EP1874899A1 - Compositions de carburants pour turbines a meilleures aptitudes au froid - Google Patents

Compositions de carburants pour turbines a meilleures aptitudes au froid

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Publication number
EP1874899A1
EP1874899A1 EP06724319A EP06724319A EP1874899A1 EP 1874899 A1 EP1874899 A1 EP 1874899A1 EP 06724319 A EP06724319 A EP 06724319A EP 06724319 A EP06724319 A EP 06724319A EP 1874899 A1 EP1874899 A1 EP 1874899A1
Authority
EP
European Patent Office
Prior art keywords
alkyl
hydrocarbyl
use according
polymer
acid
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.)
Withdrawn
Application number
EP06724319A
Other languages
German (de)
English (en)
Inventor
Wolfgang Ahlers
Frank-Olaf Mähling
Thomas Pfeiffer
Dietmar Posselt
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.)
BASF SE
Original Assignee
BASF SE
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Filing date
Publication date
Priority claimed from EP05008420A external-priority patent/EP1715027A1/fr
Priority claimed from EP05021172A external-priority patent/EP1770150A1/fr
Application filed by BASF SE filed Critical BASF SE
Priority to EP06724319A priority Critical patent/EP1874899A1/fr
Publication of EP1874899A1 publication Critical patent/EP1874899A1/fr
Withdrawn legal-status Critical Current

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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, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • 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, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • 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
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • 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, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • 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, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L2270/00—Specifically adapted fuels
    • C10L2270/04—Specifically adapted fuels for turbines, planes, power generation

Definitions

  • the invention relates to the use of polymers which comprise an ⁇ -olefin, an ester of an ⁇ , ⁇ -unsaturated carboxylic acid and optionally an alkenyl ester of a carboxylic acid in copolymerized form, as an additive for turbine fuels and in particular as a cold flow improver for turbine fuels; the turbine fuels added to these polymers; and additive packages containing such copolymers.
  • Turbine fuels also referred to as jet fuels, jet fuels, jet fuel, aviation fuel or turbo fuel, must meet high demands on their cold properties due to their use in aviation and the associated temperature conditions.
  • the freezing point of the turbine fuel must be low enough not to affect fuel flow at high temperature conditions, and to pass fuel filters easily.
  • the freezing point is the temperature at which the hydrocarbon crystals previously formed and precipitated by cooling dissolve completely again.
  • the freezing point is the temperature at which the hydrocarbon crystals previously formed and precipitated by cooling dissolve completely again.
  • the freezing point If the freezing point falls below, longer-chain paraffins crystallize out and form large, platelet-shaped wax crystals.
  • These wax crystals have a sponge-like structure and lead to the inclusion of other fuel constituents in the crystal composite.
  • the appearance of these crystals causes the fuel to pass through small openings and filters only slowly.
  • the viscosity of the fuel increases, whereby the fuel flow is deteriorated.
  • PP pour point
  • EP-A-1357168 describes a turbine fuel composition containing, in addition to a turbine fuel, at least one of the following additives: copolymers of ethylene with at least one unsaturated ester selected from vinyl esters of at least 5 carbon atoms, alkyl (meth) acrylates, dialkyl fumarates and dials - cylmaleates; Ethylene / alkene copolymers; Ethylene / vinyl acetate copolymers with less as 15 mole percent vinyl acetate; nucleators; waxes; Alkylphenol / formaldehyde condensates; Comb polymers; and organic nitrogen compounds.
  • additives are intended to ensure that turbine fuels additized thereby remain fluid even below the freezing point specified in their specification.
  • WO 01/62874 describes a composition which, in addition to a turbine fuel, contains additives which are selected from the reaction products of alkanolamines with long-chain substituted acylating agents; Phenol / aldehyde condensates; special aromatic systems; and ethylene / vinyl acetate copolymers. These additives are intended to lower the freezing point of the turbine fuel additized thereby.
  • a first aspect of the invention accordingly relates to the use of a polymer which comprises an ⁇ -olefin, an ester of an ⁇ , ⁇ -unsaturated carboxylic acid and optionally an alkenyl ester of a carboxylic acid in copolymerized form as an additive for turbine fuels.
  • those polymers are used which contain in copolymerized form the ester of the ⁇ , ⁇ -unsaturated carboxylic acid and the optionally present alkenyl ester in random distribution.
  • the polymer is a binary polymer composed essentially of the ⁇ -olefin and the ester of an ⁇ , ⁇ -unsaturated carboxylic acid, or it Alternatively, it is preferably a terpolymer, which is composed essentially of the three aforementioned monomers.
  • R 1 is H or C 1 -C 40 hydrocarbyl
  • R 2 , R 3 and R 4 are independently H or C 1 -C 4 alkyl
  • R 5 is C r C 2 o hydrocarbyl
  • R 6 , R 7 and R 8 are independently H or C 1 -C 4 alkyl
  • R 9 is d-Cig hydrocarbyl.
  • C r C 40 -hydrocarbyl is a hydrocarbon radical having 1 to 40 carbon atoms. It is preferably an aliphatic hydrocarbon radical, such as Alkyl, alkenyl, alkadienyl or alkynyl.
  • C r C 4 o-hydrocarbyl is C 1 -C 40 -alkyl.
  • a CrC o-Alkyl is a linear or branched alkyl radical having 1 to 40 carbon atoms.
  • Examples of these are methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, neopentyl, hexyl, heptyl, octyl, 2-ethylhexyl, neooctyl, nonyl, neononyl, decyl, 2 -Propylheptyl, neodecyl, undecyl, neoundecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nona-decyl, eicosyl, hencosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hex
  • C-C 2 o-hydrocarbyl radicals that is atoms by a hydrocarbon radical having 1 to 20 carbon. It is preferably an aliphatic hydrocarbon radical, such as alkyl, alkenyl, alkadienyl or alkynyl.
  • C 1 -C 20 hydrocarbyl stands for CrC ⁇ o-alkyl.
  • CrC ⁇ o-alkyl represents a linear or branched alkyl radical having 1 to 20 carbon atoms.
  • Examples of these are methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, neopentyl, hexyl, heptyl, octyl, 2-ethylhexyl, neooctyl, nonyl, neononyl, decyl, 2 -Propylheptyl, neodecyl, undecyl, neoundecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl and their constitutional isomers.
  • Ci-Cig-hydrocarbyl is a hydrocarbon radical having 1 to 19 carbon atoms. It is preferably an aliphatic hydrocarbon radical, such as alkyl, alkenyl, alkadienyl or alkynyl.
  • Crdg hydrocarbyl is C 1 -C 19 alkyl.
