DE1058674B - lubricant - Google Patents

Description

CiOM 169/008 08

/ ff 6

LONDON REPUBLIC OF GERMANY

PEOPLE

PATENT OFFICE

ία. 23 c 1/01

INTERNAT. KL. C 10 BtI

C '

EXPLAINING EDITORIAL 1058 674

W 22476 IVc / 23c

[ELDETAG: DECEMBER 23, 1957

NOTICE
THE REGISTRATION
AND ISSUE OF THE
EDITORIAL:

4. J U NI 19 5 9

The invention relates to lubricants based on mineral or synthetic oils.

The present invention seeks to provide such lubricants containing additional actives the goal, which is a high "alkali reserve" combined with a relatively low one Have ash content; these lubricants are particularly suitable for use in internal combustion engines, especially for cylinders of marine diesel engines, which are boiler oil or other fuels burn with high sulfur content. The lubricants should also have anti-corrosive properties own.

According to an older invention, there are lubricants for the cylinders of marine diesel engines, which burn boiler oil or other gels with a high sulfur content, from mineral oils that contain a Oil-soluble organic non-aromatic amine having at least 7 carbon atoms or an oil-soluble non-aromatic amine salt of a weak acid, the organic non-aromatic amine or the amine salt is represented in such a proportion that the oil contains at least 5% amine. The one here The non-aromatic amines used significantly reduce and improve cylinder wear Cleanliness of the pistons of marine diesel engines that work with boiler fuel oil; however, they suffer from certain Disadvantages in that they have a strong odor, have a caustic effect on the skin, the tendency have to remove the paint from surfaces with which they come into contact and with the in The carbon dioxide contained in the air react with the subsequent formation of carbonates which are insoluble in oil or carbamates, which form an undesirable coating on surfaces. From the amine salts On the other hand, it must be said that those with adequate solubility in oil, against whom these objections are not applicable are raised, have rather low neutralization equivalents, so that they are inexpediently large amounts must be used.

In internal combustion engines, which work with the commonly used fuels, occurs during operation cold weather as a result of the pollution of the lubricating oil by water and combustion products, which cause to the formation of a stiff emulsion or a sludge, a particular problem, namely the so-called "cold sludge formation". A serious side effect The cold sludge formation is the corrosion of the piston rings and cylinder liners as a result of the presence of water and acidic combustion products from fuel.

It is the aim of the above invention to provide lubricants which are oil-soluble, essentially neutrally reacting yet higher neutralization equivalent lubricants

Applicant:

CC Wakefield & Company Limited,
London

Representative: Dr. M. Eule, patent attorney,
ίο Munich 13, Kurfürstenplatz 2

Claimed priority:

Great Britain December 24, 1956

and December 16, 1957

John Scotchford Elliott and Eric Descamp Edwards,

London,
have been named as inventors

compounds with a faint odor

hold, which would allow the use of appropriate additional amounts. Furthermore, the lubricants, possibly with the incorporation of the usual additional active ingredients to cleanse and prevent oxidation, be able to prevent corrosion of the piston rings and the

Cylinder liners under cold operating conditions Keep out of the weather.

The lubricants according to the invention should also be usable for small two-stroke engines. If also the usual mineral lubricating oils are used for this purpose

the presence of additional active ingredients to improve the cleanliness of the pistons and often desirable for dispersing or softening oil coke deposits.

Surprisingly, it has been found that lubricating

Oil-based agent made from natural mineral oil or synthetic oil while avoiding the disadvantages mentioned then meet all expectations if they contain a certain proportion of a compound of the general formula

M, A, B _e.g.

in which M is a polyvalent metal which can form ammine coordination complexes, A is the residue of an organic acid, B is an organic di- or polyamine, χ and y are the valences of M and A, namely χ - 1 or 2, y - 1, 2 or 3 and ζ mean a number between 1 and 6 that is equal to or less than the coordination number of M.

Use as a lubricant for steam turbines is also possible, such lubricants

909 £ 29/433

have good rust-preventing properties in the presence of λόπ water or salt water; generally included such masses also use the usual anti-aging agents. The use of complex compounds as lubricant additives is known. It has already been proposed to use alkaline earth metal complexes. This acts However, they are chemically completely different compounds, especially since alkaline earth metals, as is known, for formation of ammine complexes are usually not capable.

