EP0368119B1 - Use of methyl polysiloxanes with quaternary ammonium groups as corrosion inhibitors in mainly aqueous preparations - Google Patents

Use of methyl polysiloxanes with quaternary ammonium groups as corrosion inhibitors in mainly aqueous preparations Download PDF

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Publication number
EP0368119B1
EP0368119B1 EP89120152A EP89120152A EP0368119B1 EP 0368119 B1 EP0368119 B1 EP 0368119B1 EP 89120152 A EP89120152 A EP 89120152A EP 89120152 A EP89120152 A EP 89120152A EP 0368119 B1 EP0368119 B1 EP 0368119B1
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Prior art keywords
quaternary ammonium
ammonium groups
radical
value
carbon atoms
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German (de)
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EP0368119A1 (en
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Dietmar Dr. Schaefer
Werner Höhner
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Evonik Operations GmbH
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TH Goldschmidt AG
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
    • C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
    • C23F11/14—Nitrogen-containing compounds
    • C23F11/141—Amines; Quaternary ammonium compounds
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
    • C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
    • C23F11/14—Nitrogen-containing compounds
    • C23F11/141—Amines; Quaternary ammonium compounds
    • C23F11/142—Hydroxy amines
    • 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
    • C23F11/173—Macromolecular compounds

Definitions

  • DE-PS 30 15 864 recommends polyoxyalkylenediamides with terminal carboxylic acid groups and their salts as corrosion-preventing additives for metalworking agent emulsions. These products are also said to improve the lubricating properties of the preparation.
  • R is a monovalent hydrocarbon radical with up to 18 carbon atoms
  • R ′ is a divalent hydrocarbon radical having up to 18 carbon atoms or a divalent hydrocarbonoxy radical having up to 18 carbon atoms
  • the oxygen in the hydrocarbonoxy radical being in the form of an ether bond and the hydrocarbon portion of the hydrocarbonoxy radical being in the form of a divalent alkylene radical
  • X is the anion of an acid
  • x has an average value from 1 to about 100
  • y has an average value from 0 to about 1000, where the ratio of y: x is no greater than about 50: 1.
  • the object of the invention is to find further organosilicon compounds which have improved corrosion-inhibiting properties and give the person skilled in the art the possibility of formulating aqueous systems which are particularly suitable for dissipating heat with improved corrosion protection.
  • this object is achieved by using methylpolysiloxanes with quaternary ammonium groups bonded to silicon atoms via carbon atoms, the quotient of the number of dimethylsiloxy groups and the number of quaternary ammonium groups being from 0.5 to 15, as corrosion inhibitors for predominantly water existing preparations, in particular coolants, such as water-mixed cooling lubricants, in quantities of 0.01 to 0.1% by weight, based on the total preparation in a form suitable for the application.
  • coolants such as water-mixed cooling lubricants
  • these dimethylsiloxy groups and quaternary ammonium groups which are in the specified ratio to one another, have excellent corrosion-inhibiting properties.
  • the connections are soluble or well dispersible in water. They have a high chemical resistance in aqueous solution and are effective in a very small amount. Quantities of 0.01 to 0.1% by weight, based on the total preparation, which is diluted in a form suitable for the application, are generally sufficient to achieve good corrosion protection.
  • a preferred embodiment of the subject of the present invention is that compounds of the general formula are used as methylpolysiloxanes with quaternary ammonium groups used in which R1 is the same or different in the molecule and is a methyl radical or the radical means R2 is the same or different in the molecule and denotes an alkyl radical with 1 to 18 carbon atoms or the radical R5-CONH- (CH2) 3-, in which R5 is an alkyl radical with 7 to 17 carbon atoms, R3, R4 are the same or different in the molecule and represent an alkyl radical with 1 to 4 carbon atoms, Z the rest or is X (-) is an inorganic or organic anion, n has a value from 5 to 20, m has a value from 1 to 10, wherein the quotient of the number of dimethylsiloxy groups and the number of quaternary ammonium groups has a value from 0.5 to 15.
  • R2 can have different meanings within the polymeric molecule.
  • R2 denotes an alkyl radical having 1 to 18 carbon atoms, such as e.g. the methyl, ethyl, propyl, isopropyl, butyl, isobutyl, hexyl, decyl, dodecyl or octadecyl radical.
  • R2 can also mean the radical R5-CONH- (CH2) 3-.
  • R5 is an alkyl radical with 7 to 17 carbon atoms, which is usually derived from a fatty acid R5COOH.
