CA2104505A1

CA2104505A1 - Alkenylsuccinic acid derivatives as metalworking auxiliaries

Info

Publication number: CA2104505A1
Application number: CA002104505A
Authority: CA
Inventors: Detlef Wehle; Horst Lorke
Original assignee: Individual
Current assignee: Clariant Produkte Deutschland GmbH
Priority date: 1992-08-22
Filing date: 1993-08-20
Publication date: 1994-02-23
Also published as: KR100318700B1; EP0584711A1; DE59308091D1; CZ172393A3; KR940003921A; CZ288180B6; SG49890A1; SK89493A3; EP0584711B1; JPH06206853A; SK280381B6

Abstract

Abstract Alkenylsuccinic acid derivatives as metalworking auxiliaries The present invention relates to salts of alkenylsuccinic acid alkoxyalkyl-half-amides of the formula Ia and/or Ib Ia Ib if appropriate as a mixture with salts of alkenylsuccinic acid half-ester amines of the formula IIa and/or IIb IIa IIb and/or alkenylsuccinic acid imides of the formula III

in which R1, R2, A, R3, R4, n, m and M? have the meaning given in the description.

The invention also relates to a process for the prepara-tion of salts of alkenylsuccinic acid alkoxyalkyl-half-amides of the formula Ia and/or Ib, if appropriate as a mixture with salts of alkenylsuccinic acid half-ester amines of the formula IIa and IIb and/or alkenylsuccinic acid imides of the formula III, which comprises reacting alkenylsuccinic acid anhydrides with alkoxyalkylamines of the formula IV

H2N-(CH2)n-O-(A)m-R3 IV

in which R3, n, m and A have the meaning given in the description, and carrying out this reaction in the presence of an amount of base equimolar to the alkoxy-alkylamines of the formula IV, or adding an amount of base equimolar to the alkoxyalkylamines of the formula IV
after the reaction.

The invention furthermore relates to aqueous and/or oil-containing formulations for working metals, which comprise the abovementioned salts of alkenylsuccinic acid alkoxyalkyl-half-amides of the formula Ia and/or Ib, if appropriate as a mixture with salts of alkenylsuccinic acid half-ester amines of the formula IIa and/or IIb and/or alkenylsuccinic acid imides of the formula III, and their use as anticorrosion agents, cooling lubricants and metalworking auxiliaries.

Description

- 210~0~
HOECHST AKTIENGESEL~SCHAFT HOE 92/F 266 Dr. KD/wo Description Alkenyl~uccinic acid derivatives as metalworking auxilisries The use of metalworking auxiliarie~ extends to numerous working proce3ses for pre- and after-treatment of metals.
The field of work comprises cutting and non-cutting shaping of metal components. Drilling and cutting oil~
are employed for cutting ~haping, and milling and drawing oils are employed for non-cutting shaping.

Anticorro~ion agents and emul~ifiers in emul~ifiable metalworking fluids should meet the following requirements:
1. pronounced corrosion protection properties with respect to ferrous metals 5 2. emulsifying power with respect to mineral oils, possibly also in combination with selected nonionic compounds 3. low tendency to foam or rapid collapse of foam 4. prevention of the growth of microorganisms These requirements are only partly met by the compounds which are already known.
Salts of C~-C,2-alkenylsuccinic acid half-amides and their u~e as anticorrosion agents are known from ~P-A-127 132.
However, these compounds do not exhibit an adequate emulsifying power, which leads to inadequate ~ervice lives of the emulsion to be used. Furthermore, emulsions comprising these compounds tend to foam, which is a disadvantage in particular during working processes ~uch as grinding, when the emulsion~ are exposed to high mechanical influence~.

Alkanolamine salts of C6-C,B-alkenylsuccinic acid half-amides, where a primary amine having a C1-C,O-alkyl chain is employed for half-amide formation, are de~cribed in DE-A-33 00 874.

2~0450~
.

DE-A-33 41 013 describes C~-C~-alkenyl~uccinic acid half-~mides, where ~econdary amines having 1 to 10 carbon atoms are employed for the half-amide formation.

The abovementioned requirements also cannot be met in full by the use of the~e compounds.

