DE1594612C3 - Use of lubricating oils or lubricating oil mixtures to lubricate the cylinder in engines with separate cylinder and crankshaft lubrication - Google Patents

Description

The lubrication of engines brings with completely separate lubrication of the cylinder and crankshaft Problems with the simultaneous lubrication of the cylinder and the piston of the crankcase from does not occur. These problems are mainly due to the particular lubrication system used for Engines with separate cylinder and crankshaft lubrication is used: That is used to lubricate Cylinder and piston certain oil is pressurized through one or more openings in the cylinder wall inserted into the space between the piston and cylinder and is then lost, e.g. B. by burning over the exhaust or through leakage along the piston. With the so-called "one-time smearing" the amount of lubricating oil is kept as low as possible in order to reduce the consumption of lubricating oil as much as possible largely to restrict. This leads to difficulties unknown in other types of engines which the lubricating oil covers the cylinder wall relatively abundantly and continuously between the piston and circulates in the crankcase. The oil, applied in such quantities that it is just used to lubricate the Cylinder and piston is sufficient, the cylinder and piston wall and the piston rings must also be used keep clean and protect against corrosion by the acids formed during combustion of the fuel, and it must do this job even if a large part of the oil is lost through combustion.

Because these engines are generally built for high power and to propel ships which run on cheap, high-sulfur fuels incineration produces considerable amounts of residues, which leads to a high level of residue Wear leads. This gives rise to further technical problems which are common in engines do not occur.

It has already been recommended to use emulsions of water in oil as lubricants in the aqueous phase, dissolved salts stabilized by emulsifiers, e.g. B. calcium acetate contain. Besides that lubricants are known which consist of an oil with salts or hydroxides dispersed therein. But the effect of such lubricants is above all else

ίο in view of the ever increasing Dimensions of the engines and the pressures prevailing in them are insufficient, especially as far as the Anti-wear effect comes into consideration.

It is also known that alkaline earth metal carbonates and / or hydroxides are finely dispersed in lubricating oils Form to be used, stabilizers such as alkaline earth metal salts of organic acids, be incorporated as further additives (cf., for example, GB-PS 7 86 167, 7 90471, 763608 and 7 95 172). Such alloyed lubricating oils have, however, for use in engines with separate Cylinder and crankshaft lubrication proved to be unsuitable, for the reasons mentioned above, such as high pressures inside large size engines and wear problems.

Finally, it was also known to use certain polymeric additives as ashless detergents and viscosity index improvers to use, d. This means that very special technical functions of these additives are used.

Surprisingly, it has now been shown that in engines with separate cylinder and Crankshaft lubrication wear problems that occur can be remedied by specializing in Way used composite lubricating oils and lubricating oil mixtures, in which two components one exert a synergistic effect.

The invention therefore relates to the use of lubricating oils or lubricating oil mixtures which

(a) a carbonate and / or hydroxide of an alkaline earth metal in finely dispersed form,

(b) a stabilizer in the form of a salt of an organic acid and an alkaline earth metal and

(c) oil-soluble polymers with carboxyl groups derived from olefinically unsaturated compounds, Carboxylic acid anhydride groups, hydroxyl groups, epoxy groups and / or nitrogen-containing groups in the molecule

included, for lubricating the cylinder in engines with separate cylinder and crankshaft lubrication.

The term "oil-soluble polymers" refers both to homopolymers and to Copolymers.

The combination of component (a) with component (b) gives those to be used according to the invention Lubricating oils and lubricating oil mixtures have anti-wear properties that are due to a summation the properties to be expected are far superior to the effect of the individual components. This synergetic effect is all the more remarkable as the oil-soluble polymers of the type specified as such generally do not impart anti-wear properties to the base oil which make it lubricious of engines with separate cylinder and crankshaft lubrication.

Lubricating oils can be used as base oils for lubricating oils and lubricating oil mixtures which can be used according to the invention are used, which z. B. of aromatic,

Derive naphthenic or paraffinic petroleum. Both lubricating oil distillates are suitable for this as well as residual lubricating oils and mixtures of these two types. However, there will be base oils preferably the whole or 90% or more of a lubricating oil distillate or a mixture of Lubricating oil distillates exist. The boiling range of the lubricating oil distillates converted to atmospheric pressure is usually between 350 and 550 ° C.

