EP0140274A2 - Additifs pour huile lubrifiante - Google Patents
Additifs pour huile lubrifiante Download PDFInfo
- Publication number
- EP0140274A2 EP0140274A2 EP84112445A EP84112445A EP0140274A2 EP 0140274 A2 EP0140274 A2 EP 0140274A2 EP 84112445 A EP84112445 A EP 84112445A EP 84112445 A EP84112445 A EP 84112445A EP 0140274 A2 EP0140274 A2 EP 0140274A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- mol
- acrylic acid
- meth
- proportion
- alcohols
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- 239000000654 additive Substances 0.000 title claims abstract description 50
- 239000010687 lubricating oil Substances 0.000 title claims abstract description 17
- 229920000642 polymer Polymers 0.000 claims abstract description 46
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical class CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims abstract description 28
- 150000001298 alcohols Chemical class 0.000 claims abstract description 28
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 24
- 239000000203 mixture Substances 0.000 claims abstract description 15
- 239000012188 paraffin wax Substances 0.000 claims abstract description 11
- 239000000178 monomer Substances 0.000 claims abstract description 10
- 125000000524 functional group Chemical group 0.000 claims abstract description 7
- 239000002904 solvent Substances 0.000 claims abstract description 7
- 150000001252 acrylic acid derivatives Chemical class 0.000 claims abstract description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 29
- 229920000089 Cyclic olefin copolymer Polymers 0.000 claims description 23
- 150000002148 esters Chemical class 0.000 claims description 21
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 20
- 229920001577 copolymer Polymers 0.000 claims description 6
- 150000002734 metacrylic acid derivatives Chemical class 0.000 claims description 2
- 239000000470 constituent Substances 0.000 claims 1
- 230000000996 additive effect Effects 0.000 description 18
- 239000002480 mineral oil Substances 0.000 description 18
- -1 Methacryl- Chemical group 0.000 description 12
- 235000010446 mineral oil Nutrition 0.000 description 12
- 239000003921 oil Substances 0.000 description 11
- 230000000694 effects Effects 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 6
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 6
- 239000002199 base oil Substances 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 238000013112 stability test Methods 0.000 description 5
- 230000008719 thickening Effects 0.000 description 5
- AHLWZBVXSWOPPL-RGYGYFBISA-N 20-deoxy-20-oxophorbol 12-myristate 13-acetate Chemical compound C([C@]1(O)C(=O)C(C)=C[C@H]1[C@@]1(O)[C@H](C)[C@H]2OC(=O)CCCCCCCCCCCCC)C(C=O)=C[C@H]1[C@H]1[C@]2(OC(C)=O)C1(C)C AHLWZBVXSWOPPL-RGYGYFBISA-N 0.000 description 4
- 241001602688 Pama Species 0.000 description 4
- 239000003999 initiator Substances 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 241000640882 Condea Species 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 3
- 238000006887 Ullmann reaction Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000003599 detergent Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- BWSZXUOMATYHHI-UHFFFAOYSA-N tert-butyl octaneperoxoate Chemical compound CCCCCCCC(=O)OOC(C)(C)C BWSZXUOMATYHHI-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 239000002283 diesel fuel Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 125000000623 heterocyclic group Chemical group 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 2
- 229920000193 polymethacrylate Polymers 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 230000008092 positive effect Effects 0.000 description 2
- OZFIGURLAJSLIR-UHFFFAOYSA-N 1-ethenyl-2h-pyridine Chemical compound C=CN1CC=CC=C1 OZFIGURLAJSLIR-UHFFFAOYSA-N 0.000 description 1
- OSSNTDFYBPYIEC-UHFFFAOYSA-N 1-ethenylimidazole Chemical compound C=CN1C=CN=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-N 0.000 description 1
- DPBJAVGHACCNRL-UHFFFAOYSA-N 2-(dimethylamino)ethyl prop-2-enoate Chemical compound CN(C)CCOC(=O)C=C DPBJAVGHACCNRL-UHFFFAOYSA-N 0.000 description 1
- UFQHFMGRRVQFNA-UHFFFAOYSA-N 3-(dimethylamino)propyl prop-2-enoate Chemical compound CN(C)CCCOC(=O)C=C UFQHFMGRRVQFNA-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229920002845 Poly(methacrylic acid) Polymers 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000001154 acute effect Effects 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 125000004985 dialkyl amino alkyl group Chemical group 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000010696 ester oil Substances 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000012208 gear oil Substances 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 239000010720 hydraulic oil Substances 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000010705 motor oil Substances 0.000 description 1
- KKFHAJHLJHVUDM-UHFFFAOYSA-N n-vinylcarbazole Chemical compound C1=CC=C2N(C=C)C3=CC=CC=C3C2=C1 KKFHAJHLJHVUDM-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 150000002976 peresters Chemical class 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 229920013639 polyalphaolefin Polymers 0.000 description 1
- 229920002959 polymer blend Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000003760 tallow Substances 0.000 description 1
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
- 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
- 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
- C10M149/00—Lubricating compositions characterised by the additive being a macromolecular compound containing nitrogen
- C10M149/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
-
- 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
- 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
- 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
-
- 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
Definitions
- the invention relates to multifunctional lubricating oil additives based on polyalkyl acrylates and polyalkyl methacrylates as well as systems formed from olefin copolymers (OCP) or hydrogenated styrene-diene copolymers (HSD) and PAMA.
