DE943485C - Additive to lubricating oils based on mineral oils or synthetic oils - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

ISSUED MAY 24, 1956

GERMAN PATENT OFFICE

PATENT LETTERING

CLASS 23c GROUP 1oi

W 11587 IVc 123 c

The inventors have requested not to be named

C. C. Wakefield & Company Limited, London

Additive to lubricating oils based on mineral oils or synthetic oils

Patented in the territory of the Federal Republic of Germany from July 1, 1953 Patent application published December 1, 1955

Patent granted on May 3, 1956

The priority of filings in Great Britain dated July 3, 1852 and June 24, 1953

is used

The invention relates to improvements in lubricating oils based on mineral oils or synthetic oils.

An object of the invention is to provide additives for use within a lubricating oil with extreme pressure properties, which lubricating oil both under the low speed and high torque operating conditions as well as the Operating conditions of high speed and high load can be used.

Another object of the present invention is to provide a lubricating oil which can be used is suitable in internal combustion engines and has rust-preventing properties and furthermore is protected against spoilage through oxidation and scuffing of the bearings.

It is known that the sulfurized and phosphorous derivatives are used as additives for lubricating oil of wool fat and the metal salts of such derivatives.

It has now been found that improved lubricating oils based on mineral oils or synthetic oils Oils can be obtained if one uses the reaction products as additives for such lubricating oils the unsaponifiable parts of the wool fat,

especially of wool fatty alcohols or mixtures of those with unsaturated hydrocarbons, alone or in a mixture with alcohols or phenols, with sulfur and / or up to 0.2 parts by weight of phosphorus penta- or trisulfide, especially in the form of its zinc, alkaline earth or alkali metal salt, in quantities up to 10 percent by weight of the total agent used.

Such additives have a very low fatty acid content. It is well known that fatty acids and their metal salts extremely corrosive to bearing metal alloys, such as. B. Copper-lead (lead bronze) and Kadmum-silver alloys, work and that they have a tendency to increase Temperatures with metals such as B. iron and copper, react to become oil-soluble To form ropes, which latter the oxidation of the oil with the consequent rise in the Promote acid number and the appearance of oil sludge. When using the unsaponifiable components saponified wool fat and their aforementioned mixtures this undesirable tendency to one Reduced minimum size.

Another benefit of using this unsaponifiable constituents of wool fat and their aforementioned mixtures is connected, lies in the The fact that these compounds are unsaturated to a greater extent than the wool fat itself and that it therefore it is possible to use the same larger amounts of sulfur and phosphorus to form a stable chemical To combine compound, thereby making more effective lubricating oil additives.

The lubricating oil base is preferably a mineral lubricating oil, but can also be made from a synthetic lubricating oil, e.g. B. an oil of the synthetic diester type or an oil of the polyether type exist. In a preferred embodiment of the present invention, the unsaponifiable material consists of a compound which is known under the trade name "Varwolax". "Varwolax" is produced according to the following process, which is described in greater detail in British patent specification 553 322. Class A crude wool fat is saponified by the action of solid caustic soda at about 260 ^° C., a solid mixture of sodium soaps of the mixed fatty acids and unsaponifiables present (wool fatty alcohols and products obtained by dewatering the same) being obtained. The unsaponifiable amounts to about 35 ° / ₀ of the whole and may be made of the sodium soap, e.g. by different solvents. B. a mixture of ethylene dichloride and acetone in equal parts, are extracted, leaving a dry, powdery soda soap. The solvent is distilled off in vacuo, leaving a brown, viscous oil called "Varwolax".

A typical analysis of "Varwolax" is the following:

Moisture content traces

Ashes. ' about 0.5 ° / ₀ (from the remaining Natronseife) unsaponifiables about 95 ⁰ ^ ₀

Saponifiable:

Free fatty acids zero

Bound fatty acids

and neutral substances about 5% (the equivalent of 5% soda soap from fatty acids) Other properties are:
Specific gravity ... 0.95 to 0.96 at ⁰ C 15.56

Saponification number very low

Acetyl number about 54

Iodine number (according to Wi j s) ... about 65 (Wijs - large excess) about 110

The unsaponifiable used in the present invention can optionally be selected from wool wax alcohols exist. The alcoholic components of the wool fat obtained by saponifying wool fat consist mainly of the sterols cholestrol and cholestanol and of the triterpene alcohols Agnosterol and Lanosterol, along with lesser amounts of saturated aliphatic Alcohols such as B. cetyl, ceryl, lanyl and lano octadecyl alcohol.

