AU2007253453B2

AU2007253453B2 - Corrosion inhibiting composition for non-ferrous metals

Info

Publication number: AU2007253453B2
Application number: AU2007253453A
Authority: AU
Inventors: Tassilo Habereder; Anja Keller; Karl-Heinz Michel; Eric Nehls
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 2006-05-23
Filing date: 2007-05-15
Publication date: 2012-01-19
Anticipated expiration: 2027-05-15
Also published as: CN101454429B; JP2009537681A; JP5395658B2; TW200815586A; CN101454429A; CA2650246C; US20100022425A1; WO2007135017A1; RU2008150626A; KR20090010041A; AU2007253453A1; EP2027235A1; RU2483099C2; CA2650246A1

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

WO 2007/135017 PCT/EP2007/054674 CORROSION INHIBITING COMPOSITION FOR NON-FERROUS METALS The invention relates to an additive composition for use as a metal working fluid or corrosion protection oil and a process for the protection of metals, particularly zinc or aluminium alloys, against corrosion or oxidative degradation. 5 Additives, which have the purpose to protect metals against corrosion are commonly divided in to two classes: Metal deactivators are used to protect yellow metals or alloys, such as copper or brass, and display their protective action in functional liquids, such as mineral oil or fuels, by deactivat ing the metal ions contained therein. These metal ions can have catalytic effects in undesired 10 oxidative decomposition processes of mineral oil or fuels. The protective action is explained by the formation of film-like layers on the surface of metals or by complex formation with metal ions. Corrosion inhibitors are primary used to protect ferrous metals such as iron or steel. Ana logue to metal deactivators, corrosion inhibitors, are forming also film-like layers on the sur 15 face of metals. In addition some corrosion inhibitors can prevent the corrosion, by emulsify ing water and minimizing therefore the direct contact of water with the metal surface. Presently metal protection methods focus primarily on iron and copper surfaces. However, other metals, such as zinc and aluminium and their related alloys, have become very impor tant in many technical applications. Zinc and aluminium are, for example, widely used in the 20 manufacture of automobiles. Zinc is widely used as corrosion protection coating of steels, e.g. zinc coated steel coils. Corrosion problems often occur during transport, handling and working of semi-finished metal products. Unfortunately, presently used metal deactivator compositions are less satisfactory or even unsatisfactory to protect these metal surfaces. Therefore, there is a clear need for improved metal working fluids to prevent corrosion of 25 these metals British Patent Specification No. 795,491 discloses the preparation of alkenyl succinic half esters and their applicability as steam turbine lubricant additives. British Patent Specification No. 1,043,488 lubricating oil compositions comprising substituted imidazoline compounds and phosphate partial esters. 30 U.S. Patent Application Publication No. 2005/0272614 discloses corrosion inhibiting compo sitions, wherein substituted imidazolines and neutral metal sulfonate corrosion inhibitors are present.

-2 It has surprisingly been found that mixtures of alkenyl succinic half esters, substituted imidazoline compounds and amine phosphate partial esters in functional fluids, such as oils, prevent the corrosion of zinc, zinc coated steel and aluminum metal samples. This anticorrosive effect can be increased by the further admixture of additional anti-corrosive agents, such as substituted imidazolines and amine phosphate partial esters. SUMMARY OF THE INVENTION A first aspect of the invention provides a composition, which comprises A) An additive mixture that consists of a) At least one alkenyl succinic half ester of the formula H Ri-Y- CO -OH CHi-CO-0 CHi-T-O H R2 Wherein R 1 represents C 6 -Claalkenyl, R 2 represents hydrogen or methyl and n is a numeral from 1 to 100; b) At least one imidazoline compound of the formula NN N-R 2 Wherein one of R 1 and R 2 represents hydrogen and the other one represents a substituent selected from the group consisting of C-C1 2 alkyl, hydroxy-C 2

-C

1 2 alkyl, amino-C 2

-C

12 alkyl, C 2

-C

2 oalkenyl, phenyl, phenyl-C

C

4 alkyl, C-C 4 alkylphenyl and C-C 4 alkylphenyl-C-C 4 alkyl; or Wherein both of R 1 and R 2 represent substituents selected from the group consisting of C-C 12 alkyl, hydroxy-C 2

-C

1 2 alkyl, amino-C 2

-C

1 2 alkyl, C 2 C 2 oalkenyl, phenyl, phenyl-C-C 4 alkyl, Cl-C 4 alkylphenyl and C

C

4 alkylphenyl-C-C 4 alkyl; and - 2a c) At least one amine phosphate partial ester of the formula F Ra 0 a RN + (RO)M (O~)n Re Rd Wherein m represents 1 or 2; n represents 2, if m represents 1, or represents 1, if m represents 2; R represents a substituent selected from the group consisting of C

C

12 alkyl, hydroxyC 2

-C

1 2 alkyl, amino C 2

-C

12 alkyl, phenyl, phenyl-C-C 4 alkyl,

C-C

4 alkylphenyl, C-C 4 alkylphenyl-C-C 4 alkyl, C 4

-C

8 cycloalkyl, C 4 C 8 cycloalkyl-C-C 4 alkyl, C-C 4 alkyl-C 4 -CBcycloalkyl and C-C 4 alkyl-C 4 C 8 cycloalkyl-C-C 4 alkyl; and Ra, Rb, Re and Rd independently of one another represent hydrogen or a substituent selected from the group consisting of C-C 12 alkyl, hydroxy-C 2 C 12 alkyl, amino-C 2

-C

1 2 alkyl, phenyl, phenyl-Cl-C 4 alkyl, C-C 4 alkylphenyl,

C-C

4 alkylphenyl-C-C 4 alkyl, C 4

-C

8 cycloalkyl, C 4

-C

8 cycloalkyl-C-C 4 alkyl,

C-C

4 alkyl-C 4 -Cscycloalkyl and C-C 4 alkyl-C 4

-C

8 cycloalkyl-C-C 4 alkyl; and B) A functional fluid. A second aspect of the invention provides a composition, which comprises a) At least one alkenyl succinic half ester (1), as defined in the first aspect, Wherein R 1 represents C 6 -Claalkenyl, R 2 represents methyl and n is a numeral from 1 to 100; b) At least one imidazoline compound (II), as defined in the first aspect, Wherein one of R 1 and R 2 represents hydrogen and the other one represents a substituent selected from the group consisting of C

C

1 2 alkyl, hydroxy-C 2

-C

1 2 alkyl, amino-C 2

-C

1 2 alkyl, C 2

-C

2 oalkenyl, phenyl, phenyl-C-C 4 alkyl, C-C 4 alkylphenyl and C-C 4 alkylphenyl

C-C

4 alkyl; or Wherein both of R 1 and R 2 represent substituents selected from the group consisting of C-C 12 alkyl, hydroxy-C 2

-C

1 2 alkyl, amino-C 2

-

- 2b C 12 alkyl, C 2

-C

2 oalkenyl, phenyl, phenyl-C 1

-C

4 alkyl, C 1

-C

4 alkylphenyl and C 1

-C

4 alkylphenyl-C 1

-C

4 alkyl; c) At least one amine phosphate partial ester (111), as defined in the first aspect, Wherein m represents 1 or 2; n represents 2 if m represents 1; or represents 1 if m represents 2; and R represents a substituent selected from the group consisting of C 1 C 12 alkyl, hydroxy-C 2

-C

1 2 alkyl, amino-C 2

-C

1 2 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 -Cecycloalkyl, 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 cycloalkyl-C 1

-C

4 alkyl; and Ra, Rb, Rc and Rd independently of one another represent hydrogen or a substituent selected from the group consisting of C 1

-C

12 alkyl, hydroxy-C 2

-C

1 2 alkyl, amino-C 2

-C

1 2 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 Cacycloalkyl-C 1

-C

4 alkyl, C1-C 4 alkyl-C 4

-C

8 cycloalkyl and C 1

-C

4 alkyl

C

4 -C8cycloalkyl-C 1

-C

4 alkyl; and d) Additional customary additives. A third aspect of the invention provides an additive mixture that consists of a) At least one alkenyl succinic half ester (I), as defined in the first aspect, Wherein R 1 represents C 6

