DE1594608A1 - Lubricant mixture - Google Patents

Description

Cologne, March 12, 1966 Eg / Ax

Socony Mobil Oil Company, Ino.,

150 East 42nd Street, New York, N.Y. 10017 (V.St.A.).

Lubricant mixture

The invention relates to new lubricants with excellent extreme pressure properties, namely lubricants, which contain additives which, in combination, synergistiedi the Eöohstdrucke properties of these lubricants improve

Lubricants, especially those used in metalworking, in sohweren industrial machines and Marine diesel engines are used, are not always able to withstand the b <? The lubricant must be effective at high temperatures and pressures, remove solid impurities! dissipate the heat generated and at the same time, from a chemical point of view, the damaging effects that occur during operation Resist the influences. At high temperatures, mineral oils can also oxidize and form corrosive acids, which can damage the surface of the metal being worked or the machines or motors.

So far it has been customary to check the resilience of lubricants

to improve under maximum pressure conditions by a

salt Metalloarboneäureesie?, E.g. Oaloiumaoetat, added βet «t is«

Unfortunately, however, these well-known Ho "oh β t-

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druokzueätze does not always improve the properties of the lubricants sufficiently.

The invention relates to lubricants which contain small amounts of a Brdalkali salt of a C ₁ -Cj -carboxylic acid and certain sulfur-containing substances, during the The remainder consists practically exclusively of a lubricating oil · The invention also includes additives that are composed of the Alkaline earth salts and sulphurous substances exist

Surprisingly, the combination of these duroh w 10 two additives, the HöOhstdruokeigensohaften over the sole use of each additive increased in an unexpected degree. The lubricants according to the invention have such excellent maximum pressure properties that there is obviously a synergistic effect when combined.

The Gewichtsante11 each additive in the lubricant may vary, but the Metallcarbonsäureester in amounts from 0.01 to 5036 and the sulfur compounds in amounts of 0.1-30 · -i "are effective. 0.5-203 * carboxylate and 0.5-15 # sulfur compound are particularly advantageous.

) The salts of the carboxylic acids are preferably combined, containing 1-3 carbon atoms, with sulfur compounds containing elemental sulfur, with alkyl sulfides, disulfides and polysulfides where the Number of carbon atoms in each alkyl group in the range from 1-22 and the number of sulfur atoms is in the range of 1-10, with aromatic sulfides and polysulfides, in which the aromatic ring can be substituted by alkyl radicals with a total of 1-22 alkyl carbon atoms and the number of sulfur atoms is in the range of 1-10,

of fatty acids and with sulphurized £ *** · *. Carboxylates ^ alcohols and Istern, ι · Β. sulfurized oils and fats with one Sulfur content up to 20%.

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An important advantage of adding metal salsa to » Lubricating oil is the presence of the basic metal ions, which in an advantageous manner de ». Influence of acids that form in the lubricating oil during operation, suppress For this purpose the salts of lower carboxylic acids, e.g. the calcium, magnesium and barium salts are used preferred of formic acid, acetic acid and propionic acid · The far preferred salt is oaloium acetate. The salt can also be anhydrous or hydrated.

If appropriate, the salt can also be formed in situ in the lubricant, even in the presence of the sulfur compound. A previously formed additive can be used just as well. One can use the carboxylic acid or the anhydride " and then the oxide or hydroxide of the metal, i.e.

Acetic anhydride and oaloium hydroxide, the lubricant add, after which the reaction mass is heated to form the carboxylate

These alkali metal salts, which are insoluble in oils, can be distributed in the lubricant by mechanical mixing, for example with homogenizers and mixers. However, it may be appropriate to use a dispersion stabilizer. Preferably, for this purpose, long-chain fatty acids with 4-24 C-atoms, for example §ü = e £ be A acid as described in US Patent 3,121,689, par-, particular If-Acylsarcosinverbindungen such Oleylsaroosin, as in the U. U.S. Patent 3,182,020. The acyl radical of the sarcosine compound described in the latter patent contains 9-25 carbon atoms. The presence of these stabilizers can also have a thickening effect on the lubricant.When using the saroosin compound to adjust the consistency of the lubricant, it is thus possible to obtain lubricants from thin oils to fats.The calcium acetate dispersions in oil using a stabilizer can easily be reduced known methods.

0 0 9 8 2 1/1 5 θ 1

As sulfur-containing materials or sulfur compounds are suitable for the purposes of the invention powdered elemental sulfur in any allotropic forms, sulfur bloom is preferred because the powder is very finely divided and therefore easier to distribute.

