KR20090010041A - Corrosion inhibiting composition for non-ferrous metals - Google Patents

Abstract

The invention relates an additive composition for use as a metal working fluid and a process for protection of metals, particularly zinc or aluminum, against corrosion or oxidative degradation. The composition comprises an additive mixture of an alkenyl succinic half ester, a substituted imidazoline compound and amine phosphate partial ester in a functional fluid.

Description

Corrosion inhibiting composition for non-ferrous metals

The present invention relates to additive compositions for use as metalworking solutions or corrosion protection oils and to methods for protecting metals, in particular zinc alloys or aluminum alloys, from corrosion or oxidative degradation.

Additives to protect metals from corrosion are often divided into two types:

Metal deactivators are used to protect yellow metals or alloys, such as copper or bronze, and exhibit their protective action in functional liquids such as inorganic oils or fuels by deactivating the contained metal ions. These metal ions may have a catalytic effect in the course of undesirable oxidative decomposition of inorganic oils or fuels. The protective action is explained by forming a film-like layer on the metal surface or by complexation with metal ions.

Corrosion inhibitors are mainly used to protect ferrous metals such as iron or steel. Similar to metal deactivators, corrosion inhibitors form a film-like layer on the metal surface. Some corrosion inhibitors can also prevent corrosion by emulsifying water to minimize direct contact of water with the metal surface.

Current metal protection methods focus mainly on iron and copper surfaces. However, other metals such as zinc and aluminum and their associated alloys are also becoming very important in many technical fields. Zinc and aluminum, for example, are widely used in automobile manufacturing. Zinc is used as a corrosion protection coating of steel, for example as a zinc coated steel coil. Corrosion problems are common during the transport, handling and processing of semi-metals. Unfortunately, metal deactivator compositions currently used are less satisfactory or insufficient to protect these metal surfaces. Therefore, there is a clear need for an improved metal working fluid to prevent corrosion of these metals.

British Patent 795,491 discloses the preparation of alkenyl succinic acid semiesters and their application as steam turbine lubricant additives thereof.

British patent specification 1,043,488 discloses lubricating oil compositions comprising substituted imidazoline compounds and phosphate partial esters.

US Patent Application Publication 2005/0272614 discloses a corrosion inhibiting composition in which substituted imidazolines and neutral metal sulfonate corrosion inhibitors are present.

Surprisingly, mixtures of alkenyl succinic half esters, substituted imidazoline compounds and amine phosphate partial esters in functional fluids such as oils have been found to prevent corrosion of zinc, zinc coated steel and aluminum metal samples. lost. This anticorrosive effect can be enhanced by a mixture of additional anticorrosive agents such as substituted imidazolines and amine phosphate partial esters.

The present invention

A) a) at least one alkenyl succinic acid half ester of formula (I);

   b) at least one imidazoline compound of formula (II): And

   c) an additive mixture consisting essentially of at least one amine phosphate partial ester of formula (III): And

B) a composition comprising a functional fluid:

In the formula,

R ₁ is C ₆ -C ₁₈ alkenyl, R ₂ is hydrogen or methyl and n is a number from 1 to 100;

Wherein one of R ₁ and R ₂ is hydrogen and the other is C ₁ -C ₁₂ alkyl, hydroxy-C ₂ -C ₁₂ alkyl, amino-C ₂ -C ₁₂ alkyl, C ₂ -C ₂₀ alkenyl , Phenyl, phenyl-C ₁ -C ₄ alkyl, C ₁ -C ₄ alkylphenyl and C ₁ -C ₄ alkylphenyl-C ₁ -C ₄ alkyl; or

Both R ₁ and R ₂ are C ₁ -C ₁₂ alkyl, hydroxy-C ₂ -C ₁₂ alkyl, amino-C ₂ -C ₁₂ alkyl, C ₂ -C ₂₀ alkenyl, phenyl, phenyl-C ₁ -C ₄ A substituent selected from the group consisting of alkyl, C ₁ -C ₄ alkylphenyl and C ₁ -C ₄ alkylphenyl-C ₁ -C ₄ alkyl; And

In the formula,

m is 1 or 2;

when m is 1, n is 2, or when m is 2, n is 1;

R is C ₁ -C ₁₂ alkyl, hydroxy-C ₂ -C ₁₂ alkyl, amino-C ₂ -C ₁₂ alkyl, phenyl, phenyl-C ₁ -C ₄ alkyl, C ₁ -C ₄ alkylphenyl, C _1- C ₄ alkylphenyl-C ₁ -C ₄ alkyl, C ₄ -C ₈ cycloalkyl, C ₄ -C ₈ cycloalkyl-C ₁ -C ₄ alkyl, C ₁ -C ₄ alkyl-C ₄ -C ₈ cycloalkyl and A substituent selected from the group consisting of C ₁ -C ₄ alkyl-C ₄ -C ₈ cycloalkyl-C ₁ -C ₄ alkyl; In addition

R _a , R _b , R _c and R _d independently of one another are hydrogen or C ₁ -C ₁₂ alkyl, hydroxy-C ₂ -C ₁₂ alkyl, amino-C ₂ -C ₁₂ alkyl, phenyl, phenyl-C _1- C ₄ alkyl, C ₁ -C ₄ alkylphenyl, C ₁ -C ₄ alkylphenyl-C ₁ -C ₄ alkyl, C ₄ -C ₈ cycloalkyl, C ₄ -C ₈ cycloalkyl-C ₁ -C ₄ alkyl, A substituent selected from the group consisting of C ₁ -C ₄ alkyl-C ₄ -C ₈ cycloalkyl and C ₁ -C ₄ alkyl-C ₄ -C ₈ cycloalkyl-C ₁ -C ₄ alkyl.

Preferred embodiments of the present invention,

A) a) at least one alkenyl succinic acid half ester of formula (I);

   b) at least one imidazoline compound of formula (II); And

   c) an additive mixture consisting essentially of at least one amine phosphate partial ester of formula (III); And

B) a composition comprising a functional fluid.

In formula (I),

R ₁ is C ₁₀ -C ₁₆ alkenyl, R ₂ is methyl and n is a number from 1 to 20;

In formula (II),

One of R ₁ and R ₂ is hydrogen and the other is C ₁ -C ₁₂ alkyl, hydroxy-C ₂ -C ₁₂ alkyl, amino-C ₂ -C ₁₂ alkyl and C ₁₂ -C ₁₈ alkenyl A substituent selected from; or

Both R ₁ and R ₂ are substituents selected from the group consisting of C ₁ -C ₁₂ alkyl, hydroxy-C ₂ -C ₁₂ alkyl, amino-C ₂ -C ₁₂ alkyl and C ₁₂ -C ₁₈ alkenyl;

In formula (III),

m is 1 or 2; when m is 1, n is 2, or when m is 2, n is 1;

R is a substituent selected from the group consisting of C ₁ -C ₁₂ alkyl, hydroxy-C ₂ -C ₁₂ alkyl and amino-C ₂ -C ₁₂ alkyl; In addition

R _a , R _b , R _c and R _d are independently of each other hydrogen or a substituent selected from the group consisting of C ₁ -C ₁₂ alkyl and hydroxy-C ₂ -C ₁₂ alkyl.

Particularly preferred embodiments of the present invention are

A) a) at least one alkenyl succinic acid half ester of formula (I);

   b) at least one imidazoline compound of formula (II); And

   c) an additive mixture consisting essentially of at least one amine phosphate partial ester of formula (III); And

B) a composition comprising a functional fluid.