  • R3 and R4 can also be the same or different within the polymeric molecule and mean an alkyl radical with 1 to 4 carbon atoms, such as e.g. the methyl, ethyl, propyl, isopropyl, butyl or isobutyl radical.
  • the quaternary ammonium groups are each bonded to a silicon atom via the radical Z.
  • the remainder Z corresponds to the formula
  • X (-) is the counter ion of the ammonium group, so that the number of anions X (-) corresponds to the number of quaternary nitrogen atoms.
  • X can be an inorganic or organic anion.
  • X is usually an inorganic anion, such as a chlorine ion.
  • An example of an organic anion is the acetate anion.
  • n indicates the number of difunctional units.
  • n has a value of 5 to 20.
  • m denotes the methylsiloxy groups to which quaternary ammonium groups are bound laterally in the polymeric molecule.
  • m has a value from 1 to 10. However, the condition must be fulfilled that the quotient of the number of dimethylsiloxy groups and the number of quaternary ammonium groups has a value of 0.5 to 15.
  • a further preferred embodiment of the subject of the present invention is characterized in that compounds of the general formula are used as methylpolysiloxanes with quaternary ammonium groups used where R2, R3, R4, X (-) and Z have the meaning already given and p has a value from 1 to 29.
  • these are linear methylpolysiloxanes which have quaternary ammonium groups only in the ⁇ , ⁇ position.
  • the radicals R2, R3, R4, X (-) and Z have the meaning already given.
  • the index p has a value from 1 to 29.
  • the methylpolysiloxanes containing quaternary ammonium groups to be used according to the invention are preferably added to commercially available concentrates of the preparations.
  • the compounds to be used according to the invention can e.g. dissolve in ethylene glycol, the user then diluting the stock solution to the appropriate concentration.
  • the siloxanes can be added to the concentrated, commercially available emulsion, the essential components of which are vegetable, synthetic or animal oils, water and emulsifier. This stock emulsion is then diluted with water to the application concentration at the point of use.
  • the siloxanes to be used according to the invention can be prepared, for example, according to DE-PS 37 19 086.
  • This production process uses siloxanes of the general formula as starting compounds.
  • R6 has the meaning of a methyl radical or the radical Q.
  • Q is the rest The remaining radicals and indices have the meaning already given.
  • the corrosion protection properties are determined in accordance with DIN 51 360, Part 2, for the testing of cooling lubricants in accordance with the specification of the determination of the corrosion protection properties of water-mixed cooling lubricants using the swarf / filter paper method. Reference is made to the DIN regulation for the details of the determination.
  • the water-mixed cooling lubricant is provided with the anti-corrosion agent.
  • Gray cast iron test chips which were checked visually for freedom from corrosion prior to the determination, are sieved and the fraction is used to carry out the tests used, where 30 ⁇ 5 chips have a total weight of 2 g.
  • a round filter is placed in a Petri dish measuring 80 x 20 mm. 2 g of the chips are evenly applied to the surface of the round filter. The chips are evenly wetted with 2 ml of the aqueous preparation to be tested. Then the lid of the petri dish is put on. The Petri dishes prepared in this way are then exposed to a temperature of about 8 to 22 ° C. for two hours.
  • the chips are then removed, the round filter rinsed under running water, swirled in acetone for about 5 seconds and dried at room temperature.
  • the degree of corrosion of the corrosion markings on the round filter is then determined by visual inspection. The evaluation is based on the following classification:
  • the compounds to be investigated for their corrosion-inhibiting properties are each dissolved in 0.1% by weight in the water-mixed cooling lubricant.
  • the following connections were examined and evaluated:

Description

Verwendung von Methylpolysiloxanen mit quartären Ammoniumgruppen als Korrosionsinhibitoren für überwiegend aus Wasser bestehende ZubereitungenUse of methylpolysiloxanes with quaternary ammonium groups as corrosion inhibitors for preparations consisting predominantly of water

Zur Vermeidung der Korrosion von metallischen Oberflächen, welche in Kontakt mit wäßrigen Zubereitungen in Gegenwart von Sauerstoff kommen, wie z.B. Wärmeübertragungs- oder Kühlmittel, Bohr- und Schneidölemulsionen, sind aus dem Stand der Technik zahlreiche, meist Stickstoff- oder Phosphoratome enthaltende Inhibitoren bekannt.To prevent corrosion of metallic surfaces that come into contact with aqueous preparations in the presence of oxygen, e.g. Heat transfer or coolants, drilling and cutting oil emulsions, numerous inhibitors are known from the prior art, mostly containing nitrogen or phosphorus atoms.

