RU2461609C1 - Engine oil additive batch and oil containing said batch - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: additive batch contains alkaline calcium alkylsalicylate, a solution in oil of a carbonated product of reaction of alkylbenzene sulphonic acid with calcium hydroxide, having base number less than 390 mg KOH/g, ash-free nitrogen-containing dispersant, a block copolymer of ethylene and propylene oxides based on ethylene diamine, modified dialkyl dithiophosphate, phenyl-α-naphthylamine, octylated diphenylamine - the balance. The modified dialkyl dithiophosphate is a 50% solution of a mixture of an amine salt and an amide of dialkyl dithiophosphoric acid in oil with tetra(2-ethylhexyl)thiuram disulphide, taken in weight ratio to the 50% solution ranging from 1:3 to 3:1 with atomic ratio of sulphur to phosphorus in the range of 3.25-11.5. The engine oil contains a mineral base, a batch of additives, an anti-foam additive and a polymethacrylate depressant with molecular weight from 2800 to 3200.

EFFECT: improved antioxidation, anticorrosion and deactivation properties while maintaining the level of antiwear and antifriction properties with reduction of sulphated ash and content of sulphur, phosphorus, which increases the oil-change period in an engine and time between repairs.

3 cl, 13 tbl

Description

The invention relates to the field of petrochemistry, in particular to additive packages for motor oils, and can be used in the manufacture of oils for serial and promising highly accelerated gasoline engines and turbocharged diesel engines operating in cold and arctic climatic zones.

There is an increasing need for oils that ensure reliable start-up of an unheated engine at temperatures from minus 45 ° C and lower and have high detergent and antioxidant properties at steady state engine operating conditions, characteristic for oils of viscosity class 3z / 12 and not lower than group “D” in terms of operational properties [A.A. Gureev, I.G. Fuchs, V.L. Lashkhi. Chemotology. - M .: Chemistry, 1986, - p.261].

The level of such properties is provided by metal-containing ash detergents and phosphorus-, zinc-containing antioxidants included in the oil additive package, as well as low-curing components of the oil base, which provide a gentle viscosity-temperature characteristic of the oil under appropriate temperature conditions.

It is known that phosphorus atoms have a toxic effect on catalytic exhaust gas afterburners. The increased sulfur content in the oil contributes to the pollution of the exhaust gas recirculation system, which negatively affects the environment. Metal atoms contained in additive packages, increasing the sulfate ash content of oils in general, contribute to the formation of chemical films on the surface of metal parts, which impedes the effective operation of particulate filters [Spikes N. The history and mechanisms of ZDDP // ZTribology Letters, vol.17, no. 3, 2004, p. 469-489].

Among the oils common in domestic practice and providing a low-temperature start of an unheated engine at an ambient temperature of minus 45 ° C, is the universal multigrade engine oil M-4z / 14D [GOST RV 50920].

The above leads to an intensive search for solutions aimed at reducing the composition of the additive package of compounds that adversely affect the environment, on the one hand, and at the same time improving the antioxidant, deactivating properties and viscosity-temperature characteristics of oils, on the other.

The authors were faced with the task of developing such a package of additives for motor oils and oil containing it, which would improve the antioxidant, deactivating properties and viscosity-temperature characteristics of oils under conditions of their high temperature oxidation and low (up to minus 60 ° C) application temperatures without reducing antiwear, antifriction and anticorrosive properties of oils and with a simultaneous decrease in the content of sulfur, phosphorus and sulfate ash.

When analyzing patent and scientific and technical information, technical solutions were identified that partially solved the task.

Known package containing additives in their ratio, wt.%:

di (alkyl) - and / or di (alkylaryl) zinc dithiophosphate 15-30 alkyl (C ₁₂ -C ₂₄ ) calcium salicylate 15-40 succinimide additive or high molecular weight (m.m. 1200-5000) Mannich base 20-35 mid-alkaline sulfonate reaction product calcium with alkyl (C ₁₂ -C ₂₄ ) salicylic acid up to 100 alkylbenzene fraction boiling in the range of 300-600 ° C up to 1

[RF patent No. 2235120, C10M 159/24, dated 04/27/2004].

According to this patent, petroleum and / or synthetic-based motor oil contains the above-described additive package in an amount of 4-10 wt.% And depressant and / or thickening and antifoam additives.

Also known additive package containing, wt.%:

alkyl (C ₁₂ -C ₂₄ ) calcium salicylate 10-40 highly alkaline magnesium sulfonate 5-15 the product of the interaction of neutral and highly alkaline calcium sulfonates with alkyl (C ₁₂ -C ₂₄ ) salicylic acid up to 100, alkylbenzene fraction boiling in the range of 300-600 ° C up to 1

[RF patent No. 22585899, C10M 159/24, dated 10.02.2005].

According to this patent, oil on an oil and / or synthetic basis contains the additive package described above in an amount of 3-15 wt.%, Polymethylsiloxane 0.003-0.05 wt.% And may additionally contain, wt.%:

zinc dithiophosphate 0.4-2.5 and / or ashless nitrogen-containing dispersant 1.0-3.0 depressant additive 0.1-3.0 and / or thickening additive 1.0-3.0

A motor oil is known containing a low-viscosity distillate oil with a kinematic viscosity of 2-4 mm ² / s at 100 ° C in a mixture with a residual component with a kinematic viscosity of 15-20 mm ² / s at the same temperature, alkaline calcium alkyl salicylate, alkaline calcium sulfonate, brand D polymethacrylate, polymethylsiloxane, a hydrogenated block copolymer of butadiene with styrene, a high molecular weight Mannich base, a concentrate of a mixture of mono- and bis-alkyl succinimides in oil, a modified phenol alkylation product with chloroparaffins, an oxide block copolymer ethylene and propylene based on ethyldiamine and alcohol zinc dithiophosphate in the following ratio of components, wt.%:

alkaline calcium alkyl salicylate 2.9-4.9 alkaline calcium sulfonate 0.5-1.5 D-grade polymethacrylate 1.5-2.5 polymethylsiloxane 0.003-0.005 hydrogenated butadiene block copolymer with styrene 1.75-2.25 high molecular weight Mannich base 2.0-3.0 concentrate of a mixture of mono- and bisalkylsuccinimides in oil 2.5-3.5 modified phenol alkylation product chloroparaffins 1.4-2.2 block copolymer of ethylene oxide and propylene based ethyldiamine 0.015-0.025 alcohol zinc dithiophosphate 0.6-1.6 kinematic viscosity residual component 15-20 mm ² / s at 100 ° C 6.0-5.4 low viscosity distillate oil with kinematic viscosity 2-4 mm ² / s at 100 ° C rest

[RF patent No. 2232796, C10M 161/00, dated July 20, 2004].

