HRP950611A2 - Lubricating oil and engine oil in compositions with multifunctional aditives - Google Patents

Abstract

Multifunctional engine oil composition consists of a base oil and an additive package (1.5-55 weight %) comprises: (A) 10-100 wt.% polyfunctional, ash-free detergent-dispersant additive or its oily solution comprising polymer components which are produced by reacting a polyolefin derivative, preferably a PIB derivative, injected with dicarboxylic acid (anhydride) and non-acidic comonomers with ethylenic double bond, and having an average molecular weight of 800, with compound containing amino, imino or hydroxyl groups, the polyolefin chain in the polymer component carrying 1.6-20 acid derivatives, the amount of the molecules with more than one acid derivative being at least 25 wt.%, and the derivative being an imide, amide or ester amide derivative, and 0-90 wt.% usual alkenyl succinic acid derivative; (B) usual dispersant-detergent with different base number and metal content, antioxidant, friction reducer, wear inhibitor, corrosion inhibitor, defoamer and flow point reducer; and (C) usual viscosity (index) improving polymer. Weight ratio of A:B:C is 15-85: 15-85: 0-70.

Description

The invention relates to motor and lubricating oil in a mixture of high stability, without halogens, with multi-purpose additives and, if necessary, with a low phosphorus content, which mixture consists of a base oil and a package of additives. The invention further relates to the applied package of accessories.

In order to meet the requirements of spark-ignition engines, i.e. Diesel engines, the following groups of additives are used in engine oils:

- polymers that increase viscosity and viscosity index and that lower the pour point,

- ashless dispersions,

- detergents containing metals,

- inhibitors (oxidation inhibitors, corrosion inhibitors, rust inhibitors and similar substances),

- wear inhibitors.

Additives to common motor oils can be classified into five groups based on their function and structure. The first group includes high-molecular (Mn = 5,000-2,000,000), most often homo- or copolymer additives, which usually increase the viscosity and viscosity index and lower the pour point.

Through the incorporation of polar, basic groups into the structure of the copolymer, additives with a deterging-dispersing (hereafter DD) effect can be obtained, the application of which enables a certain reduction in the concentration of low-molecular DD-additives (Mn < 2,000) in motor oil mixtures. The best-known representatives of such additives are polyalkyl methacrylates (PMA) and their derivatives, ethylene propylene copolymers (OCP), styrene-butadiene copolymers (SBCP) and polyisoprene (PIP).

The so-called ashless DD-additives represent the second group of additives, which has spread very quickly in application. Their application, which is growing in proportion to their quantity, is based on the fact that the higher performance requirements set by new engine designs, such as the reduction of black sludge formation, metal emissions harmful to the environment and actions that lead to damage to the sealing material, can only be met further development of ashless DD additives and their application with increased concentration. As low-molecular, (Mn < 2,000) ashless DD-additives, imide, amide or ester derivatives of polyalkenyl succinic acids, Mannich bases with a polyisobutene basic structure, polyolefinamines and similar substances are mostly used.

The third, fourth and fifth groups of plugins are made up of plugins with further functions. A number of compounds belong to these supplements, which have very important effects in terms of application.

These groups include, for example, metal-retaining detergents, oxidation inhibitors, corrosion inhibitors, friction modifiers and wear inhibitors, as well as antifoaming agents. A number of ashless and metal-retentive variants of these materials are known, and these are generally selected and applied with consideration of their interactions - which may be synergistic or antagonistic, based on laboratory and bench-brake studies.

In the period of the last 15 years of research, the composition of motor oils has been changed, on the one hand, through the application of new additives with increased action, which meet new requirements at a higher level, and on the other hand, by modifying the structure of previously applied additives with success, that is, by producing additives that, in addition to the main action have an additional changed action, the application of which enables a further increase in the level of action or a reduction of the required concentration to a certain level of action. Thus, for example, by chemically modifying the structure of the additives used in the mixtures, undesirable side effects, such as damage to the sealing material or corrosion of the bearing metal, were successfully reduced. The DD action was increased, for example, by modifying ashless succinimide additives with organic acids (EP O 537 386) or by optimizing the structure for the synthesis of applied polyethylene-polyamines (EP O 451 380).

By injecting common ethylene-propylene copolymers with polar groups, which increase viscosity and viscosity index, DD-interaction was successfully perfected (EP 0 400 866). Mixed polymers of ethylene-propylene-copolymers injected with polymethacrylates are suitable for stabilizing mixtures of different polymers that increase viscosity and viscosity index.

The deleterious effects of common low molecular weight alkenesuccinimide additives of fluoroelastomer sealants could be reduced with strong inorganic acids (US 5,114,402).

By using new derivatives of zinc salts of polyisobutenylsuccinic acid, according to EP O 265658, the stability of oil mixtures against oxidation at high temperatures and the formation of precipitates could be successfully increased.

In addition to the high DD-action and increased storage stability, according to EP 0 051 998 the application of ester derivatives of polyalkenyl succinic acid, ethylene glycol and fatty acids could achieve a favorable friction reduction effect.

