EP1373599A2 - Addition product, production and use thereof as corrosion inhibitor - Google Patents

Addition product, production and use thereof as corrosion inhibitor

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Publication number
EP1373599A2
EP1373599A2 EP02729987A EP02729987A EP1373599A2 EP 1373599 A2 EP1373599 A2 EP 1373599A2 EP 02729987 A EP02729987 A EP 02729987A EP 02729987 A EP02729987 A EP 02729987A EP 1373599 A2 EP1373599 A2 EP 1373599A2
Authority
EP
European Patent Office
Prior art keywords
acid
corrosion
addition product
use according
product according
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.)
Withdrawn
Application number
EP02729987A
Other languages
German (de)
French (fr)
Inventor
Andreas Hartwig
Kerstin Albinsky
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Fraunhofer Gesellschaft zur Forderung der Angewandten Forschung eV
Original Assignee
Fraunhofer Gesellschaft zur Forderung der Angewandten Forschung eV
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Priority claimed from DE10143521A external-priority patent/DE10143521B4/en
Application filed by Fraunhofer Gesellschaft zur Forderung der Angewandten Forschung eV filed Critical Fraunhofer Gesellschaft zur Forderung der Angewandten Forschung eV
Publication of EP1373599A2 publication Critical patent/EP1373599A2/en
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
    • C07D249/16—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms condensed with carbocyclic rings or ring systems
    • C07D249/18—Benzotriazoles
    • 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
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
    • C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
    • C23F11/14—Nitrogen-containing compounds
    • C23F11/141—Amines; Quaternary ammonium compounds
    • C23F11/143—Salts of amines

Definitions

  • the invention relates to an addition product, its production from one or more organic bases and one or more of the acids hexafluorosilicic acid, hexafluorotitanic acid and hexafluorozirconic acid and its use as a corrosion inhibitor, in particular for protecting light metals.
  • Conversion baths with the corrosion inhibitors hexafluorosilicic acid, hexafluorotitanic acid and hexafluorozirconic acid are used for corrosion protection of light metals or light metal alloys.
  • the light metals are treated by immersing them in the acid bath for a certain time. This creates a conversion layer that protects the treated metal from corrosion.
  • the protective effect can be extended if the metal to be protected has a coating, e.g. a varnish or adhesive, which is a reservoir for the inhibiting ions. If the coating is damaged, the inhibitor can be detached from the coating by adding water and transported to the injured area in order to have an inhibiting effect there.
  • Corrosion protection pigments such as zinc phosphate or barium metaborate are usually added as inhibitors for this purpose.
  • Metal salts of hexafluorosilicic acid, hexafluorotitanic acid and hexafluorozirconic acid can also be incorporated into polymers in the form of pigments.
  • the abovementioned salts have the disadvantage that they do not have a high solubility in water and are therefore poorly suited for rapid protection of an injured part of the metal.
  • the potential for action of these salts is lower than that of the particularly effective chromates.
  • Chromates are known to be particularly effective inhibitors. This makes it possible to use relatively poorly soluble chromates as inhibitors. Chromates used particularly frequently are zinc chromate, barium chromate and strontium chromate, and also mixtures of these compounds.
  • the object of the present invention is to overcome the disadvantages of the prior art and to provide corrosion inhibitors which ensure rapid and permanent inhibition of corrosion processes.
  • the addition products according to the invention can be prepared by means of an acid-base reaction from hexafluorosilicic acid, hexafluorotitanic acid and / or hexafluorozirconic acid with one or more organic bases.
  • Organic bases for the purposes of this invention are generally understood to mean organic compounds which, when reacted with inorganic acids, such as, in particular, hexafluorosilicic acid, hexafluorotitanic acid or hexafluorozirconic acid, give salts or salt-like compounds.
  • inorganic acids such as, in particular, hexafluorosilicic acid, hexafluorotitanic acid or hexafluorozirconic acid, give salts or salt-like compounds.
  • an organic base is preferably understood to mean organic nitrogen-containing compounds. Furthermore, due to the better handling of these, particularly non-cydic bases with a molecular weight that is greater than 105 g * mol "1 and cydic bases with a molecular weight that is greater than 70 g * mol _1 are to be understood.
  • the addition products according to the invention offer the advantage over metal salts of hexafluorosilicic acid, hexafluorotitanic acid or hexafluorozirconic acid in that they not only inhibit the anodic partial reaction but also, due to the organic component of the addition product according to the invention, inhibit the cathodic partial reaction of a corrosion process and thus result in an increased corrosion inhibition.
  • Impurities or nobler light metal alloy components mostly act as cathode; the anodic partial reaction takes place at the base points of the alloy, usually phases with a high proportion of light metals.
  • the starting point of the corrosion is usually a point at which the coating of the light metal or the light metal alloy has been damaged.
  • the addition products according to the invention also have the advantage over metal salts of hexafluorosilicic acid, hexafluorotitanic acid or hexafluorozirconic acid that they are more soluble in aqueous media.
  • the anion SiF 6 2 ' , TiF 6 2 " or ZrF 6 2' required for the anodic inhibition is made available more quickly and can be released from the coating more quickly by means of added water and transported to the injured area in order to have an inhibiting effect there.
  • the addition products according to the invention also have the advantage that they are not carcinogens such as hexavalent chromate compounds or toxic heavy metal compounds such as barium salts.
  • the addition products according to the invention can be incorporated into polymers and are therefore used to produce protective layers with an inhibitory effect can.
  • the basic constituents of paints, adhesives, primers, paints or potting compounds are to be mentioned as polymers.
  • the addition to a polymer has the advantage that a reservoir of the corrosion inhibitor is made available, which prevents corrosion under the polymer when corrosive media diffuse in or at points of injury.
  • Examples of polymers are epoxy resins, urethanes, acrylates, alkyd resins or polyvinyl acetate and their copolymers.
  • inhibitors according to the invention can not only be incorporated into polymers but, like hexafluorosilicic acid, hexafluorotitanic acid or hexafluorozirconic acid, can also be used in conversion baths and other liquids for the treatment of light metal surfaces.
  • Preferred organic bases for the preparation of the addition products according to the invention are heterocyclic nitrogen compounds.
  • Polymeric and non-polymeric heterocyclic nitrogen compounds form stable complexes with heavy metals.
  • the cathodic partial reaction of the corrosion process is blocked by the complex formation.
  • Heterocyclic nitrogen compounds which are good complexing agents with metals are therefore preferred for the preparation of the corrosion inhibitors according to the invention.
  • Heterocycles, which form stable complexes with impurities or nobler alloy components such as copper, which frequently occurs in light metal alloys, are particularly advantageous.
  • Organic bases which have at least two heteroatoms (such as N, O, S) in one or two heterocyclic rings are used to produce particularly strongly inhibiting addition products.
  • Preferred organic bases are heterocyclic nitrogen compounds such as e.g. substituted and unsubstituted 1, 2,4-triazoles, 1 H-
  • Benzotriazoles benzothiazoles, benzimidazoles, benzoxazoles, 2,2'-bichinolines, nitrones, 2,5-dimercapto-1, 3,4-thiadiazoles and 2,9-dimethylphenanthrolines.
  • heterocyclic nitrogen compounds with a particularly strongly inhibiting action are, for example, 1 H-benzotriazole, 5-methylbenzotriazole, 5-carboxybenzotriazole, benzothiazole, 2-alkylbenzothiazole, 2-mercaptobenzothiazole, 2-mercaptobenzothiazole succinic acid, benzimidazole, 2-alkylbenzimidazole, 2- (5-aminopentyl) benzimidazole, benzoxazole and 2-mercaptobenzoxazole.
  • Heterocycles with alkyl side groups reduce the water solubility and thus improve the long-term effect of the corrosion inhibitor.