The known composition of a lubricating oil containing, wt.%:

sulfur 0.01-0.3 phosphorus 0.01-0.1 salt of metal and organic acid forming 0.1-1.0% sulfate ash 0.2-7.0 sulfur mineral base oil no more than 0.1% up to 100

an ashless dispersant of the type alkenized or alkylated succinimide used in an amount corresponding to 0.01-3.0% nitrogen,

a metal-containing detergent such as an alkaline or alkaline earth salt of alkyl salicylic acid with a basic number of 10-350 mg KOH / g and an alkaline earth metal salt of an alkyl phenolic derivative with a Mannich base structure, used in an amount corresponding to 0.1-1.0 ash; zinc dialkyldithiophosphate (0.01-0.1 based on phosphorus); phenolic and / or amine-based oxidation inhibitor [US Patent No. 6,569,818, C10M 141/02, 05/27/2003].

The disadvantages of these compositions include the increased content of phosphorus, sulfur and sulfate ash in oil, which negatively affects the operation of afterburning catalysts, particulate filters and exhaust gas recirculation systems in internal combustion engines and adversely affects the environment, as well as the absence of deactivating properties and the inability to provide low-temperature engine start at ambient temperature up to minus 60 ° C.

The closest in technical essence to the invention and taken as a prototype is a package of additives for motor oils for highly accelerated diesel engines and mineral oil-based motor oil containing 9-11 wt.% And anti-foam additive in an amount of 0.003-0.005 wt.%. Moreover, the additive package contains, wt.%:

alkaline calcium alkyl salicylate 39.0-52.0 alkaline calcium sulfonate 9.0-23.0 modified zinc dialkyldithiophosphate 13.0-16.0 ethylene diamine-based block copolymer of ethylene and propylene oxides 0.9-1.1 phenyl-α-naphthylamine 2.0-3.5 ashless nitrogen-containing dispersant up to 100

[RF patent No. 2223303, C10M 167/00, dated 02/10/2004].

The disadvantage of the prototype is the high content of phosphorus, sulfur and sulfate ash due to the increased amount of the first three additives in the package, which adversely affects the environment; the inability to ensure low-temperature engine start at ambient temperature up to minus 60 ° C due to the high (minus 15 ° C) pour point of the oil, the absence of deactivating properties.

The technical result of the invention is the expansion of the temperature range of the use of oils and an increase in engine life by increasing the antioxidant, deactivating and anticorrosive properties of engine oil under conditions of high-temperature catalytic oxidation with reduced sulfur, phosphorus and sulfate ash content in the oil without reducing the antiwear and antifriction properties of the oil, and improving the viscosity -temperature characteristics of the oil at low ambient temperatures.

The specified technical result is achieved by the fact that in the known package of additives to motor oils containing alkaline calcium alkyl salicylate, alkaline calcium sulfonate, ashless nitrogen-containing dispersant, a block copolymer of ethylene and propylene oxides based on ethylene diamine, modified dialkyl dithiophosphate and phenyl-α-naphthylamine, according to the invention as an alkaline calcium sulfonate, the packet contains a carbonated product of the interaction of alkylbenzenesulfonic acid with calcium hydroxide dissolved in oil, having a gap a specific number of not less than 390 mg KOH / g, as a modified dialkyl dithiophosphate - 50% solution of a mixture of amine salt and amide of dialkyl dithiophosphoric acid in oil from tetra (2-ethylhexyl) thiuram disulfide, taken in the ratio to a 50% solution of the mixture from 1 : 3 to 3: 1 by mass fraction with an atomic ratio of sulfur to phosphorus in the range of 3.25-11.55, and additionally contains octylated diphenylamine in the following ratio of components, wt.%:

alkaline calcium alkyl salicylate 24.94-34.94 carbonated product dissolved in oil interactions of alkylbenzenesulfonic acid with hydroxide calcium having an alkaline number of not less than 390 mg KOH / g 12.97-16.97 ashless nitrogen-containing dispersant 17.96-21.96 block copolymer of ethylene oxide and propylene ethylene diamine based 0.17-0.23 50% solution of a mixture of amine salt and amide dialkyldithiophosphoric acid in oil with tetra- (2-ethylhexyl) thiuram disulfide, taken in the ratio to a 50% solution of the mixture from 1: 3 to 3: 1 by mass fraction when the atomic ratio of sulfur to phosphorus in range 3.25-11.5 8.98-10.98 phenyl-α-naphthylamine 8.98-10.98 octylated diphenylamine up to 100

A mineral-based motor oil containing an antifoam polymethylsiloxane additive according to the invention contains said additive package and additionally a depressant polymethacrylate additive with a molecular weight of from 2800 to 3200 in a ratio, wt.%:

additive package 8,695-11,345 antifoam polymethylsiloxane additive 0.003-0.005 depressant polymethacrylate additive with molecular weight from 2800 to 3200 0.1-1.0

