EP1452581A2 - Procédé d'amélioration de la compatibilité avec des élastomeres - Google Patents

Procédé d'amélioration de la compatibilité avec des élastomeres Download PDF

Info

Publication number
EP1452581A2
EP1452581A2 EP04250661A EP04250661A EP1452581A2 EP 1452581 A2 EP1452581 A2 EP 1452581A2 EP 04250661 A EP04250661 A EP 04250661A EP 04250661 A EP04250661 A EP 04250661A EP 1452581 A2 EP1452581 A2 EP 1452581A2
Authority
EP
European Patent Office
Prior art keywords
lubricating oil
oil composition
dispersant
succinimide
nitrogen
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
Application number
EP04250661A
Other languages
German (de)
English (en)
Other versions
EP1452581B1 (fr
EP1452581A3 (fr
Inventor
Jeroen Van Leeuwen
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Chevron Oronite Technology BV
Original Assignee
Chevron Oronite Technology BV
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Chevron Oronite Technology BV filed Critical Chevron Oronite Technology BV
Publication of EP1452581A2 publication Critical patent/EP1452581A2/fr
Publication of EP1452581A3 publication Critical patent/EP1452581A3/fr
Application granted granted Critical
Publication of EP1452581B1 publication Critical patent/EP1452581B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M141/00Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential
    • C10M141/06Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential at least one of them being an organic nitrogen-containing compound
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M163/00Lubricating compositions characterised by the additive being a mixture of a compound of unknown or incompletely defined constitution and a non-macromolecular compound, each of these compounds being essential
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M177/00Special methods of preparation of lubricating compositions; Chemical modification by after-treatment of components or of the whole of a lubricating composition, not covered by other classes
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/02Hydroxy compounds
    • C10M2207/023Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/02Hydroxy compounds
    • C10M2207/023Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
    • C10M2207/027Neutral salts thereof
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10Carboxylix acids; Neutral salts thereof
    • C10M2207/14Carboxylix acids; Neutral salts thereof having carboxyl groups bound to carbon atoms of six-membered aromatic rings
    • C10M2207/144Carboxylix acids; Neutral salts thereof having carboxyl groups bound to carbon atoms of six-membered aromatic rings containing hydroxy groups
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/086Imides
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/28Amides; Imides
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2223/00Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/04Phosphate esters
    • C10M2223/045Metal containing thio derivatives
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2010/00Metal present as such or in compounds
    • C10N2010/04Groups 2 or 12
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/04Detergent property or dispersant property
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/36Seal compatibility, e.g. with rubber
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00Specified use or application for which the lubricating composition is intended
    • C10N2040/25Internal-combustion engines

