EP2449063B1 - Terpolymer mit ethylen/vinylacetat/ungesättigten estern als zusatz für erhöhte kälteresistenz von flüssigen kohlenwasserstoffen wie mitteldestillate und brennstoffe - Google Patents

Terpolymer mit ethylen/vinylacetat/ungesättigten estern als zusatz für erhöhte kälteresistenz von flüssigen kohlenwasserstoffen wie mitteldestillate und brennstoffe Download PDF

Info

Publication number
EP2449063B1
EP2449063B1 EP10734559.7A EP10734559A EP2449063B1 EP 2449063 B1 EP2449063 B1 EP 2449063B1 EP 10734559 A EP10734559 A EP 10734559A EP 2449063 B1 EP2449063 B1 EP 2449063B1
Authority
EP
European Patent Office
Prior art keywords
mol
fuels
copolymer
cold
ppm
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.)
Active
Application number
EP10734559.7A
Other languages
English (en)
French (fr)
Other versions
EP2449063B2 (de
EP2449063A1 (de
Inventor
Erwan Chevrot
Laurent Dalix
Frédéric Tort
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.)
TotalEnergies Marketing Services SA
Original Assignee
Total Marketing Services SA
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
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=41716191&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=EP2449063(B1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Total Marketing Services SA filed Critical Total Marketing Services SA
Publication of EP2449063A1 publication Critical patent/EP2449063A1/de
Publication of EP2449063B1 publication Critical patent/EP2449063B1/de
Application granted granted Critical
Publication of EP2449063B2 publication Critical patent/EP2449063B2/de
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/192—Macromolecular compounds
    • C10L1/195—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C10L1/197—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and an acyloxy group of a saturated carboxylic or carbonic acid
    • C10L1/1973—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and an acyloxy group of a saturated carboxylic or carbonic acid mono-carboxylic
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/143—Organic compounds mixtures of organic macromolecular compounds with organic non-macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L10/00—Use of additives to fuels or fires for particular purposes
    • C10L10/14—Use of additives to fuels or fires for particular purposes for improving low temperature properties
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L10/00—Use of additives to fuels or fires for particular purposes
    • C10L10/14—Use of additives to fuels or fires for particular purposes for improving low temperature properties
    • C10L10/16—Pour-point depressants
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L2200/00—Components of fuel compositions
    • C10L2200/04—Organic compounds
    • C10L2200/0407—Specifically defined hydrocarbon fractions as obtained from, e.g. a distillation column
    • C10L2200/043—Kerosene, jet fuel
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L2200/00—Components of fuel compositions
    • C10L2200/04—Organic compounds
    • C10L2200/0407—Specifically defined hydrocarbon fractions as obtained from, e.g. a distillation column
    • C10L2200/0438—Middle or heavy distillates, heating oil, gasoil, marine fuels, residua
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L2200/00—Components of fuel compositions
    • C10L2200/04—Organic compounds
    • C10L2200/0407—Specifically defined hydrocarbon fractions as obtained from, e.g. a distillation column
    • C10L2200/0438—Middle or heavy distillates, heating oil, gasoil, marine fuels, residua
    • C10L2200/0446—Diesel
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L2200/00—Components of fuel compositions
    • C10L2200/04—Organic compounds
    • C10L2200/0461—Fractions defined by their origin
    • C10L2200/0469—Renewables or materials of biological origin
    • C10L2200/0476—Biodiesel, i.e. defined lower alkyl esters of fatty acids first generation biodiesel