The motor oil as a mineral base according to the invention contains a distillate oil or a mixture thereof with selective residual oil having a kinematic viscosity of 51 to 75 mm ² / s at 40 ° C and a pour point of not higher than minus 15 ° C, an oil obtained from low-sulfur paraffin oils with deep selective refining and dewaxing, with kinematic viscosity from 16 to 22 mm ² / s at 40 ° C and pour point no higher than minus 55 ° C, poly-α-olefin oil with kinematic viscosity from 3.5 to 4.5 mm ² / s at 100 ° C and the temperature SAG yvaniya not higher than minus 60 ° C, an ester formed by the reaction of sebacic acid and 2-ethylhexanol, with a kinematic viscosity of not less than 3.2 mm ² / s at 100 ° C and a pour point of not higher than minus 55 ° C and polyvinyl-n -butyl ether with a kinematic viscosity of 3200-9000 mm ² / s at 100 ° C and a molecular weight of from 15000 to 25000 in the following ratio of components, wt.%:

distillate oil or its mixture with residual kinematic selective oil viscosity 51 to 75 mm ² / s at 40 ° C and temperature solidification no higher than minus 15 ° C 10.0-20.0 oil obtained from low-sulfur paraffin oil deep selective cleaning and dewaxing, with kinematic viscosity 16 to 22 mm ² / s at 40 ° C and temperature solidification no higher than minus 55 ° C 40.0-50.0 kinematic viscosity poly-α-olefin oil from 3.5 to 4.5 mm ² / s at 100 ° C and pour point no higher than minus 60 ° С 25.0-35.0 ester obtained by reaction sebacic acid and 2-ethylhexanol, with kinematic viscosity of at least 3.2 mm ² / s at 100 ° C and temperature solidification no higher than minus 55 ° C 5.0-15.0 kinematic polyvinyl n-butyl ether viscosity 3200-9000 mm ² / s at 100 ° С and molecular weighing from 15,000 to 25,000 up to 100

The following is a description of the components that make up the additive package and engine oil base.

Calcium alkaline alkyl salicylate is a detergent additive produced by industry under the trademarks Detersol-140, Detersol-300 according to TU 38.101 290-88, TU 38.301-13-079-94. It is a colloidal solution of the calcium salt of alkylsalicylic acid with a molecular weight of 750-820 and finely divided calcium carbonate in mineral oil. The total alkalinity of the additive is not less than 155 mg KOH / g, the mass fraction of sulfate ash is not more than 24.3%. The practical introduction to the composition of the additive package for motor oils is from 20 to 45%.

Alkaline calcium sulfonate is a detergent additive produced by industry under the trademarks K-313 (TU 0257-016-40065462-01), K-312 (TU 0257-114-4006 5452-2000, S-300 (TU 38.101444-76), C-150 (TU 38.101 685-84) .Is a colloidal solution in oil of the carbonated product of the interaction of alkylbenzenesulfonic acid with calcium hydroxide, having an alkaline number of at least 390 mg KOH / g.

Ash-free nitrogen-containing dispersant is a dispersing additive developed by industry under the trademarks S-5AB (TU 38. 401-58-130-95). K-51 (TU 38.401-58383-2007), S-5A (TU 38.101 146-77). It is an oily solution of boron-modified alkyl succinimide.

Ethylene diamine-based block copolymer of ethylene and propylene oxides is an antioxidant and demulsifying additive produced by the industry under the trademark Diproxamine 157 according to TU 6-14-614-76. It is a colloidal solution with a mass fraction of nitrogen - 0.5-0.55% and a mass fraction of ash - not more than 0.5%.

50% solution of a mixture of amine salt and dialkyl dithiophosphoric acid amide in oil - antioxidant and antiwear additive [Chulkov PV, Chulkov IP A Brief Dictionary of Petroleum Products. - M.: Polytechnic, 1997, p.326]. It is produced by industry according to TU 38. 101105-84 under the trademark ADTF. Mass fraction of nitrogen is not less than 0.2%, phosphorus - not less than 3.3%.

Tetra (2-ethylhexyl) thiuramdisulfide (TDS) is an antioxidant produced in accordance with STO 08151164-110-2011. The properties are pronounced in the load range of 315-500 N. TDS is the product of the interaction of di (2-ethylhexyl) amine with carbon disulfide and sodium hydroxide and at 20 ° C it is a liquid containing 20.4 wt.% Sulfur and 4.25 wt.% nitrogen [Shkhiyants I.V., Markova E.I., Voevoda N.V., Sher V.V., Sanin P.I. The study of antioxidants such as metal dialkyl dithiocarbamates // Neftekhimiya, Volume 11, No. 6, 1971, p.919]. The use of TDS is known [S. Kumar, N.N. Roy / Wear, - 1997, - v.209. - p.1-7} as part of a multifunctional composition in conjunction with bis (aryl / alkyl) thiuram disulfide, bis (aryl) xanthate and (aryl / alkyl) dithiocarbamate. The range of the atomic ratio of sulfur to phosphorus is 3.9-4.9.

Phenyl-α-naphthylamine (N-phenyl-1-naphthylamine) is an antioxidant additive manufactured by the industry under the brand name "Neozone A" according to TU 6-14-202-74. It is a solid with melting points 62-63 ° C, boiling 224 ° C at 12 mm Hg, readily soluble in ethanol, diethyl ether, benzene and other hydrocarbon solvents.

Octylated diphenylamine is an antioxidant additive produced by the industry under the trademark DAT in accordance with TU 38.1011215-89. It is a liquid colloidal solution.

Polymethacrylate additive is a depressant produced by industry under the trademarks ПМА "Д" -110, К-110 according to TU 0257-037-40065452-03 and others. The product of polymerization of methacrylic acid esters and a mixture of fatty primary alcohols with a molecular weight of from 2800 to 3200.

Polymethylsiloxane liquid is used to improve the antifoam properties of oils and is produced by industry under the trademark PMS-200A according to OST 6-02-20-79. It is a liquid mixture of linear and cylindrical polymethylsiloxanes with a molecular weight of 2500-3500 and a mass fraction of silicon of 36-39%.