In formula (I),

R ₁ is C ₁₂ -C ₁₆ alkenyl, R ₂ is methyl and n is a number from 1 to 20;

In formula (II),

One of R ₁ and R ₂ is hydrogen and the other is a substituent selected from the group consisting of C ₁ -C ₁₂ alkyl and C ₁₂ -C ₁₈ alkenyl; or

Both R ₁ and R ₂ are substituents selected from the group consisting of C ₁ -C ₁₂ alkyl and C ₁₂ -C ₁₈ alkenyl;

In formula (III),

m is 1 or 2; when m is 1, n is 2, or when m is 2, n is 1;

R is a substituent selected from the group consisting of C ₁ -C ₁₂ alkyl and hydroxy-C ₂ -C ₁₂ alkyl; In addition

R _a , R _b , R _c and R _d are independently of each other hydrogen or a substituent selected from the group consisting of C ₁ -C ₁₂ alkyl and hydroxy-C ₂ -C ₁₂ alkyl.

The most preferable aspect of this invention,

a) at least one alkenyl succinic acid half ester of formula (I);

b) at least one imidazoline compound of formula (II);

c) at least one amine phosphate partial ester of formula (III); And

d) a composition comprising additional and customary additives:

In formula (I),

R ₁ is C ₆ -C ₁₈ alkenyl, R ₂ is methyl and n is a number from 1 to 100;

In formula (II),

One of R ₁ and R ₂ is hydrogen and the other is C ₁ -C ₁₂ alkyl, hydroxy-C ₂ -C ₁₂ alkyl, amino-C ₂ -C ₁₂ alkyl, C ₂ -C ₂₀ alkenyl, phenyl, Or a substituent selected from the group consisting of phenyl-C ₁ -C ₄ alkyl, C ₁ -C ₄ alkylphenyl and C ₁ -C ₄ alkylphenyl-C ₁ -C ₄ alkyl; or

Both R ₁ and R ₂ are C ₁ -C ₁₂ alkyl, hydroxy-C ₂ -C ₁₂ alkyl, amino-C ₂ -C ₁₂ alkyl, C ₂ -C ₂₀ alkenyl, phenyl, phenyl-C ₁ -C ₄ A substituent selected from the group consisting of alkyl, C ₁ -C ₄ alkylphenyl and C ₁ -C ₄ alkylphenyl-C ₁ -C ₄ alkyl;

In formula (III),

m is 1 or 2;

when m is 1, n is 2, or when m is 2, n is 1;

R is C ₁ -C ₁₂ alkyl, hydroxy-C ₂ -C ₁₂ alkyl, amino-C ₂ -C ₁₂ alkyl, phenyl, phenyl-C ₁ -C ₄ alkyl, C ₁ -C ₄ alkylphenyl, C _1- C ₄ alkylphenyl-C ₁ -C ₄ alkyl, C ₄ -C ₈ cycloalkyl, C ₄ -C ₈ cycloalkyl-C ₁ -C ₄ alkyl, C ₁ -C ₄ alkyl-C ₄ -C ₈ cycloalkyl and A substituent selected from the group consisting of C ₁ -C ₄ alkyl-C ₄ -C ₈ cycloalkyl-C ₁ -C ₄ alkyl; In addition

R _a , R _b , R _c and R _d independently of one another are hydrogen or C ₁ -C ₁₂ alkyl, hydroxy-C ₂ -C ₁₂ alkyl, amino-C ₂ -C ₁₂ alkyl, phenyl, phenyl-C _1- C ₄ alkyl, C ₁ -C ₄ alkylphenyl, C ₁ -C ₄ alkylphenyl-C ₁ -C ₄ alkyl, C ₄ -C ₈ cycloalkyl, C ₄ -C ₈ cycloalkyl-C ₁ -C ₄ alkyl, A substituent selected from the group consisting of C ₁ -C ₄ alkyl-C ₄ -C ₈ cycloalkyl and C ₁ -C ₄ alkyl-C ₄ -C ₈ cycloalkyl-C ₁ -C ₄ alkyl.

The aforementioned compositions are suitable as corrosion inhibitors in non-aqueous, partially aqueous or aqueous functional fluids or liquids.

The expressions and terms used above and below are preferably defined as follows in the detailed description of the invention.

In the compounds of formula (I), R ₁ , defined as C ₆ -C ₁₈ alkenyl, is preferably straight-chain or, if possible, branched radicals such as n-2-octenyl, n-2-dodecenyl, isododode Or is preferably a partial formula

의 기이며,

Is the flag of,

R ′ and R ″ independently of one another are hydrogen or substantially straight-chain hydrocarbyl groups, provided that the total number of carbon atoms in R is within the ranges indicated. Preferably R ′ and R ″ are C ₃ -C ₁₅ alkyl or C ₃ -C ₁₅ alkenyl group. In a particularly advantageous embodiment, R has about 16 to about 18 C atoms. R 'is hydrogen or C ₁ -C ₇ alkyl or C ₂ -C ₇ alkenyl and R ″ is C ₅ -C ₁₅ alkyl or C ₅ -C ₁₅ alkenyl.

R ₂ is hydrogen or preferably methyl.

In formula (I), the index n means a number from 1 to about 100. In a preferred embodiment n represents a number from 1 to about 20. Compound (I) reacts R-substituted succinic acid with ethylene oxide or ethylene glycol of the desired chain length if R ₂ is hydrogen, or propylene oxide or propylene glycol of the desired chain length if R ₂ is methyl It can be obtained by reacting with.

Compound (I) is known and at least some of them can be purchased commercially. The preparation of compound (I) is described in British Patent Specification 795,491.

Compound (I) is a known fat-soluble corrosion inhibitor and is commercially available as a solution in inorganic oils such as the product Ciba® Irgacor® L 12. Another product is the Hitec® 536, available from Ethyl Corporation, Richmond, Vermont, USA.

In compound (II), one of R ₁ and R ₂ is hydrogen and the other is C ₁ -C ₁₂ alkyl, hydroxy-C ₂ -C ₁₂ alkyl, amino-C ₂ -C ₁₂ alkyl, C ₂ -C Or a substituent selected from the group consisting of ₂₀ alkenyl, phenyl, phenyl-C ₁ -C ₄ alkyl, C ₁ -C ₄ alkylphenyl and C ₁ -C ₄ alkylphenyl-C ₁ -C ₄ alkyl; or

Both R ₁ and R ₂ are C ₁ -C ₁₂ alkyl, hydroxy-C ₂ -C ₁₂ alkyl, amino-C ₂ -C ₁₂ alkyl, C ₂ -C ₂₀ alkenyl, phenyl, phenyl-C ₁ -C ₄ And a substituent selected from the group consisting of alkyl, C ₁ -C ₄ alkylphenyl and C ₁ -C ₄ alkylphenyl-C ₁ -C ₄ alkyl.

R ₁ and R ₂ , defined as C ₁ -C ₁₂ alkyl, are for example C ₁ -C ₆ alkyl such as methyl, ethyl, n-propyl or isopropyl or n-butyl, sec-butyl or t-butyl or straight or branched Pentyl or hexyl, and C ₇ -C ₁₂ alkyl, such as straight or branched heptyl, octyl, isooctyl, nonyl, t-nonyl, decyl, undecyl or dodecyl.

R ₁ and R ₂ , defined as hydroxy-C ₂ -C ₁₂ alkyl, are for example 2-hydroxyethyl, dihydroxyethyl, 2- or 3-hydroxypropyl, 2-, 3-dihydroxypropyl, glycerol Or a C ₄ -C ₁₂ alkyl group as defined above, substituted by 1-3 hydroxy groups.

R ₁ and R ₂ , defined as amino-C ₂ -C ₁₂ alkyl, are for example the aforementioned C ₄ -C substituted by 2-aminoethyl, diaminoethyl or 2- or 3-aminopropyl or 1-3 amino groups ₁₂ alky groups.

