CS260337B1 - Lubricating oil with admixture for heavy-stressed spark-ignition engines and compression ignition engines - Google Patents

Description

The invention relates to lubricating oils for thermally and mechanically stressed positive-ignition and compression-ignition engines, used in particular in automobile and rail transport.

Lubricating oils used for piston group lubrication, cylinders, crankshaft bearings, and valve guides of high-performance internal combustion engines are exposed to relatively high temperatures in the cylinder compartment while in contact with combustion gases containing unused oxygen, oxides and products of incomplete combustion and other fossil fuels. As a result of their action, the lubricating oil is subject to oxidative conditions and other signs of 'aging' to form oxyacids and corrosive products. Oxyacids are formed by polycondensation reactions in the oil poorly soluble high carbonaceous products which are 1'ahko deposit in the form of hard carbon coatings and deposits particular functional sites of the hot piston of the engine, which may lead ^one to baking piston rings of the engine and deterioration of the disablement of the engine activities.

Serious defects also cause sludge deposits in the engine, which occur when the engine is running cold under the conditions of intermittent operation of cars in urban pro2 right, especially at lower ambient temperatures.

Due to partial oxidation products of lubricating oil hydrocarbons, mainly connecting rod bearings and wear, especially valves, valve manifold system, cams, hoists and valve weights are subject to corrosion wear.

Lubricating oils for heavy-duty spark-ignition and compression-ignition engines consist of a suitable refined petroleum oil, suitably supplemented with modifiers to reduce the freezing point and improve the theological and foaming properties, with a freezing point of not more than -10 ° C, kinematics. a viscosity of 7 to 18 mm ² / s at 100 ° C, a viscosity index of 80 to 150 and a complex of additives to improve antioxidant, anticorrosive, anti-abrasion and detergent dispersant properties that ensure good lubricating oil life and increased engine cleanliness, low wear thus operational reliability and long-term functional capability.

The base petroleum oils used are selective raffinates, obtained by solvent extraction of polar unstable components, removal of asphaltenes, for example propane, solid paraffins and ceresines, using solvents after. low temperatures and by removing the remainder of the unstable polar substances by adsorption preferably on active clays or by hydrogenation. Suitable base oils are also obtained by medium or high pressure hydrogenation by deasphalting oil distillates. Modifying components, which are commonly refined petroleum oil raffinates, are of several types. As freezing point depressants, the most widespread are polyalkyl methacrylates and alkylnaphthalenes, as antifoams, in particular silicone oils, and as viscosity modifiers with a viscosity index, polymers and copolymers of unsaturated compounds, in particular alkyl esters of acrylic and methacrylic acid, hydrocarbon polymers and ethylene copolymers and ethylene copolymers (butadiene and isoprene). For multigrade engine oils, lower kinematic viscosity base oil raffinates are used and the corresponding, relatively high proportion of viscosity modifiers gives them a fairly high viscosity at elevated operating temperatures (100 to 150 ° C) at low viscosity at low temperatures, allowing good start-up. engine under winter conditions.

An important component of lubricating oils for heavy-duty spark-ignition and compression-ignition engines is the additive complex with antioxidant, anti-abrasion and detergent-dispersant properties.

For many years, various detergent and dispersant compounds have been applied in engine oils, which have a beneficial effect on engine cleanliness by limiting the deposition and deposition of carbonaceous products on engine components. Of the known types of compounds I apply! oil-soluble salts of sulfonic acids, phenol alkyl derivatives and alkylsalicylic acid as detergent-dispersants, the effect of which is particularly pronounced at high engine temperatures, and the metal salts of phosphonic acid derivatives which even under the condition of cold, intermittent engine operation. These known types of detergent dispersants can significantly improve the application properties of motor oils, especially if they are supplemented with known inhibitors of multifunctional action of metal salts of dithiophosphoric acid diesters, which have antioxidant, anticorrosive and antiperspirant effects. However, it is known that the requirements for higher grade motor oils cannot be met individually, with only some of the high ripening of the detergent-dispersant, by using any of the listed ingredients.