"Varwolax" or something else that cannot be saponified can be sulphurised by heating with sulfur at high temperatures. The reaction can be accelerated and supported by adding a small amount of sulfur monochloride or sulfur dichloride. For most purposes, it is desirable that the sulfur is present in fairly inactive form, and 2 minutes in the material at a temperature of 143.33 ⁰ C for submerged bright copper strips must not be seriously attacked. In an optional test may copper which is immersed in an up to 5 ° / ₀ of the product-containing oil for a period of 1 hour at a temperature of 121.11 ° C, not start.

Varying amounts of sulfur can be introduced into the "Varwolax" or other unsaponifiable material by changing the amount of sulfur added as well as the reaction time and the reaction temperature.

If desired, you can use the sulfurized »Varwolax« or other unsaponifiable material then phosphorus by treating it with a phosphorus compound, such as B. phosphorus pentasulfide or phosphorus trisulfide, brings to reaction. This can be done by Heating take place at a relatively low temperature, e.g. B. at 104.44 to I2i, ii ° C. The final one Product must no longer be placed on copper at 121.11 ° C react as the original sulfurized compound.

In a further embodiment of the present invention, the "Varwolax" or other unsaponifiables at relatively low temperatures with sulfur chlorides in oil or be reacted in an inert solvent, whereupon the chlorine is replaced by sulfur or else phosphorus and sulfur are replaced by dissolving the compound in a suitable solvent or in a mixture of solvents

with, for example, sodium sulfide or. Polysulfides or the sodium salt of an organic phosphorodithioic acid to react.

It has been found that in the manufacture of sulphurized derivatives of "Varwolax" or wool wax alcohols it is preferable not to use more than one atom of sulfur for each ethylene bond present in the unsulphurised material and to use sulphurisation at a temperature of 160 to 182, 22 ° C. The use of higher sulfur concentrations or higher temperatures results in larger amounts of undesirable oil-insoluble reaction products than would otherwise be the case. As indicated above, it is generally preferred, compounds that do not attack at 121.11 ⁰ C. copper to use. However, if an "active" sulfur-containing product is desired for a particular application, then such a material can be produced in such a way that one uses more than the theoretically required amount of sulfur (for example 1.5 S atoms per double bond) and that Sulphurizing at a relatively low temperature, e.g. B. at 160 to 165.56 ⁰ C, performs. If desired, the sulfurization can be carried out in the presence of "accelerators" such as those used in the vulcanization of rubber; typical compounds for this are mercaptobenzothiazole, benzothiazole disulfide, tetramethyl and tetraethylthiuram disulfide or mixtures of these compounds with diphenylguanidine.

A preferred method of making sulfurized derivatives of "Varwolax" or wool wax alcohols consists in carrying out the sulfurization in the presence of an aliphatic, an alicyclic or reduced heterocyclic secondary amine, e.g. B. dicyclohexylamine, diethanolamine or Morpholine, the use of which to accelerate the reaction and the formation of oil-insoluble by-products seems to be delaying. The sulfurization of »Varwolax« or wool wax alcohols is made easier, when carried out in the presence of mineral oil.

The introduction of phosphorus into the sulfurized

Product is preferably made by heating with a phosphorus sulfide such as phosphorus pentasulfide or phosphorus trisulfide, at a temperature of about 104.44 to 121.11 ° C, although - if desired - also other phosphorus compounds, such as. B. the halides can be used.