Substances which, in addition to increased DD-action and improved compatibility with sealing materials, have an increased side effect of increasing viscosity and viscosity index, can be produced by extending the side chain of polyisobutenylsuccinimide polymers up to a molecular weight of 5,000 and synthesizing so-called polysuccinimide additives (US 4 234 435, WO 91/ 04 959, WO 90/03 359 and EP 0 271 937).

The production of such additives with an average molecular weight of sometimes tens of thousands is made possible by synthesizing such acylating agents, which always have more than one succinic anhydride (BA) attached to their molecules on the polyolefinic chain.

By the reaction of such intermediates and polyalkylene-polyamines and/or polyalcohols and/or alkanolamines, additives with large polar groups (imide, amide or ester) and a large DD-action. Although the structure of known additives and known production procedures are different, in all cases of mixtures containing such additives, it is possible to prove an increase in DD-action and such a side effect of increasing viscosity and viscosity index, which enables a reduction of the amount of usual polymers required by 10-30% for a certain degree of viscosity, thus reducing the cost of addition.

Despite the above-described successes in the development of high-molecular succinimides (Mn > 2,000), the use of common polymers to increase the viscosity and viscosity index in the production of multi-stage motor oils remains a basic requirement. In order to further reduce their application, other efforts can still be considered.

The amount of polymer to increase the viscosity and the viscosity index that should be applied can be reduced, for example, by using base oils produced by the hydrocracking process or synthetic oils (polyalphaolefins, diesters and similar substances) with an increasingly high viscosity index. Common polymers for increasing the viscosity and viscosity index work favorably in lubricating oils, but they, when applying the mixture and the unstable decomposition products created by the action of the created chemical pollutants, under harsh circumstances (such as high temperature and mechanical load) promote the formation of insoluble, resin-like deposits, and thus engine pollution. Due to the reduction of the molecular weight due to decomposition, these polymers can provide the desired viscosity and the desired viscosity index of the lubricating oil only to a reduced extent. The quality of motor oils can therefore be further improved by using polymers with increased stability.

During our research, we came to the unexpected realization that by applying certain amounts of properly selected base oils, various common additives and the new polyfunctional ashless DD-mixture of additives, motor and lubricating oil mixtures with high shear stability can be produced, which the usual polymers for increasing the viscosity and of viscosity index contain a significantly reduced amount or do not contain it.

The subject of the invention is therefore a lubricating oil mixture, primarily a motor oil mixture, which consists of for lubricating oils, primarily for motor oils, a suitable base oil and additives, and in an amount of 1.5 - 55% by weight, contains a package of additives, which always shows components "A", "B" and, if necessary, "C" composed of one or more additives, whereby the individual components show the following composition:

Component "A"

- 10-100% by weight of a polyfunctional, ashless mixture of additives that has a detergent-dispersing effect or its oil solution, wherein the polyfunctional, ashless mixture of additives, which has a detergent-dispersing effect, contains such polymer components, which show the same or different numerical averages molecular weight, which are produced by the reaction of a polyolefin derivative, primarily a PIB derivative, which has been injected with one or more dicarboxylic acids and/or dicarboxylic acid anhydride, and one or more non-acidic comonomers with an ethylene double bond and has a numerical average molecular weight of at least 800, with a compound containing an amino-and/or imino-and/or hydroxy group, and in the polymer components the polyolefin chain carries an average of 1.6-20 acid derivatives, and the amount of molecules with more than one acid derivative is at least 25% by weight, wherein the derivative can be an imide- and/or amide- and/or esteramide derivative, i

- 0-90% by weight of a common derivative of alkenyl succinic acid, as an imide- and/or ester- and/or esteramide derivative;

Component "B"

- one or more common additives, such as additives with different basic numbers and different metal content that act as detergent-dispersants, antioxidants, substances that reduce friction, wear inhibitors, corrosion inhibitors, anti-foaming agents and substances that lower the pour point.

Component "C"

- one or more common polymers for increasing viscosity and viscosity index;

- where the weight ratio of components "A", "B", and "C" is: 15-85 : 15-85 : 0-70.

The subject of the invention is furthermore the package of additives used in the above mixtures, which always contains components "A", "B" and, if necessary, "C", which consist of one or more additives, and which show the above-mentioned composition.

As mentioned, the supplement package according to the invention consists of three main components ("A", "B", "C"), which always contain one or more supplements. Thus, component "A" as the main component contains a new ashless polyfunctional mixture of additives with DD-effect and the effect of increasing viscosity and viscosity index, from injected polyolefin derivatives, primarily from polyisobutylsuccinic anhydride derivatives (hereinafter: polyfunctional ashless DD-mixture of additives) ; component "B" is a mixture of additives from common additives, containing ash and/or ash-free additives with different effects; component "C" is a supplementary and common additive or a mixture of additives with the effect of increasing viscosity or viscosity index. Component "C" can be omitted if necessary.

