CS53692A3 - Auxiliary agent for metal treatment - Google Patents

Abstract

Alkenylsuccinamic acid derivatives of the formulae <IMAGE> are used in water- and/or oil-containing formulations or liquids for treating metals as anticorrosive agents and emulsifiers. In the formulae A = C6-C30-alkenyl, R = H or R<1>, R<1> = -R<2>-O-(CH2CHR<3>-O)nH, R<2> = C1-C10-alkylene, R<3> = -H or -CH3, n = 0 to 50 and Me<(+)> is an alkali metal ion, a proton or an ammonium ion of the formula HN<(+)>R<4>R<5>R<6>, where R<4>, R<5> and R<6> are identical or different and denote hydrogen, C1-C6-alkyl and hydroxyalkyl.

Description

BDr. ALL THREATS '53 é - you? «« PRA PRAHA '., Zitna 25 {

Ob1ast techniques

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to metal working aids useful in a variety of pre-treatment and post-processing operations. It relates to auxiliaries for non-chip and chip metal machining. For metal cutting, it uses drilling and cutting oils, with non-cutting machining of rolling and drawing oils.

Background Art

Anti-corrosion agents and emulsifiers in emulsifiable metal working agents should meet the following requirements: - they should exhibit significant corrosion protection characteristics for ferrous metals, - they should have an emulsifying effect on mineral oils or in combination with selected non-ionic compounds, - should exhibit a slight slope they should eventually cause sudsing of the foam to foam, - they should prevent the growth of microorgamisms. In particular, the compounds disclosed in EP-A-0127132 meet all of these requirements. Semi-amides of alkenylsuccinic acid of the general formula R - CH - Clf2 - COO - K + are already known from this publication, where R is alkenyl groups used to protect against emulsification of such emulsions. CGmě t tHHHH nu nu nu of 6 to 12 carbon atoms; However, these compounds do not increase, leading to insufficient foams, which tend to foam, which is a particular drawback when the emulsions are subjected to high mechanical loading.

The present invention is directed to eliminating the drawbacks encountered in the reaction of alkenylsuccinic anhydrides with alkanoic amines.

SUMMARY OF THE INVENTION

SUMMARY OF THE INVENTION Accordingly, the present invention provides a composition based on a semi-amidalkenylsuccinic acid of the formula A - CH - CH 2 - CONRR 1 and / or A - CH - CH 2 - COO - Me + 1! COO-Me + CONRR1 optionally mixed with cyclic imides of the formula

useful as metalworking aids, in particular for corrosion protection and as emulsifiers in aqueous and / or oil-containing compositions or in diluted form in metalworking fluids. Typically, both halfamides are in the form of a mixture.

In the above formulas, A represents an alkenyl group having from 6 to 30 carbon atoms, in particular from 10 to 24 carbon atoms with a straight or branched chain, R is hydrogen or R 1 when R and R 1 are the same, these symbols R and R1 is the same or different,

R1 is - R2 - O - (CH2CHR3 --O--) nH wherein R is a C1 -C10 alkylene group, in particular a C1 -C5 carbon atom, a straight or branched chain R3 group, a hydrogen atom or a methyl group n is from 0 to 50, preferably from 0 to 5,

An alkali metal, especially sodium or potassium, Me + ion, a proton or an ammonium ion of the formula * NHR 4 R 5 R 6 where R 4, R 5 and R 6 are the same or different, hydrogen or alkyl or hydroxyalkyl of 1 to 6 carbon atoms, especially 2- hydroxyethyl or 2-hydroxypropyl.

Said imides are by-products in the preparation of the compounds of the invention and are usually present in the mixture at a concentration of 0 to 30%.

The opalescence of the emulsions obtained with the semi-amide-alkenylsuccinic acid, in contrast to the emulsions with the known products of EP-A-0127132, shows a better fine dispersion of the emulsion and thus a longer stability on standing, which makes the emulsion more usable. There is also a better fulfillment of the requirement for lower foaming or more rapid disruption of the foam.