Definitions

  • the invention relates to the use of alpha-olefin, vinyl ester and alpha, beta-unsaturated carboxylic acid ester copolymers as additives for improving the cold-running performance of fuels and lubricants, as well as fuel oils and lubricants. packages containing these copolymers.
  • the hydrocarbon compositions especially those based on middle distillate type containing paraffin waxes, such as for example diesel fuels and heating fuel oils have a significant decrease in their flow properties. It is well known that the crystallization of paraffins is a limiting factor for the use of middle distillates. Also, it is important to prepare diesel fuels adapted to the temperatures at which they will be used in motorized vehicles, that is to say to the surrounding climate. Generally, cold operability of fuels at -10 ° C is sufficient in many hot or temperate countries. But in cold climate countries, such as the Scandinavian countries, Canada, and Northeast Asian countries, fuel usage temperatures well below -20 ° C can be achieved. It is the same for domestic fuel stored outside buildings (houses, buildings, ).
  • paraffins are crystallized at the bottom of the tank, they can be driven to start in the fuel system and particularly clog filters and prefilters arranged upstream of the injection systems (pump and injectors). Similarly for the storage of domestic fuel oils, paraffins precipitate at the bottom of the tank and can be driven and obstruct the pipes upstream of the pump and the boiler supply system (nozzle and filter). It is obvious that the presence of solids, such as paraffin crystals, prevents the normal circulation of the middle distillate.
  • CFI cold flow improvers
  • CFI additives see for example US 3,048,479 , US 3,627,838 , US 3,790,359 , US 3,961,961 , EP 261 957 ) which are generally copolymers of ethylene and unsaturated ester, such as ethylene / vinyl acetate copolymers (EVA), ethylene / vinyl propionate (EVP), ethylene / vinyl ethanoate (EVE), ethylene / methacrylate methyl (EMMA), and ethylene / alkyl fumarate.
  • EVA ethylene / vinyl acetate copolymers
  • EVE ethylene / vinyl propionate
  • EMMA ethylene / vinyl ethanoate
  • EMMA ethylene / methacrylate methyl
  • the prior art also provides conventional CFI ethylene / unsaturated ester additive mixtures with lubricating agents (mono- or polycarboxylic acid esters and mono- or polyalcohols (see, for example EP 721 492 ), with anti-sedimentation agents (see for example FR 2,490,669 ), with ethers (see for example US 3,999,960 , EP187488 ).
  • lubricating agents mono- or polycarboxylic acid esters and mono- or polyalcohols
  • anti-sedimentation agents see for example FR 2,490,669
  • ethers see for example US 3,999,960 , EP187488 .
  • CFI additives which are terpolymers or copolymers derived from more than 3 different monomers.
  • US 6,509,424 discloses a process for preparing terpolymers of ethylene and at least two compounds containing ethylenic unsaturations, such as vinyl esters, (meth) acrylic esters, alkyl vinyl ethers in a tubular reactor. These terpolymers can be used as additives improving the cold flow of oils and petroleum distillates.
  • US 3,642,459 describes terpolymers comprising 40 to 89% by weight of ethylene, 10 to 40% by weight of vinyl ester derived from short chain (C2-C4) carboxylic acid, such as vinyl acetate, and unsaturated monoesters having a C10-C22 alkyl chain); these terpolymers are used as additives to lower the pour point of petroleum distillates and as anti-waxing agents and to improve their filterability.
  • C2-C459 long chain (C2-C4) carboxylic acid, such as vinyl acetate, and unsaturated monoesters having a C10-C22 alkyl chain
  • WO 2005/054314 discloses terpolymers of alpha olefin, vinyl ester and alpha-beta unsaturated mono carboxylic acid ester useful.
  • Terpolymers, particularly preferred by the applicant which contain more than 80 mol% of ethylene and less than 9 mol% of vinyl acetate are exemplified.
  • these terpolymers containing less than 9 mol% of vinyl acetate although having an effect on the reduction of TLF for middle distillates containing more than 18% of n-paraffins, are not satisfactory for on the one hand solubility and secondly the tendency to clogging (or filterability at room temperature): there is harmful filter clogging.
  • EP 1.391.498 discloses additives improving the low temperature fluidity of middle distillates which are vinyl polymers (A), preferably ethylene-vinyl ester copolymers, the amount of hexane-insoluble matter exceeds 60% by weight at -20 ° C and is less than 30% by weight at 10 ° C; examples of EP 1.391.498 clearly show that the filterability temperature (CFPP) is lowered for copolymers and terpolymers whose amount of hexane insoluble matter exceeds 60% by weight at -20 ° C and is less than 30% by weight at 10 ° C by copolymers and terpolymers having the same units of recurrence present in the same proportions but the amount of hexane insoluble material is outside the claimed range; the copolymers exemplified are EVA copolymers and ethylene-vinyl acetate-neodecanoate or 2-ethylhexanoate vinyl terpolymers.
  • A vinyl polymers
  • CFPP
  • the present invention relates to the use of copolymers as additives improving the cold resistance of fuels (CFI additives); these copolymers contain units derived from at least one alpha-olefin, at least one vinyl ester and at least one alpha-beta unsaturated mono carboxylic acid ester, and are preferably terpolymers of ethylene, vinyl acetate and ethyl-2-acrylate, hexyl.
  • the copolymers according to the invention which are random copolymers have a number-average molecular weight (Mw) measured by GPC in general of between 3,000 and 30,000, and a number-average molecular weight (Mn) measured by GPC in general between 1,000 and 15,000.
  • copolymers can be prepared in a known manner by any polymerization process (see, for example, Ullmann's Encyclopedia of Industrial Chemistry, 5th Edition, "Waxes", Vol. A 28, p.146 ; US 3,627,838 ; EP 7,590 ) in particular by radical polymerization, preferably under high pressure, typically of the order of 1000 to 3000 bar (100 to 300 MPa), preferably from 1500 to 2000 bar (150 to 200 MPa), the temperatures of reaction generally ranging from 160 to 320 ° C, preferably from 200 to 280 ° C, and in the presence of at least one radical initiator chosen in general from organic peroxides and / or oxygenated or nitrogen compounds, and from molecular weight regulator (ketone or aliphatic aldehyde, ).
  • the copolymers may for example be prepared in a tubular reactor according to the process described in US 6,509,424 .
  • hydrocarbon-based compositions in which the copolymers according to the invention are incorporated are chosen from all types of fuel oils or fuels, such as diesel fuels, heating oil for heating installations (FOD), kerosene, aviation fuel oil, fuel oil. heavy, etc.
