EP0418610A1 - Produit améliorant l'indice de viscosité, à action dispersante - Google Patents

Produit améliorant l'indice de viscosité, à action dispersante Download PDF

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Publication number
EP0418610A1
EP0418610A1 EP90116624A EP90116624A EP0418610A1 EP 0418610 A1 EP0418610 A1 EP 0418610A1 EP 90116624 A EP90116624 A EP 90116624A EP 90116624 A EP90116624 A EP 90116624A EP 0418610 A1 EP0418610 A1 EP 0418610A1
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weight
monomers
parts
meth
acrylates
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EP90116624A
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German (de)
English (en)
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EP0418610B1 (fr
Inventor
Horst Dr. Pennewiss
Ulrich Dr. Schödel
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Roehm GmbH Darmstadt
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Roehm GmbH Darmstadt
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Classifications

    • 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
    • C10M157/00—Lubricating compositions characterised by the additive being a mixture of two or more macromolecular compounds covered by more than one of the main groups C10M143/00 - C10M155/00, 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
    • C10M143/00—Lubricating compositions characterised by the additive being a macromolecular hydrocarbon or such hydrocarbon modified by oxidation
    • 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
    • C10M145/00—Lubricating compositions characterised by the additive being a macromolecular compound containing oxygen
    • C10M145/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • 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
    • 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
    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • 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
    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
    • 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
    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/06—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing conjugated dienes
    • 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
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/08—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 type
    • C10M2209/084—Acrylate; Methacrylate
    • 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
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
    • C10M2209/104—Polyethers, i.e. containing di- or higher polyoxyalkylene groups of alkylene oxides containing two carbon atoms only
    • 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
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
    • C10M2209/105—Polyethers, i.e. containing di- or higher polyoxyalkylene groups of alkylene oxides containing three carbon atoms only
    • 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
    • C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2217/02—Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2217/022—Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to an amino group
    • C10M2217/023—Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to an amino group the amino group containing an ester bond
    • 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
    • C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2217/02—Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2217/024—Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to an amido or imido group
    • 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
    • C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2217/02—Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2217/028—Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a nitrogen-containing hetero ring
    • 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
    • C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2217/06—Macromolecular compounds obtained by functionalisation op polymers with a nitrogen containing compound
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
    • C10N2040/251—Alcohol-fuelled engines
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
    • C10N2040/252—Diesel engines
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
    • C10N2040/252—Diesel engines
    • C10N2040/253—Small diesel engines
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
    • C10N2040/255—Gasoline engines
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • 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
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
    • F02B—INTERNAL-COMBUSTION PISTON ENGINES; COMBUSTION ENGINES IN GENERAL
    • F02B1/00—Engines characterised by fuel-air mixture compression
    • F02B1/02—Engines characterised by fuel-air mixture compression with positive ignition
    • F02B1/04—Engines characterised by fuel-air mixture compression with positive ignition with fuel-air mixture admission into cylinder
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
    • F02B—INTERNAL-COMBUSTION PISTON ENGINES; COMBUSTION ENGINES IN GENERAL
    • F02B3/00—Engines characterised by air compression and subsequent fuel addition
    • F02B3/06—Engines characterised by air compression and subsequent fuel addition with compression ignition
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
    • F02F—CYLINDERS, PISTONS OR CASINGS, FOR COMBUSTION ENGINES; ARRANGEMENTS OF SEALINGS IN COMBUSTION ENGINES
    • F02F7/00—Casings, e.g. crankcases or frames
    • F02F7/006—Camshaft or pushrod housings

