CS246897B1 - Multistage lubricating oil partly synthetic for petrol and oil engines - Google Patents

Abstract

The base oil contains 90-40% by weight % petroleum and 10 to SO% palpable synthetic component. resultant oil contains 1 to 22:%. weight detergent ingredients, calculated as 50% concentrates such as alkali metal sulfonates soils, calcium and magnesium alkylsalicylates, alkylphennates and; alkylfenolsulíidy calcium and barium, with a weight ratio of sulfonate additives to others is the least 1: 9, s, preferably 1: 2 to. 3L:, 2; 0.2 · to: 12.0% by weight dispersant. gossip from phosphonate and / or phosphonate a thiophosphonate and / or Mannich foils ,. calculated on the active ingredient and 0.1 to 4:, Q% weight prototype additives, thiophosphate, calculated on the active ingredient viscosity-increasing additives: and viscosity index and other commonly used ingredients as oxidation inhibitors; corrosion: and deterioration, friction modifiers, additives reducing freezing point, antifoaming, antiseptic, improving the color and smell of oils and other.

Description

The invention relates to a multi-stage lubricating oil for gasoline and diesel engines, including supercharged, consisting of a base oil of partially synthetic and quenching additives.

Multi-stage engine lubricating oils cover two or more viscosity grades and meet the requirements for both summer and winter oils. These properties of multi-stage oils, being usable both in winter and in summer, give them polymeric additives, so-called " viscosity modifiers and viscosity index enhancers (VI), which increase the viscosity and improve the viscosity-temperature properties of the oils. VI _E oils are increased above 100, often to 150-180 by these additives. Viscosity modifiers and VI enhancers are polyalkyl methacrylates, in particular those having a depressant effect on the freezing point of the oils and may also have a detergency-dispersing effect, styrene copolymers. and butadiene or styrene and isoprene, polymers and copolymers of alkenes, especially ethylene and propylene, polybutenes and polyisobutenes. Newer types of polymethacrylate additives exhibit a substantially increased shear stability close to that of the hydrocarbon copolymers. In addition to these additives, the multi-stage oils mainly comprise detergent and dispersing, antioxidant, lubricating and anti-abrasive additives. They may further comprise corrosion and rust inhibitors, antifoaming agents, oil freezing point depressants, antiseptic additives (biocides), oil color and odor enhancers and others.

The multi-stage lubricating oil, partially synthetic for petrol and diesel engines, should have a water discharge reaction of neutral or preferably alkaline with a total alkalinity (TBN) in the range of about 2.5 to 15 mg KOH / g (where the alkalinity is related to the oil class), Pour point of not more than - 25 ° C, preferably not more than - 30 ° C, VI _E not less than 100, preferably not less than 110 and viscosity at - 18 ° C not more than 15 000 mm ² . ¹ , preferably at most 10 400 mm ² .s ^-1 .

The base oil of a partially synthetic multi-stage lubricating oil for gasoline and diesel engines contains, in addition to an oil content of about 10 to 60% by weight, practically about 15 to 30% by weight (due to technical-economic) synthetic oil such as diester oils based on dicarboxylic acids. C6 to C12 and aliphatic monoalcohols Ce to C16, most branched, such as 2-ethylhexanol and oxoalcohols C10 to C18, polyol type esters based on polyols, especially neopentyl structures, such as trimethyloalkanes and pentaerythritol and aliphatic monocarboxylic acids and their in particular C5 to C9 acids, complex ester oils, or polymeric alkali hydrocarbon oils, such as polymers of 1-alkene oligomers (especially ethylene is hydrogenated. Of the ester oils, with respect to their thermal stability, diester oils are particularly suitable for gasoline and neprepl hedged diesel engines and polyol esters in the oil for supercharged diesel engines.

For base grade oils, petroleum oil components with a high VI, above 90, preferably 95 to 100, are required. Such suitable oil fractions are found, in particular, in paraffinic oils. They are used in the form of solvent raffinates, which are sometimes still subjected to medium pressure catalytic hydrogenation. Oil fractions from high pressure hydrogenation, which can also reach very high VI _E , of about 140, may also be used.

