CS246897B1 - Multi-stage lubricating oil partially synthetic for petrol and diesel engines - Google Patents

Abstract

The base oil contains 90 to 40% by weight of petroleum and 10 to 50% by weight of synthetic component. The resulting oil contains 1 to 22% by weight of detergent additives, calculated as 50% concentrates, such as alkaline earth metal sulfonates, calcium and magnesium alkyl salicylates, alkyl phenols and calcium and barium alkyl phenolsulphides, the weight ratio of sulfonate additives to the others being at least 1:9, preferably 1:2 to 3:2; 0.2 to 12.0% by weight of dispersant additives of sulfonimide and/or phosphinate and thiophosphonate and/or Mannich phosphates. calculated on the active ingredient and 0.1 to 4.0% by weight of anti-wear additives, phosphate additives, calculated on the active ingredient, additives increasing viscosity and viscosity index and other commonly used additives such as oxidation, corrosion and rust inhibitors, friction modifiers, pour point depressants, anti-foaming, antiseptic additives, colour and odour improvers of oils and others.

Description

246897

The invention relates to a multi-stage lubricating oil for gasoline and diesel engines, including turbocharged, which consists of a base oil of partially synthetic and flavoring additives.

Multi-stage lubrication oils engineered to cover two or more viscosity grades meet the requirements for both summer and winter oils. These properties of multi-stage oils, which are useful both in summer and in the summer, provide them with polymer additives, so-called viscosity modifiers and viscosity index enhancers (VI), which increase viscosity and improve the viscosity-temperature properties of oils. VIE oils increase by over 100, notably from 150 to 180, with these additives. Polyalkyl meta-crystals, especially those having a depressant effect on the freezing point of the oils, and the detergent-dispersing effect, co-polymers are used as viscosity modifiers of VI. styrene and butadiene or styrene and isoprene, polymers and copolymers of alkenes, especially ethylene and propylene, polybutenes and polyisobutenes. More recent types of poly-methacrylate additives exhibit a substantial increase in shear stability, close to those of hydrocarbon copolymers. The adjuvants include a multi-stage oil purifier, mainly detergent and dispersant, antioxidant, lubricating and counter-ionic additives. Furthermore, it may contain corrosion inhibitors and rusting agents, antifoam additives, freezing point additives, antiseptic additives, color additives and odor enhancers, and others.

Multistage Lubricating Oil Partially Synthetic for Gasoline and Diesel Engines Have a Water Shake Reaction Neutral, or Alkaline Almost with a Total Alkalinity Number (TBN) in the Range of about 2.5 to 15 mg KOH / g (wherein the Alkalinity Height is related to the Oil Class) , a freezing point of at most -25 ° C, preferably at most -30 ° C, a VIE of at least 100, preferably at least 110, and a viscosity at -18 ° C of at most 15,000 mm 2. s 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 about 10 to 60% by weight of petroleum oil, practically about 15 to 30% by weight of synthetic oil, such as oils. di-esters based on dicarboxylic acids of C6 to C12 and aliphatic monoalcohols of C 6 to C 16, especially branched, such as 2-ethylhexanol and oxo alcohols C 10 to C 13, polyol-based polyol esters of the polyol esters, especially neopentyls, for example trimethylolalkanes and pentaerythritol and aliphatic monocarboxylic acids and mixtures thereof, especially C5 to C9 acids, base-complex ester oils, or polymeric olefinic hydrocarbons, such as the oligomers of 1-alkenes (especially ethylene) hydrogenated. Of the ester oils, due to their thermal stability, the diester oils are mainly suitable for pre-benzene and non-overfilled oil engines and polyol esters for oils for supercharged diesel engines.

For multi-stage oil base oils, the high VI oil oil components above 90, preferably 95 to 100 are required. Such suitable oil fractions are mainly found in paraffinic oils. Solvent raffinates are also used, which are sometimes subjected to medium pressure catalytic hydrogenation. It is also possible to use oil fractions from high-pressure hydrogenation, which can also achieve very high VIE, of about 140.