Definitions

  • the invention relates to viscosity index (VI) improvers with good shear stability and good dispersing detergent action in lubricating oils, in particular for diesel and gasoline engines.
  • VI viscosity index
  • N-vinylpyrrolidone is particularly suitable as a dispersing monomer in addition to N-vinylimidazole.
  • graft products based on OCP or PAMA as base polymers or as constituents of concentrated polymer emulsions which are composed of both polymer classes have gained practical importance.
  • the object was therefore to provide polyalkyl (meth) acrylates, in particular in the form of highly concentrated polymer emulsions with sufficient dispersing action and detergent action, the other properties of which, in particular the ratio "thickening action to shear stability", meet modern requirements. It has now been found that the additives according to the present invention meet the requirements of technology to an outstanding degree.
  • the poly (meth) acrylates are in combination with olefin copolymers (OCP) and / or hydrogenated isoprene or butadiene-styrene copolymers (HSD) and / or hydrogenated polyisoprene or polybutadiene in the form of concentrated polymer emulsions.
  • OCP olefin copolymers
  • HSD hydrogenated isoprene or butadiene-styrene copolymers
  • polyisoprene or polybutadiene in the form of concentrated polymer emulsions.
  • the present application furthermore relates to a process for the preparation of concentrated polymer emulsions from poly (meth) acrylates and olefin copolymers suitable for improving the viscosity index in liquid carrier media for use as oil additives with improved dispersing and detergent action in diesel and gasoline engines, with monomers 80 to 99.5 parts by weight of alkyl (meth) acrylates of the formula I.
  • the polymerization of the monomers I, II, IIA, IIB and III can be carried out with the addition of 0.1 to 2.0% by weight of radical initiator and with the simultaneous presence of 0.05 up to 0.5% by weight of molecular weight regulators, in each case based on the total of the monomers.
  • the usual sulfur regulators cf. Th.Völker, H.Rauch-Puntigam, acrylic and methacrylic compounds, Springer-Verlag 1968
  • the concentrations of the monomers and polymers are preferably such that the total of the monomers and polymers present in the liquid carrier medium TM is 40 to 75% by weight, preferably 55 to 70% by weight, based on the overall system.
  • the polymerization batch is followed by At the end of the polymerization, further olefin copolymers were added in amounts such that the olefin copolymer content in the total polymer present was 31 to 80% by weight.
  • the olefin copolymer can advantageously be added tel quel, ie in undiluted form, it being advantageously emulsified using shear forces.
  • the additional olefin copolymer can also be added in the form of a solution, for example a 10-20% solution in the liquid carrier medium.
  • VI improvers namely olefin copolymers (OCP), polyalkyl (meth) acrylates (PAMA) and the aforementioned “mixed polymers” serve e.g. according to EP 14 746 as base polymers for the process according to the invention.
  • the polyalkyl (meth) acrylates are primarily those with alkyl radicals with 6-24 carbon atoms, which lead to solubility in mineral oil. Shorter alkyl residues and those with polar substituents that do not impart solubility in the mineral oil can be present to a certain extent.
  • the molecular weights M w are between 5,000 and 1,000,000, preferably between 50,000 and 500,000. Such products are described in GB-C 1 068 938, US Pat. No. 3,732,334, US Pat. No. 4,149,984, US Pat.
  • the monomers to be used in the process according to the invention are illustrated below.
  • alkyl (meth) acrylates of the formula I are copolymerized in proportions of 80 to 99.5, preferably 90 to 98.5, parts by weight.
  • monomers of the formula I are (meth) acrylic acid esters of tallow fatty alcohols (for example in the C number range 14-20, on average approx. 17.3), of coconut fatty alcohols (C number range 10 -16, on average approx. 12.6) ) or of synthetic alcohols such as Dobanol 25 R (C number range 11 - 16, on average 13.5).
  • Examples of functionalized monomers of the formula II are those with an OH group in the alkyl radical, in particular in the u-position of the alkyl radical, for example the 2-hydroxyethyl methacrylate and the -acrylate, the 3-hydroxypropyl methacrylate and -acrylate, and also the 2-position or double methyl-substituted derivatives, 4-hydroxybutyl methacrylate and acrylate, but also the 2-hydroxypropyl methacrylate and acrylate.
  • the monomers of the formula II in which R 2 stands for a frequently alkoxylated, in particular ethoxylated radical, for example 2- (2-ethoxyethoxy) ethyl methacrylate and - are of particular interest because of their low other aggressiveness under practical conditions in motor testing.