- OCP olefin copolymers
- HSD hydrogenated styrene-diene copolymers
- Lubricating oils generally contain n-paraffin hydrocarbons, which on the one hand have a positive effect on the setting of a good viscosity / temperature behavior, but on the other hand fail in crystalline form on cooling and thereby impair the flow of the oils or prevent them completely (“stagnation").
- An improvement in the low-temperature flow properties can be achieved by dewaxing. Since the costs increase considerably if one wants to lower the "pour point" beyond certain values, one generally performs only a partial dewaxing of the oils up to a pour point in the range of -15 ° C. and makes use of the further reduction Pour point (down to about -40 ° C) so-called pour point depressants, which effectively reduce the pour point already in concentrations between 0.05 and 1%.
- Paraffin-like compounds are built into the growing paraffin crystal surfaces and thus prevent the crystals from growing further and the formation of extensive crystal groups.
- pour point improvers For the mode of action of such pour point improvers, it applies that they have certain structural elements, namely sufficiently long alkyl groups to be incorporated into the growing paraffin crystals from the nucleation and side chains or side groups at greater intervals to disrupt crystal growth. (See Ullmanns, Encyklopedia of technical chemistry, 4th edition, volume 20, Verlag Chemie, 1981, p. 548).
- Technically applicable pour point depressants on the other hand, must be required to have good thermal, oxidative and chemical stability, shear strength and the like. have.
- the currently preferred pour point depressants are polymethacrylates, which lower the pour point of lubricating oils sufficiently in concentrations of 0.1-0.5% (cf. US Pat. No. 2,091,627, US Pat. No. 2,100,993, US Pat. PS 2 114 233).
- the carbon number of the alkyl radicals is between 12 and 18, the degree of branching between 10 and 30 mol%.
- Polymethacrylates in the M range between approx. 5,000 and 500,000 are available, which allow the flow behavior of light, low molecular weight to heavy, high molecular weight lubricating oils to be improved.
- multifunctional additives for mineral oils are also said to improve the viscosity / temperature behavior at high and low temperatures.
- larger amounts in the range between 1 - 30% by weight are necessary.
- multifunctional viscosity index improvers can also have dispersing / detergent properties (cf. Ullmanns Encyklopadie der Technische Chemie, 4th edition, volume 20, loc.cit., Pp. 457-671) .
- These multifunctional VI improvers are mostly based on polymethacrylic acid esters (PAMA) and combinations (mixed polymers) of PAMA with olefin copolymers (OCP) or hydrogenated styrene-diene copolymers (HSD) and less on the basis of OCP or HSD alone.
- PAMA polymethacrylic acid esters
- OCP olefin copolymers
- HSD hydrogenated styrene-diene copolymers
- the object on which the present invention is based relates to improving the viscosity / temperature behavior of mineral oils containing n-paraffin in the broadest sense, especially at low temperatures, caused by the tendency of the n-paraffins to crystallize.