Distillate oil or its mixture with selective selective residual oil is used as a component of the base of industrial and motor oils and is produced by industry under the trademark I-40A according to GOST 20799-88. It has a kinematic viscosity of 51 to 75 mm ² / s at 40 ° C and a pour point of no higher than minus 15 ° C.

The oil obtained from low-sulfur paraffinic oils by deep selective refining and dewaxing, with a kinematic viscosity of 16 to 22 mm ² / s at 40 ° C and a pour point of not higher than minus 55 ° C, is used as a component of the base of hydraulic and motor oils and is produced by industry under AU trademark in accordance with TU 38.301-29-71-94 and TU 38.1011232-89. It is a low-viscosity distillate oil with an acid value of 0.05-0.07 mg KOH / g, sulfate ash - 0.005%, flash point - 165 ° C.

Poly-α-olefin oil with kinematic viscosity from 3.5 to 4.5 mm ² / s at 100 ° C and pour point not higher than minus 60 ° C is used as a component of the base of aviation, transmission, hydraulic and motor oils and is produced by industry under the trademark PAOM-4 according to TU 0253-014-54409843-2007.

The ester obtained by the interaction of sebacic acid and 2-ethylhexanol with a kinematic viscosity of at least 3.2 mm ² / s at 100 ° C and a pour point of no higher than minus 55 ° C is produced under the trademark DOSt according to TU 6-06-11 -88. It is used mainly as a component of the base of gear and motor oils.

Polyvinyl-n-butyl ether is produced under the trademark Syntolux B-20 according to STO 57175009-005-2011 with a kinematic viscosity of 3200-9000 mm ² / s at 100 ° C and a molecular weight of 15,000 to 25,000. It is used as a thickener for base oils.

The authors are not aware of the use of TDS (page 9) in engine oil additive packages in combination with other components. The authors conducted a study of the technical effectiveness of the combination of two components: ADTF and TDS. To determine the optimal concentration of the components in the composition, samples were prepared. The composition of the samples is presented in table 1, and their characteristics according to the content of phosphorus and sulfur are shown in table 2.

Table 1 The composition of the prototype additives Additive Components Sample number and additive component ratio one 2 3 four 5 6 7 Tds 0 0.2 0.25 0.5 0.75 0.8 1,0 ADTF 1,0 0.8 0.75 0.5 0.25 0.2 0

table 2 Characterization of Prototype Additives Components included in the composition Content% Atomic ratio R S S / p Commodity additive DF-11 0.0938 0.1942 2,0703 Sample 1 0.0640 0.1325 2,0703 Sample 2 0.0480 0.1500 3.1250 Sample 3 0.0480 0.1560 3.2500 Sample 4 0,0320 0.1674 5.2312 Sample 5 0.0160 0.1848 11,5500 Sample 6 0.0160 0.1883 11,7687 Sample 7 out 0.2022 -

The ratio of ADTP and TDS in the composition is selected in the range from 1: 3 to 3: 1, giving the highest technical result. The composition is introduced into the bag in an amount of 8.98-10.98 wt.%, Which provides an increase in antioxidant properties while maintaining anti-wear and antifriction properties while reducing the sulfur, phosphorus and sulfate ash content in the oils.

To confirm the claimed ratio of the components in the composition and to identify the effectiveness of their action in the package, the prepared samples (Tables 1, 2) in comparison with the applied antioxidant and antiwear additives DF-11 were tested to evaluate the antioxidant, antiwear and antifriction properties.

Tests of a pilot sample of oil containing 1 wt.% Of the composition (sample No. 4 in Tables 1, 2) in the stated ratios, in comparison with oil (according to the prototype) containing 1 wt.% Of the trademark additive DF-11, were carried out by the motor method IKM-40 (GOST 20457) assessment of antioxidant properties (table 3).

Table 3 Assessment of antioxidant properties of oils Name of indicator Norm according to the method Sample with DF-11 Sample No. 4 from tables 1, 2 Antioxidant properties The increase in kinematic viscosity at 50 ° C during the test,% No more than 50 34 23 Anticorrosion properties The loss of mass of the liner of the lower connecting rod head, mg No more than 25 19 fourteen

The test results showed that the oil sample containing 1 wt.% Additives in the stated proportions (sample No. 4 in Tables 1, 2) is superior to the oil sample containing 1 wt.% Commodity additives DF-11 in antioxidant properties (Table 3 , line 1) and not only preserves the level, but also surpasses it (Table 3, line 2) in terms of anticorrosion properties. Tests of samples to assess anti-wear and antifriction properties (tribological characteristics) were carried out according to GOST 9490. As the test results (table 4) showed, the proposed composition of ADTF and TDS (samples 3-5 in tables 1, 2) in oil provides comparable to zinc dialkyldithiophosphate (DF-11) anti-wear and anti-friction properties, and their performance does not exceed permissible values.

Table 4 The results of the evaluation of the tribological characteristics of the samples The composition of the prototypes of the composition Antiwear properties Antifriction properties The diameter of the wear spot, D _u , mm ^* Coefficient of friction, f (60 min) ^** A mixture of I-20 and I-40 (0.5: 0.5) 0.92 0.154 Same with: 1% DF-11 0.392 0.138 1% of sample 1 0.706 0.145 1% of sample 2 0.462 0.131 1% of sample 3 0.429 0.139 1% sample 4 0.435 0.135 1% sample 5 0.449 0.140 1% sample 6 0.680 0.143 1% of sample 7 0.706 0.145 * No more than 0.45 mm allowed ** No more than 0.140 allowed

As a result of testing prototypes of the proposed composition, it was found that the additive composition consisting of a mixture of TDS and ADTP in a ratio of 0.5: 0.5 with an atomic ratio of sulfur to phosphorus of 5.2312 (sample No. 4) is optimal in composition and level of properties.

The authors have not found the use of such a combination of components in the compositions of the additive package and in the composition of the base of motor oils in the stated proportions, and the claimed composition of the additive package is conventionally called the “CEBAZOL-25-13” package. We conducted a study of the technical effectiveness of the additive package and the oil containing it.