Component "A" contains 10-100% by weight of a polyfunctional, ashless DD-mixture of additives or its oil solution, whereby the polyfunctional, ashless DD-mixture of additives contains polymer components, produced by the reaction of a polyolefin derivative, primarily a polyisobutylene derivative (PIB derivative) with with a number average molecular weight of more than 800, primarily 1,300-30,000, which is injected with one or more unsaturated dicarboxylic acids and/or their carbonic anhydride, primarily with maleic anhydride and with one or more non-acidic comonomers with an ethylene double bond or with copolymers of such comonomers (and/or with homopolymers of maleic anhydride), with a compound containing an amino-and/or imino-and/or hydroxy group, wherein the polymer components show the same or different number average molecular weights and in which the polyolefin chain, the numerical average molar weight, which is primarily equal to that of the initial substance, carries an average of 1.6-2 0 acid derivatives, whereby the amount of molecules with more than one acid derivative is greater than 25 wt.%, and the derivative can be an imide- and/or amide- and/or esteramide-derivative.

The above polyfunctional, ashless DD additive mixture contains primarily at least two polymer components with different, one lower (Mn1) and one higher (Mn11), number average molar weight, wherein the number average molar weight of the polymer component with the lower number average molar weight is lower , of six times the average molar weight of the starting polyolefin, and its weight ratio to the polymer component with a higher numerical average molar weight is 0.01-5:1.

The ratio of average numerical molar weights of polymer components with a higher and lower average molar weight is

Mn11/Mn1 = 3-50, preferably 10-20.

In the production of a polyfunctional, ashless DD additive mixture, a primarily acylating agent is produced, whereby a polar copolymer side chain of maleic anhydride and one polar or apolar , of a non-acidic comonomer with an ethylene double bond or a mixture of such comonomers. The comonomer can be a specially added compound or one (mentioned in the working process) initiator, or a compound that controls the incorporation, or an unsaturated product of the decomposition of the polyolefin raw material, or an unsaturated component from the degradation of the polyolefin (EP 0 658 572). Injecting can be carried out by gradual copulation of maleic anhydride and comonomer on a polyolefin molecule and/or addition to polyolefin of a copolymer chain produced previously from maleic anhydride and one or more comonomer or from a fraction of these. In the production of the acylating agent, we work with maleic anhydride / comonomer / polyolefin in a molar ratio of 1.2-5.5 : 0.01-3.5 : 1 in the presence or absence of a solvent and in the presence of 5-25% by weight ( in relation to maleic anhydride) radical initiator and 0.1-5 wt.% compound, which controls the monomer incorporation ratio, at a pressure between 100-1,500 kPa, in an inert atmosphere and/or a hydrocarbon atmosphere, at a temperature between 80-180° C. If necessary, the intermediate is diluted with base oil, and after clarification, it is purified by filtration. The resulting acylating agent reacts for 2-15 hours with one or more, at least bifunctional compounds with an amino- and/or imino/or hydroxy group at a molar ratio of acylating agent/amine and/or alcohol of 0.7-5.5:1 temperatures between 120-235°C in the presence or absence of a catalyst; if necessary, it is diluted with base oil, purified and modified in a known manner.

The obtained intermediate, which consists of a long apolar polyolefin chain and a bound, strongly polar copolymer chain with a statistical or alternating structure, is very suitable for the production of imide and/or ester and/or amide and/or esteramide derivatives with a high dispersing effect, whereby the groups linked on the same polyolefin chain, may be the same or different.

In the case of these raw materials, the resulting polyfunctional groups, which usually stand at the end, mostly composed of a large number of carboxyl groups, enable such polymer structures to be created during acylation with the use of appropriate, at least bifunctional basic reagents, which usefully modify the rheological properties of lubricating oils. It has become recognized that the use of polyisobutylene with a numerical average molecular weight higher than 800, preferably higher than 2,000, will result in additives, which, in addition to the favorable DD-effect, have such an effect of increasing the viscosity and viscosity index, which is greater than with polyisobutylene raw material. Polyisobutylenes with a high alphaolefin content (greater than 70% by weight) are particularly suitable for the production of such polymer components.

As a particularly favorable fact, it can be considered that polyisobutylenes can be used with the help of the invention as additives for modifying viscosity, both with respect to viscosity in hot and viscosity in cold.

According to our experimental experiences, the polyfunctional, ashless DD-mixture of additives has better thermal and oxidative stability than usual additives for increasing the viscosity index, thus increasing the stability of motor oil mixtures to an unexpected extent.

Component "A" contains, in addition to the main ingredient described above, 0-90 wt.% of common and commercial low molecular weight derivatives of alkenyl succinic acid, such as esters, esteramides, polyisobutenylsuccinimides, succinimidamides or their mixtures. Products produced according to HU 197 936 and 205 778 are particularly suitable.

