PL163838B1 - Multipurpose greasing composition - Google Patents

Abstract

A multifunctional lubricant composition containing detergent-dispersant additives, characterized by in that it contains detergent-dispersant additives in the form of calcium metal compounds in the mixture with zinc dithiophosphates and polybutene succinimides and / or polybutene succinimides and up to 20.0 parts mass acids and / or anhydrides of polybuten succinic and / or polypropylene succinic acid and / or polyethylene succinic having a molecular weight of 200 to 2,000, preferably 250 to 1,700, where calcium carriers are calcium low-base and / or overbased alkylaryl sulfonates and / or naphthosulfonates calcium with an alkaline reserve ratio of 0.01 to 25.0 and the calcium content of 0.1 to 0.75 mol / kg used in an amount of 2.0 to 50.0 parts by mass, preferably 5.0 to 30.0 parts by mass L / or sulfurized normal and / or overbased calcium alkylphenates in which the ratio of the metal content to the alkaline reserve to the metal content of normal calcium sulfur phenate is 1.05 to 10.0 and the molar ratio sulfur to calcium is 0.05 to 1.5, and is used in an amount of 1.0 to 50.0 parts by weight, preferably 5.0 to 40.0 parts by mass, and zinc dithiophosphates are derivatives of 0,0-diuphosphoric acid esters, obtained from primary alcohols containing from 3 to 12 carbon atoms in the alkoxy chain and / or secondary alcohols containing from 3 to 8 carbon atoms, preferably 3 to 6 carbon atoms in the chain alkoxy, used in an amount of 5.0 to 30.0 parts by mass, preferably 8.0 to 25.0 parts by mass of a polybutene succinimides and / or polybutene succinimides are used in an amount of 3.0 to 50.0 parts by mass, with what are the polybutene succinimides are monopoly succinimides and / or bispolybuten succinimides with a content of total nitrogen from 0.6 to 5.0% by mass and the ratio of basic nitrogen to total nitrogen, between 0.3 and 0.8, the mass ratio of monopolybutene succinimides and / or bispohbuten succinimides and / or polybutene succinimides to polysuccinic acid and / or anhydrides and / or polypropylene and polyethylene succinic in a multi-functional composition of the lubricant is up to 7.0, and the weight ratio of calcium to zinc in the formulated composition is from 0.5 to 5.0 and the weight ratio of zinc to total nitrogen is 0.5 to 5.0.

Description

The subject of the invention is a multifunctional lubricant composition used for the improvement of lubricating oils for spark-ignition and compression-ignition engines.

One of the factors that significantly reduce the useful life of finished lubricating oils is the low resistance to oxidation of the oil component and the insufficient ability to disperse low and high temperature sludge, increasing the viscosity of the lubricating oil and causing its thickening. The processes of accelerated deposition of sludge on hot and cold engine parts and excessive thickening of engine oil are favored by: engine design, improper operation of the engine and variable fuel quality. The factors that have a particular impact on excessive sludge formation in compression ignition engines include: extended oil change intervals, penetration of the coolant into the lubricating oil, increased blow-by of gases from the combustion chamber due to excessive wear of the engine rings, high engine loads at low speeds, low operating temperatures, frequent engine brake operation, poor condition of the injector, insufficient oil filtering. The function of engine oil is to prevent the consequences of these unfavorable operating conditions.

In the upper zone of the piston rings and cylinder, where engine oil contributes significantly to the tight sealing of the combustion chamber, the greatest exposure of a thin film of lubricating oil to high temperatures, in the order of 240 to 26 ° C, and contact with purge gases containing nitrogen oxides occurs. , sulfur, oxygen, carbon monoxide and dioxide, and free radicals. This leads to a rapid oxidation of the hydrocarbon component of the engine oil and associated rapid aging of the oil. The undesirable consequences of these processes are carbon deposits in the ring grooves and interring bridges, and lacquer coatings on the piston skirt. This can be counteracted to a certain extent by the use of appropriate lubricant compositions.