-C

18 alkenyl, R 2 represents hydrogen or methyl and n is a numeral of 0 to 100; b) At least one imidazoline compound (11), as defined in the first aspect, Wherein one of R 1 and R 2 represents hydrogen and the other one represents a substituent selected from the group consisting of C 1 C 1 2 alkyl, hydroxy-C 2 -C1 2 alkyl, amino-C 2

-C

1 2 alkyl, C 2

-C

2 calkenyl, phenyl, phenyl-C 1

-C

4 alkyl, C 1

-C

4 alkylphenyl and C 1

-C

4 alkylphenyl

C

1

-C

4 alkyl; or Wherein both of R 1 and R 2 represent substituents selected from the - 2c group consisting of Cl-C1 2 alkyl, hydroxy-C 2

-C

1 2 alkyl, amino-C 2 C1 2 alkyl, C 2

-C

2 oalkenyl, phenyl, phenyl-C-C 4 alkyl, C-C 4 alkylphenyl and C-C 4 alkylphenyl-C-C 4 alkyl; and c) At least one amine phosphate partial ester (Ill), as defined in the first aspect, Wherein m represents 1 or 2; n represents 2 if m represents 1; or represents 1 if m represents 2; and R represents a substituent selected from the group consisting of C

C

12 alkyl, hydroxy-C 2 -C1 2 alkyl, amino-C 2

-C

1 2 alkyl, C 2

-

2 aalkenyl, phenyl, phenyl-C-C 4 alkyl, C-C 4 alkylphenyl, C-C 2 alkylphenyl-C

C

4 alkyl, C 4 -Cecycloalkyl, C 4

-C

8 cycloalkyl-C-C 4 alkyl, C-C 4 alkyl-C 4 C 8 cycloalkyl and C-C 4 alkyl-C 4 -Cacyloalkyl-Cj-C 4 alkyl; and Ra, Rb, Re and Rd independently of one another represent hydrogen or a substituent selected from the group consisting of C-C1 2 alkyl, hydroxy-C 2

-C

1 2 alkyl, amino-C 2

-C

1 2 alkyl, C 2

-C

2 0alkenyl, phenyl, phenyl-C-C 4 alkyl, C-C 4 alkylphenyl, C-C 4 alkylphenyl-C-C 4 alkyl,

C

4

-C

8 cycloalkyl, C 4

-C

8 cycloalkyl-C-C 4 alkyl, C-C 4 alkyl-C 4 C 8 cyloalkyl and C-C 4 -alkyl-C 4 -Cecylcloalkyl-C-C 4 alkyl. A fourth aspect of the invention provides an additive mixture as defined in the third aspect, when used as a metal working fluid. A fifth aspect of the invention provides a composition as defined in the first aspect, wherein the functional fluid B) is a non-aqueous functional liquid selected from the group consisting of: lubricants, hydraulic fluids, metal working fluids, engine coolants, transformer oils and switch gear oils. A sixth aspect of the invention provides a process for protection against corrosion or oxidative degradation of metals, wherein the metal is exposed to a functional fluid comprising the additive mixture as defined in the third aspect. A seventh aspect of the invention provides a process for protection against corrosion of oxidative degradation of zinc, aluminium or alloys thereof, or zinc- - 2d coated steels, wherein zinc, aluminium or alloys thereof are exposed to a functional fluid comprising the additive mixture as defined in the third aspect. In one embodiment the present invention relates to a composition, which comprises A) An additive mixture that essentially consists of a) At least one alkenyl succinic half ester of the formula H R,-C- CO -OH r H 1 CH2-CO-O CH2-C-O+H (1), 2 n Wherein R 1 represents C 6

-C

18 alkenyl, R 2 represents hydrogen or methyl and n is a numeral from 1 to 100; b) At least one imidazoline compound of the formula y ~\ R 1 Wherein one of R 1 and R 2 represents hydrogen and the other one represents a substituent selected from the group consisting of C-C 1 2 alkyl, hydroxy-C 2 C 1 2 alkyl, amino-C 2

-C

12 alkyl, C 2

-C

2 oalkenyl, phenyl, phenyl-C-C 4 alkyl, C

C

4 alkylphenyl and C-C 4 alkylphenyl-C-C 4 alkyl; or Wherein both of R 1 and R 2 represent substituents selected from the group consisting of C-Cl 2 alkyl, hydroxy-C 2 -Cl 2 alkyl, amino-C 2 -Cl 2 alkyl, C 2 C 2 oalkenyl, phenyl, phenyl-Cr-C 4 alkyl, C-C 4 alkylphenyl and C-C 4 alkylphenyl

C-C

4 alkyl; and c) At least one amine phosphate partial ester of the formula - 2e R R R"I (RO)r '(O ) R R Wherein m represents 1 or 2; n represents 2, if m represents 1 or represents 1 if m represents 2; WO 2007/135017 PCT/EP2007/054674 -3 R represents a substituent selected from the group consisting of C 1

-C

1 2 alkyl, hy droxy-C 2

-C

1 2 alkyl, amino-C 2

-C

1 2 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 cyclo alkyl-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 cyclo 5 alkyl-C 1

-C

4 alkyl; and Ra, Rb, Rc and Rd independently of one another represent hydrogen or a substitu ent selected from the group consisting of C 1

-C

12 alkyl, hydroxy-C 2

-C

1 2 alkyl, amino-C 2

-C

1 2 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, 10 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; and B) A functional fluid. A preferred embodiment of the invention relates to a composition, which comprises A) An additive mixture that essentially consists of a) At least one alkenyl succinic half ester (1), wherein 15 R 1 represents C 1 0

-C

16 alkenyl, R 2 represents methyl and n is a numeral from 1 to 20; b) At least one imidazoline compound (II), Wherein one of R 1 and R 2 represents hydrogen and the other one represents a substituent selected from the group consisting of C 1

-C

12 alkyl, hydroxy-C 2

-C

1 2 alkyl, amino-C 2

-C

1 2 alkyl and C 1 2

-C

18 alkenyl; or 20 Wherein both of R 1 and R 2 represent substituents selected from the group consist ing of C 1

-C

12 alkyl, hydroxy-C 2

-C

1 2 alkyl, amino-C 2

-C

1 2 alkyl and C 1 2

-C

18 alkenyl; and c) At least one amine phosphate partial ester (Ill), Wherein m represents 1 or 2; n represents 2, if m represents 1, or represents 1, if m represents 2; 25 R represents a substituent selected from the group consisting of C 1

-C

12 alkyl, hy droxy-C 2

-C

1 2 alkyl and amino-C 2

-C

1 2 alkyl; and Ra, Rb, Rc and Rd independently of one another represent hydrogen or a substituent selected from the group consisting of C 1

-C

12 alkyl and hydroxy-C 2

-C

1 2 alkyl; and B) A functional fluid. 30 A particularly preferred embodiment of the invention relates to composition, which comprises WO 2007/135017 PCT/EP2007/054674 -4 A) An additive mixture that essentially consists of a) At least one alkenyl succinic half ester (1), wherein

R

1 represents C 1 2

-C

16 alkenyl, R 2 represents methyl and n is a numeral from 1 to 20; 5 b) At least one imidazoline compound (II), Wherein one of R 1 and R 2 represents hydrogen and the other one represents a substituent selected from the group consisting of C 1

-C

1 2 alkyl and C 12

-C

18 alkenyl; or Wherein both of R 1 and R 2 represent substituents selected from the group con 10 sisting of C 1

-C

12 alkyl and C 1 2

-C

18 alkenyl; and c) At least one amine phosphate partial ester (Ill), Wherein m represents 1 or 2; n represents 2, if m represents 1, or represents 1, if m represents 2; R represents a substituent selected from the group consisting of C 1

-C

12 alkyl and 15 hydroxy-C 2

-C

1 2 alkyl; and Ra, Rb, Rc and Rd independently of one another represent hydrogen or a substitu ent selected from the group consisting of C 1

-C

12 alkyl and hydroxy-C 2

-C

1 2 alkyl; and B) A functional fluid. 20 A highly preferred embodiment of the invention relates to a composition, which comprises a) At least one alkenyl succinic half ester (1), Wherein R 1 represents C 6