So sind in der DE-PS 29 07 863 Metallbearbeitungsemulsionen vom Öl-in-Wasser-Typ mit guter Stabilität und unbegrenzter Verdünnbarkeit auf der Basis von Triglyceridölen für die verformende Metallbearbeitung (spanabhebende Bearbeitung, Verformung durch Tiefziehen und Walzen) beansprucht, die als dermatologisch ungefährliche Netzmittel mit korrosionsinhibierender Wirkung Alkanolamine mit 2 bis 4 Kohlenstoffatomen im Alkanolteil oder deren Salze mit Fettsäuren enthalten. In gleicher Weise sollen auch Fettamine, welche 8 bis 18 Kohlenstoffatome aufweisen, Rost verhindern.Thus, in DE-PS 29 07 863 metal working emulsions of the oil-in-water type with good stability and unlimited dilutability on the basis of triglyceride oils for deforming metal working (machining, shaping by deep drawing and rolling) are claimed, which are dermatologically harmless Contain wetting agents with a corrosion-inhibiting effect alkanolamines with 2 to 4 carbon atoms in the alkanol part or their salts with fatty acids. In the same way, fatty amines with 8 to 18 carbon atoms are also said to prevent rust.

In der DE-PS 30 15 864 werden Polyoxyalkylendiamide mit endständigen Carbonsäuregruppen sowie deren Salze als korrosionsverhindernde Additive für Metallbearbeitungsmittelemulsionen empfohlen. Diese Produkte sollen gleichzeitig die Schmiereigenschaften der Zubereitung verbessern.DE-PS 30 15 864 recommends polyoxyalkylenediamides with terminal carboxylic acid groups and their salts as corrosion-preventing additives for metalworking agent emulsions. These products are also said to improve the lubricating properties of the preparation.

In der US-PS 3 389 160 werden Verbindungen der folgenden Struktur beansprucht:

Figure imgb0001
US Pat. No. 3,389,160 claims compounds of the following structure:
Figure imgb0001

In dieser Formel ist:
   R ein einwertiger Kohlenwasserstoffrest mit bis zu 18 Kohlenstoffatomen,
   R′ ein zweiwertiger Kohlenwasserstoffrest mit bis zu 18 Kohlenstoffatomen oder ein zweiwertiger Kohlenwasserstoffoxyrest mit bis zu 18 Kohlenstoffatomen, wobei der Sauerstoff in dem Kohlenwasserstoffoxyrest in Form einer Etherbindung vorliegt und wobei der Kohlenwasserstoffanteil des Kohlenwasserstoffoxyrestes in Form eines zweiwertigern Alkylenrestes vorliegt,
   X das Anion einer Säure,
   R˝ Wasserstoff oder, wenn X ein Halogenatom ist, entweder Wasserstoff oder eine Gruppe wie R,
   a = 0 oder 1,
   x hat einen Durchschnittswert von 1 bis etwa 100,
   y hat einen Durchschnittswert von 0 bis etwa 1000,
   wobei das Verhältnis von y : x nicht größer als etwa 50 : 1 ist.In this formula:
R is a monovalent hydrocarbon radical with up to 18 carbon atoms,
R ′ is a divalent hydrocarbon radical having up to 18 carbon atoms or a divalent hydrocarbonoxy radical having up to 18 carbon atoms, the oxygen in the hydrocarbonoxy radical being in the form of an ether bond and the hydrocarbon portion of the hydrocarbonoxy radical being in the form of a divalent alkylene radical,
X is the anion of an acid,
R˝ is hydrogen or, if X is a halogen atom, either hydrogen or a group such as R,
a = 0 or 1,
x has an average value from 1 to about 100,
y has an average value from 0 to about 1000,
where the ratio of y: x is no greater than about 50: 1.

Für die Verbindungen der vorgenannten allgemeinen Formel I sind verschiedene Verwendungszwecke angegeben:Various uses are indicated for the compounds of the aforementioned general formula I:

Verbindungen der allgemeinen Formel

Figure imgb0002

sind als Korrosionsinhibitoren für wäßrige Systeme brauchbar. Hierbei ist allerdings von Nachteil, daß diese Verbindungen nur eine sehr geringe Wasserlöslichkeit haben, so daß die Verbindungen emulgiert werden müssen oder die Verwendung eines Hilfslösungsmittels in einem wäßrigen System notwendig ist.Compounds of the general formula
Figure imgb0002
are useful as corrosion inhibitors for aqueous systems. However, it is disadvantageous here that these compounds have only a very low solubility in water, so that the compounds have to be emulsified or the use of an auxiliary solvent in an aqueous system is necessary.