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There is known from the Polish Patent Specification No. 138 651 a lubricating oil additive containing a dispersing component composed of 18 to 68% by weight of an ashless dispersant and 3 to 4OH polymer component reducing the dependence of viscosity on temperature, moreover, an oil-soluble zinc dithiophosphate in an amount corresponding to 2 to 5 wt.% Phosphorus and 2 to 5 wt.% Zinc, and 8.885 to 2 wt.% Copper and optionally 8 x 183 to 8 x 18 * mg / kg calcium and / or magnesium. The polymeric component reducing the temperature dependence of the viscosity, according to the claims of PRL 138 651, contains polymers of unsaturated esters with 4 to 28 carbon atoms or contains polymers of unsaturated mono or dicarboxylic acids with 3 to 1 (3 carbon atoms, with unsaturated monomers containing nitrogen having 4 to 28 carbon atoms or contains olefin copolymers with unsaturated dicarboxylic acid neutralized with amine, hydroxyamine or alcohols or contains polymers of ethylene with olefin with 3 to 18 carbon atoms aminated, either by grafting nitrogen-containing monomers thereon, or by grafting into the core of the unsaturated acid polymer and then reacting The composition of the lubricating oil additive is to provide, according to the invention, PRL 138 651, an oxidation-stable lubricating oil, of the acid carboxyl groups with an amine, hydroxyamine or alcohol.At the same time, it is emphasized in the patent PRL 138 651 that the amount of oil-soluble copper compound is critical.

If the concentrations are too low, the antioxidant effect will not be sufficient. At too high concentrations, the anti-wear additive can be disrupted and increased wear of the engine components is observed at many high pressure corner points. It is also known that copper compounds in many cases act catalytically in the oxidation of hydrocarbons or are oxidation reaction promoters.

The main objective of the invention is to develop a multi-functional lubricant composition intended for the refining of lubricating oils for spark ignition and compression ignition engines without the need to use oil-soluble copper compounds.

It has surprisingly been found that it is possible to obtain a multi-functional lubricant composition containing detergent-dispersant additives in the form of calcium metal compounds in a mixture with zinc dithiophosphates and polybutene succinimides and / or polybutene succinimides and up to 20.0 parts by mass of polybuten succinic and / or polypropylene succinic and / or polypropylene succinic acid and / or anhydrides. / or polyethylene succinic with a molecular weight of 288 to 2OOO, the calcium carriers being calcium low-basic and / or overbasic alkylaryl sulfonates and / or naphthosulfonates with an alkaline reserve ratio of 8.81 to 25.8, calcium counterion content 8.1 to 8.75 mol / kg, used in an amount of 2.8 to 58.8 parts by mass and / or sulfurized normal and / or overbased calcium alkylphenates, the ratio of the metal content of the alkaline reserve to the metal content of the normal sulfurized calcium phenate is 1.85 to 18.8 and the mole ratio of sulfur to calcium is 8.85 to 1.5 used in an amount of 1.8 to 58.8 parts by mass and the zinc dithiophosphates are derivatives of the 8,8-dithiophosphoric acid esters, used in an amount of 5.8 to 38.8 parts by mass, and the polybutene succinimides and / or polyblthenoblsterimides used in the amount of 3.8 to 58.8 parts by mass, the ratio being the mass of polybuten succinic acid and / or polybutene succinic esters used to the acid and / or anhydrides of polybuten succinic acid and / or polypropylene succinic acid and / or polyethylene succinic acid is up to 7.8, and the mass ratio of calcium to zinc is 8.5 to 5.8, and the mass ratio of zinc to nitrogen the total amount is 8.5 to 5.8, which shows very good washing, dispersing, neutralizing, antioxidant and anti-wear properties, resulting from the synergy of the components used, without the need to use oil-soluble copper compounds in its composition.

The multifunctional lubricant composition according to the invention, contains detergent-dispersant additives in the form of calcium metal compounds in a mixture with zinc dithiaoosOoranaml and polybutene succinimides and / or polybutene succinimides and up to 28.8 parts by mass of the acids and / or anhydrides of polybuten succinic and / or polysuccinic and / or polysuccinic and / or polysuccinic and / or polysuccinic anhydrides having a molecular weight of 288 to 2888, preferably 258 to 1788.