  • Particularly preferred organic bases are furthermore compounds such as substituted and unsubstituted phthalocyanines, chlorines and porphyrins. Due to the formation of very stable complexes with a large number of metals and thus the strong corrosion-inhibiting effect, these compounds are particularly suitable for the preparation of the addition products according to the invention.
  • the organic base for producing the addition products according to the invention is a polymer with one or more basic groups.
  • the above-mentioned heterocydic groups are in particular the basic group
  • the addition products according to the invention also include those which are prepared from polymeric bases whose basic groups are only partially protonated.
  • Copolymers can also be used as polymers.
  • derivatives of the corresponding monomeric organic bases which have a vinyl group can be polymerized together with a comonomer in order to obtain suitable polymers.
  • the choice of the comonomer can, for example, influence the solubility in water or the compatibility with constituents of a polymer matrix into which the addition product is to be incorporated.
  • the water solubility can be reduced by increasing the proportion of the alkyl side groups of the polymer and thus the long-term effect can be improved when used as a corrosion inhibitor; by using vinylimidazole monomers, the water solubility can be increased and a good short-term effect can be achieved.
  • Polymers are advantageously also used when, in addition to corrosion-inhibiting properties, it is also desirable that a proton buffer permanently fixed in the polymer is present. This binds the acid formed during corrosion. A strong buffer effect is achieved by using addition products in which not all basic groups are protonated.
  • Phosphates, borates, vanadates, molybdates, tungstates and / or phosphonates are used.
  • the use of the addition products according to the invention in combination with previously known corrosion inhibitors or anti-corrosion pigments is particularly preferred when a synergistic effect results in the specific application. This is the case, for example, if the cathodic partial reaction of the corrosion process is sufficient even through a small amount of the addition product according to the invention is inhibited, but this amount is not sufficient to inhibit the anodic partial reaction. In such a case, a previously known inhibitor is used according to the invention, which is able to inhibit the anodic partial reaction.
  • the combination with known corrosion inhibitors offers the advantage that mixtures of different inhibitors can be produced that have a wide range
  • Addition products according to the invention with a high solubility in water and known corrosion inhibitors or addition products according to the invention with a moderate solubility in water give mixtures which have both a rapid anticorrosive action (primary action) and a long-term action (secondary action).
  • the addition products according to the invention are particularly suitable for use as corrosion inhibitors.
  • the corrosion-inhibiting effect of the addition products according to the invention is e.g. demonstrated that the addition products are dissolved in water together with a corrosive substance and the resulting solution is allowed to act on the metals to be protected.
  • the content of the corrosive substance is chosen higher than that of the inhibitor.
  • the addition products according to the invention are advantageously incorporated into one or more polymers.
  • Such compositions are used to produce protective layers with an inhibitory effect.
  • polymers are to be understood as meaning paints, adhesives, primers, casting compounds, sealing compounds, paints and / or anti-corrosion primers.
  • the addition to a polymer has the advantage that a reservoir of the corrosion inhibitor is provided which prevents corrosion under the polymer when corrosive media diffuse in or at points of injury.
  • polymers are epoxy resins, urethanes, acrylates, alkyd resins or polyvinyl acetate and their copolymers.
  • the corrosion-inhibiting addition products can also be used in protective layers of any kind.
  • the addition products according to the invention are furthermore advantageously used in conversion baths. However, they can be used in general in aqueous solutions for the treatment of light metal surfaces.
  • Partial reaction can take place through the organic bases of the conversion layer.
  • the inhibitors according to the invention can also be prepared intermediately by introducing the corresponding components into the bath.
  • the addition products according to the invention are preferably used for the corrosion protection of components made of aluminum, magnesium, zinc and / or alloys of these elements and in particular for the corrosion protection of components made of copper-containing light metal alloys.
  • alloys are: the aluminum alloys AA2024, AC120 and the magnesium alloys AM50. Due to their high strength, the copper-containing aluminum alloys are widely used in aircraft construction. The corrosion protection of components for aircraft construction is therefore a preferred area of application for the inhibitors according to the invention.
  • the corrosion inhibitors according to the invention can be used here both in treatment liquids for the components and in paints, primers, adhesives, sealants or casting compounds.
  • Another preferred area of application of the corrosion inhibitors according to the invention is the corrosion protection of components which are exposed to the weather.
  • this includes components for motor vehicle construction.
  • Components which have a light metal and / or a light metal alloy and corrosion-inhibiting constituents are also claimed, the latter comprising one or more bases, preferably bases described in more detail above, which inhibit the partial cathodic reaction of the corrosion process on this component.
  • Components with a a composition containing a corrosion inhibitor are not claimed.
  • Example 3 The synthesis is carried out as described in Example 1, using 1 15 g of a 60% hexafluorotitanic acid instead of hexafluorosilicic acid.
  • Example 3 The synthesis is carried out as described in Example 1, using 1 15 g of a 60% hexafluorotitanic acid instead of hexafluorosilicic acid.
  • the synthesis is carried out as described in Example 1, 193 g of a 45% strength hexafluorozirconic acid being used instead of the hexafluorosilicic acid.
  • the corrosion-inhibiting properties are tested in comparison with the conventional inhibitors sodium chromate, barium metaborate and yttrium vanadate. For comparison, the corrosive effect of a sodium chloride solution not provided with an inhibitor is determined.
  • the corrosion-inhibiting properties are tested based on the cataplasm test.
  • the metal sample is first degreased with methyl ethyl ketone, sanded with 100 grit sandpaper and cleaned again with methyl ethyl ketone.
  • the sample is wrapped with cotton wool and soaked in the test solution.
  • the sample prepared in this way is stored in a tightly closed vessel for 1344 hours (8 weeks) at 60 ° C.
  • the test solution consists of 1% by weight of sodium chloride as a corrosive substance and 0.1% by weight of the respective corrosion inhibitor in demineralized water.
  • Aluminum AA2024 format 20 X 80 X 1 mm
  • aluminum AC120 format 25 X 100 X1 mm
  • magnesium AM50 format (25 X 100 X 3 mm) were used as samples.
  • commercially available corrosion inhibitors and a Solution without corrosion inhibitor tested as comparative examples The evaluation is based on the corroded area and the number of pitting spots formed. The results are summarized in the following table:

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)
  • Paints Or Removers (AREA)

Abstract

The invention relates to an addition product, which may be obtained from hexafluorosilicic acid and/or hexafluorotitanic acid and/or hexafluorozirconic acid by an acid-base reaction with one or several organic bases and a method for production and uses thereof. Said addition products guarantee a rapid and lasting inhibition of corrosion processes and are in particular suitable for inhibiting the corrosion of light metals.

Description

Patentanmeldung: Patent registration:
Additionsprodukt, seine Herstellung und seine Verwendung als KorrosionsinhibitorAddition product, its manufacture and its use as a corrosion inhibitor
Beschreibungdescription
Technisches GebietTechnical field
Die Erfindung betrifft ein Additionsprodukt, seine Herstellung aus einer oder mehreren organischen Basen und einer oder mehrerer der Säuren Hexafluorokieselsäure, Hexafluoro- titansäure und Hexafluorozirkoniumsäure und seine Verwendung als Korrosionsinhibitor, insbesondere zum Schutz von Leichtmetallen.The invention relates to an addition product, its production from one or more organic bases and one or more of the acids hexafluorosilicic acid, hexafluorotitanic acid and hexafluorozirconic acid and its use as a corrosion inhibitor, in particular for protecting light metals.