The viscosity index of these oils is 0, depending on the type of oil and the refining technique used to 120. It is known that lubricating oil distillates of the aromatic and naphthenic types usually have a lower viscosity index than the lubricating oil distillates, of the paraffinic type. Im generally only lightly refined lubricating oil distillates with a viscosity index of 30 or higher are used preferred, e.g. B. a distillate of a naphthenic petroleum that is purified with liquid sulfur dioxide and has been treated with fuller's earth.

The concentration of component (a) in the lubricating oil or lubricating oil mixture can be within wide limits fluctuate and is adapted to the strength of the wear that occurs. According to a very expedient Embodiment can use concentrations of 0.01 to 0.5 equivalents of the alkaline earth metal per 100 g of the lubricating oil or lubricating oil mixture can be applied.

The metals magnesium, calcium, strontium and barium come into consideration as alkaline earth metals. Their carbonates and / or hydroxides can be dispersed in the base oil in a known manner, e.g. B. with Help of a colloid mill. Another suitable method starts with a solution of the carbonate and / or hydroxide in a solvent that is mixed with or emulsified in the base oil, if desired with the help of an emulsifying agent, whereupon the solvent by evaporation or Distillation is removed from the resulting mixture and a dispersion of the carbonate and / or hydroxide remains in the oil. Such methods are described in British Patents 7,78,468 and 7,91413 been. Preferably, however, the carbonate and / or hydroxide is in situ in the presence of a Stabilizer formed. Suitable methods for this are e.g. B. in British patents 7 39 434, 7 80 058,

7 86 167, 7 90471, 7 93 608, 7 95 172, 8 18 323 and

8 18 326 has been described.

In the preparation of the dispersions of the component (a) in the base oil, the stabilizer can be used in customary in the art amount. Usually the amount used is given in equivalents per equivalent of the dispersed carbonate and / or hydroxide, e.g. B. 0.1 equivalent of stabilizer per equivalent of dispersed carbonate and / or hydroxide. In general, an amount of 0.05 equivalent of stabilizer per equivalent of the dispersed carbonate and / or hydroxide is sufficient; an amount of more than 0.5 equivalents of stabilizer is rarely required.

Examples of salts of organic acids which are suitable as stabilizers are the alkaline earth metal salts aliphatic and aromatic carboxylic acids, hydroxycarboxylic acids and aliphatic and aromatic Sulfonic acids. The alkaline earth metal salts of aliphatic carboxylic acids used in the oil industry are preferred occur as mixtures in the refining of lube oil fractions and are known as naphthenic acids are. The salts of sulfonic acids, e.g. B. that prepared by sulfonating aromatic oil fractions Sulphonic acids and the salts of alkyl salicylic acids are very suitable as stabilizers.

The concentration of the dispersed alkaline earth metal carbonate and / or hydroxide in the lubricating oils to be used according to the invention can continue within Boundaries fluctuate. However, a concentrated dispersion of the carbonate is preferred first and / or hydroxide in an oil. This concentrate is then used to make the for the Lubrication to be used lubricating oil used. Concentrates containing 10 to 25 percent by weight of the Containing carbonate and / or hydroxide in dispersed form are particularly suitable for the invention Purpose of use.

The carbonates and / or hydroxides can be used to prepare the concentrate both in a residual lubricating oil as well as being dispersed in a lubricating oil distillate. A lubricating oil distillate is preferred used. If the base oil for the lubricating oil mixture to be used according to the invention is a lubricating oil distillate or a mixture of such distillates is used, it is necessary for the preparation of the Concentrate not the same lubricating oil distillate to be used, but it can, for. B. a lower one Have viscosity.

The oil-soluble polymers that are used as component (c) can be obtained by polymerization from olefinically unsaturated compounds. They are already known as lubricating oil additives partly because of their property as cleaning agents.

The polymers used according to the invention can in principle be prepared in three ways respectively.