The object of the invention is to provide derivativee of alkenylsuccinic acids which combine the properties described above.

Surprisingly, it has now been found that thi~ object can be achieved by salts of alkenyl~uccinic ~cid half-amide~
which contain alkoxyalkylamines as the amine component, if appropriate as a mixture with ~alt~ of alkenylsuccinic acid half-amides which contain an alcoholamine as the ester group, and alkenyl~uccinic acid ;m;de6.

The invention relates to salts of alkenylsuccinic acid alkoxyalkyl-half-amides of the formula Ia and/or Ib la Ib R1-CH-CO-NHR2 R1-CH-COOeM~

CH2-COOeM~ CH2-CO-NHR2 if appropriate as a mixture with salts of alkenylsuccinic acid half-ester amines of the formula IIa and/or IIb lla llb Rl-CH-Coo-CHR4-CH2-NR5R6 Rl-CH-COOeM~

CH2-COOeM~ CH2-Coo-CHR4-CH2 NR5R6 . : ': ~ ' ' . :' ' ,' ':
.
. ~ -:

.. . .. . . ..

2 1 0 ~

and/or alkenylsuccinic acid imides of the formula III
Rl-CH-CO

CH2-CO' in which Rl i8 C6-C30-alkenyl or C6-C30-alkyl, preferably C9_C~B_ alkenyl or C9-C18-alkyl, in which Rl can be straight-chain or branched;
R2 i S ~ ( CH2 ) n~~ ( A)~-R3, where A is -CH2-C~2-O- or -CH(R')-C~2-O-, in which R3 is C1-C18-alkyl, and in which R3 can be straight-chain or branched, R4 i8 hydxogen or methyl, n i~ a number from 1 to 6, m is a number from 0 to 8 and M~ is an alkali metal or alkaline earth metal cation or an ammonium ion of the formula ~N~'R6R7, in which Rs, R6 and R' are identical or different and are hydro-gen, C1-C6-alkyl or hydroxy-(C1-C6)-alkyl, in particular 2-hydroxyethyl and 2-hydroxypropyl.

The alkenylsuccinic acid half-ester amine salts of the formula IIa and IIb and the alkenylsuccinic acid imides of the formula III can occur aB by-products during preparation of the alkenyl~uccinic acid alkoxyalkyl-half-amide salts of the formula Ia and Ib and are usually present in concentrations of 0 to 40 % by weight, prefer-ably 0 to 20 % by weight, as a mixture with the alkenyl-succinic acid alkoxyalkyl-half-amide ~alts of the formula Ia and Ib.

The invention likewise relates to a proces3 for the preparation of 6alts of alkenylsuccinic acid alkoxyalkyl-half-amide~ of the formula Ia and/or Ib, if appropriate a~ a mixture with salts of alkenylsuccinic acid half-ester amines of the formulae IIa and/or IIb and/or alkenyl6uccinic acid imide~ of the ~ormula III, which 2104~0~

comprises reacting alkenyl~uccinic acid anhydrides with alkoxyalkylamines of the formula IV

~2N- ( CH2 ) n~~ ( A)~-R3 IV

in which R3 is Cl-Cl8-alkyl, in which R3 can be ~traight-chain or branched, n is a number from 1 to 6 and m is a number from 0 to 8, in a molar ratio of 1 : 0.7 to 2.5, preferably 1 : 0.8 to 1.2, at temperatures of 20 to 120C, preferably 60 to 100C, and carrying out this reaction in the presence of an amount of base which i8 equimolar to the alkoxyalkyl-amines of the formula IV, or adding an amount of base equimolar to the alkoxyalkylamines of the formula IV
after the reaction.

Bases which are employed are alkali metal hydroxides, alkaline earth metal hydroxides, alkanolamines of the formula NR5R6R7 or mixture~ thereof.
The base is usually employed in an amount equimolar to the alkanolamines.