  • C 1 -C 19 -alkyl is a linear or branched alkyl radical having 1 to 19 carbon atoms.
  • Examples of these are methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, neopentyl, hexyl, heptyl, octyl, 2-ethylhexyl, neooctyl, nonyl, neononyl, decyl, 2 -Propylheptyl, neodecyl, undecyl, neoundecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl and their constitutional isomers.
  • CrC 10 -hydrocarbyl is a hydrocarbon radical having 1 to 10 carbon atoms. It is preferably an aliphatic hydrocarbon radical, such as alkyl, alkenyl, alkadienyl or alkynyl.
  • Crdo-hydrocarbyl is C 1 -C 10 -alkyl.
  • C 1 -C 10 -alkyl represents a linear or branched alkyl radical having 1 to 10 carbon atoms.
  • d-Cg-hydrocarbyl is a hydrocarbon radical having 1 to 9 carbon atoms.
  • CVCg hydrocarbyl is C r C 9 alkyl.
  • d-Cg-alkyl is a linear or branched alkyl radical having 1 to 9 carbon atoms.
  • Examples of these are methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, neopentyl, hexyl, heptyl, octyl, 2-ethylhexyl, neo-octyl, nylan, neononyl and the like constitutional isomers.
  • Cs-C 16 -hydrocarbyl is a hydrocarbon radical having 5 to 16 carbon atoms. It is preferably an aliphatic hydrocarbon radical, such as alkyl, alkenyl, alkadienyl or alkynyl. In particular C 5 -C 6 is hydrocarbyl for C 5 - C 16 alkyl.
  • C 5 -C 16 -alkyl represents a linear or branched alkyl radical having 5 to 16 carbon atoms.
  • Examples of these are pentyl, neopentyl, isopentyl, hexyl, isohexyl, heptyl, octyl, 2-ethylhexyl, neooctyl, nonyl, neononyl, isononyl, decyl, 2-propylheptyl, neodecyl, undecyl, neoundecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl and their constituent isomers.
  • C 8 -C 12 -hydrocarbyl is a hydrocarbon radical having 8 to 12 carbon atoms. It is preferably an aliphatic hydrocarbon radical, such as alkyl, alkenyl, alkadienyl or alkynyl. In particular C 8 -C 2 is hydrocarbyl for C 8 - C 12 alkyl.
  • C 8 -C 12 alkyl represents a linear or branched alkyl radical having 8 to 12 carbon atoms.
  • Examples of these are octyl, 2-ethylhexyl, neooctyl, nonyl, neononyl, isononyl, decyl, 2-propylheptyl, neodecyl, undecyl, neoundecyl, dodecyl and their constituent isomers.
  • C 8 -C 14 -hydrocarbyl is a hydrocarbon radical having 8 to 14 carbon atoms. It is preferably an aliphatic hydrocarbon radical, such as alkyl, alkenyl, alkadienyl or alkynyl.
  • C 8 -C 14 hydrocarbyl stands for C 8 - C 4 alkyl.
  • C 8 -C 14 alkyl represents a linear or branched alkyl radical having 8 to 14 carbon atoms. Examples of these are, in addition to the alkyl radicals mentioned above for C 8 -C 12 -alkyl, tridecyl and tetradecyl, and also their constituent isomers.
  • C 8 -C 16 -hydrocarbyl is a hydrocarbon radical having 8 to 16 carbon atoms. It is preferably an aliphatic hydrocarbon radical, such as alkyl, alkenyl, alkadienyl or alkynyl.
  • C 8 -C 16 hydrocarbyl stands for C 8 - C 6 alkyl.
  • C 8 -C 16 alkyl represents a linear or branched alkyl radical having 8 to 16 carbon atoms. Examples of these are, in addition to the alkyl radicals mentioned above for C 8 -C 14 -alkyl pentadecyl and hexadecyl and their constituent isomers.
  • C 8 -C 2 o hydrocarbyl represents a hydrocarbon radical having 8 to 20 carbon atoms. It is preferably an aliphatic hydrocarbon radical, such as alkyl, alkenyl, alkadienyl or alkynyl.
  • C 8 -C 20 hydrocarbyl stands for C 8 - C 20 alkyl.
  • C 8 -C 20 alkyl represents a linear or branched alkyl radical having 8 to 20 carbon atoms. Examples of these are, in addition to the alkyl radicals mentioned above for C 8 -C 6 -alkyl, heptadecyl, octadecyl, nonadecyl and eicosanyl, and also their constituent sisomers.
  • C 6 -C 14 -hydrocarbyl is a hydrocarbon radical having 6 to 14 carbon atoms. It is preferably an aliphatic hydrocarbon radical, such as alkyl, alkenyl, alkadienyl or alkynyl.
  • C 6 -C 14 hydrocarbyl is C 6 - C 14 alkyl.
  • C 6 -C 4 -alkyl is a linear or branched alkyl radical having 6 to 14 carbon atoms. Examples of these are, in addition to the alkyl radicals mentioned above for C 8 -C 4 -alkyl, hexyl and heptyl and also their constituent isomers.
  • C 6 -C 16 -hydrocarbyl is a hydrocarbon radical having 6 to 16 carbon atoms. It is preferably an aliphatic hydrocarbon radical, such as alkyl, alkenyl, alkadienyl or alkynyl.
  • C 6 -C 16 hydrocarbyl is C 6 - C 16 alkyl.
  • C 6 -C 16 -alkyl represents a linear or branched alkyl radical having 6 to 16 carbon atoms. Examples of these are, in addition to the alkyl radicals mentioned above for C 8 -C 16 -alkyl, hexyl and heptyl and also their constituent isomers.
  • C 6 -C 20 -hydrocarbyl is a hydrocarbon radical having 6 to 20 carbon atoms. It is preferably an aliphatic hydrocarbon radical, such as alkyl, alkenyl, alkadienyl or alkynyl.
  • C 6 -C 20 hydrocarbyl is C 6 - C 20 alkyl.
  • C 6 -C 20 -alkyl represents a linear or branched alkyl radical having 6 to 20 carbon atoms. Examples of these are, in addition to the alkyl radicals mentioned above for C 8 -C 20 -alkyl, hexyl and heptyl and also their constituent isomers.
  • C 5 -C 20 -hydrocarbyl is a hydrocarbon radical having 5 to 20 carbon atoms. It is preferably an aliphatic hydrocarbon radical, such as alkyl, alkenyl, alkadienyl or alkynyl.
  • C 5 -C 20 hydrocarbyl stands for C 5 - C 20 alkyl.
  • C 5 -C 20 -alkyl represents a linear or branched alkyl radical having 5 to 20 carbon atoms. Examples of these are, in addition to the alkyl radicals mentioned above for C 6 -C 20 -alkyl, pentyl and its constituent isomers.
