SK284909B6 - Admixture composition applicable to oil lubricating compositions, multifunctional additive engine composition and additive lubricating oil composition - Google Patents

Abstract

An admixture composition is described, which is applicable to oil lubricating compositions, advantageously to engine oil compositions, comprising 15 to 100 % by weight of components "A" and "B", each of them comprises one or more additives and to 85 % by weight of dilutent, where the component "A" comprises 10 to 100 % by weight of polyfunctional, ash-free additive composition with detergent-dispersing effect or its oily solution, comprising polymer components having the same or different average molecule weights, to 90 % by weight usual alkenyl succinic acid derivative, like an imide and/or an ester and /or ester amide; and the component "B" comprises one or more of usual additives, like additives with detergent-dispersing effect, having different base number and metal content, antioxidants, friction reducers, wear inhibitors, corrosion inhibitors, defoamer and solidification point reducers. The described admixture composition is used in multifunctional additive engine compositions and in additive lubricating oil compositions.

Description

Technical field

The present invention relates to halogen-free additive compositions suitable for lubricating oil compositions. It also relates to additive multipurpose engine oil compositions and additive lubricated oil compositions with high stability and optionally low phosphorus content consisting of a base oil and an additive mixture.

BACKGROUND OF THE INVENTION

The following groups of additives are used in engine oils suitable for spark-ignition and spark-ignition engines:

- polymers acting as viscosity modifiers, viscosity index improvers and freezing point depressants,

- ashless dispersants,

- metal-containing detergents,

- antioxidants, corrosion inhibitors, rust inhibitors and similar substances,

- anti-abrasion additives.

Common engine oil additives can be divided into five groups based on their function. The first group includes high molecular weight additives (Mn = 5,000 to 2,000,000), mostly polymers and copolymers, which mainly act as viscosity modifiers, viscosity index improvers, and freezing point depressants.

By incorporating polar basic groups into the copolymer structure, additives acting as detergent dispersants (DD) can be obtained, the use of which allows some reduction in the concentration of low molecular weight DD additives (M < 2000) in motor oil compositions. The most known such additives are polymethyl methacrylates (PMA) and derivatives thereof, ethylene-propylene copolymers (OCP), styrene-butadiene copolymers (SBCP) and polyisoprene (PIP).

Another group of additives, the use of which is considerably expanded, are so-called. ashless DD additives. The reason for the growth in the proportion of these additives in the total amount of additives used is that the requirements imposed on new engine designs -

- such as reducing the formation of black deposits, environmental pollutants and sealant damaging effects - can only be met by further development of ash-free DD additives and their use in increased concentrations. As ash-free DD-additives with low molecular weight (Mn <2000), polyisuccinic acid imide, amide and ester derivatives, Mannich bases with polyisobutylene backbone, polyolefin amines and the like are mostly used.

The third, fourth and fifth group of additives are additives with additional functions. These additives include a number of compounds whose use has very important effects.

This group includes, for example, metal-containing detergents, antioxidants, corrosion inhibitors, friction modifiers, anti-abrasive additives, as well as suds suppressors. A number of variations of these substances are known, and these substances are generally selected and used based on laboratory experiments and brake tests with respect to their interaction, which may act synergistically or antagonistically.

During the development of the last 15 years, the composition of engine oils has changed on the one hand due to the use of new enhanced performance additives that better meet the new requirements, on the other hand, the modification of the structure previously with the success of the additives used, i. j. the preparation of additives which have side effects in addition to the main effects and their use allows for further enhancement or reduction of the concentration necessary to achieve a certain effect. Thus, for example, by chemical modification of the structure of the additives found in the compositions, such adverse effects as damage to the sealing material or corrosion of the bearing material have been reduced. For example, the DD effect was enhanced by modification of ashless succinimide-based additives (EP 0 537 386) or by optimizing the structure of polyethylene polyamines (EP 0 451 380) used as starting materials for synthesis.

By attaching polar groups to the ethylene-propylene copolymers commonly used as viscosity modifiers or viscosity index improvers, a DD-side effect has been successfully obtained (EP 0 400 866). Mixtures of polymethacrylates with ethylene-propylene copolymers are suitable for enhancing the stability of various viscosity modifiers and viscosity index improvers.

By using strong inorganic acids, the harmful action of conventional low molecular weight adducts of succinimide alkenyl derivatives has been successfully reduced (US 5,114,402).

The use of the novel zinc salt derivatives of the polyisobutylene derivative of succinic acid according to EP 0 051 998 made it possible to increase the oxidation resistance of the oil compositions. In addition to the high DD-effect and increased storage stability, an excellent reduction in friction could be achieved by the process according to EP 0 051 998 using polyalkenylsuccinic acid esters, ethylene glycol and fatty acids.

Additives which exhibit increased side effects as viscosity modifiers and viscosity index enhancers in addition to the increased DD-effect and increased compatibility in relation to sealing materials can be synthesized by extending the polymer side chain of the polyisobutylene derivatives to a molecular weight of 5000 and so-called synthesis. polysuccinimide additives (US 4,234,435, WO 91/04959, WO 90/03 359 and EP 0 271 937).

The preparation of such additives with average molecular weights up to several tens of thousands has been made possible by the synthesis of such acylating agents which contain more than one succinic anhydride (Bernsteisäureanhydride BA) bound to each polyolefin chain in their molecules.

