SK280809B6 - Use of salts of alkenylsuccinic acid semi-amides as auxiliary agents for metal treatment and the auxiliary agents in which said compounds are contained - Google Patents

Abstract

The use of salts of alkenylsuccinic acid semi-amides with imids of the formula (I), whereof substituents have their meanings stated in the description, as auxiliary agents for metal treatment and the auxiliary agents, especially as anticorrosion agents and emulsifiers, in water- and/or oil-containing formulations or in liquids for treating metals. There are further disclosed auxiliary agents containing said compositions.

Description

Technical field

The invention relates to the use of metal processing aids in a variety of metal pretreatment and post-treatment operations. It concerns aids for chipless and shaving machining of metals. Drilling and cutting oils are used for metal cutting, rolling and mining oils are used for flour-free machining.

BACKGROUND OF THE INVENTION

Corrosive agents and emulsifiers in emulsifiable metal working agents should meet the following requirements:

- they should have significant anti-corrosion characteristics with respect to ferrous metals,

- they should have an emulsifying action on mineral oils, possibly also in combination with selected non-ionic compounds,

- they should have only a low tendency to foam or possibly cause rapid foam disintegration

- they should prevent the growth of micro-organisms.

In part, all of these requirements are met by the compounds disclosed in EP-A-0127132. Alkenylsuccinic acid polyamides of the general formula are already known from this specification

R - CH - CH ₂ - CO ₂ NH ₂ , LOOK ⁺ where R is C 6 -C 12 alkenyl and their use for corrosion protection. However, these compounds do not have sufficient emulsifying action, resulting in insufficient stability of these emulsions. In addition, emulsions containing this compound tend to foam, which is a drawback especially when sanding when the emulsions are subjected to high mechanical stress.

The invention is directed to eliminating the drawbacks that typically occur in the reaction of alkenylsuccinic anhydrides with alkanolamines.

SUMMARY OF THE INVENTION

Accordingly, it is an object of the invention to use alkenylsuccinic acid salts of poloamides of general formulas

A - CH - CH ₂ - CONRR ¹ and / or A - CH - CH 2 - COO Me *

I I

COOMe 'CONRR' or mixtures thereof with imides of formula (I) o

About which

A is a straight or branched chain alkenyl group having 6 to 30 carbon atoms,

R is hydrogen or R < ¹ >

R ¹ is -R ² -O- (CH ₂ CHR ³ -O) n -H, wherein

R ² is alkylene of 1 to 10 carbon atoms, straight or branched,

R ³ represents a hydrogen atom or a methyl group and n represents a number of 0 to 50 a

Me ⁺ means an alkali metal ion, a proton or an anionic ion of the formula NH ⁺ R ⁴ R ⁵ R ⁶ , wherein

R ⁴ , R ⁵ and R ⁶ are the same or different and represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or a hydroxyalkyl group having 1 to 6 carbon atoms, as metal processing aids, in particular as corrosion protective agents and emulsifiers , in aqueous and / or oil-containing preparations or in metal working fluids.

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

The emulsion opalescence achieved with the alkenylsuccinic acid poloamides has a better fine dispersion of the emulsion over the emulsions with known products according to EP-A-0127132 and thus a longer standing stability, i.e. a longer emulsion usability. There is also a better fulfillment of the requirement of lower foaming or faster foam disruption.

The invention also relates to metal processing aids, in particular as corrosion protective agents and emulsifiers, in aqueous and / or oil-containing preparations, or in metal working fluids.

The preparation of the alkenylsuccinic anhydrides used from olefins and maleic anhydride as starting materials is known. Preferred olefins are oligomers of ethylene, propylene and butylene, as well as olefins with internal double bonds. The alkylene succinic acid amides are obtained by reacting one mole of alkenyl succinic anhydride with 0.7 to 2.5, preferably 0.8 to 1.2 mol, of alkanolamine at a temperature of 0 to 60 ° C. If the proportion of cyclic amide is to be increased, a higher temperature is indicated. as expedient. Neutralization of the alkenylsuccinic acid halides obtained with amines or alkali hydroxides gives the corresponding ammonium or alkali salts of the alkenylsuccinic acid halides.