Die Verbindungen der Formeln

Figure imgb0003

und
Figure imgb0004
sollen die Grenzflächenspannung des Wassers erniedrigen und oberflächenaktive Substanzen sein. Eine Verwendbarkeit der Verbindungen der Formeln III und IV für Zwecke der Korrosionsinhibierung ist der US-PS 3 389 160 nicht zu entnehmen.The connections of the formulas
Figure imgb0003
and
Figure imgb0004
should lower the interfacial tension of the water and be surface-active substances. A usability of the compounds of the formulas III and IV for the purpose of corrosion inhibition is not apparent from US Pat. No. 3,389,160.

Der Erfindung liegt die Aufgabe zugrunde, weitere siliciumorganische Verbindungen aufzufinden, die verbesserte korrosionsinhibierende Eigenschaften aufweisen und dem Fachmann die Möglichkeit geben, wäßrige Systeme, die insbesondere zur Abführung von Wärme geeignet sind, mit verbessertem Korrosionsschutz zu formulieren.The object of the invention is to find further organosilicon compounds which have improved corrosion-inhibiting properties and give the person skilled in the art the possibility of formulating aqueous systems which are particularly suitable for dissipating heat with improved corrosion protection.

Erfindungsgemäß gelingt die Lösung dieser Aufgabe durch die Verwendung von Methylpolysiloxanen mit über Kohlenstoffatome an Siliciumatome gebundenen quartären Ammoniumgruppen, wobei der Quotient aus der Anzahl der Dimethylsiloxygruppen und der Anzahl der quartären Ammoniumgruppen einen Wert von 0,5 bis 15 hat, als Korrosionsinhibitoren für überwiegend aus Wasser bestehende Zubereitungen, insbesondere Kühlmittel, wie wassergemischte Kühlschmierstoffe, in Mengen von 0,01 bis 0,1 Gew.-%, bezogen auf Gesamtzubereitung in anwendungsgerechter Form.According to the invention, this object is achieved by using methylpolysiloxanes with quaternary ammonium groups bonded to silicon atoms via carbon atoms, the quotient of the number of dimethylsiloxy groups and the number of quaternary ammonium groups being from 0.5 to 15, as corrosion inhibitors for predominantly water existing preparations, in particular coolants, such as water-mixed cooling lubricants, in quantities of 0.01 to 0.1% by weight, based on the total preparation in a form suitable for the application.

Überraschenderweise weisen diese Dimethylsiloxygruppen und quartären Ammoniumgruppen, welche in dem angegebenen Verhältnis zueinander stehen, hervorragende korrosionsinhibierende Eigenschaften auf. Die Verbindungen sind in Wasser löslich oder gut dispergierbar. Sie haben eine hohe chemische Beständigkeit in wäßriger Lösung und sind in sehr geringer Menge wirksam. Mengen von 0,01 bis 0,1 Gew.-%, bezogen auf die Gesamtzubereitung, welche in anwendungsgerechter Form verdünnt vorliegt, reichen zur Erzielung eines guten Korrosionsschutzes in der Regel aus.Surprisingly, these dimethylsiloxy groups and quaternary ammonium groups, which are in the specified ratio to one another, have excellent corrosion-inhibiting properties. The connections are soluble or well dispersible in water. They have a high chemical resistance in aqueous solution and are effective in a very small amount. Quantities of 0.01 to 0.1% by weight, based on the total preparation, which is diluted in a form suitable for the application, are generally sufficient to achieve good corrosion protection.

Eine bevorzugte Ausführungsform des Gegenstandes vorliegender Erfindung besteht darin, daß man als Methylpolysiloxane mit quartären Ammoniumgruppen Verbindungen der allgemeinen Formel