The compounds can be freed from oil-insoluble impurities by placing them in a suitable solvent, such as. B. petroleum ether, dissolves and filtered, whereupon the solvent is removed by distillation. Optionally, it has proven to be useful to use the phosphorized and sulfurized reaction products in a solution of oil for a short time with a minor amount to heat an aqueous suspension of lime or barium oxide and then with the addition of a filter aid to filter. This appears to cause some of the insoluble constituents to hydrolyze, causing one obtains products which are often soluble in mineral oil without further purification.

The preceding description relates to the preparation of compounds which sulfur or Sulfur along with a smaller amount of phosphorus and at most very small amounts of Contain metals. Such compounds are preferred for use with extreme pressure lubricating oils.

According to a further embodiment of the present invention, considerable amounts of metal-containing compounds can be prepared by the direct reaction of "Varwolax" or wool wax alcohols with a phosphorus sulfide, preferably phosphorus sesquisulfide, which results in the neutralization of the resulting acidic products with oxides or hydroxides of the alkali or alkaline earth metals connects. In order to avoid the formation of by-products which are insoluble in oil, the amount of phosphorus sulfide must not exceed 20%, based on the weight of the raw material, and should preferably be even less. Satisfactory products were obtained from "Varwolax" at using about io ° / ₀ phosphorus sesquisulphide and a reaction temperature of 104.44 to I2i, ii ° C. Metal salts of these reaction products can be prepared either by direct reaction with a metal oxide or hydroxide in the presence of a little water, or by first neutralizing a dilute aqueous suspension of the material, for example with caustic soda, and then adding the aqueous solution of a salt of a polyvalent metal. In view of the very limited solubility of the alkali metal salts of these compounds in water, the former method is far preferred. In this way one can obtain salts of the alkali metals and the alkaline earth metals as well as of zinc and magnesium.

In a further embodiment of the present invention, mixed products can be obtained by using a mixture of "Varwolax" or wool wax alcohols and another substance, which is able to react with phosphorus sulfide, e.g. B. an alcohol or phenol, treated with a phosphorus sulfide, whereupon the product is converted to a metal salt as before. Optionally, phosphorous + sulfurized »Varwolax« or wool wax alcohols treated in the same way or theirs Metal salts mixed with other organic compounds capable of forming metal derivatives to then be converted to metal derivatives as before. Examples of suitable organic Compounds are the organic dithiophosphoric acids, phenols and phenol thioethers. It it has been found possible to use organic compounds in this manner, which normally would give metal derivatives insoluble in oil than those resulting from the previous reaction complex salts are derived from the presence of the wool wax alcohols Made radicals oil soluble.

The additive can, if desired, be cleaned and bleached, for example by treatment with fuller's earth or fuller's earth.

The present invention also includes an additive for use in a mineral or synthetic lubricating oil base, and this additive consists of a compound obtained by sulphurizing or sulphiding and Phps-. phore of unsaponifiable, that from saponified wool fat extracted, or a metal salt thereof '. The additives can be used in the following types of oils be used:

ίο i. Extreme pressure oils, especially those which operate satisfactorily under the low speed and high torque operating conditions should.

It is well known that under certain circumstances, e.g. B. for the lubrication of hypoid gears, it is necessary to use lubricants that contain chemical compounds that are able to react with metals at high temperatures and under high pressures to form films (for example made of iron sulfide, iron chloride or iron oxide ), which prevent the metal surfaces from seizing and welding. A large number of organic compounds have been proposed for this purpose, including sulfur compounds of various types with sulfur contents of various degrees of activity. It has generally proven to be advantageous to use these sulfur compounds together with lead soaps or organic halogen compounds or with both. It is now generally accepted that many such lubricants; which behave completely satisfactorily under normal operating conditions, even under high loads at high speed, under the operating conditions of high torque and low speed, e.g. B. for the lubrication of rear axles in mountainous terrain of moving vehicles fail. Under these conditions, certain lubricants, for example those containing lead soaps or sulfur in "active" form, tend to cause high wear or - in some cases - scoring or furrowing of the gear teeth and promoting rusting of the ferrous metal parts in the presence of condensation water.

