DE2026035A1 - lubricant - Google Patents

Description

. R. POSCHENRIEDER.

DR. EBOETTNER May 27

JHPL-ING. R-J. MÜLL1R '*

ν Patent Attorneys W 149

\ _· MUNICH"*
* Grahn-Straß «3 ·

»Vitco Chemical Corporation, 277 Park Avenue New York, New York 10017 (V.St.A.)

lubricant

The present invention relates to new lubricants, "the improved properties in terms of chemical stability, corrosion prevention, degradation the tendency to foam and the protection against wear and tear, and especially for High pressure lubrication purposes are suitable.

Oil-based lubricants and water-based lubricants containing certain phosphoric acid esters belong to the state of the art and are e.g. in the USA patents J 010 9OJ, 5. I69 923, 3 203 895, 3 297 098 and 3 310 489. In this last-mentioned patent specification lubricants are listed which are used in metalworking are to be, and they can consist of aqueous solutions with a content of about 0.001 to about 20 percent by weight of reaction products from various

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Amines, mainly triethanolamine, and certain phosphoric acid esters, namely phosphoric acid mono- and diesters of adducts of ethylene oxide and hydroxyl-containing adducts Compounds that have a hydrocarbon group with at least Have 9 carbon atoms in an aliphatic arrangement, examples being the phosphoric acid mono- and diesters of the adducts of 4 or 10 moles of ethylene oxide and nonylphenol or the phosphoric acid mono- and diesters of other non-ionic, surface-active adducts of ethylene oxide and long-chain alcohols or "Alkylphenols should be mentioned which - as mentioned above, a hydrocarbon group with at least 9 carbon atoms in an aliphatic arrangement. In the patent it is emphasized that the presence a hydrocarbon group having at least 9 carbon atoms in an aliphatic arrangement in the Phosphoric acid esters is of importance in order to obtain agents for those mentioned in the patent Applications are useful and do not cause staining on the metal.

For certain metalworking purposes, e.g. those at | where a synthetic cutting fluid is used as a lubricant is a specific combination of properties of paramount importance. To this : Properties include stability at high temperatures, high load-bearing capacity, the ability to protect against wear and corrosion and have a low tendency to foam. A minor one Foaming is a particularly important property for extreme pressure lubricants used in metalworking operations, a property which must be present to ensure that the circulation system is not blocked by entrainment

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- ■> .- ■■ ^

is prevented by air and the work surface is good remains manageable.

The present invention has now found that aqueous solutions of amine salts of mono- or diesters (and mixtures thereof) of phosphoric acid with an adduct of 1 to 6 moles of ethylene oxide and phenol an unexpected combination of properties in terms of load-bearing capacity, low foaming, thermal stability and corrosion prevention, which the solutions mentioned for Extremely useful for extreme pressure lubrication purposes power.

In general, the phosphoric acid esters which can be used for carrying out the present invention can be prepared in such a way that 1 mole of PpOf. with 2 to 4.5 mol, preferably about J> mol of an adduct or condensation product of 1 to 6 mol, preferably about 3 mol of ethylene oxide and 1 mol of phenol, it being possible to use the individual working methods as used for the preparation of phosphoric acid esters, for example, in US Patents 2,441,295, 2,676,975, 2,701,258, 3,004,056 and 3,004,057 and in German Patent 696,317.

As has been stated, the phenol adduct from which the phosphoric acid esters are made is not intended contain more than about 6 moles of ethylene oxide per mole of phenol, if one has the desired characteristics wants to achieve. For example, the phosphoric acid ester of the adduct of 8 moles of ethylene oxide and phenol has

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inferior properties with regard to the tendency to foam formation and the load-bearing capacity, if it is compared, for example, with the phosphoric acid ester of the adduct of phenol and 4 moles of ethylene oxide. Smaller amounts of e.g. propylene oxide can also be used instead of part of the ethylene oxide in the production of the adduct may be used, but the amount of propylene oxide used should be about 20 percent by weight generally not exceed the amount of ethylene oxide. However, it is particularly recommended to use only ethylene oxide as alkylene oxide in the manufacture of phenol adducts, which in turn serve as starting materials for the production of phosphoric acid esters, the latter then in the Agents according to the invention are used.

