperatur sowie bei Temperaturen bis zu 40°C mehrere Monate stabil. Sie behalten ihre Fließfähigkeit und entmischen sich nicht. Das ist für die Lagerung und den Transport der Dispersionen eine wichtige Eigenschaft. Für die Verwendung der Dispersionen ist es von Vorteil, dass sie wie Flüssigkeiten gehandhabt werden können und sich sehr schnell in alkalischwässrigen Systemen lösen.The anti-corrosion agents according to the invention can also in Form of aqueous dispersions can be used. As Dispersants are suitable for all surface-active compounds, especially anionic and non-ionic surfactants. Such dispersions can be thickened to be stabilized, with stabilizers in particular modified polysaccharides from xanthan, alginate, guar or Cellulose type used. This also includes cellulose ethers such as Methyl cellulose or carboxymethyl cellulose and heteropolysaccharides. Except for the dispersant and thickener the dispersions according to the invention can still more Contain auxiliaries, for example hydrotropic agents such as Urea or sodium xylene sulfonate; Antifreeze like Ethylene or propylene glycol, diethylene glycol, glycerin or sorbitol; Biocides such as chloroacetamide, formalin or 1,2-benzisothiazolin-3-one or complexing agents. To make the Dispersions are placed in the aqueous solution of the invention Anti-corrosion agent, the dispersant and Thickeners and other additives and stirs it Mix until a uniform, homogeneous dispersion arose. The dispersions thus produced are at Room temperature as well as several at temperatures up to 40 ° C Stable for months. They keep their fluidity and segregate not yourself. That is for the storage and transportation of the Dispersions are an important property. For using the Dispersions have the advantage that they are like liquids can be handled and become very quickly in alkaline water Systems.

    Die Erfindung wird durch die folgenden Beispiele näher veranschaulicht:
    Bestimmung der Korrosionseigenschaften des erfindungsgemäßen Korrosionsschutzmittels im Vergleich zu bekannten Korrosionsschutzmitteln Vergleichsbeispiele Versuchs Nr. 1 2 3 4 5 6 7 8 9 Melamin 0,65 0,65 0,65 0,65 0 78 0 0 0 0 Sebacinsäüre in % 4,35 4,35 4,35 4,35 5 22 0 0 0 4,35 Triethanolamin % (85% ige Lsg.) 65 65 65 65 65 65 65 65 65 Isononansäure in % 5 0 0 0 0 0 0 0 5 Irgacor®190 con Ciba Geigy 0 3 0 3 0 10 12 0 0 Irgacor®252 con Ciba Geigy 0 0 3 1 0 0 0 0 0 Wasser ad 100 ad 100 ad 100 ad 100 ad 100 ad 100 ad 100 ad 100 ad 100 PH-Wert 3% in DIN Wasser (51360II) 8,9 8,8 8,7 8,6 8,6 8,7 8,6 über 9,5 8,8 Posttest (DIN 51360II) 0 0-1 0-1 0 1-2 1-2 1 4 3 Irgacor®190 von Ciba-Geigy = 6,6',6"-(1,3,5-Triazin-2,4,6-triyl-triimino)-trihexansäure. Irgacor®252 von Ciba-Geigy = (2-Benzothiazolylthio)-bernsteinsäure.     The invention is illustrated in more detail by the following examples:
    Determination of the corrosion properties of the anti-corrosion agent according to the invention in comparison to known anti-corrosion agents Comparative Examples Experiment No. 1 2 3 4 5 6 7 8th 9 melamine 0.65 0.65 0.65 0.65 0 78 0 0 0 0 Sebacic acid in% 4.35 4.35 4.35 4.35 5 22 0 0 0 4.35 Triethanolamine% (85% solution) 65 65 65 65 65 65 65 65 65 % Isononanoic acid 5 0 0 0 0 0 0 0 5 Irgacor®190 with Ciba Geigy 0 3 0 3 0 10 12 0 0 Irgacor®252 with Ciba Geigy 0 0 3 1 0 0 0 0 0 water ad 100 ad 100 ad 100 ad 100 ad 100 ad 100 ad 100 ad 100 ad 100 PH value 3% in DIN water (51360II) 8.9 8.8 8.7 8.6 8.6 8.7 8.6 over 9.5 8.8 Post test (DIN 51360II) 0 0-1 0-1 0 1-2 1-2 1 4 3 Irgacor®190 from Ciba-Geigy = 6,6 ', 6 "- (1,3,5-triazine-2,4,6-triyl-triimino) -trihexanoic acid. Irgacor®252 from Ciba-Geigy = (2-benzothiazolylthio) succinic acid.

    Die Versuche zeigen, dass die Rezepturen 1, 2, 3 und 4 die besten Ergebnisse erbringen. Das Gemisch Sebacinsäure/Melamin ist bis zu ca. 6% in der Gesamtrezeptur löslich; bei höheren Konzentrationen fällt ein Niederschlag aus. Es wurden verschiedene Synergisten eingesetzt, nämlich die Irgacor-Typen 190 und 252 Ciba Geigy und Isononansäure. The tests show that recipes 1, 2, 3 and 4 produce the best results. The mixture of sebacic acid / melamine is up to approx. 6% in the total formulation soluble; precipitation occurs at higher concentrations. It different synergists were used, namely the Irgacor types 190 and 252 Ciba Geigy and isononanoic acid.

    Die Versuche 6, 7 und 8 zeigen die Ergebnisse handelsüblicher Korrosionsinhibitoren vom Irgacor-Typ ohne Zusatz des erfindungsgemäßen Korrosionsschutzmittels. In Versuch 8 ist keine Carbonsäure enthalten. Der Versuch 9 zeigt deutlich, dass beim Fehlen von Melamin der Korrosionsschutz stark vermindert ist.Experiments 6, 7 and 8 show the results more commercially Corrosion inhibitors of the Irgacor type without the addition of the Corrosion protection agent according to the invention. In trial 8 is contain no carboxylic acid. Experiment 9 clearly shows that in the absence of melamine, the corrosion protection is strong is reduced.