-C

18 alkenyl, R 2 represents methyl and n is a nu meral from 1 to 100; b) At least one imidazoline compound (II), 25 Wherein one of R 1 and R 2 represents hydrogen and the other one repre sents a substituent selected from the group consisting of C 1

-C

12 alkyl, hy droxy-C 2

-C

1 2 alkyl, amino-C 2

-C

1 2 alkyl, C 2

-C

2 0alkenyl, phenyl, phenyl-C 1

-C

4 alkyl, C 1

-C

4 alkylphenyl and C 1

-C

4 alkylphenyl-C 1

-C

4 alkyl; or Wherein both of R 1 and R 2 represent substituents selected from the group 30 consisting of C 1

-C

12 alkyl, hydroxy-C 2

-C

1 2 alkyl, amino-C 2

-C

1 2 alkyl, WO 2007/135017 PCT/EP2007/054674 -5

C

2

-C

2 oalkenyl, phenyl, phenyl-C 1

-C

4 alkyl, C 1

-C

4 alkylphenyl and

C

1

-C

4 alkylphenyl-C 1

-C

4 alkyl; c) At least one amine phosphate partial ester (Ill), Wherein m represents 1 or 2; 5 n represents 2 if m represents 1; or represents 1 if m represents 2; and R represents a substituent selected from the group consisting of

C

1

-C

12 alkyl, hydroxy-C 2

-C

1 2 alkyl, amino-C 2

-C

1 2 alkyl, phenyl, phenyl-C 1

-C

4 alkyl, C 1

-C

4 alkylphenyl, C 1

-C

4 alkylphenyl-C 1

-C

4 alkyl, 10 C 4

-C

8 cycloalkyl, C 4

-C

8 cycloalkyl-C 1

-C

4 alkyl, C 1

-C

4 alkyl-C 4

-C

8 cycloalky and

C

1

-C

4 alkyl-C 4

-C

8 cycloalkyl-C 1

-C

12 alkyl, hy droxy-C 2

-C

1 2 alkyl, amino-C 2

-C

1 2 alkyl, phenyl, phenyl-C 1

-C

4 alkyl, 15 C 1

-C

4 alkylphenyl, C 1

-C

4 alkylphenyl-C 1

-C

4 alkyl, C 4

-C

8 cycloalkyl, C 4

-C

8 cyclo alkyl-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 cyclo alkyl-C 1

-C

4 alkyl; and d) Additional customary additives. The compositions as described above are suitable as corrosion inhibitor in non-aqueous, 20 partially aqueous or aqueous functional fluids or liquids. The expressions and terms used above and below are preferably defined as follows in the description of the present invention: In a compound (1) R 1 defined C 6

-C

18 alkenyl is preferably straight chain or, where possible, branched radical, for example n-2-octenyl, n-2-dodecenyl, iso-dodecenyl, or is preferably a 25 group of the partial formula H R CH=C-C H I R Wherein R' and R" are independently of one another hydrogen or substantially straight chain hydrocarbyl groups, with the proviso that the total number of carbon atoms in R is within the indicated ranges. Preferably R' and R" are C3-Cl 5 alkyl or C 3

-C

15 alkenyl groups. In a particu- WO 2007/135017 PCT/EP2007/054674 -6 larly advantageous embodiment, R has from about 16 to about 18 C-atoms, R' is hydrogen or C1-C 7 alkyl or C2-C 7 alkenyl and R" is C 5 -Ci 5 alkyl or C5-Cl5alkenyl.

R

2 is hydrogen or preferably methyl. In a compound (1) the index n represents a numeral from 1 to about 100. According to pre 5 ferred embodiments n represents a numeral from 1 to about 20. Compounds (1) are obtain able by reacting the R-substituted succinic acid with ethylene oxide or ethylene glycol of de sired chain length, if R 2 represents hydrogen, or with propylene oxide or polypropylene glycol of desired chain length, if R 2 represents methyl. Compounds (1) are known and at least some of them are commercially available. The prepa 10 ration of compounds (1) is described in British Patent Specification No. 795,491. Compounds (1) are known oil soluble corrosion inhibitors, which are commercially available as solution in mineral oil, such as the product Ciba@ Irgacor@ L 12. Other products are Hi tec@ 536 commercially available from Ethyl Corp. Richmond VA, USA. In a compound (II) one of R 1 and R 2 represents hydrogen and the other one represents a 15 substituent selected from the group consisting of C 1

-C

12 alkyl, hydroxy-C 2

-C

1 2 alkyl, amino-C 2

-C

1 2 alkyl, C 2

-C

2 0alkenyl, 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 of R 1 and R 2 represent substituents selected from the group consisting of C 1

-C

12 alkyl, hydroxy-C 2

-C

1 2 alkyl, amino-C 2

-C

1 2 alkyl, C 2

-C

2 0alkenyl, phenyl, phenyl-C 1

-C

4 alkyl, 20 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 is, for example, C 1

-C

6 alkyl, e.g. methyl, ethyl, n-propyl or isopropyl or n-butyl, sec-butyl or tert-butyl or straight-chain or branched pentyl or hexyl, and

C

7

-C

12 alkyl, e.g. straight-chain or branched heptyl, octyl, isooctyl, nonyl, tert-nonyl, decyl, un decyl or dodecyl. 25 R 1 and R 2 defined as hydroxy-C 2

-C

1 2 alkyl, is e.g. 2-hydroxyethyl, dihydroxyethyl, 2- or 3-hydroxypropyl, 2-, 3-dihydroxypropyl, glyceryl or any of the above-mentioned C 4

-C

12 alkyl groups substituted by 1-3 hydroxy groups.

R

1 and R 2 defined as amino-C 2

-C

1 2 alkyl is e.g. 2-aminoethyl, diaminoethyl or 2- or 3-aminopropyl or any of the above-mentioned C 4

-C

12 alkyl groups substituted by 1-3 amino 30 groups.

R

1 and R 2 defined as C 2

-C

2 0alkenyl is a straight chain or, where possible, branched radical, for example vinyl, allyl, 2-butenyl, 3-butenyl, isobutenyl, n-2,4-pentadienyl, 3-methyl-2-bu tenyl, n-2-octenyl, n-2-dodecenyl or iso-dodecenyl.

WO 2007/135017 PCT/EP2007/054674 -7

R

1 and R 2 defined as phenyl-C 1

-C

4 alkyl, C 1

-C

4 alkylphenyl and C 1

-C

4 alkylphenyl-C 1

-C

4 alkyl radicals are, for example, benzyl, 1- or 2-phenethyl, 4-methyl- or 4-ethylphenyl, cumyl or 4-methylbenzyl. According to preferred embodiments one of R 1 and R 2 represents hydrogen and the other 5 one represents a substituent selected from the group consisting of C 1

-C

12 alkyl, hy droxy-C 2

-C

1 2 alkyl, amino-C 2

-C

1 2 alkyl and C 1 2

-C

18 alkenyl; or Both of R 1 and R 2 represent substituents selected from the group consisting of C 1

-C

12 alkyl, hydroxy-C 2

-C

1 2 alkyl, amino-C 2

-C

1 2 alkyl and C 1 2

-C

18 alkenyl. According to another preferred embodiment one of R 1 and R 2 represents hydrogen and the 10 other one represents a substituent selected from the group consisting of C 1

-C

1 2 alkyl and

C

1 2

-C

12 alkyl and C 1 2

-C

18 alkenyl. Compounds (II) are known compounds and applicable oil soluble corrosion inhibitors, which 15 are commercially available as solution in mineral oil, such as the product Ciba@ Amine 0. In a compound (III) m represents 1 or 2. In the event that m represents 1, n represents 2. Such compounds are represented by the formula Rd] 0 + RO - LRc In the event that m represents 2, n represents 1. Such compounds are represented by the 20 formula R 0 1+ I I N + O | 0-R O R RORO R R In a compound (III) R represents a substituent selected from the group consisting of