The effect of the ingredients is substantially improved by the use of mixtures of several kinds of ingredients, for example by the more widely used sulfonate and alkylphenolate compositions (Chimija i technologija topliv i butts No. 3, 1963 J), which are also supplemented with ingredients to improve antioxidant and antioder properties. , xanthogenates and organic phosphites (USP 3,007,869, U.S. Pat. No. 1,112,804, French Pat. 2, 009,296 and US Pat. No. 268,582).

Increased engine cleanliness, even under operating conditions, is achieved with mixtures of alkaline earth metal salts of alkylphenlates and / or alkylarylsulphonic acids or petroleum sulphonic acids with alkenylsuccinic acid amides, imides or esters whose hydrocarbon substituents have a mole%. weight preferred 800—2000.

Good effects are obtained in motor oils with compositions of additives based on metal salts of substituted sulfonic acids and alkenylphosphonic acid derivatives (USP 3,170,881, British Pat. 958,520, U.S. Pat. No. 1,290,647), especially in admixture with zinc dithiophosphoric diesters. acids (USP 3,445,386) or with compositions based on alkylphenolates and alkenylthiophosphonates of alkaline earth metals (brit. pat. 960,053 and 1,039,792, US Pat. No. 243,762, USP 3,182,019, USP 3,377,282) and with compositions containing and alkaline earth salts of sulfonic acid derivatives (No. AO No. 167 120).

As oil additives, the dispersing and antioxidant properties of the Mannich base obtained by the reaction of alkylphenols, the alkyl substituents of which are mol. weight of 300 to 1200, with formaldehyde and organic amines, in particular polyalkylene polyamines (USP 3,697,574, 3,751,365, 3,756,953).

Ingredients of the Mannich base type are not enough! with known methods for formulating engine oils suitable for heavy-duty automotive and rail transport engines.

We have found that the demanding requirements of lubricating oils for heavy-duty spark-ignition and diesel engines are met when a complex additive is used in a suitable refined base oil based on a Mannich-base compound whose total base is 50 to 150 mg KOH / g, provided colloidal dispersed carbonate and / or alkaline earth metal hydroxide in a mixture of oil concentrates. alkali earth metal salts of substituted sulfonic acids and phenol derivatives, and optionally phosphonic acid derivatives and a metallic, preferably zinc, dithiophosphoric acid diester salt.

Such engine oil has detergent, dispersing, anti-abrasion, anti-corrosion and antioxidant properties even under severe temperature conditions of heavily staged internal combustion engines.

The present invention relates to a lubricating oil for heavy-duty petroleum or regenerated petrol and diesel engines in which the aromatic carbon content is not more than 12% by weight. %, comprising, as desired, polymeric viscosity modifiers and a freezing point depressant as the base and 0.8 to 10 wt. % Of the active substances of the complex multifunctional additive, the oil base having a viscosity index of at least 75, a kinematic viscosity of 5 to 18 mm ² / s at 100 ^° C, a pour point of at least -10 ° C, a flash point of at least 190 ° C the substances of the complex additive are a mixture of 5 to 35 wt. % Of a dithiophosphoric acid-containing, preferably zinc, di-alkyl- and / or dialkylphenyl ester containing alkyl groups having 1 to 20 carbon atoms, 10 to 40 wt. % of a compound of the Mannich base type of the general formula

QH -l · · Ji—c:>

, NHA &

Ú-CKNH (c, .Η N · -}; ... CK • j 2 ⁱⁿ Z * · - i 2. r

Ktoromμ 'í in which

R 8 is alkyl or alkenyl of 8 to 80 carbon atoms,

A is C 1 H 2 _n NHX or - (C 2 H 1 NH) n X, X is hydrogen or alkyl, alkenyl or R 1 CO-, or R 1 CO.OHx ', or -B (OH) 2, -B - ^ - O, wherein R 1 is H or alkyl C1 to C20 and n is 0 to 4, further 10 to 35 wt. % Of the alkali earth metal salts of alkylarylsulfonic or petroleum sulfonic acids of average mol. 760 to 2000, 15 to 45 wt. percent of the alkaline earth metal salt of the phenol derivative of the formula n

H Zeb o

Ol ·!