Figure imgb0005

verwendet,
wobei
   R¹ im Molekül gleich oder verschieden ist und einen Methylrest oder den Rest
Figure imgb0006
bedeutet,
   R² im Molekül gleich oder verschieden ist und einen Alkylrest mit 1 bis 18 Kohlenstoffatomen oder den Rest R⁵-CONH-(CH₂)₃- bedeutet, in dem R⁵ ein Alkylrest mit 7 bis 17 Kohlenstoffatomen ist,
   R³, R⁴ im Molekül gleich oder verschieden sind und einen Alkylrest mit 1 bis 4 Kohlenstoffatomen bedeuten,
   Z der Rest
Figure imgb0007
oder
Figure imgb0008
ist,
   X(-) ein anorganisches oder organisches Anion ist,
   n einen Wert von 5 bis 20,
   m einen Wert von 1 bis 10 hat,
   wobei der Quotient aus der Anzahl der Dimethylsiloxygruppen und der Anzahl der quartären Ammoniumgruppen einen Wert von 0,5 bis 15 hat.A preferred embodiment of the subject of the present invention is that compounds of the general formula are used as methylpolysiloxanes with quaternary ammonium groups
Figure imgb0005
used
in which
R¹ is the same or different in the molecule and is a methyl radical or the radical
Figure imgb0006
means
R² is the same or different in the molecule and denotes an alkyl radical with 1 to 18 carbon atoms or the radical R⁵-CONH- (CH₂) ₃-, in which R⁵ is an alkyl radical with 7 to 17 carbon atoms,
R³, R⁴ are the same or different in the molecule and represent an alkyl radical with 1 to 4 carbon atoms,
Z the rest
Figure imgb0007
or
Figure imgb0008
is
X (-) is an inorganic or organic anion,
n has a value from 5 to 20,
m has a value from 1 to 10,
wherein the quotient of the number of dimethylsiloxy groups and the number of quaternary ammonium groups has a value from 0.5 to 15.

Es handelt sich somit um lineare Methylpolysiloxane, welche seitenständig und gegebenenfalls zusätzlich endständig quartäre Ammoniumgruppen aufweisen. Diese quartären Ammoniumgruppen tragen die Reste R², R³, R⁴. Der Rest R² kann innerhalb des polymeren Moleküls verschiedene Bedeutung haben. Dabei bedeutet R² einen Alkylrest mit 1 bis 18 Kohlenstoffatomen, wie z.B. den Methyl-, Ethyl-, Propyl-, Isopropyl-, Butyl-, Isobutyl-, Hexyl-, Decyl-, Dodecyl- oder Octadecylrest. R² kann aber auch den Rest R⁵-CONH-(CH₂)₃- bedeuten. In diesem Rest ist R⁵ ein Alkylrest mit 7 bis 17 Kohlenstoffatomen, der in der Regel von einer Fettsäure R⁵COOH hergeleitet ist.They are therefore linear methylpolysiloxanes which have quaternary ammonium groups on the side and optionally also on the terminal side. These quaternary ammonium groups carry the radicals R², R³, R⁴. The radical R² can have different meanings within the polymeric molecule. Here R² denotes an alkyl radical having 1 to 18 carbon atoms, such as e.g. the methyl, ethyl, propyl, isopropyl, butyl, isobutyl, hexyl, decyl, dodecyl or octadecyl radical. R² can also mean the radical R⁵-CONH- (CH₂) ₃-. In this radical R⁵ is an alkyl radical with 7 to 17 carbon atoms, which is usually derived from a fatty acid R⁵COOH.

R³ und R⁴ können innerhalb des polymeren Moleküls ebenfalls gleich oder verschieden sein und bedeuten einen Alkylrest mit 1 bis 4 Kohlenstoffatomen, wie z.B. den Methyl-, Ethyl-, Propyl-, Isopropyl-, Butyl-oder Isobutylrest.R³ and R⁴ can also be the same or different within the polymeric molecule and mean an alkyl radical with 1 to 4 carbon atoms, such as e.g. the methyl, ethyl, propyl, isopropyl, butyl or isobutyl radical.

Die quartären Ammoniumgruppen sind über den Rest Z jeweils an ein Siliciumatom gebunden. Dabei entspricht der Rest Z der Formel

Figure imgb0009
The quaternary ammonium groups are each bonded to a silicon atom via the radical Z. The remainder Z corresponds to the formula
Figure imgb0009

Hieraus ergibt sich, daß die Verknüpfung des Restes Z mit dem Si-Atom über eine SiC-Bindung erfolgt und die erfindungsgemäß zu verwendenden Verbindungen somit hohe hydrolytische Stabilität aufweisen.It follows from this that the linking of the radical Z with the Si atom takes place via an SiC bond and the compounds to be used according to the invention thus have high hydrolytic stability.

X(-) ist das Gegenion der Ammoniumgruppe, so daß die Anzahl der Anionen X(-) der Anzahl der quartären Stickstoffatome entspricht. X kann dabei ein anorganisches oder organisches Anion sein. Aus Gründen der Wirtschaftlichkeit und leichterer Zugänglichkeit ist X in der Regel ein anorganisches Anion, wie z.B. ein Chlorion. Beispiel eines organischen Anions ist das Acetatanion.X (-) is the counter ion of the ammonium group, so that the number of anions X (-) corresponds to the number of quaternary nitrogen atoms. X can be an inorganic or organic anion. For reasons of economy and easier accessibility, X is usually an inorganic anion, such as a chlorine ion. An example of an organic anion is the acetate anion.