By the reactions of such intermediates, polyalkylene-polyamines and / or polyalcohols or alkanolamines, even with polyolefins of higher average molecular weight than usual (M _n = 1,500 to 5,000), additives with bulky polar groups (imides, amides or esters) can be prepared ) and with a high DD-effect. Although the structures of the known additives and the known processes for their preparation are different, in all cases it is possible to show in the compositions containing such additives, an increase in the DD-effect and a side effect of modifying the viscosity and improving the viscosity index. achieving a certain viscosity of 10 to 30%, thereby reducing additive costs.

Despite the achievements in the development of high molecular weight succinimides (M > 2,000) described in the previous paragraphs, it is still necessary to use conventional polymers such as viscosity modifiers and viscosity index improvers in the manufacture of multi-purpose motor oils. However, other efforts to reduce their use may also be observed.

The amount of polymers used as viscosity modifiers and viscosity index improvers can be reduced, for example, by using base oils prepared by a hydrocracking process or synthetic base oils (poly-α-olefins, diesters and the like) with higher viscosity indexes. Conventional polymers used as viscosity modifiers and viscosity index improvers have a beneficial effect on the quality of lubricating oils, but the products resulting from the use of the respective compositions and the volatile intermediates produced by the chemical impurities produced support the presence of extreme conditions (high temperature and mechanical stress). ) formation of insoluble resin deposits and thus clogging the engine. Due to the decrease in molecular weight caused by this decomposition, it is difficult to obtain the desired viscosity and viscosity index. The quality of engine oils can therefore be further improved by using polymers with increased stability.

SUMMARY OF THE INVENTION

In the course of the research, it has been unexpectedly found that by using a plurality of appropriately selected base oils, various conventional additives, and a novel polyfunctional ashless DD additive composition, high shear-stability motor and lubricating oil compositions can be produced in which polymeric modifiers are common. viscosities and viscosity index improvers contained only to a reduced extent or not contained at all.

Accordingly, the present invention provides an additive composition suitable for lubricating oil compositions, preferably motor oil compositions, comprising 15 to 100 wt.% Of components "A" and "B", each consisting of one or more additives and up to 85 wt. % of the diluent, the component "A" having the following composition

- 10 to 100 wt. % of a polyfunctional ashless additive composition having a detergency dispersant effect or an oil solution thereof composed of polymeric components with the same or different number average molecular weights prepared by reaction of a polyolefin derivative, preferably a polyisobutylene derivative with a number average molecular weight of at least 800, modified by one or more reactions dicarboxylic acids and / or dicarboxylic acid anhydrides and one or more vinyl comonomers containing non-acidic functional groups with an amino and / or imino-containing compound and / or a hydroxy group, wherein the polyolefin chain of the polymer components bears an average of 1.6 to 20 acid groups; the content of its molecules with more than one acidic group is higher than 25 wt. %, wherein said derivative is an imide, amide or esteramide derivative; and

- up to 90 wt. a conventional alkenyl succinic acid derivative such as an imide and / or ester and / or ester amide;

and component "B" has the following composition:

one or more conventional additives, such as detergent-dispersing additives having a different number of bases and with a different metal content, antioxidants, friction modifiers, anti-wear additives, corrosion inhibitors, foaming reducing additives and freezing point reducing additives;

wherein the weight ratio of components "A" and "B" is 15 to 85: 15 to 85.

The additive composition of the present invention contains as a further component "C" having the following composition

- one or more conventional viscosity modifiers and viscosity index increasing polymers, wherein the weight ratio of components "A", "B" and "C" is 15 to 85: 15 to 85: 70.

Component "A" of the present invention contains polymeric components to which maleic anhydride is bound and can be prepared by reacting polyisobutylene with a number average molecular weight of 1,300 to 30,000, wherein the polyisobutylene reacts as a polyolefin.

More specifically, component "A" comprises at least two polymeric components with different number average molecular weights, one (M _nI ) being lower and the other (M _n11 ) being higher, wherein the number average molecular weight of the lower component average polymer component is less than six times the number average molecular weight of the starting polymer; and the ratio of the number average molecular weights of the polymer component of the lower number average molecular weight and the polymer component of the higher number average molecular weight is 3: 1 to 50: 1, preferably 10: 1 to 20: 1; components having a lower number average molecular weight and components having a higher number average molecular weight of 0.01: 1 to 5: 1.

The component "B" of the additive composition according to the invention contains, as an additive with detergent dispersing effect, potassium and magnesium salts of organic compounds such as sulfonates, sulfates, salicylates or mixtures thereof with different number of bases and with different metal content.

The additive composition according to the invention contains 0.6 to 26 wt. % of component "A". 0.3 to 18.6 wt. % of component "B" and up to 25 wt. % of component "C".

Furthermore, the invention relates to an additive multipurpose engine oil composition comprising a base oil suitable for engine oil and additives comprising 1.5 to 55 wt. % of the additive composition of the present invention.

Also described is an additive lubricating oil composition consisting of a base oil suitable for lubricating oils and additives comprising 1.5 to 55 wt. % of the additive mixture described.