R

R is

R is alkyl of 6 to 30 carbon atoms;

X is -S-, or -S-S- or -CH 2 - and a colloidally dispersed carbonate and / or alkaline earth metal hydroxide, providing a total basicity of the complex additive of 50 to 150 mg KOH / g.

In the active ingredient mixture of the complex additive, the alkaline earth metal salt ^{1 of the} phenol derivative may be partially in an amount of at most 40 wt. % replaced by the alkaline earth metal salt of the phosphonic acid derivative of the general formula

X XR ‘

11

Or

X X

II II

RP — X — PR

I I

XR ‘XR ktorej in which

R is a hydrocarbon group mol. weight of 500 to 2000,

X is oxygen or sulfur; and

R 1 is hydrogen or an alkaline earth metal equivalent or an organic amine or - (C _n H 2 _n O) _m H where n is 2 or 3 and m is 1 to 5.

The base oils used are selectively the raffinates of the vaporized middle vacuum distillate treated with a contacting bleaching clay of kinematics. viscosity according to viscosity class of lubricating oil min. 5 mm ² .s ^x at 100 ° G, flash point at least 190 ° C, preferably above 200 ° C, or hydrogenated refined vacuum oil distillates, dewaxed, or a mixture of selective dewaxed and hydrogenated raffinates, or regenerated oil raffinates such as obtained from spent oils, such as sulfuric acid, neutralization, distillation and contact with bleaching clay, or other technology. Selective raffinates are oil blends obtained from vacuum petroleum distillates, usually after dewaxing, by extraction of polar fractions, e.g. furfural, cresol or a combination of propane and cresol.

To provide the desired freezing point, viscosity and viscosity index, base oils are supplemented as necessary with a freezing point depressant such as a polyalkylmethacrylate or alkylnaphthalene type and a viscosity modifier such as polymers and copolymers of unsaturated compounds such as polybutenes or ethylene polymers or polymethacrylates styrene-isoprene.

The base oil raffinate or regenerate normally also contains components which reduce foaming and provide protective action of the oil against rusting of structural steel machine parts. Suitable anti-foaming agents are, in particular, suitable polysiloxanes and, as rust inhibitors, carboxylic acid derivatives, for example alkenylsuccinic acid, fatty acid amides, alkylimidazoline derivatives.

An important component of the lubricating oil for sine-stressed petrol and diesel engines is the complex multi-purpose additive according to the invention.

The dithiophosphoric acid diesters, if present, are obtained by reacting aliphatic alcohols or C 1 -C 20 alkylphenols or mixtures thereof with phosphorus pentasulfide and the resulting dithiophosphoric acid diesters of formula (RO) 2P-SH are treated in the next step with oxygen , metal hydroxide or carbonate to form metal salts. Preferred are the zinc salts of dialkyl dithiophosphoric esters with alkyls having 3 to 9 carbon atoms.

A compound of the Mannich base type is the product of the reaction of phenols with formaldehyde or its polymers and with organic amines. The phenolic group in the Mannich base molecule contains alkyls of 8 to 80 carbon atoms. In view of the desired dispersing effects, the alkyls have a preferred mol. The alkyl substituent is also bonded to the amino group, especially in the case of compounds of the Mannich base type with shorter alkyls on the aromatic ring.

Preferred organic amines are diamines or polyamines, in particular diethylenetriamine to tetraethylenepentamine. In order to improve its properties, the compound of the Mannich base type, depending on the nature, also contains functional groups of carboxylic acids or boric acid.

The alkali earth metal salt of alkylarylsulphonic acid or petroleum sulphonic acid is obtained by sulphonating an alkylbenzene or petroleum fraction raffinate of an average mole. % of the weight of the preferred 350-500, for example a mixture of mono- and didodenylbenzene, and the sulfonic acids obtained are converted into the neutral to high-alkaline alkaline earth metal salts in the form of oily concentrates by known methods. High-base calcium salts contain commonly colloidal dispersed carbonate and calcium hydroxide and, at a total basicity of about 300 mg KOH / g, are a major source of increased basicity of the complex additive and lubricating oil.