Definitions

  • the present invention relates to a method of improving elastomer seal compatibility and dispersancy in an internal combustion engine. More particularly, the present invention relates to a method comprising contacting elastomer seals in an internal combustion engine with a lubricating oil composition having improved elastomer seal compatibility. Moreover, the present invention relates to the use of a lubricating oil composition able to render nitrogen-containing dispersants contained in lubricating oils compatible with elastomer seals used in internal combustion engines.
  • crankcase lubricating oil compositions It is known to employ nitrogen-containing dispersants and/or detergents in the formulation of crankcase lubricating oil compositions. Many of the known dispersant/detergent compounds are based on the reaction of an alkenylsuccinic acid or anhydride with an amine or polyamine to produce an alkenylsuccinimide or an alkenylsuccinamic acid as determined by selected conditions of reaction.
  • a continuing problem in the art of lubrication is to provide lubricating oil compositions which satisfy the demands imposed upon them by the original equipment manufacturers.
  • One such requirement is that lubricants not contribute to premature deterioration of seals, clutch face plates or other parts made from elastomers such as fluoro, acrylic, silicone, nitrile and the like.
  • Elastomers are increasingly being used in fabricating the flexible seals which are used in internal combustion engines. These seals are used, for example, to prevent leakage of lubricants at the point where moving parts, such as a crankshaft, leave the engine. Any substantial leakage of lubricant from the engine is obviously undesirable.
  • elastomer seals are subject to discoloration and mechanical deterioration when used in engines which are lubricated with lubricating oils containing polyamine dispersants, i.e., nitrogen-containing dispersants.
  • the polyamine dispersants interact with the elastomer seals, causing the seals to swell and to lose mechanical and dimensional integrity.
  • the rate of attack of the elastomer seals by a polyamine dispersant appears to be directly proportional to the concentration of polyamine dispersant and to the operating temperature of the engine. As the engine operating temperature rises, the rate of decomposition of the seal rises proportionately.
  • the mechanical strength and dimensional integrity of the seal increasingly deteriorates until the seal fails to prevent the leakage of lubricant from the engine.
  • succinimides useful as dispersants and/or detergents are not always compatible with elastomer seals when present in lubricating oil compositions at concentration levels necessary to be effective in controlling engine deposits.
  • nitrogenated components normally used in lubricants bis-succinimides with dispersant action have proved particularly critical towards elastomers, either when used alone or in combination with, for example, viscosity index improvement polymers of dispersant action containing nitrogenated monomers.
  • both these classes of additive contain strongly basic amino groups (primary and/or secondary and/or tertiary).
  • U.S. Patent No. 4,873,009 is also concerned, in part, with the use of succinimides as lube oil additives.
  • This patent teaches in Col. 2, lines 28 et seq. that lube additives prepared from "long chain aliphatic polyamines", i.e., succinimides, "are excellent lube oil additives". It teaches such succinimides are "inferior to additives where the alkylene polyamine is hydroxyalkylated" (Col. 2, lines 31-32). Such hydroxyalkylated polyamine- based succinimides, however, “have the drawback that they tend to attack engine seals particularly those of the fluorocarbon polymer type" (Col. 2, lines 35-37). This patent solves the fluoroelastomer seal compatibility problem by directly borating the hydroxylated polyamine-based succinimide.
  • U.S. Patent No. 4,940,552 relates to polyamine dispersants passivated toward fluorohydrocarbon compositions.
  • the dispersants described comprise the reaction product of a Mannich polyamine dispersant with an amount of maleic anhydride sufficient to reduce the reactivity with fluorohydrocarbons of the dispersant.
  • U.S. Patent No. 5,356,552 teaches succinimide additives post-treated with a cyclic carbonate having fluoroelastomer seal compatibility and for concentration levels at which fluoroelastomer seal compatibility is achieved, possess improved dispersancy and/or detergency.
  • U.S. Patent No. 6,124,247 teaches that dispersants of mono-succinimides or bis-succinimides are even more effective if their relative basic nitrogen content is high, i.e. insofar as the number of nitrogen atoms of the polyamine is larger than the number of succinic anhydride groups substituted by a polyisobutenyl group.
  • the higher the basic nitrogen content of these dispersants the more they favor the attack of the fluoroelastomer seal used in modern engines, because the basic nitrogen tends to reach with the acidic hydrogen atoms of this type of seal, and this attack results in the formation of cracks in the elastomer surface and the loss of other physical properties sought in this type of material.
  • the patent provides that by using lubricating oil compositions containing a dispersant of mono-succinimide or bis-succinimide type, post-treated or not, in combination with a borated glycerol ester, one obtains a composition compatible with fluorocarbon elastomers.
  • U.S. Patent No. 6,162,770 teaches a process for preparing an unsulfurized, alkali metal-free, detergent-dispersant composition having from 40% to 60% alkylphenol, from 10% to 40% alkaline earth alkylphenate, and from 20% to 40% alkaline earth single aromatic-ring alkylsalicylate.
  • This composition may have an alkaline earth double aromatic-ring alkylsalicylate as long as the mole ratio of single-ring alkylsalicylate to double aromatic-ring alkylsalicylate is at least 8:1.
  • This composition may be produced by the three-step process involving neutralization of alkylphenols, carboxylation of the resulting alkylphenate, and filtration of the product of the carboxylation step.
  • the detergent-dispersant produced by the method can be used in an engine lubricating composition to improve antioxidant properties, high temperature deposit control, and black sludge control.
  • the patent does not mention that the detergent-dispersant produced provides improved elastomer
  • the present invention provides a method of improving elastomer seal compatibility and dispersancy in an internal combustion engine, said method comprising contacting the elastomer seal in the internal combustion engine with a lubricating oil composition comprising:
  • the nitrogen-containing dispersant employed in the lubricating oil composition of the present invention is an ashless dispersant such as an alkenyl succinimide, an alkenyl succinic anhydride, an alkenyl succinate ester, and the like, or mixtures of such dispersants.
  • Alkenyl succinimides are preferred. Bis-succinimides are more preferred.
  • the present invention is directed to the use of a certain carboxylated detergent-dispersant to improve the elastomer seal compatibility in a lubricating oil composition containing a basic nitrogen-containing dispersant in an internal combustion engine.
  • the present invention is based on the discovery that a certain carboxylated detergent-dispersant improves elastomer seal compatibility of lubricating oil compositions containing nitrogen-containing dispersants.