The proposed package of additives to motor oils was prepared by mixing individual additives in a certain sequence under conditions of temperature control and constant mixing throughout the volume at a given temperature until a homogeneous mass is obtained. To justify the quantitative content of the components in the additive package, samples were prepared. The composition of the samples of the additive package are presented in table 5.

The prepared samples of the additive package were tested to assess physico-chemical parameters in accordance with the specified requirements. The test results of the samples are shown in table 6.

Table 5 The composition of the pilot samples of the additive package Additive Package Components The number of additive package and the mass fraction of components in it, wt.% one 2 3 four 5 Alkaline Calcium Alkyl Salicylate 24.93 24.94 29.94 34.94 34.95 The carbonated product of the interaction of alkylbenzenesulfonic acid with calcium hydroxide dissolved in oil, having an alkaline number of at least 390 mg KOH / g 12.96 12.97 14.97 16.97 16.98 Ashless nitrogen-containing dispersant 17.95 17.96 19.96 21.96 21.97 Ethylene diamine-based block copolymer of ethylene and propylene oxides 0.16 0.17 0.20 0.23 0.24 50% solution of a mixture of amine salt and dialkyl dithiophosphoric acid amide in oil with tetra (2-ethylhexyl) thiuram disulfide taken in the ratio to a 50% solution of a 1: 1 mixture in a mass fraction at an atomic ratio of sulfur to phosphorus of 5.23 8.97 8.98 9.98 10.98 10.99 Phenyl-α-naphthylamine 8.97 8.98 9.98 10.98 10.99 Octylated diphenylamine 26.06 26.00 14.97 3.04 3.88

Table 6 Additive package test results The name of indicators Rate for the package ^* Key figure values one 2 3 four 5 Alkaline number, mg KOH / g, not less than 95.0 94.79 95.01 101,99 106.35 106.48 Mass fraction of sulfur,%, no more than 0,3 0.21 0.23 0.26 0.28 0.31 Sulphated ash,%, no more than 10.0 8.5 9.8 9.9 10.0 12.5 Mass fraction of phosphorus,%, no more than 0,05 0,040 0,043 0,045 0,048 0,053 * Standards are based on ACEA C4-08

From the data of table 6 shows that the optimal number of additives in the package that meet the requirements, are samples of additive packages No. 2-4.

Additive packages No. 2-4 in the amount of 8.695-11.345 wt.% Were introduced into the base oil M-20 (prototype).

Oil samples were prepared with additive packages in the claimed ratios, provided that the oil contained not only different packages (packages No. 2-4), but also in different concentrations (from 8.695 to 11.345%, as well as outside the stated range): sample 1 (8.695% of package No. 2); sample 2 (8.695% of package No. 3); sample 3 (8.695% of package No. 4); sample 4 (10% of package No. 2); sample 5 (10% of package No. 3); sample 6 (10% of package No. 4); sample 7 (11.345% of package No. 2); sample 8 (11.345% of package No. 3); sample 9 (11.345% of package No. 4); sample 10 (8.694% of package No. 2); sample 11 (8.694% of package No. 3); sample 12 (8.694% of package No. 4); sample 13 (11.346% of package No. 2); sample 14 (11.346% of package No. 3); sample 15 (11.346% of package No. 4).

The main physico-chemical properties of oils containing additive packages in concentrations from 8.695 to 11.345% are presented in table 7.

From the data of table 7 it is seen that the optimal composition of the additive packages in oil that meet the requirements are oil samples 4-6 with 10 wt.% Additive package No. 2-4. Samples 1-3 and 7-15 are inferior in properties to samples 4-6. The most optimal physico-chemical properties is a prototype oil with 10 wt.% Additive package No. 3.

To identify the effectiveness of the claimed ratio of the components of the additive package in oil, an oil sample with 10 wt.% Additive package No. 3 in comparison with oil containing 10 wt.% Of the known (prototype) product package was tested to evaluate antioxidant, anticorrosive, deactivating, antiwear and antifriction properties.

The antioxidant and anticorrosive properties of the oil with the additive package were evaluated on an IKM-40 installation according to the method of GOST 20457. Table 8 presents the results of the assessment of the antioxidant and anticorrosive properties of the oil.

Table 7 Basic physicochemical properties of oil containing additive package in various concentrations The name of indicators Oil sample numbers of additive packages one 2 3 four 5 6 7 8 9 10 eleven 12 13 fourteen fifteen Alkaline ¹ number, mg KOH / g 8.60 8.90 9.25 9.50 10.19 10.63 10.75 10.90 11.34 9.10 9.48 9.56 10.40 10.65 10.98 Mass fraction,%, sulfur ² 0.18 0.20 0.21 0.22 0.26 0.30 0.32 0.34 0.37 0.21 0.23 0.25 0.38 0.39 0.42 Mass fraction,%, phosphorus ³ 0,033 0,036 0,038 0,040 0,045 0,050 0.056 0,062 0,067 0,030 0,032 0,033 0.058 0,066 0,071 Mass fraction,%, calcium ⁴ 0.28 0.30 0.31 0.32 0.34 0.36 0.38 0.40 0.41 0.25 0.27 0.30 0.42 0.45 0.47 Sulphated ash ⁵ % 0.92 0.93 0.94 0.98 0.99 1.00 1.05 1.10 1.18 0.90 0.98 1.06 1.25 1.35 1.45 ¹ At least 9.5 mg KOH / g allowed ² No more than 0.3% is allowed ³ No more than 0.05% is allowed. ⁴ Allowed within 0.28-0.36% 5 No more than 1.0 allowed

Table 8 Assessment results of antioxidant and anticorrosive properties of oils Name of indicator Norm according to the method A sample with a package of the prototype (RF patent No. 2223303, C10M 167/00, from 10.02.2004) Oil with additive package No. 3 (claimed) Antioxidant properties The increase in kinematic viscosity at 50 ° C during the test,% No more than 50 16,0 13.9 Anticorrosion properties The loss of mass of the liner of the lower connecting rod head, mg No more than 25 19.0 14.0

The test results showed that the oil sample containing 10 wt.% Additive package in the declared ratios in antioxidant properties (Table 8, line 1) is superior to the oil sample containing 10 wt.% Of the known commodity additive package, and not only maintains the level, but and surpasses it (Table 8, line 2) in anti-corrosion properties.