Stand der TechnikState of the art
Zum Korrosionsschutz von Leichtmetallen oder Leichtmetalllegierungen werden Konversionsbäder mit den Korrosionsinhibitoren Hexafluorokieselsäure, Hexafluorotitansäure und Hexafluorozirkoniumsäure verwendet. Die Behandlung der Leichtmetalle erfolgt durch Eintauchen für eine bestimmte Zeit in das Säurebad. Hierbei bildet sich eine Konversionsschicht, die das behandelte Metall vor Korrosion schützt. Zum Stand der Technik wird hier beispielhaft auf die WO 9967029 verwiesen.Conversion baths with the corrosion inhibitors hexafluorosilicic acid, hexafluorotitanic acid and hexafluorozirconic acid are used for corrosion protection of light metals or light metal alloys. The light metals are treated by immersing them in the acid bath for a certain time. This creates a conversion layer that protects the treated metal from corrosion. With regard to the prior art, reference is made here, for example, to WO 9967029.
Solche Verfahren haben den Nachteil, dass die Verfahrensführung sehr aufwendig ist. Der eigentlichen Behandlung im Säurebad sind diverse Reinigungs- und Spülbäder vor- und nachgeschaltet. Vor allem ist jedoch nachteilig, dass die Konversionsschicht nur einen geringen Gehalt an den inhibierend wirkenden Ionen enthält. Hierdurch wird die schützende Wirkung zeitlich begrenzt.Such methods have the disadvantage that the procedure is very complex. Various cleaning and rinsing baths precede and follow the actual treatment in the acid bath. Above all, it is disadvantageous that the conversion layer only one contains a low content of the inhibiting ions. As a result, the protective effect is limited in time.
Die schützende Wirkung kann dadurch verlängert werden, dass das zu schützende Metall eine Beschichtung, z.B. einen Lack oder Klebstoff, aufweist, die ein Reservoir für die inhibierend wirkenden Ionen darstellt. Kommt es zu einer Verletzung der Beschichtung, so kann der Inhibitor durch hinzukommendes Wasser aus der Beschichtung gelöst und zu der verletzten Stelle transportiert werden, um dort inhibierend zu wirken. Als Inhibitoren werden hierzu üblicherweise Korrosionsschutzpigmente wie Zinkphosphat oder Bariummetaborat zugesetzt. Metallsalze der Hexafluorokieselsäure, Hexafluorotitansäure und Hexafluorozirkoniumsäure lassen sich ebenfalls in Form von Pigmenten in Polymere einarbeiten.The protective effect can be extended if the metal to be protected has a coating, e.g. a varnish or adhesive, which is a reservoir for the inhibiting ions. If the coating is damaged, the inhibitor can be detached from the coating by adding water and transported to the injured area in order to have an inhibiting effect there. Corrosion protection pigments such as zinc phosphate or barium metaborate are usually added as inhibitors for this purpose. Metal salts of hexafluorosilicic acid, hexafluorotitanic acid and hexafluorozirconic acid can also be incorporated into polymers in the form of pigments.
Die vorstehend genannten Salze haben jedoch den Nachteil, dass sie keine hohe Löslichkeit in Wasser aufweisen und daher für einen schnellen Schutz einer verletzten Stelle des Metalls nur schlecht geeignet sind. Zusätzlich ist das Wirkpotential dieser Salze geringer als das der besonders wirksamen Chromate.However, the abovementioned salts have the disadvantage that they do not have a high solubility in water and are therefore poorly suited for rapid protection of an injured part of the metal. In addition, the potential for action of these salts is lower than that of the particularly effective chromates.
Chromate sind als besonders wirksame Inhibitoren bekannt. Hierdurch ist es möglich auch relativ schwerlösliche Chromate als Inhibitoren einzusetzen. Besonders häufig verwendete Chromate sind Zinkchromat, Bariumchromat und Strontiumchromat, sowie Mischungen dieser Verbindungen.Chromates are known to be particularly effective inhibitors. This makes it possible to use relatively poorly soluble chromates as inhibitors. Chromates used particularly frequently are zinc chromate, barium chromate and strontium chromate, and also mixtures of these compounds.
Aufgrund der hohen Toxizität von Chromverbindungen (sechswertiges Chrom ist karzinogen und mutagen) ist es jedoch erforderlich, diese durch weniger giftige Ersatzstoffe zu ersetzen. Darstellung der ErfindungHowever, due to the high toxicity of chromium compounds (hexavalent chromium is carcinogenic and mutagenic), it is necessary to replace them with less toxic substitutes. Presentation of the invention
Aufgabe der vorliegenden Erfindung ist es, die Nachteile des Standes der Technik zu überwinden und Korrosionsinhibitoren bereit zu stellen, die eine schnelle und dauerhafte Inhibierung von Korrosionsprozessen gewährleisten.The object of the present invention is to overcome the disadvantages of the prior art and to provide corrosion inhibitors which ensure rapid and permanent inhibition of corrosion processes.
Die erfindungsgemäße Aufgabe wird durch das Additionsprodukt nach Anspruch 1 , das Verfahren zu dessen Herstellung nach Anspruch 9, die Verwendung nach den Ansprüchen 10 bis 17 sowie das Bauteil nach Anspruch 18 gelöst. Unteransprüche geben vorteilhafte Weiterbildungen an.The object according to the invention is achieved by the addition product according to claim 1, the method for its production according to claim 9, the use according to claims 10 to 17 and the component according to claim 18. Subclaims indicate advantageous further developments.
Die erfindungsgemäßen Additionsprodukte sind mittels einer Säure-Base-Reaktion aus Hexafluorokieselsäure, Hexafluorotitansäure und/oder Hexafluorozirkoniumsäure mit einer oder mehreren organischen Basen herstellbar. Hierdurch werden Salze mit den Anionen Hexafluorosilicat, Hexafluorotitanat und/oder Hexafluorozirkonat und Kationen aus den protonierten organischen Basen erhalten. Als organische Base im Sinne dieser Erfindung sind generell organische Verbindungen zu verstehen, die bei der Reaktion mit anorganischen Säuren wie insbesondere Hexafluorokieselsäure, Hexafluorotitansäure oder Hexafluorozirkoniumsäure Salze oder salzartige Verbindungen ergeben. Als allgemeine Reaktionsgleichung kann angegeben werden:The addition products according to the invention can be prepared by means of an acid-base reaction from hexafluorosilicic acid, hexafluorotitanic acid and / or hexafluorozirconic acid with one or more organic bases. This gives salts with the anions hexafluorosilicate, hexafluorotitanate and / or hexafluorozirconate and cations from the protonated organic bases. Organic bases for the purposes of this invention are generally understood to mean organic compounds which, when reacted with inorganic acids, such as, in particular, hexafluorosilicic acid, hexafluorotitanic acid or hexafluorozirconic acid, give salts or salt-like compounds. As a general reaction equation can be given:
m * B + n * H2EF6 ► (BH+)2n(EF6 2-)n + (m-2n) * Bm * W + n * H 2 EF 6 ► (BH + ) 2n (EF 6 2 -) n + (m-2n) * W
Hierbei ist E = Si und/oder Ti und/oder Zr;Here E = Si and / or Ti and / or Zr;
B bezeichnet die organische Base, trägt die organische Base mehr als eine basische Gruppe, so ist die basische Gruppe als B zu verstehen; m und n sind ganze Zahlen, wobei m > 2n, für nichtpolymere Verbindungen gilt insbesondere m = 2n.B denotes the organic base; if the organic base bears more than one basic group, the basic group is to be understood as B; m and n are integers, where m> 2n, for non-polymeric compounds in particular m = 2n.
Erfindungsgemäß sind unter einer organischen Base bevorzugt organische stickstoffhaltige Verbindungen zu verstehen. Weiterhin sind aufgrund der besseren Handhabung hierunter besonders bevorzugt nicht cydische Basen mit einem Molekulargewicht, das größer als 105 g*mol"1 ist, und cydische Basen mit einem Molekulargewicht , das größer als 70 g*mol_1 ist, zu verstehen.According to the invention, an organic base is preferably understood to mean organic nitrogen-containing compounds. Furthermore, due to the better handling of these, particularly non-cydic bases with a molecular weight that is greater than 105 g * mol "1 and cydic bases with a molecular weight that is greater than 70 g * mol _1 are to be understood.
