EP0789069A2 - Additive containing multifunctional lubricating oil and engine oil compositions - 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 a halogen-free, additive-containing multigrade engine oil and lubricating oil composition with high stability and possibly with a low phosphorus content, which consists of base oil and an additive package. The invention further relates to the additive package used.

• viskositäts- und viskositätsindexerhöhende, und fließpunktvermindernde Polymere,
• aschefreie Dispergenzien,
• metallhaltige Detergenzien,
• Inhibitoren (Oxydationsinhibitoren, Korrosionsinhibitoren, Verrostungsinhibitoren und ähnliche Stoffe),
• Abriebinhibitoren.

In order to meet the requirements of the tear-off spark ignition or diesel engines, the following groups of additives are used in the engine oils:

• polymers that increase viscosity and viscosity index and reduce pour point,
• ashless dispersants,
• metal-containing detergents,
• Inhibitors (oxidation inhibitors, corrosion inhibitors, rust inhibitors and similar substances),
• Abrasion inhibitors.

The additives of conventional engine oils can be classified into five groups based on their function and structure. The first group includes the large molecular (M _n = 5,000-2,000,000), mostly homo- or copolymeric additives, which usually have a viscosity and viscosity index-increasing and pour point reducing effect.

By incorporating polar, basic groups into the copolymer structure, additives with a detergent-dispersing (hereinafter referred to as DD) side effect can be obtained, the use of which enables a certain reduction in the concentration of the small-molecular DD additives (M _n <2,000) in the motor oil compositions. The most well-known representatives of such additives are the polyalkyl methacrylates (PMA) and their derivatives, ethylene-propylene copolymers (OCP), styrene-butadiene copolymers (SBCP) and polyisoprene (PIP).

Another group of additives that is rapidly spreading in use is represented by the so-called ash-free DD additives. Their increasing use in terms of quantity is due to the fact that the greater performance requirements imposed by the new engine designs - such as a reduction in the formation of black sludge, environmentally harmful metal emissions and the effects leading to damage to sealing materials - are only due to the further development of the ash-free DD additives and can be satisfied with their use with increased concentration. As small-molecular (M _n <2,000) ash-free DD additives, imide, amide or ester derivatives of polyalkenylsuccinic acids, Mannich bases with a polyisobutene basic structure, polyolefin amines and similar substances are mostly used.

The third, fourth and fifth group of additives are additives with other functions. These additives include a number of compounds which have very important effects with regard to their use.

These groups include, for example, the metal-containing detergents, oxidation inhibitors, corrosion inhibitors, friction-modifying substances and abrasion inhibitors, and anti-foaming agents. A number of metal-containing and ash-free variants of these substances are known, and these are generally selected and used in consideration of their interactions - which can be synergistic or antagonistic - on the basis of laboratory and brake test stand examinations.

During the developments in the past 15 years, the composition of the engine oils has been changed, on the one hand, by using new additives with increased effectiveness, which satisfy the new requirements at a higher level, on the other hand, by a new modification of the structure of the additives that were previously used successfully, i.e. changed by the production of additives which have an additional effect in addition to the main effect, the use of which enables a further increase in the level of performance or a reduction in the concentration required for a certain level of performance. For example, by chemical modification of the structure of the additives used in the compositions successfully reduces such undesirable side effects, such as damage to the sealing material or corrosion of the bearing metals. The DD effect was e.g. by modifying the ash-free succinimide additives with organic acids (EP 0 537 386) or by optimizing the structure of the polyethylene-polyamines used for the synthesis (EP 0 451 380).

The vaccination of conventional viscosity and viscosity index-increasing ethylene-propylene copolymers with polar groups has been successful

A DD side effect was successfully developed by inoculating conventional ethylene-propylene copolymers with polar groups that increase viscosity and viscosity index (EP 0 400 866). The mixed polymers of ethylene-propylene copolymers which have been inoculated with polymethacrylates are suitable for stabilizing the mixtures of various polymers which increase viscosity and viscosity index.

The effects of the conventional small-molecular alkenylsuccinimide additives, which damage the fluoroelastomer sealing materials, have been successfully reduced with strong inorganic acids (US 5,114,402).

According to EP 0 265 658, the resistance of the oil compositions to oxidation at high temperatures and to the formation of deposits was successfully increased by using new polyisobutenylsuccinic acid zinc salt derivatives. In addition to a high DD effect and increased storage stability, a preferred friction-reducing effect could be achieved according to EP 0 051 998 by using ester derivatives of polyalkenylsuccinic acid, ethylene glycol and fatty acids.

Additives which, in addition to an increased DD effect and improved compatibility with the sealing materials, have an increased viscosity and viscosity index-increasing side effect can be produced by extending the polymer side chain of polyisobutenylsuccinimides up to a molecular weight of 5,000 and by 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 several tens of thousands was made possible by the synthesis of those acylating agents which in their molecules each have more than one succinic anhydride (BA) attached to a polyolefin chain.

By reacting such intermediates and polyalkylene-polyamines and / or polyalcohols and / or alkanolamines - even with polyolefins with a higher average molecular weight than with the commonly used molecules (M _n = 1,500-5,000) - additives with large polar groups (imide , Amide or ester) and synthesize with a high DD effect. The structure of the known additives and the known production processes are different, In all cases, however, one can demonstrate in the compositions containing such additives the increase in the DD effect and such a viscosity and viscosity index-increasing side effect which reduces the amount of the conventional polymers required for a certain viscosity level by 10-30% and thereby the reduction the cost of the addition.