R-COO-, R-SO ₃ -,

RO-- PO -
O -

or

Ii

RO
R'O

PO
O

Herein, R and R 'are alkyl, cycloalkyl, aralkyl, alkaryl or aryl groups which have substituents can, such as B. the hydroxyl group or ester groups or halogen atoms.

M must be a metal which is able to form relatively stable ammine coordination complexes form; if possible, it should also be a metal that does not tend to reduce the rate of aging of the oil, in which the same is resolved to increase. The preferred metals are zinc, cadmium, cobalt, tin, lead, Nickel and chromium; but also others, such as B. copper, iron (divalent), mercury, silver, and manganese the rare or relatively rare elements of group VIII of the Periodic Table of the Elements, such as B. platinum, palladium, ruthenium, osmium or iridium can be used.

The complex ammine compounds used as additional active ingredients in the present invention can, although this is not the subject of the invention, be prepared by reacting a salt M _a .A "with the organic di- or polyamine.

Examples of suitable Μ ,, Α ,, - salts are the acetates Caprylates, laurates, oleates, naphthenates, benzonates, salicylates, petroleum sulfonates, alkylated aryl sulfonates as well as long chain alkyl and alkylated aryl phosphates.

Examples of the di- or polyamines B are ethylenediamine, Diethylenetriamine, triethylenetetramine, tetraethylene pentamine. Mixtures of higher polyethylene polyamines, Piperazine, p-phenylenediamine, and various commercially available long chain diamines in general formula

R "- NH - CH ₂ · CH ₂ · CH ₂ · NH ₈ ,

in which R "is obtained from a fatty acid, such as, for example, lauric acid, or from a mixture of fatty acids alkyl group derived from coconut oil, soybean oil or tallow.

The organic di- or polyamines can also contain heterocyclic compounds.

It is clear that it is more oil soluble in the production Compounds is necessary to select the amine used so that it is the metal salt with which it is to form a complex compound, fits. Is z. B. a metal petroleum sulfonate or a naphthenate is used, then a wide range of diamines or polyamines is available for the complex compound Disposal. On the other hand, if a salt of an organic acid with a short chain, such as. B. acetic acid, then you have to choose a relatively long-chain amine in order to be an oil-soluble complex compound to obtain.

If the ammine complex compounds are to be used as additional active ingredients for lubricating oils which are exposed to relatively high temperatures, then compounds must be selected which are derived from long-chain diamines or polyamines, since the compounds derived, for example, from the polyethylene polyamines have a tendency to form resinous substances to decompose, which latter form annoying encrustations on pistons and other engine parts. So if, for example, the complex compounds are to be used as an additive for the lubricating oils of internal combustion engines, then it is

ίο desirable to select those who differ from long chain Derive di- or polyamines.

The amine complex compounds can be prepared by any method known in the art. So z. B. those made from oil-soluble metal soaps or salts may conveniently in solutions, e.g. Am Mineral oil, by simply heating the same with the diamine or polyamine in the suitable proportions. In general, the molar ratio of amine to metal salt should not exceed 1: 1

ao go out; it is often an advantage to have a small excess of the metal salt, as this increases the solubility of the oil of the product is improved.

If complex compounds are made from solid metal salts that are insoluble in oil, then there is a Appropriate method is that a solution of the di- or polyamine in petroleum ether or benzene on Treated reflux with a slight excess of the salt until the latter goes into solution, whereupon the The solution is filtered and the solvent is removed by distillation. Complex compounds of this kind are generally readily soluble in hot mineral oil, but have a tendency to dissolve in some upon cooling Extent to be eliminated. More useful mixed complexes can be made by

the complex of oil-insoluble metal salt and amine is further reacted with an oil-soluble metal salt in such amounts that the molar ratio of the total metal salts to the diamine or polyamine is at least 1: 0.8 amounts to.

However, these processes are just as little subject matter as the processes mentioned below by way of example the invention.