R ₁ and R ₂ , defined as C ₂ -C ₂₀ alkenyl, are linear or, where possible, branched radicals such as vinyl, allyl, 2-butenyl, 3-butenyl, isobutenyl, n-2,4 -Pentadienyl, 3-methyl-2-butenyl, n-2-octenyl, n-2-dodecenyl or isododecenyl.

R ₁ and R ₂ , defined as phenyl-C ₁ -C ₄ alkyl, are C ₁ -C ₄ alkylphenyl and the C ₁ -C ₄ alkylphenyl-C ₁ -C ₄ alkyl radical is, for example, benzyl, 1- or 2 -Phenethyl, 4-methyl- or 4-ethylphenyl, cumyl or 4-methylbenzyl.

According to a preferred embodiment, one of R ₁ and R ₂ is hydrogen and the other is C ₁ -C ₁₂ alkyl, hydroxy-C ₂ -C ₁₂ alkyl, amino-C ₂ -C ₁₂ alkyl and C ₁₂ -C ₁₈ A substituent selected from the group consisting of alkenyl; or

Both R ₁ and R ₂ are substituents selected from the group consisting of C ₁ -C ₁₂ alkyl, hydroxy-C ₂ -C ₁₂ alkyl, amino-C ₂ -C ₁₂ alkyl and C ₁₂ -C ₁₈ alkenyl.

Compound (II) is a known compound and is applicable as a fat-soluble corrosion inhibitor and can be obtained as a solution in inorganic oil such as the product Ciba Amine 0.

In compound (III), m is 1 or 2. When m is 1, n is 2. Such compounds are represented by the formula:

When m is 2, n is 1. Such compounds are represented by the formula:

In compounds of formula III, R is C ₁ -C ₁₂ alkyl, hydroxy-C ₂ -C ₁₂ alkyl, amino-C ₂ -C ₁₂ alkyl, phenyl, phenyl-C ₁ -C ₄ alkyl, C _1- C ₄ alkylphenyl, C ₁ -C ₄ alkylphenyl-C ₁ -C ₄ alkyl, C ₄ -C ₈ cycloalkyl, C ₄ -C ₈ cycloalkyl-C ₁ -C ₄ alkyl, C ₁ -C ₄ alkyl- A substituent selected from the group consisting of C ₄ -C ₈ cycloalkyl and C ₁ -C ₄ alkyl-C ₄ -C ₈ cycloalkyl-C ₁ -C ₄ alkyl; In addition

R _a , R _b , R _c and R _d independently of one another are hydrogen or C ₁ -C ₁₂ alkyl, hydroxy-C ₂ -C ₁₂ alkyl, amino-C ₂ -C ₁₂ alkyl, phenyl, phenyl-C _1- C ₄ alkyl, C ₁ -C ₄ alkylphenyl, C ₁ -C ₄ alkylphenyl-C ₁ -C ₄ alkyl, C ₄ -C ₈ cycloalkyl, C ₄ -C ₈ cycloalkyl-C ₁ -C ₄ alkyl, It is a substituent selected from the group consisting of C ₁ -C ₄ alkyl-C ₄ -C ₈ cycloalkyl and C ₁ -C ₄ alkyl-C ₄ -C ₈ cycloalkyl-C ₁ -C ₄ alkyl.

C ₁ -C ₁₂ alkyl, hydroxy-C ₂ -C ₁₂ alkyl, amino-C ₂ -C ₁₂ alkyl, phenyl, phenyl-C ₁ -C ₄ alkyl, C ₁ -C ₄ alkylphenyl, C ₁ -C ₄ The definition of alkylphenyl-C ₁ -C ₄ alkyl corresponds to the definition given above for the compounds of formulas (I) and (II).

C ₄ -C ₈ cycloalkyl, C ₄ -C ₈ cycloalkyl-C ₁ -C ₄ alkyl, C ₁ -C ₄ alkyl-C ₄ -C ₈ cycloalkyl and C ₁ -C ₄ alkyl-C ₄ -C ₈ R _a , R _b , R _c and R _d as well as R, defined as cycloalkyl-C ₁ -C ₄ alkyl, are for example cyclopentyl, cyclohexyl, cyclopentylmethyl or cyclohexylmethyl, cyclopentyl-1,1-ethyl , Cyclohexyl-1,1-ethyl, cyclopentyl-1,2-ethyl, cyclohexyl-1,2-ethyl, cyclopentyl-1,2-propyl or cyclohexyl-1,2-propyl, these are C ₄ In the -C ₈ cycloalkyl group it may be substituted by C ₁ -C ₄ alkyl such as methyl, ethyl, n-propyl or isopropyl.

According to a preferred embodiment, R is a substituent selected from the group consisting of C ₁ -C ₁₂ alkyl, hydroxy-C ₂ -C ₁₂ alkyl and amino-C ₂ -C ₁₂ alkyl; In addition

R _a , R _b , R _c and R _d are each independently a substituent selected from the group consisting of C ₁ -C ₁₂ alkyl and hydroxy-C ₂ -C ₁₂ alkyl.

Amine phosphate partial esters represented by formula (II) are known compounds that can be prepared by known methods. Compound (III) is a fat-soluble corrosion inhibitor and is commercially available as the product Ciba® Irgalube®349.

Other amine phosphate partial esters represented by formula (III) can be obtained from Rheinchemie Rheinau GmbH, Mannheim, Germany, such as products Additin® RC 3740, RC 3741 or RC3760 (amine neutralized phosphate esters of fatty alcohols).

The term functional liquids include non-aqueous, partially aqueous and aqueous liquids, which are in contact with the metals to be protected, in particular aluminum and zinc.

Examples of non-aqueous functional liquids are fuels, such as hydrocarbon mixtures, which are liquids at room temperature and comprise inorganic oil fractions suitable for use in internal combustion engines such as internal combustion engines such as external ignition (petroleum engines) or internal ignition (diesel engines). ; For example, petroleum (usually graded or premium grade petroleum) or diesel fuels with different octane contents, and lubricating oils, working fluids, metalworking fluids (drawing oils, cutting oils, forming oils, drilling oils, etc.), engine coolants, transformer oils and switches Gear oil.

Examples of suitable partially aqueous functional liquids include w / o or o / w metalworking solutions, working fluids based on aqueous polyglycol / polyglycol ether mixtures or glycol systems, and engine cooling systems based on aqueous glycols. .

Examples of aqueous functional liquids are industrial cooling water, filling compositions of water treatment plants, steam generation systems, seawater evaporation systems, sugar evaporation systems, irrigation systems, hydrostatic boilers and heating systems or cooling systems with closed circulation.

The composition according to the invention preferably comprises from 0.01 to 10.0% by weight, in particular from 0.02 to 3.0% by weight, based on the weight of the functional liquid.

Non-aqueous functional liquids are in particular base oils with lubricating viscosity, which can be used for the production of greases, metalworking fluids, gear fluids and hydraulic fluids.

Suitable greases, metal working fluids, gear fluids and working fluids are based, for example, on inorganic or synthetic oils or mixtures thereof. Lubricants are familiar to those skilled in the art and are described in related literature such as: Chemistry and Technology of Lubricants; Mortier, RM and Orszulik, ST (Editors); 1992 Blackie and Son Ltd. for GB, VCH-Publishers NY for US, ISBN 0-216-92921-0 , cf. pages 208 et seq. and 269 et seq .; in Kirk-Othmer Encyclopedia of Chemi-cal Technology, Fourth Edition 1969, J. Wiley & Sons, New York, Vol. 13, page 533 et seq. (Hydraulic Fluids) ; Performance Testing of Hydraulic Fluids; R. Tourret and EP Wright, Hy-den & Son Ltd. GB, on behalf of The Institute of Petroleum London, ISBN 0 85501 317 6; Ullmann's Encyclopedia of Ind. Chem., Fifth Completely Revised Edition, Verlag Chemie, DE-Weinheim, VCH-Publishers for US, Vol. A 15, page 423 et seq. (Lubricants), Vol. A 13, page 165 et seq. (Hydraulic Fluids).