- This task in one of its particularly acute forms should be explained in more detail using the example of lubricating oils containing n-paraffin: Exhaustion of existing oil deposits has, as is well known, led to less productive or low-quality oil deposits being exploited. One is therefore increasingly finding an offer of poorer quality mineral oils (base oils). For example, the fact that these oils are less and less dewaxed can have a critical impact and are technologically more difficult to handle; (so-called "critical base oils”).
- Lubricating oils for the purposes of the present invention are paraffin-based and naphthenic-based vacuum distillate oils.
- inventive additives in addition to the solvents still VI improving polyolefins / olefin copolymers (OCP) and / or hydrogenated styrene-diene polymers (HSD) may contain, preferably from T y of the combination p of polyalkyl (meth) acrylates (PAMA ) and OCP (mixed polymers) as described in DE-PS 29 05 954 and US-PS 4 290 925.
- PAMA polyalkyl
- OCP mixed polymers
- the proportion of the additives in the olefin copolymers and the hydrogenated styrene-diene polymers or the polymers according to the cited DE-PS 29 05 954 or US Pat. No. 4,290,925 can be 0 to 70% by weight.
- the proportion of the polymers (P) in the additives according to the invention is 10-80% by weight, the total content of polymers is 20-80% by weight.
- the proportion of component a) in the polymer P 1 is preferably 50-100 mol%, especially 100 mol%.
- the proportion of component b ') in the polymer P 2 is preferably 20-40 mol%.
- components b) and b ') are preferably acrylic or methacrylic acid esters of straight-chain, unbranched C16-C24 alcohols, especially C 18 -C 22 alcohols.
- the tallow fatty alcohols and Alfole® (products from Condea) may be mentioned.
- Components a), b), c) and a '), b'), c ') can in turn be grafted onto polyolefins or olefin copolymers of the type indicated above (OCP).
- the molecular weights M w of the polymers P are generally in the range from 50,000 to 500,000, those of the polymers P 2 in the range from 50,000 to 500,000.
- the polymers P 1 and P 2 can be prepared by the customary radical polymerization processes.
- Component e) of the polymers P is by definition understood to mean radical-polymerizable monomers with functional groups in the molecule, in particular those whose positive effect on oil additives in the sense of dispersing or detergent activity is known.
- compounds of the general formula I may be mentioned wherein R 1 is hydrogen or methyl and Bs is an (inert) heterocyclic 5- or 6-membered ring or a radical means, where Z is oxygen or a radical -NR 4 and Q for an optionally alkylated hydrocarbon bridge with a total of 2 to 10 carbon atoms and R 2 and R 3 each for an alkyl radical with 1 to 6 carbon atoms or together including nitrogen and optionally others Heteroatoms can form a heterocyclic 5- or 6-membered ring and in which R4 represents hydrogen or an alkyl radical having 1 to 6 carbon atoms.
- Examples include C- and N-vinylpyridine, vinylpyrrolidone, vinylcarbazole, vinylimidazole and their alkyl derivatives, in particular the N-vinyl compounds, also the dialkylaminoalkyl esters of (meth) acrylic acid, especially dimethylaminoethyl acrylate and methacrylate, dimethylaminopropylacrylate, methacrylate and the corresponding amide (methacrylate) - or -methacrylamides) such as dimethylaminopropyl (meth) acrylamide.
- the above definitions (formula I) also apply to e ') in the polymer P 2 *
- the solvents (L) used in the additives according to the invention are those known for lubricating oil additives, in particular paraffin- or naphthenic-based mineral oils or the known ester oils or poly- ⁇ -olefins. (See Ullmanns Encyklopadie der techn. Chemie, Volume 20, loc.cit., Pp. 483-529).
- the preparation of the polymers follows the polymerization processes of the prior art.
- a mixture of mineral oil and a monomer mixture of a), b), c), d) and e) is placed in a reaction vessel which is suitably equipped with a stirrer, thermometer, reflux condenser and metering line.
- the mixture is heated to about 90-100 ° C. under a CO 2 atmosphere and with stirring. After this temperature has been reached and initiator (preferably per compounds such as peresters, peroxides or azo compounds) has been added, a mixture of the monomers a), b), c), d) and e) and further initiator are metered in; approx. 2 hours after the end of the inflow there will be more
- initiator preferably per compounds such as peresters, peroxides or azo compounds
- the total amount of initiator is generally 1-3% by weight, based on the total amount of monomers.