Deactivating properties with respect to copper-containing compounds were determined on the installation VO-4 according to the method of STO 08151164-012-2009. Table 9 presents the results of the evaluation of the deactivating properties of the oil.

Table 9 The results of the evaluation of the deactivating properties of oils Sample Name Oxidation time, h Kinematic viscosity at 100 ° C, mm ² / s Acid number, mg KOH / g Oxidation without catalyst A sample of oil M-20 containing 10 wt.% The inventive additive package No. 3 0 20.12 0,07 5,0 20.78 0.42 10.0 21.04 0.93 15.0 21.78 1,64 20,0 22.25 2.09 A sample of oil M-20 containing 10 wt.% The additive package of the prototype (RF patent No. 2223303, C10M 167/00, from 10.02.2004) 0 20,20 0 5,0 21.48 0.49 10.0 21,99 1.66 15.0 22.37 2.60 20,0 22.90 3.18 Oxidation with a catalyst - copper oxide A sample of oil M-20 containing 10 wt.% The inventive additive package No. 3 0 20.12 0,07 5,0 20.98 0.55 10.0 21.48 1.34 15.0 22.19 2.07 20,0 22.97 2.46 A sample of oil M-20 containing 10 wt.% The additive package of the prototype (RF patent No. 2223303, C10M 167/00, from 10.02.2004) 0 20,20 0 5,0 21.18 1.12 10.0 21.75 1.99 15.0 22.44 2.97 20,0 23.33 3.68 Oxidation with a Copper Naphthenate Promoter A sample of oil M-20 containing 10 wt.% The inventive additive package No. 3 0 20.12 0,07 5,0 21.08 0.71 10.0 21.76 1.55 15.0 22.43 2,34 20,0 23.05 2.94 A sample of oil M-20 containing 10 wt.% The additive package of the prototype (RF patent No. 2223303, C10M 167/00, from 10.02.2004) 0 20,20 0 5,0 21.38 1.36 10.0 22.66 2.09 15.0 22.98 3.18 20,0 23.70 3.88

From the data presented in table 9, it is seen that the best deactivating properties with respect to non-ferrous metal - copper, characterized by a lower value of the increase in viscosity and acid number (columns 3.4 of table 9), showed a sample of oil with 10% of the proposed additive package No. 3 . An oil sample containing 10 wt.% Of the known product package of additives (according to the prototype) is inferior to the claimed sample.

Tests of packages to assess anti-wear and antifriction properties were performed according to GOST 9490 and method MI 13.165-2002 (table 10).

Table 10 The results of the evaluation of the tribological characteristics of the packages The composition of the experienced Antiwear properties Antifriction properties composition samples The diameter of the wear spot, D _u , mm ^* Coefficient of friction, f ^** A sample of oil M-20 containing 10 wt.% The inventive additive package No. 3 0.435 0.135 A sample of oil M-20 containing 10 wt.% The additive package of the prototype (RF patent No. 2223303, C10M 167/00, from 10.02.2004) 0.429 0.131 * No more than 0.45 mm is allowed. ** Allowed not more than 0.140 in 60 minutes

As shown by the test results, the inventive additive package in oil improves anti-wear and anti-friction properties in comparison with the product package and does not exceed acceptable values.

To determine the optimal ratio of the components of the base oil in the claimed range with an assessment of its effectiveness according to the main physicochemical properties, samples were prepared (table 11).

Table 11 The composition of the prototype oil base Base Oil Components The number of the sample base oil and the mass fraction of components in it,% one 2 3 four 5 Distillate oil or its mixture with selective selective residual oil having a kinematic viscosity of 51 to 75 mm ² / s at 40 ° C and pour point not higher than minus 15 ° C 9.9 10.0 15.0 20,0 20.1 Oil obtained from low-sulfur paraffin oils by deep selective refining and dewaxing, with kinematic viscosity from 16 to 22 mm ² / s at 40 ° C and pour point not higher than minus 55 ° C 39.9 40 45 fifty 50.1 Poly-α-olefin oil with kinematic viscosity from 3.5 - to 4.5 mm ² / s at 100 ° C and pour point not higher than minus 60 ° C 24.9 25.0 30,0 35.0 35.1 The ester obtained by the interaction of sebacic acid and 2-ethylhexanol with a kinematic viscosity of at least 3.2 mm ² / s at 100 ° C and pour point not higher than minus 55 ° C 4.9 5,0 10.0 15.0 15.1 Polyvinyl n-butyl ether with a kinematic viscosity of 3200-9000 mm ² / s at 100 ° C and a molecular weight of from 15,000 to 25,000 Up to 100%

Samples of the base oil have been tested to assess the basic physical and chemical properties, and the test results are presented in table 12.

Table 12 Test results of prototypes of the base oil The name of indicators Norm for oil Oil base sample number (from table 9) one 2 3 four 5 Indicator values Kinematic viscosity at 100 ° C, mm ² / s 10.5-11.5 10.3 10.5 11.0 11.5 11.8 Pour point, ° C no higher than minus 60 minus 58 minus 60 minus 61 minus 60 minus 56 Ash content,% no more than 0,005 0.003 0.004 0.004 0.005 0.008 Flash point determined in open crucible, ° C not lower than 190 205 200 195 190 185

From the data in table 12 shows that the optimal composition and ratio of components in the base of the oil that meet the specified requirements are samples No. 2-4. Samples No. 1 and No. 5 are inferior to samples No. 2-4. The most optimal characteristics is a sample of the basis No. 3.