  • R 7 represents an alkylene dialkylamino group
  • R 7 represents an alkylene dialkylamino group
  • the corresponding amides especially the N- (3-dimethylaminopropyl) methacrylamide.
  • These comonomers can be copolymerized, for example by copolymerization, together with compounds of the formula II, but also at a later point in time.
  • the formula IIA also includes heterocyclically substituted monomers, such as, for example, the 2- (1-imidazolyl) ethyl methacrylate and acrylate, the 2- (4-morpholinyl) ethyl methacrylate and acrylate and the 1- (2-methylacryloyloxyethyl) -2-pyrrolidone, as well as the corresponding amides.
  • heterocyclically substituted monomers such as, for example, the 2- (1-imidazolyl) ethyl methacrylate and acrylate, the 2- (4-morpholinyl) ethyl methacrylate and acrylate and the 1- (2-methylacryloyloxyethyl) -2-pyrrolidone, as well as the corresponding amides.
  • the monomers of the formula IIB are of particular importance, especially N-vinylpyrrolidone-2.
  • the olefin copolymers to be used according to the invention are known per se. It is primarily composed of ethylene, propylene, butylene and / or other ⁇ -olefins with 5 to 200 carbon atoms built-up polymers, as have already been recommended as VI improvers.
  • the molecular weight M w is in general from 10,000 to 300,000, preferably between 50,000 and 150,000.
  • Such olefin copolymers are described, for example, in German Offenlegungsschriften DE-A 16 44 941, DE-A 17 69 834, DE-A 19 39 037 , DE-A 19 63 039 and DE-A 20 59 981.
  • the base copolymer consists of a hydrogenated polyisoprene or copolymer with styrene
  • commercially available hydrogenated products for example commercial products SHELLVIS 50, 200 or 250 @ are preferred.
  • Ethylene-propylene copolymers are particularly useful, and terpolymers with the known tercomponents, such as ethylidene Norbornen (cf. Macromolecular Reviews, Vol. 10 (1975)) is possible, but their tendency to cross-link during the aging process must be taken into account.
  • the distribution can be largely statistical, but sequence polymers with ethylene blocks can also be used with advantage
  • the ratio of the monomers ethylene-propylene is variable within certain limits, which can be set as the upper limit at around 75% for ethylene and around 80% for propylene.As a result of its reduced tendency to solubility in oil, polypropylene is already less suitable than ethylene-propylene copolymers .
  • the solvents therefore fall e.g. in the group of hydrocarbons such as kerosene (boiling range 180-210 degrees C), the naphthenic oils, the paraffin-based oils or the gas oils. (Cf. Ullmanns Enzyklopadie der Techn. Chemie, 4th edition, vol. 10, pp. 641-714.
  • carrier media are advantageously used which only solve OCP to a limited extent or are only swelling agents, as described in detail in "USP 4,677,151 and US Pat. No. 4,622,358.
  • phthalic esters such as dibutyl phthalate and esters of 2,2,4-trimethyladipic acid, for example with a mixture of octanol / decanol.
  • the mono- or multifunctional alcohols themselves are also suitable.
  • *** for example hexadecanol, octadecanol, diethylene glycol, tetraethylene glycol and methoxypolyethylene glycols with degrees of ethoxylation of approx. 2-50.
  • the polymerization of the alkyl (meth) acrylates is generally carried out as a monomer feed polymerization at 80-100 ° C. in a liquid carrier medium with the addition of peroxidic initiators such as t-butyl peroctoate. In the case of the production of concentrated polymer emulsions, this is done in the presence of a small amount of dissolved OCP. The polymerization is usually complete after about 8 hours. Subsequently, further monomers can be graft-polymerized at 130 ° C. with the addition of t-butyl perbenzoate. Finally, the desired final composition is then set by adding further OCP and, if appropriate, solvent or carrier medium.
  • the VI-improving additives according to the invention with dispersing / detergent action are generally available as relatively concentrated polymer solutions in the carrier media.
  • the polymer content in the concentrates is 30 to 75% by weight, preferably 40 to 70%.
  • oils or fractions are advantageously added to the oils or fractions, the viscosity indices of which are to be improved, in such amounts that they preferably contain 1 to 10% by weight of the polymeric additives according to the present invention.
  • the advantage of the additives according to the invention is an excellent dispersing and detergent effect in Otto and diesel engines with completely neutral behavior against sealing materials such as e.g. Viton ®.
  • Polymer content 60% by weight
  • Table 2 shows results of the M-102-E black sludge test.
  • Additive 4 (example 5) containing OH groups is rated significantly better than additive 5 with vinylpyrrolidone (example 6). Both additives are present as a concentrated polymer emulsion.