C

1

-C

12 alkyl, hydroxy-C 2

-C

1 2 alkyl, amino-C 2

-C

1 2 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, 25 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; and WO 2007/135017 PCT/EP2007/054674 -8 Ra, Rb, Rc and Rd independently of one another represent hydrogen or a substituent selected from the group consisting of C 1

-C

12 alkyl, hydroxy-C 2

-C

1 2 alkyl, amino-C 2

-C

1 2 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 C 1

-C

4 alkyl-C 4

-C

8 cyclo 5 alkyl-C 1

-C

4 alkyl. The definitions of C 1

-C

12 alkyl, hydroxy-C 2

-C

1 2 alkyl, amino-C 2

-C

1 2 alkyl, phenyl, phenyl-C 1

-C

4 alkyl, C 1

-C

4 alkylphenyl, C 1

-C

4 alkylphenyl-C 1

-C

4 alkyl correspond to the defini tions given above with regard to compounds (1) and (II). R as well as Ra, Rb, Rc and Rd defined as C 4

-C

8 cycloalkyl, C 4

-C

8 cycloalkyl-C 1

-C

4 alkyl, 10 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 are, for example, cyclopentyl, cyclohexyl, cyclopentylmethyl or cyclohexylmethyl, cyclopentyl-1 ,1-ethyl, cyclo hexyl-1 ,1-ethyl, cyclopentyl-1,2-ethyl, cyclohexyl-1,2-ethyl, cyclopentyl-1,2-propyl or cyclohe xyl-1,2-propyl, which can be substituted on the C 4

-C

8 cycloalkyl groups by C 1

-C

4 alkyl, e.g. methyl, ethyl, n- propyl or isopropyl. 15 According to preferred embodiments R represents a substituent selected from the group consisting of C 1

-C

1 2 alkyl, hydroxy-C 2

-C

1 2 alkyl and amino-C 2

-C

12 alkyl and hydroxy-C 2

-C

1 2 alkyl. Amine phosphate partial ester as represented by the formula III are known compounds that 20 can be prepared by known methods. Compounds (III) are applicable as oil soluble corrosion inhibitors and commercially available, such as the product Ciba@lrgalube@ 349. Other amine phosphate partial ester as represented by the formula III are commercially available from Rheinchemie Rheinau GmbH, Mannheim Germany, such as the products Ad ditin@ RC 3740, RC 3741 or RC 3760 (amine neutralized phosphoric acid ester of aliphatic 25 alcohols). The term functional liquid includes non-aqueous, partially aqueous and aqueous liquids which are in contact with metals to be protected, in particular aluminium and zinc. Examples of non-aqueous functional liquids are fuels, e.g. hydrocarbon mixtures comprising mineral oil fractions which are liquid at room temperature and are suitable for use in internal 30 combustion engines, e.g. internal combustion engines with external (petrol engines) or inter nal ignition (diesel engines), e.g. petrol having different octane contents (regular grade or premium grade petrol) or diesel fuels, and lubricants, hydraulic fluids, metal working fluids, WO 2007/135017 PCT/EP2007/054674 -9 such as drawing oil, cutting oils, forming oils, drilling oils etc, engine coolants, transformer oils and switchgear oils. Examples of suitable partially aqueous functional liquids are water-in-oil or oil-in-water metal working fluids, hydraulic fluids based on aqueous polyglycol! polyglycol ether mixtures or gly 5 col systems, and engine cooling systems based on aqueous glycol. Examples of aqueous functional liquids are industrial cooling water, filling compositions of a water conditioning plant, steam generation systems, sea water evaporation systems, sugar evaporation systems, irrigation systems, hydrostatic boilers and heating systems or cooling systems having a closed circulation. 10 The composition according to the invention preferably comprise 0.01 to 10.0% by weight, in particular 0.02 to 3.0 % by weight, of the additive mixture, as defined above, based on the weight of the functional liquid. Non-aqueous functional liquids are preferred, in particular base oils of lubricating viscosity, which can be used for the preparation of greases, metal working fluids, gear fluids and hy 15 draulic fluids. Suitable greases, metal working fluids, gear fluids and hydraulic fluids are based, for exam ple, on mineral or synthetic oils or mixtures thereof. The lubricants are familiar to a person skilled in the art and are described in the relevant literature, such as, for example, in Chem istry and Technology of Lubricants; Mortier, R.M. and Orszulik, S. T. (Editors); 1992 Blackie 20 and Son Ltd. for GB, VCH-Publishers N.Y. for U.S., ISBN 0-216-92921-0, cf. pages 208 et seq. and 269 et seq.; in Kirk-Othmer Encyclopedia of Chemical 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 E.P. Wright, Hyden & Son Ltd. GB, on behalf of The Institute of Petroleum London, ISBN 0 85501 317 6; Ullmann's Encyclopedia of Ind. 25 Chem., Fifth Completely Revised Edition, Verlag Chemie, DE-Weinheim, VCH-Publishers for U.S., Vol. A 15, page 423 et seq. (Lubricants), Vol. A 13, page 165 et seq. (Hydraulic Fluids). The lubricants are in particular oils and greases, for example based on mineral oil, synthetic oils, or vegetable and animal oils, fats, tallow and wax or mixtures thereof. Vegetable and animal oils, fats, tallow and wax are, for example, palm kernel oil, palm oil, olive oil, colza oil, 30 rapeseed oil, linseed oil, soy bean oil, cotton wool oil, sunflower oil, coconut oil, maize oil, castor oil, walnut oil and mixtures thereof, fish oils, and chemically modified, e.g. epoxidised or sulphoxidised or alkylated or hydrogenated, forms or forms prepared by genetic engi neering, for example soy bean oil prepared by genetic engineering.