By combining the obtained refined petroleum fractions, namely a light distillate fraction (spindle oil), a moderate distillate fraction of a light machine oil), a heavy distillate fraction (medium machine oil) and a residual oil fraction (residual oil fraction). each oil portion of the base oil may be partially synthetic in the multi-stage oil. However, it is not necessary to use all four fractions for the production of the base oil. Essentially, even with one (e.g., medium) fraction. However, mixtures of at least two fractions of considerable different viscosity are preferred. The type of fractions used and their proportion in the base oil depend on the viscosity grades to which the multistage oils have to respond, or what claims they are intended to meet.

The multi-stage, multi-synthetic engine oils are usually additivated by the same additives as the same types of multi-stage oil-based base oil. On the other hand, non-synthetic oils require special additives and basic additives. The multi-stage engine oils are partly synthetic, requiring more customary additives, especially detergent, dispersant and antioxidant, as well as the base oil-based oils to achieve the same efficiency, by about as much as the synthetic component in the bulk. turntable in synthetic oil.

The increased viscosity-increasing polymer additive content of the multi-stage olefin VI generally requires an increase in detergent-dispersing agent content of about 10 to 30% or more, as opposed to the one-stage analogue oils, since the polymers affect the effect of these additives and promote growth of sediments on the engine piston. The polymer content is also influenced by the type of polymer, its efficiency and the relative shear strength of the polymeric system used, as well as the degree of degree of multi-stage oil.

The content of ash-forming additives, such as the detergent-dispersing additive with the metal content of the molecule in particular, and its high-grade types, is limited by the condition that the sulfate ash content of these oils is not more than 2% by weight of the more frequent requirements and not more than 1.5% by weight of the newer requirements. Therefore, amongst other things, in a multi-stage engine overhang of an increased degree of unlike the one-step oils (in which the abovementioned limitation of sulphate ash content J is used, dispersants are used in the non-volatile ash, mainly used for Against the formation of low temperature halls, such as mucuccinimides, preferably bissuccinimides (the use of phosphonates and thiophosphonates is in the process of being used). which are further increased in partially synthetic olives, in particular: better cold start of the sea salt (improved unobstructed starterability), reduction of abrasion, mainly bearing, less oil consumption and use (thermal and shear strength) -productive polymer system, better fuel economy, especially when driving with frequent stop and start go ”).

The present invention is self-contained on a multi-stage lubricating oil, partially synthetic prebenzine and diesel engines, consisting of a base of partially synthetic and hardening additives, added in defined proportions that exhibit all known advantageous properties of multi-stage oils and satisfy fully upon - Requirements of quality indicators prescribed for individual performance class oils (B, C, D, according to the RHHP classification).

In accordance with the present invention, there can be prepared stepwise engine oils which exhibit a grading rating as described for class E oils (CD, MIL-L-45 199 B, series 3, respectively) at the post-turbocharged Pterter AVB test.

Further, according to the present invention, a multi-stage partially synthetic oil can be prepared for petrol and / or diesel engines including supercharged engines with multiple oil change intervals of more than 10,000 km. In the preparation of these oils for a long time, it is necessary to separately dissolve them, their petroleum fractions may be heavy and have a high VI so that the viscosity modifiers exhibit a high shear stability, so that the low-added content of the additives, particularly the detersive and dispersible, with such TBN is avoided. the alkalinity of these oils has remained in excess during operation.