The preparation of the alkenylsuccinic acid anhydrides used as 6tarting material~ i~ carried out by reaction of olefin~ and maleic anhydride and is known. Preferred olefins are oligomers of ethylene, propylene and butyl-ene, and olefins having an internal double bond. Forexample, n-dodecenylsuccinic anhydride can be prepared by reaction of n-dodec-l-ene with maleic anhydride at temperatures of 150 to 230C under a pres3ure of 3 to 10 bar in the presense of suitable free radical inhibitor~. The alkenylsuccinic acid anhydrides thus obtained can be employed for the preparation of the compound~ according to the invention either after purification by distillation or recrystallization or directly.

-- 210~05 The alkoxyalkylamines, for example 2-hydroxyethylamine, can be prepared by addition of acrylonitrile onto alco-hols and subsequent hydrogenation.

The salts of alkenylsuccinic acid alkoxyalkyl-half-amides S of the formula Ia and/or Ib according to the invention, if appropriate as a mixture with salts of alkenylsuccinic acid half-ester amines of the formula IIa and/or IIb and/or alkenylsuccinic acid imides of the formula III are used as metalworking auxiliaries, in particular a8 anticorrosion agents and an emulsifier in aqueous and/or oil-containing formulations or metalworking fluids.

The invention likewise relates to aqueous and/or oil-con-taining formulations for working metals, in particular for use as cooling lubricants, which comprise the above-mentioned salts of alkenylsuccinic acidalkoxyalkyl-half-amides of the formula Ia and/or Ib, if appropriate as a mixture with salts of alkenylsuccinic acid half-ester amines of the formula IIa and/or IIb and/or alkenylsuccinic acid imides of the formula III.

The alkenylsuccinic acid alkoxyalkyl-half-amide salts of the formula Ia and/or Ib prepared by the proce6ses described above, if appropriate as a mixture with salts of alkenylsuccinic acid half-ester amines of the formula IIa and/or IIb and/or alkenylsuccinic acid imides of the formula III, form a clear solution in water and, with mineral oil, give formulations which are readily emulsifiable in water. These compounds are employed in concentrated form as emulsifiers and anticorrosion agents in oil-containing and/or aqueous formulations. The concentration of the alkenylsuccinic acid alkoxyalkyl-half-amide salts of the formula Ia and/or Ib, if appro-priate as a mixture with salts of alkenylsuccinic acid half-ester amines of the formula IIa and/or IIb and/or alkenylsuccinic acid imides of the formula III, in the formulation i6 higher than that during use and is usually 10 to 80 % by weight. The formulation is diluted with -'" 210~0S

water for cutting or non-cutting ~haping, ~uch a~, for example, in drilling, cutting, drawing and milling fluids. To prepare the formulations, the product~
according to the invention are either stirred into the required amount of water or mixed with mineral oil or mineral oil/water. The re~ulting aqueous or oil-contain-ing formulations are usually diluted or emulsified with water before use. The dilution ratio iB in general 1 : 10 to 1 : lO0. The use concentration of the alkenylsuccinic acid alkoxyalkyl-half-amide salts in metalworking fluids, for example drilling, cutting, drawing and milling fluids, is in general about 0.1 to 10 % by weight, preferably 2 to 10 % by weight. The concentration men-tioned relates both to the use of the products in water and to their u~e in mineral oil/water omul~ions during metalworking. Metalworking fluids are also to be under-stood as meaning coolinq lubricants.

The alkenylsuccinic acid alkoxyalkyl-half-amide salts are employed as an emulsifier with corrosion protection in aqueous metalworking fluids containing mineral oil and a8 an anticorrosion agent in aqueous metalworking fluids which are free from mineral oil. They are suitable for mixing with customary mineral oils, in particular with naphthene-based and paraffin-based mineral oils and mineral oils on a mixed basis.
The formulations or metalworking fluids can comprise additional auxiliaries for opt;~;zing the emul~ifyinq properties and the corrosion protection. Auxiliaries which are particularly advantageous for this purpose are oxyethylates of the formula V

R~-0-(CH2-CH,-O)pH V

in which R~ is C10-C22 alkyl, C,0-C22 alkenyl or alkylphenyl having a total of 10 to 20 carbon atoms and p is a number from 2 to 10.
Fatty acid alkanolamides of the formula VI

, ' , . . . ....