By mixing the recovered refined petroleum fractions, namely the light distillate fraction (spindle oil), the middle distillate fraction of the light machine oil], the heavy distillate fraction (medium machine oil), and the residual oil fraction (residual oil, brighstockof), each fub can be produced. of a base oil over a multi-stage oil partially synthetic. However, it is not necessary to use all four fractions to produce such a petroleum base oil fraction. In principle, one (eg medium) fraction can be sufficient. However, mixtures of at least two fractions with significantly different viscosities are preferred. The type of fractions used and their proportion in the base oil depend on which viscosity classes the multi-stage oils are to respond to or the requirements according to the intended use.

Multi-stage engine oils, partially synthetic, are generally additive with the same additives as the same types of multi-stage oils based on purely petroleum base oils. On the other hand, fully synthetic oils require especially additive types and essential other additivities. Multistage semi-synthetic engine oils usually require less additives, in particular detergent, dispersant and antioxidant, than the same types of pure petroleum base oils to achieve the same functional efficiency, about as much as the percentage of the synthetic component in part in the synthetic oil.

The increased content of viscosity-increasing polymer additives and VI of multi-stage oils generally requires an increase in detergent dispersing additives of about 10 to 30% or more, compared to analogous single-stage oils, since the polymers influence the effect of these additives and promote the buildup of deposits on the engine piston. The polymer content is also influenced by the type of polymer, its efficiency and the relative shear strength of the polymer system used, as well as the degree of degree of the multi-stage oil.

The content of ash-forming additives, such as the most detergent-dispersing additives having a metal content in the molecule and in particular their high-alkaline types, is limited in multistage engine oils by the condition that the sulphated ash content of these oils may be at most 2% by weight requirements and not more than 1.5% of the employment according to more recent requirements. Therefore, among other things, this is also possible in multi-stage engine oils to an increased degree compared to single-stage oils (for which the abovementioned limitations on the ash content J do not apply the dispersants are ashless or low ash dispersants predominantly against the formation of low-temperature such as succinimides, preferably bissuccinimides (the use of phosphonates and thiophosphonates is in decline).

Already multi-stage petroleum oils for gasoline and diesel engines have advantages over single-stage oils, which are further increased for partially synthetic oils, such as better start of the sea in cold (improved start-up free), reduced abrasion, mainly bearings, less oil consumption especially with the use of a thermally and shear-stable polymer system, improved fuel economy, especially in stop-and-go driving modes.

The present invention is self-reliant on multi-stage lubricating oils partially synthetic for gasoline and diesel engines, consisting of a base of partially synthetic and refining additives, added in limited proportions that exhibit all known advantageous properties of multi-stage oils and fully meet the requirements of the quality indicators prescribed for each performance classes of these oils (B, C, D, according to the CMEA classification).

Multistage engine oils can also be prepared according to the present invention which, at the AVB test on a Petter turbocharged engine, show a rating prescribed for class E oils (CD and M-L-45 199 B, series 3, respectively).

Further, according to the present invention, 1 multi-stage partially synthetic oils can be prepared for gasoline and / or diesel engines, including turbocharged engines with extended oil change intervals of more than 10,000 km. In the preparation of these long-life oils, they need to be specially wiped if their oil refractions are narrow and have a high VI so that the viscosity modifiers have a high viscosity modifier ^; shear stability so as to have an increased content of additives, in particular detangent and dispersible with such TBN, that the alkalinity of these oils is maintained at a sufficient height during operation.