Despite the success achieved and described above in the development of large molecular succinimides (M _n > 2,000), the use of conventional viscosity and viscosity index-increasing polymers has remained a basic requirement in the production of multistage motor oils. To further reduce their use, other efforts can also be observed.

The amount of viscosity and viscosity index increasing polymers to be used may e.g. can be reduced by using base oils produced by the hydrocracking process or synthetic base oils (polyalphaolefins, diesters and similar substances) with an ever increasing viscosity index. The conventional viscosity and viscosity index increasing polymers have beneficial effects in the lubricating oils, but the unstable decomposition products resulting from the use of the composition and the effect of the chemical impurities formed under the strict circumstances (such as high temperature and mechanical stress) promote the formation of the insoluble resin-like Deposits, and thereby the pollution of the engine. Because of the reduction in molecular weight associated with the decomposition, these polymers can only ensure the desired viscosity and the desired viscosity index of the lubricating oil to a reduced extent. The quality of the engine oils can therefore be further improved by using polymers with increased stability.

During our investigations we came to the unexpected finding that by using certain amounts of appropriately selected base oils, various common additives and a new polyfunctional ash-free DD additive composition, engine oil and lubricating oil compositions can be produced with high shear stability, which the usual viscosity and viscosity index-increasing polymers in a substantially reduced amount or are free of these.

The invention therefore relates to a lubricating oil composition, preferably engine oil composition, which consists of base oil and additives suitable for lubricating oils, preferably engine oils, and contains an additive package in an amount of 1.5-55% by weight, each consisting of one or more additives Components "A", "B" and optionally "C", wherein the individual components have the following composition:

Component "A"

• 10-100% by weight polyfunctional, ash-free, detergent-dispersing additive composition or its oily solution, the polyfunctional, ash-free, detergent-dispersing additive composition containing polymer components which have the same or different numerical average molecular weights and which, by reaction of a polyolefin derivative, preferably PIB derivative, which is inoculated with one or more dicarboxylic acids and / or dicarboxylic anhydride and with one or more non-acidic comonomers with an ethylenic double bond and has a numerical average molecular weight of at least 800, with an amino and / or imino and / or hydroxyl group containing compound were prepared 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, the derivative being an imide and / or amide and / or can be an ester amide derivative, and
• 0-90% by weight of a conventional alkenylsuccinic acid derivative, such as an imide and / or ester and / or ester amide derivative;

Component "B"

• one or more conventional additives, such as detergent-dispersing additives with a different base number and different metal content, antioxidants, friction-reducing substances, abrasion inhibitors, corrosion inhibitors, anti-foaming agents and pour point reducing substances;

Component "C"

• one or more conventional viscosity and viscosity index increasing polymers; wherein the weight ratio of components "A""B" and "C" is 15-85: 15-85: 0-70.

The invention furthermore relates to the additive package used in the above compositions, each of which contains components "A", "B" and, if appropriate, "C" which have the composition indicated above and which consist of one or more additives.

As mentioned, the additive package according to the invention consists of three main components (A, B, C), each of which contains one or more additives. For example, component "A" contains a new ash-free polyfunctional additive composition with DD and viscosity and viscosity index-increasing effects from vaccinated polyolefin derivatives, preferably from polyisobutylene succinic anhydride derivatives (furthermore polyfunctional ash-free DD additive composition); component "B" is an additive mixture of conventional ash-containing and / or ash-free additives with various effects; component "C" is an additional and customary additive or an additive mixture with viscosity and viscosity index-increasing action. Component "C" can optionally be omitted.

Component "A" contains, in 10-100% by weight, a polyfunctional, ash-free DD additive composition or its oily solution, the polyfunctional, ash-free DD additive composition containing polymer components which, by reacting a polyolefin derivative, preferably a polyisobutylene Derivatives (PIB derivative) with a numerical average molecular weight of more than 800, preferably 1,300-30,000, which with one or more unsaturated dicarboxylic acids and / or their carboxylic anhydride, preferably with maleic anhydride and with one or more non-acidic comonomers with an ethylenic double bond or with copolymers thereof Comonomers (and / or with maleic anhydride homopolymers), with a compound containing an amino and / or imino and / or hydroxy group, the polymer components having the same or different numerical average molecular weights and in which the polyolefin chain e, whose numerical average molecular weight is preferably the same as that of the starting material, carries an average of 1.6-20 acid derivatives, the amount of molecules with more than one acid derivative is greater than 25% by weight and the derivative can be an imide and / or amide and / or ester amide derivative.

The above polyfunctional, ashless DD additive composition preferably contains at least two polymer _components with different - a lower (M _nI ) and a higher (M _nII ) - numerical average _{molecular weight} , the numerical average _{molecular weight of the polymer component having} a lower numerical average _{molecular weight being} less than six times that Average molecular weight of the starting polyolefin, and its weight ratio to the polymer component with higher numerical average molecular weight is 0.01-5: 1.

