EP1881053B1 - Additif destiné à l'amélioration des propriétés à froid d'huiles combustibles - Google Patents

Additif destiné à l'amélioration des propriétés à froid d'huiles combustibles Download PDF

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Publication number
EP1881053B1
EP1881053B1 EP07011538A EP07011538A EP1881053B1 EP 1881053 B1 EP1881053 B1 EP 1881053B1 EP 07011538 A EP07011538 A EP 07011538A EP 07011538 A EP07011538 A EP 07011538A EP 1881053 B1 EP1881053 B1 EP 1881053B1
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Prior art keywords
additive mixture
mol
propene
vinyl
ethylene
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EP1881053A3 (fr
EP1881053A2 (fr
Inventor
Bettina Dr. Siggelkow
Werner Dr. Reimann
Matthias Dr. Krull
Ulrike Neuhaus
Markus Kupetz
Andre Graf
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Clariant Finance BVI Ltd
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Clariant Finance BVI Ltd
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    • 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
    • C10L1/182—Organic compounds containing oxygen containing hydroxy groups; Salts thereof
    • C10L1/183—Organic compounds containing oxygen containing hydroxy groups; Salts thereof at least one hydroxy group bound to an aromatic carbon atom
    • 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
    • C10L1/146—Macromolecular compounds according to different macromolecular groups, mixtures thereof
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    • 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
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    • C10L1/19—Esters ester radical containing compounds; ester ethers; carbonic acid esters
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    • 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
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/16—Hydrocarbons
    • C10L1/1625—Hydrocarbons macromolecular compounds
    • C10L1/1633—Hydrocarbons macromolecular compounds homo- or copolymers obtained by reactions only involving carbon-to carbon unsaturated bonds
    • C10L1/1641—Hydrocarbons macromolecular compounds homo- or copolymers obtained by reactions only involving carbon-to carbon unsaturated bonds from compounds containing aliphatic monomers
    • 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
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    • C10L1/14—Organic compounds
    • C10L1/16—Hydrocarbons
    • C10L1/1625—Hydrocarbons macromolecular compounds
    • C10L1/1633—Hydrocarbons macromolecular compounds homo- or copolymers obtained by reactions only involving carbon-to carbon unsaturated bonds
    • C10L1/165—Hydrocarbons macromolecular compounds homo- or copolymers obtained by reactions only involving carbon-to carbon unsaturated bonds from compounds containing aromatic monomers
    • 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
    • C10L1/16—Hydrocarbons
    • C10L1/1625—Hydrocarbons macromolecular compounds
    • C10L1/1633—Hydrocarbons macromolecular compounds homo- or copolymers obtained by reactions only involving carbon-to carbon unsaturated bonds
    • C10L1/1658—Hydrocarbons macromolecular compounds homo- or copolymers obtained by reactions only involving carbon-to carbon unsaturated bonds from compounds containing conjugated dienes
    • C—CHEMISTRY; METALLURGY
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    • 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
    • C10L1/196—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and a carboxyl group or salts, anhydrides or esters thereof homo- or copolymers of compounds having one or more unsaturated aliphatic radicals each having one carbon bond to carbon double bond, and at least one being terminated by a carboxyl radical or of salts, anhydrides or esters thereof
    • C10L1/1966—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and a carboxyl group or salts, anhydrides or esters thereof homo- or copolymers of compounds having one or more unsaturated aliphatic radicals each having one carbon bond to carbon double bond, and at least one being terminated by a carboxyl radical or of salts, anhydrides or esters thereof poly-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, 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
    • 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
    • C10L1/198—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds homo- or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon to carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid
    • C10L1/1981—Condensation polymers of aldehydes or ketones
    • 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
    • C10L1/198—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds homo- or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon to carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid
    • C10L1/1985—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds homo- or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon to carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid polyethers, e.g. di- polygylcols and derivatives; ethers - esters
    • 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
    • C10L1/22—Organic compounds containing nitrogen
    • C10L1/222—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond
    • C10L1/224—Amides; Imides carboxylic acid amides, imides
    • 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
    • C10L1/22—Organic compounds containing nitrogen
    • C10L1/234—Macromolecular compounds
    • C10L1/236—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derivatives thereof
    • C10L1/2364—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derivatives thereof homo- or copolymers derived from unsaturated compounds containing amide and/or imide groups

Definitions

  • the present invention relates to additive mixtures comprising ethylene-propene-vinyl ester terpolymers, in addition to a further cold additive, which have improved handling properties and improved performance properties as cold additives for fuel oils.