- the total polymerization time is generally 8-9 hours.
- a viscous solution with a polymer content of generally 40-70% by weight is obtained.
- the additive according to the invention possibly together with other additives, such as DI package and OCP-VI improver, is dissolved in the base oil at 50-60 ° C. with stirring.
- the additives according to the invention can be added to the lubricating oils in a manner known per se.
- Oil formulations containing the additives according to the invention in addition to the required viscosity data at 100 ° C., show very favorable values for pour point and stable pour point as well as excellent viscosity data at -15 ° C. to 40 ° C.
- inlet 2 is started:
- the experiment is held at 130 ° C. for a further 5 hours. A cloudy, viscous solution is obtained.
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Lubricants (AREA)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3339103 | 1983-10-28 | ||
| DE19833339103 DE3339103A1 (de) | 1983-10-28 | 1983-10-28 | Additive fuer schmieroele |
Publications (4)
| Publication Number | Publication Date |
|---|---|
| EP0140274A2 true EP0140274A2 (fr) | 1985-05-08 |
| EP0140274A3 EP0140274A3 (en) | 1987-05-13 |
| EP0140274B1 EP0140274B1 (fr) | 1990-12-05 |
| EP0140274B2 EP0140274B2 (fr) | 1994-06-22 |
Family
ID=6212932
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP84112445A Expired - Lifetime EP0140274B2 (fr) | 1983-10-28 | 1984-10-16 | Additifs pour huile lubrifiante |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US4968444A (fr) |
| EP (1) | EP0140274B2 (fr) |
| JP (1) | JPH0631382B2 (fr) |
| DE (2) | DE3339103A1 (fr) |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3613992A1 (de) * | 1986-04-25 | 1987-10-29 | Roehm Gmbh | Additive fuer paraffinische schmieroele |
| EP0236844A3 (fr) * | 1986-03-07 | 1988-03-30 | Röhm Gmbh | Additifs pour huiles minérales ayant des caractéristiques modifiant le point d'écoulement |
| EP0225598A3 (en) * | 1985-12-13 | 1988-10-12 | Rohm Gmbh | High shear-stable multifunctional lubricating oil with an improved viscosity index |
| EP0384367A3 (fr) * | 1989-02-24 | 1990-10-17 | BASF Aktiengesellschaft | Mélanges concentrés de copolymères greffés d'ester insaturé et de copolymère éthylène-vinylester |
| EP0418610A1 (fr) * | 1989-09-09 | 1991-03-27 | Röhm Gmbh | Produit améliorant l'indice de viscosité, à action dispersante |
| EP0491536A1 (fr) * | 1990-12-19 | 1992-06-24 | Exxon Research And Engineering Company | Isomère de cire ayant un point d'écoulement réduit |
| FR2679444A1 (fr) * | 1991-07-25 | 1993-01-29 | Oreal | Utilisation comme agents epaississants des huiles, dans une composition cosmetique huileuse, d'une association de deux copolymeres. |
| JPH078990B2 (ja) * | 1987-08-19 | 1995-02-01 | ペンゾイル・プロダクツ・カンパニー | メタクリレート系流動点降下剤類及び組成物 |
| EP0644252A3 (fr) * | 1993-09-20 | 1995-06-28 | Rohm & Haas | Agent de compatibilité pour un mélange de polymère améliorant l'indice de viscosité. |
| EP0889114A1 (fr) * | 1997-07-03 | 1999-01-07 | Exxon Research And Engineering Company | Fluides de boites de vitesse automatique avec une faible viscosité Brookfield et une importante restistance au cisaillement |
| US6140431A (en) * | 1997-02-27 | 2000-10-31 | Rohm And Haas Company | Process for preparing continuously variable-composition copolymers |
| US6458749B2 (en) | 1997-08-22 | 2002-10-01 | Rohmax Additives Gmbh | Method for improving low-temperature fluidity of lubricating oils using high-and-low-molecular weight polymer |