Der Index n gibt die Anzahl der difunktionellen Einheiten an. n hat dabei einen wert von 5 bis 20. m bezeichnet die Methylsiloxygruppen, an welche im polymeren Molekül seitenständig quartäre Ammoniumgruppen gebunden sind. m hat einen wert von 1 bis 10. Es muß jedoch dabei die Bedingung erfüllt sein, daß der Quotient aus der Anzahl der Dimethylsiloxygruppen und der Anzahl der quartären Ammoniumgruppen einen wert von 0,5 bis 15 hat.The index n indicates the number of difunctional units. n has a value of 5 to 20. m denotes the methylsiloxy groups to which quaternary ammonium groups are bound laterally in the polymeric molecule. m has a value from 1 to 10. However, the condition must be fulfilled that the quotient of the number of dimethylsiloxy groups and the number of quaternary ammonium groups has a value of 0.5 to 15.

Eine weitere bevorzugte Ausführungsform des Gegenstandes der vorliegenden Erfindung ist dadurch gekennzeichnet, daß man als Methylpolysiloxane mit quartären Ammoniumgruppen Verbindungen der allgemeinen Formel

Figure imgb0010

verwendet,
wobei R², R³, R⁴, X(-) und Z die bereits angegebene Bedeutung haben und
   p einen wert von 1 bis 29 hat.A further preferred embodiment of the subject of the present invention is characterized in that compounds of the general formula are used as methylpolysiloxanes with quaternary ammonium groups
Figure imgb0010
used
where R², R³, R⁴, X (-) and Z have the meaning already given and
p has a value from 1 to 29.

Wie aus der Formel ersichtlich ist, handelt es sich hierbei um lineare Methylpolysiloxane, welche quartäre Ammoniumgruppen ausschließlich in α,ω-Stellung aufweisen. Die Reste R², R³, R⁴, X(-) und Z haben die bereits angegebene Bedeutung. Der Index p hat einen Wert von 1 bis 29.As can be seen from the formula, these are linear methylpolysiloxanes which have quaternary ammonium groups only in the α, ω position. The radicals R², R³, R⁴, X (-) and Z have the meaning already given. The index p has a value from 1 to 29.

Hat p einen Wert von 1, ergibt sich ein Quotient von 1/2 = 0,5. In diesem Fall liegt ein mit quartären Ammoniumgruppen in α,ω-Stellung modifiziertes Disiloxan vor.If p has a value of 1, the quotient is 1/2 = 0.5. In this case, there is a disiloxane modified with quaternary ammonium groups in the α, ω position.

Beispiele von besonders geeigneten, erfindungsgemäß zu verwendenden Verbindungen sind

Figure imgb0011
Figure imgb0012
Figure imgb0013
Figure imgb0014
Figure imgb0015
Figure imgb0016
Figure imgb0017
 Examples of particularly suitable compounds to be used according to the invention are
Figure imgb0011
Figure imgb0012
Figure imgb0013
Figure imgb0014
Figure imgb0015
Figure imgb0016
Figure imgb0017

Die erfindungsgemäß zu verwendenden, quartäre Ammoniumgruppen aufweisenden Methylpolysiloxane werden vorzugsweise handelsüblichen Konzentraten der Zubereitungen zugesetzt. Im Falle ihres Einsatzes in Wärme-übertragungs- oder Kühlflüssigkeiten kann man die erfindungsgemäß zu verwendenden Verbindungen z.B. in Ethylenglykol lösen, wobei die Stammlösung dann vom Anwender auf die anwendungsgerechte Konzentration verdünnt wird. Verwendet man die erfindungsgemäßen Verbindungen als Korrosionsinhibitoren in Metallbearbeitungsemulsionen, kann man die Siloxane der konzentrierten, handelsüblichen Emulsion zusetzen, deren wesentliche Bestandteile pflanzliche, synthetische oder tierische Öle, wasser und Emulgator sind. Diese Stammemulsion wird dann am Ort der Verwendung mit Wasser auf die Anwendungskonzentration verdünnt.The methylpolysiloxanes containing quaternary ammonium groups to be used according to the invention are preferably added to commercially available concentrates of the preparations. In the case of their use in heat transfer or cooling liquids, the compounds to be used according to the invention can e.g. dissolve in ethylene glycol, the user then diluting the stock solution to the appropriate concentration. If the compounds according to the invention are used as corrosion inhibitors in metalworking emulsions, the siloxanes can be added to the concentrated, commercially available emulsion, the essential components of which are vegetable, synthetic or animal oils, water and emulsifier. This stock emulsion is then diluted with water to the application concentration at the point of use.