The multi-stage lubricating oil, partially synthetic for gasoline and / or diesel engines, including supercharged according to the present invention, consists of an essential oil of the thiophthalic oil and a refining additive, the oil having a proportional oil content having a resultant range. the oil viscosity of about '5.0 to: 1 O mm ² s ^_1 100 ° C and a VI of most (-90 mensij TS preferred features about 100 hours pour point not more than 8 ° C, preferably not more than -.14 ° C. consists of at least one oil component, preferably with at least two oil components (distillate fractions; reduced pressure from atmospheric distillation oil residue, selectively raffinated, dewaxed, optionally previously de-asphalted and, optionally, hydrogenated or fractionated) hydrogenation of vysokoílakovej) -VI-significant rozdielmych SKOZ in this .rozsahu about 4.0 to _30, 0 mm ^second p p ^_1 at about 100 ° C, the synthetic portion of the base oil of the partially synthetic oil is about 10.0 to 60.0% by weight, typically about 15 to 30% by weight, and consists of synthetic oils as diester oils based on dicarboxylic acids C 3 to C 12 and aliphatic monoalcohols C 8 to C 18, in particular branched as 2-ethylhexanol and oxo-alcohols C 1 to C 13, polyol esters based on polyols of a non-pententyl structure, acotrimethyloalkanes and pen. taetrytritol and aliphatic monocarboxylic acids and mixtures thereof including esters of C8 to C8, oils based on complex esters, or polymeric alkali hydrocarbon oils such as hydrogenated polymers of 1-alkene oligomers, viscosity enhancers and viscosity-temperature enhancers, in particular polyalkyl methacrylates and polyalkylacrylates, which may also have a depressant effect for the setting time of oils; Polymethacrylate with increased shear stability (containing a nitrogen group in the molecule), for example P.LEXOL 956 or -957, styrene-butadiene or styrene-isoprene copolymers, for example SHELLVIS 50, alkene copolymers, in particular ethylene and propylene, polybutenes and polyisobutenes added in such an amount that the prescribed multi-stage oil viscosity to the extent of the overlapped viscosity grades has been reached, and further, the resulting oil may contain other commonly used additives as oxidation inhibitors, in particular low- and medium-temperature. in cases where there is a lower supply of detergent-dispersing ingredients having also an antioxidant effect, such as alkylphenlates and alkyl salicylates, such as mononuclear monovalent alkylphenols, not shielded, such as 2,6-di-tert-butyl-ethylethylphenol, bisrenols such as 4,4'-mertylene-; biS73,6-di-tert-ibutylphenol - (Vanlube DTB), thiohisphenols, aliphatic and aromatic amines primary, preferably secondary, such as diphenylamine, tertiary, with or without sulfur, alkylaminophenols, phenothiazines, dithiocarbamates, corrosion inhibitors, media and copper alloys such as 2,5-dimercapto-1, 3,4246897

-thiazole derivatives, rust inhibitors, friction modifiers such as molybdenum sulphate compounds, molybdenum sulphate dithiophosphate, borate additives, oil freezing point additives such as polyalkyl methacrylates, alkyl naphthalenes (Paraflow), anti-foaming agents such as polysiloxanes and additives, antisense additives other additives, characterized in that it contains 1.0 to 22.0% by weight, preferably 3.5 to 12.0% by weight. detergent dispersing agents of sulfonate, alkylsalicylate, alkylphenolate and / or alkylphenyolsulfide, calculated as 50% oil concentrates, wherein the weight ratio of the sulfonate ingredients to the other, with respect to the synergistic effect, is at least 1: 9, preferably in the range 1: 2 to 3: 2, 0.2 to 12.0% by weight, preferably 1.5 to 5.0% by weight of dispersants (mainly against low-temperature sludges) of succinimide or Mannich bases, which also have an antioxidant effect and / or phosphonate and thiophosphonate, calculated on the active ingredient, and 0.1 to 4% by weight, preferably 0.7 to 1.5% by weight, of the anti-abrasion additives of the thiophoslate calculated on the active ingredient.

The multi-stage lubricating oil partially synthetic for gasoline and diesel engines of the present invention is further characterized in that the sulfonate additives are oil-soluble alkaline earth metal sulfonates, preferably calcium and magnesium, neutral and basic, petroleum and synthetic, based on oil-soluble monosulfoacids of average molecular weight. at least 300, preferably 420 to 460, alkylsalicylate additives are calcium and magnesium alkylsalicylates, neutral and basic with C12 to C22 alkyl, preferably Ch to C18, alkylphenolate and alkylphenol sulfide additives are oil-soluble calcium, barium and magnesium salts, neutral and basic, for alkylphenol bases, preferably alkyl C 18 to C 32, succinimide additives are succinimides, bissuccinimides and mixtures thereof, and thiophosphate additives are alkyl, aryl and alkyl aryl thiophosphates, preferably zinc having a molecular weight of 435 to 43

828th

By way of illustration, examples are given that do not limit the scope of the invention.

