CS228120B2 - Concentrate of oils emulsificated in water for machining of metals - Google Patents

Abstract

Water-emulsifiable metal-working oil concentrates comprise: (a) 30-50 wt.% of prods. prepd. by reacting (i) a 12-24C alkylaromatic, cycloaliphatic, alkylcycloaliphatic or pref. aliphatic sulphonyl chloride with either (ii) NH3 or a lower aliphatic primary amine, followed by reaction of the resulting sulphonamide with a 2-11C halocarboxylic acid in the presence of alkali, or (iii) a 2-11C aminocarboxylic acid in the presence of alkali, and opt. converting the product into a mono-, di- or trialkanolamine, morpholine or cyclohexylamine salt. The prods. are mixed with (b) 20-40 wt.% of a mineral oil with a 20 degrees C viscosity of 3-5 degrees E, a paraffinic content of 50-70%, a naphthenic content of 25-30% and an aromatic content of 0-25%, (c) 5-20 wt.% of a 10-18C chloroparaffin with a Cl content of 50-70%; (d) 5-20 wt.% of a surfactant of formula R(CH2CH2O)nH (where n = 3-12 and R is 10-22C alkanoyloxy or alkenoyloxy, 8-22C alkoxy or alkenoxy, 6-16C alkylphenyl, 6-16C alkylnaphthyl or mono-, di- or tri(8-22C) alkyl- or alkenyl-amino); and (e) 5-20 wt.% of a sulphur-crosslinked reaction product of fatty acid triglycerides and unsatd. 12-30C fatty acid esters, with a S content of 5-30%. Emulsions (o/w) contg. 1-5 (pref. 2-3) wt.% of the concentrates are esp. useful for high speed grinding. They have good lubricity, EP and anticorrosion properties.

Description

(54) Emulsifiable in water. oil concentrates for working metal

The invention relates to water-emulsifiable oil concentrates for metal working.

As is known, large amounts of water-miscible lubricants with a lubricating effect are required for metal processing. These water-miscible, lubricating refrigerants consist essentially of mineral oil hydrocarbons, emulsifiers, corrosion inhibitors, stabilizers, solubilizers, high pressure additives, antifoams, microbiocides and complexing agents. For the most important ingredients, the following substances are generally considered:

Mineral oil hydrocarbons:

mixtures of aromatic, paraffinic and naphthenic hydrocarbons, in addition synthetic hydrocarbons, synthetic esters and fatty oils.

Emulsifiers:

anionic emulsifiers such as fatty acid salts (soaps), naphthenic soaps, sulfated fatty alcohols and fatty oils, as well as sulfonates such as alkylarylsulfonates and alkyl sulfonates, and nonionic emulsifiers such as ethoxylated alkylphenols; ethoxylated fatty alcohols, ethoxylated sorbitan esters and ethoxylated fatty acid amides.

Corrosion inhibitors:

carboxylic acid salts, sulfonates, amines, amides, benzoic acid derivatives, phosphoric esters, organic boron compounds, alkali metal nitrites, alkali metal carbonates, alkali metal borates or alkali metal nitrates.

High pressure additives:

chloroparaffins, chlorinated fatty oils, sulfochlorinated fatty oils, phosphoric acid esters, zinc alkyldithiophosphates.

Anti-foaming agents:

silicones.

It has now been found that an improved lubrication effect is achieved while protecting against corrosion by a special selection and combination of the components listed below.

SUMMARY OF THE INVENTION Accordingly, the present invention provides water-emulsifiable metal working oil concentrates consisting of a blend of component A in an amount of 30 to 50% by weight, consisting of reaction products prepared by reaction of sulfochlorides of alkylaromatic, cycloaliphatic, alkylcycloaliphatic or preferably aliphatic hydrocarbons. a total of about 12 to 24 carbon atoms with either ammonia or primary lower aliphatic amines to form the corresponding alkylsulfonamides and then halocarboxylic acids of 2 to 11 carbon atoms in the presence of alkali, or by reacting the above sulfochlorides in the presence of alkali with 2-aminocarboxylic acids up to 11 carbon atoms, up to 50% by weight, and from the above unreacted hydrocarbons up to 50% by weight, of mineral oil as component B, at 20 to 40% by weight, preferably 25 to 35% by weight, visko sieve in the range of 3 to ⁵⁰ E / 20 ° C, the paraffin content of the mineral oil may be in the range of 50 to 70%, the naphthen content in the range of 25 to 30% and the aroma content in the range of 0 to 25 ° / o, chloroparaffin component C, in an amount of 5 to 20% by weight, of a chain length of from 10 to 18 carbon atoms and with a chlorine content in the range of 50 to 70%, from a surfactant of the formula