---"` 21045~

R9-CH-NRI0Rll VI

in which R9 i8 Clo-C22 alkyl or C10-C22 alkenyl and Rl and R11 are identical or different and are hydrogen or hydroxy-(C1-C6)-alkyl, in particular 2-hydroxyethyl or 2-hydroxypropyl, can also be employed a~ auxiliaries.
Further suitable auxiliaries are ether-carboxylic acids of the formula VII
Rl2-(o-cH2-cH2)q-(o-cHtR')-cH2)r-cH2coo X VII

in which 0 Rl2 iB a branched or unbranched C8-C22 alkyl or C8-C22 alkenyl ratical and q and r inde-pendently of one another can assume values from O to 10, with the proviso that the sum of q and r is at least 1 and X i8 hydrogen or an alkali metal atom or alkaline earth metal atom.

Auxiliaries which are likewise ~uitable are alkoxylated primary amines of the formula VIII
Rl3-Nl(-ocH2-cH2-o)pH]lu VIII

in which R~3 i8 C12-C20-alkyl, or alkenyl, preferably Clc-Cla-alkyl, p is a number from 2 to 10, preferably 4 to 6, and u is the number 1 or 2, with the provi~o th~t if u iB 1 a hydrogen atom i~ located on the free bond of the nitrogen atom.

Other suitable auxiliaries are also fatty acid polyglycol e~ters, in particular of saturated or un~aturated fatty acids having 10 to 22 carbon atoms in the alkyl chain and 1 to 10 ethylene oxide units, 6uch as oleic acid having 4 to 6 ethylene oxide unit~. The formulations in general comprise these auxiliaries individually or in mixtures in amounts of in each case ~bout 20 to 40 ~ by weight. The formulations for this puxpose furthermore can compri~e ' ` ,, . -'.
~:
: .
, ' ''., ~ - . ,'' ," -'.,; - :
. ~ . .

~` 210~05 :

customary additives, such as foam suppressants or suit-able perservatives.

The terms used below for characterization, ~uch as acid number, amine number, ba~e nitrogen and iodine color 5 number, are determined or ascertained as follows:

Determination of the acid number:
To determine the acid number, ~tated in mg of ROH/g of substance, O .1 to O .5 g of the ~ample is weighed into a 150 ml glass beaker and di~solved in 60 to 80 ml of 10 ethanol and the solution is titrated with 0.1 N ethanolic pota~sium hydroxide solution. The end point is indicated potentiometrically ( apparatu~es: Metrohm Titroprocessor 682, Dosimat 665 with combined pH gla~s electrode ) .

15 Ascertaining the base nitrogen and the amine num~er:
To ascertain the base nitrogen, stated in % of N, 0.1 to 0.5 g of the sample is weighed into a 150 ml glas~ beaker and di~solved in 60 to 80 ml of glacial acetic acid and the solution is titrated with 0.1 N perchloric acid in 2û glacial acetic acid. The end point is indicated potentio-metrically ( apparatuses: Metrohm Titroprocessor 682, Dosimat 665 with combined pH glass electrode ) .
The amine number, stated in mg of ROH/g of substance, i8 calculated from the value for the base nitrogen from the 25 formula:

amine number tmg of KOH/g] ~ % of base N x 5.61/0.140067 The iodine color number denotes the concentration of free iodine in an iodine/potassium iodide solution ( in mg of 30 iodine per 100 ml of iodine/potassium iodide solution) and serves to characterize the color or transparency of this solution and liquids of a similar type. The basis f or the determination of the iodine color number is the iodine color scale ( comparison tubes ) . Literature:

... . . .. . . . . . .
'' '' ' '' : .' ' ' " . " ~: ' ' . ' ' . : ,, . , : ..
. .,: .
.. . .

2104~0~
g DIN 53403.