  • the present invention relates to a method of improving elastomer seal compatibility and dispersancy in an internal combustion engine. More particularly, the present invention relates to a method comprising contacting elastomer seals in an internal combustion engine with a lubricating oil composition having improved elastomer seal compatibility.
  • alkylphenol means a phenol group having one or more alkyl substituents; at least one of which has a sufficient number of carbon atoms to impart oil solubility to the phenol.
  • alkaline earth metal means calcium, barium, magnesium, strontium, potassium, sodium, and lithium.
  • alkaline earth alkylphenate means an alkaline earth metal salt of an alkylphenol.
  • alkaline earth alkylsalicylate means an alkaline earth metal salt of an alkyl salicylic acid.
  • alkaline earth single aromatic-ring alkylsalicylate means an alkaline earth alkylsalicylate having only one alkyl salicylic anion per each alkaline earth metal base cation.
  • one mole of alkaline earth single aromatic-ring alkylsalicylate will contain one mole of aromatic ring and one mole of alkaline earth base cation.
  • a calcium single aromatic-ring alkylsalicylate would have one aromatic ring for each calcium ion.
  • alkaline earth double aromatic-ring alkylsalicylate means an alkaline earth alkylsalicylate having two alkyl salicylic anions per each alkaline earth metal base cation.
  • alkaline earth double aromatic-ring alkylsalicylate will contain two moles of aromatic rings and one mole of alkaline earth base cation.
  • a calcium double aromatic-ring alkylsalicylate would have two aromatic rings for each calcium ion.
  • succinimide is understood in the art to include many of the amide, imide, etc. species which are also formed by the reaction of a succinic anhydride with an amine and is so used herein.
  • the predominant product, however, is succinimide and this term has been generally accepted as meaning the product of a reaction of an alkenyl- or alkylsubstituted succinic acid or anhydride with a polyamine.
  • Total Base Number refers to the amount of base equivalent to milligrams of KOH in l gram of sample. Thus, higher TBN numbers reflect more alkaline products and therefore a greater alkalinity reserve.
  • the TBN of a sample can be determined by ASTM D 2896 or any other equivalent procedure.
  • the base oil of lubricating viscosity of the present invention may be mineral oils or synthetic oils.
  • a base oil having a viscosity of at least about 2.5 cSt at about 40°C and a pour point below about 20°C, preferably at or below 0°C is desirable.
  • the base oils may be derived from synthetic or natural sources.
  • Mineral oils for use as the base oil in this invention include, for example, paraffinic, naphthenic and other oils that are ordinarily used in lubricating oil compositions.
  • Synthetic oils include, for example, both hydrocarbon synthetic oils and synthetic esters and mixtures thereof having the desired viscosity.
  • Hydrocarbon synthetic oils may include, for example, oils prepared from the polymerization of alpha olefins, i.e., polyalphaolefin or PAO, or from hydrocarbon synthesis procedures using carbon monoxide and hydrogen gases such as in a Fisher-Tropsch process.
  • Useful synthetic hydrocarbon oils include liquid polymers of alpha olefins having the proper viscosity. Especially useful are the hydrogenated liquid oligomers of about C 6 to about C 12 alpha olefins such as 1-decene trimer.
  • alkyl benzenes of proper viscosity such as didodecyl benzene, can be used.
  • Useful synthetic esters include the esters of monocarboxylic acids and polycarboxylic acids, as well as mono-hydroxy alkanols and polyols. Typical examples are didodecyl adipate, pentaerythritol tetracaproate, di-2-ethylhexyl adipate, dilaurylsebacate, and the like. Complex esters prepared from mixtures of mono and dicarboxylic acids and mono and dihydroxy alkanols can also be used. Blends of mineral oils with synthetic oils are also useful.
  • the lubricating oil composition of the present invention comprises a carboxylated detergent-dispersant additive (also referred to herein as "carboxylate” or “carboxylated detergent”) made by the following process.
  • alkylphenols are neutralized using an alkaline earth base in the presence of at least one C 1 to about C 4 carboxylic acid. This reaction is carried out in the absence of alkali base, and in the absence of dialcohol or monoalcohol.
  • the alkylphenols contain up to 98% of linear alkylphenol (preferably up to 35% linear alkylphenol) in mixture with up to 15% of branched alkylphenol.
  • the linear alkyl radical contains about 12 to about 40 carbon atoms, more preferably about 18 to about 30 carbon atoms.
  • the branched alkyl radical contains at least nine carbon atoms, preferably about 9 to about 24 carbon atoms, more preferably about 10 to about 15 carbon atoms.
  • alkylphenol containing up to 35% of long linear alkylphenol is particularly attractive because a long linear alkyl chain promotes the compatibility and solubility of the additives in lubricating oils.
  • long linear alkyl chain promotes the compatibility and solubility of the additives in lubricating oils.
  • relatively heavy linear alkyl radicals in the alkylphenols makes the latter less reactive than branched alkylphenols, hence the need to use harsher reaction conditions to bring about their neutralization by an alkaline earth base.
  • Branched alkylphenols can be obtained by reaction of phenol with a branched olefin, generally originating from propylene. They consist of a mixture of monosubstituted isomers, the great majority of the substituents being in the para position, very few being in the ortho position, and hardly any in the meta position. That makes them relatively reactive towards an alkaline earth base, since the phenol function is practically devoid of steric hindrance.
  • linear alkylphenols can be obtained by reaction of phenol with a linear olefin, generally originating from ethylene. They consist of a mixture of monosubstituted isomers in which the proportion of linear alkyl substituents in the ortho, para, and meta positions is much more uniformly distributed. This makes them much less reactive towards an alkaline earth base since the phenol function is much less accessible due to considerable steric hindrance, due to the presence of closer and generally heavier alkyl substituents.
  • the alkaline earth bases that can be used for carrying out this step include the oxides or hydroxides of calcium, magnesium, barium, or strontium, and particularly of calcium oxide, calcium hydroxide, magnesium oxide, and mixtures thereof.
  • slaked lime calcium hydroxide is preferred.
  • the C 1 to about C 4 carboxylic acids used in this step include formic, acetic, propionic and butyric acid, and may be used alone or in mixture. Preferably, a mixture of acids is used, most preferably a formic acid/acetic acid mixture.
  • the molar ratio of formic acid/acetic acid should be from about 0.2:1 to about 100:1, preferably between about 0.5:1 and about 4:1, and most preferably 1:1.
  • the carboxylic acids act as transfer agents, assisting the transfer of the alkaline earth bases from a mineral reagent to an organic reagent.
  • the neutralization operation is carried out at a temperature of at least 200 °C., preferably at least 215 °C., and, more preferably, at least 240 °C.