Oil samples were prepared on the basis of No. 3 with additive packages No. 2-4 in the claimed proportions, provided that the oil contained not only different composition of the packages, but also in different concentrations (from 8.695 to 11.345%, as well as outside the stated range) : sample 1 (8.695% of package No. 2); sample 2 (8.695% of package No. 3); sample 3 (8.695% of package No. 4); sample 4 (10% of package No. 2); sample 5 (10% of package No. 3); sample 6 (10% of package No. 4); sample 7 (11.345% of package No. 2); sample 8 (11.345% of package No. 3); sample 9 (11.345% of package No. 4); sample 10 (8.694% of package No. 2); sample 11 (8.694% of package No. 3); sample 12 (8.694% of package No. 4); sample 13 (11.346% of package No. 2); sample 14 (11.346% of package No. 3); sample 15 (11.346% of package No. 4).

The test results for evaluating the main physico-chemical properties of oils containing additive packages in concentrations from 8.695 to 11.345% are presented in table 13.

Table 13 Test results of oil containing additive packages No. 2-4 The name of indicators Oil sample numbers of additive packages one 2 3 four 5 6 7 8 9 10 eleven 12 13 fourteen fifteen Kinematic viscosity at 100 ° C, mm ² / s 11.5 11.6 11.7 11.8 12.0 12,2 12.3 12,4 12.5 11,4 11.3 11.1 12.7 12.9 13,2 Viscosity on CCS viscometer at minus 30 ° C, MPa · s, no more 5500 5400 5400 5300 5200 5300 5500 5700 5900 5400 5500 5600 6200 6500 6700 Viscosity on the MRV viscometer at minus 35 ° C, MPa · s, no more 31000 32500 32000 32000 33000 33500 34500 36500 37500 31900 32,400 32850 45000 48500 52000 Viscosity at 150 ° C and shear rate 10 ⁶ s ^-1 , MPa · s, not lower 2.6 2.7 2,8 3.0 2.9 3,1 3.2 3.3 3.4 3,1 3.2 3.3 2,8 2.6 2,4 Pour point, ° C, not higher minus 60 minus 60 minus 60 minus 60 minus 60 minus 60 minus 60 minus 60 minus 60 minus 59 minus 57 minus 56 minus 54 minus 55 minus 58 Flash point determined in open crucible, ° C, not lower 186 188 189 206 196 200 204 203 206 192 193 190 207 208 210

From the data of table 13 shows that the most optimal physico-chemical properties is the claimed sample of oil No. 5 with 10 wt.% Additive package No. 3.

Comparative analysis with the prototype allows us to conclude that the claimed composition of the additive package and the oil containing it differs significantly from the known introduction and combination of other components, namely

as a part of a packet - a solution of the interaction of alkylbenzenesulfonic acid with calcium hydroxide dissolved in oil, having an alkaline number of at least 390 mg KOH / g, a 50% solution of a mixture of amine salt and dialkyl dithiophosphoric amide in oil from tetra (2-ethylhexyl) thiuram disulfide taken in the ratio to a 50% solution of a 1: 1 mixture by mass fraction with an atomic ratio of sulfur to phosphorus of 5.23, and octylated diphenylamine;

in the composition of the oil is an additive package with other components in the amount of 8.695-11.345 wt.% and additionally polymethacrylate additives with a molecular weight of from 2800 to 3200 in the amount of 0.1-1.0 wt.%;

as a part of the base of the oil - distillate oil or its mixture with selective selective residual oil having a kinematic viscosity of 51 to 75 mm ² / s at 40 ° C and pour point not higher than minus 15 ° C, of oil obtained from low-sulfur paraffinic oils of deep selective refining and dewaxing, with a kinematic viscosity of 16 to 22 mm ² / s at 40 ° C and a pour point of not higher than minus 55 ° C, of a poly-α-olefin oil with a kinematic viscosity of 3.5 to 4.5 mm ² / s at 100 ° C and pour point not higher than minus 60 ° C, ester, obtained when interacting with sebacic acid and 2-ethylhexanol, with a kinematic viscosity of at least 3.2 mm ² / s at 100 ° C and a pour point of not higher than minus 55 ° C and polyvinyl n-butyl ether with a kinematic viscosity of 3200-9000 mm ² / s at 100 ° C and a molecular weight of from 15,000 to 25,000.

In addition, the known components — alkaline calcium alkyl salicylate, ashless nitrogen-containing dispersant, a block copolymer of ethylene and propylene oxides based on ethylene diamine and phenyl-α-naphthylamine — are in the package (table 5); distillate oil or a mixture thereof with selective residual oil having a kinematic viscosity of 51 to 75 mm ² / s at 40 ° C and a pour point of not higher than minus 15 ° C, an oil obtained from low-sulfur paraffinic oils by deep selective cleaning and dewaxing, with kinematic viscosity from 16 to 22 mm ² / s at 40 ° C and pour point no higher than minus 55 ° C, poly-α-olefin oil with a kinematic viscosity of from 3.5 to 4.5 mm ² / s at 100 ° C and pour point no higher than minus 60 ° C, ester obtained by reaction of sebac oic acid and 2-ethylhexanol, with a kinematic viscosity of not less than 3.2 mm ² / s at 100 ° C and a pour point of not higher than minus 55 ° C and polyvinyl-n-butyl ether having a kinematic viscosity of 3200-9000 mm ² / s at 100 ° C and a molecular weight of 15,000 to 25,000 - as part of the base oil (table 11), are used in a different percentage.

Despite the fact that in the component of the package the concentration of the active substance dissolved in oil of the carbonated product of the interaction of alkylbenzenesulfonic acid with calcium hydroxide with an alkaline number of at least 390 mg CFU / g is higher than in alkaline calcium sulfonate, the effect is achieved by introducing it in a lower concentration in oil, which reduces sulfur and sulfate ash content (table 8).