Lubricants are oils and greases based on inorganic oils, synthetic oils, or vegetable and animal oils, fats, tallows and waxes or mixtures thereof. Plant and animal oils, fats, tallows and waxes are for example palm fruit oil, palm oil, olive oil, rapeseed oil, castor oil, walnut oil and mixtures thereof, fish oil, and chemically modified, such as epoxidized or sulfur In either an exploded or alkylated or hydrogenated form or a genetically engineered form, such as soybean oil produced by genetic engineering.

Examples of synthetic lubricants include silicones of aliphatic or aromatic carboxy esters, polymerizable esters, polyalkylene oxides, phosphate esters, poly-α-olefins or diesters of dibasic acids with monohydric alcohols, such as dioctyl sebacate or dinonyl adipe Or triesters of trimethylolpropane with monobasic acids or mixtures of these acids, such as trimethylolpropane tripelagonate, trimethylolpropane tricaprylate or mixtures thereof, pentaerythritol and monobasic acids or such Tetra esters with a mixture of acids, such as pentaerythryl tetracaprylate, or complex esters of monobasic and dibasic acids with polyhydric alcohols, such as complex esters of trimethylolpropane with capryl and sebacic acid or mixtures thereof . Particularly suitable besides inorganic oils are, for example, poly-α-olefins, ester-based lubricants, phosphates, glycols, polyglycols and polyalkylene glycols and mixtures thereof with water.

The lubricant or mixtures thereof can be mixed with organic or inorganic thickeners (base fats). The metal working fluid and the working fluid can be prepared based on the same material as described above for the lubricant. These are often emulsions of substances in water or other liquids.

The lubricant composition such as grease, gear fluid, metal working fluid and working fluid may additionally also contain additional additives added to further improve the basic properties. These include antioxidants, metal deactivators, rust inhibitors, viscosity index enhancers, pour point depressants, dispersants, detergents, tackifiers, thixotropic builders, dewatering agents, defoamers, demulsifiers, high pressure additives and anti-wear additives do. Such additives are added in amounts customary for each purpose, in the range from 0.01 to 10.0% by weight. Examples of additional additives are as follows:

1. Phenolic Antioxidants

1.1. Alkylated monophenols : 2,6-di-t-butyl-4-methylphenol, 2-butyl-4,6-dimethylphenol, 2,6-di-t-butyl-4-ethylphenol, 2,6-di -t-butyl-4-n-butylphenol, 2,6-di-t-butyl-4-iso-butylphenol, 2,6-dicyclopentyl-4-methylphenol, 2- (a-methylcyclohexyl ) -4,6-dimethyl-phenol, 2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol, 2,6-di-t-butyl-4-methoxy-methyl Phenol, straight chain nonylphenol or branched nonylphenol such as 2,6-dinononyl-4-methylphenol, 2,4-dimethyl-6- (1'-methyl-undec-1'-yl) -phenol , 2,4-dimethyl-6- (1'-methylheptadec-1'-yl) -phenol, 2,4-dimethyl-6- (1'-methyl-tridec-1'-yl) -phenol and Mixtures thereof.

1.2. Alkylthiomethylphenol : 2,4-dioctylthiomethyl-6-t-butylphenol, 2,4-dioctylthio-methyl-6-methylphenol, 2,4-dioctylthiomethyl-6-ethylphenol, 2,6-didodecylthio-methyl-4-nonyl-phenol.

1.3. Hydroquinone and alkylated hydroquinone : 2,6-di-t-butyl-4-methoxyphenol, 2,5-di-t-butyl-hydroquinone, 2,5-di-t-amyl-hydroquinone, 2,6-di Phenyl-4-octadecyl-oxyphenol, 2,6-di-t-butyl-hydroquinone, 2,5-di-t-butyl-4-hydroxyanisole, 3,5-di-t-butyl-4 Hydroxy-anisole, 3,5-di-t-butyl-4-hydroxyphenylstearate, bis (3,5-di-t-butyl-4-hydroxy-phenyl) adipate.

1.4. Tocopherol : α-, β-, γ- or δ-tocopherol and mixtures thereof (vitamin E).

1.5 . Hydroxylated Thiodiphenyl Ether : 2,2'-thiobis (6-t-butyl-4-methylphenol), 2,2'-thiobis (4-octyl-phenol), 4,4'-thiobis (6-t-butyl-3-methylphenol), 4,4'-thiobis- (6-t-butyl-2-methylphenol), 4,4'-thiobis (3,6-di-sec- Amylphenol), 4,4'-bis (2,6-dimethyl-4-hydroxy-phenyl) disulfide.

1.6. Alkylidene bisphenol : 2,2'-methylenebis (6-t--butyl-4-methylphenol), 2,2'-methylene-bis (6-t-butyl-4-ethylphenol), 2,2 ' -Methylenebis [4-methyl-6- (a-methylcyclohexyl) -phenol], 2,2'-methylenebis (4-methyl-6-cyclohexyl-phenol), 2,2'-methylene-bis ( 6-nonyl-4-methyl-phenol), 2,2'-methylenebis (4,6-di-t-butylphenol), 2,2'-ethylidenebis (4,6-di-t-butyl- Phenol), 2,2'-ethylidenebis (6-t-butyl-4-isobutylphenol), 2,2'-methylenebis [6- (α-methyl-benzyl) -4-nonylphenol], 2 , 2'-methylenebis [6- (α, α-dimethylbenzyl) -4-nonyl-phenol], 4,4'-methylenebis (2,6-di-t-butylphenol), 4,4'- Methylenebis (6-t-butyl-2-methylphenol), 1,1-bis (5-t-butyl-4-hydroxy-2-methyl-phenyl) butane, 2,6-bis (3-t- Butyl-5-methyl-2-hydroxy-benzyl) -4-methyl-phenol, 1,1,3-tris (5-t-butyl-4-hydroxy-2-methylphenyl) butane, 1,1-bis (5-t-butyl-4-hydroxy-2-methyl-phenyl) -3-n-dodecyl-mercaptobutane, ethylene glycol bis [3,3-bis (3'-t- Yl-4'-hydroxyphenyl) butyrate], bis (3-t-butyl-4-hydroxy-5-methyl-phenyl) dicyclo-pentadiene, bis [2- (3'-t-butyl-2 '-Hydroxy-5'-methyl-benzyl) -6-t-butyl-4-methyl-phenyl] terephthalate, 1,1-bis (3,5-dimethyl-2-hydroxyphenyl) -butane, 2 , 2-bis (3,5-di-t-butyl-4-hydroxyphenyl) propane, 2,2-bis (5-t-butyl-4-hydroxy-2-methylphenyl) -4-n-dode Silmercaptobutane, 1,1,5,5-tetra (5-t-butyl-4-hydroxy-2-methylphenyl) pentane.

1.7. O-, N- and S-benzyl compounds : 3,5,3 ', 5'-tetra-t-butyl-4,4'-dihydroxydibenzyl ether, octadecyl 4-hydroxy-3,5- Dimethylbenzylmercaptoacetate, tridecyl-4-hydroxy-3,5-di-t-butylbenzylmercaptoacetate, tris (3,5-di-t-butyl-4-hydroxy benzyl) amine, bis ( 4-t-butyl-3-hydroxy-2,6-dimethylbenzyl) dithioterephthalate, bis (3,5-di-t-butyl-4-hydroxy-benzyl) sulfide, isooctyl 3,5 -Di-t-butyl-4-hydroxybenzylmercaptoacetate.

