CS213169B1 - Multistage lubricating oil for petrol and crude oil motors - Google Patents

Abstract

The invention relates to a method of preparation multi-stage lubricating oil for petrol and / or diesel engines, consisting of of base oil of petroleum or. \ t partial synthetic and refining ingredients. The oil contains 2.0 to 20.0 wt. ingredients % detergent, calculated as 5% concentrates such as alkali metal sulfonates soils, calcium alkylsalicylates, calcium alkyl alkyl phenol sulfides and barium, 0.2 to 10.0 wt. admixture additive counted on the effective ingredient as sfi succinimides, bissuccinimides, phosphonates and thiophosphonates, 0.2 to 4.0% lubricating additives, counted on the effective ingredient as are dithiophosphates, preferably zinc and the like a number of modifiers VI, such as polymethacrylates, copolymers of alkenes and copolymers styrene with butadiene or isoprene, to obtain the desired viscosity oil of the appropriate class

Description

The present invention relates to a multi-stage oil for gasoline and diesel engines which consists of a base oil of petroleum or partially synthetic and refining additives.

According to the classification SAE and RVHP, engine oils are divided in one stage according to their kinematic viscosity at -18 ° C and at 100 ° C into several viscosity classes and into two main groups - winter and summer oils. Multi-stage lubricating oils overlap two or more viscosity grades and meet the requirements for both summer and winter oils.

These properties of multi-stage oils, which are useful both in winter and in summer, impart to them polymeric additives, so-called " viscosity modifiers, viscosity index enhancers (VI), which increase the viscosity and improve the viscosity-temperature properties of oils. These oils increase above 100, often to 150 to 180, as viscosity modifiers and VIs. Especially polymethacrylates having the depressant effect on the freezing point of the oils and may have a detergent dispersant effect, styrene-butadiene or isoprene copolymers, alkene copolymers, in particular ethylene and propylene, polybutenes and polyisobutenes. More recent types of polymethacrylate additives exhibit substantially improved shear stability, approaching the values of styrene-isoprene or butadiene copolymers. In addition to these additives, the multi-stage oils also contain the additives getergent and dispersing, antioxidant-lubricating and anti-abrasion. They may further comprise corrosion and rust inhibitors, anti-foaming agents (biocides), oil and odor enhancing additives, and others.

The multi-stage lubricating oil for gasoline and diesel engines has a water discharge reaction of neutral or preferably alkaline and total alkalinity (TNB) in the range of about

2.5-15 mg KOH / g, wherein the alkalinity is related to the oil triod, pour point at most -25 ° C, preferably at most -30 ° C, Vlg at least 100, preferably at least 110, and viscosity at -18 ° C at most 15,000 mm ² . preferably at most 10 400 mm ² . s ^_1 .

Base oil for multi-stage oils must meet certain requirements. Petroleum oil fractions are divided into fractions with a low VI below 30, a medium VI 30 to 90, a high VI above 90. Oil components with a high VI above 90 are required for base oils of multi-stage oils. Such suitable oil frankings (exhibit a favorable point) and are found mainly in paraffinic oils. Naphthenic oil fractions exhibit a favorable pour point, up to -40 ° C, but having a VI below 45, rarely up to 65, and have an undesirably high evaporation. According to German patent no. However, 1 594 631 (1964) may be used for the manufacture of multi-stage engine oils if they have a viscosity above 5.6 oSt at 100 ° C and a VI of at least 45, while maintaining a certain ratio to paraffin oils, their disadvantages being counterbalanced by the addition VI.

In order to achieve a high VI of the oil oil fractions, these must be refined in some way. The residual fraction from atmospheric pressure distillation oil, the so-called wide residue, is distilled under destroyed pressure, usually to four fractions, namely three distillates and so-called. narrow residue. The distillation fractions obtained must be first de-asphalted (most often with propane), then de-automated (most often with furfurel) and evaporafinwanium (most often with cold in the presence of a solvent such as a mixture of methyl ethyl ketone and toluene and other solvents, or more rarely with

213 µM urea). The sequence of no less than two refining operations may also be exchanged. Sometimes the oil fractions are subjected to medium pressure catalytic hydrogenation. They also use high-pressure hydrogenation oil fractions, which can reach very high VIs, around 140.