  • the pressure is reduced gradually below atmospheric in order to distill off the water of reaction. Accordingly the neutralization should be conducted in the absence of any solvent that may form an azeotrope with water. Preferably, the pressure is reduced to no more than 7,000 Pa (70 mbars).
  • the quantities of reagents used should correspond to the following molar ratios:
  • the alkylphenate obtained is kept for a period not exceeding fifteen hours at a temperature of at least 215 °C. and at an absolute pressure of between 5,000 and 105 Pa (between 0.05 and 1.0 bar). More preferably, at the end of this neutralization step the alkylphenate obtained is kept for between two and six hours at an absolute pressure of between 10,000 and 20,000 Pa (between 0.1 and 0.2 bar).
  • the neutralization reaction is carried out without the need to add a solvent that forms an azeotrope with the water formed during this reaction.
  • the carboxylation step is conducted by simply bubbling carbon dioxide into the reaction medium originating from the preceding neutralization step and is continued until at least 20 mole % of the alkylphenate to alkylsalicylate (measured as salicylic acid by potentiometric determination). It must take place under pressure in order to avoid any decarboxylation of the alkylsalicylate that forms.
  • At least 22 mole % of the starting alkylphenols is converted to alkylsalicylate using carbon dioxide at a temperature of between 180 ° and 240 °C., under a pressure within the range of from above atmospheric pressure to 15 x 105 Pa (15 bars) for a period of one to eight hours.
  • At least 25 mole % of the starting alkylphenols is converted to alkylsalicylate using carbon dioxide at a temperature equal to or greater than 200 °C. under a pressure of 4 x 105 Pa (4 bars).
  • the product of the carboxylation step is then filtered.
  • the purpose of the filtration step is to remove sediments, and particularly crystalline calcium carbonate, which might have been formed during the preceding steps, and which may cause plugging of filters installed in lubricating oil circuits.
  • the carboxylated detergent-dispersant formed by this process can be characterized by its unique composition, with much more alkylphenol and alkaline earth metal single aromatic-ring hydrocarbyl salicylate than produced by other routes.
  • the reaction product will typically have the following composition:
  • this detergent-dispersant composition can be characterized by having only minor amounts of an alkaline earth double aromatic-ring alkylsalicylates.
  • the mole ratio of single aromatic-ring alkylsalicylate to double aromatic-ring alkylsalicylate is at least 8:1.
  • the TBN of the detergent-dispersant should be from about 100 to about 250, more preferably from about 150 to about 200.
  • the carboxylated detergent-dispersant will typically range from about 0.5 to about 15 wt %, preferably from about 1 to about 12 wt % and more preferably about 1 to about 8 wt %, based on the weight of the total lubricating oil composition.
  • the nitrogen-containing dispersant employed in the lubricating oil composition of the present invention is an ashless dispersant such as an alkenyl or alkyl succinimide, an alkenyl or alkyl succinic anhydride, an alkenyl or alkyl succinate ester, and the like, or mixtures of such dispersants.
  • Ashless dispersants are broadly divided into several groups.
  • One such group is directed to copolymers which contain a carboxylate ester with one or more additional polar function, including amine, amide, imine, imide, hydroxyl carboxyl, and the like. These products can be prepared by copolymerization of long chain alkyl acrylates or methacrylates with monomers of the above function.
  • Such groups include alkyl methacrylate-vinyl pyrrolidinone copolymers, alkyl methacrylate-dialkylaminoethy methacrylate copolymers and the like.
  • amides and polyamides or esters and polyesters such as tetraethylene pentamine, polyvinyl polysterarates and other polystearamides may be employed.
  • Preferred dispersants are N-substituted long chain alkenyl succinimides.
  • Alkenyl succinimides are usually derived from the reaction of alkenyl succinic acid or anhydride and alkylene polyamines. These compounds are generally considered to have the formula: wherein R 1 is a substantially hydrocarbon radical having a molecular weight from about 400 to about 3000, that is, R 1 is a hydrocarbyl radical, preferably an alkenyl radical, containing about 30 to about 200 carbon atoms; Alk is an alkylene radical of about 2 to about 10, preferably about 2 to about 6, carbon atoms, R 2 , R 3 , and R 4 are selected from a C 1 to about C 4 alkyl or alkoxy or hydrogen, preferably hydrogen, and x is an integer from 0 to about 10, preferably 0 to about 3.
  • the actual reaction product of alkylene succinic acid or anhydride and alkylene polyamine will comprise the mixture of compounds including succinamic acids and succinimides. However, it is customary to designate this reaction product as a succinimide of the described formula, since this will be a principal component of the mixture. See, for example, U.S. Patent Nos, 3,202,678; 3,024,237; and 3,172,892, the descriptions of which are incorporated herein by way of reference. Reduction of the alkenyl substituted succinic anhydride produces the corresponding alkyl derivative.
  • the mono alkenyl succinimide and bis alkenyl succinimide produced may depend on the charge mole ratio of polyamine to succinic groups and the particular polyamine used.
  • Charge mole ratios of polyamine to succinic groups of about 1:1 may produce predominately mono alkenyl succinimide.
  • Charge mole ratios of polyamine to succinic group of about 1:2 may produce predominately bis alkenyl succinimide.
  • alkenyl or alkyl succinimide is a mono- or bis-succinimide prepared from a succinic anhydride substituted by polyisobutene of a polyalkylene polyamine as discussed in further detail below.
  • Bis-succinimides are preferred.
  • N-substituted alkenyl succinimides can be prepared by reacting maleic anhydride with an olefinic hydrocarbon followed by reacting the resulting alkenyl succinic anhydride with the alkylene polyamine.
  • the R 1 radical of the above formula that is, the alkenyl radical, is preferably derived from a polymer prepared from an olefin monomer containing from about 2 to about 5 carbon atoms.
  • the alkenyl radical is obtained by polymerizing an olefin containing from about 2 to about 5 carbon atoms to form a hydrocarbon having a molecular weight ranging from about 400 to about 3,000.
  • Such olefin monomers are exemplified by ethylene, propylene, 1-butene, 2-butene, isobutene, and mixtures thereof.
  • the preferred polyalkylene amines used to prepare the succinimides are of the formula: wherein z is an integer of from 0 to about 10 and Alk, R 2 , R 3 , and R 4 are as defined above.
  • the alkylene amines include principally methylene amines, ethylene amines, butylene amines, propylene amines, pentylene amines, hexylene amines, heptylene amines, octylene amines, other polymethylene amines and also the cyclic and the higher homologs of such amines as piperazine and amino alkyl-substituted piperazines.
  • ethylene diamine triethylene tetraamine, propylene diamine, decamethyl diamine, octamethylene diamine, diheptamethylene triamine, tripropylene tetraamine, tetraethylene pentamine, trimethylene diamine, pentaethylene hexamine, ditrimethylene triamine, 2-heptyl-3-(2-aminopropyl)-imidazoline, 4-methyl imidazoline, N,N-dimethyl-1 ,3-propane diamine, 1,3-bis(2-aminoethyl)imidazoline, 1-(2-aminopropyl)-piperazine, 1,4-bis(2-aminoethyl)piperazine and 2-methyl-1-(2-aminobutyl)piperazine. Higher homologs such as are obtained by condensing two or more of the above-illustrated alkylene amines likewise are useful.