In the manufacture of a polyfunctional ashless additive composition having a dispersing-detergent effect, an acylating agent is preferably first prepared by binding to a polyolefin, preferably a polyisobutylene having a number average molecular weight of at least 800, preferably at least 1300, bound copolymers side chain formed by melein anhydride and a copolymer containing non-acidic functional groups or mixtures of these comonomers. The comonomer may be a separately added compound or initiator (used during the reaction), a fusion-controlling compound, an unsaturated degradation product of the starting polyolefin or an unsaturated polyolefin degradation product (EP 0 658 572). The reaction may be carried out by sequentially linking the moleic anhydride and comonomers to the polyolefin and / or adding a copolymer chain prepared beforehand from maleic anhydride and one or more comonomer molecules to the polyolefin. The synthesis of the acylating agent is based on a ratio of maleic anhydride / comonomer / polyolefin of 1.2-5.5: 0.01-3.5: 1 and the reaction is carried out in the presence or absence of solvent and at 5-25 wt. % (based on maleic anhydride) of the free radical initiator and 0.1 to 5 wt. % of the compound which controls the degree of incorporation of the monomers at a pressure of 100 to 1500 kPa in a hydrocarbon or inert atmosphere at temperatures ranging from 80 to 180 ° C. The intermediate is optionally diluted with base oil and purified by filtration. The acylating agent thus obtained is reacted with one or more at least bifunctional compounds having amino or imino groups and / or a hydro group at a molar ratio of acylating agent / amine and / or acylating agent / alcohol of 0.7 to 5.5: 1 at a temperature of 120 to 235 ° C in the presence or absence of a catalyst for 2 to 15 hours, optionally diluted with base oil, purified and modified in a manner known per se.

The obtained intermediate non-polar chain and the strongly polar chain of a copolymer having a static or alternating structure bound thereto is very suitable for the preparation of imide-, ester-, amide- and esteramide derivatives with excellent dispersing effects, the groups bound to this polyolefin chain being the same. or different. When working with these starting materials, the resulting polyfunctional end structures, which usually contain a large number of carboxyl groups, allow the formation of polymer structures which appropriately affect the flow properties of the lubricating oils using the corresponding, at least bifunctional basic reagents. Indeed, it has been found that using polyisobutylene having a number average molecular weight of greater than 800, preferably greater than 2000, provides additives which have good dispersing-detergency effects while being better viscosity modifiers and viscosity index improvers than starting materials based on polyisobutylene. Particularly suitable for the preparation of such polymer chains are polyisobutylene derivatives having a high α-olefin content (> 70% by weight).

It is particularly advantageous that the polyisobutylene derivatives according to the invention can be used as viscosity modifiers in both the high and low temperature fields.

According to our experimental findings, the polyfunctional ashless additive composition with dispersing-detergent effects has better thermal and oxidation stability than conventional viscosity index improvers, and therefore the stability of the engine oil compositions is unexpectedly increased.

Component "A" may contain 0 to 90 wt. % of the usual commercial low molecular weight alkenyl succinic derivatives such as esters, esteramides, polyisobutenylsuccinimides, succinimide amides and mixtures thereof. Particularly suitable are the substances synthesized according to HU 197 936 and 205 778.

As component "B", other additives with known effect are used in the composition according to the invention, which are practically necessary in the production of modern high-performance compositions. Preferably, one or more DD-additives are used with different metal contents and different alkalinity numbers, such as basic and superbasic sulfonates, sulfenates and salicillates; antioxidants such as zinc diacyldithiophosphate, zinc dithiocarbamate, sterically protected phenols, cresols, aromatic amines and derivatives thereof; friction modifiers and anti-abrasive additives such as aliphatic amines, amides, esters, esteramides, phosphates, thiophosphates, sulfides, polysulfides and derivatives thereof; corrosion inhibitors such as alkyltriazoles, mercaptobenztriazoles, carboxylic acids, dicarboxylic acids and derivatives thereof; antifoam additives such as polydialkylsiloxanes; Pour point depressants such as polyalkyl methacrylates, polyalkyl acrylates, ethylene vinyl acetate copolymers, dialkyl fumarate copolymers and the like.

Component "B" is preferably composed of the following components: basic and hyperbasic potassium and magnesium sulphonates and zinc dialkyldithiophosphates, ash-free dithiocarbamates, sterically protected phenols and aromatic amines, friction modifiers and fatty acid derivatives are used as metal-containing DD additives. phosphoric acids and polyalkylsiloxanes, as anti-erosion additives dithiocarbamates and vegetable oil derivatives and as freezing point depressants for polyalkyl methacrylates, and mixtures thereof.

Additives usable as component "B" are commercial products and can be readily selected by one of ordinary skill in the art based on their experience and the results of the technical tests performed.

Component "C" is a conventional polymer used as a viscosity modifier and viscosity index improver or a correspondingly selected blend of such polymers. Polymethacrylates, ethylene-propylene copolymers, styrene-diene copolymers as well as nitrogen-containing derivatives thereof are preferably used in multi-purpose engine oil compositions.

The ratio of the quantity of additives used in the components "A", "B" and "C" as well as the ratio of the quantities of the individual components are governed by different parameters. As examples of such parameters, the viscosity of the composition and the demands placed upon it in use, the properties of the base oil used as well as the dependence of the effect of the additives on their concentration may be mentioned.

For the preparation of lubricating oil compositions and motor oil compositions which exhibit favorable properties and meet high requirements, the concentrations of the individual additives in the components (A, B, C) are preferably selected within the ranges given in Table 1.

Table 1 Concentration ranges of individual additives component additive concentration range (% by weight) * polyfunctional ashless with dis- A pergation-detergent effects 0,6 - 20 B alkenylsuccinic acid derivative with dispersing detergent effects, comprising a metal corrosion inhibitor containing copper 0-6 0,1 - 10 0-0,5 antioxidant 0.1-2 corrosion anti-friction modifier 0.001 - 1 0.1-3 protipenivostné 0.0001 -0.1 freezing point reducer 2-5 C viscosity modifier and viscosity index improver 2-25 * based on the total weight of the brewing oil system present in the additives including the establishment of

In the case of multi-purpose engine oil compositions, the amount of the individual components is preferably within the concentration ranges shown in Table 2. Table 2

Preferred concentration ranges of the individual components, based on the total weight of the additive component mixture amount (wt.%)

A 15-85 B 15-85 C 0-70

It should be noted that additives which allow several effects to be achieved at the same time may be used, and their effects may be increased or decreased relative to one another. Therefore, when determining the concentrations of these additives, their interaction must be taken into account.