1.8 hydroxybenzylated malonate : dioctadecyl 2,2-bis (3,5-di-t-butyl-2-hydroxybenzyl) -malonate, dioctadecyl 2- (3-t-butyl- 4-hydroxy-5-methylbenzyl) malonate, dododecyl mercaptoethyl-2,2-bis (3,5-di-t-butyl-4-hydroxybenzyl) malonate, di- [4- ( 1,1,3,3-tetramethyl-butyl) -phenyl] -2,2-bis (3,5-di-t-butyl-4-hydroxybenzyl) malonate.

1.9 hydroxybenzyl aromatic compound : 1,3,5-tris (3,5-di-t-butyl-4-hydroxybenzyl) -2,4,6-tri-methyl-benzene, 1,4-bis ( 3,5-di-t-butyl-4-hydroxybenzyl) -2,3,5,6-tetramethylbenzene, 2,4,6-tris (3,5-di-t-butyl-4- Hydroxybenzyl) phenol.

1.10. Triazine compound : 2,4-bisoctyl mercapto-6- (3,5-di-t-butyl-4-hydroxyanilino) -1,3,5-triazine, 2-octyl mercapto-4 , 6-bis (3,5-di-t-butyl-4-hydroxyanilino) -1,3,5-triazine, 2-octyl-mercapto-4,6-bis (3,5-di -t-butyl-4-hydroxyphenoxy) -1,3,5-triazine, 2,4,6-tris (3,5-di-t-butyl-4-hydroxyphenoxy) -1, 2,3-triazine, 1,3,5-tris (3,5-di-t-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris (4-t-butyl- 3-hydroxy-2,6-dimethylbenzyl) iso-cyanurate, 2,4,6-tris (3,5-di-t-butyl-4-hydroxy-phenylethyl) -1,3,5 -Triazine, 1,3,5-tris (3,5-di-t-butyl-4-hydroxyphenyl-propionyl) -hexahydro-1,3,5-triazine, 1,3,5- Tris (3,5-dicyclohexyl-4-hydroxy-benzyl) isocyanurate.

1.11. Acylaminophenols : 4-hydroxylaurylanilide, 4-hydroxysteaanylide, octyl N- (3,5-di-t-butyl-4-hydroxyphenyl) carbamate.

1.12 . Monohydric or polyhydric alcohols such as methanol, ethanol, n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neo Pentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N'-bis (hydroxyethyl) oxamide, 3-thiaundanol , 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2.2.2] octane and β- (3,5 Ester of di-t-butyl-4-hydroxyphenyl) -propionic acid .

1.13. Monohydric or polyhydric alcohols such as methanol, ethanol, n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol , Neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N'-bis (hydroxyethyl) oxamide, 3-thia Undecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo- [2.2.2] octane and β- ( Ester of 5-t-butyl-4-hydroxy-3-methylphenyl) propionic acid .

1.14. Mono or polyhydric alcohols, for example esters of the alcohols mentioned under 1.13 above with β- (3,5-dicyclohexyl-4-hydroxyphenyl) -propionic acid .

1.15. Mono or polyhydric alcohols, for example esters of the alcohols mentioned under 1.13 above with 3,5-di-t-butyl-4-hydroxyphenyl acetic acid .

1.16. Amides of β- (3,5-di-t-butyl-4-hydroxyphenyl) propionic acid, for example N, N'-bis (3,5-di-t-butyl-4-hydroxyphenylpropionic acid) Hexamethylenediamide, N, N'-bis (3,5-di-t-butyl-4-hydroxyphenylpyrropiionyl) trimethylenediamide, N, N'-bis (3,5-di-t -Butyl-4-hydroxy-phenylpropionyl) hydrazine.

1.17. Ascorbic acid (vitamin C)

1.18. Amine antioxidants such as N, N'-di-isopropyl-p-phenylenediamine, N, N'-di-sec-butyl-p-phenylenediamine, N, N'-bis (1,4-dimethyl Pentyl) -p-phenylenediamine, N, N'-bis (1-ethyl-3-methylpentyl) -p-phenylenediamine, N, N'-bis (1-methylheptyl) -p-phenylenediamine , N, N'-dicyclohexyl-p-phenylenediamine, N, N'-diphenyl-p-phenylenediamine, N, N'-di- (2-naphthyl) -p-phenylenediamine, N-isopropyl-N'-phenyl-p-phenylenediamine, N- (1,3-dimethylbutyl) -N'-phenyl-p-phenylenediamine, N- (1-methylheptyl) -N'- Phenyl-p-phenylenediamine, N-cyclohexyl-N'-phenyl-p-phenylenediamine, 4- (p-toluenesulfamoyl) -diphenylamine, N, N'-dimethyl-N, N'- Di-sec-butyl-p-phenylenediamine, diphenylamine, N-allyldiphenylamine, 4-isopropoxydiphenylamine, N-phenyl-1-naphthylamine, N- (4-t-octyl Phenyl) -1-naphthylamine, N-phenyl-2-naphthylamine, octylated diphenylamines such as p, p'-di-t-octyldiphenylamine, 4-n-butylaminophenol, 4 -Butyrylaminophenol, 4-nonan oilamino-phenol, 4-dodecane oilaminophenol, 4-octadecane oilaminophenol, di- (4-methoxyphenyl) amine, 2,6-di-t-butyl 4-dimethylaminomethylphenol, 2,4'-di-aminodiphenylmethane, 4,4'-diaminodiphenylmethane, N, N, N ', N'-tetramethyl-4,4'-dia Minodiphenylmethane, 1,2-di-[(2-methylphenyl) amino] ethane, 1,2-di- (phenylamino) propane, (o-tolyl) biguanide, di- [4- (1 ' , 3'-dimethylbutyl) phenyl] amine, t-octylated N-phenyl-1-naphthylamine, mixture of mono- and dialkylated t-butyl / t-octyldiphenylamine, mono- and dialkylated nonyldi Mixtures of phenylamines, mixtures of mono- and dialkylated nonyldiphenylamines, mixtures of mono- and dialkylated dodecyldiphenylamines, mixtures of mono- and dialkylated isopropyl / isohexylphenylamines, mono- and dialkylated t A mixture of -butyldiphenylamine, 2,3-di-hydro-3,3-dimethyl-4H-1,4-benzothiazine, phenothione A mixture of gin, mono and dialkylated t-butyl / t-octylphenothiazine, a mixture of mono- and dialkylated t-octyl-phenothiazine, N-allylphenothiazine, N, N, N ', N'- Tetraphenyl-1,4-diaminobut-2-ene, N, N-bis (2,2,6,6-tetramethyl-piperidin-4-yl-hexamethylenediamine, bis (2,2, 6,6-tetramethylpiperidin-4-yl) sebacate, 2,2,6,6-tetramethylpiperidin-4-one, 2,2,6,6-tetramethylpiperidin-4 -Come on.

2. Additional antioxidants: aliphatic or aromatic phosphites, esters of thiodipropionic acid or thiodiacetic acid or salts of dithiocarbam or dithiophosphoric acid, 2,2,12,12-tetramethyl-5,9-di Hydroxy-3,7,11-trithiatridecane and 2,2,15,15-tetramethyl-5,12-dihydroxy--3,7,10,14-tetrathiahexadecane.

3. Additional metal deactivators :

3.1. Benzotriazole and its derivatives : 2-mercaptobenzotriazole, 2,5-dimercaptobenzotriazole, 4- or 5-alkylbenzotriazole (such as tolutriazole) and derivatives thereof, 4,5,6 , 7-tetra-hydro-benzotriazole, 5,5'-methylenebisbenzotriazole; Mannich bases of benzotriazole or tolutriazole, such as 1- [di (2-ethylhexylaminomethyl)] tolutriazole and 1- [di (2-ethylhexylamino-methyl)] benzotriazole; Alkoxyalkylbenzotriazoles such as 1- (nonyloxymethyl) -benzotriazole, 1- (1-butoxyethyl) benzotriazole and 1- (1-cyclohexyl-oxybutyl) tolutriazole.