Specific examples of the oil-soluble amine complex compounds according to the invention are:

Zinc acetate coconut fatty acid alkyl residues

NH CH ₂ CH ₂ CH ₂ NH ₂ complex, zinc naphthenate-diethylenetriamine complex (molar ratio 1: 0.8),

Zinc naphthenate-coconut fatty acid alkyl radicals -N H · CH ₂ · CH ₂ · CH ₂ · NH ₂ complex, zinc oleate-coconut fatty acid alkyl radicals-

NH CH ₂ CH ₂ CH ₂ NH ₂ complex, lead naphthenate-coconut fatty acid alkyl residues-

NH · CH ₂ · CH ₂ · CH ₂ · NH ₂ complexes, * "lead naphthenate-triethylenetetramine complex, zinc naphthenate-p-phenylenediamine complex, nickel-petroleum sulfonate-coconut fatty acid alkyl residues-

NH CH ₂ CH ₂ CH ₂ NH ₂ complexes, cadmium octyl phosphate-coconut fatty acid alkyl residues-

NH · CH ₂ '- CH ₂ · CH ₂ · NH ₂ complexes.

In particular, can be used \ ^r onnectivity,

their typical representatives of the zinc petroleum sulfonate-triethylenetetramine complex, Zinc petroleum sulfonate tetraethylene pentamine complex and the tin petroleum sulfonate triethylenetetramine complex are.

Optionally, complex compounds from certain

commercially available substances with relatively high organic acidity, such as. B. raw wool fat, be produced, with the same with a

5 6

■ suitable metal oxide or hydroxide, e.g. B. zinc oxide, additional active ingredients, such as those generally used in lubricating oils neutralized and then used with the desired needs. So z. B. can in Amine converted into the complex compound. the usual lubricating oils for internal combustion engines It is clear that the above examples are only detergents, such as. B. Metal petroleum (mahogany) - • one Overview of the complex sulfonates to be used, and anti-aging agents such. B. the zinc bonds should give, without the scope of the invention in dialkyldithiophosphate, the metal alkylphenol or restrict in any way. The following be the phosphorus and sulforated terpenes contain However, remarks may serve the scope and be.

■ the limits of the various subclasses of the for The additional active ingredients can not only be used in mineral certain lubricating oils are used in the compositions according to the invention, but also in th complex compounds. synthetic oils, such as B. the synthetic lubricating die Complex compounds of the dicarboxylic acid diester type and of the polydion type which can be used very generally are those that are made from free-in-oil glycol ether type.

soluble metal salts, such as. B. the laurates, oleates If the compositions according to the invention based on oil as and in particular the naphthenates of such metals 15 lubricants for the cylinders of marine diesel engines, such as zinc, nickel, cobalt, tin and chromium, with long-term boiler oil or other oils of high sulfur chain Diamines. The preferred metal is burn in the eye content, then the my zinc can be used, both for economical reasons from 2 to 20 weight percent of the amine com considerations and because the zinc salts contain organic complexes. When lubricating acidic acids by direct neutralization of the acids with internal combustion engines, which easily work with the more common power zinc oxide in the presence of a little water, the additional active ingredient will preferably be able to be produced. To achieve the maximum oil-soluble - used in an amount of 0.5 to 2%,
For use with turbine oils, it is generally desirable to use the selected additional active ingredients in a small excess in concentrated salt; a 25 concentrations from 0.02 to 2.0 ° / _0, preferably 0.05 to 0.2%, molar ratio of the salt to the amine is from 1: 0.8 is completely sawn though preparations are conceivable, which a fixed Sonders suitable. Complex compounds this generally borrowed higher proportion of additional active ingredients, z. B. up to 10% of my type are suitable for use in one or more.

The following examples illustrate the non-antidotes. So z. B. quite considerable amounts - up to 30 was the invention-forming production and the Eigenzu about 30 percent by weight - in cylinder oils for shafts of the complex compounds that can be used in the invented marine diesel engines, which boiler oil or other appropriate lubricants. Burning fuel with a high sulfur content, while using quite small amounts, for example Example 1
0.2% / ₀ or less, effective corrosion inhibitor. , ^. .
substances are, especially if the same in steam turbine zinc naphthenate diethylenetriamine complex
oils are used; in doing so they by no means increase in (compound A)
the demulsification values of such oils. 709 g (0.55 mol) of about 50 ° / ₀ solution of zinc complex compounds of adequate oil solubility naphthenate in mineral oil, 51.5 g (0.5 mol) Diäthylenkönnen also free oil-soluble metal salts such as triamine 40 added. An exothermic reaction takes place e.g. B. zinc naphthenate, with diethylenetriamine or other instead, after which the material at HO ⁰ C 15 minutes polyethylene polyamines are produced. This could have been long stirred. The product is a brown oil as well as corrosion inhibitors in steam turbine in a content of 4.8 ° / ₀ zinc and 2.7% nitrogen; It can be used oils, but as has already been mentioned, freely soluble in mineral oil, although the diethylenetriamine is out of the question as its use is entirely insoluble by itself.