The following embodiment examples illustrate the present invention without limiting it:

Examples:

Example 1 Preparation of Cl2/"-alkenyl~uccinic acid 3-butoxypropyl-half-amide triethanolammonium salt A mixture of 127.5 g (1.0 mol) of 3-n-butoxypropylamine, 149.1 g (1.0 mol) of triethanolamine and 30 g of water was initially int~oduced into a 1 1 three-necked fla~k with a stirrer, internal thermometer and reflux condens-er, and 279.2 g (hydrolysis number: 401.9 mg of KOH/g;
1 mol) of technical grade Cl2/l~-alkenylsuccinic acid anhydride (chain di6tribution of the starting olefin mixture: 65 % by weight of dodecene, 35 % by weight of tetradecene) were metered in over a period of 0.5 hours (exothermic reaction). The internal temperature was limited to not more than 50C by periodic cooling. When the addition had ended, the mixture was ~ubsequently stirred at 50C for a further 2 hours. At this point in time, the reaction mixture contained about 67 % of Cl2~
alkenylsuccinic acid 3-n-butoxypropyl-half-amide trietha-nolammonium/3-butoxypropylammoniu~ salt and about 33 % of Cl2/1,-alkenylsuccinic acid triethanolamine ester 3-n-butoxypropylammonium/triethanolammonium salt (determinedby base N determination).
The reaction mixture was rendered alkaline by addition of 48 g (0.6 mol) of a 50 % strength ~odium hydroxide solution. 642.1 g of a pale brown-yellow liquid having an iodine color number of 30 to 40, an amine number (deter-mined potentiometrically) of 171 mg of KOH/g, an acid number of 46 mg of KOH/g and a viscosity of 1.9 Pas (Brookfield, 28C, 10 revolutions per minute) were obtained.

-~ . . . . . . . . .
. , : ...................... . . .
. . . :

-- 210~

Example 2 Preparation of C,2/"-alkenyl~uccinic acid 3-methoxypropyl-half-amide triethanolammonium ~alt 44.6 g (O.5 mol) of 3-methoxypropylamlne were initially introduced into the apparatus described in Example 1 at 30C and 139.6 g (hydroly~is number: 401.9 mg of ~OH/g;
0.5 mol) of technical grade Cl2~ alkenyl~uccinic acid anhydride (chain di~tribution of the tarting olefin mixture: 65 ~ by weight of dodecene, 35 % by weight of tetradecene) were added dropwise in the cour~e of 30 minute~ (exothermic reaction), the internal temperature being kept at not more than 50C by periodic cooling. When the addition had ended, the mixture was ~ubsequently 6tirred at 50C for a further 2 hours (conversion according to control of the ba~e N ~ 98 %) and was neutralized by addition of 74.5 g ~0.5 mol) of triethanolamine. Finally, the reaction mixture was rendered alkaline by addition of 39 g of a 30 % strength sodium hydroxide solution (pH (1 % in demineralized 20 water): 8.4). 296 g of a dark yellow liquid having an iodine color number of 20, an amine number ~potentio-metric determination) of 151 mg of RO~/g and an acid number of 50.6 mg of KOH/g were obtained.

Example 3 Preparation of C,2~,-alkenyl~uccinic acid 3-butoxypropyl-amide methyldiethanolammonium salt 55.8 g (0.2 g) of technical grade n-Cl2/"-alkenylsuccinic acid anhydride were added dropwise to a mixture of 25.5 g (0.2 mol) of 3-butoxypropylamine, 23.8 g (0.2 mol) of N-methyl-diethanolamine and 6 g of demineralized water in the course of 30 minutes, starting at 30C (exothermic reaction), the internal temperature being kept at 50C by periodic cooling, and the mixture wa~ sub~equently stirred at 50C for 2 hour~. At this point in time, the .. ., ., - - .
..
-... . . . .:
: . - . :-.

.- . , .

5 0 ~
, reaction mixture contained, according to analysis (base N) about 86 % of n-C,2/l~-alkenyl~uccinic acid 3-butoxypropyl-half-amide triethanolammonium/3-butoxyprop-ylammonium salt and about 14 ~ of n-Cl2/l,-alkenylsuccinic acid triethanolamine e~ter 3-butoxypropyl~mmonium/tri-ethanolammonium salt. When the reaction had ended, the mixture was rendered alkaline with 9.6 g of 50 ~ fftrength sodium hydroxide and 119.1 g of a yellowish vi~cous liquid having an iodine color number of 20, an amine number of 168 mg of KOH/g and an acid number of 51 mg of ROH/g were thus obtained.