The additive composition of the present invention may also be used as a concentrate. In such cases, 0 to 85 wt. % diluent to facilitate handling. For example, base oils present in the composition can be used as diluents, such as the low viscosity base oils VK100 (1.5 x ^{10 -5} m ² .s -1) commonly used in motor oil compositions. Conventional mineral oil base oils which are prepared by solvent refining, hydrotreating, catalytic dewaxing, clay bleaching or hydrocracking process and optionally subsequently purified by catalytic dewaxing or solvent dewaxing may be used as the base oil in the composition of the invention. the desired composition of these base oils with respect to the required viscosity and conditions of use is preferably achieved by mixing base oils of different viscosities, which are commercial products. Also suitable are synthetic oils such as poly-olefins, dicarboxylic acid esters, polyol esters, as well as vegetable oils and / or derivatives thereof, the proportions of which may be chosen with respect to their use. The various blends of base oils prepared from crude paraffinic oils by combining paraffinic and hydrotreating with poly-.alpha.-olefins and dicarboxylic acids have proven to be particularly useful when using the additive composition of the present invention, the proportions of the components being determined with respect to the desired viscosity.

By using the additives of the present invention, engine oil compositions corresponding to known power grades can be produced. Thus, e.g. according to API (ASTM D4485) grade SG and SH, or CCMC grade PD-2 and GL-5 (CF cahill: Evolution of the CCMC Engine Lubricant Sequences, lecture at the 3rd International Symposium "Performance Evolution to Automotive Fuels and Lubricants', April 13, 1989).

The additive composition of the present invention can be used in addition to engine oil compositions also in other lubricating oil compositions such as automatic transmission oils (ATF), cooling oils and machine oils, as well as other compositions such as brake fluids, heat transfer oils, hardening oils, and can also be used as part of fuel to improve their properties. However, the preferred field is the production of additive-multipurpose engine oil compositions.

The production of these compositions is accomplished by conventional mixing. You can proceed by using the Addendum to Table 3:

MSA (Maleinsuric anhydride): maleic anhydride BA (Bemsteinsuric anhydride): succinic anhydride VK ₁₀₀ : kinematic viscosity at 100 ° C

PIBPOBAO-KA, PIBPOBAO-KB: The oily solution of the PIB derivative in the individual components is added individually to the base oil and the composition thus obtained is thoroughly mixed. In another method, the additive composition is first prepared by mixing the ingredients together in a desired ratio and then adjusting the viscosity to the desired level with any base oil to facilitate further processing, preferably the base oil present in the composition. The concentrate thus obtained is added to the composition mixed with an appropriate base oil.

It is necessary that the order of addition of the individual components in the preparation of the compositions be selected with regard to their possible chemical interactions. The various additives are mixed with the base oil preferably in an order that minimizes the possibility of their mutual reactions. In order to avoid thermal decomposition, the reaction is carried out at temperatures in the range of 40 to 80 ° C.

A significant advantage of the present invention is that the high molecular weight PIB, allowing the preparation of a highly effective halogen-free and ash-free additive, damages or even protects the sealing materials in normal use relative to other conventional additives. It is further characterized by increased shear resistance, thermal and oxidation resistance, is a good viscosity modifier and viscosity index improvement. As a result, its use makes it possible to reduce the amounts of conventional phosphorus-containing polymers or anti-abrasive additives used, and thus to produce highly stable, environmentally harmful compositions.

The invention will be further elucidated by means of examples, the subject matter of patent protection being not limited by these examples. Engine oil compositions which, according to the most commonly used API rating, belong to grade SG are exemplified.

DETAILED DESCRIPTION OF THE INVENTION

Example 1

Table 3 shows the preparation conditions and intermediate properties of the novel polyisobutylene-polysuccinimide derivatives which are used in component "A" as a polyfunctional ash-free additive composition with dispersing-detergent effects. Table 4 summarizes the properties of the end products prepared using these additive compositions.

succinic anhydride

Table 3

The most important conditions of preparation and properties of intermediates of polyfunctional ashless additive compositions with dispersing-detergent effects preparation condition or property intermediate product PIBPOBAO-KA PIBPOBAO-KB conditions of preparation: 2250 8000 number average molecular weight PIB M _n solvent prod. oil xylene amount of solvent, wt. % 27 27 MSA: PIB molar ratio 2 4 initiator concentration, wt. %, (based on MSA) 30 35 concentration of the compound affecting the reaction rate, wt. % 0.05 0.05 comonomer (CM) isobutylene styrene

preparation condition or property mesophase > rodukt PIBPOBAO-KA PIBPOBAO-KB CM: MSA ratio 1: 3 temperature, ° C 130-150 130-160 (180-200) (180-200) pressure, kPa 101.3 101.3 pressure to remove unreacted MSA, kPa cca 10 cca 10 diluent oil, wt. % (based on intermediate) 50 70 blackening, filtration Yes Yes Properties of intermediate: VK ₁₀₀ , m ² · sxx10 ⁶ 256.2 330.5 acid number, mgKOH / G 44.6 10.5 MSA content, mg / g 3.1 1.2 average number of BA-P1B bonds 2.4 3.3 a plurality of compounds containing the structure. units BA per molecule greater than 4 wt. % 0.4 increase in number average molecular weight relative to P1B, wt. % 13 20 amounts of compounds containing struct. units of BA per molecule greater than 1 wt. % 42