R (CH ₂ CH 2 O) _n H where n is from 3 to 12 a

R is C 10 -C 22 alkanoyloxy or C 10 -C 22 alkenoyloxy, C 8 -C 22 alkoxy or C 6 -C 16 alkylphenyl, C 6 -C 16 alkylphenyl or C 6 -C 16 alkylnaphthyl or mono-, di- or a C 8 -C 22 -alkynyl or C 3 -C 22 -alkenylamino moiety as component D in an amount of 5 to 20% by weight and of a sulfur crosslinked product as component E in an amount of 5 to 20% by weight obtained by reacting triglycerides of fatty acids with unsaturated fatty acid esters of 12 to 30 carbon atoms, the total sulfur content being in the range of 5 to 30%.

The metal working oil concentrates according to the invention may optionally comprise a component A) in which the reaction products have subsequently been converted into mono-, di- or trialkanolamine salts, morpholine or cyclohexylamine salts.

Component A) is essentially a compound of formula I,

R2 R1

R = SO2-N- (CH2h-CH-COOY (I) where)

R is an alkylaromatic, cycloaliphatic, alkylcycloaliphatic or preferably aliphatic radical, each having a total of 12 to 24 carbon atoms,

R 1 is hydrogen or methyl,

R2 is hydrogen or an alkyl or oxyalkyl radical of up to 3 carbon atoms or a radical of formula

- (CH 2) n -CH-COOY

Ri x a number from 0 to 9,

Y is hydrogen, or> one equivalent of an alkali metal, alkaline earth metal, zinc, alkanolamine or morpholine cation, and n is as defined above.

These reaction compounds can be obtained, for example, according to the process described in German patent 767 071, starting from the sulfochlorination products of aliphatic hydrocarbons. Suitable alkyl aryl sulfochlorides having 12 to 24 carbon atoms, as may be used for the preparation of reaction products A), are in particular those derived from benzene or naphthalene, such as dodecylbenzenesulfochloride, octylbenzenesulfochloride, isopropylnaphthalenesulfochloride or nonylnaphthalenesulfochloride.

Component (B) is a mineral oil containing paraffins, naphthenes and aromatics, with a viscosity in the range of 2 to ⁵⁰ E / 20 ° C, in particular ³⁰ E / 20 ° C. The proportion of paraffins may range from 50 to 70%, in particular from 55 to 65 percent, the proportion of naphthenes from 20 to 30% and the proportion of aromatics from 0 to 20%.

The substance of the chloro paraffin mentioned in paragraph Cj is a paraffin having from 10 to 18 carbon atoms, in particular from 14 to 16 carbon atoms, having a chlorine content in the range from 50 to 60%, in particular about 55%. This chloroparaffin has a viscosity of approximately 1.2 Pa. s at 20 ° C.

Suitable components D) are those nonionic surfactants which contain approximately 3 to 12 ethylene oxide units and a hydrophobic hydrocarbon residue per molecule. Suitable non-ionic compounds of this type are, for example, adducts of about 6 to 10, in particular 8 to 9 moles of ethylene oxide per mole of saturated or unsaturated fatty acid of about 10 to 12 carbon atoms, especially unsaturated fatty acids of 16 to 18 carbon atoms, adducts of about 4 to 10, preferably 5 to 6 moles of ethylene oxide per mole of saturated or unsaturated fatty alcohol of about 8 to 20 carbon atoms, especially unsaturated fatty alcohol of 16 to 18 carbon atoms, adducts of about 4 to 12, especially 6 to 8 moles of ethylene oxide per 1 mole of alkylphenol or alkylnaphthol, wherein the alkyl radicals may contain from about 6 to 16, preferably from 8 to 12, carbon atoms and may have a straight or branched chain as well as reaction products of about 3 to 10; preferably 5 to 7 moles of ethylene oxide with 1 mole of a primary, secondary or tertiary saturated or unsaturated alkylamine having 8 to 22, preferably 14 to 17 carbon atoms in the alkyl radical. The proportion of component D) in the concentrate is preferably 8 to 14% by weight.

The sulfur-crosslinked reaction products (E) are obtained by reacting triglycerides of animal and vegetable fatty acids (fatty oils) with esters - especially methyl esters - of unsaturated fatty acids, the carbon chain length of the fatty acids used may range from 12 to 30 carbon atoms, preferably from 15 to 20 carbon atoms. The total sulfur content of such condensation products is in the range of from 5 to 30%, preferably from 15 to ^: 20%, and the active sulfur content (determined according to ASTM-D-1662) is in the range of 4 to 8%. , preferably 5

In addition to the components A) to E), the metal working oil-in-situ of the invention may contain, to a small extent, other auxiliaries and additives which serve primarily to prevent the emulsion from foaming and to protect it against attack by bacteria. Such anti-foaming agents are, for example, silicone oil emulsions, fluorine surfactants and / or fatty acids which produce anti-foaming lime soaps. The proportion of the components A) to E) may vary. within these limits. The optimum amount of these components in individual cases can be readily determined by one skilled in the art by preliminary orientation experiments.