Calcium carriers in the multifunctional lubricant composition according to the invention are low-basic and / or over-basic calcium alkylsulfonates and / or calcium-otosulfonates with an alkaline reserve ratio of 8.81 to 25.8 and a calcium counterion content of 8.1 to 8.75 mol / kg

163 838 used in an amount of 2.0 to 50.0 parts by mass, preferably 5.0 to 30.0 parts by mass and / or sulfurized normal and / or overbased calcium alkylphenates, in which the ratio of the metal content in the alkaline reserve to the metal content in the normal the sulfurized calcium phenate is 1.05 to 10.0 and the molar ratio of sulfur to calcium is 0.05 to 1.5, used in an amount of 1.0 to 50.0 parts by weight, preferably 5.0 to 40.0 parts by weight.

The zinc phosphorithiophosphates contained in the multifunctional lubricant composition according to the invention are derivatives of dithiophosphoric acid 0-diesters obtained from primary alcohols containing from 3 to 12 carbon atoms in the alkoxy chain and / or secondary alcohols containing from 3 to 8 carbon atoms, preferably 3 to 6 carbon atoms in the alkoxy chain, used in an amount of 5.0 to 30.0 parts by mass, preferably 8.0 to 25.0 parts by mass.

The polybutene succinimides and / or polybutene succinimides present in the composition of the multifunctional lubricant composition in the amount of 3.0 to 50.0 parts by mass are monopolysuccinimides and / or bispolybuten succinimides with a total nitrogen content from 0.6 to 5.0% by mass and the ratio of basic nitrogen to total nitrogen between 0.3 and 0.8. The mass ratio of monopolybutene succinimides and / or bispolybuten succinimides and / or polybutene succinimides to polybuten succinic or polypropylene succinic or polyethylenesuccinic acid and / or anhydrides in the multifunctional lubricant composition according to the invention is up to 7.0 by mass ratio, and the mass ratio is from 0.5 to zinc, to 5.0 and the weight ratio of zinc to total nitrogen is 0.5 to 5.0.

It has been found that the multifunctional lubricant composition according to the invention, used in spark ignition and compression ignition engine oils, prevents the deposition of oil oxidation products and products of incomplete fuel combustion on hot surfaces of engine components by forming an adsorbent film with a protective effect. Insoluble products of hydrocarbon oil oxidation, pyrolysis decomposition and mechanical impurities are kept dispersed in the oil thanks to the good solubilizing and peptizing properties of the multifunctional lubricant composition.

The multifunctional lubricant composition according to the invention shows an appropriate reactivity with sulfuric acid, which guarantees the engine oils good ability to neutralize aggressive acids and protects the piston rings against excessive corrosive wear. The appropriately selected composition and characteristics of the components used in the multifunctional lubricant composition according to the invention prevent the formation of a water microemulsion in oil, which in an underheated engine together with solid and liquid impurities, insoluble in oil, can form harmful low-temperature sludges.

The unexpected and unexpected synergistic effects of the ingredients contained in the multifunctional lubricant composition according to the invention make it possible to obtain engine oils containing no oil-soluble copper compounds, which in some cases have the ability to catalyze the oxidation reaction of the hydrocarbon component of the lubricating oil. This multifunctional nature of the lubricant composition, resulting from the composition and synergism of the components used, was found by using the multifunctional lubricant composition according to the invention in engine oils of the C8, CC, SO / CC, SE, CD classes in engine tests.

The invention is further elucidated in the following embodiments illustrating both the composition of the multi-functional lubricant composition and the evaluation of the multi-functional lubricant composition in engine oils, preventing the formation and accumulation of carbon deposits, varnishes and high-temperature sludge on the hot surfaces of engine components, preventing corrosive wear of the piston rings, mechanical wear of the system decomposition, oxidation and thickening of engine oil and many other disadvantages, therefore, cannot be considered as limiting the invention as they are illustrative in nature.