| WO2011134694A1 (fr) * | 2010-04-26 | 2011-11-03 | Evonik Rohmax Additives Gmbh | Polymère utile comme agent améliorant l'indice de viscosité |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4956111A (en) * | 1987-08-19 | 1990-09-11 | Pennzoil Products Company | Methacrylate pour point depressants and compositions |
| US4844829A (en) * | 1987-08-19 | 1989-07-04 | Pennzoil Products Company | Methacrylate pour point depressants and compositions |
| US5349019A (en) * | 1988-12-24 | 1994-09-20 | Hoechst | New copolymers, mixtures thereof with poly(meth)acrylate esters and the use thereof for improving the cold fluidity of crude oils |
| US5229021A (en) * | 1991-12-09 | 1993-07-20 | Exxon Research & Engineering Company | Wax isomerate having a reduced pour point |
| US5534175A (en) * | 1992-12-28 | 1996-07-09 | The Lubrizol Corporation | Copolymers of unsaturated fatty esters, their use as viscosity improver and lubricating oil containing said copolymers |
| HUT69298A (en) | 1993-07-23 | 1995-09-28 | Rohm & Haas | Method of making a copolymer useful as viscosity index improving additive for hydraulic fluids |
| JP2748104B2 (ja) * | 1994-03-08 | 1998-05-06 | 三洋化成工業株式会社 | 粘度指数向上剤及び潤滑油 |
| US6228819B1 (en) | 1994-04-14 | 2001-05-08 | Rohm And Haas Company | Process for making a viscosity index improving copolymer |
| IT1270673B (it) * | 1994-10-19 | 1997-05-07 | Euron Spa | Additivo multifunzionale per olii lubrificanti compatibili con fluoroelastomeri |
| US5520832A (en) * | 1994-10-28 | 1996-05-28 | Exxon Research And Engineering Company | Tractor hydraulic fluid with wide temperature range (Law180) |
| US5969068A (en) * | 1995-06-19 | 1999-10-19 | The Lubrizol Corporation | Dispersant-viscosity improvers for lubricating oil compositions |
| US5821313A (en) | 1995-06-19 | 1998-10-13 | The Lubrizol Corporation | Dispersant-viscosity improvers for lubricating oil compositions |
| US6124249A (en) | 1998-12-22 | 2000-09-26 | The Lubrizol Corporation | Viscosity improvers for lubricating oil compositions |
| US6255261B1 (en) * | 1999-09-22 | 2001-07-03 | Ethyl Corporation | (Meth) acrylate copolymer pour point depressants |
| US6323164B1 (en) | 2000-11-01 | 2001-11-27 | Ethyl Corporation | Dispersant (meth) acrylate copolymers having excellent low temperature properties |
| RU2203931C1 (ru) * | 2001-12-27 | 2003-05-10 | Общество с ограниченной ответственностью "Научно-производственное объединение "Юник Пром" | Способ получения присадки к смазочным маслам |
| DE10335360B4 (de) * | 2002-08-02 | 2010-09-09 | Sanyo Chemical Industries, Ltd. | Verwendung eines öllöslichen Copolymers als Viskositätsindex-Verbesserer |
| RU2233865C1 (ru) * | 2002-12-26 | 2004-08-10 | Зиненко Сергей Александрович | Способ получения присадки к смазочным маслам |
| US7378379B2 (en) * | 2003-06-10 | 2008-05-27 | The Lubrizol Corporation | Functionalized polymer composition for grease |
| US20060252660A1 (en) * | 2005-05-09 | 2006-11-09 | Akhilesh Duggal | Hydrolytically stable viscosity index improves |
| CN101679902B (zh) * | 2007-06-08 | 2013-06-12 | 东邦化学工业株式会社 | 润滑油用倾点下降剂 |
| WO2011084997A1 (fr) * | 2010-01-05 | 2011-07-14 | Novomer Inc. | Additifs à base d'hydrocarbures |
| US20130219868A1 (en) | 2010-10-29 | 2013-08-29 | Evonik Oil Additives Gmbh | Diesel motor having improved properties |