Suitable alkyl sulfides are the dialkyl sulfides and disulfides, Asymmetric alkyl sulfides, disulfides and polysulfides in which the alkyl radicals contain 1-20 0 atoms. Suitable aromatic sulfides are the phenyl sulfides and the substituted aryl polysulfides. Preferred of these aromatic sulfides is dibenzyl di-sulfide. Biese sulphides can contain up to 10 sulfur atoms per mole of the sulfide «

The sulfur compounds used according to the invention also include those in the TJ. SA Patent 2,993,858 compounds described. The "corrosive", sulfur-containing organic compounds in which the sulfur is "loosely bound" are suitable. These include sulfurized animal oils, marine oils or planting Liehe oils with 12 to 20 percent -. $> Sulfur, sulfurized mineral oils including paraffinic oils naphthenisehen and up to $ 5 Schwefelzuaatz and sulfurized terpenes and mercaptans. Particularly advantageous are the corrosive sulfurized bacon and Spermazetöle with 12-2OJ6, preferably 15 wt. -I "sulfur.

The so-called "non-corrosive" sulphurized ones are also suitable Fabrics that are labeled as "tightly bound" (as opposed to "loosely bound"). These substances include sulfurized animal oils, marine animal oils and vegetable oils with up to 10 wt .- # sulfur, e.g. sulfurized Bacon and sperm oils,

As base oils for the lubricants described here A wide variety of lubricating oils including solvent-refined mineral oils can be used. The sulfurized ones mentioned above can expediently

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Mineral oils themselves can be used as the base oil. In this pail, the base oil can contain 0.1-5% by weight of "loosely bound" sulfur. Bin such oil is prepared by sulfurizing a mineral oil (having a Viskositätsbereic_h of 40-300 SUS at 38 ⁰ C) according to known methods.

Of interest in the production of the new additional combination according to the invention is a concentrated oil preparation, that a relatively small amount of a lubricating oil carrier necessary to maintain the salt dispersion is sufficient, and 30-60 wt .- ^ of the bound salt, | contains the stabilizer and the sulfur compound · This concentrate can easily be made any desired Add lubricant before use,

Evaluation of additives

The standard tests for evaluating the extreme pressure properties of lubricants are the test with the four-ball apparatus and the drilling test,

A. The four ball apparatus test is performed as follows: Three balls made of tool steel 52-100 with a diameter of 12.7 mm are clamped in place by a chuck. One fourth ball is clamped with a vertical, rotatable shaft (and runs with sliding motion on the three fixed balls, with the Bfrodukte to be tested can be used as a lubricant. A series of tests is carried out with increasing load (increase of each 10 kg) until the balls seize. The higher the load at which the seizure occurs, the more so the tested lubricant is more effective.

Comparative Examples A and B and Example 1

Three coarse dispersions of öalciumacetat and sulfur of a solvent-refined oil (coastal oil) were prepared using, which had a viscosity of 60 SUS at 99 ⁰ O. These dispersions contained ^ ''

10 wt .- # sulfur bloom in the oil (comparative example! A). . '* <Φ ^ 009821/1581 \

10 wt. ~ # Oleum acetate in the oil (Comparative Example B) and 5% by weight of sulfur and 5% by weight of caleium acetate, which are described in 90 wt .- # oil had been incorporated with stirring (Example 1). These three dispersions were tested with the four ball apparatus described above. The following Results were obtained:

example Table I.

Sulfur-calcium blossom acetate

oil welding load wt .- # in the four-ball apparatus, kg

Comparison
example A 10 10 90 above 390 Comparative
example B 5 90 210 1 5 90 620

Comparative examples g and D and example 2

It was found that calcium acetate separates out of the dispersions according to Example 1 after a certain storage time. A dispersion stabilizer was added to the lubricating oil to keep the salt in dispersion. In this second series of dispersions, a premixed dispersion was prepared which contained 4-0% by weight of calcium acetate, 3% by weight of If-oleylsaroosin and 57% by weight of the aforementioned oil. This material is referred to as (Comparative Example 0) Dispersion A. Dispersion A was combined in lubricants with an alkyl polysulfide, namely di-t-nonyl polysulfide (DTNPS), which contained about 40 # sulfur (Example 2). The polysulfide was also tested on its own (Comparative _{Example D) 8 The} following results were obtained when testing with the four-ball apparatus:

example Tabel II Oil,
Gew » Sweat load
-4> in four-ball appa-
advice, k « 'Si 10982 Comparative
example 0 Dispersion A, DTNPS,
Wt .- ^ 75 320 m
'% __ *
"N.
—K Comparative
game D 25th 25 (1096
Sohwefel) 75 470 (n
0 » 2 _- 12.5 over 620 "·, 12.5 BATH ORIGINAL

1 59A608

Comparative examples B, 0 and Ξ and examples 3 and 4

Dibenzyl disulfide was used as representative of aromatic sulfides (Comparative example E) tested on the four-ball apparatus with calcium acetate (example 3) and the previously described pre-stabilized dispersion A (example 4). The results are given in Table III below.

example Table III

Dibenzyl-Oaloium Disulfide, acetate, wt .- # wt .- #

Diaper oil,
sion A, Grew
Wt .-? 6

Sweat load in the four- ball apparatus, kg

Comparative example E.