The component of the alkaline earth metal salt of the phenol derivative is the preferred sulfides and disulfides of mono- and dialkylphenols having from C 1 to C 30 alkyl. Applying! and methylene-bis-alkylphenols, often in admixture with sulphated alkyl- or arylalkylphenols. Most preferred are calcium salts of alkylphenol derivatives in which the basicity is usually increased by the content of colloidal dispersed carbonate and calcium hydroxide to values of 100 to 250 mg KOH / g. They contribute to the antioxidant and detergent dispersant properties of the complex additive and the thermal stability of the lubricating oil.

The properties of the complex additive are improving! as necessary with phosphonic acid derivatives. The phosphonic acid derivatives according to the invention are the reaction products of olefins mol. weight of 300 to 2000 based on polymers of propene or butenes with phosphorus sulphide or a mixture thereof with phosphorus pentoxide. In order to increase the conversion, the products of this reaction, containing thiophosphonic acid thioanhydrides, are preferably subjected to hydrolysis, increasing the alkyl- and alkenylphosphonic and thiophosphonic acids. The thiophosphonic and phosphonic acids formed in this reaction are further processed to the compounds of the above formula, for example, metal salts, preferred alkaline earth metal salts by reaction with a hydroxyl group, oxygen or carbonate of a Group 2 perlodic system or by reaction with organic amines or urea derivatives. to amine salts, amides or imides of phosphonic and thiophosphonic acid derivatives or to hydroxyalkyl esters by reaction with ethylene oxide or propylene oxide.

The complex additive according to the invention is preferably prepared by mixing the ingredients in an appropriate weight ratio. It may also be obtained by reacting a stoichiometric excess of an alkaline earth hydroxide or oxygen, for example calcium, with a mixture of alkylaryl or petroleum sulfonic acids or their salts and phenol derivatives, and introducing carbon dioxide in the presence of promoters, e.g. AO 190 767, and after treatment by sequential admixing of a phosphonic acid derivative, a Mannich base compound and a metal salt of a dithiophosphoric acid diester derivative.

The lubricating oil of the present invention may also contain other ingredients to improve the antioxidant, anticorrosive, anti-abrasion and detergency dispersant properties of, for example, succinic acid and the metal alkylsalicylic acid salt.

The additive lubricating oil for the heavily stressed petrol and diesel engines of the present invention is prepared by mixing the oil base of the required viscosity and viscosity index preferably with a preformed complex multifunctional additive, but can also be prepared by mixing the individual components of the complex additive into the oil base.

Depending on the application conditions, the additive lubricating oil may be a single-stage SAE 20, 30 or 40 viscosity triode, or multi-stage, in particular SAE classes 10W / 30, 10W / 40, 15W / 40 and 15W / 50, and depending on the additive content Classes B to E, respectively. B1 / C2, C1 / C2, D1 / D2, C2, D2 and E (according to GOST 1479-72).

The good application properties of the lubricating oils and the complex multifunctional additive according to the invention result from the Petter engine test evaluation, which follows from the following examples.

Examples

The following tables show the engine test evaluations of the additives according to the invention (samples 1 to 6) and the composition data with characteristic parameters and the comparative oils (samples 7 and 8).

Oil base:

- selective dewaxed raffinate, hydrotreated with 0.7 wt. % selective methacrylate additive (with the exception of sample No 3, containing 1,5% w / w styrene-isoprene copolymer, - selective dewaxed oil raffinate, bleached clay containing 0,7% w / w polymethacrylate additive, - heavy dewaxed hydrogenate, doraffinated bleaching clay, preferably redistilled, containing 0.7% by weight of polymethacrylic additive.