The additives according to the invention are, if they are used together with organic halogenated compounds, such as B. chlorinated paraffin, intended to be used under these ratios Ensure effective lubrication of the hypoid gear »50.

If the lubricant is intended to be used under very difficult operating conditions, then the addition of a further compound with a relatively high proportion of sulfur is of advantage. Such compounds must be free of "active" sulfur, ie they may be copper not attack markedly at temperatures on the order of 121.11 ^0C. Examples of suitable compounds are dibenzyl disulfide, di- (3-carbomethoxy-4-hydroxyphenyl) disulfide and sulfurized terpenes, ζ. B. sulfurized alpha pinene.

2. Internal combustion engine oils in which the additives according to the invention are used both as dispersants as well as acting as anti-aging agents. You can either stand alone or together with an additional: dispersing or anti-aging agents or both can be used together.

A particular problem - which one one often faces what has to do with engines that are in operation in cold weather is the so-called cold sludge formation as a result of the penetration of water and burn products, which gives rise to the formation of a stiff emulsion or sludge. The ones with these Oils normally used as cleaning agents or aging protection agents contribute to 7.5 general, although they are at high operating temperatures and are very effective under heavy loads, hardly contribute to solving this problem. It is a The aim of the invention to create additives which are not only of good effect in relation to oxidation at increased. Prevent temperatures, but also the extent of piston ring corrosion, which the most serious side effect of cold sludge formation is to delay significantly. The cleaning additives, which can be used together with the additives according to the invention, may be of different types, although MetaUpetroleum (mahogany) sulfonate is preferred, ζ. Β. Calcium, tin, or basic barium petroleum sulfonate should be used.

3. Oils for storing and coating metal parts and, more generally, anti-rust oils and compositions. The addition of one or more Metal petroleum sulfonate is beneficial.

4. Cutting and emulsion oils.

5. hydraulic oils; in these for use as an anti-aging agent as well as an anti-corrosion agent.

The proportions of the additive used can amount to the following amounts:

a) high pressure oils 1 to 10% additive, preferably 2 to 5 ° / _0;

b) lubricating oils for internal combustion engines: 0.1 to 2 ° / ₀ of additive;

c) Oils for storage: 1 to 10% of additives. It is clear that the additives according to the invention

can be used in conjunction with other known additives. Examples of this are except the already mentioned organic halogen compounds and metal petroleum sulfonates, metal salts of organic dithiophosphoric acids, metal salts of alkylated phenols and phenol thioethers, phosphoric acid and phosphorous acid esters, such as tricresyl phosphate, and also viscosity index improvers, Pour point depressants and anti-foaming agents.

Below is a description by way of examples of several processes for the production of Additives for incorporation in lubricant bases according to the present invention.

example 1

A mixture of 750 g "Varwolax", 250 g mineral oil (viscosity 1.74 ° E at 60 ⁰ C), 45 g of sulfur and 4.5 g of dicyclohexylamine was with efficient

mechanical stirring for 4 hours at 165.56 ⁰ C heated. The product was allowed to cool to 115.56 ° C. and 15 g of phosphorus sesquisulfide - P ₄ S ₃ - was added and stirring was continued at this temperature for 3 hours.

Now, a further 500 g of mineral oil were added, then allowed to cool the mixture to about 82.22 ^0C. There was then added a suspension of 15 g of slaked lime in 20 cm ³ of water added, and the mass was heated under stirring slowly to 115.56 ⁰ C and held for 1 hour at this temperature. After adding. 37.5 g of a filter aid, the product was suction filtered and gave a shiny, dark brown, viscous

Oil containing 2.7% sulfur and 0.6% phosphorus.

Copper did not run in an 8 ° / ₀ aqueous solution of this product in mineral oil at ⁰ C 121.11.

^ao example 2

78 g of "Varwolax" were dissolved in 200 cm ^{3 of} dry benzene and 20.6 g of sulfur dichloride were slowly added with cooling and stirring; the temperature of the solution was kept below 35 ° C. The reaction was terminated by refluxing the mixture on a water bath for 3 hours, evolving hydrogen chloride. After removal of benzene by distillation in vacuo, a dark brown, very viscous liquid was obtained with a content of 2.8 ° / ₀ chlorine and 6.5 ° / o sulfur.