Example 4 Preparation of Cl2/"-alkenylsuccinic acid 3-methoxypropyl-amide triethanolammonium salt 44,6 g (0,5 mol~ 3-Meth~proQyl~ was added d~*~se to 139.8 g (0.5 mol) of n-C,2~l~-alkenylsuccinic acid anhydride in the course of 0.5 hours, with periodic cooling, such that the internal temperature did not exceed 50C, and the mixture was subsequently stirred for 1 hour and neutralized with a mixture of 75.6 g of triethanolamine and 14.2 g of water to give, after post-reaction for 1 hour at 50C, a reaction mixture having a half-amide/ester ratio of 93.7 (analysis by base N). After the mixture had been rendered alkaline with 24 g of 50 % strength sodium hydroxide solution, 291.6 g of a dark yellow liquid having an amine number of 160 mg of KOH/g, an acid number of 46 mg of KOH/g and a vi~cosity of 2.3 Pas were obtained.

Example 5 Preparation of tripropyl~uccinic acid 3-methoxypropyl-amide triethanolammonium salt 111.5 g (0.5 mol) of technical grade tripropenyl~uccinic anhydride were added dropwi~e to a mixture of 44.6 g (O.S mol) of 3-methoxypropylamine, 74.5 g (O.5 mol) of ~` 2104~0~

triethanolamine and 13.6 g of water in the course of 0.5 hours, starting at 30C, with periodic cooling, such that the internal temperature did not exceed 50C, and the mixture was then subsequently stirred at this temper-ature for a further 2 hours. At this point in time, thereaction mixture contained about 63 % of half-amide and 37 % of half-ester. After the mixture had been rendered alkaline with 24 g of 50 % strength Botium hydroxide solution, 266.2 g of a pale yellow viscous liquid having an amine number of 206 mg of ROH/g and an acid number of 56 mg of KOH/g were obtained.

- ~04~0~

Table 1: Applications properties of alkenylsuccinic acid 3-alkoxypropylamide6 I~ P10 __ _ __I

App-nr~nc- of 3 ~ ntr-ngtb nqu-ou~ ~olutLon-~
di~tLll-d l~nt-r 1~-dLut-ly ol-~r el-nr el--r c~-~r ol-nr ~ft-r 2~ hr~ ol-~r prr nt el-nr el--r el-~r 10 Foull h-ight1~
Lu~-dint-ly ~ 50 > 50 > 50 > 50 > 50 ft-r 5 ~in~ > 511 > 50 > 50 20 12 l~-dl~t-ly cl-~r tr n - el-~r el--r cloudy .ft.r 2~ hr~ el-~r tr~n-- el-~r el-nr eloudy 0-~ h-ightl) L~-dl-t-ly ~ 50 50 > 50 ~ 50 ~5 ¦ nft-r 5 ~in- J - 50 o Co~ro-ion prot-ction ~ 3-rb-rt t--t ~D5N 51360/1) dl-tLll-d 1120 1 0 ~ R0/80 Ro/~iO RotS0 R0/~o R0/L0 20 dll 3 0 ~ R0/50 Ro/~o R0/00 R0/00 R0/Oo b ) FLlt-r p-p-r t--t (DIN 51360/2) dL-tLll-d 2 1 5 ~ 0 1 0 0 ¦ 20 d~3 3 0 ~ 0 0 0 0 0 I!~ul-Lfi-~ilLty pon- pon- pon- p~ln- npon-t-n-ou~ tnn-ou~ tnn-ou~ t-n-ou- tnn-ou-l ~ l Notes on Table 1:
1) To determine the foaming properties, in each ca~e 50 ml of 3 % ~trength agueous ~olutions of the to~t productR were introduced into a graduated 100 ml measuring cylinder and the cylinder was closed with a gla~ stopper and shaken vigorously 20 x in the horizontal direction. The evaluation wa~ carried out after the waiting periods stated by mea~uring the amount of foam in ml.

Information on the test procedure:

, . .
;

.