| WO2012076285A1 (fr) | 2010-12-10 | 2012-06-14 | Evonik Rohmax Additives Gmbh | Composition lubrifiante |
| WO2013062924A2 (fr) * | 2011-10-27 | 2013-05-02 | The Lubrizol Corporation | Composition lubrifiante contenant un polymère estérifié |
| US20130340325A1 (en) * | 2012-06-22 | 2013-12-26 | Baker Hughes Incorporated | Charged Block Co-polymers as Pour Point Depressants |
| US20160348026A1 (en) * | 2014-01-21 | 2016-12-01 | Evonik Oil Additives Gmbh | Pour point depressants for improving the low-temperature viscosity of aged lubricating oil |
| CN105585657B (zh) * | 2014-10-24 | 2018-03-20 | 中国石油化工股份有限公司 | 一种润滑油降凝剂及其制备方法 |
| CN105524209B (zh) * | 2014-10-24 | 2017-09-29 | 中国石油化工股份有限公司 | 丙烯酸酯系共聚物及其应用和润滑油降凝剂及其制备方法 |
| JP6438069B2 (ja) * | 2016-04-26 | 2018-12-12 | 三洋化成工業株式会社 | 潤滑油組成物 |
Family Cites Families (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2114233A (en) * | 1933-05-22 | 1938-04-12 | Rohm & Haas | Polymeric materials |
| US2091627A (en) * | 1934-06-08 | 1937-08-31 | Rohm & Haas | Composition of matter and process |
| US2100993A (en) * | 1934-12-14 | 1937-11-30 | Rohm & Haas | Process for preparing esters and products |
| US2655479A (en) * | 1949-01-03 | 1953-10-13 | Standard Oil Dev Co | Polyester pour depressants |
| US3251775A (en) * | 1962-05-24 | 1966-05-17 | Rohm & Haas | Lubricating oil compositions |
| US3386998A (en) * | 1964-05-19 | 1968-06-04 | Rohm & Haas | Nu-alkenoyloxy-2-morpholinones and their corresponding hydrolysis products |
| US3513096A (en) * | 1968-12-03 | 1970-05-19 | Exxon Research Engineering Co | Oil concentrate containing a compatible mixture of polyisobutylene and ethylene-alpha olefin copolymer |
| US3772196A (en) * | 1971-12-03 | 1973-11-13 | Shell Oil Co | Lubricating compositions |
| PH10685A (en) * | 1972-12-29 | 1977-08-10 | Texaco Development Corp | Oil compositions having improved viscosity index and pour paint properties |
| US4146492A (en) * | 1976-04-02 | 1979-03-27 | Texaco Inc. | Lubricant compositions which exhibit low degree of haze and methods of preparing same |
| US4071407A (en) * | 1976-11-16 | 1978-01-31 | The Board Of Trustees Of The University Of Alabama | Novel maltase enzyme produced by a new yeast strain |
| DE2657570C3 (de) * | 1976-12-18 | 1980-11-20 | Bayer Ag, 5090 Leverkusen | Elektrochemische Zelle zum Nachweis von Schwefelwasserstoff in einem Gasgemisch |
| GB1559952A (en) * | 1977-10-26 | 1980-01-30 | Shell Int Research | Lubricating oil compositions |
| DE2835192C2 (de) * | 1978-08-11 | 1986-12-11 | Röhm GmbH, 6100 Darmstadt | Schmieröladditive |
| DE2905954C2 (de) * | 1979-02-16 | 1982-10-28 | Röhm GmbH, 6100 Darmstadt | Konzentrierte Polymerisatemulsionen als Viskositätsindexverbesserer für Mineralöle |
| DE3544061A1 (de) * | 1985-12-13 | 1987-06-19 | Roehm Gmbh | Hochscherstabile mehrbereichsschmieroele mit verbessertem viskositaetsindex |
-
1983
- 1983-10-28 DE DE19833339103 patent/DE3339103A1/de not_active Ceased
-
1984
- 1984-10-16 DE DE8484112445T patent/DE3483714D1/de not_active Expired - Lifetime
- 1984-10-16 EP EP84112445A patent/EP0140274B2/fr not_active Expired - Lifetime
- 1984-10-24 JP JP59222331A patent/JPH0631382B2/ja not_active Expired - Fee Related
-
1988
- 1988-12-27 US US07/291,387 patent/US4968444A/en not_active Expired - Lifetime
Cited By (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0225598A3 (en) * | 1985-12-13 | 1988-10-12 | Rohm Gmbh | High shear-stable multifunctional lubricating oil with an improved viscosity index |