By mixing the recovered refined fractions, namely the light distillate fraction (spindle oil), the middle distillate fraction (light 8-engine oil), the heavy distillate fraction (medium machine oil) and the residual oil fraction (residual oil, brightstock), each base can be made. However, it is not necessary to use all four fractions to produce such a base oil. In principle, one (eg medium) fraction can be sufficient. However, mixtures of at least two fractions with significantly different viscosities are preferred. The nature of the fractions used and their proportion in the base oil depends on the viscosity grades of the multi-stage oils or the requirements according to the intended use.

Further improvement of the functional properties of the multi-stage oils can be achieved by the addition of suitable synthetic oils, so-called " partially synthetic oils. The base oil of the partially synthetic multi-stage lubricating oil for gasoline and diesel engines contains about 10 to 60% by weight, practically (for technical and economic reasons) about 15 to 30% by weight of synthetic oil such as diester oils based on dicarboxylic acids. g of aliphatic monoalcohols C8 to C18, in particular branched as 2-ethylhexanol and oxoalcohols Ο ^ θ to oils of the type of polyol polyol esters, in particular pentaerythritol and aliphatic monocarboxylic acids, in particular Οθ to Οθ, oils based on complex esters, or polymeric alkene hydrocarbons, such as hydrogenated polymers of 1-alkene oligomers. Of the ester oils, with regard to their thermal stability, diester oils are particularly suitable for oils for gasoline and non-turbocharged diesel engines and polyol esters as well as for turbocharged diesel engines.

Multistage semi-synthetic engine oils are generally additive with the same additives as the same types of pure petroleum base oil. On the other hand, full-synthetic oils require special additives and fundamentally different additives. Multistage partially synthetic motor oils usually require less additives, in particular detergent, dispersant and antioxidant, as well as types of pure petroleum base oil to achieve the same performance. For example, with a synthetic component content of partially synthetic oil of about 20% by weight, the reduction in the addition of said additives may be up to about 20%.

Increased content of viscosity-increasing polymeric additives and VI of multi-stage oils generally requires an increase in detergent-dispersant ingredients of about 10 to 30% or more, compared to analogous single-stage oils, because the polymers affect the effect of these additives and promote the build-up. 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, in particular, detergent-dispersants with a metal content of the molecule and, in particular, their high-base types, is present in multi-stage motor oils.

213 IBS subject to the condition that the sulphated ash content of these oils may not exceed 2% by weight in accordance with the earlier requirements and not more than 1,5% by weight in accordance with the more recent requirements. For this reason, among other things, dispersants of ash-free or low-ash type, mainly acting against the formation of low-temperature sludge, such as succinimides, are increasingly used in multi-stage engine oils as compared to single-stage oils (to which the above-mentioned sulphated ash content is not limited). preferably bissuccinimides, phosphonates and thiophosphonates.

The total content of detergent, dispersant, antioxidant and oil lubricant enhancers under elevated pressure varies between the various groups of multi-stage engine oils specified in the engine oil specification by application, recommended by the Permanent HVHP Commission for the oil and gas industry (in parentheses) approximate matching API group) within approximately the following ranges:

Group B: Bj, Bg (SC, CA): 3-6% wt Group C: C C, Cg (SD, CB): 5-10% wt Group D1, Dg (SE, CC): 8-15 wt group Et (CD): 12 to 20 wt.

Multistage engine oils for petrol and diesel engines have the following advantages over single-stage oils: better cold start (improved helpless start-up), reduced abrasion, mainly bearings, less oil consumption, especially using heat and shear stable polymer system fuel, especially when driving with frequent stopping and stop-and-go.

The present invention is directed to multi-stage lubricating oils for gasoline and diesel engines, consisting of a base oil of petroleum or partially synthetic and quenching additives added in limited proportions, which exhibit all known advantageous properties of multi-stage oils and fully meet the quality requirements prescribed for each the performance classes of these oils (B, C, D, according to the CMEA classification) and evaluated by internationally recognized laboratory physicochemical, application and ethanoan motor tests. In particular, it should be pointed out (as can be seen from Examples 2 and 3) that multi-stage engine oils can also be prepared according to the present invention, which have a grade E prescribed rating (CD or MIL-L- 45 199 B, Series 3). According to the present invention, it is also possible to prepare types of multi-stage engine oils which are also suitable for a mixed fleet of gasoline and diesel engines, which are currently under constant development.