  • ethylene amines are especially useful. They are described in some detail under the heading "Ethylene Amines” in Encyclopedia of Chemical Technology, Kirk-Othmer, Vol. 5, pp. 898-905 (Interscience Publishers, New York, 1950).
  • ethylene amine is used in a generic sense to denote a class of polyamines conforming for the most part to the structure: H 2 N(CH 2 CH 2 NH) a H wherein a is an integer from 1 to about 10.
  • ethylene diamine diethylene triamine
  • triethylene tetraamine tetraethylene pentamine
  • pentaethylene hexamine pentaethylene hexamine
  • alkenyl succinimides are post-treated succinimides such as post-treatment processes involving ethylene carbonate and boric acid disclosed by Wollenberg, et al., U.S. Patent No. 4,612,132; Wollenberg, et al., U.S. Patent No. 4,746,446; and the like as well as other post-treatment processes each of which are incorporated herein by reference in its entirety.
  • the nitrogen-containing dispersant is a polyalkylene succinimide, preferably a polyisobutylene succinimide. More preferably, the nitrogen-containing dispersant is a polyisobutylene bis-succinimide.
  • the nitrogen-containing dispersant employed in the present invention will be present in sufficient quantity to impart the desired dispersant properties to the lubricating oil composition in order to prevent the deposit of contaminants formed in oil during operation of the internal combustion engine.
  • the nitrogen-containing dispersant will typically range from about 2 to about 13 wt %, preferably from about 4 to about 8 wt % and more preferably about 6 to about 7.5 wt %, based on the weight of the total lubricating oil composition.
  • additive components are examples of some of the components that can be favorably employed in the present invention. These examples of additives are provided to illustrate the present invention, but they are not intended to limit it:
  • a carboxylated detergent-dispersant was prepared as follows:
  • a charge of 875 g of branched dodecylphenol (DDP) having a molecular mass of 270, (i.e. 3.24 moles) and 875 g of linear alkylphenol having a molecular mass of about 390 (i.e. 2.24 moles) was placed in a four-necked 4 liter glass reactor above which was a heat-insulated Vigreux fractionating column.
  • DDP branched dodecylphenol
  • linear alkylphenol having a molecular mass of about 390 i.e. 2.24 moles
  • the agitator was started up and the reaction mixture was heated to 65°C, at which temperature 158 grams of slaked lime Ca(OH) 2 (i.e. 2.135 moles) and 19 g of a mixture (50/50 by weight) of formic acid and acetic acid were added.
  • the reaction medium underwent further heating to 120°C at which temperature the reactor was placed under a nitrogen atmosphere, then heated up to 165°C and then the nitrogen introduction was stopped. Distillation of water commenced at this temperature.
  • the temperature was increased to 240°C and the pressure was reduced gradually below atmospheric until an absolute pressure of 5,000 Pa (50 mbars) was obtained.
  • the reaction mixture was kept for five hours under the preceding conditions.
  • the reaction mixture was allowed to cool to 180°C, then the vacuum was broken under a nitrogen atmosphere and a sample was taken for analysis.
  • the total quantity of distillate obtained was about 120 cm 3 ; demixing took place in the lower phase (66 cm 3 being water).
  • Step (A) The product obtained in Step (A) was transferred to a 3.6-liter autoclave and heated to 180°C. At this temperature, scavenging of the reactor with carbon dioxide (CO 2 ) was commenced and continued for ten minutes. The amount of CO 2 used in this step was in the order of 20 grams.
  • the present invention was evaluated for compatibility with elastomer seals in a bench test (PV 3344) by suspending a fluorocarbon test piece (AK 6) in an oil-based solution heated to 150 °C. for 282 hours, the oil being renewed every 92 hours, then by measuring the variation in the physical properties of the sample, in particular the tensile strength break (TSB) and the elongation at break (ELB), in accordance with procedure DIN 53504, by observing whether any cracks had formed at 100% elongation.
  • the passing test criteria included the following: no evidence of crack development; a tensile strength break greater than 8N/mm2 and an elongation at break greater than 160%. This test procedure will be designated above and later simply as the "VW Bench Test".
  • the formulation tested comprised a polyisobutenyl (PIB) bis-succinimide (the PIB having a molecular weight of 2300 and the bis-succinimide having been post-treated with ethylene carbonate)(6.5 wt %), low overbased (LOB) calcium sulfonate (0.68 wt %), carboxylated detergent, prepared in the manner described in Example 1, (2.45 wt %), high overbased (HOB) calcium alkylphenate (1.13 wt %), zinc dithiophosphate (0.69 wt %), a molybdenum-based anti-oxidant (0.05 wt %), a diphenylamine-based antioxidant (0.3 wt %), a friction modifier (0.25 wt %), a foam inhibitor (0.0025 wt %), a pour point depressant (0.15 wt %), a viscosity index improver (6.4 wt %), and a base oil
  • Comparative Example A was conducted as described in Example 2 except that 1.97 wt % of a commercial medium overbased (MOB) calcium phenate was substituted for the carboxylate and 0.5 wt % of the friction modifier was used instead of 0.25 wt %.
  • MOB medium overbased
  • Example 2 and Comparative Example A are presented below in Table 1.
  • Volkswagen PV 3344 Seal Test VW EAM Acrylate Seals
  • VW ACM Acrylate Seals
  • VW AK-6 Fluoroelastomer Seals Result
  • Tensile Strength % (Limit ⁇ -40) Elongation, % (Limit ⁇ -40) Cracks in Seal (Limit: None)
  • Example 1 The results in Table 1 indicate that the detergent-dispersant employed in the present invention enables you to pass the seal tests whereas a comparable commercial detergent, on an equal molar basis, fails these tests.
  • Example 2 showed no seal cracks and were well within the passing limits of the Volkswagen VW seal test.
  • Oil-Elastomer Compatibility is aimed at determining the degree of compatibility of lubricating oils and cured elastomers used in the automotive industry. Elastomer test pieces are immersed in the test oil for a given period of time and a given temperature. The size, the volume, the hardness, and the stress-strain properties are determined before and after immersion. The compatibility of the oil and the elastomer is estimated by the change in these characteristics.
  • Example 3 The test in Example 3 was repeated with a lubricating oil composition containing the carboxylated detergent-dispersant (Formulation 4) employed in the present invention and compared with a lubricating oil composition containing a comparable commercially available detergent (Formulation 5) without the detergent-dispersant. The results are shown in Table 3.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Lubricants (AREA)
EP04250661A 2003-02-27 2004-02-06 L' utilisé d'un carboxylate pour amèliorer la compatibilité avec les élastomers Expired - Lifetime EP1452581B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US377915 2003-02-27
US10/377,915 US20040171501A1 (en) 2003-02-27 2003-02-27 Method for improving elastomer compatibility