Die erfindungsgemäß zu verwendenden Siloxane können z.B. gemäß der DE-PS 37 19 086 hergestellt werden. Bei diesem Herstellungsverfahren setzt man Siloxane der allgemeinen Formel

Figure imgb0018

als Ausgangsverbindungen ein. R⁶ hat dabei die Bedeutung eines Methylrestes oder des Restes Q. Q ist dabei der Rest
Figure imgb0019
Die übrigen Reste und Indices haben die bereits angegebene Bedeutung.The siloxanes to be used according to the invention can be prepared, for example, according to DE-PS 37 19 086. This production process uses siloxanes of the general formula
Figure imgb0018
as starting compounds. R⁶ has the meaning of a methyl radical or the radical Q. Q is the rest
Figure imgb0019
The remaining radicals and indices have the meaning already given.

Diese Ausgangsverbindungen werden mit tertiären Aminen der allgemeinen Formel

Figure imgb0020

worin R², R³, R⁴ die bereits angegebene Bedeutung haben, in an sich bekannter Weise umgesetzt. Man führt die Umsetzung in Gegenwart eines Säureäquivalentes HX, bezogen auf zu quaternierendes Stickstoffatom, durch. Die Reaktionstemperatur beträgt dabei etwa 40 bis 120°C. Die Verbindungen sind hellgelb bis rötlich gefärbte, mittel- bis hoch-viskose Produkte.These starting compounds are with tertiary amines of the general formula
Figure imgb0020
where R², R³, R⁴ have the meaning already given, implemented in a conventional manner. The reaction is carried out in the presence of an acid equivalent of HX, based on the nitrogen atom to be quaternized. The reaction temperature is about 40 to 120 ° C. The compounds are light yellow to reddish colored, medium to highly viscous products.

In den folgenden Beispielen werden die korrosionsinhibierenden Eigenschaften der erfindungsgemäß zu verwendenden Siloxane gezeigt. Die Bestimmung der Korrosionsschutzeigenschaften erfolgt dabei entsprechend DIN 51 360, Teil 2, für die Prüfung von Kühlschmierstoffen entsprechend der Vorschrift der Bestimmung der Korrosionsschutzeigenschaften von wassergemischten Kühlschmierstoffen mit dem Späne/Filtrierpapier-Verfahren. Auf die Einzelheiten der Bestimmung wird auf die DIN-Vorschrift verwiesen. Im Prinzip wird dabei der wassergemischte Kühlschmierstoff mit dem Korrosionsschutzmittel versehen. Prüfspäne aus Grauguß, die vor der Bestimmung auf Korrosionsfreiheit visuell geprüft wurden, werden gesiebt und für die Durchführung der Versuche die Fraktion verwendet, bei der 30 ± 5 Späne ein Gesamtgewicht von 2 g aufweisen. In einer Petri-Schale der Abmessung 80 x 20 mm wird ein Rundfilter eingelegt. Auf die Fläche des Rundfilters werden 2 g der Späne gleichmäßig aufgegeben. Die Späne werden mit 2 ml der zu prüfenden, wäßrigen Zubereitung gleichmäßig benetzt. Anschließend wird der Deckel der Petri-Schale aufgelegt. Die so vorbereiteten Petri-Schalen werden nun zwei Stunden lang einer Temperatur von etwa 8 bis 22°C ausgesetzt.The following examples show the corrosion-inhibiting properties of the siloxanes to be used according to the invention. The corrosion protection properties are determined in accordance with DIN 51 360, Part 2, for the testing of cooling lubricants in accordance with the specification of the determination of the corrosion protection properties of water-mixed cooling lubricants using the swarf / filter paper method. Reference is made to the DIN regulation for the details of the determination. In principle, the water-mixed cooling lubricant is provided with the anti-corrosion agent. Gray cast iron test chips, which were checked visually for freedom from corrosion prior to the determination, are sieved and the fraction is used to carry out the tests used, where 30 ± 5 chips have a total weight of 2 g. A round filter is placed in a Petri dish measuring 80 x 20 mm. 2 g of the chips are evenly applied to the surface of the round filter. The chips are evenly wetted with 2 ml of the aqueous preparation to be tested. Then the lid of the petri dish is put on. The Petri dishes prepared in this way are then exposed to a temperature of about 8 to 22 ° C. for two hours.

