EP0789069A2 - Compositions d'huile lubrifiante multifonctinnelle lontenant des aclditifs - Google Patents

Compositions d'huile lubrifiante multifonctinnelle lontenant des aclditifs Download PDF

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Publication number
EP0789069A2
EP0789069A2 EP95119299A EP95119299A EP0789069A2 EP 0789069 A2 EP0789069 A2 EP 0789069A2 EP 95119299 A EP95119299 A EP 95119299A EP 95119299 A EP95119299 A EP 95119299A EP 0789069 A2 EP0789069 A2 EP 0789069A2
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Prior art keywords
component
average molecular
weight
molecular weight
numerical average
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EP95119299A
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German (de)
English (en)
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EP0789069A3 (fr
EP0789069B1 (fr
Inventor
Janos Auer
Jeno Baladincz
Laszlo Dr. Bartha
Eva Bobest
Gyula Dr. Deak
Ferenc Dr. Dénes
Jeno Dr. Hancsok
Janos Kis
Margit Lenti
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VESZPREMI EGYETEM
Mol Magyar Olaj es Gazipari Rt
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VESZPREMI EGYETEM
Mol Magyar Olaj es Gazipari Rt
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M167/00—Lubricating compositions characterised by the additive being a mixture of a macromolecular compound, a non-macromolecular compound and a compound of unknown or incompletely defined constitution, each of these compounds being essential
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
    • C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
    • C10M129/04—Hydroxy compounds
    • C10M129/10—Hydroxy compounds having hydroxy groups bound to a carbon atom of a six-membered aromatic ring
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    • C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
    • C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
    • C10M129/26—Carboxylic acids; Salts thereof
    • C10M129/28—Carboxylic acids; Salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M129/38—Carboxylic acids; Salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having 8 or more carbon atoms
    • C10M129/40—Carboxylic acids; Salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having 8 or more carbon atoms monocarboxylic
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    • C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
    • C10M129/26—Carboxylic acids; Salts thereof
    • C10M129/28—Carboxylic acids; Salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M129/38—Carboxylic acids; Salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having 8 or more carbon atoms
    • C10M129/42—Carboxylic acids; Salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having 8 or more carbon atoms polycarboxylic
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    • C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
    • C10M129/86—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of 30 or more atoms
    • C10M129/95—Esters
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    • C10M133/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen
    • C10M133/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of less than 30 atoms
    • C10M133/04—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M133/12—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to a carbon atom of a six-membered aromatic ring
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    • C10M133/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of less than 30 atoms
    • C10M133/38—Heterocyclic nitrogen compounds
    • C10M133/44—Five-membered ring containing nitrogen and carbon only
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    • C10M133/52—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of 30 or more atoms
    • C10M133/56—Amides; Imides
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    • C10M135/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium
    • C10M135/12—Thio-acids; Thiocyanates; Derivatives thereof
    • C10M135/14—Thio-acids; Thiocyanates; Derivatives thereof having a carbon-to-sulfur double bond
    • C10M135/18—Thio-acids; Thiocyanates; Derivatives thereof having a carbon-to-sulfur double bond thiocarbamic type, e.g. containing the groups
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    • C10M135/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium
    • C10M135/32—Heterocyclic sulfur, selenium or tellurium compounds
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    • C10M137/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus
    • C10M137/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus having no phosphorus-to-carbon bond
    • C10M137/04—Phosphate esters
    • C10M137/10—Thio derivatives
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    • C10M143/00—Lubricating compositions characterised by the additive being a macromolecular hydrocarbon or such hydrocarbon modified by oxidation
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    • C10M143/00—Lubricating compositions characterised by the additive being a macromolecular hydrocarbon or such hydrocarbon modified by oxidation
    • C10M143/02—Polyethylene
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    • C10M143/00—Lubricating compositions characterised by the additive being a macromolecular hydrocarbon or such hydrocarbon modified by oxidation
    • C10M143/04—Lubricating compositions characterised by the additive being a macromolecular hydrocarbon or such hydrocarbon modified by oxidation containing propene
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    • C10M143/00—Lubricating compositions characterised by the additive being a macromolecular hydrocarbon or such hydrocarbon modified by oxidation
    • C10M143/12—Lubricating compositions characterised by the additive being a macromolecular hydrocarbon or such hydrocarbon modified by oxidation containing conjugated diene
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    • C10M145/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M145/06—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to an acyloxy radical of a saturated carboxylic or carbonic acid
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    • C10M145/10—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate
    • C10M145/12—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate monocarboxylic
    • C10M145/14—Acrylate; Methacrylate
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    • C10M149/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M149/06—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to an amido or imido group
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    • C10M159/12—Reaction products
    • C10M159/20—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products
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    • C10M159/20—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products
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    • C10M2219/02—Sulfur-containing compounds obtained by sulfurisation with sulfur or sulfur-containing compounds
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    • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/04—Phosphate esters
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    • C10M2223/042—Metal salts thereof
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    • C10M2223/047—Thioderivatives not containing metallic elements
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    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/04—Groups 2 or 12
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    • C10N2040/00—Specified use or application for which the lubricating composition is intended
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    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/08—Hydraulic fluids, e.g. brake-fluids
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    • C10N2040/22—Metal working with essential removal of material, e.g. cutting, grinding or drilling
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    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
    • C10N2040/251—Alcohol-fuelled engines
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    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
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    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
    • C10N2040/255—Gasoline engines
    • C10N2040/28—Rotary engines