To a cold solution of 40 g of this material

in 100 cm ^{3 of} benzene, a solution of 7.85 g of sodium sulfide - Na ₂ S + 9 H ₂ O - and 2.1 g of sulfur in 50 cm ^{3 of} alcohol was added slowly and with stirring. The reaction was completed by treatment on the water bath and under reflux for 3 hours, after which the solid sodium chloride was filtered off from the solution and the product was freed from the solvent by distillation in vacuo. It was then dissolved in petroleum ether and a substantial amount (about 25%) of insoluble material was filtered off and the solvent was removed as before.

The product was a dark brown, stiff, fat-like material containing 10.3% sulfur and 0.5% chlorine; it turned out to copper at 121.11 ⁰ C. active.

Example 3

100 g "Varwolax" were placed in a beaker of 600 cm ³ and heated with efficient mechanical stirring at ⁰ C 115.56. Phosphorus trisulfide (10 g) was then added slowly and very gradually while blowing a stream of air through the reaction mixture. The temperature was maintained without external heating to about 115.56 ⁰ C, and by changing the added compound in the unit time quantity of P ₄ S _3, and 'the amount of blown air therethrough. And the temperature began to fall, heating was resumed from the outside, and the reaction mixture was held for 3 hours to about 115.56 ⁰ C, after which time the smoke had virtually ceased. We have now added 200 g of mineral oil having a viscosity of 2.4 ⁰ E at 60 ⁰ C, the mixture was heated to 126,67 ⁰ C, and 35 g of barium hydroxide - Ba (OH) ₂ + 8 H ₂ O - were very added slowly and with good stirring over the course of about 20 minutes. The heating and stirring were continued at this temperature for a total of ι hour.

. After 15 g of a filter aid had been added, the product was filtered off with suction; one received a clear brown oil with a content of 2.7% barium, 1.26% phosphorus and 1.06% sulfur.

Example 4

300 g of the here provided by the process described in the Example 3 process substance were mixed with 7.5 g of crude cresol and heated with stirring to 93.33 ⁰ C. There were then added 62 g of barium hydroxide, and the mixture was kept under stirring ι hour on 93.33 ⁰ C, after which it was slowly heated to 160 ⁰ C. After adding a filter aid, the product was filtered off with suction. There was a clear brown oil with a content of 6.1 ° / ₀ barium, go 0.59% sulfur and 0.87 ° / ₀ phosphorus.

Examples of lubricants made in the manner of the invention are summarized below with the. Test results listed; the latter are indicative of the effectiveness of the Compounds according to the invention as additives for various types of lubricating oils.

A. Extreme pressure lubricants

i. The tests were carried out with the well-known Ahnen high pressure testing machine. the Effect of typical additives on film tear strength a solvent refined bright stock with a viscosity of 19 ° E at 60 ° C - Oil A - is shown in the table below:

test
No. Additive salary
in % Movie
tear
strength
in kg / cm ² I.
2
3 none 6th
I. 281.2
703.0
703.0 Product of example 1 ..
Product of example 2 ..

2. Another series of tests was made on the well-known Timken testing machine, whereby the following results were obtained:

The base oil used - Oil B - consisted of a mixture of 27 parts by weight of one in the The usual way of refined bright stock with a viscosity of 19 ° E at 6o ° C, 34 parts by weight of a Hid-Continent bright stock refined in the usual way with a viscosity of 24 ° E at 60 ° C, 23 parts by weight of a solvent refined mineral oil with a viscosity of 2.4 ° E

at 60 ° C, 3 parts by weight of a conventionally refined mineral oil with a viscosity of 2.4 ° E at 6o ° C.

In another series of tests, the Timken machine was used to determine the wear parameters to determine the additives according to the invention. The machine was left under the for 6 hours running constant load of 14.97 kg; after this The weight loss of the ring and the block and the block scratch area were determined experimentally

test
No.