The invention also relates to aqueous and / or oil-containing compositions and to metal working fluids which include the abovementioned compounds as corrosion protection agents as emulsifiers. The preparation of the starting alkali succinic anhydride from olefins and maleic anhydride is known. Preferred olefins include the oligomers of ethylene, propylene and butylene as well as olefins with internal double bonds. Semiamides of alkylene succinic acid are obtained by reacting one mole of anhydrides of an allyl succinic acid with 0.7 to 2.5 moles, preferably 0.8 to 1.2 moles, of alkanolamine at 0 to 60 ° C. higher heat as effective. By neutralizing the obtained alkali-alkanoic acid half-amides with amines or alkali hydroxides, the corresponding amino or alkali salts of the semi-alkenylsuccinic acid are obtained.

Particularly preferred compounds of the present invention are the ammonium salts of Me * NHR4R-Rh, wherein R4 is R5 equals R6 and is C1 -C4 -hydroxy-alkyl. of an alkenylsuccinic acid amide with corresponding amine.

Semiamides of alkenylsuccinic acid according to the invention provide water-clear solutions in the past and provide water-emulsifiable compositions with mineral oil. These compounds are used in concentrated form as emulsifiers and in oil-containing anti-corrosion agents and / or in aqueous formulations. The concentration of the semi-amides in the composition is higher than the use and is generally 20 to 80% by weight. In chip and chipless machining, for example in drilling, cutting, drawing and rolling fluids, the composition is diluted with water.

For the preparation of the composition, the products according to the invention are mixed into the required amount of water or mixed with the mineral oil or, if appropriate, the oil / water mixture containing the oil is emulsified by the user. The dilution ratio is generally 1:

The concentration of semi-amides in metalworking fluids, for example in drilling, cutting, drawing and rolling liquids, is generally about 0.1 to 10% by weight, preferably 2 to 10% by weight. The concentrations given refer to the use of products in. water and mineral oil / water emulsions for metal processing. Coolant lubricants are also counted among the metal working fluids.

The alkenylsuccinic acid semi-amides are used in aqueous mineral oil-containing liquids for the treatment of the obtained aqueous or, optionally, 10 to 1: 100. metals as emulsifiers and corrosion protection agents. 5

They are suitable for mixing with all common mineral oils, especially mineral oils not naphthenic, paraffin-based and mixed-base.

Metal working agents or fluids may additionally contain auxiliaries to optimize emulsification behavior and corrosion protection. Oxethylates of the general formula are particularly preferably used for this purpose

RJ - C - (CH 2 --CH 2 --O) r -H where R 7 is C 10 -C 22 alkyl, C 10 -C 22 alkenyl or C 1 -C 20 alkylphenyloxy and n is 2 to 10.

As auxiliaries, it is also possible to use amide fatty acids of the formula R 8 - CO - NR 10 R 10 wherein R 8 is C 10 -C 22 alkyl, C 10 -C 22 alkenyl and R q and R 10 which are the same or different. different, each hydrogen, C 1 -C 5 hydroxyalkyl, especially 2-hydroxyethyl or 2-hydroxypropyl.

Suitable excipients are also glycerol ester fatty acids, especially saturated or unsaturated fatty acids having from 10 to 22 carbon atoms in the alkyl chain and from 1 to 10 ethylene oxide units, such as oleic acids with 4 to 6 ethylene oxide units. These excipients are contained in the compositions individually or in a mixture in an amount of approximately 20 to 40% by weight.

In addition, commonly used additives, such as an antifoam additive, can be used in the compositions for these purposes.