Table 4

Most important preparation conditions and properties of polyfunctional ashless additive compositions with dispersing detergent effects Preparation condition or property ________

PIBPSI-2 ** PIBPSI-2 **

preparation conditions: type PIBPOBAO * KA KB amount of PIBPOBAO *, mol 20 10 polyamine amount: ΤΕΡΑ ***, mol 5 4 DETA ***, mol 2 - catalyst triethanolamine malic acid amount of catalyst, wt. % 0, 1 0.2 heating at 175-180 ° C, hr. at 101.3 kPa 5 - at 50 kPa 1 5 at 30 kPa 1 - at 30 kPa 1 3 Product characteristics: VK ₁₀₀ m ² .s''xl0 ⁶ 456 689 nitrogen content, wt. % 0.8 0.17 TBN, mgKOH / g 6.4 3, 1 diluent oil, wt. % 50 25 the ratio of higher and lower molecular weight polymers 0.33 -

* oily solution of polyisobutylan-succinic anhydride adduct ** polyisobutylene-polysuccinimide *** ΤΕΡΑ = tetraethylenepentamine

DETA = ditylene triamine

Example 2

The polyfunctional ashless additive compositions with dispersing-detergent effects of Example 1 (PIBPSI-1, PIBPSI-2) were used to prepare the following motor oil composition. Also disclosed is the preparation of an engine oil composition for K-1 to K-14 test engines.

The reaction vessel, the contents of which can be heated to a temperature of up to 120 ° C or cooled by means of a duplicator and equipped with a mechanical stirrer, is first introduced at room temperature with the oil component of the composition of the lowest viscosity (including synthetic components). The oil components are then added in the order of their increasing viscosity with heating and stirring. The oil mixture is heated to 70 ° C and, if appropriate, pour point depressants (PPD) heated up to 60 ° C, various viscosity index improvers (V. 1.1. - 1, 2, and 4) are added in an appropriate amount, such as also ashless dispersing agents used with these additives.

The mixture is stirred for 1 hour, then the necessary amounts of zinc dithiophosphate, detergent mixture and antioxidant are added to the mixture, which has been cooled to about 60 ° C. After stirring for 1 hour, the mixture was cooled to room temperature. The composition of the 14 test engine compositions obtained in this manner with a performance level corresponding to SC / CD grades for the API evaluation is shown in Table 5.

The following are the most important parameters characterizing the substances used to prepare the following compositions for test engines:

The mineral oil raffinates SN-80, SN-150 and SN-350 are paraffin-free fractions, made from distillate fractions of mineral oils of Hungarian origin, refined with N-methylpyrrolidone as solvent and hydrogenated. The kinematic viscosity of the inn 100 C 3.42 trr.s'xlO ^6th 5.40 m ² s ⁴ xlO ^f and 8.62 m ² .s' xl0 ^<i, the viscosity index is 95 and 102.106, the aromatic content is 4.9%, 4.6% and 7.7%, and their pour points are -18 ° C, -18 ° C and -15 ° C. The base oil SAE 10 / 95H is a refined paraffinless oil prepared by a hydrocracking process under mild conditions followed by redistillation. The kinematic viscosities of SAE 10 / 95H are at 100 ° C and at 40 ° C 5.29 and 31.7 m ² .s'x10 ⁶ , this oil has a viscosity index of 100, a Brandes aroma content of 7.7%, a content of sulfur 0.04%, pour point -18 ° C. The PAO-4 and PAO-6 components are poly-α-olefins available as commercial products.

The additive which lowers the freezing point of the P.P.D. is a polymethacrylate additive.

The following viscosity index improvers (V. 1.I.) are also used:

V. I. I. - 1 is a polymethacrylate commonly used in motor oils,

V. 1. I. - 2 is a solution of styrene-isoprene copolymer in SN-150 base oil,

V. 1.1. - 3 is polyisoprene,

V. 1.1. - 4 is a solution of an olefin copolymer in a base oil

SN-150th

The base oil SN-150, used in combination with V.I.I. - 2, 3 and 4, has the quality parameters required for base oils.

The ZDDP component is zinc dialkyldithiophosphate, often used as an additive in motor oil compositions for compression ignition and spark ignition engines and prepared using primary and secondary alcohols, Zinc content 9.2%, phosphorus content 8.4%, and as an antioxidant contains derivatives diphenylamine.

The DET component is a detector consisting of a mixture of basic potassium and magnesium salicylates containing 4.9 wt. % Ca, 2.6 wt. % Mg and its alkali number according to ASTM D 2896 is 2.53 mg KOH / g.

Table 5

Compatibility of engine, oil compositions with sealants

Composition (label)

Dispersant, wt. % Komad-301

P1BPSI-1 PIBPS1-2

CEC tests

RE1,

Change Fix. tensile (%)

Change drag. pri pretr.

D1DC hardness change

Change in volume (%) of RE2,

Change Fix. tensile (%)

Change drag. pri pretr.

D1DC hardness change

Change in volume (%) of RE3,

Change Fix. tensile (%)

Change drag. pri pretr.

DIDC Hardness Change

Volume change (%)

RE1 +

Change Fix. tensile (%)

Change drag. pri pretr.