As component "B", such further additives of known effect are used in the mixture according to the invention, which are practically necessary in the production of modern high-performance mixtures. One or more such DD additives with different metal content and different base number (TBN), such as basic and hyperbasic calcium- and magnesium-sulfonates, -phenatene and -salicylates, are primarily used here; antioxidants, such as zinc-dialkyldithiophosphates and -dithiocarbamates, spatially restricted phenols, cresols, aromatic amines and their derivatives; additives that reduce friction and wear, such as aliphatic amines, amides, esters, esteramides, phosphates, thiophosphates, sulfides, polysulfides and their derivatives; corrosion inhibitors, such as alkyltriazoles, mercaptobenztriazoles, monocarboxylic acids, dicarboxylic acids and their derivatives; antifoaming agents, such as dialkylsilicone polymers; additives that lower the pour point, such as polyalkyl methacrylates, polyalkyl acrylates, ethylene vinyl acetate copolymers, dialkyl fumarate copolymers and similar substances.

Suitable components of component "B" are, as metal-containing DD-additives, basic and hyperbasic calcium- and magnesium-sulfonates, -phenates and salicylates; as inhibitors: zinc-dialkyldithiophosphates, ashless dithiocarbamates, spatially limited phenols and aromatic amines; as agents that reduce friction: derivatives of fatty acids and phosphoric acids and polyalkyl siloxanes; as wear inhibitors: dithiocarbamates, sulfurized vegetable oil derivatives and as substances for lowering the solidification point: polyalkyl methacrylates, as well as mixtures of the above substances.

Based on past experience and the results of technically applicable previous research, the educated expert will easily choose as component "B", the applicable commercial additives.

Component "C" is a known viscosity and viscosity index increasing polymer or a suitably selected mixture of such polymers. Polyalkyl methacrylates, ethylene-propylene copolymers, styrene-diolefin copolymers, as well as their nitrogen-containing derivatives are primarily used for multipurpose motor oil mixtures.

The ratio of additives to be applied in components "A", "B" and "C", within the components as well as the ratio of individual components to each other, will be determined through different parameters. As an example of these parameters, we can mention the degree of viscosity and the effect of the mixture produced, the properties of the applied base oil, as well as the effect of additives depending on the concentration.

For the production of lubricating oil mixtures and motor oil mixtures with effective and favorable properties, the concentration of additives applied in individual components (A, B, C) is selected, primarily within the range specified in table 1.

Table 1:

Areas of additive concentration

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* Refers to the entire preparation, including the thinning oil present in the additives.

In the case of multipurpose motor oil mixtures, the amount of individual components is adjusted primarily to the areas listed in table 2.

Table 2:

Primary areas of concentration of components in relation to the package of accessories

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It is worth mentioning that such supplements can also be applied, which can fulfill several functions at the same time, whereby their effects on each other can increase or decrease the other. Their concentration is therefore determined with consideration of their mutual effects.

The package of supplements according to the invention can also be used as a concentrate. In such cases, the additive package is preferably dissolved in a 0-85% by weight diluent to facilitate handling. As thinners can be used, for example, base oils applied in a mixture, such as, in motor oil mixtures, common base oils of low viscosity, VK100 < 15 mm2/s.

In the mixture according to the invention, such common base oils based on mineral oils can be used as the base oil, which can be produced by solvent refining and/or hydrogenation refining and/or catalytic release of paraffin and/or active clay refining and/or final hydrogenation refining and /or by the hydrocracking process, and if necessary purified by subsequent release of solvents and/or catalytic release of paraffin, whereby the composition of these base oils is adjusted primarily by mixing commercially common base oils of different viscosities with regard to the desired degree of viscosity and effect. Synthetic oils are also preferred, such as polyalphaolefins, dicarboxylic acid esters or polyolesters, as well as vegetable oils and/or their derivatives, the ratio of which should be adjusted according to the needs of the application. When applying the package of additives according to the invention, different mixtures of base oils produced from paraffinic crude oils by a combination of solvent refining and/or hydrogenation refining, with polyalphaolefins and dicarboxylic acid esters, where the proportions are adjusted with regard to the desired viscosity, are evaluated as particularly favorable.

By applying the additive package according to the invention, it is possible to produce motor oil mixtures corresponding to the known performance levels. Thus, for example, according to the API-classification (ASTM D4485), SG and SH levels can be achieved, or according to the CCMC-classification (lecture by G.F. Cahill: Evolution of the CCMC Engine Lubricant Sequences, in CEC IIIrd International Symposium of Performance Evolution to Automotive Fuels and Lubricants, April 13, 1989), grade PD-2 and GL-5.

The package of additives according to the invention can be used in addition to motor oil mixtures also in other lubricating oil mixtures, such as gearbox oils, hydraulic fluids, automatic transmission oils (ATF), cooling oils and machine oils; as well as in other compounds, such as brake fluids, heat transfer oils, and curing oils, as well as engine propellants, to improve the properties of these. However, the primary application is the production of motor oil mixtures with multipurpose additives.