The invention is further illustrated by the following non-limiting examples. EXAMPLES Example 1 Preparation of Triethanolamine / Sodium Salt of Hydroxyethylsamido-Dipropenyl Succinic Acid

To a three-necked flask equipped with a dropping funnel, a thermometer stirrer, was charged 61 g (1.0 mol) of monoethanolamine and 90 gE-water. 1.0 mol of anhydride tripropenyl succinic acid is then added dropwise over 30 minutes while maintaining the cooling temperature at a maximum of 30 ° C. After the dropwise addition, the stirrer was stirred at 30 ° C for three hours.

149 g (1.0 mol) of triethanolamine are now added to this solution at 30 DEG C., stirred for 5 minutes, and then 48 g (0.6 mol) of sodium hydroxide (in the form of 50 l of solution) are added. The resulting solution is homogenized at 60 ° C for one hour. 572 g of a brown, viscous oil are obtained. Addition of trihanolamine is also possible already in the reaction of monoethanolamine with tripropenylsuccinic acid anhydride. EXAMPLE 2 Preparation of Triethyanolamine / Sodium Salt of Hydroxyethylpoamido alkenyl succinic acid with a 12-carbon n-alkenyl moiety of a carbon / n-alkeylic residue with 14 carbon atoms

The procedure of Example 1 was followed. 1.0 ml of C12 / C14 anhydride anhydride was added dropwise. 623.8 g of a brown, viscous oil are obtained. Example 3 7 Preparation of triethanolamine / sodium with 1 i / hydroxyethylpoamate penta-propenyl succinic acid

The procedure of Example 1 is followed. 348 g (1.0 mol) of pentapropenylsuccinic anhydride are added dropwise to 48.8 g (0.8 mol) of amine monoethanoic acid. 683.8 g of a brown, viscous oil are obtained. The anhydride content of penta-propenylsuccinic acid anhydride is about 68% by weight. Example 4 Preparation of Triethanolamine / Sodium Salt of Hydroxyisopropyl Polyester Perentapropenylsuccinic Acid

60 g (0.8 mol) of monoisopropylamine and 90 gE-water are charged into a three-necked flask equipped with a dropping funnel, with a thermometer stirrer. 348 g (mol) of anhydridupentapropenyl succinic acid are then added dropwise over a period of 30 minutes while maintaining a temperature of at most 30 ° C with cooling. After the addition is complete, it is stirred for three hours at 30 ° C. 149 g (1.0 mol) of triethanolamine, stirred for 5 minutes, are then added to this solution at 30 DEG C. and then 48 g (0.6 moles of sodium hydroxide (as a 50% aqueous solution) are added. 695 g of a brown, viscous oil are obtained Example 5 Preparation of triethanolamine / diglycoyl sodium salt after pentapro-penyl succinic acid 1amamide

84 g (0.8 mol) of E-water are introduced into a three-necked flask equipped with a dropping stirrer. 348-pentapropenylsuccinic acid is added dropwise over 30 minutes, maintaining the temperature at the maximum of 30 ° C by cooling with a funnel, thermoglycolamine and 90 gg (1.0 molar) of anhydride. After closure, stir for three hours at 30 ° C. 149 g (1.0 moles (triethanolamine) are added to this sena solution at 30 ° C and then 5 g (0.6 moles) of sodium hydroxide (in the form of a 50% aqueous solution) are added. 719 g of a brown, viscous oil are obtained Example 6 Preparation of triethanolamine / sodium hydroxyethylpoamido alkenyl succinic acid with a 10-carbon n-alkenyl / n-alkenyl radical of 14 carbon atoms

The procedure of Example 1 was followed. 263 g (1.0 mol) of C10 / C14-alkenylsuccinic anhydride were added dropwise. 611 g of a brown, viscous oil are obtained. Example 7 Preparation of triethanolamine / sodium bis / hydroxyethyl / semiamidopentapropenylsuccinic acid