DIDC Hardness Change

Volume Change (%) VW-3344 Test Tensile Strength, MPa Elongation

rupture

Rating

K-5 10W-40 K-6 10W-40 K-7 10W-40 K-8 10W-40 K-3 15W-40 Boundary values 7.2 7.2 7.6 7.2 12 -68 2 -1 -1.9 -9.8 -50-0 -75 -35 -16 -29 -20 -60-0 6 1 1 -2 0 0-5 10 1 1.2 0.5 0.2 0-5 11 8 1, 1 13 3.8 -15-10 2 -18 -10 -22 -23 -35-10 6 5 2 3 4 -5-5 2 0 0.7 1.4 1.5 -5-5 -36 25 -12 -19 -26 -30-10 -11 4 -6 0.7 -13 -20-10 -7 -22 -15 -16 -19 -25-0 17 12.1 8 14.4 17 0-30 -33 -6.1 -3.8 -8.8 -4.2 -20-0 -51 -31 -26 -47 -39 -50-0 3 0 0 1 0 -5-0 8 1.5 0.5 0.3 1 -5-0 5 9, 1 10.4 9.9 8.3 8 119 209 235 228 183 160 52 do not recognize. bad good good good' good

Example 3

The beneficial results achieved by the present invention are demonstrated based on the properties of the K1 to K14 compositions.

Seal material compatibility

A known drawback of conventional succinimide detergents is that, especially at concentrations above 3-4%, they cause undesirable damage to the sealing materials used in engines. Based on measurements made with K-6, K-7, K-8 and K-3 engine oil compositions, good compatibility of these compositions with sealants was found. As comparative results, the results obtained with composition K-5 containing conventional succinimide (Komad-301) are used. A CEC-test of the effects of the compositions on four different elestomers was performed, as well as a VW-3344 test under difficult conditions of VW-3344, in which the fluoroelastomer was exposed to these compositions. The results are shown in Table 6.

The partially synthetic compositions K-5, K-6, K-7 and K-8 correspond to the SAE 10W-40 viscosity grade and have the same composition except succinimides (composition K-8 contains PAO-6, the other three compositions contain PAO-4) . The K-3 composition is based on mineral oil, containing mineral oil raffinate, which was obtained by the hydrocracking process under mild conditions and has a viscosity grade SAE 15W-40.

Very good evaluation of compositions K-3, K-4, K-7 and

K-8, in contrast to the poor results obtained with the K-5 composition being compared, shows the preference of the compositions of the invention.

Table 6

The composition of the engine oil compositions of the present invention and the oil compositions to be compared

Composition grade SAE K-11W-40 K-2 15W-40 K-3 15W-40 K-4 15W-40 K-5 10W-40 K-6 10W-40 K-7 I0W-40 K-8 10W-40 K-9 10W-30 K-10 10W-30 C-II 10W-30 K-12 5W-50 K-1 3 5W-50 K-14 5W-50 composition (wt%) base oil-SN 80 5.2 8.6 6.7 prod. oil-SN 150 prod. oil- 44.1 53.8 57.2 44.6 34.8 47 45.8 59.1 63.6 65.2 77.5 -SAE10 / 95H prod. olq-SN 350 35 27.9 24.4 40 29.4 19.3 22.2 5.4 ΡΛΟ-4 15 15 15 6.4 2.9 6.6 PAO-6 15 70.6 75.6 73.6 P.P.D. (PMA) V. I.J. -1 (PMA) 0.2 0.2 1 0.2 0.2 0.2 0.2 1 0.2 0.2 0.2 11 9.5 3.6 V. 1.1. -2 (SIC) V. 1.1. -3 (PIB) V.I.-4 (OCP) 8.7 6 5.2 8.6 6.5 6 19 14 ZDDP 1.3 1.4 1.3 1.3 1.3 1.3 1.3 1.3 1.3 1.3 1.3 1.3 1.3 1.3 AO 0.2 DET 3.5 3.5 3.5 3.5 3.5 3.5 3.5 4.5 3.5 3.5 3.5 3.5 3.5 3.5 Komad-301 PIBPSI-1 7.2 7.2 7.2 2.4 7.2 7.2 7.6 7.2 7.2 1.8 7.2 7.2 PIBPSI-2 8 12 9 12

Komad-301 is the trade name of bissuccinimide (M _n PIB = 1000, polyamine = tetraethylenepentamine)

Anti-abrasion effect

As can be seen from the data in Table 7, the new formulations exhibit anti-abrasion effects in certain circumstances.

The K-9 composition, which was prepared with a conventional dispersing additive, and the K-103 composition containing the additive composition of the present invention, have OK-loads in a Timken apparatus (ASTM D 2782), which in both cases equals 22 kg. However, after a three-hour abrasion test at a load of 19.5 kg, the composition of the invention has a 60% lower abrasion.

Table 7

Anti-abrasion effect of motor oil compositions composition

K-9 C-II SAE degree 100W-30 10W-30 dispersing agent, wt. % 7.2 Komad-301 PIBPSI - 1 1.8 PIBPSI-2 3.0 OK-load - Timken, kg 22 22 block and ring abrasion, 3 hours 19.5 kg - Timken, mg 4.7 1.9

Viscosity-modifying effects, replacement of polymeric viscosity modifiers

One of the greatest advantages of the compositions of the present invention is that the novel additives exhibit increased efficacy as viscosity modifiers and viscosity index improvers.