Further, multi-stage oils for gasoline and / or diesel engines with extended oil change intervals above 10,000 km, up to about 100,000 km, can be prepared according to the present invention. When preparing these oils, particular care should be taken that their oil fractions are narrow and small in high VI, that the viscosity modifiers exhibit high shear stability, that the increased content of additives, particularly detergent and dispersant, be maintained and that the alkalinity of these oils is maintained at? sufficient height.

Multistage lubricating oil for petrol and / or diesel engines according to the invention,

213 131 consists of a base oil of petroleum or partially synthetic and quenching additives, the base oil having a viscosity of about 5.5 to 9.5 mm 2, depending on the respective range of viscosity classes of the resulting oil. with ^{1 1} at 100 ° C and VI of at least 90, preferably about 100, pour point at most -8 ° C, preferably at most -12 ° C and flash point * at least 200 ° C and consists of at least one oil component, preferably from two or more oil components (fractions obtained by distillation under reduced pressure from an atmospheric distillate petroleum residue, selectively refined, dewaxed, optionally previously asphalted and, if appropriate, still hydrogenated, or fractions from high pressure hydrogenation of different viscosities in the range of 4,0 to 1 rt

30,0 mm. and at 100 ° C and the partially synthetic base oil contains, in addition to the oil fraction, the above compositions of about 10.0 to 60.0% by weight, typically about 15.0 to 25.0% by weight of a synthetic oil such as diester oils based on dicarboxylic acids mainly Cg and ^a aliphatic monoalkohélov Cg-C ^ g, especially branched chain such as 2-ethylhexanol, and oxo-alcohol Ο ^ θ to ^C 13 'oil-type polyol esters based on polyols mainly neopentyl structure, such as trimetylolalkány and pentaerythritol esters of aliphatic monocarboxylic acids, especially to Οθ , oils based on complex esters or polymeric alkali hydrocarbon oils such as polymers of 1-alkene oligomers hydrogenated and viscosity enhancers and improving viscosity-temperature properties, added in such an amount as to achieve the prescribed viscosity of the multistage oil according to the range of overlapping viscosities polymethacrylates who They also have a depregnating effect on the freezing point of the oils and, if appropriate, a dispersing effect, in particular polymethacrylates having improved shear stability, styrene copolymers with butadiene or isoprene, copolymers of olefins, in particular ethylene and propylene, preferably polydiphenyls and polybutenes, polybutenes. it also contained other commonly used additives such as low- and medium-temperature oxidation inhibitors, especially when the detergent-dispersant additive is also less antioxidant than eu alkylphenols and alkyl salicylates such as mononuclear monovalent alkylphenols, in particular shielded, bisphenols, bisphenols, aliphatic and aromatic amines primary, preferably secondary, tertiary, sulfur-containing or free of sulfur, alkylaminophenols, phenothiazines, dithiocarbamates, corrosion and rust inhibitors, friction modifiers, oil freezing point depressants, anti-foaming additives, for polysiloxanes, antiseptic (biocides), oil-improving and odor-improving oils and others, characterized in that it contains 2.0 to 22.0% by weight, preferably 3.5 to 12.0% by weight, of the getergent-dispersing additives of the sulfonate, alkylsalioylate, alkylphenolate and / or alkylphenol sulfide, calculated as 50% oil concentrates, the weight ratio of eulfonate additives to others, with a view to providing a synergistic effect, of at least 1 to 9 and preferably in the range of 1 to 2 and 3 to 2 0.2 to 10.0 wt.%, Preferably 1.5 to 5.0 wt. % of dispersing agents (mainly against low-temperature sludges) of the eukoinimide and / or the phonate and thiophoate, calculated on the active ingredient and 0.2 to 4.0 wt.%, and preferably 0.7 to 1.4 wt. antiperspirant di-thiophosphate, calculated for the active ingredient.