WO 2007/135017 PCT/EP2007/054674 -10 Examples of synthetic lubricants include lubricants based on aliphatic or aromatic carboxylic esters, polymeric esters, polyalkylene oxides, phosphoric acid esters, poly-ax-olefins or sili cones of the diester of a dibasic acid with a monohydric alcohol, e.g. dioctyl sebacate or di nonyl adipate, of a triester of trimethylolpropane with a monobasic acid or with a mixture of 5 such acids, e.g. trimethylolpropane tripelargonate, trimethylolpropane tricaprylate or mixtures thereof, of a tetra ester of pentaerythritol with a monobasic acid or with a mixture of such ac ids, e.g. pentaerythrityl tetracaprylate, or of a complex ester of monobasic and dibasic acids with polyhydric alcohols, e.g. a complex ester of trimethylolpropane with caprylic and sebacic acid or of a mixture thereof. Particularly suitable in addition to mineral oils are, for example, 10 poly-a-olefins, ester-based lubricants, phosphates, glycols, polyglycols and polyalkylene gly cols and mixtures thereof with water. Said lubricants or mixtures thereof can also be mixed with an organic or inorganic thickener (base fat). Metal working fluids and hydraulic fluids can be prepared on the basis of the same substances as described above for the lubricants. These are frequently also emulsions of 15 such substances in water or other liquids. Said lubricant compositions, e.g. greases, gear fluids, metal working fluids and hydraulic flu ids, may additionally contain further additives which are added in order further to improve their fundamental properties. These include: antioxidants, metal deactivators, rust inhibitors, viscosity index improvers, pour point depressants, dispersants, detergents, tackyfiers, 20 thixotropic builders, dewatering agents, antifoam agents, demulsifiers, high pressure addi tives and antiwear additives. Such additives are added in the amounts customary in each case for the purpose, each in the range from 0.01 to 10.0% by weight. Examples of further additives follow: 1. Phenolic antioxidants 25 1.1. Alkylated monophenols: 2,6-di-tert-butyl-4-methylphenol, 2-butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,6-d i-tert-butyl-4-n-butylphenol, 2,6-di-tert-butyl-4-iso butylphenol, 2,6-dicyclopentyl-4-methylphenol, 2-(a-methylcyclohexyl)-4,6-di methyl phenol, 2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol, 2,6-di-tert-butyl-4 methoxymethylphenol, linear nonylphenols or nonylphenols which are branched in 30 the side chain, e.g. 2,6-dinonyl-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 WO 2007/135017 PCT/EP2007/054674 - 11 1 .2. Alkylthiomethylphenols: 2,4-dioctylthiomethyl-6-tert-butylphenol, 2,4-dioctylthiomethyl 6-methylphenol, 2,4-dioctylthiomethyl-6-ethylphenol, 2,6-didodecylthiomethyl-4-nonyl phenol 1.3. Hydroquinones and alkylated hydroquinones: 2,6-di-tert-butyl-4-methoxyphenol, 2,5 5 di-tert-butyl-hydroquinone, 2,5-di-tert-amyl-hydroquinone, 2,6-diphenyl-4-octadecyl oxyphenol, 2,6-di-tert-butyl-hydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole, 3,5-di tert-butyl-4-hydroxyanisole, 3,5-d i-tert-butyl-4-hyd roxyphenylstearate, bis(3,5-di-tert butyl-4-hydroxyphenyl) adipate 1.4. Tocopherols: a-, P-, y- or 6-tocopherols and mixtures thereof (vitamin E) 10 1.5. Hydroxylated thiodiphenyl ethers: 2,2'-thiobis(6-tert-butyl-4-methylphenol), 2,2'-thiobis(4-octylphenol), 4,4'-thiobis(6-tert-butyl-3-methylphenol), 4,4'-thiobis-(6 tert-butyl-2-methylphenol), 4,4'-thiobis(3,6-di-sec-amylphenol), 4,4'-bis(2,6-dimethyl 4-hydroxyphenyl) disulphide 1.6. Alkylidene bisphenols: 2,2'-methylenebis(6-tert-butyl-4-methylphenol), 2,2' 15 methylenebis(6-tert-butyl-4-ethy phenol), 2,2'-methylenebis[4-methyl-6-(a-methylcy clohexyl)-phenol], 2,2'-methylenebis(4-methyl-6-cyclohexylphenol), 2,2'-methylene bis(6-nonyl-4-methylphenol), 2,2'-methylenebis(4,6-di-tert-butylphenol), 2,2' ethylidenebis(4,6-di-tert-butylphenol), 2,2'-ethylidenebis(6-tert-butyl-4-isobutylphenol), 2,2'-methylenebis[6-(a-methylbenzyl)-4-nonylphenol], 2,2'-methylenebis[6-(a,a-di 20 methylbenzyl)-4-nonylphenol], 4,4'-methylenebis(2,6-di-tert-butylphenol), 4,4'-methyl enebis(6-tert-butyl-2-methylphenol), 1,1 -bis(5-tert-butyl-4-hydroxy-2-methyl phenyl)butane, 2,6-bis(3-tert-butyl-5-methyl-2-hydroxybenzyl)-4-methylphenol, 1,1,3 tris(5-tert-butyl-4-hydroxy-2-methylphenyl)butane, 1,1-bis(5-tert-butyl-4-hydroxy-2 methyl-phenyl)-3-n-dodecylmercaptobutane, ethylene glycol bis[3,3-bis(3'-tert-butyl 25 4'-hydroxyphenyl)butyrate], bis(3-tert-butyl-4-hydroxy-5-methyl-phenyl)d icyclopenta diene, bis[2-(3'-tert-butyl-2'-hydroxy-5'-methyl-benzyl)-6-tert-butyl-4-methyl-phenyl] terephthalate, 1,1-bis(3,5-dimethyl-2-hydroxyphenyl)-butane, 2,2-bis(3,5-di-tert-butyl 4-hydroxyphenyl)propane, 2,2-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)-4-n-dode cylmercaptobutane, 1,1,5,5-tetra(5-tert-butyl-4-hydroxy-2-methylphenyl)pentane 30 1.7. 0-, N- and S-benzyl compounds: 3,5,3',5'-tetra-tert-butyl-4,4'-dihydroxydibenzy ether, octadecyl 4-hydroxy-3,5-dimethylbenzylmercaptoacetate, tridecyl-4-hydroxy-3,5-di tert-butylbenzylmercaptoacetate, tris(3,5-di-tert-butyl-4-hydroxybenzyl)amine, bis(4- WO 2007/135017 PCT/EP2007/054674 -12 tert-butyl-3-hydroxy-2,6-dimethylbenzyl) dithioterephthalate, bis(3,5-di-tert-butyl-4-hy droxybenzyl) sulphide, isooctyl 3,5-di-tert-butyl-4-hydroxybenzylmercaptoacetate 1.8. Hydroxybenzylated malonates: dioctadecyl 2,2-bis(3,5-di-tert-butyl-2-hydroxybenzyl) malonate, dioctadecyl 2-(3-tert-butyl-4-hydroxy-5-methylbenzyl)malonate, didodecyl 5 mercaptoethyl-2,2-bis(3,5-d i-tert-butyl-4-hyd roxybenzyl)malonate, di-[4-(1,1,3,3 tetramethylbutyl)-phenyl]-2,2-bis(3,5-d i-tert-butyl-4-hyd roxybenzyl)malonate 1.9. Hydroxybenzyl aromatics: 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethyl benzene, 1,4-bis(3,5-d i-tert-butyl-4-hyd roxybenzyl)-2,3,5,6-tetramethyl benzene, 2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)phenol 10 1.10. Triazine compounds: 2,4-bisoctylmercapto-6-(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5 triazine, 2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazine, 2 octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,3,5-triazine, 2,4,6 tris(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,2,3-triazine, 1,3,5-tris(3,5-di-tert-butyl-4-hy droxybenzyl) isocyanurate, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) iso 15 cyanurate, 2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenylethyl)-1,3,5-triazine, 1,3,5 tris(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hexahydro-1,3,5-triazine, 1,3,5 tris(3,5-dicyclohexyl-4-hydroxybenzyl) isocyanurate 1.11. Acylaminophenols: 4-hydroxylauranilide, 4-hydroxystearanilide, octyl N-(3,5-di-tert butyl-4-hydroxyphenyl) carbamate 20 1.12. Esters of beta-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionic acid with monohydric or polyhydric alcohols, e.g. with methanol, ethanol, n-octanol, isooctanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentylglycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl) isocyanurate, N,N'-bis(hydroxyethyl)oxalamide, 3-thiaundecanol, 25 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1 phospha-2,6,7-trioxabicyclo[2.2.2]octane 1.13. Esters of beta-(5-tert-butyl-4-hydroxy-3-methylphenyl)propionic acid (with monohydric or polyhydric alcohols), e.g. the alcohols with methanol, ethanol, n-octanol, isooc tanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, 30 neopentylglycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentae rythritol, tris(hydroxyethyl) isocyanurate, N,N'-bis(hydroxyethyl)-oxalamide, 3 thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hy droxymethyl-1 -phospha-2,6,7-trioxabicyclo[2.2.2]octane WO 2007/135017 PCT/EP2007/054674 -13 1.14. Esters of beta-(3,5-dicyclohexyl-4-hydroxvphenvl)propionic acid with monohydric or polyhydric alcohols, e.g. the alcohols stated under 13. 