Additives ring

Weight loss
in mg

Block weight
loss
in mg

Total loss of ring and block in mg

Average scratch width in mm

4th
5

5% chlorinated wax (40% Cl)

5% chlorinated wax

4 ° / o phosphorous and sulphurized ^ Varwolaxüf *)

5% chlorinated wax "I.

8% product from Example 1

1% dibenzyl disulfide J.

Commercial high pressure lubricant (average figures)

2.1

5.3

10.0

1.4
0.8

1.8
1.5

4.5 2.9

2.9

2.5

3.7

*) This material was prepared by a procedure similar to that in the example procedures described ι prepared, but using a somewhat higher proportion of sulfur and under sulfurizing at 176.67 ⁰ C. Instead of the treatment with lime it was of the oil-insoluble impurities by Dissolve in petroleum ether and filter free. A 5o ° / ₀ sodium oil concentrate contained 2.3% sulfur and 0.52% phosphorus, and 8% thereof were used as listed in Table 4% addition.

The chlorinated wax - commercially available under the name "Chlor-wax" - was a chlorinated one Paraffin with about 40% chlorine.

The commercial extreme pressure lubricant used for Test No. 7 gave a very satisfactory one Lubrication of hypoid gears at high speeds, but failed under the operating conditions low speed and high torque.

B. Lubricating oils for internal combustion engines i. The cleaning properties of metal salts the additives of the invention have been demonstrated by performing tests with normal Lauson engines of type S-2, which were kept in operation under the following conditions:

Cooling water jacket temperature ... f. 176.67 ° C

Oil sump temperature 107.22 ° C

Duration of the attempt,. 100 hours

Unleaded fuel

The test results were as follows;

lubricant Number of stuck • f Pistons LcLger- Viscosity Remarks or sticking paint measure weighted
loses increase in test OilC + i% zinc Piston rings (Visual dimension in mg used First and second rings IN THE. Di- (a-methyl-iso- 2 after
CRC) 4th Oil
i *% clamped; Stripping 8th amyl) -dithio- kl. ■ 5.6 II ring slightly tight. phosphate As with test 8 Wiper ring slot 2 9 easily clogged. Ven 9 . (get stuck) 3.8 IO tilspindeln and col bolt tight. OilC + o, 8% zinc- Scraper ring clean. Di- (cc-methyl-iso- 0 7th Valves and spindles IO amyl) -dithio- 6.5 14th free. phosphate + 3% Product of Example 3

lubricant Number of fixed persons Pistons Camp- Viscosity Remarks the same or sticking paint measure certain
vörlust increased the XcSl
No. As under io under Piston rings (Visual dimension in mg used Stripping clean. Using a O after
CRC) 3 Oil
in% Valves and spindles II other lot 6.5 12th free. Additive, her placed after Example 3 the same Oil E (very similar Oil C) + 0.8% O 5 12th Zinc-di- (ct-methyl- 7.5 l8 isoamyl) -dithio- phosphate + 3% Product after Example 4 the same O 5 13th 7.0 17th

The piston used in Test # 9 was not of the normal type, and this may well add to that unusually poor condition of the engine after this attempt.

The CRC inspection on inspection was carried out in accordance with the one established by the Co-ordinating Research Council Method of Assessing Piston Cleanliness According to the Normal Chevrolet Test I-4 of 36 hours duration, during which a pure piston would receive the code number 10.

2. The favorable properties of the additives according to the invention with regard to the inhibition of piston ring corrosion under the conditions of " cold sludge formation" were demonstrated by carrying out tests with normal Lauson engines of type H-2 under the following operating conditions:

every hour of continuous running

¹⁵ Μ · ¹¹¹ "? ¹¹ £ ^{d n == 7} °°) i
5 minutes at η = 2400 J

Cooling water outlet temperature .... 15.56 to 18.33 ° C Oil sump temperature (not regulated) 21.11 to 29.44 ° C Using lead gas as fuel.
No crankcase ventilation.

Under these conditions there was a very large amount of cold sludge formation, and so did the extent of piston ring corrosion was unusually high.