Example 1

A partially synthetic viscosity grade SAE 15 W / 40 automotive engine oil belonging to group C according to the RVHP specification (approximate to SD, CB according to API specification) was prepared, having the following composition:

Partially synthetic base oil composition:

20.0% wt. synthetic component (ester of technical pentaerythritol and a mixture of monocarboxylic acids Cs to C9)

64.0% wt. R 935 (petroleum selective raffinate, hydrogenated, viscosity 6,03 mm ² s ^-1 at 100 ° C)

18.0% wt. R 953 (petroleum selective raffinate having a viscosity of 15.28 mm ² s ^-1 at 100 ° C) together with 100.0 wt.

Composition of the resulting additive partially synthetic oil:

1.2% wt. Zn-dithiophosphate (Multadit OB)

3.0 wt. succinamide additive S 5A (a mixture of mono- and bis-succinimide

0.4% wt. 2,6-di-tert-butyl-4-methylphenol (jonol)

0.3 wt. 4,4‘-methylene-his-2,6-di-tert-butylphenol (Vanlube DTB)

2.5 ° / o wt. basic alkyl salicylate

2.5 wt. calcium alkylphenolate, basic sulfur.

3.0 wt. Calcium petroleum sulfonate, low base (PS-30 ex)

2.5 wt. polymethacrylate viscosity modifier and reducer b. t. oil (Plexol 957 M)

0.7% wt. viscosity modifier (Shellvis 50)

83.9 wt. base oil total 100.0 wt.

Results of the evaluation of the resulting oil by laboratory and AVI tests on a Petter single-cylinder petrol engine:

kinematic viscosity at 40, MRA ² s ^ 87.0 at 100 ° C, mm ² .s ⁴ 12.6 VI _E 140 flash point at 0 ° C, ° C 208 pour point, ° C -38 TBN, mg KOH / g 8.5 carbonization residue,% wt. 1.55 sulfate burn,% wt. 1.3 dynamic viscosity (per CCS), at -17.8% Pa.s 4.9 mechanical stability, DIN 51 382, viscosity drop after 30 cycles,% 3.8 AVI test on petrol engine Petter points (average of 2 tests j 90.5

The evaluation results confirm the very good quality of this oil. The result of the AVI test on the Petter gasoline engine lies in the upper half of the prescribed point rating for Group C oils according to the RVHP specification (approximate Group CB according to API specification).

Example 2

An automotive, semi-synthetic, 15 W / 40 viscosity grade automotive oil belonging to Groups D2 to E of the RVHP specification (approximately equivalent to Groups CC to CD of the API specification) was prepared as follows:

Partially synthetic base oil composition:

27.0% wt. a synthetic component as in Example 1

56.0% wt. petroleum oil R 935 as in Example 1

17.0% wt. petroleum oil R 953 as in Example 1 together 100.0 wt.

Composition of the resulting additive partially synthetic oil:

1.4 % hm. 0.3 % hm. 0.6 % hm. 0.75 % hm. 4.0 % hm. 3.0 % hm. 1.0 % hm. 4.0 "/about hm. 2.6 % hm.

Zn-dithiophostate (Multadit OB) diphenylamine

4,4'-methylene-bis-2,6-di-tert-butylphenol (Vanlube DTB) molybdenum-sulfur trioxide modifier and antioxidant (Molyvan 822) succinamide additive (S 5A) calcium alkylsalicylate basic alkyl alkylphenolate calcium sulphated basic succinamide additive -30 ex.) Polymethacrylate viscosity modifier and reducer b. t. oil (Plexol 956)

0.7% wt. viscosity modifier (Shellvis 50)

0.002% wt. Silicone antifoam (Lukoil FM) up to 100% wt. Base oil partially synthetic.