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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)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Detergent Compositions (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
EP90116624A 1989-09-09 1990-08-30 Produit améliorant l'indice de viscosité, à action dispersante Expired - Lifetime EP0418610B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT90116624T ATE100489T1 (de) 1989-09-09 1990-08-30 Dispergierwirksame viskositaets-index-verbesserer.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3930142A DE3930142A1 (de) 1989-09-09 1989-09-09 Dispergierwirksame viskositaets-index-verbesserer
DE3930142 1989-09-09

Publications (2)

Publication Number Publication Date
EP0418610A1 true EP0418610A1 (fr) 1991-03-27
EP0418610B1 EP0418610B1 (fr) 1994-01-19

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EP90116624A Expired - Lifetime EP0418610B1 (fr) 1989-09-09 1990-08-30 Produit améliorant l'indice de viscosité, à action dispersante

Country Status (8)

Country Link
US (1) US5188770A (fr)
EP (1) EP0418610B1 (fr)
JP (1) JP2941392B2 (fr)
AT (1) ATE100489T1 (fr)
DE (2) DE3930142A1 (fr)
DK (1) DK0418610T3 (fr)
ES (1) ES2062234T3 (fr)
HK (1) HK155396A (fr)

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0644252A3 (fr) * 1993-09-20 1995-06-28 Rohm & Haas Agent de compatibilité pour un mélange de polymère améliorant l'indice de viscosité.
EP0697457A1 (fr) * 1994-08-03 1996-02-21 Röhm GmbH Huile pour moteur à haute capacité de dispersion et bonne protection contre l'usure
EP0691355A3 (fr) * 1994-07-04 1996-04-10 Roehm Gmbh Cooligomère et copolymère à action dispersant
EP0708170A1 (fr) * 1994-10-19 1996-04-24 AGIP PETROLI S.p.A. Additif multifonctionnel pour huiles lubrifiantes compatible avec des élastomères fluorés
WO1999027037A1 (fr) * 1997-11-21 1999-06-03 Rohmax Additives Gmbh Additif pour biodiesels et biocarburants
EP1808476A1 (fr) * 2004-10-22 2007-07-18 Nippon Oil Corporation Formule de lubrifiant pour transmission
EP2235149A1 (fr) * 2007-12-10 2010-10-06 Chevron U.S.A. Inc. Procédé pour former des lubrifiants finis
DE102010001040A1 (de) 2010-01-20 2011-07-21 Evonik RohMax Additives GmbH, 64293 (Meth)acrylat-Polymere zur Verbesserung des Viskositätsindexes
US8728997B2 (en) 2006-04-20 2014-05-20 Nippon Oil Corporation Lubricating oil composition
RU2749905C2 (ru) * 2016-08-15 2021-06-18 Эвоник Оперейшнс Гмбх Содержащие функциональные группы полиалкил(мет)акрилаты, обладающие улучшенной деэмульгирующей способностью