Production of mixtures is carried out by usual joint mixing. Here, it is possible to proceed in such a way that the additives applied in the components are individually added to the base oil, and the entire mixture is thoroughly mixed. Another possibility is the pre-production of additive packages, whereby the additives are mixed together in the desired quantities; then, in order to facilitate further processing, the viscosity is adjusted to the desired level with an arbitrary base oil, primarily the one used in the mixture. The resulting concentrate mixed with the desired base oil is processed into a mixture.

During the production of mixtures, the order of introduction of additives should be determined with regard to possible chemical reactions. The various additive components are mixed into the base oil primarily in such an order, which minimizes the probability of reaction between compounds of different chemical structures and reaction capabilities. To avoid thermal decomposition, it is done at a temperature between 40-80°C.

A characteristic advantage of the invention is that the high-molecular raw material PIB applied in a halogen-free and ash-free additive enables the production of a DD-additive with an increased effect, which, when applied with appropriate amounts of other common additives, only damages elastomeric sealing materials to a small extent, or even protects them. Furthermore, it has increased resistance to shear, heat and oxidation, the effect of increasing viscosity and viscosity index, as well as the additional effect of wear inhibition, and thus enables the reduction or omission of common polymers or wear inhibitors that retain phosphorus, and thus the production of highly stable and environmentally acceptable mixture.

The invention is explained in more detail on the basis of the following examples, without the intention of limiting the claim to examples. In the examples, motor oil mixtures are presented, which have the SG degree according to the most widespread API classification.

Example 1

The production parameters and features of intermediates for polyisobutylene-polysuccinimide derivatives with a new structure, which are used in component "A" as a polyfunctional ashless DD-mixture, are included in table 3, and the features of the final product synthesized from these are in table 4.

Table 3:

The most important parameters of the synthesis and features of the polyfunctional ashless DD-admixture intermediate

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PIBPOBAO-KA; PIBPOBAO-KB: oil solution of PIB-succinic anhydride intermediate.

Table 4:

The most important synthesis parameters and quality features of the polyfunctional ashless DD-mixture of additives

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* Polyisobutylenepolyanthric anhydride, oil solution

** Polyisobutylenepolysuccinimide

*** TEPA Tetraethylenepentamine

DETA Diethylenetriamine

Example 2

The following motor oil mixtures are produced with the use of polyfunctional ashless DD-mixtures of additives according to example 1 (PIBPSI-1, PIBPSI-2). Experimental mixtures of motor oils from K-1 to K-14 are produced as follows:

In the device, which is equipped with heating through the jacket up to a temperature of 120°C, i.e. suitable cooling through the jacket and an internal mechanical mixer, the oil component present in the mixture with the lowest viscosity (including synthetic components) at ambient temperature is placed first. Then, with heating and constant mixing, at ambient temperature, further oil components are added in the order corresponding to the increase in viscosity. The oil mixture is heated to a temperature of 70°C, and for easier handling, substances heated up to 60°C can be added to reduce the pour point (P.P.D.), various substances to increase the viscosity index (V.I.I.-1, 2, 3) and 4), as well as ashless dispersants applied together with these.

The mixture of the above substances is then gently stirred for one hour, then the desired amount of zinc dithiophosphate, detergent mixture and antioxidant is added to the mixture cooled to a temperature of about 60°C. After stirring for one hour, cool the mixture to ambient temperature. The composition of the 14 test mixtures obtained in this way with the performance level of SG/CD according to API is listed in Table 5.

The most important features of the substances used for the production of experimental mixtures are the following:

Mineral oil raffinates SN-80, SN-150 and SN-350 are paraffin-free, with N-methyl-pyrrolidone as a solvent refined and hydrated fraction of distillates, produced from Hungarian mineral oil. Their kinematic viscosity at 100°C is 3.42 mm2/s, 5.40 mm2/s and 8.62 mm2/s, their viscosity index is 102, 106 and 95, their aromatic content according to Brandes is 4.9% , 4.6% and 7.7%, their pour points are -18°C, -18°C and -15°C. Base oil SAE 10/95H is a refined, paraffin-free oil, which is produced by a light hydrocracking process and subsequent redistillation. SAE 10/95H oil shows a kinematic viscosity at 100°C and 40°C of 5.29 and 31.7mm2/s, a viscosity index of 100, an aromatics content according to Brandes of 7.7%, a sulfur substance content of 0, 04 %, pour point of -18°C. Components PAO-4 and PAO-6 are commercial polyalphaolefins.

The PPD substance that lowers the pour point is a polymethacrylate additive.

Of the four substances that modify the viscosity index, they are V.I.I.-1 polymethacrylate commonly used in motor oils, V.I.I.-2 a solution of styrene isoprene copolymer in base oil SN-150, V.I.I.-3 polyisoprene that modifies viscosity, V.I.I.-4 a solution of olefin copolymer in base oil SN- 150. Base oil SN-150, which was used in V.I.I.-2, 3 and 4, exhibits the characteristics presented in base oils.

The ZDDP component is zinc dialkyldithiophosphate, which is widely used as an additive to engine oil mixtures for Diesel and gasoline engines, and which is produced with mixed primary and secondary alcohols. It shows a zinc content of 9.2 wt.% and a phosphorus content of 8.4 wt.%, and as an antioxidant (AO) it contains diphenylamine derivatives.