Die erfindungsgemäßen Additionsprodukte bieten gegenüber Metallsalzen der Hexafluorokieselsäure, Hexafluorotitansäure oder Hexafluorozirkoniumsäure den Vorteil, dass sie nicht nur die anodische Teilreaktion sondern aufgrund des organischen Bestandteils des erfindungsgemäßen Additionsprodukts auch die kathodische Teilreaktion eines Korrosionsprozesses inhibieren und damit eine gesteigerte Korrosionsinhibierung zur Folge haben. Als Kathode wirken hierbei meist Verunreinigungen oder edlere Leichtmetalllegierungsbestandteile; die anodische Teilreaktion findet an den unedlen Stellen der Legierung, meist Phasen mit einem hohen Anteil der Leichtmetalle, statt. Der Startpunkt der Korrosion ist in der Regel eine Stelle, an der eine Verletzung der Beschichtung des Leichtmetalls oder der Leichtmetalllegierung stattgefunden hat. Die erfindungsgemäßen Additionsprodukte bieten gegenüber Metallsalzen der Hexafluorokieselsäure, Hexafluorotitansäure oder Hexafluorozirkoniumsäure weiterhin den Vorteil, dass sie in wässrigen Medien besser löslich sind. Hierdurch wird das für die anodische Inhibierung benötigte Anion SiF6 2', TiF6 2" oder ZrF6 2' schneller zur Verfügung gestellt und kann durch hinzukommendes Wasser schneller aus der Beschichtung gelöst und zu der verletzten Stelle transportiert werden um dort inhibierend zu wirken. Die erfindungsgemäßen Additionsprodukte haben außerdem den Vorteil, dass sie keine Karzinogene wie sechswertige Chromatverbindungen oder toxische Schwermetallverbindungen wie Bariumsalze darstellen.The addition products according to the invention offer the advantage over metal salts of hexafluorosilicic acid, hexafluorotitanic acid or hexafluorozirconic acid in that they not only inhibit the anodic partial reaction but also, due to the organic component of the addition product according to the invention, inhibit the cathodic partial reaction of a corrosion process and thus result in an increased corrosion inhibition. Impurities or nobler light metal alloy components mostly act as cathode; the anodic partial reaction takes place at the base points of the alloy, usually phases with a high proportion of light metals. The starting point of the corrosion is usually a point at which the coating of the light metal or the light metal alloy has been damaged. The addition products according to the invention also have the advantage over metal salts of hexafluorosilicic acid, hexafluorotitanic acid or hexafluorozirconic acid that they are more soluble in aqueous media. As a result, the anion SiF 6 2 ' , TiF 6 2 " or ZrF 6 2' required for the anodic inhibition is made available more quickly and can be released from the coating more quickly by means of added water and transported to the injured area in order to have an inhibiting effect there. The addition products according to the invention also have the advantage that they are not carcinogens such as hexavalent chromate compounds or toxic heavy metal compounds such as barium salts.
Überraschenderweise wurde festgestellt, dass sich die erfindungsgemäßen Additionsprodukte im Gegensatz zu den freien Säuren in Polymere einarbeiten lassen und daher zur Herstellung inhibierend wirkender Schutzschichten verwendet werden können. Als Polymere sind hierbei insbesondere die Grundbestandteile von Lacken, Klebstoffen, Primern, Farben oder Vergussmassen zu nennen. Der Zusatz zu einem Polymer hat den Vorteil, dass ein Reservoir des Korrosionsinhibitors zur Ver ügung gestellt wird, das die Korrosion unter dem Polymer bei der Eindiffusion korrodierender Medien oder an Verletzungsstellen verhindert. Beispielhaft seien als Polymere Epoxidharze, Urethane, Acrylate, Alkydharze oder Polyvinylacetat und seine Copolymere genannt. Die erfindungsgemäßen Inhibitoren lassen sich aber nicht nur in Polymere einarbeiten sondern wie Hexafluorokieselsäure, Hexafluorotitansäure oder Hexafluorozirkoniumsäure auch in Konversionsbädern und anderen Flüssigkeiten zur Behandlung von Leichtmetalloberflächen einsetzen.Surprisingly, it was found that, in contrast to the free acids, the addition products according to the invention can be incorporated into polymers and are therefore used to produce protective layers with an inhibitory effect can. The basic constituents of paints, adhesives, primers, paints or potting compounds are to be mentioned as polymers. The addition to a polymer has the advantage that a reservoir of the corrosion inhibitor is made available, which prevents corrosion under the polymer when corrosive media diffuse in or at points of injury. Examples of polymers are epoxy resins, urethanes, acrylates, alkyd resins or polyvinyl acetate and their copolymers. However, the inhibitors according to the invention can not only be incorporated into polymers but, like hexafluorosilicic acid, hexafluorotitanic acid or hexafluorozirconic acid, can also be used in conversion baths and other liquids for the treatment of light metal surfaces.
Bevorzugte organische Basen zur Herstellung der erfindungsgemäßen Additionsprodukte sind heterocyclische Stickstoffverbindungen.Preferred organic bases for the preparation of the addition products according to the invention are heterocyclic nitrogen compounds.
Polymere und nicht polymere heterocyclische Stickstoffverbindungen bilden stabile Komplexe mit Schwermetallen. Durch die Komplexbildung wird die kathodische Teilreaktion des Korrosionsprozesses blockiert. Zur Herstellung der erfindungsgemäßen Korrosionsinhibitoren sind daher heterocyclische Stickstoffverbindungen bevorzugt, die gute Komplexbildner mit Metallen sind. Besonders vorteilhaft sind Heterocyclen, die mit Verunreinigungen oder edleren Legierungsbestandteilen wie Kupfer, das häufig in Leichtmetalllegierungen vorkommt, stabile Komplexe bilden.Polymeric and non-polymeric heterocyclic nitrogen compounds form stable complexes with heavy metals. The cathodic partial reaction of the corrosion process is blocked by the complex formation. Heterocyclic nitrogen compounds which are good complexing agents with metals are therefore preferred for the preparation of the corrosion inhibitors according to the invention. Heterocycles, which form stable complexes with impurities or nobler alloy components such as copper, which frequently occurs in light metal alloys, are particularly advantageous.
Zur Herstellung besonders stark inhibierender Additionsprodukte werden organische Basen eingesetzt, die mindestens zwei Heteroatome (wie N, O, S) in einem oder zwei heterocyclischen Ringen aufweisen. Bevorzugte organische Basen sind heterocyclische Stickstoffverbindungen wie z.B. substituierte und unsubstituierte 1 ,2,4-Triazole, 1 H-Organic bases which have at least two heteroatoms (such as N, O, S) in one or two heterocyclic rings are used to produce particularly strongly inhibiting addition products. Preferred organic bases are heterocyclic nitrogen compounds such as e.g. substituted and unsubstituted 1, 2,4-triazoles, 1 H-
Benzotriazole, Benzothiazole, Benzimidazole, Benzoxazole, 2,2'-Bichinoline, Nitrone, 2,5- Dimercapto-1 ,3,4-thiadiazole und 2,9-Dimethylphenanthroline. Besonders bevorzugte heterocyclische Stickstoffverbindungen mit einer besonders stark inhibierenden Wirkung sind z.B. 1 H-Benzotriazol, 5-Methylbenzotriazol, 5-Carboxybenzotriazol, Benzothiazol, 2-Alkylbenzothiazol, 2-Mercaptobenzothiazol, 2-Mercaptobenzothiazolsuccinsäure, Benzimidazol, 2-Alkylbenzimidazol, 2-(5-Aminopentyl)benzimidazol, Benzoxazol und 2-Mercaptobenzoxazol. Heterocyclen mit Alkyl-Seitengruppen verringern die Wasserlöslichkeit und verbessern damit die Langzeitwirkung des Korrosionsinhibitors.Benzotriazoles, benzothiazoles, benzimidazoles, benzoxazoles, 2,2'-bichinolines, nitrones, 2,5-dimercapto-1, 3,4-thiadiazoles and 2,9-dimethylphenanthrolines. Particularly preferred heterocyclic nitrogen compounds with a particularly strongly inhibiting action are, for example, 1 H-benzotriazole, 5-methylbenzotriazole, 5-carboxybenzotriazole, benzothiazole, 2-alkylbenzothiazole, 2-mercaptobenzothiazole, 2-mercaptobenzothiazole succinic acid, benzimidazole, 2-alkylbenzimidazole, 2- (5-aminopentyl) benzimidazole, benzoxazole and 2-mercaptobenzoxazole. Heterocycles with alkyl side groups reduce the water solubility and thus improve the long-term effect of the corrosion inhibitor.