  • crude oils and middle distillates obtained by distillation of crude oils such as gas oil, diesel oil or fuel oil
  • crude oils and middle distillates obtained by distillation of crude oils contain different amounts of n-paraffins, which crystallize out as platelet-shaped crystals when the temperature is lowered and partly agglomerate with the inclusion of oil.
  • the flow properties of the oils or distillates deteriorate, which can lead to disruptions in the extraction, transport, storage and / or use of the mineral oils and mineral oil distillates.
  • the phenomenon of crystallization especially in winter, can lead to deposits on the pipe walls and in individual cases, e.g. at standstill of a pipeline, even lead to their complete blockage.
  • a known and widely used for the improvement of the cold properties of mineral oils and middle distillates produced therefrom additive class are copolymers of ethylene and vinyl esters, especially ethylene and vinyl acetate. These are partially crystalline polymers, the mode of action of which is explained by co-crystallization of their poly (ethylene) sequences with the n-paraffins precipitated on cooling from the middle distillates. Through this physical interaction, the shape, size and adhesion properties of the precipitated wax crystals are modified to produce many small crystals that pass through the fuel filter and can be supplied to the combustion chamber.
  • the ethylene copolymers used as nucleating agents or nucleating agents must have a low solubility in the oil in order to fulfill their function in order to crystallize out on cooling of the oil with or shortly before the paraffins.
  • Ethylene copolymers having a low comonomer content and thus long free poly (ethylene) sequences which are particularly well suited for co-crystallization with the long-chain paraffins which precipitate out of the oil are preferably used as nucleators.
  • these ethylene-vinyl ester copolymers require due to their increased intrinsic crystallinity, handled and metered at elevated temperature or alternatively transported in high dilution with solvents and processed to become. Otherwise, there is a risk that the additives remain undissolved, whereby they can not develop their full effectiveness and can also give rise to filter occupancy and filter blockages.
  • injection units and pumps require current engine concepts very clean fuels. Even small amounts of undissolved additive components are highly undesirable in this context. Removal of such minor constituents of polymers by filtration is very expensive, if at all possible.
  • short-chain branches are formed by intramolecular chain transfer reactions ("back-biting mechanism") during radical polymerization and essentially consist of butyl and ethyl radicals (see, for example, US Pat Macromolecules 1997, 30, 246-256 ).
  • back-biting mechanism intramolecular chain transfer reactions
  • U.S. 3,961,916 discloses fuel oils containing two copolymers of ethylene and unsaturated esters which act as nucleators for paraffin crystallization to improve cold flow properties.
  • EP-A-0 190 553 discloses terpolymers of ethylene, 20-40 wt .-% of vinyl acetate and propene having a degree of branching 8-25 CH 3/100 CH 2 groups. These polymers, which are to be regarded as growth inhibitors, show hardly any activity as cold flow improvers alone and are used to improve the solubility of conventional EVA copolymers with a comparable vinyl acetate content.
  • U.S. 4,178,950 discloses terpolymers of ethylene, 10 to 45% by weight of vinyl acetate, 0.01 to 5.0% by weight of propene or butene and their use as a pour point depressant for residual oils. Polymer blends are not disclosed.
  • DE-A-2 037 673 discloses polymer blends of ethylene-vinyl acetate copolymers of different molecular weight as cold flow improvers, which may also contain propene in addition to ethylene as the olefin.