Í0

Components of a complex multifunctional additive:

Component A --- salts of dialkyldithiophosphoric acid

Al-Zn salt of dialkyldithiophosphoric acid with C4 and C3 alkyls containing 8.6 wt. % Zn, 7.7 wt. % P;

% Active ingredient concentrate

A2 - Zn salt of dialkyldithiophosphoric acid with straight chain alkyl of 6 to 10 carbon atoms, 7.5 wt. % Zn, 7.0 wt. % P, 80% of active ingredients

Component B - alkaline earth metal salt of phenol derivative

B1 - oil concentrate of Ca-salts of alkylphenol sulphide, C1-C20 alkyls, active ingredient content 50%, Ca content 5.1 wt. %, S 2.8 wt. %, TBN 145 mg KOH / g

B2 - oil concentrate of Ca-salts of alkylphenol sulphide, 50 wt. % of active ingredients, 9.2 wt. % Ca, 3.2 wt.% S, TBN 250 mg KOH / g ⁷ Wl

Component C - of an alkaline earth metal in oil-soluble sulfonic acid

Cl - oil concentrate of petroleum Ca-sulfonates, 32 wt. % of active substance, avg. mol. weight 870, 2.1 wt. Ca / TBN 12 mg KOH / g

C2 - oil concentrate of high base petroleum sulfonate, 28 wt. % sulfonates, avg. mol. weight 900, 11.8 wt. % Ca, TBN 290 mg KOH / g

Component D of a compound of the Mannich base type - bis hydroxyalkylbenzylamine

D1 - oil concentrate 40 wt. % of active substance, alkyl polybutene C. 15-C70, amine tetraethylenepentamine borate, content B 0.2 wt. %, N 1.1 wt. %, TBN 25 mg KOH / g

D2 - oil concentrate 40 wt. % of active ingredient, alkyl polypropylene C20-Cbo, amine diethylenetriamine, N content 1.2 wt. percent, TBN 32 mg KOH / g

Component E - phosphonic acid derivative

E1 - oil concentrate of Ca salts of alkenylthiophosphonic acids, content 50 wt. % of active ingredients, 2.0 wt. % Ca, 2.0 wt. % P, alkyl polypropylene average mol. weight 720, TBN 50 mg KOH / g

E2 - oil concentrate of alkenylthiophosphonic acid hydroxyalkyl ester based on polybutene average mol. 940 and ethylene oxide, phosphorus: ethylene oxide 1: 0.5 (mol), treated with urea, contains 2.3 wt. %

1,9, 1.9 wt. % S, 0.4 wt. % N, active ingredient content 50 wt. ° / o, TBN 32 mg KOH / g

E3 - oil solution of Ba-alkenylthiophosphonic acid salts, active substance content 50 wt. θ / ο, 9.2 wt. % Ba, 1.1 wt. percent P, alkyl polybutene average mol. weight 780, TBN 65 mg KOH / g.

Table

Sample number 1 2 3 7 Oil base - type 1 2 1 1 Content of oil concentrate additive mass % 4.2 4.2 5.2 4.0 Active substance content of complex additive mass % 2.02 2.02 2.39 2.04 Kinemat. viscosity at 100 ° C mm ² / s 12.6 12.4 15.1 12.4 Viscosity index 91 92 142 92 Freezing point ° C —26 —26 —32 —26 Apparent viscosity at -18 ° C Pa. with - - 2.4 - Flash point ° C 232 234 198 232 Active ingredients of a complex additive: Component A - kind AI AI AI AI oil content % 0.64 0.64 0.64 0.64 content in complex mass additive % 31.7 31.7 26.8 31.3 Component B - kind Bl Bl Bl B2 oil content % 0.4 0.4 0.5 0.45 content in complex mass additive % 19.8 19.8 20.9 22.1 Component C - kind Cl Cl Cl Cl oil content % 0.16 0.16 0.16 0.35 content in complex mass additive % 7.9 7.9 6.7 17.2 species C2 C2 C2 - oil content % 0.17 0.17 0.25 - content in complex mass additive % 8.4 8.4 10.4 - Component D - kind Dl D2 Dl - oil content % 0.4 0.4 0.64 - content in complex mass additive % 19.8 19.8 26.8 - Component E - kind El El El E2 oil content % 0.25 0.25 0.2 0.6 content in complex mass additive % 12.4 12.4 8.4 29.4 Petter Engine Rating AVI AVI AVI AVI Total points 87.4 86.9 86.8 83.0