3.2. 1,2,4-triazole and its derivatives : 3-alkyl (or aryl) -1,2,4-triazole, Mannich bases of 1,2,4-triazole, such as 1- [di (2- Ethylhexyl) amino-methyl] -1,2,4--triazole; Alkoxyalkyl-1,2,4-triazoles such as 1- (1-butoxyethyl) -1,2,4-triazole; Acylated 3-amino-1,2,4-triazole.

3.3. Imidazole derivatives : 4,4'-methylenebis (2-undecyl-5-methylimidazole), bis [(N-methyl) -imidazol-2-yl] carbinol octyl ether.

3.4. Sulfur-containing heterocyclic compounds : 2-mercaptobenzothiazole, 2,5-di-mercapto-1,3,4-thiadiazole, 2,5-dimercaptobenzothiadiazole and derivatives thereof; 3,5-bis [di- (2-ethylhexyl) aminomethyl] -1,3,4-thiadiazolin-2-one.

3.5. Amino compounds : salicylidenepropylenediamine, salicylicaminoguanidine and salts thereof.

4. Corrosion inhibitors :

4.1. Organic acids, their esters, metal salts, amine salts and anhydrides: alkyl- and alkenylsuccinic acids and partial esters of these with alcohols, diols or hydroxycarboxylic acids, alkyl- and alkenylsuccinic acids, 4-nonylphenoxyacetic acid, alkoxy- And alkoxyethoxycarboxylic acids such as dodecyl acetic acid, partial amides of dodecyloxy (ethoxy) acetic acid and salts thereof, and also N-oleylsarcosine, sorbitan monooleate, lead naphthenate, alkenylsuccinic anhydride Such as dodecenylsuccinic anhydride, 2- (2-carboxyethyl) -1-dodecyl-3-methylglycerol and salts thereof, in particular sodium salts and triethanolamine salts.

4.2. Nitrogen-containing compounds :

4.2.1 Tertiary aliphatic and cycloaliphatic amines and amine salts of organic and inorganic acids, such as fat-soluble alkylammonium carboxylates, and also 1- [N, N-bis- (2-hydroxyethyl) amino] -3- (4- Nonyl-phenoxy) -propan-2-ol.

4.2.2 Heterocyclic compounds such as substituted imidazolines and oxazolines such as 2-heptadecenyl-1- (2-hydroxyethyl) -imidazoline.

5. Sulfur-containing compounds : barium dinonylnaphthalenesulfonate, calcium petroleum sulfonate, alkylthio-substituted aliphatic carboxylic acids, esters of aliphatic 2-sulfocarboxylic acids and salts thereof

6. Viscosity index improvers : polyacrylates, polymethacrylates, vinylpyrrolidone / methacrylate copolymers, polyvinylpyrrolidone, polybutenes, olefin copolymers, styrene / acrylate copolymers, polyethers.

7. Pour point depressants : poly (meth) acrylates, ethylene-vinyl acetate copolymers, alkyl polystyrenes, fumarate copolymers, alkylated naphthalene derivatives.

8. Dispersants / Surfactants : polybutenylsuccinamide or polybutenylsuccinimide, polybutenylphosphonic acid derivatives, basic magnesium, calcium and barium sulfonate and phenolate.

9. High pressure and abrasion resistant additives : sulfur- and halogen-containing compounds such as hydrogenated paraffins, sulfonated olefins or vegetable oils (soybean oil, rapeseed oil), alkyl or aryl di- or trisulfides, benzotriazoles or Derivatives thereof such as bis (2-ethylhexyl) aminomethyl tolutriazole, dithiocarbamates such as methylenebisdibutyl dithiocarbamate, derivatives of 2-mercaptobenzothiazole such as 1- [ N, N-bis (2-ethylhexyl) aminomethyl] -2-mercapto-1H-1,3-benzothiazole, derivatives of 2,5-dimercapto-1,3,4-thiadiazole, such as 2,5-bis (t-nonyldithio) -1,3,4-thiadiazole.

10. Materials to reduce the coefficient of friction : lard oil, oleic acid, tallow, rapeseed oil, sulfurized fats, amines. Another example is described in EP-A-0 565 487.

11. Special additives : For water / oil metal processing and working fluids.

11.1. Emulsifiers : Petroleum sulfonates, amines, polyoxyethylated fatty amines, nonionic surface active substrates.

11.2. Buffer : alkanolamine

11.3 Biocides: Triazine, thiazolinone, trisnitromethane, morpholine, sodium pyridinethiol.

11.4 Processing Speed Enhancers : Calcium Sulfonate and Barium Sulfonate.

11.5 Adhesive : Acrylamide copolymer, polyisobutene resin.

11.6 Thixotropic builders : microcrystalline waxes, oxidized waxes and oxidized esters.

11.7 Dehydrating agents : polyglycol ether, butyldiglycol.

The component can be mixed with the lubricant in a manner known in the art. Depending on the intended application, so-called additive packages or concentrates can be prepared which can be diluted to the use concentration for the corresponding lubricant.

The ratio of component a) to component b) to component c) present in the additive mixture A) may vary within the range of about 10:10:80 to 80:10:10 to 10:80:10 weight percent.

Although the total content of the additive mixture A) in the composition is not critical, the preferred total content of the additive mixture A) in the composition is in the range of 10.0 to 0.01, preferably 10.0 to 0.1 or 3.0 to 0.1% by weight, based on the total weight of the composition. to be.

Another aspect of the invention

a) at least one alkenyl succinic acid half ester of formula (I)

b) at least one imidazoline compound of formula (II): And

c) an additive mixture consisting essentially of at least one amine phosphate partial ester of formula (III):

In formula (I),

R ₁ is C ₆ -C ₁₈ alkenyl, R ₂ is hydrogen or methyl and n is a number from 1 to 100;

In formula (II),

One of R ₁ and R ₂ is hydrogen and the other is C ₁ -C ₁₂ alkyl, hydroxy-C ₂ -C ₁₂ alkyl, amino-C ₂ -C ₁₂ alkyl, C ₂ -C ₂₀ alkenyl, phenyl, Or a substituent selected from the group consisting of phenyl-C ₁ -C ₄ alkyl, C ₁ -C ₄ alkylphenyl and C ₁ -C ₄ alkylphenyl-C ₁ -C ₄ alkyl; or

Both R ₁ and R ₂ are C ₁ -C ₁₂ alkyl, hydroxy-C ₂ -C ₁₂ alkyl, amino-C ₂ -C ₁₂ alkyl, C ₂ -C ₂₀ alkenyl, phenyl, phenyl-C ₁ -C ₄ A substituent selected from the group consisting of alkyl, C ₁ -C ₄ alkylphenyl and C ₁ -C ₄ alkylphenyl-C ₁ -C ₄ alkyl; And

In formula (III),

m is 1 or 2;

when m is 1, n is 2, or when m is 2, n is 1;

R is C ₁ -C ₁₂ alkyl, hydroxy-C ₂ -C ₁₂ alkyl, amino-C ₂ -C ₁₂ alkyl, phenyl, phenyl-C ₁ -C ₄ alkyl, C ₁ -C ₄ alkylphenyl, C _1- C ₄ alkylphenyl-C ₁ -C ₄ alkyl, C ₄ -C ₈ cycloalkyl, C ₄ -C ₈ cycloalkyl-C ₁ -C ₄ alkyl, C ₁ -C ₄ alkyl-C ₄ -C ₈ cycloalkyl and A substituent selected from the group consisting of C ₁ -C ₄ alkyl-C ₄ -C ₈ cycloalkyl-C ₁ -C ₄ alkyl; In addition

R _a , R _b , R _c and R _d independently of one another are hydrogen or C ₁ -C ₁₂ alkyl, hydroxy-C ₂ -C ₁₂ alkyl, amino-C ₂ -C ₁₂ alkyl, phenyl, phenyl-C _1- C ₄ alkyl, C ₁ -C ₄ alkylphenyl, C ₁ -C ₄ alkylphenyl-C ₁ -C ₄ alkyl, C ₄ -C ₈ cycloalkyl, C ₄ -C ₈ cycloalkyl-C ₁ -C ₄ alkyl, A substituent selected from the group consisting of C ₁ -C ₄ alkyl-C ₄ -C ₈ cycloalkyl and C ₁ -C ₄ alkyl-C ₄ -C ₈ cycloalkyl-C ₁ -C ₄ alkyl.