  • EP-A-0 406 684 discloses polymer blends comprising A) copolymers of ethylene, 25-35% by weight of vinyl acetate, optionally 5 to 15% by weight of an olefin and a degree of branching of 3 to 15 CH 3 groups, and B) another ethylene-vinyl acetate Copolymer and optionally C) contain a polyalkyl (meth) acrylate.
  • the terpolymer of ethylene, vinyl acetate and diisobutylene used in the example is used as a cold flow improver together with a low comonomer content EVA copolymer to be considered as a nucleating agent.
  • the use of propene as a comonomer for nucleators is shown neither in combination with arrestors nor in combination with comb polymers.
  • additive concentrates which contain, as nucleating agents for paraffins, terpolymers of ethylene, propene and unsaturated esters with few short-chain branching properties are very easy to handle and mix at low temperatures, and at the same time a superior one Show effectiveness as a cold additive.
  • these additives contain less difficultly soluble portions of the known ethylene copolymers of the prior art.
  • Another object of the invention is the use of additive mixtures of A) and B) to improve the low-flowability of fuel oils.
  • Another object of the invention is a method for improving the low-temperature flowability of fuel oils by adding an additive mixture of A) and B) to the fuel oil.
  • Another object of the invention are fuel oils with improved cold flowability, containing an additive mixture of A) and B).
  • Unsaturated esters suitable for component A) according to the invention are in particular vinyl esters of carboxylic acids having 1 to 4 carbon atoms and also esters of acrylic and methacrylic acid with fatty alcohols having 1 to 3 carbon atoms.
  • suitable vinyl esters are vinyl acetate, vinyl propionate, vinyl butyrate and vinyl isobutyrate. Especially preferred is vinyl acetate.
  • Suitable esters of acrylic and methacrylic acid include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n- and iso-propyl (meth) acrylate and mixtures of these comonomers. Methyl acrylate and ethyl acrylate are particularly preferred.
  • the content of the terpolymer A) of unsaturated ester is preferably between 7.0 and 11.5 mol% and in particular between 8.0 and 11.0 mol%, for example between 8.5 and 10.5 mol%.
  • the content is preferably between 12.0 and 29.0% by weight and in particular between 18 and 28% by weight, for example between 20.0 and 27.0% by weight.
  • the comonomer content is determined by pyrolysis of the polymer and subsequent titration of the eliminated carboxylic acid.
  • the terpolymers A may additionally contain minor amounts of, for example, up to 4 mol%, preferably up to 2.5 mol%, such as 0.1 to 2.0 mol%, of structural units derived from unsaturated esters with longer alkyl chains .
  • Suitable unsaturated esters for this purpose are vinyl esters of the formula (1) and / or (meth) acrylic acid esters of the formula (2) in which R 2 and R 3 independently of one another are an alkyl radical having 4 to 20 C atoms. These alkyl radicals can be linear or branched. Preferably, they are branched.
  • the content of the terpolymer A) of methyl groups derived from the propene is preferably between 0.7 and 3.5 and in particular between 1.0 and 3.0, for example between 1.1 and 2.5 methyl groups per 100 aliphatic carbon atoms. atoms.
  • the number of propene-derived methyl groups per 100 aliphatic carbon atoms in terpolymer A) is determined by 13 C NMR spectroscopy.
  • terpolymers of ethylene, vinyl ester and propene show characteristic signals of methyl groups attached to the polymer backbone of between about 19.3 and 20.2 ppm, which have a positive sign in the DEPT experiment.
  • the integral of this signal of the propene-derived methyl side groups of the polymer backbone is related to that of all aliphatic carbon atoms of the polymer backbone between about 22 and 44 ppm.
  • Optionally derived from the alkyl radicals of the unsaturated ester and superimposed with the signals of the polymer backbone signals are subtracted based on the signal of the carbonyl group of the unsaturated ester adjacent methine group of the total integral of the aliphatic C-atoms. Leave such measurements For example, with NMR spectrometers at a measurement frequency of 125 MHz at 30 ° C in solvents such as CDCl 3 or C 2 D 2 Cl 4 perform.
