DE2308940A1 - HIGH PRESSURE ACCESSORIES - Google Patents

Description

C ¹ ARBWERKE HOECHST AG formerly Master Lucius & Brüning

Λ.

File number: HOE 73 / F 061

Date: February 22, 1973 Dr.Gr/Ha

HIGH PRESSURE ADDITIVES

In technology, lubricants are of great importance for reducing friction and stress between moving metal parts. In many processes such high pressure loads or high sliding speeds occur between the moving metal parts that it is difficult for the lubricating effect necessary coherent film of the lubricant to maintain between the friction partners. This film of lubricant tears and if the metal parts come into direct contact, the friction increases sharply and ultimately leads to local welds, which result in severe surface roughness and signs of wear. As a result, it can seize or The poorly lubricated parts break.

To overcome these difficulties additives to lubricating base materials are known, which also under extreme conditions the Improve the resilience or resistance of the lubricating base materials and thus prevent harmful direct contact between metal parts and wear and tear. Such Additives are generally referred to as i-hole pressure additives (EP additives). Their mode of action is based on the reaction occurring in the boundary friction area at higher temperatures with the metal surface, whereby tough, coherent and firmly adhering

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Reaction layers as a separating agent between the metal surfaces (cf. G. H. Göttner "Introduction to Schaiertechnik" 2nd part (1966)).

High-pressure additives are available for the lubrication tasks mentioned all compounds in practical use, which are characterized by a content of halogen, sulfur or phosphors are. For example, halogenated paraffins, especially the chlorinated paraffins class, and chlorinated fatty acid esters are widely used as effective high-pressure additives. In these compounds contain the chlorine in a random distribution in the alkyl chain. This affects the utility value of such high pressure additives insofar as part of the chlorine in these compounds is chemically bound in such a way that it has nothing to do with the resilience or resistance of the lubricating base materials or contributes little. In practice, there is therefore still a need for effective high-pressure additives which contain the chlorine in the most active and readily available form.

The present invention is therefore based on the object of developing lubricant additives which, due to a high proportion of active chlorine, have excellent extreme pressure properties and have a wear-inhibiting effect.

It has been found that 2,2-dichlorocarboxylic acids and 2,2,4-trichlorocarboxylic acids and their salts or esters reduce the wear behavior and improve the extreme pressure properties of mineral oils and synthetic lubricating base materials much more than this, for example, with chlorinated paraffins or chlorinated fatty acid esters ■ it succeeds in randomly distributing the chlorine atoms in the molecule.

The subject matter of the invention is thus high-pressure additives from compounds that have the general formula

? ^l f?

R - CH - CH ₀ - ς - C - O - H (I)

X Cl

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in which X is hydrogen or chlorine and R is an alkyl group of 4 to 28 carbon atoms, or the salts

or alkyl esters of these compounds as well as such high pressure »! - Lubricants containing sets.

As alkyl esters of di- and trichlorocarboxylic acids, those come in Consider derived from normal or branched chain alcohols having 1 to 4 carbon atoms. With the salts it can alkali, alkaline earth, aluminum or ammonium salts or salts with mono-, di- or trialkanolamines, special ones Triethanolamines or salts with mono-, di- or trialkylamine with lower alkyl radicals of 1 to about 4 carbon atoms. Calcium, sodium or potassium salts, the esters or the free di- or trichlorocarboxylic acids are preferably used. Mixtures of the free acids, esters or salts can also be used.

The extreme pressure additives according to the invention can be added to the lubricating base materials in the usual amounts of about 0.1 to 10 percent by weight, preferably 0.5 to 5 percent by weight.

As examples of the high pressure additives according to the invention, without to express a restriction, called the following: 2,2,4-trichloroctanoic acid ethyl ester, 2,2,4-trichlorodecanoic acid methyl ester, 2,2,4-trichlorododecanoic acid propyl ester, 2,2,4-trichlorohexadecanoic acid ethyl ester, 2,2,4-trichloroicosanoic acid ethyl ester, 2,2-Dichlorodecanoic acid ethyl ester and the corresponding free carboxylic acids and their salts. Also mentioned are those produced by the addition of dichloro or trichloroacetic esters to commercially available ones Mixtures of chlorocarboxylic acid esters produced from Cm-olefins and the free acids derived therefrom and their salts.

The dichlorocarboxylic or trichlorocarboxylic acid esters to be used as high-pressure additives according to the invention can be prepared by processes such as those described, for example, in J. An \. Chera. Soc. 6-7, p. 1626 (1945) and J. Org. Chem. 29 p. 2104 to 2105 (1964). The 2,2,4-trichlorocarboxylic acid esters can also be prepared by reacting trichloroacetic acid esters of the formula II ./.