The definitions of components a), b) and c) present in the additive mixture correspond to the definitions of components a), b) and c) present in the composition as described above.

According to a preferred embodiment, the present invention relates to an additive mixture used as an additive in a metal working liquid as defined above.

The invention also relates to a method of protecting against corrosion or oxidative degradation of metals when the metal is exposed to a functional fluid comprising an additive mixture as defined above.

According to a preferred embodiment, the present invention relates to a method for protecting zinc, aluminum or alloys thereof from corrosion or oxidative degradation, which is exposed to a functional fluid comprising an additive mixture as described above.

Another aspect of the invention relates to at least one alkenyl succinic acid half ester of formula (I) as described above wherein R ₁ is C ₆ -C ₁₈ alkenyl, R ₂ is hydrogen or methyl and n is from 1 to 100 And zinc, aluminum or alloys thereof exposed to functional fluids from corrosion or oxidative degradation.

The following examples illustrate the invention in detail.

Application Example

 A typical test procedure for testing corrosion inhibition is the climate chamber test according to DIN EN ISO 6270-2. This test was slightly modified by using several different metal samples and more severe conditions. Each sample was processed in the following test cycles:

Exposure for 8 hours in a sealed climate room at 50 ± 3 ° C. and approximately 100% humidity is followed by 16 hours in an open climate room and cooled at 21 ± 3 ° C. and humidity approaching the surrounding environment. The test cycle was repeated until 100% corrosion was visually detected. If the test sample is not corroded, the test procedure is stopped after 24 cycles.

Reference oil: as mentioned in May 2003 "VDA-Prufblatt"; VDA 230-201;

Mixture A = 3% Irgacor® L12 in paraffin base oil

Mixture B = 5% Irgalube®349 in paraffin base oil

Mixture C = 0.9% IRGACOR L12 in naphthenic base oils; 1.5% amine O; 0.6% IRGALUBE 349

Mixture D = 0.6% IRGACOR L12 in paraffinic base oil; 0.9% amine O; 1.5% IRGALUBE 349.

Claims (10)

A) a) at least one alkenyl succinic acid half ester of formula (I);    b) at least one imidazoline compound of formula (II): And    c) an additive mixture consisting essentially of at least one amine phosphate partial ester of formula (III): And B) a composition comprising a functional fluid:

(I) In the formula, R ₁ is C ₆ -C ₁₈ alkenyl, R ₂ is hydrogen or methyl and n is a number from 1 to 100;

(II) Wherein one of R ₁ and R ₂ is hydrogen and the other is C ₁ -C ₁₂ alkyl, hydroxy-C ₂ -C ₁₂ alkyl, amino-C ₂ -C ₁₂ alkyl, C ₂ -C ₂₀ alkenyl , Phenyl, phenyl-C ₁ -C ₄ alkyl, C ₁ -C ₄ alkylphenyl and C ₁ -C ₄ alkylphenyl-C ₁ -C ₄ alkyl; or Both R ₁ and R ₂ are C ₁ -C ₁₂ alkyl, hydroxy-C ₂ -C ₁₂ alkyl, amino-C ₂ -C ₁₂ alkyl, C ₂ -C ₂₀ alkenyl, phenyl, phenyl-C ₁ -C ₄ A substituent selected from the group consisting of alkyl, C ₁ -C ₄ alkylphenyl and C ₁ -C ₄ alkylphenyl-C ₁ -C ₄ alkyl; And