For use, these concentrates are emulsified in water, the aqueous emulsion containing 1 to 5%, preferably 2 to 3% of these concentrates. Such concentrates-based oil-in-water emulsions according to the invention are used both as coolants and as lubricants in the treatment of ferrous metals (steel and cast iron materials), but also of non-ferrous metals (heavy metals) such as cutting, cutting and drilling threading, grinding, milling under.

Of particular importance is the use of the oil concentrate emulsions according to the invention for grinding at high speed, i.e. grinding at grinding speeds above 60 m / s. This workflow is increasingly important for technological and economic reasons. The prior art coolants do not meet the increased requirements, in particular as regards the lubricating effect.

The advantageous high lubrication effect, while at the same time having an excellent anti-corrosion effect, results from the comparison described below with metal working oils commonly used in practice. Percentages are by weight percent.

Metal Working Oil 1 (Comparative Product):

% mineral oil, consisting of about 50% paraffins, 25% aromatics and 25% naphthenes, having a viscosity of about 3 ° E / 20 ° C% sodium / triethanoic acid and an alkylsulfonamidoacetic acid, sodium salt; % adduct of 6 moles of ethylene oxide per mole of nonylphenol

Metal Working Oil 2 (Comparative Product):

% mineral oil as in Example 1 having a viscosity of about 3 ° E / 20 ° C,% sodium / triethanolammonium salt of olkylsulfonamidoacetic acid,% chlorinated paraffin of 10 to 18 carbon atoms with about 55% chlorine.

Oil for working metal (according to the invention), consisting of

(a) 40% of the reaction product produced as described below. The fraction of aliphatic hydrocarbons having a distillation range of 250 to 330 ° C, which does not contain aromatic fractions, is sulphochtorized in a known manner until approximately half of the hydrocarbons. is converted essentially to monosulfochloride. However, the reaction product is treated with ammonia to give a mixture consisting of 50% hydrocarbons of about 47-53% alkylsulfonamides. This product is treated with chloroacetic acid, neutralized with caustic soda and adjusted to approximately 5% water. A mixture consisting of approximately 35% of alkylsulfamideacetic acid sodium salt, 14% of alkylsulfamides of alkylsulfimides, 44% of hydrocarbons of 5% of water is obtained;

(b) 30% mineral oil, containing about 50% paraffins and equal proportions of naphthenes with aromatics having a viscosity of about 30 E / / 20 ° C;

c) 1C% chloroparaffin of 14 to 16 carbon atoms with about 55% chlorine;

d) 10% reaction product of 1 mole of nonylphenol with 6 moles of ethylene oxide;

(e) a 10% sulfur-reinforced 18-carbon fatty oil reaction product of a 18-carbon unsaturated fatty acid methyl ester, with a sulfur content of about 15%.

Oil for metal working (according to the invention), consisting of components

(a) to (d) as with metal working oil 3;

(e) 10% sulfur-crosslinked 18-carbon fatty oil product with 18-carbon unsaturated fatty acid methyl ester, with a sulfur content of approximately 28%.

Metal working oil (according to the invention) consisting of components

a) to d) as in the case of metal working oil 3;

(e) 10% sulfur crosslinked reaction product of a fatty, 18-carbon oil and an unsaturated 18-carbon fatty acid methyl ester, with a sulfur content of 16. %.

To determine the lubricating effect, 3% aqueous emulsions are prepared from the concentrates to be tested and the specific surface pressure in bars measured by Reichert scales to determine the friction wear, as a measure of the lubricating effect; results are shown in the table

AND.

&.

Table I Product Load number 20 kg Load 30 kg

110 bar (11 MPa)

225 bar (22.5 MPa)

375 bar (37.5 MPa)

425 bar (42.5 MPa)

305 bar (30.5 MPa) bar (8.5 MPa)

145 bar (14.5 MPa)

205 'bars' (20.5 MPa)

260 bar (26.0 MPa)

185 bar (18.5 MPa)

The good lubricating effect of the concentrates according to the invention results from the nipple load N (i.e., the load at which the balls are welded) measured with said 3% aqueous emulsions in a four-ball apparatus, the results are shown in Table II.

Table II Product no.

seam load (measured in four-ball. apparatus)

10.5N

24,0 N

29.5N

29.5N

24.5N

These results clearly show the advantageous lubricating effect of these emulsions.