  • C 4 -C 14 -hydrocarbyl is a hydrocarbon radical having 4 to 14 carbon atoms. It is preferably an aliphatic hydrocarbon radical, such as alkyl, alkenyl, alkadienyl or alkynyl.
  • C 4 -C 14 hydrocarbyl stands for C 4 - C 14 alkyl.
  • C 4 -C 4 -alkyl represents a linear or branched alkyl radical having 4 to 14 Carbon atoms. Examples of these are, in addition to the alkyl radicals mentioned above for C 6 -C 14 -alkyl, pentyl and its constituent isomers, and also n-butyl, sec-butyl, isobutyl and tert-butyl.
  • C 4 -C 16 -hydrocarbyl is a hydrocarbon radical having 4 to 16 carbon atoms. It is preferably an aliphatic hydrocarbon radical, such as alkyl, alkenyl, alkadienyl or alkynyl.
  • C 4 -C 16 hydrocarbyl stands for C 4 - Cie-alkyl.
  • C 4 -C 16 -alkyl represents a linear or branched alkyl radical having 4 to 16 carbon atoms. Examples thereof are, in addition to the alkyl radicals mentioned above for C 6 -C 16 -alkyl pentyl and its constituent isomers and n-butyl, sec-butyl, isobutyl and tert-butyl.
  • C 4 -C 2 o hydrocarbyl represents a hydrocarbon radical having 4 to 20 carbon atoms. It is preferably an aliphatic hydrocarbon radical, such as alkyl, alkenyl, alkadienyl or alkynyl. In particular, is C 4 -C 2 o hydrocarbyl is C 4 - C 2 o alkyl.
  • C 4 -C 2 o alkyl is a linear or branched alkyl radical having 4 to 20 carbon atoms. Examples of these are, in addition to the alkyl radicals mentioned above for C 5 -C 20 -alkyl, n-butyl, sec-butyl, isobutyl and tert-butyl.
  • C r C 4 -hydrocarbyl is a hydrocarbon radical having 1 to 4 carbon atoms. It is preferably an aliphatic hydrocarbon radical, such as alkyl, alkenyl, alkadienyl or alkynyl.
  • C r C 4 hydrocarbyl is C 1 -C 4 alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl and tert-butyl.
  • the hydrocarbyl radicals may be unsubstituted or monosubstituted or polysubstituted.
  • Suitable substituents are, for example, OH, C 1 -C 4 -alkoxy, NR 11 R 12 (R 11 and R 12 are each independently H or C 1 -C 4 -alkyl) or carbonyl (COR 11 ). Preferably, however, they are unsubstituted.
  • C 1 -C 4 -alkoxy is a C r C 4 -alkyl radical bonded via an oxygen atom. Examples of these are methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, 2-butoxy, isobutoxy and tert-butoxy.
  • C ⁇ C ⁇ AIkanol represents a C T C-alkyl radical which is substituted by 1 to 3 hydroxyl groups on different carbon atoms.
  • C 1 -C 4 -alkanol represents a C 1 -C 10 -alkyl radical which is substituted by 1 to 6 hydroxyl groups on different carbon atoms.
  • C 1 -C 20 -alkanol represents a C 1 -C 4 -alkyl radical substituted by 1 to 6 hydroxy groups on different carbon atoms.
  • C r C 40 -alkanol is a C 1 -C 4 -alkyl radical which is substituted by 1 to 6 hydroxyl groups on different carbon atoms.
  • CrC t -alkanols are methanol, ethanol, n- Propanol, isopropanol, n-butanol, sec-butanol, isobutanol, tert-butanol, ethylene glycol, propylene glycol and glycerol.
  • Cio alkanol is furthermore, for example, pentanol, hexanol, heptanol, octanol, 2-ethylhexanol, N ⁇ nanol, decanol, their constitutional isomers, and also for erythritol, pentaerythritol and sorbitol.
  • C 1 -C 20 -alkanol is, for example, undecanol, dodecanol, tridecanol, tetradecanol, pentadecanol, hexadecanol, heptadecanol, octadecanol, nona-decanol and eicosanol and also their constitutional isomers.
  • the monomers M1, M2 and M3 may be present in the polymer in the following molar proportions (Mx / (M1 + M2 + M3)):
  • M1 preferably 0.60 to 0.99
  • M2 preferably 0.01 to 0.40
  • M3 preferably 0 to 0.20.
  • M1 preferably 0.60 to 0.99, more preferably 0.7 to 0.95, especially 0.75 to 0.85; M2: preferably 0.01 to 0.6, particularly preferably 0.05 to 0.3, in particular 0.05 to 0.25.
  • M1 preferably 0.60 to 0.98, more preferably 0.7 to 0.95, especially 0.75 to 0.9;
  • M2 preferably 0.01 to 0.20, particularly preferably 0.01 to 0.17, in particular 0.015 to 0.16; M3: preferably 0.01 to 0.20, more preferably 0.02 to 0.15, especially 0.03 to 0.12, especially 0.03 to 0.11.
  • the monomers M1 are preferably monoalkenes having a terminal double bond, such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, their constitution isomers and the higher monounsaturated homologs with up to 40 carbon atoms.
  • R 1 is preferably H or C r C 2 o-hydrocarbyl, particularly preferably H or Ci-Cio-hydrocarbyl, and more preferably H or dC 4 - hydrocarbyl.
  • Hydrocarbyl is preferably alkyl.
  • R 1 is H, methyl or ethyl.
  • monomer M1 is in particular ethylene, propylene or 1-butene.
  • R 1 is H, ie M1 is specifically ethylene.
  • the radicals R 2 , R 3 and R 4 are preferably H or methyl. Particularly preferably, two of the radicals R 2 , R 3 and R 4 are H and the other radical is H or methyl. In particular, all three radicals R 2 , R 3 and R 4 are H.
  • the monomer M2 is preferably the esters of ⁇ , ⁇ -unsaturated carboxylic acids which are selected from acrylic acid, methacrylic acid, crotonic acid and isocrotonic acid, particularly preferably among acrylic acid and methacrylic acid and in particular acrylic acid.
  • Examples of such preferred ⁇ , ⁇ -unsaturated carboxylic acid esters M2 are: acrylic esters of CrC 2 o-alkanols, such as methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, acrylic acid n-pentyl ester, n-pentyl acrylate, isopropyl acrylate, hexyl acrylate, isohexyl acrylate, heptyl acrylate, octyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, acrylonyl acrylate, acrylonyl neonate, acrylic acid decyl ester, acrylic acid neodecyl ester, 2-propylheptyl acrylate, acrylic acid lauryl ester
  • R 5 is C 1 -C 2 o hydrocarbyl, preferably -C 2 -alkyl.