First of all, these polymers can be prepared by direct polymerization from olefinically unsaturated compounds, which at least partially have polar groups.

Furthermore, they can by direct polymerization of olefinically unsaturated compounds that are not polar Have groups, and after-treatment of the polymers are obtained in the case of the polymer polar groups are incorporated.

Finally, a polymerization of such olefinically unsaturated compounds that at least partially have polar groups, the polymer obtained is subjected to an aftertreatment, in which the existing polar groups are converted into polar groups of a different kind.

Both polymers which have only one type of polar groups and also polymers can be used polar groups which are different from each other can be used as component (c).

The polymers having only one type of polar groups can either be obtained by homopolymerization of a monomer with polar groups of one kind or through copolymerization of different monomers, having the same polar groups can be obtained. If so desired, this can be done polymerizing mixture also contain monomers without polar groups. The polymers with different polar groups can either be obtained by homopolymerization of a monomer that

<> Has 5 different polar groups, or by Interpolymerization of different monomers with different polar groups can be obtained. In this case, too, can be polymerized

Mixture containing monomers without polar groups.

The olefinically unsaturated monomers can, according to the nature of the polar groups they have, can be classified as follows:

1. Monomers with carboxyl groups, e.g. B. acrylic acid, methacrylic acid, fumaric acid, maleic acid, itaconic acid and monododecyl maleate.

2. Monomers with carboxylic anhydride groups, e.g. B. maleic anhydride.

3. Monomers with hydroxyl groups, e.g. B. allyl alcohol, oc-hydroxylethyl methacrylate and pentaerythritol monomethacrylate.

4. monomers with epoxy groups, e.g. B. glycidyl methacrylate and glycidyl vinyl ether.

5. Monomers with nitrogen-containing groups, e.g. B.

(a) Monomers having a nitrile group, e.g. B. acrylonitrile and / J-cyanoethyl acrylate.

(b) monomers with an amide group, e.g. B. acrylamide and N-octadecyl methacrylamide.

(c) monomers with heterocyclically bonded nitrogen, e.g. B. vinyl pyridine and N-vinyl pyrrolidone.

(d) monomers with an imide group, e.g. B. Lauryl maleimide and N-vinyl succinimide.

(e) monomers having an amino group, e.g. B. p-aminostyrene and jS-aminoethyl vinyl ether.

6. Monomers in which different polar groups occur, e.g. B.

(a) Monomers having an imide group in combination with an amino group, e.g. B. the reaction product of maleic anhydride and tetraethylene pentamine.

(b) Monomers having an amide group in combination with an amino group, e.g. B. N- (j3-Dimethylaminoethyl) acrylamide.

(c) monomers having a nitrile group in combination with an amino group, e.g. B. N-cyano-N-tert-dodecylaminoethyl acrylate.

(d) monomers having an amide group in combination with a hydroxyl group, e.g. B. N- (j3-Hydroxylethyl) methacrylamide and N, N'-Di- (J? - Hydroxyethyl) maleic acid diamide.

Examples of olefinically unsaturated monomers without polar groups, those with polar groups Monomers can be copolymerized are vinyl esters of saturated monocarboxylic acids, such as Vinyl palmitate and vinyl stearate, allyl esters of saturated monocarboxylic acids, such as allyl aurate and allyl myristate, Alkyl esters of unsaturated monocarboxylic acids such as lauryl acrylate and stearyl methacrylate, dialkyl esters of unsaturated ones Dicarboxylic acids such as dilauryl fumarate and distearyl maleate, alkyl vinyl ethers such as lauryl vinyl ether and Stearyl vinyl ethers, monoolefins such as isobutene and styrene, diolefins such as butadiene and isoprene, alkyl allyl carbonate esters, such as (Ce-CisV-alkyl allyl carbonate ester.

The following compounds are examples of oil-soluble polymers which are olefinically formed by direct polymerization unsaturated compounds which have at least partially polar groups can be obtained be able.

Polymers containing only carboxyl groups as polar groups, e.g. B. unsaturated copolymers Monocarboxylic acids with alkyl esters of unsaturated monocarboxylic acids or with monoolefins.