To a three-necked flask equipped with a dropping funnel, a thermometer stirrer, 0.8 mol of diethanolamine and 90 g of E-water are added. Then, 348 g (1.0 mol) of anhydride pentapropenylsuccinic acid is added dropwise over 30 minutes while maintaining the cooling temperature at a maximum of 30. ° C. After the dropwise addition, stir for three hours at 30 ° C. 1.0 mol of triethanolamine is added to this solution at 30 DEG C., stirred for 5 minutes and then 0.6 mol of sodium hydroxide (50% aqueous solution) is added. Finally, it is homogenized at 60 ° C for one hour. 719 g of brown, viscous oil are obtained. EXAMPLE 8 The mixture of emulsifiers 370 g of the product of Example 1, 310 g of tall oil diethanolamide, 320 g of oleyl alcohol polyglycol ether (2 mol of ethylene oxide) was stirred at room temperature and stirred until a clear solution was obtained. EXAMPLES 9-14 Preparing the emulsifier mixtures using 370 g of the product of Examples 2 to 7, analogously to Example 8, with the compounds of Example 8. Preferred properties of the compounds prepared, for example mixtures, are as follows. from the values given in the following tables. / The term "dH" in the tables always means German degrees of water hardness. / -10- '> 5 G rd' £? I-1 '> 5 Gr — 1 I — 1 r4 • with CO CO what CO what CO Ολ Λ4 Λ4 Λ4 Λ4 X4 X)

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Industrial usability

The alkenylsuccinic acid semi-amides as an additive to liquids used in metal working to prevent foaming, which prolongs the life of these liquids.

Claims (4)

«Ť.TITLE &amp; A tí V ^ ^ 11504 PRA. '- <?> PATENT CLAIMS CLAIMS: 1. A metal working aid which protects the corrosion and acts as an emulsifier in aqueous and / or oil-containing compositions or fluids, characterized in that it comprises a semi-amide-alkenylsuccinic acid of the formula A - CH - CH - CONRR1 and / or A - CH - CH2 - COCr-Me COO- In the case of a mixture + CONRRi 5i with cyclic imides of the general formula ΛΑ3Γ90VΛΖΠγΝΛΛ OHdnvgn with A being alkenyl of up to 24 atomsR hydrogen atom of R1 represents a group of the general formula with 6 to 30 carbon atoms, especially with VLQ straight or branched carbon, or R1, 5 6 Ίΐ 7 5 ·. -JLT ΐ 0 T 0 - 5 - R 2 - O - (CH 2 CHR 3 --O -) nH where up to 10 carbon atoms, especially R 2 alkylene group with 1 to 5 carbon atoms, straight or branched chain, R 3 atom hydrogen or methyl group 0 to 50, preferably 0 to 5, Me + alkali metal ion of the formula NH + R 4 R 5 R 6 proton or ammonium ion 1 where R 4, R 5 and R 6 are the same or different, hydrogen or alkyl a group or hydroxyl group having from 1 to 6 carbon atoms. Use of the alkeynlsuccinic acid semi-amides according to claim 1, wherein the water and / or mineral anti-corrosion agent of the oil-containing composition together with oxethylates of the general formula R 7 -O- (CH 2 -CH 2 -O) n -H wherein R 7 is a C 10 -C 22 alkyl group , (C až-C 22 alk) alkenyl or (C až-C 20 alkyl) alkylphenyl group (C až-C 10 NR) and / or fatty acid alkanolamides of the formula (R8) - CO CONR'Riocde is an R® alkyl group of 10 to 22 atoms carbon or alkenyl having 10 to 22 carbon atoms, and those which are the same or different, hydrogen or C 1 -C 6 hydroxyalkyl, especially 2-hydroxyethyl or 2-hydroxypropyl and / or and / or polyglycol fatty acid esters. Compositions comprising water and / or metal working oil, in particular for cooling and lubrication, comprising alkenyl succinic acid semi-amides according to claim 1. Metal working fluids comprising water and / or oil, in particular for cooling and lubrication, comprising alkenylsuccinic acid semi-amides according to claim 1.