The gaseous oil for gasoline and / or diesel engines according to this invention5

213 189 lezu sa is 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 having a molecular weight of at least 300, preferably 350 to 390, alkylsalicylate additives are alkylsalicylates of calcium neutral and basic and with alkyl groups C ₁₂ to C ₂₂ , preferably C ₁₄ to C ₁₄ , the alkylphenol and alkylphenol sulfide additives are oil-soluble calcium and barium salts (magnesium has practically not spread), neutral and basic, based on alkylphenols and sulphated alkylphenols , preferably alkyl, and n _s váščimi, succinimide additives are succinimides, and mixtures bissukcinimidy and thiophosphate additives include alkyl, aryl and alkylaryltiofosfáty, preferably zinc, with a molecular weight of at least 435, preferably 635-826.

By way of illustration of the invention, non-limiting examples of the invention are given.

Example 1

Group C multi-stage engine oil, based on petroleum base oil and additives, was prepared and evaluated for its physicochemical and functional properties.

Base oil was prepared from three petroleum oil components by mixing them at 50 ° C: 40% by weight fraction with a viscosity of 4.90 mm ² . with ^ / 100 ° C and VI 95, 35% by weight of a fraction having a viscosity of 5.86 mm ² . with ^-1 / 100 ° C and VI 92 and 25% w / w fractions of viscosity 13.00 mm ² . with ^A1 ° C and VI 91.

The resulting multistage oil aa was prepared from the base oil and additives with stirring under an inert nitrogen atmosphere of the following composition:

calcium petroleum sulphonate low base oil concentrate calcium alkylsalicytate neutral, 50% calcium alkylphenolate basic, 50% zinc diacyldithiophosphate eucinimide additive (succinimide / bissuccinimide blend) polymethacrylate base with high shear base

Oil evaluation results: kinematic viscosity at 37.8 ° C, mm ² . s ¹ kinematic viscosity at 98,9 ° 0 mm ² . s ¹ viscosity index (VI _e ) flash point in mesh, ° C bSd solidification, ° C viscosity at -17,8 ° C, Pa.and aspiration base (THI), mg KOH / g

5.0 % hm 2.0 % hm 1.0 % hm 1.2 % hm 2.5 % hm 4.8 % hm 85.5 % hm

108.1

U 2

128.4

218.0

-36.0

5.9 (5900 cP) 7.90

213 IBS

Gonrads. carbonized. residue,% wt 1.41 kraft ash,% wt 1.12 platelet test according to Wolf (2 x 6 h at 250 C), sediment, mg 10, B test panel Coker (315 ° C, 8 h) coke area,% 6.5 AV 1 on Petter petrol engine, points (average of 2 tests) 89.7

The evaluation results show very good quality of this oil. The result of the scoring according to the AV 1 test on a Petter gasoline engine is in the upper half of the point range for Group C (approximate API CB).

Example 2

Preparation of multi-stage engine oil for categories D to E, based on petroleum base oil and additives, and evaluation of its physicochemical and functional properties.

The base oil was prepared from two petroleum oil components by mixing them at 48 ° C and a total of 73% by weight oil fraction having a viscosity of 6.43 mm ² . with ^11/100 ° C and VI 95.3 and 27% by weight oil fraction and viscosity 13.57 mm ² · s ^ / 100 ° C and VI 91.8.

Additives were added to the base oil under stirring, at 60 ° C, under a nitrogen atmosphere. The resulting oil had such a composition calcium petroleum sulfonate low base oil concentrate 5.0% wt calcium alkylphenolate basic 0.9% wt calcium alkyl salicylate neutral 2.2% wt calcium alkyl salicylate high base 2.3% wt zinc dialkyl dithiophosphate 1.1% wt biasuclimide 1.3% wt Plexol 937 (polymethacrylate additive) 3.2% wt Shellvis 50 solid (atyrene-isoprene copolymer) 0.8% wt base oil 83.2% wt

Results, evaluation of oil kinematic viscosity at 37.8 ° C <mm ² . s ^{1 1} kinematic viscosity at 98,9 ° C, mm ² . with ^{1 1} viscosity index (VI _# ) flash point in mesh, ° C freezing point, ° C viscosity at -17,9 ° C, Pa.and aspen base (TBN), mg KOH / g

Conrad. Carbon remainder,% ha and kraft ash,% wt wafers according to Wolf (2x6 h,

250 ° C) sediments, mg test Panel Ooker (315 8c, 8 h), cured area,%

167.1 18.47

133.2

222

8.95 (8950, cP) 12.6

1.62

1.48

12.5

213 IBS AVB battery on turbocharged diesel engine

Petter, points (average of two tests) 88.9

The evaluation results confirm the very good properties of this oil. The achieved AVB rating on the Petter site turbocharged diesel engine exceeds Group D (approximate CC by API) and responses to Group E (approximate API by CD).