  • R 5 represents a hydrocarbyl radical having at least 5 carbon atoms, for example C 5 -C 20 -hydrocarbyl. 5 particularly preferably, R represents a hydrocarbyl radical having at least 6 carbon atoms, for example C 6 -C 2 o hydrocarbyl, preferably C 6 -C 16 - hydrocarbyl or particularly preferably C 6 -C 4 hydrocarbyl. In particular, R 5 is a hydrocarbyl radical having at least 8 carbon atoms, for example C 8 -C 20 -
  • Hydrocarbyl preferably C 8 -C 16 hydrocarbyl and more preferably C 8 -C 14 hydrocarbyl.
  • R 5 is C 8 -C 12 hydrocarbyl.
  • Hydrocarbyl is preferably alkyl.
  • R 5 is preferably an alkyl radical having at least 5 carbon atoms, for example C 5 -C 20 -alkyl.
  • R 5 is an alkyl radical having at least 6 carbon atoms, for example C 6 -C 20 -alkyl, preferably C 6 -C 16 -alkyl or particularly preferably C 6 -C 14 -alkyl.
  • R 5 is an alkyl radical having at least 8 carbon atoms, for example C 8 -C 20 -alkyl, preferably C 8 -C 16 -alkyl and particularly preferably C 8 -C 14 -alkyl. Specifically, R 5 is C 8 -C 12 alkyl.
  • R 5 is C 4 -C 20 -hydrocarbyl, for example C 4 -C 18 -hydrocarbyl or C 4 - C 16 -hydrocarbyl or C 4 -C 14 -hydrocarbyl or C 4 -C 12 -hydrocarbyl, particularly preferably C 5 -C 20 -hydrocarbyl, for example C 5 -C 18 -hydrocarbyl or C 5 -C 16 - Hydrocarbyl or C 5 -C 14 hydrocarbyl or C 5 -C 12 hydrocarbyl, more preferably C 6 -C 20 hydrocarbyl, eg C 6 -C 18 hydrocarbyl or C 6 -C 16 hydrocarbyl or C 6 - C 14 - hydrocarbyl or C 6 -C 12 hydrocarbyl, and in particular C 8
  • R 5 is C 8 -C 12 hydrocarbyl. Hydrocarbyl is preferably alkyl. Accordingly, in this case R 5 is preferably C 4 -C 20 -alkyl, for example C 4 -C 18 -alkyl or C 4 -C 16 -alkyl or C 4 -C 14 -alkyl or C 4 -C 12 -alkyl , particularly preferably for C 5 -C 20 -alkyl, for example for C 5 -C 18 -alkyl or C 5 -C 16 -alkyl or C 5 -C 14 -alkyl or C 5 -C 12 -alkyl, more preferably for C C 6 -C 20 -alkyl, for example C 6 -C 18 -alkyl or C 6 -C 16 -alkyl or C 6 -C 14 -alkyl or C 6 -C 12 -alkyl, and in particular C 8 -C 20 - Alkyl, for example for C 4
  • Preferred alkyl radicals R 5 are independent of their chain length and independently of DA, whether the polymer is an alkenyl ester, especially the monomer M3 contains or copolymerized not, preferably linear or slightly branched. Easily branched means that at n carbon atoms in the longest carbon chain of the alkyl radical there are maximal (n-3) branches.
  • slightly branched alkyl radicals are isopentyl (- (CH 2 ) 2 -CH (CH 3 ) 2 ), isohexyl (- (CH 2 ) 3 -CH (CH 3 ) 2 ), 2-ethylhexyl, isononyl (3,5 , 5-dimethylhexyl), 2-propylheptyl and the like.
  • Alkyl radical R 5 linear or contains at most 2 branches. In particular, it is linear or contains a branch.
  • the monomer M2 is particularly preferably octyl acrylate, 2-ethylhexyl acrylate, n-nonyl acrylate, isonyl acrylate, n-decyl acrylate, 2-propylheptyl acrylate, n-undecyl acrylate, acrylic acid acrylate and n-tridecyl acrylate selected.
  • the monomer M2 is selected from 2-ethylhexyl acrylate and acrylic acid lauryl ester. Specifically, it is 2-ethylhexyl acrylate.
  • the monomer M3 is the alkenyl ester, e.g. the vinyl or propenyl ester, an aliphatic carboxylic acid which may be unsaturated or preferably saturated.
  • R 6 , R 7 and R 8 independently of one another are preferably H or methyl and particularly preferably H.
  • R 9 is preferably CrCg hydrocarbyl.
  • Hydrocarbyl is preferably alkyl. More preferably R 9 is ethyl or methyl and especially methyl.
  • the monomer M3 is vinyl acetate.
  • the copolymer used according to the invention contains the monomer M3 in copolymerized form and is thus composed of monomers comprising the monomers M1, M2 and M3
  • the polymers used according to the invention are preferably composed essentially of the above-defined monomers M1, M2 and optionally M3. Depending on the manufacturing process, small amounts of a compound used as regulator (chain terminator) may optionally be present.
  • the polymers used according to the invention also have a number average molecular weight M n in the range from about 1000 to 20,000, particularly preferably from 1000 to 10,000, in particular from 1500 to 6000 and especially from 1500 to 5000.
  • the polymers may also have a weight-average molecular weight M w of from 1000 to 30 000, in particular 2000 to 20 000 and / or an M w / M n ratio of from 1.5 to 5.0, preferably from 1.8 to 4.0 and in particular of 1, 9 to 3.5.
  • the number-average and weight-average molecular weights M n and M w relate to values obtained by means of gel permeation chromatography (GPC).
  • the viscosity of such polymers is about 5 to 25,000 mm 2 / s, preferably about 10 to 1000 mm 2 / s, in particular about 50 to 700 mm 2 / s, each at a temperature of about 120 0 C.
  • Preferably used polymers are selected from the copolymers of ethylene and C 5 -C 2 o-alkyl acrylates, for example C 5 -C 18 -alkyl acrylates or C 5 -C 16 -alkyl acrylates or C 5 -C 14 -alkyl acrylates, and the copolymers of ethylene , Vinyl acetate and C 5 -C 20 -alkyl acrylates, for example C 5 -C 18 -alkyl acrylates or C 5 -C 16 -alkyl acrylates or C 5 -C 14 -alkyl acrylates.
  • Particularly preferably used polymers are selected from the copolymers of ethylene and C 6 -C 2 o-alkyl acrylates, for example C 6 -C 18 -alkyl acrylates or C 6 -C 16 -alkyl acrylates or C ⁇ -Cu-alkyl acrylates, and the copolymers of ethylene, Vinyl acetate and C 6 -C 20 -alkyl acrylates, for example C 6 -C 18 -alkyl acrylates or C 6 -C 16 -alkyl acrylates or Ce-Cu-alkyl acrylates.