Introduction into the bag of a 50% solution of a mixture of amine salt and dialkyl dithiophosphoric acid amide in oil with tetra (2-ethylhexyl) thiuram disulfide taken in proportion to a 50% solution of a 1: 1 mixture in a mass fraction at an atomic ratio of sulfur to phosphorus 5, 23, leads to a decrease in the adverse environmental impact of the content of sulfur, phosphorus and sulfate ash in engine oil and a simultaneous increase in deactivating and anticorrosive properties under conditions of high temperature catalytic oxidation of oils without reducing the level of prot wear and antifriction properties (tables 7-10). The additional introduction of octylated diphenylamine in the additive package leads to an improvement in the antioxidant properties of the oil (table 8).

The combination in the composition of the base oil in the claimed percentage of distillate oil or a mixture thereof with selective residual oil having a kinematic viscosity of 51 to 75 mm ² / s at 40 ° C and pour point not higher than minus 15 ° C, oil obtained from low-sulfur paraffin oils with deep selective refining and dewaxing, with a kinematic viscosity of 16 to 22 mm ² / s at 40 ° C and a pour point of no higher than minus 55 ° C, of a poly-α-olefin oil with a kinematic viscosity of 3.5 to 4.5 mm ² / c at 100 ° C and the temperature SAG yvaniya not higher than minus 60 ° C, the ester obtained by reacting sebacic acid and 2-ethylhexanol, with a kinematic viscosity of not less than 3.2 mm ² / s at 100 ° C and a pour point of not higher than minus 55 ° C, and polyvinyl-n -butyl ether with a kinematic viscosity of 3200-9000 mm ² / s at 100 ° C and a molecular weight of 15000 to 25000 provides a low-temperature start-up of an unheated engine at an ambient temperature of minus 60 ° C.

The use of the invention will allow the production of motor oils for highly accelerated gasoline engines and turbocharged diesel engines with improved antioxidant, anticorrosive deactivating properties while maintaining the level of antiwear and antifriction properties and at the same time reducing sulfur, phosphorus and sulfate ash, which helps to increase the time for changing the oil in the engine and its overhaul life.

Claims (3)

1. A motor oil additive package containing alkaline calcium alkyl salicylate, alkaline calcium sulfonate, an ash-free nitrogen-containing dispersant, a block copolymer of ethylene-propylene oxides based on ethylene diamine, a modified dialkyl dithiophosphate and phenyl-α-naphthylamine, characterized in that it is an alkaline calcium sulfonate it contains a carbonated product of the interaction of alkylbenzenesulfonic acid with calcium hydroxide dissolved in oil, having an alkaline number of at least 390 mg KOH / g, as a modified dialkyl of thiophosphate - a 50% solution of a mixture of the amine salt and dialkyl dithiophosphoric amide in oil with tetra (2-ethylhexyl) thiuram disulfide, taken in proportion to a 50% solution of the mixture from 1: 3 to 3: 1 by mass fraction at an atomic sulfur ratio to phosphorus in the range of 3.25-11.55, and additionally contains octylated diphenylamine in the following ratio of components, wt.%:
alkaline calcium alkyl salicylate 24.94-34.94 carbonated in oil reaction product of alkylbenzenesulfonic acid with calcium hydroxide having an alkaline number not less than 390 mg KOH / g 12.97-16.97 ashless nitrogen-containing dispersant 17.96-21.96 block copolymer of ethylene oxide and propylene ethylene diamine based 0.17-0.23 50% solution of a mixture of amine salt and amide dialkyldithiophosphoric acid in oil with tetra (2-ethylhexyl) thiuramdisulfide taken in the ratio to a 50% solution of the mixture from 1: 3 to 3: 1 by mass fraction with an atomic ratio of sulfur to phosphorus in the range of 3.25-11.5 8.98-10.98 phenyl-α-naphthylamine 8.98-10.98 octylated diphenylamine rest 2. Mineral-based motor oil containing an additive package and an antifoam additive, characterized in that it contains an additive package according to claim 1 and additionally a depressant polymethacrylate additive with a molecular weight of from 2800 to 3200 in the following ratio of components, wt.%:
anti-foam additive ПМС-200А 0.003-0.005 additive package according to claim 1 8,695-11,345 molecular depressant weighing from 2800 to 3200 0.1-1.0 mineral-based motor oil rest 3. The engine oil according to claim 2, characterized in that it contains a distillate oil or a mixture thereof with selective selective residual oil having a kinematic viscosity of 51 to 75 mm ² / s at 40 ° C and a pour point of not higher than the mineral base minus 15 ° C; oil obtained from low-sulfur paraffin oils by deep selective cleaning and dewaxing, with a kinematic viscosity of 16 to 22 mm ² / s at 40 ° C and pour point not higher than minus 55 °; poly-α-olefin oil with a kinematic viscosity of from 3.5 to 4.5 mm ² / s at 100 ° C and pour point not higher than minus 60 ° C; ester obtained by the interaction of sebacic acid and 2-ethylhexanol with a kinematic viscosity of at least 3.2 mm ² / s at 100 ° C and a pour point of not higher than minus 55 ° C and polyvinyl n-butyl ether with a kinematic viscosity of 3200- 9000 mm ² / s at 100 ° C and a molecular weight of from 15000 to 25000 in the following ratio of components, wt.%:
distillate oil or its mixture with residual kinematic selective oil viscosity from 51 to 75 mm ² / s at 40 ° C and temperature solidification not higher than minus 15 ° С 10-20 oil obtained from low-sulfur paraffin oils by deep selective refining and dewaxing, with kinematic viscosity from 16 to 22 mm ² / s at 40 ° C and pour point no higher than minus 55 ° C 40-50 kinematic poly-α-olefin oil viscosity from 3.5 to 4.5 mm ² / s at 100 ° C and pour point no higher than minus 60 ° C 25-35 ester obtained by reaction sebacic acid and 2-ethylhexanol, with kinematic viscosity of at least 3.2 mm ² / s at 100 ° C and temperature solidification no higher than minus 55 ° C 5-15 kinematic polyvinyl n-butyl ether viscosity 3200-9000 mm ² / s at 100 ° С and molecular weighing from 15,000 to 25,000 up to 100