Those used in practicing the present invention phosphoric acid esters used can be represented by the following formulas, of which the Formula (i) represent the monoester and formula (II) represent the diester:

OH 0 - (CH ₀ -CH ₀ -O) -P = O

OH

(D

0 -

= 0 (II)

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In these formulas, η denotes an integer from 1 to about 6, preferably from 5 to 5, and most preferably a number worth about 4. It should be emphasized that that the esters mentioned are free of any hydrocarbon groups, at least Contains 9 carbon atoms in an aliphatic arrangement.

The amine, which is used as a reaction component or to a salt with the phosphoric acid ester in the Forming lubricants according to the invention can be selected from a large group of amines having with the proviso, however, that the water solubility of the product is guaranteed. So can those mentioned Amines of primary, secondary or tertiary nature, they can be straight or branched chain and saturated or unsaturated, and they can be aliphatic, araliphatic or aromatic in nature. Of special Hydroxyalkylamines or alkanolamines, such as mono-, di- and triethanolamine, or mixtures are of value the same, especially triethanolamine. As - other examples of amines that can be used, are to be mentioned dimethylamine, diethylamine, triethylamine, propylamine, monoisopropylamine, diisopropylamine, triisopropylamine and technical mixtures of the mentioned isopropylamines, butylamine, amylamine, monoisopropanolamine, Diisopropanolamine, triisopropanolamine and technical Mixtures of the mentioned isopropanolamines, polyamines, such as aminoethylethanolamine, ethylenediamine, diethylenetriamine, Hydroxyethylethylenediamine and hexamethylenediamine, Hexylamine, cyclohexylamine, methylcyclohexylamine, alkylalkanolamines, such as ethyl diethanolamine and diethylethanolamine, piperidine, 2-amino-2-methyl-1-propanol, 2-amino-1-butanol, methylpiperidine, benzyl

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amine, naphthylamine, aniline, methylaniline and mutually compatible devices of two or more of these Amines.

Only small amounts of the reaction product of the amine and the phosphoric acid ester are required to produce a lubricant which has the above-mentioned superior properties. If its preferred concentration can be about 0.1 to 0.2 percent by weight in water, it can also be used in concentrations down to 0.01 % and up to several percent, for example 5 to 10 % but such higher concentrations are not necessary.

To achieve special effects, if desired Additives are added in small amounts, examples of which are corrosion inhibitors Certain metals, means for increasing the load-bearing capacity and the like are to be listed.

The invention is now intended to be explained with the aid of the following examples, but in no way restricted thereby. All percentages given here are percentages by weight. ₍

example 1

A 0.1 # solution of the triethanolamine salt of a Phosphoric acid ester obtained by reacting Po ^ c with an adduct of 4 moles of ethylene oxide and 1 mole of phenol was prepared in water, the Palex load test subject to the load-bearing capacity

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to illustrate. For purposes of comparison, the numerical values are also given, which were obtained with the phosphoric acid ester an adduct of phenol and 8 moles of ethylene oxide, which is also used as a 0.1 # strength triethanolamine salt solution in Water was used. In short, the test uses a Faville-LeVally lubricant tester used with an automatic strainer, strain gauge, Torque meter, brass shear bolts, steel pins and steel support brackets. The lubricant is loaded into the machine and the torque readings are in load increments of 250 pounds made until break occurs or maximum load of 4500 pounds is reached. A break is recognizable either by the sudden shearing off of the brass locking bolts or by wear and tear, the increases so much that the pawl for the load (loading ratchet) is no longer able to hold the load and this actually decreases. The results are shown in the following table (all pound information is in English Pound mean) compiled.

Numerical values determined in the Falex wear test

load

(Pounds) Torque (inches - pounds)

Phosphoric acid ester of the phosphoric acid ester adduct of phenol and the adduct of 4 moles of phenol ethylene oxide and 8 moles of ethylene oxide

13-15.5 20-19

'21.5 - 22

24-23

250 5-5 500 7-9 750 12-11 1000 13-14

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High pressure load

Break at: 1750 pounds 1000 pounds

Test conditions:

Temperature: 65 * 6 C

Time: 2 minutes each at 250, 500 and

750 pounds and 15 minutes at 1000 pounds.