Danach werden die Späne entfernt, das Rundfilter unter fließendem Wasser abgespült, in Aceton etwa 5 Sekunden lang geschwenkt und bei Raumtemperatur getrocknet. Danach wird der Korrosionsgrad der Korrosionsabzeichnungen auf dem Rundfilter durch Sichtprüfung festgestellt. Die Bewertung erfolgt nach folgender Klassifikation:

Figure imgb0021
The chips are then removed, the round filter rinsed under running water, swirled in acetone for about 5 seconds and dried at room temperature. The degree of corrosion of the corrosion markings on the round filter is then determined by visual inspection. The evaluation is based on the following classification:
Figure imgb0021

Die auf ihre korrosionsinhibierenden Eigenschaften zu untersuchenden Verbindungen werden zu jeweils 0,1 Gew.-% im wassergemischten Kühlschmierstoff gelöst. Dabei wurden folgende Verbindungen untersucht und bewertet:The compounds to be investigated for their corrosion-inhibiting properties are each dissolved in 0.1% by weight in the water-mixed cooling lubricant. The following connections were examined and evaluated:

Verbindung 1 (erfindungsgemäß)Compound 1 (according to the invention)

Figure imgb0022
Figure imgb0022

Verbindung 2 (erfindungsgemäß)Compound 2 (according to the invention)

Figure imgb0023
Figure imgb0023

Verbindung 3 (nicht erfindungsgemäß)Compound 3 (not according to the invention)

Figure imgb0024
Figure imgb0024

Verbindung 4 (nicht erfindungsgemäß)Compound 4 (not according to the invention)

Fettsäurepolydiethanolamid (C₁₂→C₁₈)
im Handel erhältlich unter der Bezeichnung Comperlan PVDFatty acid polydiethanolamide (C₁₂ → C₁₈)
commercially available under the name Comperlan PVD

Verbindung 5 (nicht erfindungsgemäß)Compound 5 (not according to the invention)

Fettsäurepolydiethanolamid (pflanzl. Öle)
im Handel erhältlich unter der Bezeichnung Comperlan PVDFatty acid polydiethanolamide (vegetable oils)
commercially available under the name Comperlan PVD

Verbindung 6 (nicht erfindungsgemäß)Compound 6 (not according to the invention)

Aminseife/Fettsäuregemisch
im Handel erhältlich unter der Bezeichnung Texamin KL

Figure imgb0025
Amine soap / fatty acid mixture
commercially available under the name Texamin KL
Figure imgb0025

Claims (3)

  1. Use of methylpolysiloxanes having quaternary ammonium groups bound via carbon atoms to silicon atoms, the quotient of the number of dimethylsiloxy groups and of the number of quaternary ammonium groups having a value from 0.5 to 15, as corrosion inhibitors for preparations consisting predominantly of water, especially coolants, such as water-mixed cooling lubricants, in quantities from 0.01 to 0.1% by weight, relative to the total preparation in the form ready for use.
  2. Use of polysiloxanes according to Claim 1, characterised in that compounds of the general formula
    Figure imgb0031
     where
       R¹ in the molecule is identical or different and denotes a methyl radical or the radical
    Figure imgb0032
        R₂ in the molecule is identical or different and denotes an alkyl radical having 1 to 18 carbon atoms or the radical R⁵-CONH- (CH₂)₃-, in which R⁵ is an alkyl radical having 7 to 17 carbon atoms,
    R³ and R⁴ in the molecule are identical or different and denote an alkyl radical having 1 to 4 carbon atoms,
       Z is the radical
    Figure imgb0033
     or
    Figure imgb0034
        X(-) is an inorganic or organic anion,
       n has a value from 5 to 20 and
       m has a value from 1 to 10,
    are used as the methylpolysiloxanes having quaternary ammonium groups, the quotient of the number of dimethylsiloxy groups and of the number of quaternary ammonium groups having a value from 0.5 to 15.
  3. Use of polysiloxanes according to Claim 1, characterised in that compounds of the general formula
    Figure imgb0035
     where
    R², R³, R⁴, X(-) and Z have the meanings already given and
    p has a value from 1 to 29,
    are used as the methylpolysiloxanes having quaternary ammonium groups.
EP89120152A 1988-11-08 1989-10-31 Use of methyl polysiloxanes with quaternary ammonium groups as corrosion inhibitors in mainly aqueous preparations Expired - Lifetime EP0368119B1 (en)

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