Polymers which only have carboxylic anhydride groups as polar groups, e.g. B. copolymers of anhydrides of unsaturated dicarboxylic acids with alkyl esters of unsaturated monocarboxylic acids or with Vinyl esters of saturated monocarboxylic acids.

Polymers which only have hydroxyl groups, e.g. B. copolymers of unsaturated alcohols, Hydroxyalkyl esters of unsaturated monocarboxylic acids and partly with unsaturated monocarboxylic acids esterified polyhydric alcohols with alkyl esters of unsaturated monocarboxylic acids.

Polymers which only have epoxy groups, e.g. B. Copolymers of unsaturated glycidyl esters ίο Monocarboxylic acids with alkyl esters of unsaturated monocarboxylic acids.

Polymers which only have nitrogen-containing groups of the same type as polar groups, e.g. B. Copolymers of unsaturated amides, nitriles, amines, imides and heterocyclic compounds with alkyl esters unsaturated monocarboxylic acids.

Polymers which have both carboxyl groups and nitrogen-containing groups, e.g. B. copolymers of unsaturated monocarboxylic acids with amides of unsaturated monocarboxylic acids and with monomers without polar groups.

Polymers which have both carboxyl groups and hydroxyl groups, e.g. B. copolymers of unsaturated monocarboxylic acids with hydroxyalkyl esters of unsaturated monocarboxylic acids or with Partial esters of polyhydric alcohols and unsaturated monocarboxylic acids and with monomers without polar groups.

Polymers which have both hydroxyl groups and amide groups, e.g. B. copolymers of N-hydroxyalkyl-substituted amides of unsaturated monocarboxylic acids with monomers without polar Groups.

Polymers which have both amide groups and amino groups, e.g. B. copolymers of N-aminoalkyl-substituted amides of unsaturated monocarboxylic acids with alkyl esters of unsaturated monocarboxylic acids and copolymers of unsaturated ones Amides with unsaturated amines and with monomers without polar groups.

Polymers containing both amide groups as well

Have groups with heterocyclically bonded nitrogen, e.g. B. copolymers of unsaturated Amides with vinyl pyridine or its derivatives and with monomers without polar groups.

Polymers that contain both imide groups as well

Have amino groups, e.g. B. copolymers of imides and unsaturated dicarboxylic anhydrides Polyalkylenepolyamines with alkyl esters of unsaturated monocarboxylic acids.

Polymers which have both nitrile groups and amino groups, e.g. B. copolymers of N-cyano-N-alkylamino-alkyl esters of unsaturated monocarboxylic acids with alkyl esters of unsaturated monocarboxylic acids.

The following compounds are examples of oil-soluble compounds

Polymers obtained by polymerizing olefinically unsaturated compounds without polar groups and Introduction of polar groups obtained by post-treatment of the polymer:

Homopolymers of alkyl esters of unsaturated monocarboxylic acids or copolymers of alkyl esters of unsaturated monocarboxylic acids with one another or with monoolefins, the "non-polar" ester groups having been converted into polar amide groups by aminolysis with a mono- or polyamine.
Homopolymers of vinyl esters of saturated mono-

809 607/29

nocarboxylic acids or copolymers of vinyl esters saturated monocarboxylic acids with monoolefins, the "non-polar" ester groups through Hydrolysis have been converted into polar hydroxyl groups.

Homopolymers of vinyl esters of saturated monocarboxylic acids or copolymers of vinyl esters of saturated monocarboxylic acids, the »not polar «ester groups by hydrolysis and subsequent treatment with an alkyl isocyanate polar hydroxyl groups have been converted into polar carbamate groups.

Homopolymers of unsaturated aldehydes and alkyl vinyl ketones, with the "non-polar" carbonyl groups converted to polar imino groups by treating the polymer with a primary amine have been.

Copolymers of unsaturated aldehydes and alkyl esters of unsaturated monocarboxylic acids, with the non-polar carbonyl groups into polar oxime groups by treating the polymer with hydroxylamine have been converted.

Homopolymers of vinyl esters of saturated monocarboxylic acids, the non-polar ester groups by partial hydrolysis and subsequent treatment of the polymer with acrylonitrile via polar Hydroxyl groups have been converted into polar cyanoethyl groups.