Families Citing this family (49)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4137269A1 (de) * 1991-11-13 1993-05-19 Roehm Gmbh Motorenoele mit hohem dispergiervermoegen
EP0569639A1 (fr) * 1992-03-20 1993-11-18 Rohm And Haas Company Agent dispersant polyméthacrylate améliorant l'index de viscosité
CA2090200C (fr) * 1992-03-20 2005-04-26 Chung Y. Lai Polymeres de polymethacrylate utilises comme agent dispersant sans cendre
DE4212569A1 (de) * 1992-04-15 1993-10-21 Roehm Gmbh Syntheseöle enthaltend Cooligomere, bestehend aus 1-Alkenen und (Meth)acrylsäureestern
JP2769974B2 (ja) * 1994-04-22 1998-06-25 三洋化成工業株式会社 潤滑油添加剤及び潤滑油
DE19518786A1 (de) * 1995-05-22 1996-11-28 Roehm Gmbh Schmierstoffadditive
DE19603696A1 (de) * 1996-02-02 1997-08-07 Roehm Gmbh Demulgatoren
US5834408A (en) * 1997-10-24 1998-11-10 Ethyl Corporation Pour point depressants via anionic polymerization of (meth)acrylic monomers
US5888946A (en) * 1997-12-30 1999-03-30 Chevron U.S.A. Inc. Tractor hydraulic fluid
US5955405A (en) * 1998-08-10 1999-09-21 Ethyl Corporation (Meth) acrylate copolymers having excellent low temperature properties
DE19927561C1 (de) * 1999-06-17 2000-12-14 Clariant Gmbh Verwendung hydroxylgruppenhaltiger Copolymere zur Herstellung von Brennstoffölen mit verbesserter Schmierwirkung
EP1063280A1 (fr) * 1999-06-21 2000-12-27 Quaker Chemical Corporation Fluides de travail des métaux
US6642189B2 (en) 1999-12-22 2003-11-04 Nippon Mitsubishi Oil Corporation Engine oil compositions
US6746993B2 (en) * 2001-04-06 2004-06-08 Sanyo Chemical Industries, Ltd. Viscosity index improver and lube oil containing the same
EP1379617B1 (fr) * 2001-04-11 2006-12-13 The Lubrizol Corporation Procede de lubrification de transmissions avec des lubrifiants contenant un copolymere olefinique et un copolymere d'acrylate
US20040132629A1 (en) * 2002-03-18 2004-07-08 Vinci James N. Lubricants containing olefin copolymer and acrylate copolymer
US6586375B1 (en) * 2002-04-15 2003-07-01 The Lubrizol Corporation Phosphorus salts of nitrogen containing copolymers and lubricants containing the same
DE10249292A1 (de) * 2002-10-22 2004-05-13 Rohmax Additives Gmbh Polymerdispersionen mit geringer Viskosität und Verfahren zur Herstellung
DE10249294A1 (de) * 2002-10-22 2004-05-13 Rohmax Additives Gmbh Stabile Polymerdispersionen und Verfahren zur Herstellung
DE10249295A1 (de) * 2002-10-22 2004-05-13 Rohmax Additives Gmbh Polymerdispersionen mit hoher Stabilität und Verfahren zur Herstellung
US20040092409A1 (en) * 2002-11-11 2004-05-13 Liesen Gregory Peter Alkyl (meth) acrylate copolymers
US7378379B2 (en) * 2003-06-10 2008-05-27 The Lubrizol Corporation Functionalized polymer composition for grease
US20050138859A1 (en) * 2003-12-16 2005-06-30 Graham Jackson Cold flow improver compositions for fuels
EP1795581B1 (fr) * 2004-07-16 2018-09-19 Kuraray Co., Ltd. Huile de lubrification contenant un polymère acrylique
DE102004037929A1 (de) * 2004-08-04 2006-03-16 Rohmax Additives Gmbh Verfahren zur radikalischen Polymerisation ethylenisch-ungesättigter Verbindungen
US20060135380A1 (en) * 2004-12-20 2006-06-22 The Lubrizol Corporation Method of fatigue control
US7560420B2 (en) * 2004-12-23 2009-07-14 Rohmax Additives Gmbh Oil composition for lubricating an EGR equipped diesel engine and an EGR equipped diesel engine comprising same
US20060252660A1 (en) * 2005-05-09 2006-11-09 Akhilesh Duggal Hydrolytically stable viscosity index improves
US20070117725A1 (en) * 2005-11-22 2007-05-24 Shih-Ying Hsu Acrylic synthetic lubricant
JP5205699B2 (ja) * 2006-03-02 2013-06-05 日油株式会社 燃料油用潤滑性向上剤及びそれを含有する燃料油組成物
JP3987555B1 (ja) 2006-03-28 2007-10-10 三洋化成工業株式会社 粘度指数向上剤および潤滑油組成物
US20080033114A1 (en) * 2006-07-28 2008-02-07 Sanjay Srinivasan Alkyl acrylate copolymer VI modifiers and uses thereof
US8143202B2 (en) * 2006-11-07 2012-03-27 Ciba Corp. Methacrylate copolymer pour point depressants
US20100099588A1 (en) * 2007-01-30 2010-04-22 The Lubrizol Corporation Dispersant Combination for Improved Transmission Fluids
EP2497819B1 (fr) 2008-10-07 2017-01-04 JX Nippon Oil & Energy Corporation Composition de lubrifiant
DE102009001447A1 (de) * 2009-03-10 2010-09-16 Evonik Rohmax Additives Gmbh Verwendung von Kammpolymeren zur Verbesserung des Lasttragevermögens
EP2439259A4 (fr) 2009-06-04 2014-03-12 Jx Nippon Oil & Energy Corp Composition d'huile lubrifiante
JP5584049B2 (ja) * 2010-08-17 2014-09-03 株式会社Ａｄｅｋａ 潤滑油用極圧剤及びそれを含有する潤滑油組成物
KR20150037750A (ko) 2012-07-24 2015-04-08 제이엑스 닛코닛세키에너지주식회사 폴리(메타)아크릴레이트계 점도 지수 향상제, 및 당해 점도 지수 향상제를 함유하는 윤활유 첨가제 및 윤활유 조성물
US20150203782A1 (en) 2012-07-24 2015-07-23 Jx Nippon Oil & Energy Corporation Poly(meth)acrylate viscosity index improver, and lubricating oil composition and lubricating oil additive containing said viscosity index improver
CN104395445A (zh) 2012-07-24 2015-03-04 吉坤日矿日石能源株式会社 聚(甲基)丙烯酸酯系粘度指数改进剂、以及含有该粘度指数改进剂的润滑油添加剂及润滑油组合物
US9783757B2 (en) 2012-07-24 2017-10-10 Jx Nippon Oil & Energy Corporation Poly(meth)acrylate-based viscosity index improver, lubricant additive and lubricant composition containing viscosity index improver
JP2014114329A (ja) * 2012-12-06 2014-06-26 Sanyo Chem Ind Ltd 粘度指数向上剤及び潤滑油組成物
JP6411633B2 (ja) 2015-03-20 2018-10-24 三洋化成工業株式会社 粘度指数向上剤、潤滑油組成物及び潤滑油組成物の製造方法
FR3045657B1 (fr) * 2015-12-22 2020-09-11 Total Marketing Services Additif detergent pour carburant et copolymeres utilisables dans cette application
EP3992271B1 (fr) 2019-06-26 2024-08-28 Sanyo Chemical Industries, Ltd. Composition d'amélioration d'indice de viscosité et composition d'huile lubrifiante
US11965140B2 (en) * 2019-12-12 2024-04-23 Evonik Operations Gmbh High viscosity polyacrylate base fluids
US20230340357A1 (en) 2020-08-20 2023-10-26 Sanyo Chemical Industries, Ltd. Viscosity index improver composition and lubricating oil composition
DE112021004098T5 (de) 2020-09-14 2023-07-06 Sanyo Chemical Industries, Ltd. Viskositätsindex-Verbesserer und Schmieröl-Zusammensetzung

Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1173356A (fr) * 1957-03-26 1959-02-24 California Research Corp Composition lubrifiante
US3001942A (en) * 1958-12-15 1961-09-26 California Research Corp Lubricant composition
GB974473A (en) * 1960-02-29 1964-11-04 Rohm & Haas Preparation of copolymers
US3198739A (en) * 1960-11-25 1965-08-03 Shell Oil Co Lubricants and polymeric additives therefor
US3377285A (en) * 1965-05-07 1968-04-09 Shell Oil Co Non-thickening oil concentrates
FR2069681A5 (fr) * 1969-11-21 1971-09-03 Shell Int Research
GB2003893A (en) * 1977-09-08 1979-03-21 Roehm Gmbh Lubricating oil additives
EP0014746A1 (fr) * 1979-02-16 1980-09-03 Röhm Gmbh Additifs pour huile lubrifiante
EP0032175A2 (fr) * 1980-01-12 1981-07-22 Röhm Gmbh Additifs pour huile lubrifiante, stables au cisaillement
EP0088904A1 (fr) * 1982-03-01 1983-09-21 Röhm Gmbh Dispersions concentrées de copolymères oléfiniques
EP0140274A2 (fr) * 1983-10-28 1985-05-08 Röhm Gmbh Additifs pour huile lubrifiante