Besonders bevorzugte organische Basen sind weiterhin Verbindungen wie substituierte und unsubstituierte Phthalocyanine, Chlorine und Porphyrine. Aufgrund der Bildung sehr stabiler Komplexe mit einer Vielzahl von Metallen und damit der starken korrosionsinhibierenden Wirkung sind diese Verbindungen besonders geeignet zur Herstellung der erfindungsgemäßen Additionsprodukte.Particularly preferred organic bases are furthermore compounds such as substituted and unsubstituted phthalocyanines, chlorines and porphyrins. Due to the formation of very stable complexes with a large number of metals and thus the strong corrosion-inhibiting effect, these compounds are particularly suitable for the preparation of the addition products according to the invention.
In einer bevorzugten Form ist die organische Base zur Herstellung der erfindungsgemäßen Additionsprodukte ein Polymer mit einer oder mehreren basischen Gruppen. Als basische Gruppe sind hierbei insbesondere die vorstehenden heterocydischenIn a preferred form, the organic base for producing the addition products according to the invention is a polymer with one or more basic groups. The above-mentioned heterocydic groups are in particular the basic group
Verbindungen zu verstehen, aber ganz allgemein auch Polymere mit kurzen Seitenketten wie beispielsweise Polyvinylamin.To understand compounds, but very generally also polymers with short side chains such as polyvinylamine.
Unter den erfindungsgemäßen Additionsprodukten sind auch solche zu verstehen, die aus polymeren Basen, deren basische Gruppen nur teilweise protoniert sind, hergestellt werden. Als Polymere können auch Copolymere eingesetzt werden. Beispielsweise kann man Derivate der entsprechenden monomeren organischen Basen, die eine Vinylgruppe aufweisen, zusammen mit einem Comonomer polymerisieren um geeignete Polymere zu erhalten. Durch die Wahl des Comonomers kann beispielsweise die Löslichkeit in Wasser oder die Verträglichkeit mit Bestandteilen einer Polymermatrix, in die das Additionsprodukt eingearbeitet werden soll, beeinflusst werden. So kann etwa durch Erhöhung des Anteils der Alkyl-Seitengruppen des Polymers die Wasserlöslichkeit verringert werden und damit bei einer Anwendung als Korrosionsinhibitor die Langzeitwirkung verbessert werden; durch den Einsatz von Vinylimidazolmonomeren kann die Wasserlöslichkeit erhöht werden und eine gute Kurzzeitwirkung erzielt werden. Polymere werden vorteilhafterweise auch dann eingesetzt, wenn neben korrosionsinhibierenden Eigenschaften auch erwünscht ist, dass ein permanent im Polymer fixierter Protonenpuffer vorliegt. Dieser bindet bei der Korrosion gebildete Säure. Eine starke Pufferwirkung wird erreicht, indem Additionsprodukte eingesetzt werden, bei denen nicht alle basischen Gruppen protoniert sind.The addition products according to the invention also include those which are prepared from polymeric bases whose basic groups are only partially protonated. Copolymers can also be used as polymers. For example, derivatives of the corresponding monomeric organic bases which have a vinyl group can be polymerized together with a comonomer in order to obtain suitable polymers. The choice of the comonomer can, for example, influence the solubility in water or the compatibility with constituents of a polymer matrix into which the addition product is to be incorporated. For example, the water solubility can be reduced by increasing the proportion of the alkyl side groups of the polymer and thus the long-term effect can be improved when used as a corrosion inhibitor; by using vinylimidazole monomers, the water solubility can be increased and a good short-term effect can be achieved. Polymers are advantageously also used when, in addition to corrosion-inhibiting properties, it is also desirable that a proton buffer permanently fixed in the polymer is present. This binds the acid formed during corrosion. A strong buffer effect is achieved by using addition products in which not all basic groups are protonated.
Überraschenderweise wurde festgestellt, dass durch Polymere und Copolymere eine zusätzliche haftvermittelnde Wirkung erreicht werden kann. Durch diese zusätzliche haftvermittelnde Wirkung wird eine bessere Haftung einer Polymermatrix, in die das erfindungsgemäße Additionsprodukt eingearbeitet wurde bzw. der daraus hergestellten inhibierend wirkenden Schutzschicht mit einem Substrat erreicht. Generell bieten erfindungsgemäße Additionsprodukte auf Polymerbasis einen dauerhaften Schutz von Oberflächen gegen Korrosion.Surprisingly, it was found that an additional adhesion-promoting effect can be achieved by means of polymers and copolymers. This additional adhesion-promoting effect results in better adhesion of a polymer matrix into which the addition product according to the invention has been incorporated or the inhibiting protective layer produced therefrom with a substrate. In general, polymer-based addition products according to the invention offer permanent protection of surfaces against corrosion.
In besonderer Ausgestaltung werden die erfindungsgemäßen Additionsprodukte zusammen mit Metallsalzen mit den Anionen SiF6 2", TiF6 2' und/oder ZrF6 2" und/oder zusätzlichIn a special embodiment, the addition products according to the invention, together with metal salts with the anions SiF 6 2 " , TiF 6 2 ' and / or ZrF 6 2" and / or additionally
Phosphaten, Boraten, Vanadaten, Molybdaten, Wolframaten und/oder Phosphonaten eingesetzt.Phosphates, borates, vanadates, molybdates, tungstates and / or phosphonates are used.