This effect is apparent from the data contained in Table 8 concerning the test results of three compositions, namely SAE grade 15W-40 mineral oil compositions, partially synthetic grade SAE 10W-40, and synthetic grade SAE 5W-50, comprising a conventional Komad-301 additive and a polyfunctional ashless additive composition having a dispersing-detergent action according to the present invention, the compositions having the same composition for the other ingredients. The most important rheological data are shown in Tables 8 and 9. The compositions were adjusted within each viscosity step by varying the viscosity of the base oil and the amount of polymer used as the viscosity modifier to almost the same level.

The increase in viscosity caused by the additive composition PIBPSI-1 is lower compared to the increase caused by the second polyfunctional ashless additive composition with dispersing-detergent effects, but this increase also allows a one-third reduction in the amount of polymer with viscosity-modifying effect. with the amount needed when comparative additive Komad-301 is used. In the 10W-40 stage, this reduction is achieved, i.e.. j. polymer savings of about 25%, and at 5W-50, about 15%.

The additive composition PIBPSI-2, which has a higher effect than the viscosity modifier, allows the K-4 and K-6 compositions to replace the entire amount of polymer used as a viscosity modifier for SAE grades 15W-40 at the concentration required to achieve SG grade ΑΡΓ. 10W-40th In the SAE grade 5W-50 oil composition, the use of the additive composition PIBPSI-2 reduced the consumption of the polymer acting as a viscosity modifier compared to the comparative additive DD composition to one third. A comparison of hot and cold viscosities and a comparison of these viscosities with base oils suggests that they are very close and that the DD additives used in the additive composition do not increase the viscosity of the cold oils more than the usual polymers used as viscosity modifiers.

Table 8

Replacement of polymers used. as viscosity modifiers (V. J. I) with the additive compositions PIBPSI -1 and PIBPSI-2

Composition grade SAE K-L 15W-40 K-2 15W-40 C-4 15W-40 K-5 10W-40 K-6 10W-40 K-7 10W-40 K-12 5W-40 K-1 3 5W-50 K-14 5W-50 Used V. 1.1. - 1, wt. % V. 1.1. -1 - - - - - - 11.0 9.5 3.6 V. 1.1.-3 - - - 8.6 6.5 - - - V. 1.1. -4 8.7 6.0 - - EXP. dispersant, wt. % Komad-301 7.2 - - 7.2 - - 7.2 PIBPSI - 1 - 7.2 2.4 - 7.2 - - 7.2 - PIBPSI - 2 - - 8.0 - - 12.0 - - 12.0 Cinema. viscosity oil at íoo τ, Λ - 'ιο ⁵ 6.6 6.3 6.7 5.9 5.6 5.7 6, 1 6.0 6, 1 End product Cinema. viscosity at ΙΟΟθε, ηΓ.Κ'.ΙΟ ⁶ 14.61 14.62 14.33 13.93 14.64 14.25 18.53 18.69 18.2 Viscosity index 134 138 137 148 152 158 217 217 194 Dynes, viscosity at-15 ° C, Pas 3320 3110 3390 - - - - - - at -20 ° C, Pas - - - 3370 3480 3370 - - - at -25 ° C, Pas - - - - - - 3410 3310 3480 Pour point ° C -30 -30 -30 -36 -36 -36 under -40 under -40 under -40

Shear stability

The shear stability data given in Table 9 shows that their values, as determined by the shear stability test performed in a Bosch injector (ASTM D 3934), are for K-7, K-13 and K-14 engine oil compositions. containing, in whole or in part, succinimides as viscosity modifiers, similar to composition K-12, which comprises a comparative succinimide (Komad-301) and a viscosity index improver (VII) based on polymethacrylate.

Table 9

Shear stability of the composition of the invention

composition K-7 K-12 K-13 K-14 SAE degree 10W-40 5W-50 5W-50 5W-50 used V. I. I., wt. % Komad 301 - 7.2 - - PIBPSI - 1 - - 7.2 - PIBPSI - 2 12.0 - - 12.0 cinema. viscosity, m ² · sx10 ^ó 100 ° C 14.95 18.53 18.69 17.94 Deň: 32 ° C 97.2 94.7 95.7 102.4 viscosity index 161 217 217 194 CCS-15 ° C, Pa.s. CCS-25 ° C, Pa.s. 3.1 3.41 3.31 3.26 shear stability - Bosch K V./100 ° C, 30 cycle, m / m x ^{10 6} 12.09 13.99 14.77 14.4 S. S. I.,% 31 37 31 30 V.I., 30 cycles 150 To V./100 ° C, 250 cycles, m ² · sx10 ⁶ 11.70 13.38 14.21 14.01 S. S. 1.,% 36 41 35 31 V. 1., 250 cycles 148 base oil viscosity, 100 ° C, m ² · sx10 ⁶ 5.8 6.1 6.0 6, 1

Detergent-dispersing effect, power on engine brake

The engine brake tests, the results of which are decisive for determining the quality of the engine oil compositions, are summarized in Table 10. Oil compositions K-2 and K-3 were tested on Petter W1, M 102 E, Sequence IIIE and PV 1431 engine brakes. The build-up of sediment found on the M 102 E and Sequence IIIE engine brakes shows excellent dispersing performance and cylinder cleanliness factors found on the Sequence IIIE and PV 1431 engine brakes are evidence of adequate detergency performance of additives used in oil compositions. The suitability of the compositions of the present invention was further confirmed by the results of the anti-abrasion effect measurements on the Petter M 102 E engine brake and in particular on the Sequence III E engine brake and the very low bearing wear found by the Petter W-1 engine brake tests.