P r z k ł a d I. 30 g of low-basic calcium alkylaryl sulfate with an alkaline reserve factor of 0.5 and a calcium counterion content of 0.5 mol / kg of detergent, 50 g of overbased sulfurized calcium phenolam, in which the ratio of calcium in the alkaline reserve to the content of the detergent, are introduced into a mixer equipped with a stirrer and heating. of calcium in normal sulfurized calcium phenate is 6.6 and the molar ratio of sulfur to calcium is 0.12, 40 g of zinc dithiophosphate with a zinc content of 8.2H by weight obtained from primary alcohol, 30 g of monopolybutene succinimide with a total

163 838 nitrogen content of 3.5% by mass, with the ratio of basic nitrogen to total nitrogen being 0.5, 40 g of bispolysuccinimide with a total nitrogen content of 1.8% by mass, with the ratio of basic nitrogen to total nitrogen being 0.4, and 10 g of polybuten succinic acid anhydride and mixed for 60 minutes at 60 to 70 ° C to obtain a multi-functional lubricant composition with the following characteristics:

- total base number, mg KOH / g 115

- calcium content, * by weight 4.2

- zinc content,% by mass 1 ,,

- nitrogen content,% by mass 0.85

- sulfur content, * 3.8 by weight.

Example II. In a mixer provided with an agitator and heating, 360 g of overbased sulfurized calcium phenate are introduced, in which the ratio of calcium in the alkaline reserve to that of normal sulfated calcium phenate is 6.6 and the molar ratio of sulfur to calcium is 0.12, 120 g of dithiophosphate zinc with a zinc content of 10.5% by weight obtained on mixed primary and secondary alcohols isopropyl, isobutyl, isooctyl, 250 g of monopolybuten succinimide with a total nitrogen content of 2.1% by weight, with the ratio of basic nitrogen to total nitrogen being 0.40, 200 g of bispolybuten succinimide with a total nitrogen content of 1.4% by mass and a ratio of basic nitrogen to total nitrogen of 0.40 and 70 g of polybuten succinic acid anhydride and mixed for 60 minutes at 60 to 70C to obtain a multi-functional lubricant composition with the following characteristics:

- total base number, mg KOH / g 155

- calcium content,% maa 5,0

- zinc content,% nma 132

- aaotu content,% rassowy 0, 8

- sulfur content, mesic% 2.70.

Example III. 400 g of overbased calcium alkylarylsulfonate with an alkaline reserve ratio of 4.8 and a calcium counterion content of 0.27 mol / kg of detergent, 400 g of overbased sulfurized calcium phenate, in which the ratio of calcium in the alkaline reserve to the content of the detergent are introduced into a mixer provided with an agitator and heating. of calcium in normal sulfurized calcium phenate is 6.6 and the molar ratio of sulfur to calcium is 0.12, 400 g of zinc dithiophosphate with a zinc content of 8.2% by mass obtained from primary alcohol, 300 g of aonopolybutene sucroseaad with a total nitrogen content of 4% by mass, with the ratio of basic nitrogen to total nitrogen is 0.5, 400 g of balpolabutenoburltnoaad with a total nitrogen content of 1.8% by mass, with the ratio of basic nitrogen and total nitrogen being 0.43, 100 g of polybuten succinic anhydride and mixing for 60 minutes at a temperature of 60 - / 0 ° C, obtaining a multifunctional composition of the following character acteristics:

- total base number, mg KOH / g 127

- calcium content, * mass 4.0

- zinc content, * by weight 1.7

- nitrogen content, * 0087 by mass

- sulfur content, * by mass 43

Example IV. Class CD SAE 15W / 40 engine oil was prepared by mixing 46.9 mass parts of selectively refined, dewaxed and hydrated crude oil with a kinematic viscosity of 5.2 mm / s at 100 ° C in a mixer at the temperature of 8O ° C, 43 0 parts by mass of a selectively refined, dewaxed and hydrotreated crude oil fraction with a kinematic viscosity of 11.1 mm / s at 100 ° C, 1.1 parts by mass of a viscous additive of hydrogenated styrene-butadiene copolymer, 0.004 parts by mass of silicone antifoam additive, 8, 5 parts by mass of the multifunctional composition as in Example 1 and 0.5 parts by mass of the calcined calcium alkylarylsulfonate additive with an alkaline carbonate reserve having an alkaline reserve factor of 16.2 and a calcium excess content of 0.15. The engine oil obtained in this way had a kinematic viscosity of 14.2 mm / s at a temperature of 100 ° C, a viscosity index of 133 and a total number of

163,838 to 11.5 mg KOH / g. The operational properties of the obtained oil were examined in engine tests). Oil resistance to oxidation and corrosive effects were tested in a Petter W-1 engine, cleaning properties were tested in a supercharged four-stroke Petter AVB engine.