Particularly preferred compounds of the invention are ammonium salts with Me ¹ equal to NHR ⁴ R ⁵ R ⁶ , wherein R ⁴ equals R ⁵ equals R ⁶ and represents a hydroxyalkyl group having 1 to 4 carbon atoms. These alkanolamine salts are prepared by the reaction of the initially formed alkenylsuccinic acid halides of the invention, form clear solutions in water and provide readily emulsifiable compositions with mineral oil in water. These compounds are used in concentrated form as emulsifiers and corrosion protection agents in oil containing and / or aqueous compositions. The concentration of poloamides in the composition is higher than in use and is generally 20 to 80% by weight. In the case of chip and chipless machining, for example in drilling, drawing and rolling liquids, the composition is diluted with water.

For the preparation of the composition, the products according to the invention are mixed in the necessary amount of water or mixed with mineral oil or, optionally, with an oil-water mixture. The aqueous or oil-containing compositions obtained are diluted or emulsified by the user with water. The dilution ratio is generally 1: 10 to 1: 100. The concentration of poloamides in metal working fluids, such as drilling, cutting, drawing and rolling fluids, is generally about 0.1 to 10% by weight, preferably 2 to 10% by weight. The concentrations indicated relate to the use of the products in water and in mineral oil / water emulsions for metalworking. Coolants are also included in the metal working fluids.

Alkenyl succinic acid amides are used in aqueous, mineral oil-containing metalworking fluids as emulsifiers and corrosion protection agents. They are suitable for mixing with all customary mineral oils, in particular naphthene-based, paraffin-based and mixed-base mineral oils.

The metalworking means or fluids may contain additional auxiliaries to optimize emulsifying behavior and protect against corrosion. For this purpose they are particularly preferably the ethoxylates and / or fatty acid alkanolamides and / or fatty acid polyglycol esters, such as oleic acid having 4 to 6 CH ₂ CH ₂ O- units. These excipients are present in the compositions individually or in a mixture in an amount of about 20 to 40% by weight.

In addition, conventional additives such as e.g. anti-foaming agent.

The invention is illustrated by the following examples.

DETAILED DESCRIPTION OF THE INVENTION

Example 1

Preparation of triethanolammonium and / or sodium salt of triphenylsuccinic acid hydroxyethylpoloamide.

A three-necked flask equipped with a dropping funnel, a thermometer and a stirrer was charged with 61 g (1.0 mol) of monoethanolamine and 90 g of E-water. Then 1.0 mol of tripropenylsuccinic anhydride is added dropwise over 30 minutes, maintaining the temperature at maximum 30 ° C by cooling. 149 g (1.0 mol) of triethanolamine are now added to this solution at 30 ° C, stirred for 5 minutes and then 48 g (0.6 mol) of sodium hydroxide (as a 50% solution) are added. The solution obtained is homogenized at 60 ° C for one hour. 572 g of a brown, viscous oil are obtained. The addition of triethanolamine is also possible in the reaction of the monoethanolamine with tripropenylsuccinic anhydride.

Example 2

Preparation of a triethanolammonium and / or sodium salt of an alkenylsuccinic acid hydroxyethylpoloamide having an n-alkenyl moiety of 12 carbon atoms and / or an n-alkenyl moiety of 14 carbon atoms.

The procedure of Example 1 was followed. 1.0 mol of a mixture of alkenylsuccinic anhydrides having 12 and 14 carbon atoms in alkenyl is added dropwise. 623.8 g of a brown viscous oil are obtained.

Example 3

Preparation of triethanolammonium and / or sodium salt of hydroxyethylpoloamide pentapropenes (succinic acid)

The procedure of Example 1 was followed. 1.0 mol of pentapropenylsuccinic anhydride was added dropwise to 48.8 g (0.8 mol) of monoethanolamine. 683.8 g of a brown viscous oil are obtained. The anhydride content of industrial pentapropenylsuccinic anhydride is approximately 68% by weight.

Example 4 Preparation of pentapropenylsuccinic acid triethanolamine and / or sodium salt of hydroxyisopropylpoloamide

A three-necked flask equipped with a dropping funnel, a thermometer and a stirrer was charged with 60 g (0.8 mol) of monoisopropylamine and 90 g of E-water. 348 g (1.0 mol) of pentapropenylsuccinic anhydride are then added dropwise over a period of 30 minutes, maintaining the temperature at maximum 30 ° C by cooling. After the addition was complete, the mixture was stirred for three hours at 30 ° C. 149 g (1.0 mol) of triethanolamine are added to this solution at 30 ° C, stirred for 5 minutes and then 48 g (0.6 mol) of sodium hydroxide (as a 50% aqueous solution) are added. Finally, the solution is homogenized for one hour at 60 ° C. 695 g of a brown viscous oil are obtained.