  • the number of chain ends originating from the methyl groups in the terpolymers A) is preferably from 2.0 to 7.0 CH 3/100 CH 2 groups and in particular from 2.5 to 6.5 CH 3/100 CH 2 groups such as 3.0 to 6.0 CH 3/100 CH 2 groups.
  • the number of methyl groups derived from chain ends is understood to mean all those methyl groups of the terpolymer A) which do not originate from the unsaturated esters used as comonomers. Consequently, this includes both the methyl groups located at the main chain ends, including the methyl groups derived from structural units of the moderator, and the methyl groups derived from short chain branches.
  • the number of methyl groups derived from chain ends is determined by 1 H-NMR spectroscopy, in which the integral of the signals usually appearing in the 1 H-NMR spectrum with a chemical shift of between about 0.7 and 0.9 ppm (versus TMS) Methyl protons is compared with the integral of appearing at 0.9 to 1.9 ppm signals of the methylene protons.
  • the methyl and methylene groups derived from alkyl radicals of the comonomers, for example the acetyl group of the vinyl acetate, are not included or excluded.
  • the signals generated by the structural units of the moderator are assigned according to the methyl or methylene protons.
  • the number of propene-derived methyl groups is subtracted to obtain the number of methyl groups derived from chain ends.
  • Suitable 1 H NMR spectra for example, at a measurement frequency of 500 MHz at 30 ° C in solvents such as CDCl 3 or C 2 D 2 Cl 4 are recorded.
  • the two summands are to be added as dimensionless numbers.
  • the weight-average molecular weight M w of the terpolymers A) determined by means of gel permeation chromatography against poly (styrene) standards is preferably between 2,500 and 50,000 g / mol, preferably between 4,000 and 30,000 g / mol, for example between 5,000 and 25,000 g / mol.
  • the melt viscosity of the terpolymers A) determined at 140 ° C. is between 100 and 5,000 mPas, preferably between 150 and 2,500 mPas and in particular between 200 and 2,000 mPas.
  • the polymer is previously freed for two hours at 140 ° C in vacuo (100 mbar) of residual monomers and any solvent components.
  • the ethylene polymers A) and also B1) can be prepared independently of one another by customary copolymerization processes, for example suspension polymerization, solvent polymerization, gas-phase polymerization or high-pressure bulk polymerization.
  • the high-pressure mass polymerization is preferably carried out at pressures above 100 MPa, preferably between 100 and 300 MPa, for example between 150 to 275 MPa and temperatures of 100 to 340 ° C., preferably 150 to 310 ° C., for example between 200 and 280 ° C.
  • the propene content as well as the extent of short chain branches / chain ends can be adjusted. In particular, low reaction temperatures and / or high pressures lead to low fractions of short chain branches and thus to a low number of chain ends.
  • the reaction of the monomers is initiated by free radical initiators (free radical initiators).
  • This class of substances includes, for example, oxygen, hydroperoxides, peroxides and azo compounds such as cumene hydroperoxide, t-butyl hydroperoxide, dilauroyl peroxide, dibenzoyl peroxide, bis (2-ethylhexyl) peroxide carbonate, t-butyl perpivalate, t-butyl permaleinate, t-butyl perbenzoate, dicumyl peroxide, t-butyl cumyl peroxide, di (t-butyl) peroxide, 2,2'-azobis (2-methylpropanonitrile), 2,2'-azobis ( 2-methylbutyronitrile).
  • the initiators are used individually or as a mixture of two or more substances in amounts of 0.01 to 10 wt .-%, preferably 0.05 to 5 wt .-%, based on the monomer mixture.
  • the high-pressure mass polymerization is carried out batchwise or continuously in known high-pressure reactors, for example autoclaves or tubular reactors, and continuously operated tubular reactors have proven particularly suitable.
  • Solvents such as aliphatic and / or aromatic hydrocarbons or hydrocarbon mixtures, benzene or toluene may be present in the reaction mixture. Preferred is the substantially solvent-free operation.
  • the comonomers as well as the moderators can be metered into the reactor both together with ethylene and separately via side streams.