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- CO ₂ R ¹ (II)

with pC-olefins of the formula III

R ² - CII = CH ₂ (III)

in which R is an alkyl radical with about 4 to 28 carbon atoms, at elevated temperature in the presence of radical-forming Funds are made. As radical-forming means come here alongside the known compounds that generate radicals, such as di-tert-butyl peroxide or diacetyl peroxide, also high-energy rays, such as UV rays or δ radiation. The after some Hours of reaction time at temperatures of about 100 to 180 ° C obtained trichlorocarboxylic acid can easily by saponification into the corresponding free carboxylic acids of the formula I or, by reaction with salt-forming bases, into the corresponding salts thereof Acids are transferred.

As lubricant base materials, which the extreme pressure additives according to the invention The products known for this purpose, such as mineral oils and fats and synthetic lubricants, can be added of various kinds, as for example in "Synthetic Lubricants" by R.C. Gunderson and A.W. Hart, New York (19G2), are described in particular on pages 30 to 60, can be used. Polyalkylene glycols are preferred as such synthetic lubricants based on ethylene oxide and / or propylene oxide, ester oils and also phosphoric acid esters or phosphonic acid esters for Use. Mixtures of such aesthetic agents are also suitable Lubricants with mineral oils.

The results of the comparative studies described below show that even low concentrations of the high-pressure additives according to the invention reduce the load-bearing capacity of the lubricating base materials greatly increase and that they significantly increase the lubricants give better high pressure and wear resistance properties

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as known extreme pressure additives.

Because of these excellent properties, the high pressure additives according to the invention are suitable, for example, for formulating bearing and gear lubricants, power transmission fluids and metalworking aids
for cutting and non-cutting metal deformation.

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example 1

2,2,4-Trlchloroctansriureäthylester

624 g of ethyl trichloroacetate are heated to 140 ° C. on a reflux condenser with stirring and nitrogen. then 84 g of hexenil) together with 15 g of di-tert-butyl peroxide are added dropwise at this temperature over a period of 5 hours. Afterward The mixture is stirred for a further 1 hour at 140 ° C. and the reaction vessel is worked up by distillation. At 65 ° C / 15 mm it will be first the excess ethyl trichloroacetate is distilled off. By fine fractionation in a high vacuum, the 2,2,4-Trichloroctanoic acid ethyl ester obtained in 73% yield.

^K P / _0.3 mm - ⁹² - ⁹³ ° ^C

Molecular weight calculated 275

found 274

Chlorine calculated 38.8%

found 39.4 %

Example 2 2,2,4-trichlorodecanoic acid ethyl ester

311 g of ethyl trichloroacetate are heated to 140 ° C. on a reflux condenser while stirring and passing over nitrogen. then 5G g of octene (I) together with 116 g of di-tert-butyl peroxide are added dropwise at this temperature in the course of 3 hours. The mixture is then stirred for a further hour at 140 ° C. and the reaction mixture is worked up by distillation. At 68 ° C / 18 mm, the excess ethyl trichloroacetate is first distilled off, By fine fractionation in a high vacuum, the ethyl 2,2,4-trichlorodecanoate is finally obtained in 89% yield.

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Molecu larweight ber. 303 % found 310 % chlorine boron. 35.2 found 35.7

Example 3

Sodium salt of 2,2,4-trichloroctanoic acid

27.5 g of 2,2,4-trichloroctanoic acid _{ethyl ester y} prepared according to Example! Are refluxed with 4.0 g of sodium hydroxide in 150 ccra of ethanol for 20 minutes. It is then concentrated to dryness and 25 g of the sodium salt of 2,2,4-trichloroctanoic acid are obtained in the form of a colorless pasty product.

Chlorine calc. 39.0% _E ef. 37.7 %

Example 5

Calcium salt of 2,2,4-trichloro cicos ansfuire

43.3 g of ethyl 2,2,4-trichloroicosanoate, prepared according to the procedure of Example I _1, are refluxed with 9.0 g of calcium hydroxide in 150 ecm of ethanol for 30 minutes. 100 ecm of isobutanol are then added, the mixture is filtered and the residue is evaporated to dryness. 37 g of the calcium salt of trichloroicosanoic acid are obtained in the form of a solid, colorless product.

Chlorine calculated 24.2%

found 21.1% 409837/0 919

To assess the quality of those described in Examples 1 to 5 High-pressure additives according to the invention and for comparative assessment compared to the known high-pressure additives and chlorinated paraffin Methyl pentachloroate tests were carried out using the Reichert friction-grinding balance. This device consists essentially of two steel friction partners of different hardness, of one of which, a slip ring, is movable and the other, a test roller, is rigidly arranged. During the test will be slip ring and test roll pressed against each other in an axially crossed manner using a double lever system with a defined force. The slip ring dives partially into the lubricant mixture to be examined and at the same time performs a rotary movement, with a constant Lubricant transport to the frictional wear zone between the test roller and slip ring is guaranteed. The turning movement creates Depending on the pressure absorption capacity of the respective lubricant on the test roller, a more or less large elliptical one Wear mark. From this abrasion area created after a certain running time and the respective contact pressure, a

Numerical value with the dimension £ _ kp / cm J, which is referred to as the specific surface pressure and is used as a measure of the load-bearing capacity of lubricating films. (See magazine "Mineralöl-Technik" 3 (1958) No. 2, pages 1-17).