The DET component is a detergent from a mixture of basic calcium and magnesium salicylates, it shows a Ca content of 4.9 wt.%, a Mg content of 2.6 wt.% and a base number of 2.53 mg KOH/g according to ASTM D 2896.

Table 5:

Composition of motor oil mixtures according to the invention and reference oil mixtures

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* Piece-301 commercial bisuccinimide (MnPIB=1000, Polyamine=Tetraethylenepentamine)

Example 3

The beneficial effects of the invention are proven on the basis of the properties of the mixtures from K-1 to K-14.

Compatibility with sealing material

A known disadvantage of common succinimide detergents is, especially in concentrations above 3-4 tei.%, undesirable damage to sealing materials used in engines. The good compatibility of the invention with sealing materials is proven on the basis of the research of K-6, K-7, K-8 and K-3 motor oil mixtures. As a reference oil mixture, the data of the K-5 mixture, which contains the usual succinimide (Komad-301), are cited. In addition to CEC-testing performed with four elastomers, the compounds were also tested with VW-3344-testing, however, performed under strict circumstances. The results are listed in Table 6.

Partially synthetic mixtures K-5, K-6, K-7 and K-8 corresponding to SAE viscosity grade 10W-40 show, with the exception of succinimide, the same composition (mixture K-8 contains PAO-6, the other three mixtures contain PAD-4 ). The K-3 mixture is based on mineral oil, contains mineral oil raffinate produced by a light hydrocracking process, and exhibits an SAE viscosity grade of 15W-40. In Table 6, the good and very good grades of mixtures K-3, K-6, K-7 and K-8 prove the advantage of the invention compared to the poor results of mixture K-5.

Table 6:

Compatibility of engine oil mixtures with sealing materials

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Inhibitory effect on wear

According to the data in Table 7, the new preparations show, under certain circumstances, an inhibitory effect on wear.

Mixture K-9, which was made with a conventional dispersant, and Mixture K-10, which was made with an additive package according to the invention, both showed an OK load (ASTM D 2782) of 45 lb (22 kg) in the Timken apparatus. After a 3-hour wear test at a load of 40 lb (19.5 kg), however, the K-11 compound according to the invention shows 60 wt.% less wear.

Table 7:

The inhibitory effect of motor oil mixtures on wear

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Viscosity-modifying action, substitute for viscosity-modifying polymers

One of the greatest advantages of the new mixtures according to the invention arises from the increased effect of the new additives on increasing the viscosity and viscosity index.

This effect is shown in Table 8 by data from three mixtures, in which the common additive Komad-301 and the polyfunctional ashless DD-mixture of additives according to the invention were tested in mixtures based on mineral oil and SAE grade 15W-40, in partially synthetic mixtures SAE grade 10W- 40, as well as in synthetic mixtures of SAE grade 5W-50, whereby the mixtures show the same composition in relation to further ingredients. The most important rheological data are listed in Tables 8 and 9. The mixtures were adjusted to an approximately equal level within the individual viscosity grades, by changing the viscosity of the base oil and the amount of viscosity-modifying polymer.

Of these polyfunctional, ashless DD-mixture additives according to the invention, PIBPSI-1 shows less viscosity-increasing action, however this also allows the amount of viscosity-modifying polymer to be reduced by a third in SAE grade 15W-50 compared to the amount used in the reference DD- Addendum Komad-301. With SAE grade 10W-40, the polymer content is reduced, which means a saving of about 25%, and with grade 5W-50, about 15%.

The mixture of additives PIBPSI-2, which shows a greater action of modifying viscosity, allows in K-4 and K-b mixtures at the DD-concentration required for API grade SG, to replace the entire amount of viscosity modifying polymer for SAE grades 15W-40 and 10W-40; in the grade 5W-50 mixture, its application required only a third of the amount of viscosity-modifying polymers compared to the reference DD-mixture. As it follows from the viscosity in cold and warm, which are almost equal in viscosity grades, and from the similar viscosities of the base oils, the DD-additives applied in the additive package according to the invention as polymers for modifying the viscosity do not increase the viscosity of the oil in cold, more than usual polymers .

Table 8:

Replacement for Viscosity Modifying Polymers (V.I.I.) with PIBPSI-1 and PIBPSI-2

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Shear resistance

According to the shear strength data shown in Table 9, it follows that the injector shear strength according to Bosch (ASTM D3934) is a mixture of K-7, K-13 and K-14 engine oils, which partially or fully contain succinimides as a modifying additive viscosity, similar to the shear strength of the K-12 motor oil mixture, which contains the reference succinimide (Komad-301) and V.I.I.-1 based on polymethacrylate.