Bevorzugt wird bei diesen vorbekannten korrosionsinhibierenden Metallsalzen mit den Anionen SiF6 2", TiF6 2" und/oder ZrF6 2" und/oder konventionellen Korrosionsschutzpigmenten auf Basis von Phosphaten, Boraten, Vanadaten, Molybdaten, Wolframaten undPreference is given to these previously known corrosion-inhibiting metal salts with the anions SiF 6 2 " , TiF 6 2" and / or ZrF 6 2 " and / or conventional corrosion protection pigments based on phosphates, borates, vanadates, molybdate, tungstates and
Phosphonaten das Metall ausgewählt aus der Gruppe bestehend aus Kalium, Natrium, Zink, Barium, Strontium, Calcium, Magnesium, Mangan, Cobalt, Nickel, Zinn, Zirkonium, Aluminium und den Seltenerdmetallen. Besonders geeignet sind hierbei Barium, Strontium und Calcium und in Abhängigkeit vom Anwendungsfall auch Zink. Die Anwendung der erfindungsgemäßen Additionsprodukte in Kombination mit vorbekannten Korrosionsinhibitoren bzw. Korrosionschutzpigmenten ist insbesondere dann bevorzugt, wenn eine synergistische Wirkung bei dem spezifischen Anwendungsfall resultiert. Dies ist z.B. der Fall, wenn die kathodische Teilreaktion des Korrosionsprozesses bereits durch eine kleine Menge des erfindungsgemäßen Additionsprodukts hinreichend inhibiert wird, diese Menge für die Inhibierung der anodischen Teilreaktion aber nicht ausreicht. In einem solchen Fall wird erfindungsgemäß zusätzlich ein vorbekannter Inhibitor eingesetzt, der in der Lage ist die anodische Teilreaktion zu inhibieren. Weiterhin bietet die Kombination mit vorbekannten Korrosionsinhibitoren den Vorteil, dass Gemische verschiedener Inhibitoren hergestellt werden können, die ein breitesPhosphonates the metal selected from the group consisting of potassium, sodium, zinc, barium, strontium, calcium, magnesium, manganese, cobalt, nickel, tin, zirconium, aluminum and the rare earth metals. Barium, strontium and calcium and, depending on the application, zinc are particularly suitable. The use of the addition products according to the invention in combination with previously known corrosion inhibitors or anti-corrosion pigments is particularly preferred when a synergistic effect results in the specific application. This is the case, for example, if the cathodic partial reaction of the corrosion process is sufficient even through a small amount of the addition product according to the invention is inhibited, but this amount is not sufficient to inhibit the anodic partial reaction. In such a case, a previously known inhibitor is used according to the invention, which is able to inhibit the anodic partial reaction. Furthermore, the combination with known corrosion inhibitors offers the advantage that mixtures of different inhibitors can be produced that have a wide range
Anwendungsspektrum aufweisen. Durch erfindungsgemäße Additionsprodukte mit einer hohen Wasserlöslichkeit, und vorbekannter Korrosionsinhibitoren bzw. erfindungsgemäßer Additionsprodukte mit einer mittelmäßigen Löslichkeit in Wasser werden Gemische erhalten, die sowohl eine schnelle antikorrosive Wirkung besitzen (Primärwirkung) als auch eine Langzeitwirkung (Sekundärwirkung) aufweisen.Show range of applications. Addition products according to the invention with a high solubility in water and known corrosion inhibitors or addition products according to the invention with a moderate solubility in water give mixtures which have both a rapid anticorrosive action (primary action) and a long-term action (secondary action).
Die erfindungsgemäßen Additionsprodukte eignen sich insbesondere zum Einsatz als Korrosionsinhibitoren.The addition products according to the invention are particularly suitable for use as corrosion inhibitors.
Die korrosionsihibierende Wirkung der erfindungsgemäßen Additionsprodukte wird z.B. dadurch nachgewiesen, dass die Additionsprodukte zusammen mit einer korrodierend wirkenden Substanz in Wasser gelöst werden und man die entstehende Lösung auf das zu schützende Metalle einwirken lässt. Um eine ausreichende Differenzierung zu erreichen, wird der Gehalt der korrodierend wirkenden Substanz höher gewählt als der des Inhibitors.The corrosion-inhibiting effect of the addition products according to the invention is e.g. demonstrated that the addition products are dissolved in water together with a corrosive substance and the resulting solution is allowed to act on the metals to be protected. In order to achieve sufficient differentiation, the content of the corrosive substance is chosen higher than that of the inhibitor.
Zur Anwendung als Korrosionsinhibitoren werden die erfindungsgemäßen Additionsprodukte vorteilhafterweise in ein oder mehrere Polymere eingearbeitet. Solche Zusammensetzungen werden zur Herstellung inhibierend wirkender Schutzschichten verwendet. Insbesondere sind hierbei unter Polymeren Lacke, Klebstoffe, Primer, Vergußmassen, Dichtungsmassen, Farben und/oder Korrosionsschutzprimer zu verstehen. Der Zusatz zu einem Polymer hat den Vorteil, dass ein Reservoir des Korrosionsinhibitors zur Verfügung gestellt wird, das die Korrosion unter dem Polymer bei der Eindiffusion korrodierender Medien oder an Verletzungsstellen verhindert. Beispielhaft seien als Polymere Epoxidharze, Urethane, Acrylate, Alkydharze oder Polyvinylacetat und seine Copolymere. Ganz allgemein können die korrosionsinhibierenden Additionsprodukte auch in Schutzschichten jeder Art eingesetzt werden. Die erfindungsgemäßen Additionsprodukte werden weiterhin vorteilhafterweise in Konversionsbädern verwendet. Sie können aber ganz allgemein in wässrigen Lösungen zur Behandlung von Leichtmetalloberflächen eingesetzt werden.For use as corrosion inhibitors, the addition products according to the invention are advantageously incorporated into one or more polymers. Such compositions are used to produce protective layers with an inhibitory effect. In particular, polymers are to be understood as meaning paints, adhesives, primers, casting compounds, sealing compounds, paints and / or anti-corrosion primers. The addition to a polymer has the advantage that a reservoir of the corrosion inhibitor is provided which prevents corrosion under the polymer when corrosive media diffuse in or at points of injury. Examples of polymers are epoxy resins, urethanes, acrylates, alkyd resins or polyvinyl acetate and their copolymers. In general, the corrosion-inhibiting addition products can also be used in protective layers of any kind. The addition products according to the invention are furthermore advantageously used in conversion baths. However, they can be used in general in aqueous solutions for the treatment of light metal surfaces.
Hierbei haben sie den Vorteil, dass zusätzlich zu der Inhibierung der anodischen Teilreaktion der Korrosion durch das SiF6 2", TiF6 2" oder ZrF6 2' eine Inhibierung der kathodischenThey have the advantage that, in addition to the inhibition of the anodic partial reaction of corrosion by the SiF 6 2 " , TiF 6 2" or ZrF 6 2 ', an inhibition of the cathodic
Teilreaktion durch die organischen Basen der Konversionsschicht erfolgen kann. Im Falle des Einsatzes in einem chemischen Bad können die erfindungsgemäßen Inhibitoren auch intermediär durch Eintrag der entsprechenden Komponenten in das Bad hergestellt werden.Partial reaction can take place through the organic bases of the conversion layer. In the case of use in a chemical bath, the inhibitors according to the invention can also be prepared intermediately by introducing the corresponding components into the bath.
Die erfindungsgemäßen Additionsprodukte werden bevorzugt zum Korrosionsschutz von Bauteilen aus Aluminium, Magnesium, Zink und/oder Legierungen dieser Elemente und insbesondere zum Korrosionsschutz von Bauteilen aus kupferhaltigen Leichtmetall- Legierungen verwendet. Als Legierungen sind beispielsweise zu erwähnen: die Aluminiumlegierungen AA2024, AC120 und die Magnesiumlegierungen AM50. Aufgrund der hohen Festigkeit werden die kupferhaltigen Aluminiumlegierungen vielfach im Flugzeugbau eingesetzt. Der Korrosionsschutz von Bauteilen für den Flugzeugbau ist demnach ein bevorzugtes Anwendungsgebiet der erfindungsgemäßen Inhibitoren. Die Anwendung der erfindungsgemäßen Korrosionsinhibitoren kann hier sowohl in Behandlungsflüssigkeiten für die Bauteile erfolgen als auch in Lacken, Primern, Klebstoffen, Dichtstoffen oder Vergussmassen.The addition products according to the invention are preferably used for the corrosion protection of components made of aluminum, magnesium, zinc and / or alloys of these elements and in particular for the corrosion protection of components made of copper-containing light metal alloys. Examples of alloys are: the aluminum alloys AA2024, AC120 and the magnesium alloys AM50. Due to their high strength, the copper-containing aluminum alloys are widely used in aircraft construction. The corrosion protection of components for aircraft construction is therefore a preferred area of application for the inhibitors according to the invention. The corrosion inhibitors according to the invention can be used here both in treatment liquids for the components and in paints, primers, adhesives, sealants or casting compounds.