The following compounds are examples of oil-soluble polymers which are olefinic by polymerization unsaturated compounds having at least partially polar groups have been obtained, wherein the polar groups by post-treatment of the polymer into polar groups of a different type have been converted.

Copolymers of anhydrides of unsaturated dicarboxylic acids with monoolefins or other monomers without polar groups, the carboxylic acid anhydride groups by treating the polymer with a primary amine have been converted to imide groups.

Copolymers of unsaturated monocarboxylic acids with alkyl esters of unsaturated monocarboxylic acids, the carboxyl groups being formed into hydroxyethyl groups by ethoxylation of the polymer with ethylene oxide have been converted.

In general, it is sufficient to incorporate an oil-soluble polymer into the lubricating oil mixture, if desired however, it can be two or more. The following polymers are preferred: Copolymers of olefinically unsaturated compounds which have heterocyclically bonded nitrogen with alkyl esters unsaturated monocarboxylic acids, preferably copolymers of vinyl-substituted pyrrolidones or vinyl-substituted pyridines with alkyl esters of unsaturated monocarboxylic acids, in particular one Copolymer of N-vinyl-pyrrolidone with a mixture of alkyl methacrylates with 4 to 18 Carbon atoms in the alkyl group and a copolymer of 2-methyl-5-vinyIpyridine with one Mixture of methyl, lauryl and stearyl methacrylate.

Copolymers of unsaturated monocarboxylic acids with alkyl esters of unsaturated monocarboxylic acids, where the polymers have been treated with alkylene oxide, in particular a copolymer of methacrylic acid with lauryl methacrylate and stearyl methacrylate, the polymer having been treated with ethylene oxide is.

The concentration in which the oil-soluble polymer is used, depending on the type, structure and the molecular weight of the polymer used and the anti-wear effect to be achieved fluctuate within wide limits. In some cases an amount of 0.1% by weight is sufficient, calculated on the lubricating oil mixture in order to achieve the synergetic anti-wear effect. In most Cases, an amount of 10% by weight is sufficient. In

ίο some cases can be higher and lower Concentrations than those mentioned can be applied.

The oil-soluble polymers are used as a component

of the lubricating oil mixture used. They do not need to have any lubricating oil properties themselves and theirs The viscosity therefore does not need to be in the viscosity range that is usual for lubricating oils. Finally, oil-soluble polymers of different viscosity and thus of different viscosity can also be used Molecular weight can be used.

Particularly good lubricating oil mixtures which can be used according to the invention can be prepared from

a) a lubricating oil distillate cleaned with liquid sulfur dioxide and post-treated with fuller's earth, which has a viscosity index of 30 to 60 and a viscosity of 60 to 75 cS at 50 ° C,

b) a concentrated dispersion of calcium carbonate, which is stabilized with 0.08 to 0.12 equivalents of calcium naphthenate per equivalent of calcium carbonate is, in a mineral oil with a viscosity of 7.0 to 21 cS at 50 ° C,

c) additionally with either an oil-soluble copolymer of acrylates or methacrylates vinyl-substituted pyrrolidones or vinyl-substituted pyridines or an oil-soluble ethoxylated one Copolymer of acrylic acid or methacrylic acid with acrylates or methacrylates. The invention is illustrated in more detail by the following examples.

example 1

Base oil (naphthenic lubricating oil distillate with a viscosity index of 45 and a viscosity of 68 cS at 50 C and 10.2 cS at 98.9 ¹ C)

Copolymer of lauryl methacrylate with stearyl methacrylate and Methacrylic acid in a molar ratio of 5: 5: 4, with the carboxyl groups by treatment of the polymer have been converted into hydroxyethyl groups with ethylene oxide; average Molecular weight of the polymer 1,200,000

65.2% by weight

Concentrate of calcium carbonate dispersed in lubricating oil distillates, stabilized with 0.10 equivalent calcium naphthenate, Ca content

7.35% by weight

B c i s ρ i e I 2 base oil according to example! 1

Copolymer of a mixture of alkyl methacrylates with 4 to 8 carbon atoms in the alkyl