  • fuel oils or fuels such as diesel fuels, heating oil for heating installations (FOD), kerosene, aviation fuel oil, fuel oil. heavy, etc.
  • the sulfur content of the hydrocarbon compositions is less than 5000 ppm, preferably less than 500 ppm, and more preferably less than 50 ppm, or even less than 10 ppm and advantageous without sulfur.
  • the hydrocarbon-based compositions comprise middle distillates having a boiling point of between 100 and 500 ° C .; their starting crystallization temperature Tcc is often greater than or equal to -20 ° C, generally between -15 ° C and + 10 ° C.
  • These distillates may, for example, be chosen from distillates obtained by direct distillation of crude hydrocarbons, vacuum distillates, hydrotreated distillates, distillates obtained from catalytic cracking and / or hydrocracking of vacuum distillates, distillates resulting from conversion processes such as ARDS (by atmospheric residue desulphurisation) and / or visbreaking, distillates from the recovery of Fischer Tropsch cuts, distillates resulting from BTL (biomass to liquid) conversion of plant and / or animal biomass, taken alone or in combination and / or esters of vegetable and animal oils or mixtures thereof.
  • the hydrocarbon compositions may also contain distillates resulting from more complex refining operations than those resulting from the direct distillation of hydrocarbons which may for example be derived from cracking, hydrocracking and / or catalytic cracking processes and visbreaking processes.
  • These new fuel bases can be used alone or in combination with conventional middle oil distillates as fuel base and / or base of domestic fuel oil; they generally comprise long paraffinic chains greater than or equal to 10 carbon atoms and preferably C14 to C30.
  • copolymers as defined previously of Mw between 5,000 and 27,000 and Mn between 1,500 and 22,000, preferably Mw between 5,000 and 25,000 and Mn between 1,500 and 20,000 are particularly effective. when they are incorporated in light middle distillates and / or low sulfur (typically less than 50 ppm) and / or low initial crystallization temperature (typically up to - 20 ° C).
  • light middle distillates distillates whose n-paraffin content having 24 or more carbon atoms ranges from 0 to about less than 0.7% by weight of the total fuel composition; wherein the C18-C23 n-paraffins represent about 3 to about 5% of the total weight of the fuel and whose weight ratio of C18-C23 n-paraffins to paraffins C24 and higher is generally from 10 to 35.
  • Copolymers of Mw between 5,000 and 10,000 and Mn between 1,500 and 8,000, preferably Mw between 5,000 and 8,000 and Mn between 1,500 and 5,000 are particularly effective when they are incorporated in heavy middle distillates and / or at a rather high starting crystallization temperature (typically ranging from 0 to 15 ° C.).
  • Heavy middle distillates are distillates whose n-paraffin content with 24 or more carbon atoms ranges from about 0.7 to about 2% by weight of the total fuel composition; wherein the C18-C23 n-paraffins represent about 1 to about 10% of the total weight of the fuel and whose mass ratio of C18-C23 n-paraffins to C24 + paraffins is generally from 1 to 10.
  • copolymers may be added as such in the hydrocarbon compositions or, preferably, in the form of concentrated solutions, in particular solutions containing from 50 to 80%, preferably from 60 to 70% by weight of copolymer (s) in a mixture.
  • solvent such as aliphatic or aromatic hydrocarbons, alone or as a mixture (naphtha, kerosene, hydrocarbon fractions, such as solvent Solvesso, paraffinic hydrocarbons, such as pentane, hexane.
  • the hydrocarbon compositions comprise from 10 to 5000 ppm by weight of at least one copolymer described above, preferably from 100 to 1000 ppm, and advantageously from 150 to 500 ppm.
  • the hydrocarbon compositions may also contain one or more other additives different from the copolymers according to the invention, chosen from detergents, anti-corrosion agents, dispersants, demulsifiers, defoamers, biocides, deodorants, procetane additives, friction modifiers, lubricity additives or lubricity additives, combustion assistants (catalytic combustion promoters and soot) , cloud point improvers, pour point, filterability limit temperature, anti-settling agents, anti-wear agents and / or conductivity modifiers.
  • additives different from the copolymers according to the invention, chosen from detergents, anti-corrosion agents, dispersants, demulsifiers, defoamers, biocides, deodorants, procetane additives, friction modifiers, lubricity additives or lubricity additives, combustion assistants (catalytic combustion promoters and soot) , cloud point improvers, pour point, filterability limit temperature, anti-settling agents, anti-wear agents and
  • additives are generally added in an amount ranging from 100 to 1000 ppm (each).
  • the improved cold-strength additives according to the invention may be added to the hydrocarbon compositions within the refinery, and / or may be incorporated downstream of the refinery, optionally mixed with other additives, in the form of a package. or package of additives.
  • high-pressure radical polymerization (1400 to 2500 bar (140 to 250 MPa) and a polymerization temperature of 200 to 280 ° C. are synthesized by terpolymers of ethylene, vinyl acetate and The synthesis is carried out using an aliphatic aldehyde (propanal) to control the molecular weights and using peroxides as polymerization initiators
  • Mn are indicated.
  • GOM 1 and GOM 2 The ability to improve the cold strength of these terpolymers is evaluated by incorporating them into two distillates of the diesel engine type called GOM 1 and GOM 2, the characteristics of which are given in Table 2 below.
  • Table 2 Fuel Characteristics ASTM D86 Distillation GOM 1 GOM 2 T90-T20 (° C) 129.6 100.4 PF-T90 (° C) 19.5 24.9 T95 (° C) 353.5 362.4 Cloud point (° C) NF EN 23015 -6 -4 TLF (° C) EN 116 -6 -7 Pour point (° C) NF T 60105 -15 -10 Paraffin content (% mass) Chromatography 14.72 14.68 TCC (° C) IP 389 -6.2 -6.3 Sulfur content (ppm) EN ISO 20846 18.6 38
  • the terpolymer 17 according to the invention is the most effective on the GOM 1 gas oil. Moreover, from the results of Table 3, it can be seen that the terpolymer 17 added at the rate of 400 ppm in the GOM 1 does not degrade. the tendency to clogging. This is not the case of comparative terpolymers 6; 7; 16 and 18 according to WO 2005/054314 which greatly degrade the clogging tendency measured according to IP 387 and are not as effective in TLF as the additive 17 of the invention.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Combustion & Propulsion (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Liquid Carbonaceous Fuels (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Claims (12)