Publications (3)

Publication Number Publication Date
EP1452581A2 true EP1452581A2 (fr) 2004-09-01
EP1452581A3 EP1452581A3 (fr) 2004-12-22
EP1452581B1 EP1452581B1 (fr) 2010-07-28

Family

ID=32771539

Family Applications (1)

Application Number Title Priority Date Filing Date
EP04250661A Expired - Lifetime EP1452581B1 (fr) 2003-02-27 2004-02-06 L' utilisé d'un carboxylate pour amèliorer la compatibilité avec les élastomers

Country Status (6)

Country Link
US (1) US20040171501A1 (fr)
EP (1) EP1452581B1 (fr)
JP (1) JP2004256817A (fr)
CA (1) CA2457082A1 (fr)
DE (1) DE602004028304D1 (fr)
SG (1) SG135942A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1710294A1 (fr) 2005-04-06 2006-10-11 Infineum International Limited Une méthode pour améliorer la stabilité ou la compatibilité des tensioactifs
EP1803797A2 (fr) * 2005-12-27 2007-07-04 Chevron Japan Ltd. Procédé pour améliorer la compatibilité d'un matériau d'étanchéité en caoutchouc acrylique dans un moteur à combustion interne
GB2464590A (en) * 2008-09-11 2010-04-28 Infineum Int Ltd A detergent for use in a lubricating oil
EP2559748A1 (fr) * 2011-08-19 2013-02-20 Infineum International Limited Composition dýhuile lubrifiante