0.8 wt%

34.0% by weight

65.2% by weight

11th

group with N-vinylpyrrolidone in a molar ratio of about 7.5: 1; polymer average molecular weight 800,000

Concentrate of dispersed calcium carbonate according to example 1

Example 3
Base oil according to Example 1

Copolymer of methyl methacrylate, lauryl methacrylate and stearyl methacrylate with 2-methyl-5-vinylpyridine in a weight ratio of 16.0: 49.7, 7:29, 3: 5.0; average Polymer molecular weight 800,000

Concentrate of the dispersed calcium salt according to example 1

Comparative oil

Base oil (naphthenic residue lubricating oil with a viscosity at 98.9 C from 16.12 cS)

Concentrate of dispersed calcium carbonate according to example 1

0.8 wt% 34.0 wt%

65.2% by weight

0.8 wt%

66% by weight

34% by weight

The oils are tested in a DM 1 engine. This is a single cylinder four stroke engine whose Cylinder bore χ displacement 320 χ 450 mm. This motor has separate lubrication from Cylinder and crankshaft. The test duration is 13 hours at 50 HP load and one speed from 250 rpm.

The cylinder is lubricated with the above oils. A residue fuel is used as the fuel used with a sulfur content of 3.5%.

The following table shows the test results.

Werkspoor 13-hour test

Test oil's iron content of the

Cylinder of dripping oil

34.0 wt% 20

Oil according to Example 1 0.025

Oil according to Example 2 0.025

Oil according to Example 3 0.028

Comparative oil 0.034

These examples show the good anti-wear effect of the oils that can be used according to the invention compared with a comparison oil with the same metal content.

Claims (18)