Table continuation

Sample number 4 5 6 8 Oil base - type 1 2 3 1 Content of oil concentrate additive mass % 12.0 12.0 12.3 13.7 Active substance content of complex additive mass % 4.97 4.97 5.16 6.11 Kinemat. viscosity at 100 ° C mm ² / s 12.3 12.2 12.4 12.2 Viscosity index 91 92 94 93 Freezing point ° C —30 —28 —30 —30 Flash point ° C Active ingredients of a complex additive: 228 230 232 226 Component A - kind Al A2 Al Al oil content % 0.64 0.64 0.64 0.48 content in the complex additive hm-ot. % 12.9 12.9 12.4 7.8 Component B - kind Bl Bl Bl B2 oil content % 1,8 1.55 2,0 2.4 content in complex mass additive % 36.2 31.2 38.8 39.3 Component C - kind Cl Cl Cl Cl oil content % 0.54 0.54 0.48 1.63 content in complex mass additive % 10.9 10.9 9.3 26.7 species C2 C2 C2 - oil content % 0.87 0.87 0.84 - content in complex mass additive % 17.5 17.5 16.3 - Component D - kind Dl Dl Dl n oil content % 1.12 1.12 1,2 1.0 content in complex mass additive % 22.5 22.5 23.2 16.4 Component E - kind - El - E3 volley mass content % - 0.25 - 0.6 content in complex mass additive % - 5.0 - 9.8 Petter Engine Rating AVB AVB AVB AVB Total points 81.7 81.4 80.2 82.2

Explanatory Notes: ¹ ] Succinimide type ashless dispersant

Claims (2)

Lubricating oil with additive for heavy-duty petroleum and diesel engines based on petroleum oil or regenerator, in which the aromatic carbon content is max. 12% by weight. %, Comprising, if desired, polymeric viscosity modifiers and a freezing point depressant as a base and 0.8 to 10 wt. % of active ingredients of a complex multifunctional additive, characterized in that the oil basis has a viscosity index of at least 75, a kinematic viscosity of 5 to 18 m ² / s at 100 ° C, a pour point of at most - 10 ° C, a flash point of at least 190 ^° C , and the active ingredients of the complex multifunctional additive are a mixture of 5 to 35 wt. % of a metal, optionally zinc salt of a dialkyl and / or dialkylphenyl dithiophosphoric ester containing alkyl groups of 1 to 20 carbon atoms, 10 to 40 wt. % of a compound of the Mannich base type of the general formula OH X. o 'J' Oh i Oh -7 ' IN. 280337 in which R is alkyl or alkenyl of 8 to 80 carbon atoms, A is - C _n H 2 _n NHX or - (C ₂ H 4 NH) _n X, X is hydrogen or alkyl, alkenyl or R 1 CO - or R 1 CO. . OH2 ⁺ , or - B (OH) 2, —B = O, wherein R1 is H or C1-C20 alkyl, and n is 0 to 4; 10 to 35 wt. % of an alkali earth metal salt of alkylarylsulfonic or petroleum sulfonic acid of an average mol. 760 to 2000, 15 to 45 wt. % of the alkaline earth metal salt of the phenol derivative of the general formula in which it is R is alkyl of 6 to 30 carbon atoms and X is -S-, or -S-S-, or -CH 2 -, and a colloidal dispersed carbonate and / or alkaline earth metal hydroxide, providing an overall basicity of the complex additive of 50 to 150 mg KOH) G. 2. Additive lubricating oil for heavy-duty spark-ignition and compression-ignition engines according to Claim 1, characterized in that the alkaline earth metal salt of the phenol derivative is present in an amount of at most 40% by weight in the mixture of active ingredients of the complex additive. % replaced by a phosphonic acid derivative of the formula or X X RP — X — PR, XR ‘XR ktorom in which R is a hydrocarbon group mol. X is oxygen or sulfur and R 1 is hydrogen or an alkaline earth metal equivalent or amine or - (C _n H 2 _n O) _m H where n is 2 or 3 and _m is 1 to 5. X XR ‘ 11 RP \ XR ‘