The ratio of the numerical average molecular weights of the polymer components with higher and smaller average molecular weights is $${\text{M}}_{\text{nII}}{\text{/ M}}_{\text{nI}}\text{= 3-50, preferably 10-20.}$$

In the production of the polyfunctional, ash-free DD additive composition, an acylating agent is preferably first produced, with a polar copolymeric side chain composed of maleic anhydride and a polar or .alpha. Being based on a polyolefin, preferably PIB, with a numerical average molecular weight of at least 800, preferably at least 1,300 Vaccinates apolar, non-acidic comonomer with an ethylenic double bond or a mixture of such comonomers. The comonomer can be a separately added compound or an initiator (used in the process), or a compound controlling the incorporation or the unsaturated decomposition product of the polyolefin base, or an unsaturated component from the degradation of the polyolefin (EP 0 658 572). The inoculation can be carried out by a stepwise coupling of maleic anhydride and comonomers to the polyolefin molecule and / or by adding a copolymer chain previously prepared from maleic anhydride and one or more comonomers or parts thereof to the polyolefin. The acylating agent is prepared in addition to a maleic anhydride / comonomer / polyolefin molar ratio of 1.2-5.5: 0.01-3.5: 1 in the presence or absence of solvent and in the presence of 5-25% by weight % (based on the maleic anhydride) of a radical initiator and 0.1-5% by weight of a compound which controls the incorporation ratio of the monomers, at a pressure between 100-1,500 kPa, in an inert and / or hydrocarbon atmosphere, at a temperature between 80-180 ° C. If necessary, the intermediate is diluted with base oil and, after clarification, filtered. The acylating agent obtained is mixed with one or more, at least bifunctional, compounds having an amino and / or imino and / or hydroxyl group in an acylating agent / amine and / or alcohol molar ratio of 0.7-5.5: 1 at a temperature between 120- 235 ° C in the presence or absence of a catalyst for 2-15 hours, optionally diluted with base oil, cleaned and modified in a known manner.

The intermediate obtained, which consists of a long, apolar polyolefin chain and a linked, strongly polar copolymer chain with a statistical or alternating structure, is of high quality for the production of imide and / or ester and / or amide and / or ester amide derivatives dispersing effect very well, the groups attached to the same polyolefin chain may be the same or different. With these raw materials, the resulting polyfunctional, mostly terminal groups, which usually consist of a large number of carboxyl groups, enable polymer structures to be formed during acylation using appropriate, at least bifunctional, basic reagents, which advantageously modify the flow properties of lubricating oils. It was recognized that when using polyisobutylenes with a numerical average molecular weight of more than 800, preferably more than 2,000, additives are obtained which, in addition to the favorable DD effect, have such a viscosity-increasing and viscosity-index-increasing effect which is higher than that of the Polyisobutylene raw materials. Polyisobutylenes with a high alpha olefin content (greater than 70% by weight) are particularly preferably suitable for the production of such polymer components.

It can be considered a particularly advantageous fact that polyisobutylenes can be used with the invention as viscosity-modifying additives, both in terms of the warm viscosity and also in terms of the cold viscosity.

According to our experimental experience, the polyfunctional, ash-free DD additive composition has better thermal and oxidation stability than the usual viscosity index-increasing additives, and thus the stability of the engine oil compositions is increased to an unexpected degree.

Component "A" contains - in addition to the main component described above - optionally 0-90% by weight of conventional and commercially available small-molecular alkenylsuccinic acid derivatives, such as esters, esteramides, polyisobutenylsuccinimides, succinimidamides or mixtures thereof. The products manufactured according to HU 197 936 and 205 778 are particularly preferred.

As component "B", such additional additives with a known effect are used in the composition according to the invention which are practically indispensable in the production of modern, high-performance oil compositions. One or more such DD additives with different metal content and different base number (TBN), such as basic and hyperbased calcium and magnesium sulfonates, phenates and salicylates, are preferably used here; Antioxidants such as zinc dialkyldithiophosphates and dithiocarbamates, sterically prevented phenols, cresols, aromatic amines and their derivatives; friction and abrasion-reducing additives, such as aliphatic amines, amides, esters, ester amides, phosphates, thiophosphates, sulfides, polysulfides and their derivatives; Corrosion inhibitors, such as alkyltriazoles, mercaptobenzotriazoles, monocarboxylic acids, dicarboxylic acids and their derivatives; Anti-foaming agents such as dialkyl silicone polymers; pour point reducing additives, such as polyalkyl methacrylates, polyalkyl acrylates, ethylene-vinyl acetate copolymers, dialkyl fumarate copolymers and similar substances.

Preferred constituents of component "B" are the basic and hyperbasic calcium and magnesium sulfonates, phenates and salicylates as metal-containing DD additives, the inhibitors are zinc dialkyldithiophosphates, ashless dithiocarbamates, sterically prevented phenols and aromatic amines, and the friction-reducing substances are the fat-reducing substances - And phosphoric acid derivatives and polyalkylsiloxanes, as abrasion inhibitors the dithiocarbamates, sulfurized vegetable oil derivatives and as solidification point reducing substances the polyalkyl methacrylates, as well as mixtures of the above substances.

The commercially available additives which can be used as component "B" can easily be selected by a trained specialist on the basis of previous experience and results of preliminary technical investigations.