The base oil used in all of these tests consisted of a 23% blend of a dough a solvent of refined oil medium V -.- I. (V.-I. = viscosity index) with a viscosity of 4.8 ° E at 60 ° C, 58% of a solvent-refined oil high V.-I. similar viscosity, 9.5% of a solvent refined bright stock having a viscosity. 19 ° E at 60 ° C, 9.5% of a customarily refined Penna Brightstock of similar 95 viscosity.

The uppermost piston ring was weighed before the test and after running for 30 and 6 hours. It was found necessary that the losses measured during the first 30 hour period should be unaffected. to be taken into account, since the same is due to a combination of wear due to corrosion and by mechanical effects were due and did not show good reproducibility. the during the period after the lapse of 30 hours i ° 5 Losses measured up to the lapse of 60 hours were, however, quite reproducible; it it was believed that they were almost entirely due to corrosion wear was.

The following results were obtained:

test
No.

Oil mixture

Supreme
Piston ring
Weight loss in mg
| 3 to 6o hours)

Piston code
(60 hours)

14th
16

Motor oil type »Premium <■ <·, based on oil D, with a content of 0.25% zinc di (alpha-methyl-isoamyl) dithiophosphate

the same

HD-type oil, based on oil D, with a content of 0.375% zinc di (alpha-methyl-isoamyl) dithiophosphate -) - 1.2% basic Barium petroleum sulfonate

the same

141
160

145
140

3.0 2.0

10.0
9.3

test
No.

Oil mixture supreme
Piston ring
Weight loss in mg
(30 to 60 hours)

Piston code number (6o hours)

i8
19th

Oil D + 0.6% zinc-di- (älpha-methyl-isoamyl) - & thiophosphate + 0.8% Product of Example 3 -

Oil D + 0.6% zinc-di- (alpha-metliyl-isoamyl) -dithiophosphate -f- o.8% of the product prepared as described in Example 4

83

91

9.0 to 9.5

9.0.

The piston index (maximum value 10) was estimated according to geig, taking into account the paint or coating deposits and the corrosion of the piston skirt, the latter in the case of tests 14 and 15 The course of 60 hours was quite significant.

C. Anti-rust oil compositions

The value of the compounds according to the invention as inhibitors against rust formation was demonstrated by the following tests: Round mild steel rods were ^{suspended in a mixture of the oil (280 cm 3} ) and distilled water (30 cm ³ ). This mixture was stirred mechanically at 60 ° C. for 48 hours using a small paddle stirrer.

test
No. Oil mixture Per- State of the pattern 20th Oil C At- Quite strong on roast. The attempt was after 18 hours the canceled. 21 ÖIC + 2% of dukts after game ι The pattern was after 48 hours almost pure.

The superiority of the additives according to the invention over the known additives mentioned at the beginning . is explained in more detail by the comparative tests listed below:

Test procedure -

400 cm ^{3 of} lubricating oil were weighed into tall beakers without a snout with a ^{capacity of 1500 cm 3.}

Eight of these glasses were heated in a circular, electrically heated oil bath, the temperature of which was regulated by a thermostat in order to keep the lubricating oil temperature constant at 140 ° C. The beakers had tightly fitting aluminum lids with slides in the middle, which were normally closed but could be opened to introduce a test sample. When the gate valves were closed, there was still enough room for the steel stirring rods in the middle to rotate freely. The latter were driven by a common drive shaft with a speed of η = '400 i 40 and carried at their lower end slotted holders to which lead test pieces were screwed. Rectangular sheets of pure lead measuring 44.45 X 25.4 mm were used as test pieces; they were mounted vertically so that they reached just below the surface of the lubricating oil, with the longer axis in the horizontal. Copper strips of 12.7 mm serving as catalysts, bent to a semicircle 95.25 mm in diameter, were placed entirely below the surface of the lubricating oil and hung from corks in the beaker lids by means of vertical copper wires.