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3089832A (en) * 1955-12-01 1963-05-14 Exxon Research Engineering Co Polymeric lubricating oil additives
NL6903485A (nl) * 1968-01-23 1970-09-08 Roehm & Haas Gmbh Werkwijze voor het bereiden van entcopolymeren respectievelijk van smeerolietoevoegsels
JPS5120237B1 (fr) * 1964-06-06 1976-06-23
DE1644941C3 (de) * 1966-09-23 1978-06-22 E.I. Du Pont De Nemours And Co., Wilmington, Del. (V.St.A.) Legiertes Mineralschmieröl
BE759962A (fr) * 1969-12-08 1971-06-07 Exxon Research Engineering Co Procede de polymerisation
DE2805826C2 (de) * 1978-02-11 1987-05-14 Röhm GmbH, 6100 Darmstadt Verbesserte Pfropfverfahren
US4229311A (en) * 1979-07-18 1980-10-21 Rohm Gmbh Lubricating oil additives
DE3207292A1 (de) * 1982-03-01 1983-09-08 Röhm GmbH, 6100 Darmstadt Konzentrierte emulsionen von olefincopolymerisaten
DE3544061A1 (de) * 1985-12-13 1987-06-19 Roehm Gmbh Hochscherstabile mehrbereichsschmieroele mit verbessertem viskositaetsindex
DE3607444A1 (de) * 1986-03-07 1987-09-10 Roehm Gmbh Additive fuer mineraloele mit stockpunktverbessernder wirkung
DE3613992C2 (de) * 1986-04-25 2000-05-04 Roehm Gmbh Additive für paraffinische Schmieröle