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1914295B1 (fr) * 2006-10-11 2013-12-04 Total Marketing Services Lubrifiant marin pour fioul à basse et haute teneur en soufre
US8993496B2 (en) 2010-03-31 2015-03-31 Chevron Oronite Company Llc Method for improving fluorocarbon elastomer seal compatibility
US9150811B2 (en) 2010-03-31 2015-10-06 Cherron Oronite Company LLC Method for improving copper corrosion performance
US8933001B2 (en) 2010-03-31 2015-01-13 Chevron Oronite Company Llc Method for improving fluorocarbon elastomer seal compatibility
US8901050B2 (en) 2010-03-31 2014-12-02 Chevron Oronite Company Llc Method for improving copper corrosion performance
US8716202B2 (en) * 2010-12-14 2014-05-06 Chevron Oronite Company Llc Method for improving fluorocarbon elastomer seal compatibility
EP2697343A4 (fr) * 2011-04-11 2014-11-12 Vanderbilt Chemicals Llc Additifs d'huile lubrifiante à base de dithiocarbamate de zinc
JP5746994B2 (ja) * 2012-03-14 2015-07-08 Jx日鉱日石エネルギー株式会社 潤滑油組成物及び内燃機関の潤滑方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1993007242A1 (fr) * 1991-10-08 1993-04-15 Chevron Research And Technology Company Additifs protegeant les joints d'etancheite au fluorocarbone destines aux huiles de graissage
US5356552A (en) * 1993-03-09 1994-10-18 Chevron Research And Technology Company, A Division Of Chevron U.S.A. Inc. Chlorine-free lubricating oils having modified high molecular weight succinimides
EP0933417A1 (fr) * 1998-01-30 1999-08-04 Chevron Chemical S.A. Additif pour huiles lubrifiantes exempt de soufre et de métal alcalin

Family Cites Families (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4379064A (en) * 1981-03-20 1983-04-05 Standard Oil Company (Indiana) Oxidative passivation of polyamine-dispersants
US4940552A (en) * 1981-03-20 1990-07-10 Amoco Corporation Passivation of polyamine dispersants toward fluorohydrocarbon compositions
US4873009A (en) * 1982-03-29 1989-10-10 Amoco Corporation Borated lube oil additive
US4612132A (en) * 1984-07-20 1986-09-16 Chevron Research Company Modified succinimides
US4746446A (en) * 1984-07-20 1988-05-24 Chevron Research Company Modified succinimides
FR2625219B1 (fr) * 1987-12-23 1990-12-21 Orogil Additifs detergents-dispersants a base de sels de metaux alcalino-terreux et alcalins pour huiles lubrifiantes
FR2625220B1 (fr) * 1987-12-23 1990-12-21 Orogil Procede de preparation d'additifs detergents-dispersants suralcalinises pour huiles lubrifiantes
US5162086A (en) * 1991-05-22 1992-11-10 Texaco Inc. Dispersant additive and lubricating oil composition containing same
US5188745A (en) * 1991-12-23 1993-02-23 Texaco Inc. Viton seal compatible dispersant and lubricating oil composition containing same
DE4214653A1 (de) * 1992-05-02 1993-11-04 Henkel Kgaa Motorengrundoele mit verbesserter dichtungsvertraeglichkeit
US5334321A (en) * 1993-03-09 1994-08-02 Chevron Research And Technology Company, A Division Of Chevron U.S.A. Inc. Modified high molecular weight succinimides
US6001785A (en) * 1996-11-25 1999-12-14 Chevron Chemical Company Llc Detergent-dispersant additives for lubricating oils of the sulphurised and superalkalised, alkaline earth alkylsalicylate-alkaylphenate type
FR2762848B1 (fr) * 1997-05-05 2000-02-04 Chevron Res & Tech Utilisation de composes borates pour ameliorer la compatibilite d'huiles lubrifiantes avec des elastomeres fluorocarbones
CA2277412A1 (fr) * 1998-07-17 2000-01-17 The Lubrizol Corporation Huile pour moteur ayant un dispersant et de l'aldehyde/epoxide pour ameliorer le comportement du joint d'etancheite, et pour empecher l'accumulation de depots
DE69827625T2 (de) * 1998-09-09 2005-12-08 Chevron Chemical S.A. Verfahren zur Herstellung von Erdalkalimetall-Salzen mit hoher Basizität, insbesondere von einem an einem Ring gebundenen Hydrocarbylsalicylat-carboxylat
US6348438B1 (en) * 1999-06-03 2002-02-19 Chevron Oronite S.A. Production of high BN alkaline earth metal single-aromatic ring hydrocarbyl salicylate-carboxylate
US6770605B1 (en) * 2000-09-11 2004-08-03 The Lubrizol Corporation Modified polyisobutylene succinimide dispersants having improved seal, sludge, and deposit performance

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1993007242A1 (fr) * 1991-10-08 1993-04-15 Chevron Research And Technology Company Additifs protegeant les joints d'etancheite au fluorocarbone destines aux huiles de graissage
US5356552A (en) * 1993-03-09 1994-10-18 Chevron Research And Technology Company, A Division Of Chevron U.S.A. Inc. Chlorine-free lubricating oils having modified high molecular weight succinimides
EP0933417A1 (fr) * 1998-01-30 1999-08-04 Chevron Chemical S.A. Additif pour huiles lubrifiantes exempt de soufre et de métal alcalin
US6162770A (en) * 1998-01-30 2000-12-19 Chevron Chemical Company Llc Unsulfurized alkali metal-free, additive for lubricating oils
US6262001B1 (en) * 1998-01-30 2001-07-17 Chevron Chemical Company Llc Unsulfurized, alkali meta-free, additive for lubricating oils