Component "C" is a known viscosity and viscosity index increasing polymer or a correspondingly selected mixture of such polymers. For multigrade engine oil compositions, polyalkyl methacrylates, Ethylene-propylene copolymers, styrene-diolefin copolymers, and their nitrogen-containing derivatives are used.

The ratio of the additives used in components "A", "B" and "C" within the components and the ratios of the individual components to one another are determined by various parameters. The viscosity level and performance of the composition to be produced, the properties of the base oil used and the concentration-dependent effect of the additives can be mentioned as examples of these parameters.

For the production of lubricating oil compositions and engine oil compositions with highly effective and favorable properties, the concentration of the additives used in the individual components (A, B, C) are preferably selected within the ranges given in Table 1. Table 1 Concentration ranges of the additives component Additive Concentration range (% by weight) * A Polyfunctional ashless DD- 0.6-20 Alkenyl succinic acid derivative 0-6 B Metal-containing DD 0.1-10 Copper corrosion inhibitor 0.0-0.5 Antioxidant 0.1-2 Anti-rust agent 0.001-1 Friction and abrasion inhibitor 0.1-3 Anti-foaming agent 0.0001-0.1 Pour point reducing agent 0-2 C. polymer that increases viscosity and viscosity index 0-25 * Based on the entire preparation, including the diluent oil in the additives.

In the case of multi-grade engine oil compositions, the amount of the individual components is preferably set in the ranges given in Table 2. Table 2 Preferred concentration ranges of the components based on the additive package component Quantity (% by weight) A 15-85 B 15-85 C. 0-70

It is noteworthy that it is also possible to use additives which can simultaneously perform several functions, the effects of which can increase or decrease each other. Their concentration is therefore determined taking their interactions into account.

The additive package according to the invention can also be used as a concentrate. In such cases, the additive package is preferably taken up in 0-85% by weight of diluent in order to facilitate handling. The base oils used in the composition, such as the base oils with a low viscosity that are common in motor oil compositions, VK100 <15 mm ² / s, can be used as diluents.

In the composition according to the invention, conventional base oils based on mineral oils, which can be produced by solvent refining and / or hydrogenation refining and / or catalytic paraffin removal and / or bleaching earth refining and / or final hydrogen refining and / or hydrocracking process, and, if appropriate, by subsequent solvents, can be used as the base oil - And / or catalytic paraffin removal have been cleaned, the composition of these base oils preferably being adjusted by mixing commercially available base oils with different viscosities with regard to the desired viscosity level and performance. Also preferred are the synthetic oils, such as polyalphaolefins, dicarboxylic acid esters or polyol esters, as well as vegetable oils and / or their derivatives, the proportion of which should be adjusted according to the needs of use. When using the additive package according to the invention, various mixtures of base oils made from paraffinic crude oils by a combination of solvent and / or hydrogenation refining were produced, evaluated with polyalphaolefins and dicarboxylic acid esters as particularly advantageous, the proportions being adjusted with regard to the desired viscosity.

By using the additive package according to the invention, engine oil compositions corresponding to the known power levels can be produced. So you can e.g. according to the API classification (ASTM D4485) the level SG and SH, or according to the CCMC classification (presentation by GF Cahill: Evolution of the CCMC Engine Lubricant Sequences, in CEC IIIrd International Symposium of Performance Evolution to Automotive Fuels and Lubricants, 13 April 1989) reach levels PD-2 and GL-5.

In addition to the engine oil compositions, the additive package according to the invention can also be used in other lubricating oil compositions, such as gear oils, hydraulic fluids, automatic gear oils (ATF), cooling oils and machine oils; as well as in other compositions, such as brake fluids, heat supply oils, and hardening oils, as well as in motor fuels to improve the properties of these. However, the preferred area of use is the production of multi-grade engine oil compositions containing additives.

The compositions are produced by the usual mixing. The procedure here is to add the additives used in the components individually to the base oil and to mix the entire composition thoroughly. The other possibility is the prior production of the additive package, the additives being mixed together in the desired amounts, then the viscosity, in order to facilitate further work-up, being adjusted to the desired level with any base oil which is preferably used for the composition. The concentrate obtained in this way is mixed with the desired base oil and processed into a composition.

When producing the compositions, the order in which the additives are added should be determined taking into account the possible chemical reactions. The various additive components are preferably mixed into the base oil in an order that minimizes the likelihood of reaction between the compounds with different chemical structures and reaction capabilities. To avoid thermal decomposition, a temperature between 40-80 ° C is used.

A characteristic advantage of the invention is that the large-molecular PIB base material used for the halogen-free and ash-free additive enables the production of a DD additive with increased performance, which, with appropriate amounts of other conventional additives, only slightly damages the elastomeric sealing materials, or just protected. Furthermore, it has increased shear, heat and oxidation stability, viscosity and viscosity index-increasing action, and an additional abrasion-inhibiting side effect, and thereby enables the reduction or omission of the usual polymers or phosphorus-containing abrasion inhibitors, and thus the production of highly stable and environmentally friendly compositions.