Patent claims: 1. Use of lubricating oils or lubricating oil mixtures, which a) a carbonate and / or hydroxide of an alkaline earth metal in finely dispersed form, b) a stabilizer in the form of a salt of an organic acid and an alkaline earth metal as well as ίο c) oil-soluble polymers with carboxyl groups derived from olefinically unsaturated compounds, Carboxylic acid anhydride groups, hydroxyl groups, epoxy groups and / or nitrogen-containing groups in the molecule included, for lubricating the cylinder in engines with separate cylinder and crankshaft lubrication. 2. Use of a lubricating oil which contains 90 percent or more of a lubricating oil distillate, according to claim 1 for lubricating the cylinder in engines with separate cylinder and crankshaft lubrication. 3. Using a lubricating oil that is 90 percent or more slightly refined Contains lubricating oil distillate with a viscosity index of 30 or higher, according to claims 1 and 2 for lubricating the cylinder in engines with separate cylinder and crankshaft lubrication. 4. Use of a lubricating oil that is 90 percent or more one with liquid sulfur dioxide Purified lubricating oil distillate from a naphthenic base, after-treated with fuller's earth Contains petroleum, according to claims 1 to 3 for lubricating the cylinder in engines with separate Cylinder and crankshaft lubrication. 5. Use of lubricating oils or lubricating oil mixtures containing dispersed carbonate or Hydroxide in an amount corresponding to 0.01 to 0.5 equivalents of the alkaline earth metal per 100 g of the Lubricating oil or lubricating oil mixture according to claims 1 to 4 for lubricating the cylinder Engines with separate cylinder and crankshaft lubrication. 6. Use of lubricating oils or lubricating oil mixtures, containing 0.05 to 0.5 equivalents of component (b) per equivalent of component (A), according to claims 1 to 5 for lubricating the cylinder in engines with separate cylinder and Crankshaft lubrication. 7. Use of lubricating oils or lubricating oil mixtures containing as component (b) a Alkaline earth metal salt of a naphthenic acid according to claims 1 to 6 for lubricating the cylinder Engines with separate cylinder and crankshaft lubrication. 8. Use of lubricating oils or lubricating oil mixtures in the form of a concentrated dispersion, which contains 10 to 25 percent by weight of the carbonate or hydroxide in a lubricating oil as a base oil, according to claims 1 to 7 for lubricating the cylinder in engines with separate cylinder and Crankshaft lubrication. 9. Use of lubricating oils or lubricating oil mixtures containing, as component (c) polymers, by direct polymerization of olefinically unsaturated compounds with at least partly carboxyl groups, carboxylic acid anhydride groups, hydroxyl groups, epoxy groups and / or nitrogen-containing groups have been obtained according to claims 1 to 8 to Lubricating the cylinder in engines with separate cylinder and crankshaft lubrication. 10. Use of lubricating oils or mixtures of Schmjer oil, containing as component (c) polymers, which by polymerization of olefinic unsaturated compounds without carboxyl groups, carboxylic acid anhydride groups, hydroxyl groups, Epoxy groups and / or nitrogen-containing groups and post-treatment of the polymer in such a way that one or more of the groups mentioned above are introduced into the polymer, have been obtained according to claims 1 to 8 for lubricating the cylinder in engines with separate cylinder and crankshaft lubrication. 11. Use of lubricating oils or lubricating oil mixtures, containing as component (c) polymers, which by polymerization of olefinic unsaturated, at least partially carboxyl groups, carboxylic acid anhydride groups, hydroxyl groups, Compounds containing epoxy groups and / or nitrogen-containing groups and aftertreatment of the polymer in such a way that the groups contained in the polymer fall into other groups of the aforementioned type have been obtained according to the claims 1 to 8 for lubricating the cylinder in engines with separate cylinder and crankshaft lubrication. 12. Use of lubricating oils or lubricating oil mixtures, containing as component (c) a copolymer of olefinically unsaturated compounds with heterocyclically bound nitrogen and alkyl esters of unsaturated monocarboxylic acids, according to claim 9 for lubricating the cylinder in engines with separate cylinder and crankshaft lubrication. 13. Use of lubricating oils or lubricating oil mixtures, containing as component (c) a copolymer of vinyl-substituted pyrrolidones or vinyl-substituted pyridines with alkyl esters of unsaturated monocarboxylic acids according to claim 12 for lubricating the cylinder in engines with separate cylinder and crankshaft lubrication. 14. Use of lubricating oils or lubricating oil mixtures containing * "as component (c) Copolymer of N-vinylpyrrolidone with a mixture of methacrylates with 4 to 18 carbon atoms in the alkyl group according to claim 13, for lubricating the cylinder in engines with separate cylinder and crankshaft lubrication. 15. Use of lubricating oils or lubricating oil mixtures, containing as component (c) a copolymer of 2-methyl-5-vinylpyridine and a mixture of methyl, lauryl and stearyl methacrylate, according to claim 12 for lubricating the Cylinder in engines with separate cylinder and crankshaft lubrication. 16. Use of lubricating oils or lubricating oil mixtures, containing as component (c) a copolymer treated with alkylene oxide unsaturated monocarboxylic acids and alkyl esters of unsaturated monocarboxylic acids according to claim 11 for lubricating the cylinder in engines with separate cylinder and crankshaft lubrication. 17. Use of lubricating oils or lubricating oil mix, containing as component (c) a copolymer treated with ethylene oxide Methacrylic acid, lauryl methacrylate and stearyl methacrylate, according to claim 16 for lubricating the Cylinder in engines with separate cylinder and crankshaft lubrication. 18. Use of lubricating oils or lubricating oil mixtures, consisting of a) a lubricating oil distillate cleaned with liquid sulfur dioxide and aftertreated with bleaching earth with a viscosity index of 30 to 60 and a viscosity at 50 ^° C. of 60 to 75 cS, b) a concentrated dispersion of calcium carbonate containing 0.08 to 0.12 equivalents Calcium naphthenate is stabilized per equivalent of dispersed calcium carbonate, in one Mineral oil with a viscosity of 7 to 12cS at 60 ° C and c) either a copolymer of acrylates or methacrylates with vinyl-substituted ones Pyrrolidones or vinyl-substituted pyridines or an ethoxylated copolymer of Acrylic acid or methacrylic acid with acrylates or methacrylates according to Claims 1 to 17, for lubricating the cylinder in engines with separate cylinder and crankshaft lubrication.