(III) In the formula, m is 1 or 2; when m is 1, n is 2, or when m is 2, n is 1; R is C ₁ -C ₁₂ alkyl, hydroxy-C ₂ -C ₁₂ alkyl, amino-C ₂ -C ₁₂ alkyl, phenyl, phenyl-C ₁ -C ₄ alkyl, C ₁ -C ₄ alkylphenyl, C _1- C ₄ alkylphenyl-C ₁ -C ₄ alkyl, C ₄ -C ₈ cycloalkyl, C ₄ -C ₈ cycloalkyl-C ₁ -C ₄ alkyl, C ₁ -C ₄ alkyl-C ₄ -C ₈ cycloalkyl and A substituent selected from the group consisting of C ₁ -C ₄ alkyl-C ₄ -C ₈ cycloalkyl-C ₁ -C ₄ alkyl; In addition R _a , R _b , R _c and R _d independently of one another are hydrogen or C ₁ -C ₁₂ alkyl, hydroxy-C ₂ -C ₁₂ alkyl, amino-C ₂ -C ₁₂ alkyl, phenyl, phenyl-C _1- C ₄ alkyl, C ₁ -C ₄ alkylphenyl, C ₁ -C ₄ alkylphenyl-C ₁ -C ₄ alkyl, C ₄ -C ₈ cycloalkyl, C ₄ -C ₈ cycloalkyl-C ₁ -C ₄ alkyl, A substituent selected from the group consisting of C ₁ -C ₄ alkyl-C ₄ -C ₈ cycloalkyl and C ₁ -C ₄ alkyl-C ₄ -C ₈ cycloalkyl-C ₁ -C ₄ alkyl. The method of claim 1, A) a) at least one alkenyl succinic acid half ester of formula (I);    b) at least one imidazoline compound of formula (II); And    c) an additive mixture consisting essentially of at least one amine phosphate partial ester of formula (III); And B) a composition comprising a functional fluid: In formula (I), R ₁ is C ₁₀ -C ₁₆ alkenyl, R ₂ is methyl and n is a number from 1 to 20; In formula (II), One of R ₁ and R ₂ is hydrogen and the other is C ₁ -C ₁₂ alkyl, hydroxy-C ₂ -C ₁₂ alkyl, amino-C ₂ -C ₁₂ alkyl and C ₁₂ -C ₁₈ alkenyl A substituent selected from; or Both R ₁ and R ₂ are substituents selected from the group consisting of C ₁ -C ₁₂ alkyl, hydroxy-C ₂ -C ₁₂ alkyl, amino-C ₂ -C ₁₂ alkyl and C ₁₂ -C ₁₈ alkenyl; In formula (III), m is 1 or 2; when m is 1, n is 2, or when m is 2, n is 1; R is a substituent selected from the group consisting of C ₁ -C ₁₂ alkyl, hydroxy-C ₂ -C ₁₂ alkyl and amino-C ₂ -C ₁₂ alkyl; In addition R _a , R _b , R _c and R _d are independently of each other hydrogen or a substituent selected from the group consisting of C ₁ -C ₁₂ alkyl and hydroxy-C ₂ -C ₁₂ alkyl. The method of claim 1, A) a) at least one alkenyl succinic acid half ester of formula (I);    b) at least one imidazoline compound of formula (II); And    c) an additive mixture consisting essentially of at least one amine phosphate partial ester of formula (III); And B) a composition comprising a functional fluid: In formula (I), R ₁ is C ₁₂ -C ₁₆ alkenyl, R ₂ is methyl and n is a number from 1 to 20; In formula (II), One of R ₁ and R ₂ is hydrogen and the other is a substituent selected from the group consisting of C ₁ -C ₁₂ alkyl and C ₁₂ -C ₁₈ alkenyl; or Both R ₁ and R ₂ are substituents selected from the group consisting of C ₁ -C ₁₂ alkyl and C ₁₂ -C ₁₈ alkenyl; In formula (III), m is 1 or 2; if m is 1, n is 2, or when m is 2 n is 1; R is a substituent selected from the group consisting of C ₁ -C ₁₂ alkyl and hydroxy-C ₂ -C ₁₂ alkyl; In addition R _a , R _b , R _c and R _d are independently of each other hydrogen or a substituent selected from the group consisting of C ₁ -C ₁₂ alkyl and hydroxy-C ₂ -C ₁₂ alkyl. a) at least one alkenyl succinic acid half ester of formula (I); b) at least one imidazoline compound of formula (II); c) at least one amine phosphate partial ester of formula (III); And d) compositions comprising additional and customary additives: In formula (I), R ₁ is C ₆ -C ₁₈ alkenyl, R ₂ is methyl and n is a number from 1 to 100; In formula (II), One of R ₁ and R ₂ is hydrogen and the other is C ₁ -C ₁₂ alkyl, hydroxy-C ₂ -C ₁₂ alkyl, amino-C ₂ -C ₁₂ alkyl, C ₂ -C ₂₀ alkenyl, phenyl, Or a substituent selected from the group consisting of phenyl-C ₁ -C ₄ alkyl, C ₁ -C ₄ alkylphenyl and C ₁ -C ₄ alkylphenyl-C ₁ -C ₄ alkyl; or Both R ₁ and R ₂ are C ₁ -C ₁₂ alkyl, hydroxy-C ₂ -C ₁₂ alkyl, amino-C ₂ -C ₁₂ alkyl, C ₂ -C ₂₀ alkenyl, phenyl, phenyl-C ₁ -C ₄ A substituent selected from the group consisting of alkyl, C ₁ -C ₄ alkylphenyl and C ₁ -C ₄ alkylphenyl-C ₁ -C ₄ alkyl; In formula (III), m is 1 or 2; if m is 1, n is 2, or when m is 2 n is 1; R is C ₁ -C ₁₂ alkyl, hydroxy-C ₂ -C ₁₂ alkyl, amino-C ₂ -C ₁₂ alkyl, phenyl, phenyl-C ₁ -C ₄ alkyl, C ₁ -C ₄ alkylphenyl, C _1- C ₄ alkylphenyl-C ₁ -C ₄ alkyl, C ₄ -C ₈ cycloalkyl, C ₄ -C ₈ cycloalkyl-C ₁ -C ₄ alkyl, C ₁ -C ₄ alkyl-C ₄ -C ₈ cycloalkyl and A substituent selected from the group consisting of C ₁ -C ₄ alkyl-C ₄ -C ₈ cycloalkyl-C ₁ -C ₄ alkyl; In addition R _a , R _b , R _c and R _d independently of one another are hydrogen or C ₁ -C ₁₂ alkyl, hydroxy-C ₂ -C ₁₂ alkyl, amino-C ₂ -C ₁₂ alkyl, phenyl, phenyl-C _1- C ₄ alkyl, C ₁ -C ₄ alkylphenyl, C ₁ -C ₄ alkylphenyl-C ₁ -C ₄ alkyl, C ₄ -C ₈ cycloalkyl, C ₄ -C ₈ cycloalkyl-C ₁ -C ₄ alkyl, A substituent selected from the group consisting of C ₁ -C ₄ alkyl-C ₄ -C ₈ cycloalkyl and C ₁ -C ₄ alkyl-C ₄ -C ₈ cycloalkyl-C ₁ -C ₄ alkyl. a) at least one alkenyl succinic acid half ester of formula (I) b) at least one imidazoline compound of formula (II): And c) an additive mixture consisting essentially of at least one amine phosphate partial ester of formula (III): In formula (I), R ₁ is C ₆ -C ₁₈ alkenyl, R ₂ is hydrogen or methyl and n is a number from 1 to 100; In formula (II), One of R ₁ and R ₂ is hydrogen and the other is C ₁ -C ₁₂ alkyl, hydroxy-C ₂ -C ₁₂ alkyl, amino-C ₂ -C ₁₂ alkyl, C ₂ -C ₂₀ alkenyl, phenyl, Or a substituent selected from the group consisting of phenyl-C ₁ -C ₄ alkyl, C ₁ -C ₄ alkylphenyl and C ₁ -C ₄ alkylphenyl-C ₁ -C ₄ alkyl; or Both R ₁ and R ₂ are C ₁ -C ₁₂ alkyl, hydroxy-C ₂ -C ₁₂ alkyl, amino-C ₂ -C ₁₂ alkyl, C ₂ -C ₂₀ alkenyl, phenyl, phenyl-C ₁ -C ₄ A substituent selected from the group consisting of alkyl, C ₁ -C ₄ alkylphenyl and C ₁ -C ₄ alkylphenyl-C ₁ -C ₄ alkyl; And In formula (III), m is 1 or 2; when m is 1, n is 2, or when m is 2, n is 1; R is C ₁ -C ₁₂ alkyl, hydroxy-C ₂ -C ₁₂ alkyl, amino-C ₂ -C ₁₂ alkyl, phenyl, phenyl-C ₁ -C ₄ alkyl, C ₁ -C ₄ alkylphenyl, C _1- C ₄ alkylphenyl-C ₁ -C ₄ alkyl, C ₄ -C ₈ cycloalkyl, C ₄ -C ₈ cycloalkyl-C ₁ -C ₄ alkyl, C ₁ -C ₄ alkyl-C ₄ -C ₈ cycloalkyl and A substituent selected from the group consisting of C ₁ -C ₄ alkyl-C ₄ -C ₈ cycloalkyl-C ₁ -C ₄ alkyl; In addition R _a , R _b , R _c and R _d independently of one another are hydrogen or C ₁ -C ₁₂ alkyl, hydroxy-C ₂ -C ₁₂ alkyl, amino-C ₂ -C ₁₂ alkyl, phenyl, phenyl-C _1- C ₄ alkyl, C ₁ -C ₄ alkylphenyl, C ₁ -C ₄ alkylphenyl-C ₁ -C ₄ alkyl, C ₄ -C ₈ cycloalkyl, C ₄ -C ₈ cycloalkyl-C ₁ -C ₄ alkyl, A substituent selected from the group consisting of C ₁ -C ₄ alkyl-C ₄ -C ₈ cycloalkyl and C ₁ -C ₄ alkyl-C ₄ -C ₈ cycloalkyl-C ₁ -C ₄ alkyl. The additive mixture of claim 5 for use as a metal working liquid. The composition of claim 1, wherein the working fluid B) is a non-aqueous functional liquid selected from the group consisting of lubricants, working fluids, metalworking fluids, engine coolants, transformer oils and switch gear oils. A method for protecting a metal from corrosion or oxidative degradation, which is exposed to a functional fluid comprising the additive mixture according to claim 5. A method for protecting zinc, aluminum or alloys thereof, or zinc-coated steel from corrosion or oxidative degradation, which is exposed to a functional fluid comprising the additive mixture according to claim 5. A method of protecting zinc, aluminum or an alloy thereof, or zinc-coated steel from corrosion or oxidative degradation, exposed to a functional fluid comprising at least one alkenyl succinic acid half ester of formula (I):

(I) In the formula, R ₁ is C ₆ -C ₁₈ alkenyl, R ₂ is hydrogen or methyl and n is a number from 1 to 100.