  • More preferably used polymers are selected from the copolymers of ethylene and C 8 -C 20 -alkyl acrylates, for example C 8 -C 18 -alkyl acrylates or C 8 -C 16 -alkyl acrylates or C 8 -C 4 -alkyl acrylates or C 8 -C 12 Alkyl acrylates, and the copolymers of ethylene, vinyl acetate and C 8 -C 20 -alkyl acrylates, for example C 8 -C 18 -alkyl acrylates or C 8 -C 16 -alkyl acrylates or C 8 -C 14 -alkyl acrylates or C 8 -C 12 - alkyl acrylates.
  • polymers selected from ethylene / acrylic acid 2-ethylhexyl ester polymers, ethylene / acrylic acid 2-ethylhexyl ester / vinyl acetate polymers and ethylene / acrylic acid lauryl ester / vinyl acetate polymers are used.
  • AEH 4 to 80 wt.%, Preferably 5 to 62 wt.%, In particular about 7 to 47 wt.%
  • VAC 1 to 42 wt.%, Preferably 1 to 30 wt.%, In particular about 1 to 25 wt .-%, especially 1 to 20 wt .-%
  • the difference to 100 wt .-% corresponds to the proportion of ethylene.
  • the polymers are used as cold flow improvers. They are particularly preferably used for lowering the pour point (PP) of the turbine fuel additized therewith.
  • the above-described polymers are used alone or in combination with other such polymers in amounts which are sufficient to have an effect on the cold properties, in particular on the cold flow behavior of the turbine fuel additized therewith.
  • the polymers used according to the invention can also be used in combination with other conventional cold flow improvers and / or other turbine fuel additives.
  • the polymers used according to the invention are prepared by methods known per se. They are preferably prepared by free-radical polymerization, in particular high-pressure polymerization, of the monomers M1, M2 and optionally M3. Such processes for direct free-radical high-pressure copolymerization of unsaturated compounds are known from the prior art (cf., for example, Ullmann's Encyclopedia of Industrial Chemistry, 5th edition, keyword: Waxes, Vol. A 28, pp. 146 ff., VCH Weinheim, Basel, Cambridge, New York, Tokyo, 1996; also US 3,627,838; DE-A 2515805; DE-A 3141507; EP-A 0007590).
  • copolymers to be used according to the invention obtainable by the polymerization process are preferably composed essentially of the above-defined monomers M1, M2 and optionally M3. Due to production reasons if necessary, small amounts of a compound used as a regulator (chain terminator) may be included.
  • the polymers are preferably prepared in stirred high-pressure autoclaves or in high-pressure tubular reactors or combinations of the two.
  • the ratio of length to diameter in ranges from 5: 1 to 30: 1, preferably 10: 1 to 20: 1, predominantly affects them.
  • Suitable pressure conditions for the polymerization are 1000 to 3000 bar, preferably 1500 to 2000 bar.
  • the reaction temperatures are, for example, in the range from 160 to 320 ° C., preferably in the range from 200 to 280 ° C.
  • a regulator for adjusting the molecular weight of the copolymers used for example, an aliphatic aldehyde or an aliphatic ketone of the general formula I.
  • radicals R a and R b are the same or different and selected from
  • C 1 -C 6 -alkyl such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, neopentyl, 1, 2 Dimethylpropyl, isoamyl, n-hexyl,
  • C 3 -C 12 cycloalkyl such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl and cyclododecyl; preferred are cyclopentyl, cyclohexyl and cycloheptyl;
  • R a and R b may also be covalently linked together to form a 4- to 13-membered ring.
  • R a and R b may together form the following alkylene groups: - (CH 2 ) 4 -, - (CH 2 ) 5 -, - (CH 2 ) 6 , - (CH 2 J 7 -, -CH (CH 3 ) -CH 2 -CH 2 - CH (CH 3 ) - or -CH (CHa) -CH 2 -CH 2 -CH 2 -CH (CH 3 ) -.
  • propionaldehyde or ethyl methyl ketone as a regulator is most preferred.
  • Further suitable regulators are unbranched aliphatic hydrocarbons, for example propane or branched aliphatic hydrocarbons having tertiary H atoms, for example isobutane, isopentane, isooctane or isododecane (2,2,4,6,6-pentamethylheptane).
  • olefins such as propylene, can be used.
  • the amount of regulator used corresponds to the amounts customary for the high-pressure polymerization process.
  • radical initiators such as organic peroxides, oxygen or azo compounds
  • mixtures of several radical starters are suitable.
  • a radical initiator e.g. one or more peroxides, selected from the following commercially available substances:
  • di-tert-butyl peroxide, tert-butyl peroxypivalate, tert-butyl peroxyisononanoate or dibenzoyl peroxide or mixtures thereof are particularly suitable.
  • azo compound azobisisobutyronitrile ("AIBN") is exemplified.
  • AIBN azobisisobutyronitrile
  • the free-radical initiators are metered in amounts customary for polymerizations.
  • the polymers to be used according to the invention are prepared by reacting a mixture of the monomers M1, M2 and optionally M3 in the presence of the regulator at a temperature in the range of about 20 to 50 0 C, such as from 3O 0 C, preferably continuously passed through a stirred autoclave which is maintained at a pressure in the range of about 1500 to 2000 bar, such as from about 1700 bar.
  • the temperature in the reactor at the desired reaction temperature such as at 200 to 250 0 C, maintained.
  • the resulting after the relaxation of the reaction mixture polymer is then isolated in a conventional manner.
  • Another object of the invention relates to turbine fuel compositions containing a greater weight fraction of a turbine fuel and a smaller weight fraction of at least one polymer used in the invention according to the above definition.
  • the polymers used according to the invention can be used in combination with other conventional cold flow improvers and / or other turbine fuel additives.
  • the turbine fuel composition contains a major amount of liquid turbine fuel, which may be a conventional turbine fuel in civil or military aviation. These include, for example, fuels named Jet A, Jet A-1, Jet B, JP-4, JP-5, JP-7, JP-8 and JP-8 + 100. Jet A and Jet A-1 are commercially available turbine fuel specifications based on kerosene. The associated standards are ASTM D 1655 and DEF STAN 91-91. Jet A and Jet A-1 have their specification maximum freezing point of -40 0 C and -47 0 C. Jet B is sinfr hopeen a wide cut fuel based on naphtha and kerosene. JP-4 is equivalent to Jet B.