The comparatively tested active substances listed in Table 1 were in the specified concentrations of 1.3 and 5 percent by weight in an additive-free spindle oil with a viscosity of 3.3 ° E / 20 ° C incorporated. The active substances 1 to 5 are high-pressure additives according to the invention. The active substances No. 6th and 7 are comparative prior art products. Chlorinated paraffin is a commercially available product, by chlorinating paraffin hydrocarbons on average about 10 to 13 carbon atoms up to a chlorine content of approx. 64 mol% is obtained,

In further comparative tests of the high pressure additives, the Shell-Boerlage four-ball apparatus used (cf. DIN 51 530).

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For these investigations, too, the Iloch pressure additives were used in concentrations of 1.3 and 5 percent by weight in spindle oil with a viscosity of 3.3 E / 20 C. The results of these investigations are compiled in Table 2.

In addition, comparative tests were carried out on the series wear balance and the four-ball apparatus with some active substances made of 1,6-hexanediol diisononanate as a synthetic lubricating oil. The results of these investigations are contained in Tables 3 and 4.

The results of the tests show the effectiveness of the high-pressure additives according to the, which is superior to the comparison substances Invention when used in mineral oils as well as in synthetic lubricating oils.

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TABEL

Active ingredient in
Spindle oil Weight percent
Active ingredient 1
3
5 special area
Q
pressing! kp / cm 'I. 1.2,2,4-trichloro
oc tansäureätliy 1-
ester 1
3
5 1050
1110
1250 2.2,4-trichloro
decanoic acid
ethyl ester 1
3
5 195
280
800 3.2,4-trichloro
decanoic acid 1
3 890
1175
1250 4. sodium salt of
2,2,4-trichloro
octanoic acid 1
3
5 195
890 5. Calciurasalz der
2,2,4-trichloro
eicosanoic acid 1
3
5 195
890
3210 6. Chlorinated paraffin 1
3
5 130
195
475 7. Pentachloroleic acid
methyl ester 135
195
445 8. Blind test
(Spindle oil 3.3 ° E /
2O ° C) 84

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TABLE 2

Active ingredient in
Spindle oil Weight percent
Active ingredient Welding load
(kp) 1.2,2,4-trichloro
ethyl octanoic acid
ester 1
3
5 250
370
490 2. Calcium salt of
2,2,4-trichloro
eicosanoic acid e 1
3
5 190
250
270 3.2,4-trichloro
decanoic acid 1
3
5 250
290
350 4. Chlorinated paraffin
fluid 1
3
5 190
210
230 5. Pentachloro oil ~
acid methyl ester 1
3
5 210
210
250

6. Blind test

(Spindle oil 3.3 ° E / 20 ° C)!

190

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-ft

TABLE 3

Active ingredient in
1,6-hexanediol-di-
isononanate Weight percent
Active ingredient 1, 2,2,4-trichloro
octanoic acid
ethyl ester 1
3
5 2. Chlorinated paraffin 64
fluid 1
3
5 3. Pentachloro Oil
acid methyl ester 1
3
5 4. Blind test
(1,6-hexanediol-di-
isononanate)

spec. Surface pressure kp / cm

180 485

3025

160 200 245

160 215 245

110

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TABLE 4

Active ingredient in
1,6-Ilexanediol-di-
isononanate Weight percent
Active ingredient Welding load
(kp / cm) 1.2,2,4-trichloro
octansäui'edi-
ethyl ester 1
3
5 190
310
350 2. Calcium salt of
2,2,4-trichloro
eicosanoic acid ί 190
230
250 3.2,4-trichloro
decanoic acid 1
3
5 190
270
310 4. Chlorinated paraffin
fluid 1
3
5 170
190
190 5. Pentachloro Oil
acid methyl ester 1
3
5 170
170
190 6. Blind test
(1,6-IIcxanediol-di-
isononanate) , _ 170 -

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Claims (2)

HOE 73 / F 061 claims 1. Lubricants, characterized by a content of compounds of the general formula I. Cl O R-QH- CH ₀ -QCOH (I), X Cl in which X is hydrogen or chlorine and R is an alkyl radical having about 4 to 28 carbon atoms, or salts or alkyl esters of these compounds as extreme pressure additives. 2. Lubricant according to claim 1, characterized in that it has a content of about 0.1 to 10 percent by weight of the Have extreme pressure additives. Use of compounds of the general formula I. Cl 0 f Il R-CH- CH ₀ -CCOH (I), X Cl in which X is hydrogen or chlorine and R is an alkyl radical means about 4 to 28 carbon atoms, or of salts or alkyl esters of these compounds as extreme pressure additives for lubricants based on mineral oils or synthetic lubricants, 409837/0919