Example 5

Preparation of triethanolamine and / or sodium salt of diglycolpoloamide pentapropenylsuccinic acid

A three-necked flask equipped with a dropping funnel, a thermometer and a stirrer was charged with 84 g (0.8 mol) of diglycolamine and 90 g of E-water. 348 g (1.0 mol) of pentapropenylsuccinic anhydride are then added dropwise over 30 minutes, maintaining the cooling temperature at a maximum of 30 ° C. After the addition was complete, the mixture was stirred for three hours at 30 ° C. 149 g (1.0 mol) of triethanolamide are now added to this solution at 30 ° C, stirred for 5 minutes and then 48 g (0.6 mol) of sodium hydroxide (as a 50% aqueous solution) are added. Finally, the solution is homogenized for one hour at 60 ° C. 719 g of a brown viscous oil are obtained.

Example 6

Preparation of a triethanolamine and / or sodium salt of an alkenylsuccinic acid hydroxyethylpoloamide having a n-alkenyl radical of 10 carbon atoms and / or an n-alkenyl radical of 14 carbon atoms.

Proceed as described in Example 1. 263 g (1 mol) of a mixture of alkenylsuccinic anhydrides having 10 and 14 carbon atoms in n-alkenyl are added dropwise.

Example 7

Preparation of pentapropenylsuccinic acid triethanolammonium and / or sodium salt of bis (hydroxyethyl) poloamide.

A three-necked flask equipped with a dropping funnel, a thermometer and a stirrer was charged with (0.8 mol) diethanolamine and 90 g of E-water. 348 g (1.0 mol) of pentapropenylsuccinic anhydride are then added dropwise over a period of 30 minutes, maintaining the temperature at maximum 30 ° C by cooling. After completion of the dropwise addition, the mixture is stirred for a further three hours at 30 ° C. To this solution was added 1.0 mol of triethanolamine at 30 ° C, stirred for 5 minutes and then 0.6 mol of sodium hydroxide (as a 50% aqueous solution) was added. Finally, the solution is homogenized for one hour at 60 ° C. 719 g of a brown viscous oil are obtained.

Example 8

At room temperature, an emulsifier mixture of 370 g of the product of Example 13 was mixed and stirred with 310 g of tall oil diethanolamide, 320 g of oleyl alcohol polyglycol ether (2 moles of ethylene oxide) until a clear solution was obtained.

Examples 9 to 14

Emulsifier mixtures were prepared in each case using 370 g of the product of Examples 2 to 7 in analogy to Example 8 with the two compounds mentioned in Example 8.

Advantageous properties according to the examples of prepared compounds or mixtures result from the values given in the following tables. The term "dH" in the tables always means German degrees of water hardness./

Prklad 1 2 3 4 5 6 7 AppearanceOl) ^- C black-brown clear liquid PH value. 1% in dest 6.3 M 8? 9.0 9.0 8.5 9.1 Solubility 3% solution in waterO'dH immediately mp. limpid “ ^Ný limpid cloudy O'dH for 24 hours transp limpid cloudy limpid cloudy 20 * dH immediately lorional) KILN transp transp. cloudy cloudy limpid cloudy 20 * dHza 24 throws 1.) cloudy transp. cloudy cloudy limpid cloudy 20 dH immediately (synthetic) DIN 51360/1) cloudy cloudy transp. cloudy cloudy Ary cloudy 20 * dH per 24 hrs / syn. D1N 51360/1) cloudy cloudy transp. cloudy cloudy limpid cloudy