The tests were carried out in a maximum total time of 12 hours, namely in periods of 6 hours, with the copper and lead samples removed every 2 hours and replaced with fresh pure samples have been replaced. The copper catalysts were cleaned with carborundum powder and in petroleum ether washed. The lead patterns were flattened, scraped off with a scraper and finally polished, by brushing them in one direction with a stiff wire brush before washing them with benzene and were weighed. After 2 hours, there was another wash in benzene, brushing with a Camel hair brush and reweighing. The total corrosion at any given time was calculated by adding up the weight loss of the lead samples every 2 hours. These total losses were entered in a curve sheet against the time. From the curves thus obtained the time was read off which was required to achieve certain fixed corrosion losses.

This test procedure was devised to determine the tendency of an oil to oxidize and / or break away corrosive acidic substances at elevated temperatures, such as those found in e.g. B. in the operation of internal combustion engines are to be found.

Tested connections

The following connections were tested:
a) Representatives of compounds according to the present invention:

Compound ι: product of example 1.

. Compound 2: A product similar to that in Example 1 is almost exactly the same and was manufactured using the same ■ process, but below Use of 51.5 g of sulfur, 5.15 g of dicyclohexylamine and 22.5 g of phosphorus fisumd. This material contained 3% sulfur and 0.8% phosphorus.

b) Representatives of the already known technology:

Compound 3: This was a sulfurized and phosphorous Sperm oil, made exactly as described in British Patent 663 071 (p. 2, Lines 17 to 32). The time for the second heating period was about 1 hour and the product contained 9.55% sulfur and 0.12% phosphorus.

Compound 4: This was prepared as described in U.S. Patent 2,498,628 (p. 6, lines 26 to 35) is described, about 2% phosphorus sesquisulfide being used in the second reaction stage.

This product contained 7.8 ° / ₀ sulfur and 1.06 ° / ₀ phosphorus.

The comparison oil or the oil base

The mineral lubricating oil base used in this series of tests was a mixture of approximately 88% of a paraffin type mineral oil refined in a solvent having a viscosity of about 4.8 ° E at 60 ° C and 12% of a mixture with a viscosity of about 12.8 ° E at 60 ° C and a Brightstock salary.

Test results

additive

. Existing heat additive

Weight loss
overall at
Lead pattern according to
6 hours in mg

Time to total weight loss in hours

of 20 mg

of 30 mg

Connection 1

Connection 2

Connection 3

Connection 3

Connection 4

None (mineral oil alone) ..

1.0

2.5 1.0

5.0 0.8

The times in the last two columns have been rounded down to the nearest half hour.

Conclusions

From the above test results it is clear that the compounds of the invention, like them are represented here by compounds 1 and 2, are corrosion inhibitors, whereas those from the typical joints 3 and 4 known from the prior art do not inhibit corrosion; link 3 even promotes corrosion.

Claims (1)

PATENT CLAIMS: i. Use of reaction products of the unsaponifiable parts of wool fat, especially wool fat alcohols or mixtures of those with unsaturated hydrocarbons, alone or in a mixture with alcohols or phenols, with sulfur and / or up to 0.2 parts by weight of phosphorus penta- or trisulfide, especially in the form of its zinc -, alkaline earth or alkali salt, 7.4
19.2
61.0
182.0
48.6
55.4 7.0
6.0
2.0
o, 5
2.5
4.0 8.0
ii, 5
4.5
i, 5
6.0 5.5 in amounts up to 10 percent by weight of the total composition as an additive to lubricating oils based on mineral oils or synthetic oils. 2. Embodiment of the invention according to claim i, characterized by the use one of a mixture of sulfurized and phosphorized unsaponifiables of the wool fat with organic dithiophosphoric acids, phenols or phenol thioethers by treatment with a Metal oxide or hydroxide obtained oil-soluble complex metal salt. 3. Embodiment of the invention according to claim i, characterized by the further use known lubricant additives, such as chlorinated paraffin, zinc salts of organic dithiophosphoric acids, Dibenzyl disulfide and alkaline earth petroleum sulfonates. Referred publications:
British Patent No. "663 071;
U.S. Patent Nos. 2,498,628, 2,550,406. 609 512 5.