    Die Bestimmung der Korrosionsschutzeigenschaften des erfindungsgemäßen Korrosionsschutzmittels erfolgte gemäß der Vorschrift der DIN 51360 Teil II. Als Maß der Korrosion dienen dabei die Korrosionszeichnungen auf einem Rundfilterpapier, die bei der Einwirkung von künstlich korrosiv gemachten Wasser auf Graugussspäne in Gegenwart des Korrosionsschutzmittels entstehen. Der Versuch wird dabei in folgender Weise durchgeführt:The determination of the anti-corrosion properties of the invention Corrosion protection agent was carried out according to the Regulation of DIN 51360 part II. Serve as a measure of corrosion the corrosion drawings on a round filter paper, which when exposed to artificially corrosive water on gray cast iron chips in the presence of the anti-corrosion agent arise. The test is carried out in the following way:

    Entsprechend der Vorschrift der DIN 51360 Teil II wird in ein Becherglas Wasser mit einer Gesamthärte von 3,58 mMol hergestellt, aus CaCl2 x 6 H2O und MgSO4 x 7 H2O, mit 3% des obengenannten Korrosionsschutzmittels versetzt und mit dieser Lösung, die in einer Petrischale auf Rundfilter verteilten Graugussspäne benetzt. Nach einer Verweilzeit von 2 Stunden bei Zimmertemperatur werden die Graugussspäne vom Rundfilter entfernt, das Rundfilter gespült und getrocknet und dann der Korrosionsgrad visuell entsprechend der Tabelle der DIN 51360, Teil II bestimmt. Die dabei erhaltenen Ergebnisse sind in der obenstehenden Tabelle aufgeführt.According to the specification of DIN 51360 Part II, water with a total hardness of 3.58 mmol is made from CaCl 2 x 6 H 2 O and MgSO 4 x 7 H 2 O, mixed with 3% of the above-mentioned corrosion protection agent and with this Solution that wets gray cast iron chips distributed on round filters in a Petri dish. After a dwell time of 2 hours at room temperature, the gray cast iron chips are removed from the round filter, the round filter rinsed and dried, and the degree of corrosion is then determined visually in accordance with the table in DIN 51360, Part II. The results obtained are shown in the table above.

    Claims (12)

    1. Corrosion inhibitor, characterized in that it contains melamine and an organic polycarboxylic acid of the formula I
      Figure 00130001
      in a molar ratio of from 1:1.5 to 1:5, X being a straight-chain or branched alkylene or alkylidene radical which has 1 to 20 carbon atoms and may carry one or more hydroxyl or carboxyl groups and may contain a cyclopentylene, cyclohexylene or phenylene group.
    2. Corrosion inhibitor according to Claim 1, characterized in that the molar ratio melamine : polycarboxylic acid is 1:3.
    3. Corrosion inhibitor according to Claims 1 and 2, characterized in that it contains a mixture of a plurality of different polycarboxylic acids.
    4. Corrosion inhibitor according to any of Claims 1 to 3, characterized in that it contains one or more dicarboxylic acids as the polycarboxylic acid.
    5. Corrosion inhibitor according to Claim 4, characterized in that it contains sebacic acid as the dicarboxylic acid.
    6. Corrosion inhibitor according to any of Claims 1 to 5, characterized in that it additionally contains a monocarboxylic acid.
    7. Corrosion inhibitor according to Claim 6, characterized in that it contains isononanoic acid as the monocarboxylic acid.
    8. Aqueous system, characterized in that the corrosion inhibitor of Claims 1 to 7 which consists of melamine and organic polycarboxylic acids is contained in an amount of from 0.1 to 10 per cent by weight.
    9. Aqueous system according to Claim 8, characterized in that it also contains one or more further corrosion inhibitors.
    10. Aqueous system according to Claims 8 and 9, characterized in that the free carboxyl groups are neutralized by alkali metal, ammonium or triethanolammonium cations.
    11. Aqueous system according to any of Claims 8 to 10, characterized in that it also contains further additives, such as dispersants, precipitating agents, oxygen scavengers, complexing agents, antifoams, disinfectants, high pressure additives or other known additives, in addition to corrosion inhibitors.
    12. Aqueous system according to any of Claims 8 to 11, characterized in that it is a water circulation, an aqueous machine liquid, an aqueous glycolic hydraulic fluid or an aqueous coating material.
    EP99106518A 1999-03-30 1999-03-30 Melamine containing corrosion inhibiting composition Expired - Lifetime EP1041174B1 (en)

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    WO2003080895A1 (en) * 2002-03-18 2003-10-02 The Lubrizol Corporation Corrosion inhibiting salts, concentrates and metal working fluids containing same
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    US7632458B2 (en) * 2006-01-31 2009-12-15 General Electric Company Corrosion inhibitor treatment for closed loop systems
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    CN102296298B (en) * 2011-08-30 2012-12-05 吴江市精工铝字制造厂 Aluminum alloy corrosion inhibitor of saline medium
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    US4402907A (en) * 1980-08-13 1983-09-06 Ciba-Geigy Corporation Triazine carboxylic acids as corrosion inhibitors for aqueous systems
    US4647392A (en) * 1985-12-27 1987-03-03 Texaco Inc. Monobasic-dibasic acid/salt antifreeze corrosion inhibitor
    GB9201165D0 (en) * 1992-01-18 1992-03-11 Ciba Geigy Corrosion inhibiting compositions
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