Lubricants that use relatively high temperatures The alkali reserve of this complex compound is permanently exposed are. put to 176 mg KOH / g, while the alkali reserve of the complex compounds from metal petroleum sulfonates original zinc naphthenate concentrate to about or from the metal salts of synthetic oil-soluble alky- 80 mg KOH / g.

Lated aromatic sulfonates are also free in oil 50. The alkali reserve is determined by treatment on

soluble if they reflux a weighed amount of the specimen with a long-chain diamines or polyamines

getting produced. Satisfactory oil-soluble known excess of 0.1 η-hydrochloric acid in a solution,

Materials as well can be made of other amines with 5% methanol, 45% ethanol, 50 ° / ₀ Water,

getting produced. These compounds are good and back titration with 0.1 η sodium hydroxide solution using

Corrosion inhibitors, however, also tend to use methyl orange powder as an indicator.

Emulsifiers to work, which is why their use in similarly zinc naphthenate coconut

Turbine oils is not appropriate. These compounds, fatty acid alkyl radicals -NH CH ₂ CH ₂ CH ₂ NH ₂ -Com-

such as those made from the metal salts of organic plex (compound B).

Derive phosphoric acids, have a lower alkali It contains 4.3% zinc and has an alkali reserve of

reserve than those that differ from the metal carboxylates 60 about 110.

derive, because the organic sulfonic and phosphoric acids are strong acids which are produced according to known processes and which cannot easily be displaced from the zinc acetate-coconut _{fatty acid alkyl radicals-NH · CH 2} bond with the metal. -CH ₈ -CH ₂ · NH ₂ complex contains 13.6% zinc and has

Complex compounds consisting of aromatic or an alkali reserve of about 550 mg KOH / g.

heterocyclic di- or polyamines, such as. B. p-phen- 65 zinc acetate naphthenate-coconut fatty acid alkyl residues-

ylendiamine be prepared are as NH-CH ₂ -CH ₂ -CH generally _a · NH ₂ complex (molar ratio:

Corrosion inhibitors less satisfactory than the 1: 0.5: 1) gives when diluted with an equal

classes already described. Weight mineral oil a clear permanent 36% oil

The additional active ingredients according to the invention can - concentrate with a content of 5.2% zinc and a

if so desired - together with other 70 alkali reserves of about 130 mg KOH / g.

Example 2

Complex of the zinc salt of raw wool fat and coconut fatty acid alkyl residues -NH · CH ₂ · CH ₂ · CH ₂ · NH ₂ -

Complex (compound C)

To 256 g (0.2 mol) of a crude wool fat with a free acidity corresponding to an equivalent weight of 1278, 10 g of zinc oxide, which has been mixed with water to form a paste, are added. The mixture is thoroughly stirred at 90 ⁰ C, has come to the zinc oxide for the most part to the reaction, is heated and the product to 15O ⁰ C, remove the water.

7.9 g (0.032 mol) of coconut fatty acid alkyl radicals —NH _{—CH 2 —CH 2 —CH 2 —NH 2 are} added to 100 g (0.038 mol) of this product, which is kept at a temperature of 90.degree. An exothermic reaction takes place, whereupon the mixture is heated with stirring until the temperature has risen to 120 ° C.

The product is a dark brown solid body having a content of 3.04 ° / ₀ zinc.

According to the general method outlined above, not forming the subject of the invention, a large Number of complex compounds that are to be used

ίο suitable for the oil-based compositions according to the invention are to be produced. Direct heating as in Examples 1 and 2 is generally preferred.

Details of these compounds used in the tests are given in Table I below:

Table I.

Complex compound

Connection D

Complex lead naphthenate-triethylenetetramine

Connection E

Nickel Petroleum Sulphonate Complex — Coconut Fatty Acid Alkyl Residuals-NH · CH ₂ · CH ₂ · CH ₂ -NH ₂

Connection F

Complex zinc oleate — coconut fatty acid alkyl radicals — NH • CH ₂ • CH ₂ • CH ₂ • NH ₂

Connection G

Complex lead naphthenate — coconut fatty acid alkyl residues — NH · CH ₂ · CH ₂ · CH ₂ · NH _2. "....