The test results are presented in Table 1.

Table 1

Subject of the assessment Oil requirement Superol CD SAE 15W / 4O according to ZN-88 / MPChiL / NF-185 Test oil 1 2 3 Resistance to oxidation and corrosion in a Petter W-l carbureted engine - degree of sealing of the outer surface of the piston, points, not less than 9.5 10.0 - degree of contamination of the ring channels channels channels scraper clear clear - degree of sealing or jamming rings rings sealing rings free free - contamination of the inner surface of the piston, % of the surface covered with brown varnish, not more than 5 100% pure - mass loss of connecting rod shells after the test, mg, not more than 25 14.0 - increase in the kinematic viscosity of the oil at 4O “C after 36 hours. research,%, me more than 50 3.2 Cleaning properties test in a supercharged four-stroke Petter AV-B engine - degree of immobilization of sealing rings, points, not less than 10.0 10.0 - degree of contamination of the scraper ring channels, points), not less than 10.0 10.0 - degree of contamination of the piston surface x 10: 7, points, not less than 80 85.5

Example 5 SO SAE 2OW / 4O class motor oil was prepared by mixing 49.2 mass parts of a selectively refined, dewaxed and hydrotreated crude oil fraction at a temperature of 8O ° C in a mixer with a kinematic viscosity of 5.2 mm / s at a temperature of 100 ° C, 44.7 parts by mass of a selectively refined, dewaxed and hydrotreated crude oil fraction with a viscosity of 11.1 mm / s at 100 ° C, 1.1 parts by mass of the viscosity additive of hydrogenated styrene-butadiene copolymer, 0.004 parts by mass of silicone antifoam additive and 5 parts bulk multi-functional composition as in Example II.

The engine oil thus obtained had a kinematic viscosity of 14.4 mm / s at 100 ° C, a viscosity index of 133 and a total base number of 7.7 mg KOH / g. The performance of the obtained oil was tested in engine tests. Oil resistance to oxidation and corrosion was tested in a Petter W-1 engine, cleaning properties were tested in a supercharged four-stroke Petter AV8 engine.

The test results are given in Table 2.

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Table 2

Subject of the assessment Requirement for Selektol SO oil SAE 2OW / 4O Test oil 1 2 3 Resistance to oxidation and corrosion in a Petter W-l carbureted engine - degree of sealing of the outer surface of the piston skirt, points, not less than 9.8 18.8 the degree of contamination of the inner surface of the piston skirt, \ the surface covered with light brown varnish, not more than 18 188% pure - the degree of contamination of the ring channels channels channels scraper clear clear - degree of seizure or jamming rings rings sealing rings free free - mass loss of connecting rod shells after the test, mg, not more than 25 16.1 increase in the kinematic viscosity of the oil at 4O ° C after 36 hours. research, H, no more than 48 8.4 Washing properties - test in a supercharged four-stroke Petter AV-3 engine - degree of immobilization of the rings sealing points, not less than 18.8 18.8 - degree of contamination of the scraper ring channels, points, not less than 18.8 18.8 the degree of contamination of the surface of the piston x 18: 7, points, not less than 68 74.8

Example VI. Class CD SAE 15W / 4ϋ motor oil was prepared by mixing 47.5 mass parts of the selectively refined, dewaxed and hydrotreated crude oil with a kinematic viscosity of 5.2 mm / s at the temperature of 18C) 'C, 43.4 parts by mass of selectively refined. of a dewaxed and hydroOirated fraction of crude oil with a kinematic viscosity of 11.1 m "/ tonne at a temperature of 188 ° C, 1.1 parts by mass of the viscosity additive of a hydrogenated styrene-butadiene copolymer, 8.884 parts by mass of a silicone anti-pie additive ^^^^ ·.? , 6 parts by mass of the multifunctional composition as in Example II. The engine oil obtained in this way had a kinematic viscosity

14.2 mm / s at 188 ° C, a viscosity index of 133 and a total base number of 12.5 mg KOH / g. Functional properties of the obtained baaano oil in engine tent. The resistance of oil to oxidation and corrosion was tested in the Petter W-1 engine, cleaning properties in a supercharged four-stroke Petter AV8 engine.