  • JP 4, JP-5, JP-7, JP-8 and JP-8 + 100 are military turbine fuels such as those used by the Navy and Air Force. These standards sometimes refer to formulations which already contain other additives, such as corrosion inhibitors, anti-icing agents, static dissipators, etc.
  • Preferred turbine fuels are Jet A, Jet A-1 and JP 8.
  • the polymer used in the invention is preferably used in a proportion based on the total amount of the turbine fuel composition, which in itself has a substantially sufficient influence on the cold flow properties of the turbine fuel composition.
  • the polymer is preferably used in an amount of 10 to 10,000 mg / l, particularly preferably 50 to 7000 mg / l, in particular 100 to 5000 mg / l, based on 1 l of the turbine fuel composition.
  • the polymers used according to the invention can be added to the turbine fuel compositions individually or as a mixture of such polymers and optionally in combination with other additives known per se.
  • Suitable additives which may be present in the turbine fuel compositions according to the invention include further additives improving the cold properties of the fuel (cold flow improvers), detergents, corrosion inhibitors, antioxidants, such as sterically hindered tert-butylphenols or N-butylphenylenediamines, metal deactivators, such as N, N '.
  • Conventional cold flow improvers in particular include:
  • Polymers are different;
  • the monomer is preferably selected from alkenylcarboxylic acid esters, (meth) acrylic acid esters, fumaric acid esters, maleic acid esters and olefins.
  • Suitable olefins are, for example, those having 3 to 20 carbon atoms and having 1 to 3, preferably 1 or 2, in particular having one, carbon-carbon double bond. In the latter case, the carbon-carbon double bond can be arranged both terminally ( ⁇ -olefins) and internally.
  • ⁇ -olefins particularly preferably ⁇ -olefins having 3 to 20, more preferably 3 to 10 and in particular 3 to 6 carbon atoms, such as propene, 1-butene, 1-pentene and 1-hexene.
  • Suitable (meth) acrylic esters are, for example, esters of (meth) acrylic acid with C r C 10 -alkanols, in particular with methanol, ethanol, propanol, isopropanol, n-
  • (meth) acrylic acid is meant to include that both acrylic acid and methacrylic acid are included.
  • Suitable alkenylcarboxylic esters are, for example, the vinyl and propenyl esters of carboxylic acids having 2 to 20 carbon atoms, the hydrocarbon radical of which may be linear or branched. Preferred among these are the vinyl esters.
  • carboxylic acids having a branched hydrocarbon radical preferred are those whose branch is in the ⁇ -position to the carboxyl group, the ⁇ -carbon atom being particularly preferably tertiary, ie. H. the carboxylic acid is a so-called neocarboxylic acid.
  • alkenylcarboxylic acid esters examples include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl neopentanoate, vinyl hexanoate, vinyl octanoate, vinyl 2-ethylhexanoate, vinyl neononanoate, vinyl neodecanoate and the corresponding propenyl esters, the vinyl esters being preferred.
  • a particularly preferred alkenyl carboxylic acid ester is vinyl acetate.
  • the ethylenically unsaturated monomer is selected from among alkenylcarboxylic acid esters.
  • copolymers which contain two or more mutually different alkenylcarboxylic acid esters in copolymerized form, these differing in the alkenyl function and / or in the carboxylic acid group. Also suitable are copolymers which, in addition to the alkenylcarboxylic ester (s), contain at least one olefin and / or at least one (meth) acrylic acid ester in copolymerized form.
  • the ethylenically unsaturated monomer is copolymerized in the copolymer in an amount of preferably from 1 to 50 mol%, particularly preferably from 10 to 50 mol% and in particular from 5 to 20 mol%, based on the total copolymer.
  • the copolymer (a) preferably has a number average molecular weight M n of from 1000 to 20 000, more preferably from 1000 to 10000 and in particular from 1000 to 6000.
  • Such ethylene copolymers (a) are described, for example, in WO 01/62874 or EP-A-1357168, to which reference is hereby fully made.
  • Comb polymers (b) are, for example, those described in Comb-Like Polymers, Structure and Properties, N.A. Plate and V.P. Shibaev, J. Poly. Be. Macromolecular Revs. 8, pages 117 to 253 (1974) are described. Of the described there, for example, comb polymers of the formula II are suitable
  • D is R 17 , COOR 17 , OCOR 17 , R 18 , OCOR 17 or OR 17
  • E is H, CH 3 , D or R 18
  • G is H or D
  • J is H, R 18 , R 18 COOR 17 'aryl or heterocyclyl
  • K is H, COOR 18 , OCOR 18 , OR 18 or COOH
  • L is H, R 18 , COOR 18 , OCOR 18 , COOH or aryl , in which
  • R 17 is a hydrocarbon radical having at least 10 carbon atoms, preferably having 10 to 30 carbon atoms,
  • R 18 is a hydrocarbon radical having at least one carbon atom, preferably having 1 to 30 carbon atoms, m is a mole fraction in the range of 1, 0 to 0.4 and n is a mole fraction in the range of 0 to 0.6.
  • Preferred comb polymers are, for example, by the copolymerization of maleic anhydride or fumaric acid with another ethylenically unsaturated monomer, for example with an ⁇ -olefin or an unsaturated ester, such as vinyl acetate, and subsequent esterification of the anhydride or acid function with an alcohol having at least 10 carbon atoms available.
  • Further preferred comb polymers are copolymers of ⁇ -olefins and esterified comonomers, for example esterified copolymers of styrene and maleic anhydride or esterified copolyesters. polymers of styrene and fumaric acid. Also mixtures of comb polymers are suitable. Comb polymers may also be polyfumarates or polymaleinates.
  • homo- and copolymers of vinyl ethers are suitable comb polymers.
  • Suitable nucleators (c) are, in particular, polyoxyalkylenes, for example polyoxyalkylene esters, ethers, esters / ethers and mixtures thereof.
  • the polyoxyalkylene compounds preferably contain at least one, particularly preferably at least two, linear alkyl groups having from 10 to 30 carbon atoms and at least one polyoxyalkylene group having a molecular weight of up to 5,000.
  • the alkyl group of the polyoxyalkylene radical preferably contains from 1 to 4 carbon atoms.
  • Such polyoxyalkylene compounds are described, for example, in EP-A-0 061 895, in EP-A-1357168 and in US Pat. No. 4,491,455, to which reference is hereby fully made.
  • Preferred polyoxyalkylene esters, ethers and esters / ethers have the general formula III
  • R 19 and R 20 are each independently R 21 , R 21 is CO-, R 21 is -O-CO (CH 2 ) Z - or R 21 is -O-CO (CH 2 ) Z -CO-, wherein R 21 is is linear C 1 -C 6 -alkyl, y is a number from 1 to 4, x is a number from 2 to 200, and z is a number from 1 to 4.