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1173356A (fr) * 1957-03-26 1959-02-24 California Research Corp Composition lubrifiante
US3001942A (en) * 1958-12-15 1961-09-26 California Research Corp Lubricant composition
GB974473A (en) * 1960-02-29 1964-11-04 Rohm & Haas Preparation of copolymers
US3198739A (en) * 1960-11-25 1965-08-03 Shell Oil Co Lubricants and polymeric additives therefor
US3377285A (en) * 1965-05-07 1968-04-09 Shell Oil Co Non-thickening oil concentrates
FR2069681A5 (fr) * 1969-11-21 1971-09-03 Shell Int Research
GB2003893A (en) * 1977-09-08 1979-03-21 Roehm Gmbh Lubricating oil additives
EP0014746A1 (fr) * 1979-02-16 1980-09-03 Röhm Gmbh Additifs pour huile lubrifiante
EP0032175A2 (fr) * 1980-01-12 1981-07-22 Röhm Gmbh Additifs pour huile lubrifiante, stables au cisaillement
EP0088904A1 (fr) * 1982-03-01 1983-09-21 Röhm Gmbh Dispersions concentrées de copolymères oléfiniques
EP0140274A2 (fr) * 1983-10-28 1985-05-08 Röhm Gmbh Additifs pour huile lubrifiante

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0644252A3 (fr) * 1993-09-20 1995-06-28 Rohm & Haas Agent de compatibilité pour un mélange de polymère améliorant l'indice de viscosité.
EP0691355A3 (fr) * 1994-07-04 1996-04-10 Roehm Gmbh Cooligomère et copolymère à action dispersant
EP0697457A1 (fr) * 1994-08-03 1996-02-21 Röhm GmbH Huile pour moteur à haute capacité de dispersion et bonne protection contre l'usure
EP0708170A1 (fr) * 1994-10-19 1996-04-24 AGIP PETROLI S.p.A. Additif multifonctionnel pour huiles lubrifiantes compatible avec des élastomères fluorés
WO1999027037A1 (fr) * 1997-11-21 1999-06-03 Rohmax Additives Gmbh Additif pour biodiesels et biocarburants
EP1808476A1 (fr) * 2004-10-22 2007-07-18 Nippon Oil Corporation Formule de lubrifiant pour transmission
EP1808476A4 (fr) * 2004-10-22 2008-12-03 Nippon Oil Corp Formule de lubrifiant pour transmission
US8846589B2 (en) 2004-10-22 2014-09-30 Nippon Oil Corporation Lubricating oil composition for transmission
US8728997B2 (en) 2006-04-20 2014-05-20 Nippon Oil Corporation Lubricating oil composition
EP2235149A4 (fr) * 2007-12-10 2012-10-31 Chevron Usa Inc Procédé pour former des lubrifiants finis
US8540869B2 (en) 2007-12-10 2013-09-24 Chevron U.S.A. Inc. Method for forming finished lubricants
EP2235149A1 (fr) * 2007-12-10 2010-10-06 Chevron U.S.A. Inc. Procédé pour former des lubrifiants finis
WO2011088929A1 (fr) 2010-01-20 2011-07-28 Evonik Rohmax Additives Gmbh Polymère de méth(acrylate) pour l'amélioration de l'indice de viscosité
DE102010001040A1 (de) 2010-01-20 2011-07-21 Evonik RohMax Additives GmbH, 64293 (Meth)acrylat-Polymere zur Verbesserung des Viskositätsindexes
US9200233B2 (en) 2010-01-20 2015-12-01 Evonik Rohmax Additives Gmbh (Meth)acrylate polymers for improving the viscosity index
RU2749905C2 (ru) * 2016-08-15 2021-06-18 Эвоник Оперейшнс Гмбх Содержащие функциональные группы полиалкил(мет)акрилаты, обладающие улучшенной деэмульгирующей способностью

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ATE100489T1 (de) 1994-02-15
ES2062234T3 (es) 1994-12-16
EP0418610B1 (fr) 1994-01-19
JP2941392B2 (ja) 1999-08-25
DE59004308D1 (de) 1994-03-03
US5188770A (en) 1993-02-23
JPH03100099A (ja) 1991-04-25
DK0418610T3 (da) 1994-04-11
DE3930142A1 (de) 1991-03-21
HK155396A (en) 1996-08-23

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