2~04~0S

The tests were carried out on formulations comprising:
18 % of emulsifier mixture 4 % of nonylphenol ethoxylate 2 % of water 578 % of naphthene-based mineral oil Emulsifier mixture:
37 % of product according to the example 32 % of oleyl alcohol ~ 2EO (ethylene oxide) 31 % of tall oil fatty acid diethanolamide . .

.

Claims

1. A salt of an alkenylsuccinic acid alkoxyalkyl-half-amide of the formula Ia or Ib Ia Ib if appropriate as a mixture with a salt of an alkenylsuccinic acid half-ester amine of the formula IIa or IIb IIa IIb and/or an alkenylsuccinic acid imide of the formula III

III

in which R1 is C6-C30-alkenyl or C6-C30-alkyl, preferably C9-C18-alkenyl or C9-C18-alkyl, in which R1 can be straight-chain or branched;
R2 is -(CH2)n-O-(A)m-R3, where A is -CH2-CH2-O- or -CH(R4)-CH2-O-, in which R3 is C1-C19-alkyl, and in which R3 can be straight-chain or branched, R4 is hydrogen or methyl, n is a number from 1 to 6, m is a number from 0 to 8 and M+ is an alkali metal or alkaline earth metal cation or an ammonium ion of the formula HNR5R6R7, in which R5, R6 and R7 are identical or different and are hydrogen, C1-C6-alkyl or hydroxy-(C1-C6)-alkyl, in particular

2-hydroxyethyl and 2-hydroxypropyl.

2. A compound as claimed in claim 1, wherein a salt of an alkenylsuccinic acid half-ester amide of the formula IIa or IIb and an alkenylsuccinic acid imide of the formula III are present in a concentration of up to 40 % by weight, preferably up to 20 % by weight, as a mixture with a salt of an alkenylsuc-cinic acid alkoxyalkyl-half-amide of the formula Ia or Ib.

3. A process for the preparation of a salt of an alkenylsuccinic acid alkoxyalkyl-half-amide of the formula Ia or Ib, if appropriate as a mixture with a salt of an alkenylsuccinic acid half-ester amine of the formula IIa or IIb and/or an alkenylsuccinic acid imide of the formula III, which comprises reacting an alkenylsuccinic acid anhydride with an alkoxyalkylamine of the formula IV

H2N-(CH2)n-O-(A)m-R3 IV

in which R3 is C1-C18-alkyl, in which R3 can be straight-chain or branched, n is a number from 1 to 6 and m is a number from 0 to 8, in a molar ratio of 1 : 0.7 to 2.5, preferably 1 : 0,8 to 1.2, at temperatures of 20 to 120°C, preferably 60 to 100°C, and carrying out this reaction in the presence of an amount of base which is equimolar to the alkoxyalkylamine of the formula IV, or adding an amount of base equimolar to the alkoxyalkylamine of the formula IV after the reaction.

4. The process as claimed in claim 3, wherein an alkali metal hydroxide, alkaline earth metal hydroxide, alkanolamine of the formula NR5R6R7 or a mixture thereof is employed as the base.

5. The process as claimed in claim 3, wherein 2-hy-droxyethylamine and/or 2-hydroxypropylamine are employed as the alkoxyalkylamine of the formula IV.

6. An aqueous or oil-containing formulation for working metals, in particular for use as a cooling lubricant, which comprises a salt of an alkenyl-succinic acid alkoxyalkyl-half-amide of the formula Ia or Ib, if appropriate as a mixture with a salt of an alkenylsuccinic acid half-ester amine of the formula IIa or IIb and/or an alkenylsuccinic acid imide of the formula III, as claimed in claim 1.

7. A formulation as claimed in claim 6, which comprises a compound as claimed in claim 1 in a concentration of 10 to 80 % by weight.

8. An aqueous or oil-containing metalworking fluid for working metals, in particular for use as a cooling lubricant, which comprises a salt of an alkenyl-succinic acid alkoxyalkyl-half-amide of the formula Ia or Ib, if appropriate as a mixture with a salt of an alkenylsuccinic acid half-ester amine of the formula IIa or IIb and/or an alkenylsuccinic acid imide of the formula III, as claimed in claim 1.