The test results are given in Table 3.

Table 3

Subject of the assessment Oil requirements Superol CD SAE 15W / 4O according to ZN-88 / MPChiL / NF-185 Test oil 1 2 3 Resistance to oxidation and corrosion in a Petter W-1 carburetor engine - degree of sealing of the outer surface of the piston skirt, points, not less than 9.5 18.8

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Table 3 continued

1 2 3 - degree of contamination of the ring channels channels channels scraper clear clear - degree of sealing or jamming rings rings sealing rings free free - contamination of the inner surface of the piston skirt, S surface covered with brown varnish, not more than 5 100H clean - mass loss of connecting rod shells after the test, mg, not more than 25 12.0 - increase in the kinematic viscosity of the oil at 4O'C after 36 hours research, %, no more than 50 7.4 Washing properties - test in a supercharged four-stroke Petter AV-B engine - degree of immobilization of the rings sealing points », not less than 10.0 10.0 - degree of contamination of the scraper ring channels, points, not less than Z 10.0 10.0 - degree of contamination of the piston surface x 10: 7, points, not less than 80 86.8

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Claims (1)

Patent claim Multifunctional lubricant composition containing detergent-dispersant additives, characterized in that it contains detergent-dispersing additives in the form of calcium metal compounds in a mixture with zinc dithiophosphates and polybutene succinimides and / or polybutene succinimides and up to 20.0 parts by mass of acids and / or anhydrides of the acid and / or anhydrides of polybuten succinic acid and polybuten succinimides. / or polypropylene succinic and / or polyethylene succinic with a molecular weight of 200 to 2,000, preferably 250 to 1,700, the calcium carriers being low-basic and / or overbased calcium alkylarylsulfonates and / or calcium naphthosulfonates with an alkaline reserve factor of 0.01 to 25.0 and a counter-ion content parts of calcium 0.1 to 0.75 mol / kg used in an amount of 2.0 to 50.0 parts by mass, preferably 5.0 to 30.0 parts by mass, and / or sulfurized normal and / or overbased calcium alkylphenates, the ratio of which is the metal in reserve to the metal content in normal sulfurized calcium phenate is 1.05 to 10 0 and the molar ratio of sulfur to calcium is 0.05 to 1.5, and are used in an amount of 1.0 to 50.0 parts by mass, preferably 5.0 to 40.0 parts by mass, and the zinc dithiophosphates are derivatives of 0, O-dithiophosphoric acid esters, obtained from primary alcohols containing from 3 to 12 carbon atoms in the alkoxy chain and / or secondary alcohols containing from 3 to 8 carbon atoms, preferably 3 to 6 carbon atoms in the alkoxy chain, used in an amount of 5, 0 to 30.0 parts by mass, preferably 8.0 to 25.0 parts by mass, and the polybutene succinimides and / or polybutene succinimides are used in an amount of 3.0 to 50.0 parts by mass, the polybutene succinimides being monopolysuccinimides and / or bispolybutenuccinimides with nitrogen content a total of 0.6 to 5.0% by mass and a ratio of basic nitrogen to total nitrogen of 0.3 to 0.8, the mass ratio of monopolybutene succinimides and / or bispolybuten succinimides and / or polybutene succinimides used d o the acid and / or anhydrides of polypropylene succinic acid and / or polypropylene succinic acid and / or polyethylene succinic acid in the multifunctional lubricant composition is up to 7.0, and the weight ratio of calcium to zinc in the formulated composition is from 0.5 to 5.0, and the weight ratio of zinc to total nitrogen is 0.5 to 5.0.