| US4822508A (en) * | 1985-12-13 | 1989-04-18 | Rohm Gmbh | Shear stable multirange oils having an improved viscosity index |
| EP0236844A3 (fr) * | 1986-03-07 | 1988-03-30 | Röhm Gmbh | Additifs pour huiles minérales ayant des caractéristiques modifiant le point d'écoulement |
| US4867894A (en) * | 1986-03-07 | 1989-09-19 | Rohm Gmbh | Pour point improving additives for mineral oils |
| FR2601029A1 (fr) * | 1986-04-25 | 1988-01-08 | Roehm Gmbh | Additifs pour huiles lubrifiantes paraffiniques |
| US5043087A (en) * | 1986-04-25 | 1991-08-27 | Rohn Gmbh | Addives for paraffinic lubricants |
| DE3613992C2 (de) * | 1986-04-25 | 2000-05-04 | Roehm Gmbh | Additive für paraffinische Schmieröle |
| DE3613992A1 (de) * | 1986-04-25 | 1987-10-29 | Roehm Gmbh | Additive fuer paraffinische schmieroele |
| JPH078990B2 (ja) * | 1987-08-19 | 1995-02-01 | ペンゾイル・プロダクツ・カンパニー | メタクリレート系流動点降下剤類及び組成物 |
| EP0384367A3 (fr) * | 1989-02-24 | 1990-10-17 | BASF Aktiengesellschaft | Mélanges concentrés de copolymères greffés d'ester insaturé et de copolymère éthylène-vinylester |
| EP0418610A1 (fr) * | 1989-09-09 | 1991-03-27 | Röhm Gmbh | Produit améliorant l'indice de viscosité, à action dispersante |
| US5149452A (en) * | 1990-12-19 | 1992-09-22 | Exxon Research And Engineering Company | Wax isomerate having a reduced pour point |
| EP0491536A1 (fr) * | 1990-12-19 | 1992-06-24 | Exxon Research And Engineering Company | Isomère de cire ayant un point d'écoulement réduit |
| WO1993001797A1 (fr) * | 1991-07-25 | 1993-02-04 | L'oreal | Composition cosmetique huileuse contenant comme agent epaississant une association de deux copolymeres et contenant facultativement un correcteur de rheologie amphiphile |
| FR2679444A1 (fr) * | 1991-07-25 | 1993-01-29 | Oreal | Utilisation comme agents epaississants des huiles, dans une composition cosmetique huileuse, d'une association de deux copolymeres. |
| US5519063A (en) * | 1991-07-25 | 1996-05-21 | L'oreal | Oily cosmetic composition containing, as a thickener, an association of two copolymers and optionally containing an amphiphilic rheology corrector |
| EP0644252A3 (fr) * | 1993-09-20 | 1995-06-28 | Rohm & Haas | Agent de compatibilité pour un mélange de polymère améliorant l'indice de viscosité. |
| US6140431A (en) * | 1997-02-27 | 2000-10-31 | Rohm And Haas Company | Process for preparing continuously variable-composition copolymers |
| EP0889114A1 (fr) * | 1997-07-03 | 1999-01-07 | Exxon Research And Engineering Company | Fluides de boites de vitesse automatique avec une faible viscosité Brookfield et une importante restistance au cisaillement |
| US6458749B2 (en) | 1997-08-22 | 2002-10-01 | Rohmax Additives Gmbh | Method for improving low-temperature fluidity of lubricating oils using high-and-low-molecular weight polymer |
| WO2011134694A1 (fr) * | 2010-04-26 | 2011-11-03 | Evonik Rohmax Additives Gmbh | Polymère utile comme agent améliorant l'indice de viscosité |
| US9481849B2 (en) | 2010-04-26 | 2016-11-01 | Evonik Oil Additives Gmbh | Polymer useful as viscosity index improver |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0140274B1 (fr) | 1990-12-05 |
| JPH0631382B2 (ja) | 1994-04-27 |
| US4968444A (en) | 1990-11-06 |
| EP0140274A3 (en) | 1987-05-13 |
| DE3483714D1 (de) | 1991-01-17 |
| JPS60110790A (ja) | 1985-06-17 |
| EP0140274B2 (fr) | 1994-06-22 |
| DE3339103A1 (de) | 1985-05-09 |
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