PrlkiM 1 2 3 4 5 e 7 Foam solution 5 ml W shaken vigorously for 1 min. vŽJOml uratv. cylinders with siumkou dest.voda nned all the foam thick foam siná foam thick foam thick foam oo 5 meters disintegration 20 ‘dH (natural foam foam little penj foam foam foam foam after 5 minutes disintegration 20 * dH (synt.) Immediately foam foam had foam foam foam foam foam 20 * dHC) after 5m n foam foam disintegration foam foam foam foam Protection (xot corrosion CIN 51360/1 destil.voda 1% no birch no rust No rust no rust no rust no rust 20 * dH.frirod 2.5% stnpa rots iladn-hniz. jealous rot máhihrtje no rust little hidje 3% Stope rust little horror rust trace of rust little rust OIN 5138012 desí.voda 1.8% žiackia hidza no rust rust 20 * dH.frirod. 2.5% no horror no rust ¾ "" · "" footprint hntze rust rust 20 * dH, Synth. 3% track of pride supa hrúze no rust no rust No rust No rust

Example 8 9 10 11 12 13 14 5% emulsion of 80% mineral, ej ley and 20% eniiifiátofl a) emulsifying behavior destH.voda immediately milky i "» Milk Stuff dairy op * opaline milk opators for 24 hours we are la novy creamy cut name no unchanged unchanged unchanged unchanged 20 * dH rihečne pečery mkečne opaline mtiecne ooálový after 24 hours creamy creamy unchanged unchanged unchanged unchanged unchanged after 20 'dH rnt '' 'I' oplNový SSaSrt dairy milk X * 9P * k » p> 24hML creamy smtxanavo unchanged unchanged unchanged unchanged unchanged t) corrosion protection DIN 51360/1 2% distilled water 20 * dH no rust no rust no rust no rust no rust no rust no rust rust rust no rust little hidze princess little rust little class d penivosľ 20 * dH acc now foam foam Footprint of foam foam Dena foam r * to to 5 min foam no foam the price the price pH value 1% in dest e, and 9.0 9.1 9.0 9.0 88 91

Industrial applicability

Alkenyl succinic acid polyamides as an additive to metalworking corrosion protection fluids, reducing foaming and extending the life of such fluids.

Claims (3)

PATENT CLAIMS Use of an alkenylsuccinic acid poloamide salt of the general formulas A - CH - _CH2 - CONRR ¹ and / or A - CH - CH ₂ - COO Me * I I COOMe * CONRR ¹ or mixtures thereof with imides of formula (I) in which A is a straight or branched chain alkenyl group having 6 to 30 carbon atoms, R is a hydrogen atom or R ¹ and R ¹ is -R ² -O- (CH ² CHR ³ -O) n H, wherein: R ² is alkylene of 1 to 10 carbon atoms, straight or branched, R ³ represents a hydrogen atom or a methyl group and n represents a number of 0 to 50 a Me ⁺ represents an alkali metal ion, a proton or an ammonium ion of the formula HN ⁺ R ⁴ R ⁵ R ⁶ , wherein R ⁴ , R ⁵ , R ⁶ are the same or different and represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or a hydroxyalkyl group having 1 to 6 carbon atoms, as metal processing aids, in particular as corrosion protective agents and emulsifiers , in aqueous and / or oil-containing preparations or in metal working fluids. Use of the alkenylsuccinic acid poloamides or mixtures thereof with imides according to claim 1, characterized in that in the above general formulas they preferably mean: And alkenyl having 10 to 24 carbon atoms, R ² an alkylene group having 1 to 6 carbon atoms, n is 0 to 10 °. 3. Metal working auxiliaries comprising alkenylsuccinic acid halide salts or mixtures thereof with imides according to claim 1, characterized in that they further comprise at least one of oxethylates of the general formula: R ⁷ -O- (CH ₂ -CH ₂ -O) _n H wherein R ⁷ represents an alkyl group having 10 to 22 carbon atoms, an alkenyl group having 10 to 22 carbon atoms, or an alkylphenyl group having a total of 10 to 20 carbon atoms, and n is an integer of 2 to 10, and / or alkanolamides of fatty acids of the formula R ⁸ -CO-NR ⁹ R ¹⁰ wherein R ⁸ represents an alkyl group having 10 to 22 carbon atoms or an alkenyl group having 10 to 22 carbon atoms, and R ⁹ and R ¹⁰ are the same or different and represent a hydrogen atom or a hydroxyalkyl group having 1 to 6 carbon atoms, in particular a 2-hydroxyethyl or 2-hydroxypropyl group, and / or polyglycol esters of saturated or unsaturated fatty acids having 10 to 22 carbon atoms in alkyl and 1 to 10 CH ₂ -CH ₂ -O-units.