The invention is explained in more detail with reference to the following examples, without restricting the request for protection to the examples. In the examples, engine oil compositions are presented which have the level SG according to the most common API classification.

example 1

The production parameters and characteristics of the intermediates for polyisobutylene-polysuccinimide derivatives with a new structure, which are used in component "A" as a polyfunctional ash-free DD additive composition, are shown in Table 3 and the characteristics of the end product synthesized from them are shown in Table 4 summarized.

Example 2

The following engine oil compositions are produced using the polyfunctional ash-free DD additive compositions according to Example 1 (PIBPSI-1, PIBPSI-2). The test engine oil compositions K-1-K-14 are produced as follows:

In a device that is equipped with jacket heating up to a temperature of 120 ° C, or corresponding jacket cooling and an internal mechanical stirrer, first place the oil component with the lowest viscosity (including the synthetic components) in the composition at ambient temperature. Then the other oil components are added with heating and constant stirring in an order corresponding to the viscosity increase at ambient temperature. The oil mixture is heated to a temperature of 70 ° C, and in an appropriate amount, for easier handling, pour point depressants (PPD) heated to 60 ° C, various viscosity index-increasing additives (VII-1, 2, 3 and 4), as well as together with these are mixed with the ash-free dispersants used.

The mixture of the above substances is then stirred for one hour, then the to a temperature of cca. 60 ° C cooled mixture added the desired amount of zinc dithiophosphate, detergent mixture and antioxidant. After stirring for 1 hour, the mixture is cooled to ambient temperature. The composition of the 14 test compositions thus obtained with a performance level of SG / CD according to API is summarized in Table 5.

The most important quality characteristics of the substances used to manufacture the test compositions are as follows:

The mineral oil refinates SN-80, SN-150 and SN-350 are paraffin-free, hydrogenated fractions of distillates made from Hungarian mineral oil, refined with N-methyl-pyrrolidone as solvent. Their kinematic viscosity at 100 ° C is 3.42 mm ² / s, 5.40 mm ² / s and 8.62 mm ² 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 point is -18 ° C, -18 ° C and -15 ° C. The base oil SAE 10 / 95H is a refined, paraffin-free oil that is produced by a light hydrocracking process and subsequent Redistillation was produced. The SAE 10 / 95H oil shows a kinematic viscosity at 100 ° C and 40 ° C of 5.29 and 31.7 mm ² / s, a viscosity index of 100, an aromatic content after fire of 7.7%, a sulfur content of 0 , 04%, a pour point of -18 ° C. The components PAO-4 and PAO-6 are commercially available polyalphaolefins.

The pour point reducing substance PPD is a polymethacrylate additive.

Of the four viscosity index modifiers, VII-1 is a polymethacrylate commonly used in motor oils, VII-2 is a solution of styrenoprene copolymer in base oil SN-150, VII-3 is a viscosity-modifying polyisoprene, VII-4 is a solution of olefin copolymer in base oil SN -150. The base oil SN-150, which was used for V.I.I.-2, 3 and 4, has the quality characteristics shown for the base oils.

The component ZDDP is a zinc dialkyldithiophosphate, which is widely used as an additive for engine oil compositions for diesel and gasoline engines, and was produced with mixed primary and secondary alcohols. It has a zinc content of 9.2% by weight and a phosphorus content of 8.4% by weight, and contains diphenylamine derivatives as antioxidants (AO).

The DET component is a detergent composed of a mixture of basic calcium and magnesium salicylates, it has a CA content of 4.9% by weight, a Mg content of 2.6% by weight and a base number of 2.53 mg KOH / g according to ASTM D 2896.

Example 3

The advantageous effects of the invention are demonstrated on the basis of the properties of the compositions K-1-K-14.

Compatibility with the sealing material

The known disadvantage of the usual succinimide detergents, especially in concentrations above 3-4% by weight, is the undesirable damage to the sealing materials used in the motors. The good compatibility of the invention with the sealing materials is proven on the basis of the studies of the engine oil compositions K-6, K-7, K-8 and K-3. The specifications of composition K-5, which contains conventional succinimide (Komad-301), are given as the reference oil composition. In addition to the CEC test performed with four elastomers, the compositions were also tested with the VW 3344 test performed with a fluoroelastomer, but under stricter conditions. The results are shown in Table 6.

The partially synthetic compositions K-5, K-6, K-7 and K-8 corresponding to SAE viscosity grade 10W-40 show the same composition with the exception of succinimides (composition K-8 contains PAO-6, which contain other three compositions PAO-4). The composition K-3 is based on mineral oil, contains mineral oil raffinate, which was produced by a light hydrocracking process, and has an SAE viscosity level of 15W-40.