1.15. Ester of 3,5-di-tert-butyl-4-hydroxyphenylacetic acid with monohydric or polyhydric alcohols, e.g. the alcohols stated under 13. 5 1.16. Amides of beta-(3,5-di-tert-butVl-4-hVdroxVphenVl)propionic acid, e.g. N,N'-bis(3,5-di tert-butyl-4-hydroxyphenylpropionyl)hexamethylenediamine, N,N'-bis(3,5-di-tert-butyl 4-hydroxyphenylpropionyl)trimethylenediamine, N,N'-bis(3,5-di-tert-butyl-4-hydroxy phenylpropionyl)hydrazine 1.17. Ascorbic acid (vitamin C) 10 1.18. Amine antioxidants: N,N'-diisopropyl-p-phenylenediamine, N,N'-di-sec-butyl-p phenylenediamine, N,N'-bis(1,4-dimethylpentyl)-p-phenylenediamine, N,N'-bis(1 ethyl-3-methylpentyl)-p-phenylenediamine, N,N'-bis(1-methyl-heptyl)-p phenylenediamine, N,N'-dicyclohexyl-p-phenylenediamine, N,N'-diphenyl-p phenylenediamine, N,N'-di-(naphth-2-yl)-p-phenylenediamine, N-isopropyl-N'-phenyl 15 p-phenylenediamine, N-(1,3-dimethyl-butyl)-N'-phenyl-p-phenylenediamine, N-(1 methylheptyl)-N'-phenyl-p-phenylenediamine, N-cyclohexyl-N'-phenyl-p phenylenediamine, 4-(p-toluenesulphonamido)diphenylamine, N,N'-dimethyl-N,N'-di sec-butyl-p-phenylenediamine, diphenylamine, N-allyldiphenylamine, 4-isopropoxy diphenylamine, N-phenyl-1-naphthylamine, N-(4-tert-octylphenyl)-1-naphthylamine, 20 N-phenyl-2-naphthylamine, octylated diphenylamine, e.g. p,p'-di-tert-octyldiphenyl amine, 4-n-butylaminophenol, 4-butyrylaminophenol, 4-nonanoylamino-phenol, 4-do decanoylaminophenol, 4-octadecanoylaminophenol, di-(4-methoxyphenyl)amine, 2,6 di-tert-butyl-4-dimethylaminomethylphenol, 2,4'-diaminodiphenylmethane, 4,4'-diami nodiphenylmethane, N,N,N',N'-tetramethyl-4,4'-diaminodiphenylmethane, 1,2-di-[(2 25 methyl-phenyl)-amino]ethane, 1,2-di-(phenylamino)-propane, (o-tolyl)biguanide, di-[4 (1',3'-dimethyl-butyl)phenyl]amine, tert-octylated N-phenyl-1-naphthylamine, mixture of mono- and dialkylated tert-butyl/tert-octyldiphenylamines, mixture of mono- and dialkylated nonyldiphenylamines, mixture of mono- and dialkylated dodecyldiphenyl amines, mixture of mono- and dialkylated isopropyl/isohexyldiphenylamines, mixtures 30 of mono- and dialkylated tert-butyldiphenylamines, 2,3-dihydro-3,3-dimethyl-4H-1,4 benzothiazine, phenothiazine, mixture of mono- and dialkylated tert-butyl tert-octyl phenothiazines, mixture of mono- and dialkylated tert-octylphenothiazines, N-allyl phenothiazine, N,N,N',N'-tetraphenyl-1,4-diaminobut-2-ene, N,N-bis-(2,2,6,6-tetrame- WO 2007/135017 PCT/EP2007/054674 -14 thylpiperidin-4-yl)-hexamethylenediamine, bis-(2,2,6,6-tetramethylpiperidin-4-yl) seba cate, 2,2,6,6-tetramethylpiperidin-4-one, 2,2,6,6-tetramethylpiperidin-4-ol 2. Further antioxidants: aliphatic or aromatic phosphites, esters of thiodipropionic acid or thiodiacetic acid or salts of dithiocarbamic or dithiophosphoric acid, 2,2,12,12-tetra 5 methyl-5,9-dihydroxy-3,7,1 1-trithiatridecane and 2,2,15,15-tetramethyl-5,12-dihy droxy-3,7,10,14-tetrathiahexadecane 3. Further metal deactivators: 3.1. Benzotriazoles and derivatives thereof: 2-mercaptobenzotriazole, 2,5-dimercaptoben zotriazole, 4- or 5-alkylbenzotriazoles (e.g. tolutriazole) and derivatives thereof, 10 4,5,6,7-tetrahydrobenzotriazole, 5,5'-methylenebisbenzotriazole; Mannich bases of benzotriazole or tolutriazole, such as 1-[di(2-ethylhexylaminomethyl)]tolutriazole and 1-[di(2-ethylhexylaminomethyl)]benzotriazole; alkoxyalkylbenzotriazoles, such as 1 (nonyloxymethyl)-benzotriazole, 1 -(1 -butoxyethyl)benzotriazole and 1 -(1 -cyclohexyl oxybutyl)tolutriazole 15 3.2. 1,2,4-Triazoles and derivatives thereof: 3-alkyl (or aryl)-1,2,4-triazoles, Mannich bases of 1,2,4-triazoles, such as 1-[di(2-ethylhexyl)aminomethyl]-1,2,4-triazole; alkoxyalkyl-1,2,4-triazoles, such as 1-(1-butoxyethyl)-1,2,4-triazole; acylated 3-amino 1,2,4-triazoles 3.3. Imidazole derivatives: 4,4'-methylenebis(2-undecyl-5-methylimidazole), bis[(N 20 methyl)imidazol-2-yl]carbinol octyl ether 3.4. Sulphur-containinq heterocyclic compounds: 2-mercaptobenzothiazole, 2,5-dimer capto-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, salicylaminoguanidine and salts 25 thereof 4. Corrosion inhibitors: WO 2007/135017 PCT/EP2007/054674 -15 4.1. Organic acids, their esters, metal salts, amine salts and anhydrides: alkyl- and al kyenylsuccinic acids and partial esters thereof with alcohols, diols or hydroxycarbox ylic acids, partial amides of alkyl- and alkenylsuccinic acids, 4-nonylphenoxyacetic acid, alkoxy- and alkoxyethoxycarboxylic acids, such as dodecyloxyacetic acid, dode 5 cyloxy(ethoxy)acetic acid and amine salts thereof, and furthermore N-oleoylsarcosine, sorbitan monooleate, lead naphthenate, alkenylsuccinic anhydrides, e.g. dodecenyl succinic anhydride, 2-(2-carboxyethyl)-1-dodecyl-3-methylglycerol and salts thereof, in particular sodium salts and triethanolamine salts 4.2. Nitrogen-containinq compounds: 10 4.2.1 Tertiary aliphatic and cycloaliphatic amines and amine salts of organic and inorganic acids, e.g. oil-soluble alkylammonium carboxylates, and furthermore 1-[N,N-bis-(2-hy droxyethyl)amino]-3-(4-nonylphenoxy)propan-2-ol 4.2.2 Heterocyclic compounds, e.g. substituted imidazolines and oxazolines, e.g. 2-hepta decenyl-1 -(2-hydroxyethyl)-imidazoline 15 5. Sulphur-containinq compounds: barium dinonylnaphthalenesulphonates, calcium petroleum sulphonates, alkylthio-substituted aliphatic carboxylic acids, esters of ali phatic 2-sulphocarboxylic acids and salts thereof 6. Viscosity index improvers: polyacrylates, polymethacrylates, vinylpyrroli done/methacrylate copolymers, polyvinylpyrrolidiones, polybutenes, olefin copoly 20 mers, 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: polybutenylsuccinamides or polybutenylsuccinimides, polybutenylphosphonic acid derivatives, basic magnesium, calcium and barium sul 25 phonates and phenolates 9. Hiqh pressure and antiwear additives: sulphur- and halogen-containing compounds, e.g. chlorinated paraffins, sulphonated olefins or vegetable oils (soy bean oil, rape seed oil), alkyl or aryl di- or trisulphides, benzotriazoles or derivatives thereof, such as WO 2007/135017 PCT/EP2007/054674 -16 bis (2-ethylhexyl)aminomethyl tolutriazoles, dithiocarbamates, such as methylenebis dibutyl dithiocarbamate, derivatives of 2-mercaptobenzothiazole, such as 1-[N,N bis(2-ethylhexyl)aminomethyl]-2-mercapto-1 H-1,3-benzothiazole, derivatives of 2,5 dimercapto-1,3,4-thiadiazole, such as 2,5-bis(tert.nonyldithio)-1,3,4-thiadiazole 5 10. Substances for reducing the coefficient of friction: lard oil, oleic acid, tallow, rapeseed oil, sulphurised fats, amines. Further examples are stated in EP-A-0 565 487 11. Special additives for use in water/oil metal processing and hydraulic fluids: 11.1 Emulsifiers: petroleum sulphonates, amines, such as polyoxyethylated fatty amines, non-ionic surface-active substances 10 11.2 Buffers: alkanolamines 11.3 Biocides: triazines, thiazolinones, trisnitromethane, morpholine, sodium pyridinethiol 11.4 Processinq speed improvers: calcium sulphonates and barium sulphonates 11.5 Tackifiers: acrylamide copolymer, polyisubutene resins. 11.6 Thixotropic builders: microcrystalline waxes, oxidized waxes and oxidized esters 15 11.7 Dewaterinq agents: polyglycol ethers, butyldiglycols. Said components can be mixed with the lubricants in a manner known per se. It is also possi ble to prepare a concentrate or a so-called additive package, which can be diluted to the con centrations of use for the corresponding lubricant according to the application purposes as intended. 20 The ratio of component a) to component b) to component b) present in the additive mix ture A) may vary within the ranges of approximately from 10 : 10 : 80 and 80 : 10 : 10 to 10 80: 10% by weight. 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 between 25 10.0 and 0.01, preferably 10.0 and 0.1 or 3.0 and 0.1% by weight, based on the total weight of the composition.