  1. Verwendung, als Additiv zur Erhöhung der Kälteresistenz und der Filtrierbarkeit von Kraftstoffen, mindestens eines Copolymers, umfassend:
    - von 81 bis 87 Mol-% mindestens eines alpha-Olefins,
    - von 10,5 bis weniger als 12 Mol-% mindestens eines Vinylesters,
    - von 1 bis 8,5 Mol-% mindestens eines alpha-beta-ungesättigten Monocarbonsäureesters, wobei das Copolymer in ein Viereck ABCD eingeschrieben wird, wobei A, B, C und D die Eckpunkte des Vierecks darstellen und Molprozentsätzen mindestens des Vinylesters und mindestens des alpha-beta-ungesättigten Monocarbonsäureesters entsprechen:
    A: 12 ; 1
    B: 12 ; 6
    C: 10,5 ; 4
    D: 10,5 ; 8,5.
  2. Verwendung, als Additiv zur Erhöhung der Kälteresistenz und der Filtrierbarkeit von Kraftstoffen, mindestens eines Copolymers nach Anspruch 1, das in ein Viereck A1BC1D eingeschrieben wird, wobei A1, B, C1 und D die Eckpunkte des Vierecks darstellen und Molprozentsätzen mindestens des Vinylesters und mindestens des alpha-beta-ungesättigten Monocarbonsäureesters entsprechen:
    A1: 12 ; 2
    B: 12 ; 6
    C1: 10,5 ; 5
    D: 10,5 ; 8,5.
  3. Verwendung, als Additiv zur Erhöhung der Kälteresistenz und der Filtrierbarkeit von Kraftstoffen, mindestens eines Copolymers nach einem der Ansprüche 1 oder 2,
    wobei das alpha-Olefin Ethylen ist, und/oder der Vinylester Vinylacetat ist, und/oder der alpha-beta-ungesättigte Monocarbonsäureester Ethyl-2-hexylacrylat ist.
  4. Verwendung nach einem der Ansprüche 1 bis 3 mindestens eines Terpolymers, umfassend von Ethylen stammende Einheiten, von Vinylacetat stammende Einheiten und von Ethyl-2-hexylacrylat stammende Einheiten.
  5. Verwendung nach einem der Ansprüche 1 bis 4 mindestens eines Copolymers mit einer Zahlen-Molmasse (Mw), gemessen durch GPC, zwischen 3 000 und 30 000, vorzugsweise 3 000 bis 20 000, und einer zahlenmittleren Molmasse (Mn), gemessen durch GPC, allgemein zwischen 1 000 und 20 000, vorzugsweise von 1 500 bis 15 000.
  6. Verwendung nach einem der Ansprüche 1 bis 5 mindestens eines Copolymers als Additiv zur Erhöhung der Kälteresistenz und der Filtrierbarkeit ohne Verschlechterung der Blockiertendenz von Mitteldestillaten, wie Dieselkraftstoffen, Heizöl für Heizinstallationen (FOD), Kerosin, Flugzeugkraftstoffen, Schwerölen.
  7. Verwendung nach einem der Ansprüche 1 bis 6 mindestens eines Copolymers als Additiv zur Erhöhung der Kälteresistenz und der Filtrierbarkeit von Kraftstoffen, deren Schwefelgehalt kleiner ist als 5 000 ppm, vorzugsweise kleiner als 500 ppm, bevorzugter kleiner als 50 ppm, sogar kleiner als 10 ppm, und vorteilhaft von Kraftstoffen ohne Schwefel.
  8. Kohlenwasserstoffzusammensetzung, umfassend eine mehrheitliche Menge eines Mitteldestillats mit einer Siedetemperatur von 100 bis 500°C und von 10 bis 5 000 ppm, bezogen auf das Gewicht, mindestens eines Copolymers, umfassend:
    - von 81 bis 87 Mol-% mindestens eines alpha-Olefins,
    - von 10,5 bis weniger als 12 Mol-% mindestens eines Vinylesters,
    - von 1 bis 8,5 Mol-% mindestens eines alpha-beta-ungesättigten Monocarbonsäureesters,
    wobei das Copolymer in ein Viereck ABCD eingeschrieben wird, wobei A, B, C und D die Eckpunkte des Vierecks darstellen und Molprozentsätzen mindestens des Vinylesters und mindestens des alpha-beta-ungesättigten Monocarbonsäureesters entsprechen:
    A: 12 ; 1
    B: 12 ; 6
    C: 10,5 ; 4
    D: 10,5 ; 8,5.
  9. Zusammensetzung nach Anspruch 8,
    dadurch gekennzeichnet, dass diese Biodiesel tierischen und/oder pflanzlichen Ursprungs enthält.
  10. Zusammensetzung nach Anspruch 8 oder 9,
    dadurch gekennzeichnet, dass diese ausgewählt ist aus Dieselkraftstoffen, Heizöl für Heizinstallationen (FOD), Kerosin, Flugzeugkraftstoffen, Schwerölen.
  11. Zusammensetzung nach einem der Ansprüche 8 bis 10,
    dadurch gekennzeichnet, dass diese 100 bis 1 000 ppm, bezogen auf das Gewicht, des Copolymers umfasst, vorzugsweise von 150 bis 500 ppm.
  12. Zusammensetzung nach einem der Ansprüche 8 bis 11,
    dadurch gekennzeichnet, dass diese ein oder mehrere andere Additive als die Copolymere gemäß der Erfindung umfasst, ausgewählt aus Detergenzien, Antikorrosionsmitteln, Dispergiermitteln, Demulgatoren, Antischaummitteln, Bioziden, Reodorantien, Cetanzahl-Verbesserern, Friktionsmodifikatoren, Schmieradditiven oder Schmierfähigkeitsadditiven, Verbrennungshilfsmitteln (katalytischen Verbrennungspromotoren und Ruß), Mitteln zur Verbesserung des Trübungspunkts, des Fließpunkts, der Grenztemperatur der Filtrierbarkeit, Antisedimentationsmitteln, Antiverschleißmitteln und/oder Leitfähigkeitsmodifikatoren.
EP10734559.7A 2009-07-03 2010-06-25 Terpolymer mit ethylen/vinylacetat/ungesättigten estern als zusatz für erhöhte kälteresistenz von flüssigen kohlenwasserstoffen wie mitteldestillate und brennstoffe Active EP2449063B2 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR0903278A FR2947558B1 (fr) 2009-07-03 2009-07-03 Terpolymere et ethylene/acetate de vinyle/esters insatures comme additif ameliorant la tenue a froid des hydrocarbures liquides comme les distillats moyens et les carburants ou combustibles
PCT/IB2010/052922 WO2011001352A1 (fr) 2009-07-03 2010-06-25 Terpolymere ethylene/acetate de vinyle/esters insatures comme additif ameliorant la tenue a froid des hydrocarbures liquides comme les distillats moyens et les carburants ou combustibles