  • Preferred polyoxyalkylene compounds of the formula III in which both R 19 and R 20 are R 21 are polyethylene glycols and polypropylene glycols having a number average molecular weight of 100 to 5,000.
  • Preferred polyoxyalkylenes of the formula III in which one of the radicals R 19 is R 21 and the other is R 21 -CO- are polyoxyalkylene esters of fatty acids having 10 to 30 carbon atoms, such as stearic acid or behenic acid.
  • Preferred polyoxyalkylene compounds in which both R 19 and R 20 are R 21 -CO- are diesters of fatty acids having 10 to 30 carbon atoms, preferably stearic or behenic acid.
  • Suitable nucleators (c) are block copolymers, as described, for example, in EP-A-1357168, the contents of which are hereby incorporated by reference.
  • Suitable block copolymers comprise at least one crystallizable block and at least one non-crystallizable block.
  • the copolymers may be diblock, triblock or higher block polymers.
  • Preferred triblock polymers have a crystallizable block on both polymer ends.
  • such block copolymers are composed of butadiene and isoprene units.
  • the polar nitrogen compounds (d) are also referred to as wax anti-settling additives (WASA). They are suitably oil-soluble, may be both ionic and non-ionic, and preferably have at least one, more preferably at least 2, substituents of the formula> NR 22 in which R 22 is a C 8 -C 4 0 hydrocarbon radical .
  • the nitrogen substituents may also be quaternized, that is in cationic form.
  • An example of such nitrogen compounds are ammonium salts and / or amides obtainable by reacting at least one amine substituted with at least one hydrocarbyl radical with a carboxylic acid having 1 to 4 carboxyl groups or with a suitable derivative thereof.
  • the amines preferably contain at least one linear C 8 -C 40 -alkyl radical.
  • suitable primary amines are octylamine, nonylamine, decylamine, undecylamine, dodecylamine, tetradecylamine and the higher linear homologs.
  • Suitable secondary amines are, for example, dioctadecylamine and methylbehenylamine.
  • amine mixtures in particular industrially available amine mixtures, such as fatty amines or hydrogenated tallamines, as described, for example, in Ullmann's Encyclopedia of Industrial Chemistry, 6th edition, 2000 electronic release, chapter "Amines, aliphatic".
  • Suitable acids for the reaction are, for example, cyclohexane-1, 2-dicarboxylic acid, cyclohexene-1, 2-dicarboxylic acid, cyclopentane-1, 2-dicarboxylic acid, naphthalenedicarboxylic acid, phthalic acid, isophthalic acid, terephthalic acid and succinic acids substituted by long-chain hydrocarbon radicals.
  • polar nitrogen compounds are ring systems bearing at least two substituents of the formula -A-NR 23 R 24 wherein A is a linear or branched aliphatic hydrocarbon group optionally substituted by one or more groups selected from O, S , NR 35 and CO, is interrupted, and R 23 and R 24 are a C 9 -C 4 o-hydrocarbon radical, optionally interrupted by one or more groups selected from O, S, NR 35 and CO, and or substituted by one or more substituents selected from OH, SH and NR 35 R 36 , wherein R 35 is CrC 40 -AlkVl optionally substituted by one or more moieties selected from CO, NR 35 , O and S, interrupted, and / or substituted by one or more radicals selected from NR 37 R 38 , OR 37 , SR 37 , COR 37 , COOR 37 , CONR 37 R 38 , aryl or heterocyclyl, wherein R 37 and R 38 in each case independently ngig are selected from H
  • A is a methylene or polymethylene group having 2 to 20 methylene units.
  • suitable radicals R 23 and R 24 are 2-hydroxyethyl, 3-hydroxypropyl, 4-hydroxybutyl, 2-ketopropyl, ethoxyethyl and propoxypropyl.
  • the cyclic system may be homocyclic, heterocyclic, condensed polycyclic or non-condensed polycyclic systems.
  • the ring system is preferably carbo- or heteroaromatic, in particular carboaromatic.
  • polycyclic ring systems examples include condensed benzoid structures, such as naphthalene, anthracene, phenanthrene and pyrene, condensed nonbenzoic structures, such as azulene, indene, hydrindene and fluorene, uncondensed polycycles, such as diphenyl, heterocycles, such as quinoline, indole, dihydroindole, Benzofuran, coumarin, isocoumarin, benzthiophene, carbazole, diphenylene oxide and diphenylene sulfide, non-aromatic or partially saturated ring systems, such as decalin, and three-dimensional structures, such as ⁇ -pinene, camphene, bornylene, norborane, norbornene, bicyclo-octane and bicyclooctene.
  • condensed benzoid structures such as naphthalene, anthracene, phenanthrene and
  • Suitable polar nitrogen compounds are condensates of long-chain primary or secondary amines with carboxyl group-containing polymers.
  • Suitable polar nitrogen compounds are e.g. also in DE-A-198 48 621, DE-A-196 22 052, EP-A-1357168 or EP-B-398 101, to which reference is hereby made.
  • Suitable sulfocarboxylic acids / sulfonic acids or their derivatives (e) are, for example, those of the general formula IV A X
  • R 26 and R 27 are alkyl, alkoxyalkyl or polyalkoxyalkyl having at least 10 carbon atoms in the main chain, R 28 is C 2 -C 5 -alkylene, Z "is an anion equivalent and
  • a and B are alkyl, alkenyl or two substituted hydrocarbon radicals or together with the carbon atoms to which they are attached form an aromatic or cycloaliphatic ring system.
  • Suitable poly (meth) acrylic esters (f) are both homo- and copolymers of acrylic and methacrylic acid esters. Preferred are acrylic ester homopolymers derived from CrCo alcohols. Also preferred are copolymers of at least two different (meth) acrylic acid esters, which differ with respect to the fused alcohol. Optionally, the copolymer contains a further, different of which olefinically unsaturated monomer copolymerized. The weight average molecular weight of the polymer is preferably 50,000 to 500,000.
  • a particularly preferred polymer is a copolymer of methacrylic acid and methacrylic acid esters of saturated C 4 and C 15 alcohols wherein the acid groups are neutralized with hydrogenated tallamine.
  • Suitable poly (meth) acrylates are described, for example, in WO 00/44857, to which reference is hereby fully made.
  • the acylating agents used are preferably those which contain a hydrocarbon radical having 8 to 50 carbon atoms.
  • examples thereof are succinic acids or succinic acid derivatives which are substituted by C 8 -C 50 , preferably C 12 -C 35 -alkyl or alkenyl radical.