Table 10

Test results of oil compositions containing a polyfunctional ashless additive composition PIBPSI-1 with dispersing-detergent effects.

limit values according to CCMC G4 / PD-2

composition K-2 K-3 SAE degree 15W-40 15W-40 content of additives, wt. % 0.2 P. P. D. V. 1.1. - 1 - 1.0 V. I. I. - 2 6.0 - ZDDP 1.3 1.3 AO - 0.2 PIBPSI-1 7.2 7.2 (1) motor tests brake Petter W-l bearing wear, mg 2. engine tests 4.7 max. 25 brake M 102 E average engine build-up factor 9.4 min. 8.5 seizure ring ASF = 16 ASF = max. 30 deposits on the piston groove 1 30.1 max. 30 groove 2 19.1 max. 25.9 average cam wear, μτη 3.0 max. 5.7 average bumper wear, gm 3. engine brake tests Sequence IIIE viscosity increase at 40 ° C,% coating on piston coating on ring 1.9 38 9.38 7.40 max. 3.1 max. 300 min. 8.9 min. 3.5 wear factor, cam and impact- 9.57 min. 9.2 niche 3.7 max. 30 average, μτη maximum, / im 11.0 max. 60

limit values according to CCMC _________________________________________________ G4 / P13-2 4. engine brake tests PV 1431 - impermissible book seizure (ASF = 0) (ASF = 0) piston cleanliness 70 min. 69.4

Example 4

The composition of the concentrates of the additive mixtures of the present invention and the engine oil compositions prepared by diluting them is shown in the following table:

Table 11

Additive concentrate concentrates and motor oil compositions prepared by diluting an additive concentrate or oil composition

L-L P-2 P-3 P-4 M-I M-2 component "A" Komad-301 - 11.4 6, 1 - 10.4 7.2 P1BPSI -1 15.6 - 33.0 7.8 PIBPSI-2 52 57.0 26.0 component "B" 5.0 5.0 P. P. D. (PMD) 1.3 1.3 1.0 0.7 ZDDP 8.4 8.2 6.6 4.2 DET 22.7 22.1 17.8 11.3 of “C” V. 1.1. - 3 (PIP) base oil SN-150 35.5 50 6.5

blend of base oils 15W-40

Claims (9)

PATENT CLAIMS An additive composition suitable for lubricating oil compositions, preferably for motor oil compositions, characterized in that it comprises 15 to 100 wt. % of components "A" and "B", each consisting of one or more additives and up to 85 wt. % of the diluent, the component "A" having the following composition - 10 to 100 wt. % of a polyfunctional ashless additive composition with detergent dispersing effects or an oil solution thereof, composed of polymeric components with the same or different number average molecular weights, prepared by reaction of a polyolefin derivative, preferably a polyisobutylene derivative with a number average molecular weight of at least 800, modified by one or more reactions dicarboxylic acids and / or dicarboxylic acid anhydrides and one or more vinyl comonomers containing non-acidic functional groups with an amino and / or imino-containing compound and / or a hydroxy group, wherein the polyolefin chain of the polymer components bears on average 1.6 to 20 acid groups; the content of its molecules with more than one acidic group is higher than 25 wt. %, wherein said derivative is an imide, amide or esteramide derivative; and - up to 90 wt. a conventional alkenyl succinic acid derivative such as an imide and / or ester and / or ester amide; and component "B" has the following composition: one or more conventional additives such as detergent-dispersing additives with different number of bases and with different metal content, antioxidants, friction modifiers, anti-wear additives, corrosion inhibitors, foaming reducing additives and freezing point additives; wherein the weight ratio of components "A" and "B" is 15 to 85: 15 to 85. Additive mixture according to claim 1, characterized in that it contains as component C a component having the following composition: - one or more conventional viscosity modifiers and viscosity index increasing polymers, wherein the weight ratio of components "A", "B" and "C" is 15 to 85: 15 to 85: 70. Additive mixture according to claim 1 or 2, characterized in that its component "A" contains polymeric components to which maleic anhydride is bound. Additive mixture according to any one of claims 1 to 3, characterized in that its component "A" comprises polymeric components prepared by the reaction of polyisobutylene having a number average molecular weight of 1300 to 30 000, in which the polyisobutylene reacts as a polyolefin. Additive mixture according to any one of claims 1 to 5 4, characterized in that its component "A" comprises at least two polymeric components with different number average molecular weights, one (M _nl ) being lower and the other (M _nII ) being higher, the number average molecular weight of the polymer component having the lower number average is less than six times the number average molecular weight of the starting polymer and the ratio of the number average molecular weights of the polymer component of the lower number average molecular weight to the polymer component of the higher number average molecular weight is 3: 1 to 50: 1, preferably 10: 1 to 20: 1, wherein the weight ratio of the lower number average molecular weight component to the higher number average molecular weight component is 0.01: 1 to 5: 1. Additive mixture according to any one of claims 1 to 6 5, characterized in that its component "B" contains potassium and magnesium salts of organic compounds such as sulfonates, sulfenates, salicylates or mixtures thereof with a different number of bases and with a different metal content as an additive with detergent-dispersing properties. Additive composition according to any one of claims 1 to 10 6, characterized in that it contains 0.6 to 26 wt. % of component "A", 0.3 to 18.6 wt. % of component "B" and up to 25 wt. % of component "C". An additive multipurpose engine oil composition consisting of a base oil suitable for engine oil and additives, comprising 1.5 to 55 wt. % of the additive composition according to any one of claims 1 to 7. An additive lubricating oil composition comprising a base oil suitable for lubricating oils and additives, comprising 1.5 to 55 wt. % of the additive composition according to any one of claims 1 to 7.