Publications (3)

Publication Number Publication Date
EP2449063A1 EP2449063A1 (de) 2012-05-09
EP2449063B1 true EP2449063B1 (de) 2018-11-21
EP2449063B2 EP2449063B2 (de) 2021-07-28

Family

ID=41716191

Family Applications (1)

Application Number Title Priority Date Filing Date
EP10734559.7A Active EP2449063B2 (de) 2009-07-03 2010-06-25 Terpolymer mit ethylen/vinylacetat/ungesättigten estern als zusatz für erhöhte kälteresistenz von flüssigen kohlenwasserstoffen wie mitteldestillate und brennstoffe

Country Status (19)

Country Link
US (1) US20120102825A1 (de)
EP (1) EP2449063B2 (de)
JP (1) JP2012532225A (de)
KR (1) KR102002887B1 (de)
CN (1) CN102549120A (de)
AR (1) AR077631A1 (de)
AU (1) AU2010267626B2 (de)
BR (1) BRPI1016080B1 (de)
CA (1) CA2765245C (de)
CL (1) CL2011003342A1 (de)
EA (1) EA201270129A1 (de)
ES (1) ES2706903T5 (de)
FR (1) FR2947558B1 (de)
MX (1) MX363328B (de)
PT (1) PT2449063T (de)
SG (1) SG177381A1 (de)
TW (1) TWI496883B (de)
WO (1) WO2011001352A1 (de)
ZA (1) ZA201109307B (de)

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10356595A1 (de) * 2003-12-04 2005-06-30 Basf Ag Brennstoffölzusammensetzungen mit verbesserten Kaltfließeigenschaften
FR2925916B1 (fr) * 2007-12-28 2010-11-12 Total France Terpolymere ethylene/acetate de vinyle/esters insatures comme additif ameliorant la tenue a froid des hydrocarbures liquides comme les distillats moyens et les carburants ou combustibles
CN103370400B (zh) * 2011-03-25 2016-12-14 赢创油品添加剂有限公司 用于改进燃料油氧化稳定性的组合物
FR2987052B1 (fr) 2012-02-17 2014-09-12 Total Raffinage Marketing Additifs ameliorant la resistance a l'usure et au lacquering de carburants de type gazole ou biogazole
FR3005061B1 (fr) 2013-04-25 2016-05-06 Total Raffinage Marketing Additif pour ameliorer la stabilite a l'oxydation et/ou au stockage de carburants ou combustibles hydrocarbones liquides
AR100387A1 (es) * 2014-02-18 2016-10-05 Basf Se Copolímeros que comprenden etileno, ésteres de vinilo y ésteres de ácido (met)acrílico, sus formulaciones y usos como depresor del punto de fluidez, inhibidor de cera y potenciador de flujo para petróleos crudos
TWI576384B (zh) * 2014-11-25 2017-04-01 鴻明環保科技股份有限公司 高植物源含量之乙烯-醋酸乙烯共聚物混合物發泡材料、其製造方法及應用
CN105733712B (zh) * 2014-12-08 2017-12-05 中国石油天然气股份有限公司 用于航空生物燃料的润滑减磨添加剂
JP7585615B2 (ja) * 2019-03-25 2024-11-19 東ソー株式会社 樹脂組成物および蓋材用フィルム
FR3113063B1 (fr) 2020-07-31 2022-08-12 Total Marketing Services Utilisation de copolymères à distribution de masse molaire spécifique pour abaisser la température limite de filtrabilité de carburants ou de combustibles

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0922716A1 (de) 1997-12-09 1999-06-16 Clariant GmbH Verfahren zur Herstellung von Ethylen-Terpolymeren und deren Verwendung als Zusatz zu Mineralöl und Mineralöldestillaten
EP0931825A2 (de) 1998-01-24 1999-07-28 Clariant GmbH Verfahren zur Verbesserung der Kaltfliesseigenschaften von Brennstoffölen
EP0931824A2 (de) 1998-01-24 1999-07-28 Clariant GmbH Verfahren zur Verbesserung der Kaltfliesseigenschaften von Brennstoffölen
EP1391498A1 (de) 2001-05-08 2004-02-25 Sanyo Chemical Industries, Ltd. Fliessfähigkeitsverbesserer und brennölzusammensetzung
WO2005054314A2 (de) 2003-12-04 2005-06-16 Basf Aktiengesellschaft Brennstoffölzusammensetzungen mit verbesserten kaltfliesseigenschaften
WO2008059055A1 (de) 2006-11-17 2008-05-22 Basf Se Kaltfliessverbesserer
WO2009106744A2 (fr) 2007-12-28 2009-09-03 Total Raffinage Marketing Terpolymere ethylene/acetate de vinyle /esters insatures comme additif ameliorant la tenue a froid des hydrocarbures liquides comme les distillats moyens et les carburants ou combustibles