Table 9:

Shear resistance of oil mixtures according to the invention

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Detergent-dispersing effect, effect on a test bench with a brake

Investigations on a test bench with a brake, as a decisive feature for qualifying engine oil mixtures, are shown in Table 10. Oil mixtures K-2 and K-3 were tested on test benches with a brake Petter W-1, M 102 E, Sequence IIIE and PV 1431. Engine sludge test numbers on the M 102 E and Sequence IIIE brake test bench show excellent dispersing action, and the piston cleanliness numbers on the Sequence IIIE and PV 1431 brake test bench prove the adequate deterging action of the additives applied in the oil mixtures. The favorable composition of the compounds according to the invention was further determined by the good wear properties measured on the test bench with the Petter M 102 E brake, and especially on the test bench with the Sequence IIIE brake, and by the very low wear of the bearings measured on the test bench with the Petter W-1 brake.

Table 10:

Testing of a mixture containing PIBPSI-1, a polyfunctional, ashless DD additive mixture, by testing on a test bench with a brake

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Example 4

The composition of the additive package concentrate according to the invention and from this diluted engine oil mixture is shown in table 11.

Table 11:

Additive package concentrate and engine oil mixture diluted from it (wt.%)

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Claims (18)

1. A mixture of motor oil with multi-purpose additives, which consists of base oil suitable for motor oil and additives, characterized by the fact that it contains an additive package of 1.5-55 wt.%, which always contains from one or more additives composed of component "A" , "B" and, if necessary, "C", whereby the individual components show the following composition: Component "A" - 10-100% by weight of a polyfunctional, ashless additive mixture that acts as a detergent-dispersant or its oil solution, wherein the polyfunctional, ashless additive mixture that acts as a detergent-dispersant contains such polymer components, which show the same or different numerical average molar weight, which are produced by the reaction of a polyolefin derivative, primarily a PIB-derivative, which has been injected with one or more dicarboxylic acids and/or dicarboxylic acid anhydride, and one or more non-acidic comonomers with an ethylene double bond and has a number average molecular weight of at least 800 , with a compound containing an amino and/or imino- and/or hydroxy group, and in the polymer components the polyolefin chain carries an average of 1.6-20 acid derivatives, and the amount of molecules with more than one acid derivative is at least 25% by weight, whereby the derivative can be an imide- and/or amide- and/or esteramide derivative, i - 0-90% by weight of a common derivative of alkenyl succinic acid, as an imide- and/or ester- and/or esteramide derivative; Component "B" - one or more common additives, such as additives with different basic numbers and different metal content that act as detergent-dispersants, antioxidants, substances that reduce friction, wear inhibitors, corrosion inhibitors, anti-foaming agents and substances that lower the pour point. Component "C" - one or more common polymers for increasing viscosity and viscosity index; where the weight ratio of components "A", "B" and "C" is: 15-85 : 15-85 : 0-70. 2. Motor oil mixture according to claim 1, characterized in that component "A" contains such polymer components, which are injected with maleic anhydride. 3. Motor oil mixture according to claim 1 or 2, characterized in that component "A" contains such polymer components, which are produced by converting polyisobutylene with a number average molar weight of 1300-30,000 as polyolefin. 4. Engine oil mixture according to one of claims 1-3, characterized in that component "A" contains at least two such polymer components, which have different numerical average molecular weight, one lower (Mn1) and one higher (Mn11), whereby is the numerical average molecular weight of the polymer component with a lower numerical average molecular weight is less than six times the average molecular weight of the starting polyolefin, the ratio of the average molecular weight of the polymer component with a lower numerical average molecular weight to the polymer component with a higher numerical average molecular weight is 3-50:1 , preferably 10-20:1, and the weight ratio of the polymer component with a lower number average molar weight to the component with a higher number average molar weight is 0.01-5:1. 5. Engine oil mixture according to one of the claims 1-4, characterized in that component "B" contains organic calcium or magnesium salts, such as -sulfonates, -phenates, - salicylates or their mixtures as a detergent-dispersant effective additive with different base numbers and different metal content. 6. Engine oil mixture according to one of claims 1-5, characterized in that it contains 0.6-26 wt.% of component "A", 0.3-18.6 wt.% of component "B" and 0-25 wt.% component "C". 7. Lubricating oil mixture, which consists of base oil suitable for lubricating oils and additives, characterized by the fact that it contains 1.5-55 wt.% of the additive package, which always contains one or more additives composed of component "A", "B" and if necessary "C", whereby the components show the following composition: Component "A" - 10-100% by weight of a polyfunctional, ashless mixture of additives that has a detergent-dispersing effect or its oil solution, wherein the polyfunctional, ashless mixture of additives, which has a detergent-dispersing effect, contains such polymer components, which show the same or different numerical averages molecular weight, which are produced by the reaction of a polyolefin derivative, primarily a PIB derivative, which has been injected with one or more dicarboxylic acids and/or dicarboxylic acid anhydride, and one or more non-acidic comonomers with an ethylene double bond and has a numerical average molecular weight of at least 800, with a compound containing an amino and/or imino- and/or hydroxy group, and in the polymer components the polyolefin chain carries an average of 1.6-20 acid derivatives, and the amount of molecules with more than one acid derivative is at least 25% by weight, at where the derivative can be an imide- and/or amide- and/or esteramide derivative, i - 0-90% by weight of a common derivative of alkenyl succinic acid, as an imide- and/or ester- and/or esteramide derivative; Component "B" - one or more common additives, such as additives with different base numbers and different metal content, which act as detergents-dispersants, antioxidants, substances that reduce friction, wear inhibitors, corrosion inhibitors, anti-foaming agents and substances that lower the pour point. Component "C" - one or more common polymers for increasing viscosity and viscosity index; where the weight ratio of components "A", "B" and "C" is: 15-85 : 15-85 : 0-70. 