Ein weiteres bevorzugtes Anwendungsgebiet der erfindungsgemäßen Korrosionsinhibitoren ist der Korrosionsschutz von Bauteilen, die der Witterung ausgesetzt sind. Insbesondere gehören dazu Bauteile für den Kraftfahrzeugbau.Another preferred area of application of the corrosion inhibitors according to the invention is the corrosion protection of components which are exposed to the weather. In particular, this includes components for motor vehicle construction.
Beansprucht werden auch Bauteile, die ein Leichtmetall und/oder eine Leichtmetalllegierung sowie korrosionsinhibierende Bestandteile aufweisen, wobei letztere eine oder mehrere Basen, bevorzugt vorstehend näher beschriebene Basen, umfassen, die die kathodische Teilreaktion von Korrosionsprozesses an diesem Bauteils inhibieren. Bauteile, die mit einer einen Korrosionsinhibitor enthaltenden Zusammensetzung geklebt wurden, werden nicht beansprucht.Components which have a light metal and / or a light metal alloy and corrosion-inhibiting constituents are also claimed, the latter comprising one or more bases, preferably bases described in more detail above, which inhibit the partial cathodic reaction of the corrosion process on this component. Components with a a composition containing a corrosion inhibitor are not claimed.
AnwendungsbeispieleExamples of use
Ohne Einschränkung der Allgemeinheit werden die erfindungsgemäßen Korrosionsinhibitoren nachfolgend anhand von Anwendungsbeispielen näher erläutert.Without restricting generality, the corrosion inhibitors according to the invention are explained in more detail below with the aid of application examples.
Beispiel 1example 1
Synthese von 1 H-BenzotriazolhexafluorosilicatSynthesis of 1 H-benzotriazole hexafluorosilicate
Es werden 242 g einer 25%igen wässrigen Lösung von Hexafluorokieselsäure vorgelegt und unter Rühren 100,1 g 1 H-Benzotriazol im Verlauf einer halben Stunde eingetragen. Die ersten Portionen gehen klar in Lösung. Im späteren Stadium der Reaktion fällt das entstehende Reaktionsprodukt teilweise bereits wieder aus. Nach beendeter Zugabe des 1 H-Benzotriazols werden 300 ml 96%iges Ethanol zugegeben und die Mischung zwei Stunden gerührt. Der entstandene Niederschlag wird im Büchnertrichter abfiltriert und der Filterkuchen bis zur Gewichtskonstanz im Vakuum bei 50°C getrocknet. Um weiteres Produkt zu gewinnen, wird das Filtrat auf die Hälfte eingeengt und der Niederschlag ebenso aufbereitet wie die Hauptmenge des Produktes. Das getrocknete Produkt wird in der Kugelmühle gemahlen und mit einem 30 μm Sieb gesiebt.242 g of a 25% strength aqueous solution of hexafluorosilicic acid are introduced and 100.1 g of 1 H-benzotriazole are added with stirring over the course of half an hour. The first portions are clearly in solution. In the later stage of the reaction, the resulting reaction product partially precipitates again. When the addition of 1 H-benzotriazole has ended, 300 ml of 96% ethanol are added and the mixture is stirred for two hours. The resulting precipitate is filtered off in the Büchner funnel and the filter cake is dried to constant weight in a vacuum at 50 ° C. In order to obtain further product, the filtrate is concentrated in half and the precipitate is processed in the same way as the main amount of the product. The dried product is ground in a ball mill and sieved with a 30 μm sieve.
Beispiel 2Example 2
Synthese von 1 H-BenzotriazolhexafluorotitanatSynthesis of 1 H-benzotriazole hexafluorotitanate
Die Synthese erfolgt wie in Beispiel 1 beschrieben, wobei anstelle der Hexafluorokieselsäure 1 15 g einer 60%igen Hexafluorotitansäure verwendet werden. Beispiel 3The synthesis is carried out as described in Example 1, using 1 15 g of a 60% hexafluorotitanic acid instead of hexafluorosilicic acid. Example 3
Synthese von 1 H-BenzotriazolhexafluorozirconatSynthesis of 1 H-benzotriazole hexafluorozirconate
Die Synthese erfolgt wie in Beispiel 1 beschrieben, wobei anstelle der Hexafluorokieselsäure 193 g einer 45%igen Hexafluorozirconsäure verwendet werden.The synthesis is carried out as described in Example 1, 193 g of a 45% strength hexafluorozirconic acid being used instead of the hexafluorosilicic acid.
Beispiel 4Example 4
Prüfen der korrosionsinhibierenden EigenschaftenCheck the corrosion-inhibiting properties
Die korrosionsinhibierenden Eigenschaften werden im Vergleich mit den konventionellen Inhibitoren Natriumchromat, Bariummetaborat und Yttriumvanadat geprüft. Zum Vergleich wird die korrodierende Wirkung einer nicht mit einem Inhibitor versehenen Natriumchloridlösung bestimmt. Die Prüfung der korrosionsinhibierenden Eigenschaften erfolgt in Anlehnung an den Kataplasmatest. Die Metallprobe wird zunächst mit Methylethylketon entfettet, mit Schleifpapier der Körnung 100 geschliffen und noch einmal mit Methylethylketon gereinigt. Die Probe wird mit Watte umwickelt und mit der Prüflösung getränkt. Die so vorbereitete Probe wird in einem dicht verschlossenen Gefäß 1344 Stunden (8 Wochen) bei 60°C gelagert. Die Prüflösung besteht aus 1 Gew.-% Natriumchlorid als korrodierend wirkender Substanz und 0,1 % Gew.-% des jeweiligen Korrosionsinhibitors in demineralisiertem Wasser. Als Proben wurden Aluminium AA2024 (Format 20 X 80 X 1 mm), Aluminium AC120 (Format 25 X 100 X1 mm) und Magnesium AM50 (Format (25 X 100 X 3 mm) verwendet. Neben Beispielen der erfindungsgemäßen Korrosionsinhibitoren wurden handelsübliche Korrosionsinhibitoren und eine Lösung ohne Korrosionsinhibitor als Vergleichsbeispiele geprüft. Die Bewertung erfolgt anhand der korrodierten Fläche und der Zahl der gebildeten Lochfraßstellen (Pits). Die Ergebnisse sind in folgender Tabelle zusammengestellt: The corrosion-inhibiting properties are tested in comparison with the conventional inhibitors sodium chromate, barium metaborate and yttrium vanadate. For comparison, the corrosive effect of a sodium chloride solution not provided with an inhibitor is determined. The corrosion-inhibiting properties are tested based on the cataplasm test. The metal sample is first degreased with methyl ethyl ketone, sanded with 100 grit sandpaper and cleaned again with methyl ethyl ketone. The sample is wrapped with cotton wool and soaked in the test solution. The sample prepared in this way is stored in a tightly closed vessel for 1344 hours (8 weeks) at 60 ° C. The test solution consists of 1% by weight of sodium chloride as a corrosive substance and 0.1% by weight of the respective corrosion inhibitor in demineralized water. Aluminum AA2024 (format 20 X 80 X 1 mm), aluminum AC120 (format 25 X 100 X1 mm) and magnesium AM50 (format (25 X 100 X 3 mm) were used as samples. In addition to examples of the corrosion inhibitors according to the invention, commercially available corrosion inhibitors and a Solution without corrosion inhibitor tested as comparative examples. The evaluation is based on the corroded area and the number of pitting spots formed. The results are summarized in the following table:
*die Pits befinden sich nur an der Schnittkante / Blechrand* the pits are only on the cutting edge / sheet edge
Die Ergebnisse zeigen, dass die erfindungsgemäßen Inhibitoren dem Chromat ebenbürtig sind, und eine höhere Wirksamkeit entfalten als die anderen handelsüblichen Korrosionsinhibitoren. The results show that the inhibitors according to the invention are on a par with chromate and are more effective than the other commercially available corrosion inhibitors.