Family Cites Families (40)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3048479A (en) 1959-08-03 1962-08-07 Exxon Research Engineering Co Ethylene-vinyl ester pour depressant for middle distillates
US3627838A (en) 1964-12-11 1971-12-14 Exxon Research Engineering Co Process for manufacturing potent pour depressants
US3642459A (en) 1968-04-01 1972-02-15 Exxon Research Engineering Co Copolymers of ethylene with unsaturated esters and oil compositions containing said copolymers
US3790359A (en) 1969-03-17 1974-02-05 Exxon Research Engineering Co Middle distillate fuel having increased low temperature flowability
CA1000501A (en) 1972-06-21 1976-11-30 Levi C. Parker Low pour point fuel compositions
US3999960A (en) 1972-08-30 1976-12-28 Exxon Research And Engineering Company Wax crystal modifiers for petroleum oils
US3961961A (en) 1972-11-20 1976-06-08 Minnesota Mining And Manufacturing Company Positive or negative developable photosensitive composition
DE2960183D1 (en) 1978-07-26 1981-04-02 Basf Ag Middle distillates of petroleum, suitable as diesel fuel or as light heating oil, and with improved filtration properties
FR2490669A1 (fr) 1980-09-19 1982-03-26 Elf France Nouvelles compositions d'additifs permettant l'amelioration de la temperature limite de filtrabilite et l'inhibition simultanee des cristaux de n-paraffines formes lors du stockage a basse temperature des distillats moyens
FR2510598A1 (fr) 1981-07-30 1983-02-04 Inst Francais Du Petrole Utilisation d'additifs azotes comme agents d'abaissement du point de trouble des distillats moyens d'hydrocarbures et compositions de distillats moyens d'hydrocarbures renfermant lesdits additifs
FR2528066A1 (fr) 1982-06-04 1983-12-09 Inst Francais Du Petrole Additifs azotes utilisables comme agents d'abaissement du point de trouble des distillats moyens d'hydrocarbures et compositions de distillats moyens d'hydrocarbures renfermant lesdits additifs
FR2528051B1 (fr) 1982-06-08 1986-05-02 Inst Francais Du Petrole Additifs azotes utilisables comme agents d'abaissement du point de trouble des distillats moyens d'hydrocarbures et compositions de distillats moyens d'hydrocarbures renfermant lesdits additifs
FR2528423B1 (fr) 1982-06-10 1987-07-24 Inst Francais Du Petrole Additifs azotes utilisables comme agents d'abaissement du point de trouble des distillats moyens d'hydrocarbures et compositions de distillats moyens d'hydrocarbures renfermant lesdits additifs
FR2535723A1 (fr) 1982-11-09 1984-05-11 Inst Francais Du Petrole Additifs azotes utilisables comme agents d'abaissement du point de trouble des distillats moyens d'hydrocarbures et compositions de distillats moyens d'hydrocarbures renfermant lesdits additifs
FR2567536B1 (fr) 1984-07-10 1986-12-26 Inst Francais Du Petrole Compositions d'additifs destinees notamment a ameliorer les proprietes de filtrabilite a froid des distillats moyens de petrole
US4755189A (en) 1984-12-12 1988-07-05 Exxon Research And Engineering Company Middle distillate fuel having improved low temperature flow properties
EP0261959B1 (de) 1986-09-24 1995-07-12 Exxon Chemical Patents Inc. Brennstoffezusätze
IN184481B (de) 1986-09-24 2000-08-26 Exxon Chemical Patents Inc
FR2607139B1 (fr) 1986-11-21 1989-08-18 Inst Francais Du Petrole Polymeres a fonctions azotees derives de polyesters insatures et leur utilisation comme additifs d'abaissement du point d'ecoulement des distillats moyens d'hydrocarbures
FR2613371B1 (fr) 1987-04-01 1989-07-07 Inst Francais Du Petrole Copolymeres azotes, leur preparation et leur utilisation comme additifs pour ameliorer les proprietes d'ecoulement des distillats moyens d'hydrocarbures
FR2626578B1 (fr) 1988-02-03 1992-02-21 Inst Francais Du Petrole Polymeres amino-substitues et leur utilisation comme additifs de modification des proprietes a froid de distillats moyens d'hydrocarbures
GB9104138D0 (en) 1991-02-27 1991-04-17 Exxon Chemical Patents Inc Polymeric additives
FR2676062B1 (fr) 1991-05-02 1993-08-20 Inst Francais Du Petrole Polymere amino-substitues et leur utilisation comme additifs de modification des proprietes a froid de distillats moyens d'hydrocarbures.
GB9200694D0 (en) 1992-01-14 1992-03-11 Exxon Chemical Patents Inc Additives and fuel compositions
GB9219962D0 (en) 1992-09-22 1992-11-04 Exxon Chemical Patents Inc Additives for organic liquids
DE69309842T2 (de) 1992-10-09 1997-10-16 Elf Antar France Aminephosphate mit einem Imid Endring, deren Herstellung, und deren Verwendung als Zusätze für Motorkraftstoffe
FR2699550B1 (fr) 1992-12-17 1995-01-27 Inst Francais Du Petrole Composition de distillat moyen de pétrole contenant des additifs azotés utilisables comme agents limitant la vitesse de sédimentation des paraffines.
GB9301119D0 (en) 1993-01-21 1993-03-10 Exxon Chemical Patents Inc Fuel composition
GB9315205D0 (en) 1993-07-22 1993-09-08 Exxon Chemical Patents Inc Additives and fuel compositions
FR2735494B1 (fr) 1995-06-13 1997-10-10 Elf Antar France Additif bifonctionnel de tenue a froid et composition de carburant
FR2751982B1 (fr) 1996-07-31 2000-03-03 Elf Antar France Additif d'onctuosite pour carburant moteurs et composition de carburants
FR2753455B1 (fr) 1996-09-18 1998-12-24 Elf Antar France Additif detergent et anti-corrosion pour carburants et composition de carburants
DE59708189D1 (de) 1997-01-07 2002-10-17 Clariant Gmbh Verbesserung der Fliessfähigkeit von Mineralölen und Mineralöldestillaten unter Verwendung von Alkylphenol-Aldehydharzen
JPH10237467A (ja) 1997-02-26 1998-09-08 Tonen Corp ディーゼルエンジン用燃料油組成物
US5730029A (en) 1997-02-26 1998-03-24 The Lubrizol Corporation Esters derived from vegetable oils used as additives for fuels
FR2772784B1 (fr) 1997-12-24 2004-09-10 Elf Antar France Additif d'onctuosite pour carburant
FR2772783A1 (fr) 1997-12-24 1999-06-25 Elf Antar France Additif d'onctuosite pour carburant
DE10324101A1 (de) * 2003-05-27 2005-01-05 Basf Ag Brennstoffzusammensetzungen mit verbesserten Kaltfließeigenschaften
US20050223631A1 (en) 2004-04-07 2005-10-13 Graham Jackson Fuel oil compositions
US20070094920A1 (en) * 2004-12-03 2007-05-03 Basf Aktiengesellschaft Fuel oil compositions with improved cold flow properties

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0922716A1 (de) 1997-12-09 1999-06-16 Clariant GmbH Verfahren zur Herstellung von Ethylen-Terpolymeren und deren Verwendung als Zusatz zu Mineralöl und Mineralöldestillaten
EP0931825A2 (de) 1998-01-24 1999-07-28 Clariant GmbH Verfahren zur Verbesserung der Kaltfliesseigenschaften von Brennstoffölen
EP0931824A2 (de) 1998-01-24 1999-07-28 Clariant GmbH Verfahren zur Verbesserung der Kaltfliesseigenschaften von Brennstoffölen
EP1391498A1 (de) 2001-05-08 2004-02-25 Sanyo Chemical Industries, Ltd. Fliessfähigkeitsverbesserer und brennölzusammensetzung
WO2005054314A2 (de) 2003-12-04 2005-06-16 Basf Aktiengesellschaft Brennstoffölzusammensetzungen mit verbesserten kaltfliesseigenschaften
WO2008059055A1 (de) 2006-11-17 2008-05-22 Basf Se Kaltfliessverbesserer
WO2009106744A2 (fr) 2007-12-28 2009-09-03 Total Raffinage Marketing Terpolymere ethylene/acetate de vinyle /esters insatures comme additif ameliorant la tenue a froid des hydrocarbures liquides comme les distillats moyens et les carburants ou combustibles