The multi-stage lubricating oil, partially synthetic for gasoline and / or diesel engines, including the supercharged compositions of the present invention, consists of base oil and synthetic and refining additives, wherein the petroleum base oil (" base " Any (appropriate range of viscosity grades (resulting oil viscosity 5.0 to 1D mm 2.s -1 at 100 ° C and VI most unstained -90, µs-preferably around 100, solidification hour at most 88) ° C, preferably at most -14 ° C - at least one oil component, preferably at least two oil components (fractions obtained by distillation; under reduced pressure from an atmospheric distillation oil, selectively refined, paraffinized, possibly prior to the deasphalted and optionally hydrogenated or high-pressure hydrogenation fractions, the considerable difference in viscosity found within the range of 4.0 to 30.0 mm 2. 0 ° C, a syn-lethal base oil of a partial synthetic is about 10.0 to about 60.0% by weight, typically about 15 to about 30% by weight, and consists of synthetic oils as diester oils: based on dicarboxylic acids mainly Cs to U12 and aliphatic monoalcohols Cs to C18, the most branched to 2-ethylhexanol and oxo-alcohols Cro to Cm, but are polyol-based polyol esters such as trimethyloalkanes and penetrythetritol and aliphatic monocarboxylic acids and mixtures thereof include, in particular, C 5 -C 8 -alkyl, oils based on complex esters, or polymeric oils of alkane-hydrogen; 1-alkene-hydrogenated oligomer oligomers, viscosity-enhancing additives, and viscosity-temperature enhancing properties, such as polyalkyl methacrylates and polyalkyl acrylates, which can also have a de-stagnant oil solidification effect, a dispersant effect, najma dr polymethacrylate polystyrene with enhanced shear stability (containing a nitrogen moiety in the molecule), for example -PLEXOL 956 or -957, copolymers of styrene-butadiene or styrene-isoprene, for example SHELLIV 50, copolymers of al-kenes , in particular ethylene and propylene, polybutylenes and polyisobutenes added in such a quantity as to obtain a predetermined viscosity of the downstream oil in the range of the overlapped viscosity classes, and furthermore, the resulting oil may contain other commonly used additives such as low- and medium-temperature oxidation-inhibiting inhibitors - especially when the lowering of detergent-dispersing beacons is also an antioxidant effect, such as alkylphenates and alkyl- salicylates - as mononuclear monovalent alkylphenols , especially diminished, such as 2,6-di-tert-butylphenolphenol, bis-salts such as 4,4'-methyl-ethylenedioxy-di-tert-butylphenol - (VanlubeDTB), thiobisphenols, aliphatic and aro primary amines, preferably secondary, acodiphenylamine, tertiary, non-sulfur, alkylaminophenols, phenothiazines, dithiocarbamates, corrosion inhibitors, media and copper alloys such as 2,5-dimercapto-1,3,4-246897-thiazole derivatives, rust inhibitors friction modifiers such as molybdenum compounds; molybdenum dithiophosphate; borate additives; characterized in that it contains 1.0 to 22.0% by weight, preferably 3.5 to 12.0% by weight. detergent-dispersing additives of sulfonate, alkylsalicylate, alkylphenate and / or alkylphenylsulfide, calculated as 50% / oily oil concentrates, wherein the weight ratio of sulfonate additives to others, with respect to synergistic effect, is at least 1: 9 , preferably from 1: 2 to 3: 2, from 0.2 to 12.0% by weight, preferably from 1.5 to 5.0% by weight, of dispersing agents (mainly against low temperature slurries) of succinimide or Mannich bases, They also have an antioxidant effect and / or a phosphonate and thiophosphonate, calculated active ingredient, and 0.1 to 4% by weight, preferably 0.7 to 1.5% by weight, of thiophosate propionate additives effective to component.

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 alkaline earth metal oil-soluble sulfonates, preferably calcium and magnesium, neutral and basic, petroleum and synthetic. oil-soluble monosulfonic acid bases having an average molecular weight of at least 300, preferably 420 to 460, alkyl salicylate additives, calcium and magnesium alkylsalicylates, neutral and basic with C12 to C22, preferably C to C18, alkylphenol and alkylphenol sulfide additives are oil-soluble calcium, barium and magnesium salts, neutral and basic salts, based on alkylphenols, preferably C18 to C32 alkyls, succinimide additives are succinimides, bissuccinimides and mixtures thereof and thiophosphate additives are alkyl, aryl and alkylarylthiophosphates, preferably zi. -substances with a molecular weight of 435 to 828.

For illustrative purposes, examples are given that do not limit the scope of the invention. Example 1 Automotive oil of the semi-synthetic viscosity grade SAE15 W / 40, belonging to group C according to the RVHP specification (approximate to SD groups, CB according to API specification), was prepared:

Partially synthetic base oil: 20.0% wt. synthetic component (ester of technical peneterythritol and mixtures of monocarboxylic acids Cs to C9) 64.0% w / w R 935 (petroleum selective raffinate hydrogenated with a viscosity of 6.03mm2. s_1 at 100 ° C) 18.0% w / w R 953 (petroleum selective raffinate, viscosity 15.28 mm 2, s -1 at 100 ° C) total 100.0% wt.