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1710294A1 (fr) 2005-04-06 2006-10-11 Infineum International Limited Une méthode pour améliorer la stabilité ou la compatibilité des tensioactifs
EP1803797A2 (fr) * 2005-12-27 2007-07-04 Chevron Japan Ltd. Procédé pour améliorer la compatibilité d'un matériau d'étanchéité en caoutchouc acrylique dans un moteur à combustion interne
EP1803797A3 (fr) * 2005-12-27 2010-07-28 Chevron Japan Ltd. Procédé pour améliorer la compatibilité d'un matériau d'étanchéité en caoutchouc acrylique dans un moteur à combustion interne
GB2464590A (en) * 2008-09-11 2010-04-28 Infineum Int Ltd A detergent for use in a lubricating oil
GB2464590B (en) * 2008-09-11 2011-06-22 Infineum Int Ltd A detergent for use in a lubricating oil
EP2559748A1 (fr) * 2011-08-19 2013-02-20 Infineum International Limited Composition dýhuile lubrifiante
US10000719B2 (en) 2011-08-19 2018-06-19 Infineum International Limited Lubricating oil composition

Also Published As

Publication number Publication date
EP1452581B1 (fr) 2010-07-28
US20040171501A1 (en) 2004-09-02
SG135942A1 (en) 2007-10-29
JP2004256817A (ja) 2004-09-16
CA2457082A1 (fr) 2004-08-27
EP1452581A3 (fr) 2004-12-22
DE602004028304D1 (de) 2010-09-09

Similar Documents

Publication Publication Date Title
US6001780A (en) Ashless lubricating oil formulation for natural gas engines
JP5431642B2 (ja) 高負荷ディーゼルエンジン用低硫黄低リン潤滑油組成物
US8383562B2 (en) System oil formulation for marine two-stroke engines
JP5431641B2 (ja) 低硫黄低リン潤滑油組成物
EP3072948B1 (fr) Compositions d'huile lubrifiante pour machines de construction
US9175237B2 (en) Trunk piston engine lubricating oil compositions
EP1452581B1 (fr) L' utilisé d'un carboxylate pour amèliorer la compatibilité avec les élastomers
EP1803797B1 (fr) Utilisation d'une composition lubrifiante pour améliorer la compatibilité d'un matériau d'étanchéité en caoutchouc acrylique dans un moteur à combustion interne
KR20170033245A (ko) 윤활유 조성물의 제형화를 위한 첨가제 농축물
JP2007169639A (ja) 潤滑油組成物
CA2280238A1 (fr) Composition d'additif pour huile lubrifiante ayant un coefficient de frottement eleve a hautes temperatures
US20030224948A1 (en) Lubricating oil additive comprising EC-treated succinimide, borated dispersant and corrosion inhibitor
JP2007154199A (ja) 潤滑油組成物
US20130157910A1 (en) Diesel engine oils
JPH1135962A (ja) 潤滑油組成物
JP3936823B2 (ja) エンジン油組成物
KR20240151798A (ko) 윤활유 조성물

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LI LU MC NL PT RO SE SI SK TR

AX Request for extension of the european patent

Extension state: AL LT LV MK

PUAL Search report despatched

Free format text: ORIGINAL CODE: 0009013

AK Designated contracting states

Kind code of ref document: A3

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LI LU MC NL PT RO SE SI SK TR

AX Request for extension of the european patent

Extension state: AL LT LV MK

17P Request for examination filed

Effective date: 20050615

AKX Designation fees paid

Designated state(s): DE FR GB NL

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

RTI1 Title (correction)

Free format text: USE OF A CARBOXYLATE FOR IMPROVING ELASTOMER COMPATIBILITY

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): DE FR GB NL

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REF Corresponds to:

Ref document number: 602004028304

Country of ref document: DE

Date of ref document: 20100909

Kind code of ref document: P

REG Reference to a national code

Ref country code: NL

Ref legal event code: T3

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed

Effective date: 20110429

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 602004028304

Country of ref document: DE

Effective date: 20110429

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 13

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 14

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 15

REG Reference to a national code

Ref country code: DE

Ref legal event code: R082

Ref document number: 602004028304

Country of ref document: DE

Representative=s name: HL KEMPNER PATENTANWAELTE, SOLICITORS (ENGLAND, DE

Ref country code: DE

Ref legal event code: R082

Ref document number: 602004028304

Country of ref document: DE

Representative=s name: HL KEMPNER PATENTANWALT, RECHTSANWALT, SOLICIT, DE

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 20210212

Year of fee payment: 18

REG Reference to a national code

Ref country code: NL

Ref legal event code: MM

Effective date: 20220301

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20220301

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20221230

Year of fee payment: 20

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20230110

Year of fee payment: 20

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20221230

Year of fee payment: 20

P01 Opt-out of the competence of the unified patent court (upc) registered

Effective date: 20230530

REG Reference to a national code

Ref country code: DE

Ref legal event code: R071

Ref document number: 602004028304

Country of ref document: DE

REG Reference to a national code

Ref country code: GB

Ref legal event code: PE20

Expiry date: 20240205

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION

Effective date: 20240205