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
"1H-NMR-Spektrum des 2-Butanons", UNIVERSITY OF COLORADO, XP055637506, Retrieved from the Internet <URL:http://www.orgchemboulder.com/Spectroscopy/nmrtheory/integ1H.shtml>
ENERGY INSTITUTE: "Determination of filter blocking tendency", ERRATA FOR IP 387/14 ASTM D20-68-10, UK, pages 1 - 12
TAMSON INSTRUMENTS: "User manual Tamson Filter Blocking Tendency (TFBT)", TFBT MAN REV 2.03, 2019, pages 1 - 43, XP055637519, Retrieved from the Internet <URL:https://tamson-instruments.com/media/pdf/tfbt%20man.pdf>

Also Published As

Publication number Publication date
CA2765245A1 (fr) 2011-01-06
BRPI1016080A2 (pt) 2016-05-10
KR20120040161A (ko) 2012-04-26
CN102549120A (zh) 2012-07-04
ES2706903T3 (es) 2019-04-01
TW201116617A (en) 2011-05-16
FR2947558B1 (fr) 2011-08-19
EP2449063B2 (de) 2021-07-28
SG177381A1 (en) 2012-02-28
TWI496883B (zh) 2015-08-21
EA201270129A1 (ru) 2012-05-30
EP2449063A1 (de) 2012-05-09
ZA201109307B (en) 2012-09-26
CL2011003342A1 (es) 2012-07-06
WO2011001352A1 (fr) 2011-01-06
MX363328B (es) 2019-03-20
PT2449063T (pt) 2019-02-04
US20120102825A1 (en) 2012-05-03
FR2947558A1 (fr) 2011-01-07
CA2765245C (fr) 2017-07-25
ES2706903T5 (es) 2021-12-14
AU2010267626A1 (en) 2012-02-02
BRPI1016080B1 (pt) 2018-10-16
AR077631A1 (es) 2011-09-14
KR102002887B1 (ko) 2019-07-23
AU2010267626B2 (en) 2016-05-12
MX2012000172A (es) 2012-02-28
JP2012532225A (ja) 2012-12-13

Similar Documents

Publication Publication Date Title
EP2238225B1 (de) Terpolymer von ethylen, vinylacetat und ungesättigten estern als additiv zur verbesserung der tieftemperaturbeständigkeit von flüssigen kohlenwasserstoffen
EP2449063B1 (de) Terpolymer mit ethylen/vinylacetat/ungesättigten estern als zusatz für erhöhte kälteresistenz von flüssigen kohlenwasserstoffen wie mitteldestillate und brennstoffe
EP2231728B1 (de) Verwendung von pfropfmodifizierten copolymeren aus ethylen und/oder propylen und vinylestern als bifunktionelle schmierfähige und kältebeständige zusätze für flüssige kohlenwasserstoffe
EP2049625B1 (de) Verwendung von effizienzanzeigenden verbindungen aus filterbarkeitszusätzen in kohlenwasserstoffdestillaten und brennstoffzusammensetzung damit
EP3844251B1 (de) Zusammensetzung von additiven mit mindestens einem copolymer, einem kaltfliessverbesserer und einem antiabsetzadditiv
EP4189048B1 (de) Verwendung von copolymeren mit spezifischer molmassenverteilung zur senkung des kaltfilter-stopfenpunktes von kraftstoffen
WO2024084136A1 (fr) Composition de carburant marin a basse teneur en soufre
EP3844250A1 (de) Verwendung spezieller copolymere zur verbesserung der kälteeigenschaften von kraftstoffen oder brennstoffen

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

17P Request for examination filed

Effective date: 20120109

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO SE SI SK SM TR

DAX Request for extension of the european patent (deleted)
RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: TOTAL MARKETING SERVICES

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

Free format text: STATUS: EXAMINATION IS IN PROGRESS

17Q First examination report despatched

Effective date: 20170411

REG Reference to a national code

Ref country code: DE

Ref legal event code: R079

Ref document number: 602010055257

Country of ref document: DE

Free format text: PREVIOUS MAIN CLASS: C10L0001180000

Ipc: C10L0010140000

RIC1 Information provided on ipc code assigned before grant

Ipc: C10L 1/16 20060101ALI20180425BHEP

Ipc: C10L 1/197 20060101ALI20180425BHEP

Ipc: C10L 1/14 20060101ALI20180425BHEP

Ipc: C10L 10/14 20060101AFI20180425BHEP

Ipc: C10L 10/16 20060101ALI20180425BHEP

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

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

Free format text: STATUS: GRANT OF PATENT IS INTENDED

INTG Intention to grant announced

Effective date: 20180606

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAJ Information related to disapproval of communication of intention to grant by the applicant or resumption of examination proceedings by the epo deleted

Free format text: ORIGINAL CODE: EPIDOSDIGR1

GRAL Information related to payment of fee for publishing/printing deleted

Free format text: ORIGINAL CODE: EPIDOSDIGR3

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

Free format text: STATUS: EXAMINATION IS IN PROGRESS

INTC Intention to grant announced (deleted)
GRAR Information related to intention to grant a patent recorded