Compound H
Zinc naphthenate complex - heterocyclic polyamine

Compound I.

Chromcaproate — coconut fatty acid alkyl radicals -NH • CH ₂ • CH ₂ • CH ₂ • NH ₂ complex

Compound J

K obalt stearate — coconut fatty acid alkyl radicals NH · CH ₂ · CH ₂ · CH ₂ · NHj complex

Approximate
Molar ratio
Salt to amine

1: 0.8
1: 1
1: 0.85

1: 1.1
1: 1.1

1: 0.8
1: 0.9

Approximate
Alkali reserve
(mgKOH / g)

320

80

230

300
220

210
205

Where the composition of the di- or polyamine was not known with certainty, the amount was that was to be converted into a complex compound with the metal salt, from a determination of the basicity of the Amine calculated.

In order to demonstrate the anti-corrosive properties of the lubricants according to the invention, the additional active ingredients in a typical steam turbine base oil, consisting of about 80 percent by weight mineral oil * A "and 20 percent by weight mineral oil" B ", dissolved and on its effect on the demulsification number and rust-preventive properties in the presence of Examined salt water. The test methods used here are described in Testing of crude oil and its products- (16th edition - February 1957), serial no. I. P. 19/55 and I. P. 135/56. The results of a number of tests are summarized in Table II.

Table II

test / - ΙΐΛα Ci ^ (AJjLK? Weight percent Demulsive Results of a 24 hour Kr. none in oil number Salt water corrosion - test at 6O ⁰ C 1 Connection A 60 Heavy rusting 2 Connection B 0.2 180 No rust formation 3 Connection B 2.0 300 No rust formation 4th Compound C 0.1 240 No rust formation 5 \ ^T connection D 0.2 over 1200 No rust formation 6th Connection E 0.2 270 No rust formation 7th Connection F 0.2 720 No rust formation 8th Connection G 0.2 570 No rust formation 9 Compound H 0.2 390 No rust formation 10 Connection I *) 1.0 75 Moderate rust formation 11 Connection J *) 0.2 150 Rust attachment 12th 0.2 150 No rust formation

*) In mineral oil "B" (demulsification Kr. 30).

Oil "Α" was a mineral oil with a viscosity of about 70 seconds Redwood I at 60 ^° C., Oil "B" an oil refined with a solvent and a viscosity of 65 seconds Redwood I at 60 ^° C.

From the table it can be seen that while many of the tested Additives effectively inhibited corrosion under the conditions of this test, some of which in particular the compounds C and E, the demulsification number of the oil increased in an inadmissible manner and therefore for were not suitable for use with turbine oils.

Oil-based composite compositions characteristic of the present invention were subjected to a test subjected to very difficult conditions for the purpose of using the same for anti-corrosion engine lubricating oils, Designed to protect aircraft engines from corrosion during storage and shipping overseas.

The test procedure is described in DEF 2181, Hand B of the Department of Defense (March 13, 1953 edition); It comprises the immersion of sheet metal made of mild steel in a solution of hydrobromic acid in luminescent kerosene with subsequent immersion in the oil-based mass diluted with petroleum ether, furthermore draining and holding the test strips at a temperature of 20 ± 2 ^C C for a period of 24 hours all in one Glass vessel over saturated zinc sulfate solution. Protection against corrosion was considered adequate when the average weight gain of the test strips (tested four times) did not exceed 5 mg. The results of these tests are summarized in Table III.

Table III
All of these compositions of the invention were oil based

Ingredients
(Weight percent)

5% compound B

4 ° / ₀ sodium petroleum sulfonate solution (about 45% oil

concentrate)

10% compound C

5% compound C

4% sodium petroleum sulfonate solution (about 45% oil

concentrate)

10 ° / ₀ connection D

Average weight gain ( ^m S)

The mineral oil "C" was refined in a conventional manner paraffin oil fmreihe - Brighstock - having a viscosity of about 600 seconds Redwood I at 60 ⁰ C.

From the table above it can be seen that 10% of the compound D a satisfactory protection against resulted in corrosion, while 10% of Compound C did not provide adequate protection. A satisfactory one Protection could, however, by the use of mixtures of compound B or C with sodium petroleum sulfonates be achieved.