Example 3

Preparation of multi-stage semi-synthetic engine oil for categories D to B and its evaluation. The oil was prepared by mixing 80 parts by weight of the resulting multistage engine oil as in case 2, and 20 parts by weight of a polyol ester prepared on the basis of pentaerethritol and monocarboxylic acids up to ^C 12 ^{with a} diameter of Cr, P ¹ and a temperature of 50 ° C.

Oil rating results:

kinematic viscosity at 37.8 ° C, mm ² . s ^-1 156.4 kinematic viscosity at 98.9 ° C, mm ² . s ^-1 17.60 viscosity index (VI _e ) 131.5 flash point in mesh, ° C 218 pour point -35 viscosity at -17.8 ° C, Pa.s ₊ 8.4 total run out, mg KOH / g 10.1

Conrads. carbon, residue,% wt 1.44 kraft ash,% wt 1.20 Wolf test plate (2 x 6h, 250 ° C), sediment, mg 6.1 Panel Coker test (280 ° C, 8h), coke area,% 22 AVB test on Petter turbocharged diesel engine, points (average of 2 tests) 87,2

The evaluation results express the very good physico-chemical and functional properties of this oil. For the AVB test on a turbocharged Petter diesel engine, the oil crosses the group boundary to the point range of Group E (approximate API CD).

(8400 cP) property and spa-

Claims (4)

Multistage lubricating oil for petrol and / or diesel engines, consisting of a base oil of petroleum or semi-synthetic and additives, the base oil having a viscosity of about 5,5 to 9,5 mm. s at 100 ° C and VI of at least 90.0, preferably about 100, and preferably consists of at least two oil components of substantially different viscosity in the range of 4.0 to 30.0 mm ² . s ^{1 1} at 100 ° C, the base oil partially synthetic contains, in addition to an oil fraction of said composition, about 10.0 to 60.0% by weight, preferably about 15.0 to 25.0% by weight of a synthetic oil such as ester oils or polymeric oils alkene-alkali bases 210 µs of water and viscosity enhancing additives and improving oil temperature-viscosity properties are added in an amount to achieve the prescribed viscosity of the multi-stage oil over a range of overlapping viscosity grades, and the oil may also contain other commonly used oxidation and corrosion additives gels, friction modifiers, oil-freezing point additives, anti-foaming, antiseptic, color and odor enhancing additives, and others, characterized in that it contains 2.0 to 22.0% by weight of the composition; % and preferably 3.5 to 12.0 wt. detergent-dispersing additives of the sulfonate, alkylsallcylate, alkylphenolate and / or alkylphenol sulfide, calculated as 50% oil concentrates, the weight ratio of the sulfonate to the other being at least 1: 9, preferably in the range of 1 &lt; 2 to 10.0 wt.%, Preferably 1.5 to 5.0 wt. diapergative agents of the aucoinimide and / or phosphonate and thiophosphonate counts, based on the active ingredient, and 0.2 to 4.0 wt.%, preferably 0.7 to 1.4 wt. Multistage lubricating oil for petrol and / or diesel engines according to claim 1, characterized in that the sulphonate, alkylaalicylate and / or alkylphenol sulphide additives are oil-soluble alkaline earth metal sulphonates, preferably calcium and magnesium, neutral and basic, petroleum and synthetic, alkylsalicylate calcium neutral and basic, alkylphenols and alkylphenolsulphides of calcium and ammonium, neutral and basic. 3. Multi-stage lubricating oil for petrol and / or diesel engines according to item 1, characterized in that the succinimide additives are succinimides, bissuccinimides and mixtures thereof. Multistage lubricating oil for petrol and / or diesel engines according to claim 1, characterized in that the thiophosphate additives are alkyl and alkyllarylthiophosphates, preferably zinc.