Free format text: ORIGINAL CODE: EPIDOSNIGR71

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

Free format text: STATUS: GRANT OF PATENT IS INTENDED

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

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

Free format text: STATUS: THE PATENT HAS BEEN GRANTED

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO SE SI SK SM TR

INTG Intention to grant announced

Effective date: 20181012

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

Free format text: LANGUAGE OF EP DOCUMENT: FRENCH

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 602010055257

Country of ref document: DE

REG Reference to a national code

Ref country code: AT

Ref legal event code: REF

Ref document number: 1067522

Country of ref document: AT

Kind code of ref document: T

Effective date: 20181215

REG Reference to a national code

Ref country code: PT

Ref legal event code: SC4A

Ref document number: 2449063

Country of ref document: PT

Date of ref document: 20190204

Kind code of ref document: T

Free format text: AVAILABILITY OF NATIONAL TRANSLATION

Effective date: 20190125

REG Reference to a national code

Ref country code: NL

Ref legal event code: FP

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2706903

Country of ref document: ES

Kind code of ref document: T3

Effective date: 20190401

REG Reference to a national code

Ref country code: AT

Ref legal event code: MK05

Ref document number: 1067522

Country of ref document: AT

Kind code of ref document: T

Effective date: 20181121

REG Reference to a national code

Ref country code: GR

Ref legal event code: EP

Ref document number: 20190400144

Country of ref document: GR

Effective date: 20190422

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

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190321

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20181121

Ref country code: NO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190221

Ref country code: HR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20181121

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20181121

Ref country code: AT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20181121

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20181121

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

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20181121

Ref country code: AL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20181121

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

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20181121

Ref country code: PL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20181121

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

Ref country code: IE

Payment date: 20190610

Year of fee payment: 10

REG Reference to a national code

Ref country code: DE

Ref legal event code: R026

Ref document number: 602010055257

Country of ref document: DE

PLBI Opposition filed

Free format text: ORIGINAL CODE: 0009260

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

Ref country code: SM

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20181121

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20181121

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20181121

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20181121

PLAX Notice of opposition and request to file observation + time limit sent

Free format text: ORIGINAL CODE: EPIDOSNOBS2

26 Opposition filed

Opponent name: BASF SE

Effective date: 20190820

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

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20181121

PLBB Reply of patent proprietor to notice(s) of opposition received

Free format text: ORIGINAL CODE: EPIDOSNOBS3

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

Ref country code: MC

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20181121

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

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

Ref country code: TR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20181121

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

Ref country code: IE

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

Effective date: 20190625

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

Ref country code: LU

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

Effective date: 20190625

Ref country code: CH

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

Effective date: 20190630

Ref country code: LI

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

Effective date: 20190630

PLBP Opposition withdrawn

Free format text: ORIGINAL CODE: 0009264

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

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20181121

PUAH Patent maintained in amended form

Free format text: ORIGINAL CODE: 0009272

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

Free format text: STATUS: PATENT MAINTAINED AS AMENDED

27A Patent maintained in amended form

Effective date: 20210728

AK Designated contracting states

Kind code of ref document: B2

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO SE SI SK SM TR

REG Reference to a national code

Ref country code: DE

Ref legal event code: R102

Ref document number: 602010055257

Country of ref document: DE

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

Ref country code: HU

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT; INVALID AB INITIO

Effective date: 20100625

Ref country code: MT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20181121

REG Reference to a national code

Ref country code: NL

Ref legal event code: FP

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

Ref country code: IT

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

Effective date: 20200625

REG Reference to a national code

Ref country code: GR

Ref legal event code: EP

Ref document number: 20210402170

Country of ref document: GR

Effective date: 20211013

REG Reference to a national code

Ref country code: ES

Ref legal event code: DC2A

Ref document number: 2706903

Country of ref document: ES

Kind code of ref document: T5

Effective date: 20211214

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

Ref country code: MK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20181121

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

Effective date: 20230523

REG Reference to a national code

Ref country code: BE

Ref legal event code: PD

Owner name: TOTALENERGIES ONETECH; FR

Free format text: DETAILS ASSIGNMENT: CHANGE OF OWNER(S), OTHER; FORMER OWNER NAME: TOTALENERGIES MARKETING SERVICES

Effective date: 20240423

Ref country code: BE

Ref legal event code: HC

Owner name: TOTALENERGIES MARKETING SERVICES; FR

Free format text: DETAILS ASSIGNMENT: CHANGE OF OWNER(S), CHANGE OF OWNER(S) NAME; FORMER OWNER NAME: TOTAL MARKETING SERVICES

Effective date: 20240423

REG Reference to a national code

Ref country code: DE

Ref legal event code: R081

Ref document number: 602010055257

Country of ref document: DE

Owner name: TOTALENERGIES ONETECH, FR

Free format text: FORMER OWNER: TOTAL MARKETING SERVICES, PUTEAUX, FR

REG Reference to a national code

Ref country code: NL

Ref legal event code: PD

Owner name: TOTALENERGIES ONETECH; FR

Free format text: DETAILS ASSIGNMENT: CHANGE OF OWNER(S), ASSIGNMENT; FORMER OWNER NAME: TOTALENERGIES MARKETING SERVICES

Effective date: 20240926

Ref country code: NL

Ref legal event code: HC

Owner name: TOTALENERGIES MARKETING SERVICES; FR

Free format text: DETAILS ASSIGNMENT: CHANGE OF OWNER(S), CHANGE OF OWNER(S) NAME; FORMER OWNER NAME: TOTAL MARKETING SERVICES

Effective date: 20240926

REG Reference to a national code

Ref country code: ES

Ref legal event code: PC2A

Owner name: TOTALENERGIES ONETECH

Effective date: 20250210

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

Ref country code: DE

Payment date: 20250618

Year of fee payment: 16

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

Ref country code: GB

Payment date: 20250618

Year of fee payment: 16

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

Ref country code: NL

Payment date: 20250618

Year of fee payment: 16

Ref country code: BE

Payment date: 20250618

Year of fee payment: 16

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

Ref country code: PT

Payment date: 20250612

Year of fee payment: 16

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

Ref country code: FR

Payment date: 20250624

Year of fee payment: 16

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

Ref country code: GR

Payment date: 20250620

Year of fee payment: 16

Ref country code: BG

Payment date: 20250619

Year of fee payment: 16

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

Ref country code: CZ

Payment date: 20250617

Year of fee payment: 16

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

Ref country code: ES

Payment date: 20250728

Year of fee payment: 16