In order to determine the effectiveness of certain of the oil-based compositions according to the invention as cylinder lubricants for marine diesel engines which burn boiler fuel oil, engine tests were carried out on a two-cylinder Lister engine (model 12-2, bore: 4V ₂ ZoU = 114.3 mm, Stroke: 5V ₂ ZoU = 139.7 mm), modified for the separate mechanical lubrication of a cylinder. The engine was run under the following operating conditions:

Speed., 700 rev / min.

Active power 608.24 kgmp = 5.97 kilowatts

Temperature in the oil sump 51.67 ± 2.77 C ⁰

Leaving Water Temperature 46.11 ± 1.11 C ⁰

Inlet water temperature about 42.22 ° C

Fuel 50% boiler oil \ sulfur content

50% gas oil% S / 2.0%

Cylinder no. 1 was mechanically lubricated with 20 cm ^{3 of} the test oil per hour per lubricator, i.e. a total of 40 cm ³ per hour, while cylinder no. 2 was lubricated in the normal way with oil from the sump, i.e. by centrifugal lubrication.

In the tests, the results of which are summarized in Table IV, the base oil (mineral oil "T>") was used throughout the sump, while various of the lubricants according to the invention were used to lubricate cylinder No. 1. Since these lubricants were based exclusively on the mineral oil »Ό« , a direct measure of the effectiveness of the additional active ingredients could be obtained in each of the tests by comparing the wear on both cylinders and the cleanliness of the two pistons.

The mineral oil "Ό" was a refined by a solvent oil with a viscosity of about 170 seconds Redwood I at 6O ⁰ C.

TabeUe IV test on the Lister engine

test lubricant Mineral oil »Ώ« Test duration cylinder Weight loss on No. (Cylinder no. 1) (Hours) No. top piston ring
( ^m s) 17th 93.5% mineral oil "T>" 50 1 113 5.0% Basic Barium Petroleum Sulphonate Solution 2 113 18th (about 45% in mineral oil) 44 1 174 1.5% zinc dihexyldithiophosphate solution (approx 2 172 50% in mineral oil) 91% mineral oil »T>« 8% compound B 19th 1% basic baritone petroleum sulfonate 96 1 73 (about 45% in mineral oil) 2 290 As with test no.19 20th 100 1 74 2 381

909 529/435

Table IV (continued)

12th

test
Xr. Total weight loss of all piston rings
( ^m g) Piston skirt Piston code
Piston lands Coating in the
Piston ring grooves 17th 229
245 29.4
29.2 4.6
4.7 1.6
1.3 18th 310
317 29.5
29.0 6.9
7.3 - 19th 161
522 30.0
26.3 9.9
3.2 7.6
0 20th 111
660 30.0
27.5 9.9
4.9 7.9
0.2

Maximum code number

for the piston skirt 30.0

for the piston ring lands 10.0

for the coating in the piston ring grooves 10.0

These maximum index numbers are arbitrarily assumed and mean that the parts concerned are perfect are clean. A minimum number of 0 would mean that the piston is completely black or that the piston ring lands and grooves are completely covered with dirty black paint.

From the table above it can be seen that, although in the various tests using the The same base oil showed some variations in the weight loss of the piston rings, a typical one mass according to the invention (tests no. 19 and 20) shows a very considerable decrease in wear in comparison brought about the base oil; that went hand in hand with a noticeable increase in the cleanliness of the Pistons. When both cylinders were lubricated with the base oil (Test No. 17), there was no significant difference to be established between the two pistons. Became one of the usual H. D. oils with a content of additional active ingredients used in the proportions according to »Appendix 1« (test no. 18), then there was no noticeable improvement to be determined compared to the base oil.

Another series of tests was done on a Petter engine Model AV-I executed under the following operating conditions:

20th

Duration of the test ....

rotational speed

Real power

Cooling the engine

Oil sump temperature

Leaving water temperature

Entering water temperature

The fuel used in the tests with the Lister engine are in Table V below

100 hours 1500 rev / min.

5HPe

Normal water cooling (flow) 70 ± 2.77 ° C 65 ± 1.11 ° C 55 ± 1.11 ° C was the same as ·. The test results summarized.