9. An aqueous and/or oil-containing metal working liguid as claimed in claim 8, which comprises compounds as claimed in claim 1 in a concentration of 0.1 to 10 % by weight, preferably 2 to 10 % by weight.

10. A formulation as claimed in claim 6, which comprises as additional auxiliaries an oxyethylate of the formula V
R8-O-(CH2-CH2-O)pH

in which R8 is C10-C22-alkyl, C10-C22 alkenyl or alkylphenyl having a total of 10 to 20 carbon atoms and p is a number from 2 to 10, and/or a fatty acid alkanolamide of the formula VI

in which R9 is C10-C22-alkyl or C10-C22-alkenyl and R10 and R11 are identical or different and are hydrogen or hydroxyl-(C1-C6)-alkyl, in particular 2-hydroxy-ethyl or 2-hydroxypropyl, and/or an ether-carboxylic acid of the formula VII
R12-(O-CH2-CH2)q-(O-CH(R1)-CH2)r-CH2COO-X+

in which R12 is a branched or unbranched C8-C22-alkyl or C8-C22-alkenyl radical and q and r independently of one another have values from 0 to 10, with the proviso that the sum of q and r is at least 1, and X is hydrogen, an alkali metal atom or an alkaline earth metal atom, an alkoxylated primary amine of the formula VIII
R13-N[(-OCH2-CH2-O)pH]]u in which R13 is C12-C20-alkyl, or alkenyl, preferably C16-C18-alkyl, p is a number from 2 to 10, preferably 4 to 6, and u is the number 1 or 2, with the proviso that if u is 1, a hydrogen atom is located on the free bond of the nitrogen atom, and/or a fatty acid polyglycol ester, in particular of a saturated or unsaturated fatty acid having 10 to 22 carbon atoms in the alkyl chain and 1 to 10 ethylene oxide units, preferably oleic acid having 4 to 6 ethylene oxide units.

11. A formulation as claimed in claim 10, which com-prises the auxiliaries in a concentration of 20 to 40 % by weight.

12. A formulation as claimed in claim 6, which comprises a foam suppressant and/or preservative.

13. A metalworking fluid as claimed in claim 8, which comprises as additional auxiliaries an oxyethylate of the formula V

R8-O-(CH2-CH2-O)pH

in which R8 is C10-C22-alkyl, C10-C22 alkenyl or alkylphenyl having a total of 10 to 20 carbon atoms and p is a number from 2 to 10, and/or a fatty acid alkanolamide of the formula VI

in which R9 is C10-C22-alkyl or C10-C22-alkenyl and R10 and R11 are identical or different and are hydrogen or hydroxyl-(C1-C6)-alkyl, in particular 2-hydroxy-ethyl or 2-hydroxypropyl, and/or an ether-carboxylic acid of the formula VII
R12-(O-CH2-CH2)q-(O-CH(R1)-CH2)r-CH2COO-X+

in which R12 is a branched or unbranched C8-C22-alkyl or C8-C22-alkenyl radical and q and r independently of one another have values from 0 to 10, with the proviso that the sum of q and r is at least 1, and X is hydrogen, an alkali metal atom or an alkaline earth metal atom, an alkoxylated primary amine of the formula VIII

R13-N[(-OCH2-CH2-O)pH]]u in which R13 is C12-C20-alkyl, or alkenyl, preferably C16-C18-alkyl, p is a number from 2 to 10, preferably 4 to 6, and u is the number 1 or 2, with the proviso that if u is 1, a hydrogen atom is located on the free bond of the nitrogen atom, and/or a fatty acid polyglycol ester, in particular of a saturated or unsaturated fatty acid having 10 to 22 carbon atoms in the alkyl chain and 1 to 10 ethylene oxide units, preferably oleic acid having 4 to 6 ethylene oxide units.

14. The use of a salt of an alkenylsuccinic acid alkoxy-alkyl-half-amide of the formula Ia or Ib, if appro-priate as a mixture with a salt of an alkenylsuc-cinic acid half-ester amine of the formula IIa or IIb and/or an alkenylsuccinic acid imide of the formula III as a metalworking auxiliary, in par-ticular as an anticorrosion agent and enulsifier in an aqueous and/or oil-containing formulation or metalworking auxiliary.