The good and very good ratings of compositions K-3, K-6, K-7 and K-8 given in Table 6 demonstrate the advantage of the invention in comparison with the poor results of composition K-5. Table 6 Compatibility of the engine oil compositions with the sealing materials preparation K-5 K-6 K-7 K-8 K-3 Limits SAE level 10W-40 10W-40 10W-40 10W-40 15W-40 Dispersant, wt.% Komad-301 7.2 - - - - PIBPSI-1 - 7.2 - 7.6 7.2 PIBPSI-2 - - 12.0 - - CEC test RE1, Change in breaking strength,% -68 +2.0 -1.0 +1.9 -9.8 -50-0 Elongation at break,% -75 -35 -16 -29 -20 -60-0 Change in DIDC hardness +6 +1 +1 -2 0 0- + 5 Change in volume,% +10 +1.0 +1.2 +0.5 +0.2 0- + 5 RE2, Change in breaking strength,% +11 +8 +1.1 +13 +3.8 -15- +10 Elongation at break,% +2 -18 -10 -22 -23 -35- + 10 Change in DIDC hardness +6 +5 +2 +3 +4 -5- + 5 Change in volume,% +2.0 0 +0.7 +1.4 +1.5 -5- + 5 RE3, Change in breaking strength,% -36 -25 -12 -19 -26 -30- + 10 Change in bridge elongation,% -11 +4 -6.0 +0.7 -13 -20- + 10 Change in DIDC hardness -7 -22 -15 -16 -19 -25-0 Change in volume,% +17.0 +12.1 +8.0 +14.4 +17.0 0- + 30 RE + Change in breaking strength,% -33.0 -6.1 -3.8 -8.8 -4.2 -20-0 Elongation at break,% -51.0 -31 -26 -47 -39 -50-0 Change in DIDC hardness +3 0 0 +1 0 -5- + 5 Change in volume,% +8.0 +1.5 +0.5 +0.3 +1.0 -5- + 5 VW-3344 test Breaking strength, MPa 5.0 9.1 10.4 9.9 8.3 > 8.0 Strain,% 119 209 235 228 183 > 160 fracture 52 - - - - not possible rating bad Well Well Well Well

Abrasion-inhibiting effect

According to the information in Table 7, the new preparations show an abrasion-inhibiting effect under certain circumstances.

Composition K-9 made with common dispersant and composition K-10 made with the additive package of the invention show an OK load (ASTM D 2782) equally of 45 lb (22 kg) in a Timken device. . After a 3-hour abrasion test at a load of 40 lb (19.5 kg), however, the composition K-11 according to the invention shows 60% less abrasion. Table 7 Abrasion-inhibiting effect of the engine oil compositions composition K-9 K-11 SAE level 10W-30 10W-30 Dispersant, wt.% Komad-301 7.2 PIBPSI-1 1.8 PIBPSI-2 3.0 Timken-OK load, lb 45 45 Timken abrasion of ring and block, 3 h, 40 lb, mg 4.7 1.9

Viscosity-modifying effect, replacement of viscosity-modifying polymers

One of the greatest advantages of the new compositions according to the invention arises from the increased viscosity and viscosity index-increasing action of the new additives.

This effect is shown by the information given in Table 8 of three compositions, in which the usual additive Komad-301 and the polyfunctional ash-free DD additive composition according to the invention in compositions based on mineral oil and SAE level 15W-40, in partially synthetic compositions of SAE level 10W -40, as well as in synthetic compositions of SAE level 5W-50 were tested, the compositions showing the same composition with regard to the other components. The most important rheological information are given in Tables 8 and 9. The compositions were adjusted to almost the same level within the individual viscosity levels by changing the viscosity of the base oil and the amount of the viscosity-modifying polymer.

Of the two polyfunctional ash-free DD additive compositions according to the invention, PIBPSI-1 shows the smaller viscosity-increasing effect, but this too enables the amount of viscosity-modifying polymers to be reduced by a third at the SAE stage 15W-50 compared to the amount which is used in the DD- Reference additive Komad-301 was used. At SAE level 10W-40, the reduction in polymer content, i.e. the saving is about 25%, and with the level 5W-50 about 15%.

The additive composition PIBPSI-2, which shows a higher viscosity-modifying effect, enables in compositions K-4 and K-6 at a DD concentration required for API level SG the replacement of the entire amount of viscosity-modifying polymers for SAE levels 15W-40 and 10W-40, in the level 5W-50 composition, due to its application, only a third amount of viscosity-modifying polymers was required compared to the DD reference composition. As can be seen from the cold and warm viscosities, which are almost the same in stages, and from the similar viscosities of the base oils, the DD additives used in the additive package according to the invention as viscosity-modifying polymers do not increase the cold viscosity of the oils more than the conventional polymers.

Shear stability

According to the information on the shear stability shown in Table 9, it can be seen that the Bosch injector shear stability (ASTM D3934) of the engine oil compositions K-7, K-13 and K-14, which contain part or all of succinimides as a viscosity-modifying additive, the shear stability of the engine oil composition K. -12, which contains reference succinimide (Komad-301) and VII-1 based on polymethacrylate. Table 9 Shear stability of the oil compositions according to the invention composition K-7 K-12 K-13 K-14 SAE level 10W-40 5W-50 5W-50 5W-50 VII% by weight used PPD 0.2 - - - VII-1 - 11.0 9.5 3.6 Dispersant used,% by weight Komad-301 - 7.2 - - PIBPSI-1 - - 7.2 - PIBPSI-2 12.0 - - 12.0 features Kinem.Visk 100 ° C, mm ² / s 14.95 18.53 18.69 17.94 40 ° C, mm ² / s 97.2 94.7 95.7 102.4 Viscosity index 161 217 217 194 CCS-15 ° C, mPas 3100 CCS-25 ° C, mPas 3410 3310 3260 Bosch shear KV / 100 ° C, 30 cycles, mm ² / s 12.09 13.99 14.77 14.43 SSI,% 31 37 31 30th VI 30 cycles 150 KV / 100 ° C 250 cycles, mm ² / s 11.70 13.38 14.21 14.01 SSI,% 36 41 35 31 VI 250 cycles 148 Base oil viscosity at 100 ° C, mm ² / s 5.8 6.1 6.0 6.1