Table V Tests on the Petter engine

test

35

40

45

21
22nd

23 24

lubricant

Mineral oil "D"

90% mineral oil »D« 10 ° / ₀ compound A

91% mineral oil "D" 8% / ₀ compound B

1 ° / ₀ basic barium petroleum sulfonate solution (about 45 ° / o in oil)

74% mineral oil "D" 25% compound B

1% basic barium petroleum sulfonate solution (about 45% in oil)

Table V (continued)

Engine parts

Maximum too test Test results test test reaching 21 test 23 24 Code number 3.9 22nd 4.1 3.9 5.0 4.1 3.6 5.1 5.2 10.0 9.0 3.7 10.0 10.0 10.0 0.6 7.5 5.3 9.7 10.0 22.3 0.0 29.2 30.0 30.0 28.0 28.2 35.0 35.0 35.0 0.9 11.7 5.1 3.1 10.0 892 mg 0.0 419 mg 261 mg - 1475 mg 459 mg 623 mg 464 mg - 745 mg

Piston crown wear

General parts

Oil control ring sludge

Piston lands

Piston skirt

Burning of the piston ring

Oil coke in the top groove

Weight loss top ring

Total weight loss of the piston rings *) ...

*) Refers to the total weight loss of five piston rings, except for test No. 22, where only four piston rings were used.

From this table it can be seen that the typical reasons mentioned were, however, the compound B Compounds according to the invention (test no. 22 to 24) the compositions contained in terms of piston ring fixed-piston ring corrosion significantly reduce the masses with the compound A in comparison to burning the simple mineral oil (test no. 21). From the already; 70 borrowed superior. It will be noted that the 25% of the

Compound B containing compound (Test # 24) both an exceptionally clean flask and one showed very little piston ring weight loss. This mass contained only about 14% of the respective Additional active ingredient, since compound B was a 55% oil concentrate.

In contrast to the previously known oil-soluble amine-containing lubricating oils for the cylinders of marine diesel engines the compositions according to the invention have only a weak odor and have no corrosive effect on the skin and do not remove paint, moreover they are permanent and react with long-term storage not with the carbon dioxide in the atmosphere, and at normal operating temperatures they are without any noteworthy effects Effect on metals, such as B. copper, brass, phosphor bronze, zinc and aluminum.

Claims (9)

Patent claims: 1. Lubricants based on mineral or synthetic oils, characterized by a Content of an oil-soluble complex compound of the general formula M. A ₁₁ B _z in which M is a polyvalent metal that can form ammine coordination complexes, A is the residue of an organic acid and B is an organic di- or polyamine, χ and y are the valence of M and A, namely χ = 1 or 2, y = 1, 2 or 3 and ζ denote an integer between 1 and 6 which completely or partially satisfies the coordination number of M. 2. Lubricant according to claim 1, characterized in that A has one of the following formulas RCOO-, RSO ₃ -, RO - P-O - or RO —P-O - wherein R or R 'is alkyl, cycloalkyl, aralkyl, alkaryl or aryl groups, with or without hydroxyl, Ester or halogen substituents. 3. Lubricant according to claim 1 or 2, characterized in that M cadmium, cobalt, tin, lead, Nickel or chromium, but preferably zinc. 4. Lubricant according to claim 1 to 3, characterized in that B ethylenediamine, diethylenetriamine, Triethylenetetramine, tetraethylenepentamine or a mixture of higher polyethylene polyamines is. 5. Lubricant according to claim 1 to 3, characterized in that B is a long-chain diamine of the general formula R "- NH - CH ₂ - CHg - CH ₈ - NH ₂ in which R "is an alkyl group having 8 to 18 carbon atoms. 6. Lubricant according to claim 1 to 5, characterized in that A is a naphthenic acid. 7. Lubricant according to claim 1 to 6, characterized in that the ammine complex compound a zinc petroleum sulfonate-triethylenetetramine complex, a zinc petroleum sulfonate-tetraethylene pentamine complex, is a tin petroleum sulf ona t-triethylenetetramine complex. 8. Lubricant according to claim 7, characterized by a content of the ammine complex compound in amounts from 0.02 to 2, optionally from 0.5 to 2 percent by weight, based on the total weight the lubricant preparation. 9. Lubricant according to claim 1 to 8, characterized by a further content of known Detergents and / or antioxidants. RO ' Considered publications:
French Patent No. 1,083,354. © 909 529/433 $ .59