Results of the evaluation of the resulting additive oil by laboratory tests and by AVB test (IP 279 / 77J on stationary single cylinder turbocharged diesel engine - Petter:

kinematic viscosity

at 40 ° C, mm ² .s ^-1 94.5 at 100 ° C, mm ² .s ^d 12.8 VI _E 131 flash point at o. ° C 212 pour point, ° C -40 TBN, mg KOH / g 8.6 carbonization residue,% wt. 1.45 sulphated ash,% wt. 1.2 dynamic viscosity (CCS) at -17.8 ° C, Pa. with 5.0

AVB test on Petter diesel turbocharged engine:

1st piston groove, points 7,8

1st bridge, points 7.5 piston shell, points 10 inner bottom, points 8.7 compression rings, points 10 total value, points 89.4

Note: Maximum points - for individual indicators 10 - for the overall score 100

The evaluation results express the very good physicochemical and functional properties of this oil, both in laboratory and in turbocharged diesel engine operating conditions. According to the achieved rating in the AVB test on a Petter Station Turbocharger, the oil exceeds the point limit for Group D oils and falls within the Group E point range (as specified by the RVHP specification), which corresponds to the approximate Group CD (API).

Claims (4)

A multi-stage lubricating oil, partially synthetic, for gasoline and diesel engines, including supercharged, consisting of a partially synthetic base oil and additives, wherein the crude oil base oil has a viscosity of about 5.0 to 10.0 mm ² . . ¹ at 100 ° C and VI of at least 90 and consists of at least one, preferably two, oil components of significantly different viscosities in the range of 4.0 to 30.0 mm ² . . ¹ at 100 ^° C and the synthetic base oil content is 10.0 to 60.0% by weight, typically about 15.0 to 30.0% by weight, and consists of synthetic oils such as diester oils, polyol ester type oils, base ester complexes, or alkali hydrocarbon polymeric oils hydrogenated, and viscosity enhancers and viscosity index enhancers such as polyalkyl methacrylates, styrene-isoprene copolymers and styrene-butadiene copolymers are added in an amount to achieve the prescribed viscosity grade of the admixture. The oil may also contain other commonly used additives such as oxidation inhibitors, corrosion inhibitors of copper and copper alloys, rust inhibitors, friction modifiers, oil freezing point additives, antifoaming additives, antiseptic additives, oil and odor enhancing additives and other ingredients characterized in that it contains 1.0 to 22.0% by weight, preferably 3.5 to 12.0% by weight, of detergent-dispersant additives of suffonate, alkyl salicylate, alkylphenolate and / or alkylphenol sulfide, calculated as 50% oily The weight ratio of the sulfonate additives to the others is at least 1: 9, preferably in the range of 1: 2 to 3: 2, 0.2 to 12.0% by weight, preferably 1.5 to 5.0% by weight dispersants of succinimide and / or phosphonate and thiophosphonate and / or Mannich bases, based on the active ingredient and 0.1 to 4.0% by weight, preferably 0.7 to 1.5% by weight, of the anti-abrasion additives of thiophosphonate based on the active ingredient. Multistage lubricating oil partially synthetic for gasoline and diesel engines according to item 1, characterized in that the sulfonate, alkyl salicylate, alkylphenolate and / or alkylphenol sulfide additives are oil-soluble alkaline earth metal sulfonates, preferably calcium and / or magnesium, neutral and basic, petroleum and synthetic based on monosulfoacids having an average molecular weight of at least 300, calcium and / or magnesium alkylsalicylates neutral and basic with C1 to C22 alkyls, calcium, barium and magnesium alkylphenols and alkylphenolsulphides, neutral and basic, preferably C1 to C32 alkyl. 3. A multi-stage lubricating oil partially synthetic for the gasoline and diesel engines of item 1, characterized in that the succinimide additives are succinimides, bissuccinimides and mixtures thereof. 4. A multi-stage lubricating oil partially synthetic for petrol and diesel engines according to claim 1, characterized in that the thiophosphonate additives are alkyl-, aryl- and alkylaryl-dithiophosphates, preferably zinc having a molecular weight of 435 to 828.