Detergent-dispersing effect, performance on brake test bench

The tests on the brake test bench, as a crucial feature for the qualification of engine oil compositions, have been summarized in Table 10. The oil compositions K-2 and K-3 were tested on brake test benches Petter W-1, M 102 E, Sequence IIIE and PV 1431. The engine sludge values of the tests on the brake test bench M 102 E and Sequence IIIE show an excellent, dispersing effect, and the values of the piston cleanliness on the brake test bench Sequence IIIE and PV 1431 show a corresponding detergent effect of the additives used in the oil compositions. The advantageous composition of the compositions according to the invention was further demonstrated by the good abrasion properties measured on the Petter M 102 E brake test stand and in particular on the Sequeence IIIE brake test stand and by the very small bearing wear measured on the Petter W-1 brake test stand. Table 10 Brake test stand testing of the PIBPSI-1 polyfunctional, ash-free DD - additive composition CCMC G4 / PD-2 limits composition K-2 K-3 SAE level 15W-40 15W-40 Additive content,% by weight PPD 0.2 - VII -1 - 1.0 VII -2 6.0 5.2 ZDDP 1.3 1.3 AO - 0.2 PIBPSI-1 7.2 7.2 features 1. Petter W-1 Bearing wear, mg 4.7 Max. 25th 2. M 102 E. Average engine sludge 9.4 min. 8.5 Ring fixed race ASF = 16 ASF = max. 30 Piston bedding Groove 1 30.0 Max. 30th Slot 2 19.1 Max. 25.9 Cam wear average, µm 3.0 Max. 5.7 Butt foot wear, average, µm 1.9 Max. 3.1 3. Sequence IIIE 40 ° C viscosity increase,% 38 Max. 300 Piston coating 9.38 min. 8.9 Ring zone varnishing 7.40 min. 3.5 Sludge value number 9.57 min. 9.2 Ring and valve lever fixed run no no Cam and butt foot wear, average, µm 3.7 Max. 30th max., µm 11.0 Max. 60 4. W 1.6; TC brake tester (PV 1431) Ring fixed race none (ASF = 0) none (ASF = 0) Piston cleanliness 70 min. 69.4

Example 4

The composition of the additive package concentrate according to the invention and the engine oil composition diluted therefrom are shown in Table 11. Table 11 Additive package concentrate and the engine oil composition diluted therefrom (% by weight) composition P-1 P-2 P-3 P-4 M-1 M-2 Component "A" 10.4 7.2 Komad-301 - 11.4 6.1 - PIBPSI-1 15.6 - 33.0 7.8 PIBPSI-2 52 57.0 - 26.0 Component "B" 5.0 5.0 PPD (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 Component "C" 6.5 VII-3 (PIP) 35.5 Base oil SN-150 50.0 Base oil blend 15W-40 84.6 81.3

Claims (18)