Comparative example B

Comparative Example O

10

90

340

10 mm 90 210 VJl - 90 5IO - 25th 75 320 - 12.5 82.5 590

Β «The suitability of a cutting oil is determined by the drilling test. The drilling test involves making a series of! Holes in a test metal, e.g. hot-rolled steel SAE 1020 with a Drilling machine drilled, which is provided with a table that rotates freely around the center on ball bearings. At this floating table is attached to a brake arm, in turn actuated a spring scale so that the actual torque during drilling with the oil to be assessed is measured directly. The same conditions that are used in evaluating the test oil are used in drilling applied with a high strength oil that has been arbitrarily attributed to $ 100 potency. That average torque with the test oil is compared with the torque of the comparative sample, and a relative Effectiveness is on a percentage basis such as like is calculated as follows:

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-8- 1 "5 9 A 6 O 8

Torque with the comparison oil 19f3 Torque with the test oil 19 $ Q

Relative effectiveness of the test oil 19 «3 _v

T§7Ü ^x

This exam is carried out by 0 »D · Plemming and L.H. Brewing wood in "Iubrieation Engineering" Volume 12, No. 3, May-June 1956, Pages 199-203.

Comparison examples 0 and ff-H and examples 5 and 6

The effectiveness of a number of lubricants in the drilling test was determined in the manner described above. To the An additional concentrate (concentrate A) was added to the lubricant.

ulben, the 20 $ oaloium acetate, 0.2 $ water, 5 $ oil * iic acid and 74> 8? 6 of a sulphurized lard oil with 15 wt .- $ / en ^ This sulphurised Speok oil is known as an extreme pressure additive for lubricating oils. The concentrate was prepared by mixing were simultaneously added to the kettle a drill all the above ingredients and the contents were heated to 138 ⁰ G · the contents was then allowed to cool with stirring to room temperature.

The above-described concentrate A was added to a sulfurized naphthenic mineral oil, the one Viscosity of 150 SUS at 38 ° C / and 1% by weight added Contained sulfur. Various combinations of concentrate, sulphurized bacon oil and sulphurized naphthenic oil were tested in the drilling test. The result- * nits are summarized below.

Table IV

Example Concentrate Sulphurized Sulphur- Effectiveness occurred A, Bacon oil, tes oil, in the drilling test,

Comparative example P-t- - 100 90

Comparative

for example G- \

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97 109 97 119 BAD ORiGINAL

The sulfurized Speok oil described above was alone (comparative example H) in the mineral oil of the previous examples with the four-ball apparatus and in the presence of the Dispersion A (Example 6) tested. The results are summarized below.

Table V

Example sulphurized dispersion A, oil, sweat

Bacon oil, GeWo- # - / load at

Weight "- # <* ew.-y & four ball apparatus, kg

Comparative example H 10-90 320

Comparative Example 0 25 75 320

6 5 12.5 82.5 360

The values in the five columns show that the simultaneous Presence of alkaline earth carboxylates and sulphurous carbon . regardless of whether the sulfur is present as an element or in a compound, lubricating oils are obtained, which have surprisingly better high pressure properties, than they are obtained with the additives used alone. The test results with the preferred oaloium acetate-sulfur mixtures leave without further ado a synergy Recognize the effect.

Other additives can also be added to the lubricants with which further desirable properties are imparted. These include viscosity index improvers, Pour point regulators, detergents and antioxidants.

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Claims (1)

Τ59Λ6Ό8 - ίο - Claims 1. The lubricant mixture comprising a lubricating oil, from 0.01 to 50 wt.% Of an alkaline earth metal salt of a carboxylic acid having 1 to 4 C atoms and 0.1 to J50 wt.% Of a Schwererenthaitenden material. 2. Lubricant mixture according to claim 1, characterized in that the sulfur-containing material is elemental sulfur, alkyl sulfides, alkyl polysulfides, aromatic sulfides or polysulfides, alkyl-substituted aromatic sulfides or polysulfides, preferably / 21 to 22 carbon atoms in the alkyl radical, sulfurized fats or oils, preferably with a sulfur content of up to 20 %, are present. 5. Lubricant mixture according to claim 2, characterized in that that sulfides with 1 to 10 sulfur atoms are present in the molecule. 4. The lubricant mixture of any one of claims 1 to 3, characterized in that the alkaline earth metal salt is present in proportions of 0.5 to 20 wt.%. 5. The lubricant mixture of any one of claims 1 to 4, characterized in that the sulfur-containing material is present in proportions of 0.5 to 15 wt.%. 6. Lubricant mixture according to one of claims 1 to 5 * characterized in that the alkaline earth salt is the Is the salt of a carboxylic acid with 1 to 5 carbon atoms. 7. Lubricant mixture according to one of claims 1 to 6, characterized in that the alkaline earth salt is calcium acetate. BATHROOM OFtIGINAL 009821/1581 8. lubricant mixture according to one of claims 1 to 7 * characterized by the further addition of a Dispersion stabilizer. 9. lubricant mixture according to claim 8, characterized in that that the dispersion stabilizer is a long-chain fatty acid with 4 to 24 carbon atoms, preferably oleic acid, or an N-acylsarcosine compound with 9 to 25 carbon atoms in the acyl radical, preferably N-oleylsarcosine, is used. BATH ORIGINAL 009821/1581