The composition of the resulting additive-oiled synthetic: 1.2 wt. Zn-dithiophosphate (Multaitit OB) 3.0% wt. succinamide additive S 5A (mono-abis-succinimide mixture) 0.4 wt. 2,6-di-tert-butyl-4-methylphenol (ionol) 0.3% wt. 4,4‘-methylene-bis-2,6-di-tert-butylphenol (Vanlube DTB) 2.5 ° / wt. Calcium alkyl salicylateBasic 2.5 wt. calcium alkylphosphate basic. 3.0 wt. Low Calcium Petroleum Sulfonate (PS-30 ex) 2.5% wt. polymethacrylate viscosity modifier and oil reducer (Plexol 957 M) 0.7 wt. viscosity modifier (Shellvis 50) 83.9% wt. base oil total 100.0% wt. The results of the evaluation of the resulting oil by labo-boron tests and the AVI test by a single-cylinder gasoline engine Petter: kinematic viscosity at 40 ° C, mm 2 s = 87.0 at 100 ° C, mm 2.s4 12.6 VIE 140 flash point at 0 k. , ° C 208 freezing point, ° C —38 TBN, mg KOH / g 8.5 carbonization residue,% wt. 1.55 sulfate ash,% wt. 1.3 dynamic viscosity (on CCS), at -17.8% Pa.s 4.9 mechanical stability, DIN 51 382, viscosity drop after 30 cycles,% 3.8 test AVI on petrol engine Petter, points (average from 2 tests) 90.5 246897 The results of the evaluation confirm the high quality of this oil. The result of the AVI assessment on the petrol enginePetter lies in the upper half of the prescribed point-to-point assessment of the C-group oils according to the CMEA specification (approximate API group according to API specification). Example 2 Automotive, semi-synthetic, viscosity grade 15W / 40 automotive oil, belonging to Groups D2 to E of the RVHP Specification (approximate CC to CD specification according to API specification), was prepared:

Partial Synthetic Base Oil: 27.0% wt. the synthetic component of Example 1 was 56.0 wt. petroleum oil R 935 a of Example 1 17.0 wt. petroleum oil R 953 a of Example 1 together 100.0% wt.

The composition of the resulting additive-treated oil-synthetic: 1.4 wt. 0.3% wt. 0.6% wt. 0.75% wt. 4.0% wt. 3.0 wt. 1.0 wt. 4.0% w / w wt. 2.6% wt.

Zn-dithiophosphate (MuliditOB) diphenylamine 4,4'-methylene-bis-2,6-di-tert-butylphenol (Vanlube DTB) molybdenum-sulfuric friction modifier and anti-oxidant (Molyvan 822) succinamide additive (S 5A) calcium alkylsalicylate calcium basic calcium calcium alkylphosphate basic succinimide adductscobasic (PS-30ex.) polymethacrylate viscosity modifier and oil bt reducer (Plexol 956) 10 0.7 wt. viscosity modifier (Shellvis 50} 0.002 wt% silicone defoamer (Lukoil FM) to 100 wt% base oil partially synthetic. Results of evaluation of the resultant additive oil by laboratory tests of AVB (IP 279/77) on a supercharged diesel engine - Petter: kinematic viscosity at 40 ° C, mm2.s_1 94,5 at 100 ° C, mm2.sd 12,8 VIE 131 flash point at ok, ° C 212 freezing point, ° C —40 TBN, mg KOH / g 8.6 carbonization residue,% wt 1.45 sulfate ash,% wt 1.2 dynamic viscosity (on CCS) at -17.8 ° C, Pa s s

AVB test on a diesel turbocharger Petter: 1. piston groove, points 7.8 1st bridge, points 7.5 piston shell, points 10 inner bottom, points 8.7 compression rings sealing, points 10 total value, points 89.4

Note: Maximum points - for individual indicators 10 - for overall evaluation 100 The results of the evaluation express very good physico-chemical and functional properties of this oil according to laboratory and diesel engine turbocharged tests. According to the AVB test score achieved on a fixed fuel diesel engine, the oil exceeds the Group D pre-spot point limit and falls within the Group E point range (as specified by the CMEA), corresponding to the approximate CD group (according to aAPI).

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.