WO 2007/135017 PCT/EP2007/054674 -17 A further embodiment of the invention relates to an additive mixture that essentially consists of a) At least one alkenyl succinic half ester (1), Wherein R 1 represents C 6

-C

18 alkenyl, R 2 represents hydrogen or methyl 5 and n is a numeral from 0 to 100; b) At least one imidazoline compound (II), Wherein one of R 1 and R 2 represents hydrogen and the other one repre sents a substituent selected from the group consisting of C 1

-C

12 alkyl, hy droxy-C 2

-C

1 2 alkyl, amino-C 2

-C

1 2 alkyl, C 2

-C

2 0alkenyl, phenyl, 10 phenyl-C 1

-C

4 alkyl, C 1

-C

4 alkylphenyl and C 1

-C

4 alkylphenyl-C 1

-C

4 alkyl; or Wherein both of R 1 and R 2 represent substituents selected from the group consisting of C 1

-C

12 alkyl, hydroxy-C 2

-C

1 2 alkyl, amino-C 2

-C

1 2 alkyl,

C

2

-C

2 0alkenyl, phenyl, phenyl-C 1

-C

4 alkyl, C 1

-C

4 alkylphenyl and

C

1

-C

4 alkylphenyl-C 1

-C

4 alkyl; and 15 c) At least one amine phosphate partial ester (Ill), Wherein m represents 1 or 2, n represents 2, if m represents 1; or repre sents 1, if m represents 2; R represents a substituent selected from the group consisting of

C

1

-C

12 alkyl, hydroxy-C 2

-C

1 2 alkyl, amino-C 2

-C

1 2 alkyl, C 2

-C

2 0alkenyl, phenyl, 20 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

C

1

-C

4 alkyl-C 4

-C

8 cycloalkyl-C 1

-C

12 alkyl, hy 25 droxy-C 2

-C

1 2 alkyl, amino-C 2

-C

1 2 alkyl, C 2

-C

2 0alkenyl, 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

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 corresponds to the 30 definitions of components a), b) and c) present in the compositions as defined above. According to a preferred embodiment, the invention relates to the additive mixture, as de fined above, used as additives in a metal working fluid.

WO 2007/135017 PCT/EP2007/054674 -18 The invention also relates to the process for protection against corrosion or oxidative degra dation of metals, wherein the metal is exposed to a functional fluid comprising the additive mixture as defined above. According to a preferred embodiment, the invention relates to the process for protection 5 against corrosion or oxidative degradation of zinc, aluminum or alloys thereof, wherein zinc, aluminum or alloys thereof are exposed to a functional fluid comprising the additive mixture as defined above. A further embodiment of the invention relates to a process for protection against corrosion or oxidative degradation of zinc, aluminum or alloys thereof, wherein zinc, aluminum or alloys 10 thereof are exposed to a functional fluid comprising at least one alkenyl succinic half ester of the formula I as defined above, wherein R 1 represents C 6

-C

18 alkenyl, R 2 represents hydrogen or methyl and n is a numeral from 1 to 100. The following Examples illustrate the invention: Application Examples 15 A typical test procedure to test the corrosion inhibition is the climate chamber test according to DIN EN ISO 6270-2. This test is slightly modified by using several different metal samples and more severe conditions. Each sample is treated in the following test cycle: Exposure for 8 hours in a closed climate chamber at 50 ± 3 0C, humidity ca. 100%, followed by 16 hours in an open climate chamber, cooling at 21 ± 30C and humidity approaching am 20 bient. The test cycles are repeated until 100% corrosion is detected visually. In the event that the test sample is not corroded, the test procedure is stopped after 24 cycles.

- 19 Reference oil Zinc 19 app. 15-20% Mixture A Zinc > 24 3% Mixture B Zinc > 24 5% Mixture C Zinc > 24 3% Mixture D Zinc 20 3% Reference oil Aluminum 0 app. 15-20% Mixture A Aluminum > 15 3% Mixture B Aluminum > 15 5% Mixture C Aluminum > 15 3% Mixture D Aluminum > 15 3% Reference oil: As mentioned In "VDA-Profblatt" from May 2003; VDA 230- 201: Mixture A = 3% Irgacor@ L12 in a paraffinic base oil Mixture B = 5% Irgalube@ 349 in a parafinic base oil Mixture C = 0.9% IRGACOR L12; 1.5% Amine 0; 0.6% IRGALUBE 349 In an naphthenlc base oil Mixture D = 0.6% IRGACOR L12; 0.9% Amine 0; 1.5% IRGALUBE 349 In a paraffinic base oil. Throughout this specification and the claims which follow, unless the context requires otherwise, the word "comprise", and variations such as "comprises" or "comprising", will be understood to imply the inclusion of a stated integer or step or group of integers or steps but not the exclusion of any other integer or step or group of integers or steps. The reference in this specification to any prior publication (or information derived from it), or to any matter which is known, is not, and should not be taken as an acknowledgment or admission or any form of suggestion that that prior publication (or information derived from it) or known matter forms part of the common general knowledge in the field of endeavour to which this specification relates.

Claims

1. A composition, which comprises A) An additive mixture that consists of a) At least one alkenyl succinic half ester of the formula H Rj-9- CO -OH CH-CO- CH--O H R2 Wherein R 1 represents C 6 -C 1 aalkenyl, R 2 represents hydrogen or methyl and n is a numeral from 1 to 100; b) At least one imidazoline compound of the formula N.,, N-R 2 R( Wherein one of R 1 and R 2 represents hydrogen and the other one represents a substituent selected from the group consisting of C 1 -C1 2 alkyl, hydroxy-C 2 -C 1 2 alkyl, amino-C 2 -C 12 alkyl, C 2 -C 2 oalkenyl, phenyl, phenyl-C 1 C 4 alkyl, C 1 -C 4 alkylphenyl and C 1 -C 4 alkylphenyl-C 1 -C 4 alkyl; or Wherein both of R 1 and R 2 represent substituents selected from the group consisting of C 1 -C1 2 alkyl, hydroxy-C 2 -C1 2 alkyl, amino-C 2 -C1 2 alkyl, C 2 C 2 oalkenyl, phenyl, phenyl-C 1 -C 4 alkyl, C 1 -C 4 alkylphenyl and C 1 C 4 alkylphenyl-C 1 -C 4 alkyl; and c) At least one amine phosphate partial ester of the formula 0 (RO)M '(O~)b R Rd - - n ii Wherein m represents 1 or 2; n represents 2, if m represents 1, or represents 1, if m represents 2; R represents a substituent selected from the group consisting of C1 C 12 alkyl, hydroxyC 2 -C1 2 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 - - 21 Cecycloalkyl-C 1 -C 4 alkyl, C1-C 4 alkyl-C 4 -Cacycloalkyl and C 1 -C 4 alkyl-C 4 C8cycloalkyl-C 1 -C 4 alkyl; and Ra, Rb, R: and Rd independently of one another represent hydrogen or a substituent selected from the group consisting of C 1 -C 1 2 alkyl, hydroxy-C 2 C1 2 alkyl, amino-C 2 -C 1 2 alkyl, phenyl, phenyl-C 1 -C 4 alkyl, C1-C 4 alkylphenyl, C1-C 4 alkylphenyl-C 1 -C 4 alkyl, C 4 -Cacycloalkyl, 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 cycloalkyl-C 1 -C 4 alkyl; and B) A functional fluid.