Claims

Patentansprüche claims
1. Additionsprodukt, herstellbar mittels einer Säure-Base-Reaktion aus Hexafluorokieselsäure und/oder Hexafluorotitansäure und/oder Hexafluorozirkoniumsäure mit einer oder mehreren organischen Basen.1. addition product which can be prepared by means of an acid-base reaction from hexafluorosilicic acid and / or hexafluorotitanic acid and / or hexafluorozirconic acid with one or more organic bases.
2. Additionsprodukt nach Anspruch 1 , dadurch gekennzeichnet, dass die organische Base eine heterocyclische Verbindung ist.2. addition product according to claim 1, characterized in that the organic base is a heterocyclic compound.
3. Additionsprodukt nach Anspruch 2, dadurch gekennzeichnet, dass die organische Base ausgewählt wird aus der Gruppe, bestehend aus 1 ,2,4-Triazol, 1 H-3. addition product according to claim 2, characterized in that the organic base is selected from the group consisting of 1, 2,4-triazole, 1 H-
Benzotriazol, Benzothiazol, Benzimidazol, Benzoxazol, 2,2'-Bichinolin, Nitron, 2,5- Dimercapto-1 ,3,4-thiadiazol und 2,9-Dimethylphenanthrolin sowie Derivaten dieser Grundkörper.Benzotriazole, benzothiazole, benzimidazole, benzoxazole, 2,2'-bichinoline, nitron, 2,5-dimercapto-1, 3,4-thiadiazole and 2,9-dimethylphenanthroline as well as derivatives of these basic bodies.
4. Additionsprodukt nach Anspruch 3, dadurch gekennzeichnet, dass die organische Base ausgewählt wird aus der Gruppe, bestehend aus 1 H-Benzotriazol, 5-Methylbenzotriazol, 5-Carboxybenzotriazol, Benzothiazol, 2-Alkylbenzothiazol, 2- Mercaptobenzothiazol, 2-Mercaptobenzothiazolsuccinsäure, Benzimidazol, 2- Alkylbenzimidazol, 2-(5-Aminopentyl)benzimidazol, Benzoxazol, 2-Mercaptobenzoxazol.4. addition product according to claim 3, characterized in that the organic base is selected from the group consisting of 1 H-benzotriazole, 5-methylbenzotriazole, 5-carboxybenzotriazole, benzothiazole, 2-alkylbenzothiazole, 2-mercaptobenzothiazole, 2-mercaptobenzothiazole succinic acid, benzimidazole , 2-alkylbenzimidazole, 2- (5-aminopentyl) benzimidazole, benzoxazole, 2-mercaptobenzoxazole.
5. Additionsprodukt nach Anspruch 2, dadurch gekennzeichnet, dass die organische Base ausgewählt wird aus der Gruppe, bestehend aus Phthalocyanin, Chlorin und Porphyrin sowie Derivaten dieser Grundkörper. 5. addition product according to claim 2, characterized in that the organic base is selected from the group consisting of phthalocyanine, chlorine and porphyrin and derivatives of these basic bodies.
6. Additionsprodukt nach den Ansprüchen 1 bis 5, dadurch gekennzeichnet, dass die organische Base ein Polymer mit einer oder mehreren basischen Gruppen ist.6. addition product according to claims 1 to 5, characterized in that the organic base is a polymer with one or more basic groups.
7. Zusammensetzung, enthaltend ein oder mehrere Additionsprodukte nach einem oder mehreren der Ansprüche 1 bis 6 sowie ein oder mehrere Metallsalze mit den Anionen7. Composition containing one or more addition products according to one or more of claims 1 to 6 and one or more metal salts with the anions
SiF6 2", TiF6 2" und/oder ZrF6 2\SiF 6 2 " , TiF 6 2" and / or ZrF 6 2 \
8. Zusammensetzung, enthaltend ein oder mehrere Additionsprodukte nach einem oder mehreren der Ansprüche 1 bis 6 sowie Phosphate, Borate, Vanadate, Molybdate, Wolframate und/oder Phosphonate.8. Composition containing one or more addition products according to one or more of claims 1 to 6 and phosphates, borates, vanadates, molybdates, tungstates and / or phosphonates.
9. Verfahren zur Herstellung des Additionsproduktes nach den Ansprüchen 1 bis 6, dadurch gekennzeichnet, dass9. A method for producing the addition product according to claims 1 to 6, characterized in that
Hexafluorokieselsäure und/oder Hexafluorotitansäure und/oder Hexafluorozirkoniumsäure sowie eine oder mehrere organische Basen einer Säure-Base- Reaktion unterworfen werden.Hexafluorosilicic acid and / or hexafluorotitanic acid and / or hexafluorozirconic acid and one or more organic bases are subjected to an acid-base reaction.
10. Verwendung eines Additionsproduktes nach den Ansprüchen 1 bis 6 als Korrosionsinhibitor.10. Use of an addition product according to claims 1 to 6 as a corrosion inhibitor.
1 1. Verwendung nach Anspruch 10, dadurch gekennzeichnet, dass das Additionsprodukt in eines oder mehrere Polymere eingearbeitet wird.1 1. Use according to claim 10, characterized in that the addition product is incorporated into one or more polymers.
12. Verwendung nach Anspruch 10 in Konversionsbädern.12. Use according to claim 10 in conversion baths.
13. Verwendung nach Anspruch 1 1 , dadurch gekennzeichnet; dass das Polymer ein Lack, ein Klebstoff, ein Primer, eine Vergussmasse, eine Dichtungsmasse, eine Farben und/oder ein Korrosionsschutzprimer ist. 13. Use according to claim 1 1, characterized; that the polymer is a lacquer, an adhesive, a primer, a sealing compound, a sealing compound, a paint and / or a corrosion protection primer.
14. Verwendung nach Anspruch 10 bis 13 zum Schutz von Bauteilen aus kupferhaltigen Leichtmetall-Legierungen.14. Use according to claim 10 to 13 for protecting components made of copper-containing light metal alloys.
15. Verwendung nach Anspruch 10 bis 14 zum Schutz von Bauteilen aus Aluminium, Magnesium, Zink und/oder Legierungen dieser Elemente.15. Use according to claim 10 to 14 for the protection of components made of aluminum, magnesium, zinc and / or alloys of these elements.
16. Verwendung nach Anspruch 15 im Flugzeugbau.16. Use according to claim 15 in aircraft construction.
17. Verwendung nach Anspruch 10 bis16 zum Schutz von Bauteilen, die der Witterung ausgesetzt sind.17. Use according to claim 10 to 16 for the protection of components that are exposed to the weather.
18. Bauteil, umfassend ein Leichtmetall und/oder eine Leichtmetalllegierung sowie korrosionsinhibierende Bestandteile dadurch gekennzeichnet, dass die korrosionsinhibierenden Bestandteile eine oder mehrere Basen, insbesondere nach den Ansprüchen 2 bis 6, umfassen, die die kathodische Teilreaktion von18. Component comprising a light metal and / or a light metal alloy and corrosion-inhibiting components, characterized in that the corrosion-inhibiting components comprise one or more bases, in particular according to claims 2 to 6, which the cathodic partial reaction of
Korrosionsprozesses an diesem Bauteils inhibieren, wobei Bauteile, die mit einer einen Korrosionsinhibitor enthaltenden Zusammensetzung geklebt wurden, nicht beansprucht werden. Inhibit corrosion process on this component, wherein components that were glued with a composition containing a corrosion inhibitor are not stressed.
EP02729987A 2001-03-16 2002-03-11 Addition product, production and use thereof as corrosion inhibitor Withdrawn EP1373599A2 (en)

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