  • the alkanolamines are, for example, diethanolamine, dipropanolamine, dibutanolamine, N-methylethanolamine or N-ethylethanolamine. Such compounds are described, for example, in WO 01/62874, to which reference is hereby made.
  • the hydroxyaromatics used for the preparation of the condensation products of hydroxyaromatics with aldehydes (h) are those which are substituted by a linear or branched hydrocarbon radical.
  • the hydroxyaromatic can be either a substituted phenol or any other hydroxy group-containing aromatic such as naphthol.
  • aldehyde component both the aldehydes themselves and suitable aldehyde sources can be used.
  • aldehydes examples include formaldehyde (which can be used, for example, as paraldehyde or trioxane), acetaldehyde, propanal, butanal, isobutyraldehyde, heptanal, 2-ethylhexanal and glyoxylic acid.
  • formaldehyde which can be used, for example, as paraldehyde or trioxane
  • acetaldehyde propanal
  • butanal isobutyraldehyde
  • heptanal 2-ethylhexanal
  • 2-ethylhexanal 2-ethylhexanal
  • glyoxylic acid examples include glyoxylic acid.
  • Suitable waxes (i) are both linear and non-linear paraffins.
  • the n-paraffins are preferably C 8 -C 35 -, more preferably C 8 -C 30 - and in particular C 8 -C 2 s-alkanes.
  • the non-linear paraffins include preferably amorphous solids having a melting point of 10 to 60 0 C and a MoIe- weight of from 150 to 500. Such waxes are described for example in EP-A-1357168, is hereby incorporated by reference.
  • a final subject of the invention also relates to additive packages comprising at least one polymer used according to the invention as defined above and at least one further conventional turbine fuel additive and optionally at least one diluent.
  • Suitable conventional turbine fuel additives are the previously described co-additives.
  • Preferred co-additives are anti-icing additives; in addition, the said conventional cold flow improvers, those of group (a) being preferred; Corrosion inhibitors; detergents; antioxidants; Antistatic agents and metal deactivators.
  • the additive package contains, in addition to at least one of the above-described polymers, at least one anti-icing agent and optionally at least one of the following coadditives: conventional cold flow improvers, those of group (a) being preferred; Corrosion inhibitors; detergents; antioxidants; Antistatic agents and metal deactivators.
  • the polymer used according to the invention is present in an amount of preferably from 0.1 to 99% by weight, more preferably from 1 to 95% by weight and in particular from 5 to 90% by weight.
  • the additive package may optionally contain at least one diluent.
  • Suitable diluents are, for example, fractions obtained in petroleum processing, such as kerosene, naphtha or bright stock. Also suitable are aromatic hydrocarbons such as Solvent Naphtha heavy, Solvesso ® or Shellsol ®, and aliphatic hydrocarbons.
  • the polymer used according to the invention is preferably present in the concentrates in an amount of from 0.1 to 90% by weight, more preferably from 1 to 80% by weight and in particular from 10 to 70% by weight. %, based on the total weight of the concentrate.
  • the inventive use of the described polymers improves the cold flow properties of turbine fuels additized therewith. Above all, the freezing point, the cloud point (CP) and in particular the pour point (PP) are lowered.
  • a total of 28 different polymers to be used according to the invention were prepared by high-pressure polymerization of ethylene and 2-ethylhexyl acrylate (AEH) or of ethylene, 2-ethylhexyl acrylate (AEH) or acrylic acid lauryl ester (AL) and vinyl acetate (VAC).
  • AEH 2-ethylhexyl acrylate
  • AAC acrylic acid lauryl ester
  • VAC vinyl acetate
  • Table 1 summarizes the properties of the polymers used in the following test examples.
  • the content of ethylene, AEH or AL and VAC in the resulting polymers was determined by NMR spectroscopy.
  • the viscosities were determined according to Ubbelohde DIN 51562 at 120 0 C.
  • the Jet A turbine fuel additized with the copolymers used according to the invention has a significantly lower pour point than the non-additized fuel, whereas the conventional ethylene / vinyl acetate copolymer has no effect on the pour point.

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Abstract

L'invention concerne l'utilisation de polymères contenant une alpha-oléfine, un ester d'un acide carboxylique a,ß insaturé et éventuellement un ester alcényle d'un acide carboxylique, ces éléments étant incorporés par polymérisation, comme additifs de carburants pour turbines, notamment pour améliorer l'aptitude à l'écoulement à froid de ces carburants. La présente invention porte également sur des carburants pour turbines contenant ces polymères, et sur des ensembles d'additifs contenant des polymères de ce type.
EP06724319A 2005-04-18 2006-04-13 Compositions de carburants pour turbines a meilleures aptitudes au froid Withdrawn EP1874899A1 (fr)

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EP05008420A EP1715027A1 (fr) 2005-04-18 2005-04-18 Composition de combustible pour turbine ayant des propriétés à froid améliorées
EP05021172A EP1770150A1 (fr) 2005-09-28 2005-09-28 Compositions de turbocombustible ayant des caractéristiques d'écoulement à froid améliorées
EP06724319A EP1874899A1 (fr) 2005-04-18 2006-04-13 Compositions de carburants pour turbines a meilleures aptitudes au froid
PCT/EP2006/003428 WO2006111326A1 (fr) 2005-04-18 2006-04-13 Compositions de carburants pour turbines a meilleures aptitudes au froid

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ATE547472T1 (de) 2009-09-25 2012-03-15 Evonik Rohmax Additives Gmbh Zusammensetzung zur verbesserung der kaltflusseigenschaften von brennstoffölen
EP2488613B1 (fr) 2009-10-14 2018-08-22 Palox Limited Protection des combustibles liquides
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WO2012004240A2 (fr) * 2010-07-06 2012-01-12 Basf Se Copolymère à homogénéité chimique élevée et son utilisation pour l'amélioration de l'écoulement à froid d'huiles combustibles
US8721744B2 (en) 2010-07-06 2014-05-13 Basf Se Copolymer with high chemical homogeneity and use thereof for improving the cold flow properties of fuel oils
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AU2006237132B2 (en) 2011-06-23
CA2604026A1 (fr) 2006-10-26
NO20075538L (no) 2007-11-15
RU2388795C2 (ru) 2010-05-10
AU2006237132A1 (en) 2006-10-26
WO2006111326A1 (fr) 2006-10-26
KR20080000654A (ko) 2008-01-02
US20080178523A1 (en) 2008-07-31
SG161220A1 (en) 2010-05-27
BRPI0610725A2 (pt) 2018-07-10
RU2388795C9 (ru) 2011-01-20
CA2604026C (fr) 2014-06-03
ZA200709899B (en) 2015-07-29
JP2008536984A (ja) 2008-09-11
RU2007142338A (ru) 2009-05-27

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