2. A composition according to claim 1, which comprises A) An additive mixture that consists of a) At least one alkenyl succinic half ester (1), wherein R 1 represents C10-C 16 alkenyl, R 2 represents methyl and n is a numeral from 1 to 20; b) At least one imidazoline compound (II), Wherein one of R 1 and R 2 represents hydrogen and the other one represents a substituent selected from the group consisting of C1 C 12 alkyl, hydroxy-C 2 -C 1 2 alkyl, amino C 2 -C 12 alkyl and C 12 -C 18 alkenyl; or Wherein both of R 1 and R 2 represent substituents selected from the group consisting of C 1 -C 12 alkyl, hydroxy-C 2 - 12 alkyl, amino-C 2 C1 2 alkyl and C 12 -C 18 alkenly; and c) At least one amine phosphate partial ester (111), Wherein m represents 1 or 2; n represents 2, if m represents 1, or represents 1, if m represents 2; R represents a substituent selected from the group consisting of C 1 C 1 2 alkyl, hydroxy-C 2 -C 1 2 alkyl and amino-C 2 -C 12 alkyl; and Ra, Rb, R, and Rd independently of one another represent hydrogen or a substituent selected from the group consisting of C 1 -C 12 alkyl and hydroxy-C 2 -C 1 2 alkyl; and B) A functional fluid -22

3. A composition according to claim 1, which comprises A) An additive mixture that consists of a) At least one alkenyl succinic half ester (1) as defined in claim 1, wherein R 1 represents C- 12 -C 16 alkenyl, R 2 represents methyl and n is a numeral from 1 to 20; b) At least one imidazoline compound (II) as defined in claim 1, Wherein one of R 1 and R 2 represents hydrogen and the other one represents a substituent selected from the group consisting of C1 C 12 alkyl and C 12 -C 16 alkenyl; or Wherein both of R, and R 2 represents substituents selected from the group consisting of C 1 -C 12 alkyl and C 12 -C 18 alkenyl; and c) At least one amine phosphate partial ester (111) as defined in claim 1, Wherein m represents 1 or 2; n represents 2 if m represents 1; or represents 1 if m represents 2; and R represents a substituent selected from the group consisting of C 1 C 12 alkyl and hydroxy-C 2 -C 1 2 alkyl; and Ra, Rb, Re and Rd independently of one another represent hydrogen or a substituent selected from the group consisting of C 1 -C 12 alkyl and hydroxy-C 2 -C 1 2 alkyl; and B) A functional fluid.

4. A composition, which comprises a) At least one alkenyl succinic half ester (1), as defined in claim 1, Wherein R 1 represents C 6 -Clsalkenyl, R 2 represents methyl and n is a numeral from 1 to 100; b) At least one imidazoline compound (II), as defined in claim 1, Wherein one of R 1 and R 2 represents hydrogen and the other one represents a substituent selected from the group consisting of C 1 C 12 alkyl, hydroxy-C 2 -C 1 2 alkyl, amino-C 2 -C 1 2 alkyl, C 2 -C 2 oalkenyl, phenyl, phenyl-C 1 -C 4 alkyl, C 1 -C 4 alkylphenyl and C 1 -C 4 alkylphenyl- - 23 C 1 -C 4 alkyl; or Wherein both of R 1 and R 2 represent substituents selected from the group consisting of C 1 -C 12 alkyl, hydroxy-C 2 -C 1 2 alkyl, amino-C 2 C 12 alkyl, C 2 -C 2 oalkenyl, phenyl, phenyl-C 1 -C 4 alkyl, C 1 -C 4 alkylphenyl and C 1 -C 4 alkylphenyl-C 1 -C 4 alkyl; c) At least one amine phosphate partial ester (Ill), as defined in claim 1, Wherein m represents 1 or 2; n represents 2 if m represents 1; or represents 1 if m represents 2; and R represents a substituent selected from the group consisting of C 1 C 12 alkyl, hydroxy-C 2 -C 1 2 alkyl, amino-C 2 -C 1 2 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 C 1 -C 4 alkyl C 4 -C 8 cycloalkyl-C 1 -C 4 alkyl; and Ra, Rb, Re and Rd independently of one another represent hydrogen or a substituent selected from the group consisting of C1-C 1 2 alkyl, hydroxy-C 2 -C 1 2 alkyl, amino-C 2 -C 1 2 alkyl, phenyl, phenyl-C 1 -C 4 alkyl, C 1 -C 4 alkylphenyl, C 1 -C 4 alkylphenyl-C1-C 4 alkyl, C 4 -C 8 cycloalkyl, C 4 Cacycloalkyl-C 1 -C 4 alkyl, C1-C 4 alkyl-C 4 -C 8 cycloalkyl and C 1 -C 4 alkyl C 4 -C 8 cycloalkyl-C 1 -C 4 alkyl; and d) Additional customary additives.

5. An additive mixture that consists of a) At least one alkenyl succinic half ester (1), as defined in claim 1, Wherein R 1 represents C 6 -C 18 alkenyl, R 2 represents hydrogen or methyl and n is a numeral of 0 to 100; b) At least one imidazoline compound (11), as defined in claim 1, Wherein one of R 1 and R 2 represents hydrogen and the other one represents a substituent selected from the group consisting of C 1 C 12 alkyl, hydroxy-C 2 -C 1 2 alkyl, amino-C 2 -C 1 2 alkyl, C 2 -C 2 0alkenyl, - 24 phenyl, phenyl-C 1 -C 4 alkyl, C 1 -C 4 alkylphenyl and C 1 -C 4 alkylphenyl C 1 -C 4 alkyl; or Wherein both of R 1 and R 2 represent substituents selected from the group consisting of C 1 -C 12 alkyl, hydroxy-C 2 -C 1 2 alkyl, amino-C 2 C 12 alkyl, C 2 -C 2 oalkenyl, phenyl, phenyl-C 1 -C 4 alkyl, C 1 -C 4 alkylphenyl and C 1 -C 4 alkylphenyl-C 1 -C 4 alkyl; and c) At least one amine phosphate partial ester (1ll), as defined in claim 1, Wherein m represents 1 or 2; n represents 2 if m represents 1; or represents 1 if m represents 2; and R represents a substituent selected from the group consisting of C 1 C 12 alkyl, hydroxy-C 2 -C 1 2 alkyl, amino-C 2 -C 1 2 alkyl, C 2 -C 2 oalkenyl, phenyl, phenyl-C 1 -C 4 alkyl, C1-C 4 alkylphenyl, C 1 -C 2 alkylphenyl-C 1 C 4 alkyl, C 4 -Cacycloalkyl, C 4 -Cacycloalkyl-C 1 -C 4 alkyl, C 1 -C 4 alkyl-C 4 Cacycloalkyl and C1-C4alkyl-C 4 -C 8 cycloalkyl-Cl-C 4 alkyl; and Ra, Rb, Rc and Rd independently of one another represent hydrogen or a substituent selected from the group consisting of C 1 -C 12 alkyl, hydroxy-C 2 -C 1 2 alkyl, amino-C 2 -C 1 2 alkyl, C 2 -C 2 oalkenyl, 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 -Cacycloalkyl-C 1 -C 4 alkyl, C 1 -C 4 alkyl-C 4 Cacyloalkyl and C1-C 4 -alkyl-C 4 -C 8 cylcloalkyl-C 1 -C 4 alkyl.

6. The additive mixture according to claim 5, when used as a metal working fluid.

7. A composition according to claim 1, wherein the functional fluid B) is a non aqueous functional liquid selected from the group consisting of: lubricants, hydraulic fluids, metal working fluids, engine coolants, transformer oils and switch gear oils.

8. A process for protection against corrosion or oxidative degradation of - 25 metals, wherein the metal is exposed to a functional fluid comprising the additive mixture according to claim 5.

9. A process for protection against corrosion of oxidative degradation of zinc, aluminium or alloys thereof, or zinc-coated steels, wherein zinc, aluminium or alloys thereof are exposed to a functional fluid comprising the additive mixture according to claim 5.

10. A composition as defined in any one of claims 1 to 4, substantially as hereinbefore described with reference to the Examples.