Multi-grade engine oil composition containing additives, which consists of base oil and additives suitable for engine oil, characterized by a content of 1.5-55% by weight of an additive package, each consisting of one or more additives "A", "B" and optionally "C "contains, where the individual components have the following composition:
Component "A" - 10-100% by weight polyfunctional, ash-free, detergent-dispersing additive composition or its oily solution, the polyfunctional, ash-free, detergent-dispersing additive composition containing polymer components which have the same or different numerical average molecular weights and which are obtained by reacting a polyolefin Derivative, preferably PIB derivative, which is inoculated with one or more dicarboxylic acids and / or dicarboxylic acid anhydride and with one or more non-acidic comonomers with an ethylenic double bond, and has a numerical average molecular weight of at least 800, with an amino and / or imino and / or hydroxy group-containing compound, 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, the derivative being an imide and / or amide - un d / or ester amide derivative, and - 0-90% by weight of conventional alkenylsuccinic acid derivative, such as imide and / or ester and / or ester amide derivative; Component "B" one or more customary additives, such as detergent-dispersing additives with different base numbers and different metal contents, antioxidants, friction-reducing substances, abrasion inhibitors, corrosion inhibitors, anti-foaming agents and pour point reducing substances; Component "C" one or more customary viscosity and viscosity index-increasing polymers; wherein the weight ratio of components "A""B" and "C" is 15-85: 15-85: 0-70. Motor oil composition according to claim 1, characterized by a content of component "A" in such polymer components which are inoculated with maleic anhydride. Motor oil composition according to claim 1 or 2, characterized in that component "A" contains such polymer components which have been prepared by reacting polyisobutylene with a numerical average molecular weight of 1300-30,000 as a polyolefin. Motor oil composition according to one of claims 1-3, characterized in that the component "A" contains at least two such polymer components which have different - a lower (M _nI ) and a higher (M _nII ) - numerical average _{molecular weight} , the numerical average _{molecular weight of} the Polymer component with a lower numerical average molecular weight is smaller than six times the average molecular weight of the starting polyolefin, the ratio of the average molecular weights 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 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. Motor oil composition according to one of claims 1-4, characterized in that the component "B" contains organic calcium or magnesium salts, such as sulfonates, phenates, salicylates or a mixture thereof as a detergent-dispersing additive with a different base number and different metal content. Motor oil composition according to one of claims 1-5, characterized by a content of 0.6-26% by weight of component "A", 0.3-18.6% by weight of component "B" and 0-25% by weight the component "C". Lubricating oil composition, which consists of base oil and additives suitable for lubricating oils, characterized by a content of 1.5-55% by weight of an additive package, each of which consists of one or more additives "A", "B" and optionally "C" contains, the components having the following composition:
Component "A" 10-100% by weight of polyfunctional, ash-free, detergent-dispersing additive composition or its oily solution, the polyfunctional, ash-free, detergent-dispersing additive composition containing polymer components which have the same or different numerical average molecular weights and which, by reaction of a polyolefin derivative, preferably PIB derivative, which is inoculated with one or more dicarboxylic acids and / or dicarboxylic anhydride and with one or more non-acidic comonomers with an ethylenic double bond, and has a numerical average molecular weight of at least 800, with an amino and / or imino and / or hydroxyl group containing compound, 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, the derivative being an imide and / or amide and / or can be an ester amide derivative, and - 0-90% by weight of conventional alkenylsuccinic acid derivative, such as imide and / or ester and / or ester amide derivative; Component "B" one or more customary additives, such as detergent-dispersing additives with different base numbers and different metal contents, antioxidants, friction-reducing substances, abrasion inhibitors, corrosion inhibitors, anti-foaming agents and pour point reducing substances; Component "C" one or more customary viscosity and viscosity index-increasing polymers; wherein the weight ratio of components "A""B" and "C" is 15-85: 15-85: 0-70. Lubricating oil composition according to claim 7, characterized in that component "A" contains such polymer components which are inoculated with maleic anhydride. Lubricating oil composition according to claim 7 or 8, characterized in that component "A" contains such polymer components which have been prepared by reacting polyisobutylene with a numerical average molecular weight of 1300-30,000 as polyolefin. Lubricating oil composition according to one of claims 7-9, characterized in that component "A" contains at least two polymer components which have different - a lower (M _nI ) and a higher (M _nII ) - numerical average _{molecular weight} , the numerical average _{molecular weight of the} polymer component with a lower numerical average molecular weight is smaller than six times the average molecular weight of the starting polyolefin, the ratio of the average molecular weights 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 Polymer component with lower numerical average molecular weight to the component with higher numerical average molecular weight is 0.01-5: 1. Lubricating oil composition according to one of claims 7-10, characterized by a content of component "B" in organic calcium or magnesium salts, such as sulfonates, phenates, salicylates or a mixture thereof as a detergent-dispersing additive with a different base number and different metal content. Lubricating oil composition according to one of claims 7-11, characterized by a content of 0.6-26% by weight of component "A", 0.3-18.6% by weight of component "B" and 0-25% by weight the component "C". Additive package which is suitable for lubricating oil compositions, preferably for motor oil compositions, characterized by a content of 15-100% by weight of components "A", "B" and optionally "C", each consisting 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 polyfunctional, ash-free, detergent-dispersing additive composition or its oily solution, the polyfunctional, ash-free, detergent-dispersing additive composition containing polymer components which have the same or different numerical average molecular weights and which are converted by reaction a polyolefin derivative, preferably a PIB derivative, which is inoculated with one or more dicarboxylic acids and / or dicarboxylic acid anhydride and with one or more non-acidic comonomers with an ethylenic double bond and has a numerical average molecular weight of at least 800, with an amino and / or imino - and / or hydroxy group-containing compound, 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, the derivative being an imide and / or amide u nd / or ester amide derivative, and - 0-90% by weight of conventional alkenylsuccinic acid derivative, such as imide and / or ester and / or ester amide derivative; Component "B" one or more customary additives, such as detergent-dispersing additives with different base numbers and different metal contents, antioxidants, friction-reducing substances, abrasion inhibitors, corrosion inhibitors, anti-foaming agents and pour point reducing substances; Component "C" one or more customary viscosity and viscosity index-increasing polymers; wherein the weight ratio of components "A""B" and "C" is 15-85: 15-85: 0-70. Additive package according to claim 13, characterized in that the component "A" contains such polymer components which are inoculated with maleic anhydride. Additive package according to claim 13 or 14, characterized in that component "A" contains such polymer components which have been prepared by reacting polyisobutylene with a numerical average molecular weight of 1300-30,000 as a polyolefin. Additive package according to one of claims 13-15, characterized by a content of component "A" in at least two such polymer components, which have different - a lower (M _nI ) and a higher (M _nII ) - numerical average _{molecular weight} , the numerical average _{molecular weight of} the Polymer component with a lower numerical average molecular weight is smaller than six times the average molecular weight of the starting polyolefin, the ratio of the average molecular weights 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 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. Additive package according to one of claims 13-16, characterized in that the component "B" contains organic calcium or magnesium salts, such as sulfonates, phenates, salicylates or a mixture thereof as a detergent-dispersing additive with a different base number and different metal content. Additive package according to one of Claims 13-17, characterized by a content of 0.6-26% by weight of component "A", 0.3-18.6% by weight of component "B" and 0-25% by weight the component "C".