Example 2

A.

The low foaming tendency exhibited by an agent according to the invention is illustrated by the following Numerical values illustrated after the Ross-Mlles foam test were determined in which the phosphoric acid esters were tested in their free acid form. to For purposes of comparison, the numerical values obtained with the phosphoric acid ester of an adduct are also given Phenol and 8 moles of ethylene oxide and with a phosphoric acid ester of an ethoxylated long-chain alcohol, both of which were also tested in the form of their free acids were obtained. All test solutions were 0.1 percent by weight solutions in water.

t Ross Miles foam test

mm foam 5 minutes Phosphoric acid ester 0 minutes 1 minute 0 1. of the adduct
Phenol and 4 moles
Ethylene oxide 5 0 2 2. of the adduct
Phenol and 8 moles
Ethylene oxide 25 5 50 3. "Antara LS-500" ⁺ ' 70 55

'one from an ethoxylated long chain aliphatic

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Phosphoric acid ester produced by alcohol, which is sold under the name given by the company General Aniline and Film Corp. is sold in the trade.

B.

To illustrate in another way how small the tendency of the phosphoric acid esters used according to the teaching of the present invention to foam the numerical values that were determined in the dynamic foam test are given below. This test generally consists of stirring 100 ml of the test solution at high speed and measure the foam volume at equal time intervals. Regarding the technical details of this Test method is based on the information in Journal of the American Oil Chemists * Society, Volume 31 (195 ^) pages 254-257.

Dynamic foam test

Degree of the maximum foam-foam volume (after a phosphoric acid ester generation, stirring time of 5 min.)

1. of the adduct
Phenol and 4 moles

Ethylene Oxide 7 # 5 15

2. of the adduct
Phenol and 8 moles

Ethylene Oxide 17.5 ^ 5

3. "Antara LS-5OO" 20 40

Example 3

The triethanolamine salt of the phosphoric acid ester of the adduct of phenol and k mol of ethylene oxide was tested for its corrosion-inhibiting properties. In this test, k g of cast iron filings are placed in 50 ml of a test solution (aqueous solution) for 15 minutes

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and periodically whirled around in it. After the 15 minutes have elapsed, the solution is decanted off and the excess Liquid is removed by placing the chips on absorbent paper. The damp ones Chips are then visually inspected for rust formation.

Concentration of

Test solution rust formation

0.1 % weak

0.5 % 'none

1 % none

2 % none

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Claims (1)

Claims 1. Lubricant., Characterized in that it consists of Water with a content of at least about 0.01 percent by weight of an amine salt of an ester, which in turn consists of the mono- or diester or a mono- and diester mixture of phosphoric acid with an adduct of 1 mole of phenol and about 1 to about 6 moles of ethylene oxide. 2. Means according to claim 1, characterized in that said phosphoric acid ester from the group of esters of the following formulas OH - P = OH and 0 - (CH ₂ -CH ₂ -O) _n P. «0 is selected in which η is an integer in value from about 3 to 5 means. 3 · Means according to claim 1, characterized in that the amine consists of a low molecular weight alkanolamine, 109849/1582 202603S Means according to claim 3 * characterized in that the alkanolamine consists of triethanolamine. 5. Lubricant according to claim 1, characterized in that it contains about 0.1 to about 0.2 ^ of the triethanolamine salt of a phosphoric acid ester selected from the group of esters of the following formulas OH -0 - (CH ₂ -CH ₂ -O) _n -P = O OH and • 0 - (CH ₂ -CH ₂ -O) _n OH i. is selected in which η is an integer in value of about 4 means. 6. Method of providing lubrication in metalworking processes, characterized in that one is exposed to the machining metal surface a lubricant according to claim 1 applies. 7. Method of achieving lubrication in metalworking processes, characterized in that one is exposed to the machining metal surface a lubricant according to claim 5 applies. 1 09849/1582