Metal working oil (according to the invention) consisting of components

(a) as for metal working oil 3, but neutralized with sodium hydroxide solution and adjusted to a water content of 5%;

b) 30% mineral oil containing 60% paraffins, 20% aromatics and 20% naphthenes having a viscosity of 3 ° E / 20 ° C;

(c) 10% chloroparaffin of 14 to 16 carbon atoms with approximately 55% chlorine;

d) 10% of a reaction product of 1 mole of oleyl alcohol with 5 moles of ethylene oxide;

e) as for metal working oil 3.

Metal working oil 7 (according to the invention).

a) as with oil. 3 for working metal, but neutralized with triethanolamine and adjusted to a water content of approximately 5%;

(b) 30% 'mineral' oil, containing 60% paraffins, 30% naphthenes and 10% aromatics;

(c) 10% C 14-16 C16 with about 65% chlorine;

d) 10% reaction product of 1 mole of oleic acid with 6 moles of ethylene oxide;

e) as for metal working oil 3.

Metal working oil (according to the invention) consisting of components

(a) as with metal working oil 3, but neutralized with morpholine and adjusted to a water content of 5%;

b) as for metal processing oil 3;

c) 10% chloro-paraffin of 14 to 16 carbon atoms with about 70% chlorine;

d) 10% reaction product of 1 mole of oleylamine with 5 mole of ethylene oxide;

e) as for metal working oil 3.

Metal working oils 6 to 8 are characterized by a lubricating effect as determined with a 3% aqueous emulsion of the tested concentrates using a Reichert Friction Wear to measure specific surface pressure (in bar) as a measure of the lubricating effect. The results are shown in Table III.

Table III Product Load number 20 kg Load 30 kg

380 bar = 38 MPa

400 bar - 40 MPa

410 bar = 41 MPa

210 bar = 21 MPa

235 bar - 23.5 MPa

240 bar = 24.0 MPa

The good lubricating effect of the concentrates according to the invention results from the seaming device N (ball-welding load) measured with said 3% aqueous emulsions of the concentrates tested in a four-ball apparatus; the results are shown in Table IV.

Table IV Product No. Welding Equipment (measured, in a four-ball apparatus)

30.0N

25.0N

26.0N

These results clearly show the advantageous lubricating effect of the oil emulsions 6 to 6

8.

Claims (3)

SUBJECT 1. A water-emulsifiable oil concentrates for working metal, characterized in that they consist of a mixture as component A in hmot.množství ³⁰ watts to about 50 ° / o, consisting of the reaction products formed by reaction sulphochlorides alkylaromatic, cycloaliphatic alkylcykloalifatických or preferably aliphatic hydrocarbons having a total of about 12 to 24 carbon atoms with either ammonia or primary lower aliphatic amines to form the corresponding alkylsulfonamides and then with 2-11 carbon atoms of the carboxylic acids in the presence of alkali, or by reacting the above sulfochlorides in the presence of alkali with aminocarboxylic acids of 2 to 11 carbon atoms, in an amount of up to 50% by weight, and of the abovementioned unreacted hydrocarbons, in an amount of up to 50% by weight, of mineral oil as component B in an amount of 20 to 40%; 35%, with a viscosity in the range of 3 to 5 Έ / 20 ° C, the paraffin content of the mineral oil may be in the range of 50 to 70%, the naphthen content in the range of 25 to 30%, and the aroma content in the range of 0 to 25%, of chlorparaffin as component C, 5 to 20% by weight, of a chain length of from 10 to 18 carbon atoms and having a chlorine content in the range of 50 to 70%, and of a surfactant of the formula VYNALEZU R (CH ₂ CH 2 O) _n H where n is from 3 to 12 a R is C 10 -C 22 alkanoyloxy or aikenoyloxy, C 8 -C 22 alkoxy or C 6 -C 16 alkylphenyl, C 6 -C 16 alkylphenyl, C 6 -C 16 alkylnaphthyl or mono-, di- or a C8 -C22 triacyl or B-alkenylamino moiety as component D in an amount of 5 to 20% by weight and a sulfur crosslinked product as component E in an amount of 5 to 20% by weight obtained by reacting fatty acid triglycerides with unsaturated fatty acid esters of 12 to 30 carbon atoms, the total sulfur content being in the range of 5 to 30%. 2. Concentrates according to claim 1, characterized in that they consist of 35 to 45% of component A, 25 to 35% of component V and in each case 8 to 12% of components C, D and E. 3. Concentrates according to claim 1 or 2, characterized in that they contain component A, the reaction products of which have subsequently been converted into mono-, di- or trialkanolamine salts, morpholine or cyclohexylamine salts.