Definitions

  • 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.
  • the additives of conventional engine oils can be classified into five groups based on their function and 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.
  • DD detergent-dispersing
  • 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).
  • ash-free DD additives 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.
  • 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.
  • 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.
  • 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.
  • 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).
  • 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.
  • 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 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.
  • 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.
  • 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:
  • 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.
  • the additive package according to the invention consists of three main components (A, B, C), each of which contains one or more additives.
  • 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
  • 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.
  • an acylating agent is preferably first produced, with a polar copolymeric side chain composed of maleic anhydride and a polar or .alpha.
  • a polyolefin preferably PIB
  • 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.
  • 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.
  • 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 are particularly preferably suitable for the production of such polymer components.
  • 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.
  • 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.
  • 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.
  • DD additives with different metal content and different base number 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
  • 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.
  • component "B” 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.
  • 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.
  • the concentration of the additives used in the individual components 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.
  • 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
  • the additive package according to the invention can also be used as a concentrate.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • API classification ASTM D4485
  • 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
  • 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.
  • gear oils such as gear oils, hydraulic fluids, automatic gear oils (ATF), cooling oils and machine oils
  • other compositions such as brake fluids, heat supply oils, and hardening oils, as well as in motor fuels to improve the properties of these.
  • brake fluids such as brake fluids, heat supply oils, and hardening oils
  • 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.
  • 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 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:
  • 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.
  • PPD pour point depressants
  • VII-1, 2, 3 and 4 various viscosity index-increasing additives
  • 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.
  • 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.
  • composition 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).
  • 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.
  • 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- + +
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • compositions according to the invention were 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.
  • 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

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Lubricants (AREA)
  • Processing Of Solid Wastes (AREA)
  • Medicines Containing Material From Animals Or Micro-Organisms (AREA)
  • Saccharide Compounds (AREA)
  • Lubrication Of Internal Combustion Engines (AREA)
EP95119299A 1995-09-25 1995-12-07 Composition d'huile lubrifiante et huile de moteur multigrade contenant des additifs Expired - Lifetime EP0789069B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
HU9502797 1995-09-25
HU9502797A HU213255B (en) 1995-09-25 1995-09-25 Multiple- stage engineoil and lubricant composition and additive-pocket

Publications (3)

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EP0789069A2 true EP0789069A2 (fr) 1997-08-13
EP0789069A3 EP0789069A3 (fr) 1998-05-13
EP0789069B1 EP0789069B1 (fr) 2007-06-20

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EP (1) EP0789069B1 (fr)
AT (1) ATE365202T1 (fr)
CZ (1) CZ294327B6 (fr)
DE (1) DE59511080D1 (fr)
EE (1) EE9500079A (fr)
ES (1) ES2289741T3 (fr)
HR (1) HRP950611B1 (fr)
HU (1) HU213255B (fr)
PL (1) PL179150B1 (fr)
RO (1) RO119233B1 (fr)
RS (1) RS49806B (fr)
RU (1) RU2161179C2 (fr)
SK (1) SK284909B6 (fr)
UA (1) UA43339C2 (fr)

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WO2022005486A1 (fr) 2020-07-02 2022-01-06 Halliburton Energy Services, Inc. Sac d'étanchéité pour joint d'étanchéité d'une pompe submersible électrique
US11708838B2 (en) 2020-07-02 2023-07-25 Halliburton Energy Services, Inc. Chemical sequestration of wellbore fluids in electric submersible pump systems
RU2769603C1 (ru) * 2021-03-17 2022-04-04 Федеральное государственное бюджетное образовательное учреждение высшего образования «Тамбовский государственный технический университет» (ФГБОУ ВО «ТГТУ») Невысыхающий состав для защиты стальных изделий

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US4767551A (en) * 1985-12-02 1988-08-30 Amoco Corporation Metal-containing lubricant compositions
US5167848A (en) * 1989-05-30 1992-12-01 Exxon Chemical Patents Inc. Grafted viscosity index improver
FR2706469B1 (fr) * 1993-06-16 1995-10-13 Inst Francais Du Petrole Polyisobutènes polyfonctionnels, leur préparation, leur formulation et leur utilisation.
JP3001385B2 (ja) * 1993-12-13 2000-01-24 シェブロン ケミカル カンパニー ポリマー分散剤
HU211439B (en) * 1993-12-16 1996-02-28 Veszpremi Egyetem Ash-free detergent-dispergant polymer type additive composition and process for preparing thereof
HU214008B (hu) * 1994-04-15 1998-04-28 MOL Magyar Olaj- és Gázipari Rt. Detergens-diszpergens adalékok belső égésű motorok kenőolajaihoz és előállítási eljárásuk

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SK162995A3 (en) 1997-07-09
RS49806B (sr) 2008-08-07
ES2289741T3 (es) 2008-02-01
SK284909B6 (sk) 2006-02-02
HU9502797D0 (en) 1995-11-28
UA43339C2 (uk) 2001-12-17
PL312098A1 (en) 1997-04-01
YU80395A (sh) 1998-07-10
HRP950611A2 (en) 1998-02-28
ATE365202T1 (de) 2007-07-15
EP0789069A3 (fr) 1998-05-13
HRP950611B1 (en) 2008-08-31
RU2161179C2 (ru) 2000-12-27
EE9500079A (et) 1997-04-15
CZ341095A3 (cs) 1998-04-15
HU213255B (en) 1997-05-28
RO119233B1 (ro) 2004-06-30
EP0789069B1 (fr) 2007-06-20
DE59511080D1 (de) 2007-08-02
PL179150B1 (pl) 2000-07-31
CZ294327B6 (cs) 2004-11-10

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