8. Lubricating oil mixture according to claim 7, characterized in that component "A" contains such polymer components, which are injected with maleic anhydride. 9. Lubricating oil mixture according to claim 7 or 8, characterized in that component "A" contains such polymer components, which are produced by conversion of polyisobutylene with a number average molar weight of 1300-30,000 as polyolefin. 10. Lubricating oil mixture according to one of claims 7-9, characterized in that component "A" contains at least two polymer components, which have different numerical average molecular weights, one lower (Mn1) and one higher (Mn11), whereby the numerical average molecular weight of the polymer component with a lower numerical average molecular weight is less than six times the average molecular weight of the starting polyolefin, the ratio of the average molecular weight of the polymer component with a lower numerical average molecular weight to the polymer component with a higher numerical average molecular weight is 3-50 : 1, preferably 10-20:1, and the weight ratio of the polymer component with a lower numerical average molar weight to the component with a higher numerical average molar weight is 0.01-5:1. 11. Lubricating oil mixture according to one of claims 7-10, characterized by the fact that component "B" contains organic calcium or magnesium salts, such as -sulfonates, -phenates, - salicylates or their mixtures as a detergent-dispersant effective additive with different base numbers and different metal content. 12. Lubricating oil mixture according to one of claims 7-11, characterized in that it contains 0.6-26 wt.% of component "A", 0.3-18.6 wt.% of component "B" and 0-25 wt. .% of component "C". 13. A package of additives that is suitable for lubricating oil mixtures, primarily for motor oil mixtures, characterized by the fact that it contains 15-100 wt.% of components "A", "B" and, if necessary, "C", which always consist of one or more additives, and 0-85% by weight of diluent, the components having the following composition: Component "A" - 10-100% by weight of a polyfunctional, ashless mixture of additives that has a detergent-dispersing effect or its oil solution, wherein the polyfunctional, ashless mixture of additives, which has a detergent-dispersing effect, contains such polymer components, which show the same or different numerical averages molecular weight, which are produced by the reaction of a polyolefin derivative, primarily a PIB derivative, which has been injected with one or more dicarboxylic acids and/or dicarboxylic acid anhydride, and one or more non-acidic comonomers with an ethylene double bond and has a numerical average molecular weight of at least 800, with a compound containing an amino and/or imino- and/or hydroxy group, and in the polymer components the polyolefin chain carries an average of 1.6-20 acid derivatives, and the amount of molecules with more than one acid derivative is at least 25% by weight, at where the derivative can be an imide- and/or amide- and/or esteramide derivative, and 0-90% by weight of the usual alkenyl derivative succinic acid, as an imide- and/or ester- and/or esteramide derivative; Component "B" - one or more common additives, such as additives with different base numbers and different metal content, which act as detergents-dispersants, antioxidants, substances that reduce friction, wear inhibitors, corrosion inhibitors, anti-foaming agents and substances that lower the pour point. Component "C" - one or more common polymers for increasing viscosity and viscosity index; where the weight ratio of components "A", "B" and "C" is: 15-85 : 15-85 : 0-70. 14. Package of supplements according to claim 13, characterized in that component "A" contains such polymer components, which are injected with maleic anhydride. 15. Package of additives according to claim 13 or 14, characterized in that component "A" contains such polymer components, which are produced by conversion of polyisobutylene with a number average molecular weight of 1300-30,000 as polyolefin. 16. A package of supplements according to one of claims 13-15, characterized in that component "A" contains at least two such polymer components, which have different numerical average molecular weights, one lower (Mn1) and one higher (Mn11), wherein the numerical average molecular weight of the polymer component with a lower numerical average molecular weight is less than six times the average molecular weight of the starting polyolefin, the ratio of the average molecular weight of the polymer component with a lower numerical average molecular weight to the polymer component with a higher numerical average molecular weight is 3-50:1, preferably 10-20:1, and the weight ratio of the polymer component with a lower numerical average molecular weight to the component with a higher numerical average molecular weight is 0.01-5:1. 17. A package of additives according to one of claims 13-16, characterized in that component "B" contains organic calcium or magnesium salts, such as -sulfonates, -phenates, -salicylates or their mixtures as a detergent-dispersing effective additive with a different base number and with different metal content. 18. A package of additives according to one of claims 13-17, characterized in that it contains 0.6-26 wt.% of component "A", 0.3-18.6 wt.% of component "B" and 0-25 wt.% of component "C".