  • the monomer streams can be composed differently ( EP-A-0 271 738 and EP-A-0 922 716 ).
  • Preferred moderators are, for example, saturated and unsaturated hydrocarbons such as propane, hexane, heptane and cyclohexane and alcohols such as butanol and in particular aldehydes such as acetaldehyde, propionaldehyde, n-butyraldehyde and isobutyraldehyde and ketones such as acetone, methyl ethyl ketone, methyl propyl ketone, methyl isopropyl ketone, Methyl butyl ketone, methyl isobutyl ketone and cyclohexanone. Hydrogen is also suitable as a moderator.
  • the polymers according to the invention contain, in addition to vinyl esters and propene, 0.3 to 5.0% by weight, preferably 0.5 to 3.5% by weight, of structural units derived from at least one carbonyl-containing moderator ,
  • concentration of these structural elements derived from the moderator in the polymer can also be determined by means of 1 H NMR spectroscopy. This can be done, for example, by correlating the intensity of the vinyl ester-derived signals, the proportion of which in the polymer is known, with the signals appearing at about 2.4 to 2.5 ppm of the methylene or methine group adjacent to the carbonyl group of the moderators.
  • Suitable as component B1) are one or more copolymers of ethylene and olefinically unsaturated compounds whose total comonomer content is at least 2, preferably 3 mol% higher than that of component A.
  • Suitable ethylene copolymers are, in particular, those which have ethylene 9 to 21 mol%, in particular 10 to 18 mol% comonomers.
  • Comonomers may be other olefinically unsaturated compounds in addition to olefinically unsaturated esters.
  • total comonomer content is meant the content of monomers other than ethylene.
  • the olefinically unsaturated compounds are preferably vinyl esters, acrylic esters, methacrylic esters, alkyl vinyl ethers and / or alkenes, it being possible for the abovementioned compounds to be substituted by hydroxyl groups.
  • One or more comonomers may be included in the polymer.
  • said alkyl groups may be substituted with one or more hydroxyl groups.
  • these ethylene copolymers contain vinyl acetate and at least one further vinyl ester of the formula 1 in which R 4 is C 4 to C 30 -alkyl, preferably C 4 to C 16 -alkyl, especially C 6 - to C 12 -alkyl ,
  • R 4 is a branched alkyl radical or a neoalkyl radical having 7 to 11 carbon atoms, in particular having 8, 9 or 10 carbon atoms.
  • Particularly preferred vinyl esters are derived from secondary and especially tertiary carboxylic acids whose branching is in the alpha position to the carbonyl group.
  • Suitable vinyl esters include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl hexanoate, vinyl heptanoate, vinyl octanoate, vinyl pivalate, vinyl 2-ethylhexanoate, vinyl laurate, vinyl stearate and versatic acid esters such as vinyl neononanoate, vinyl neodecanoate, vinyl neoundecanoate.
  • Suitable acrylic esters include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n- and isobutyl (meth) acrylate, hexyl, octyl, 2-ethylhexyl, decyl, dodecyl, tetradecyl , Hexadecyl, octadecyl (meth) acrylate and mixtures of these comonomers.
  • said alkyl groups may be substituted with one or more hydroxyl groups.
  • An example of such an acrylic ester is hydroxyethyl methacrylate.
  • the alkenes are preferably simple unsaturated hydrocarbons having 3 to 30 carbon atoms, especially 4 to 16 carbon atoms and especially 5 to 12 carbon atoms.
  • Suitable alkenes include propene, butene, isobutylene, pentene, hexene, 4-methylpentene, octene, diisobutylene and norbornene and its derivatives such as methylnorbornene and vinylnorbornene.
  • said alkyl groups may be substituted with one or more hydroxyl groups.
  • Particularly preferred terpolymers of 2-ethylhexanoic acid vinyl ester, vinyl neononanoate or vinyl neodecanoate contain, in addition to ethylene, preferably 3.5 to 20 mol%, in particular 8 to 15 mol% vinyl acetate and 0.1 to 12 mol%, in particular 0.2 to 5 mol% of the respective long-chain vinyl ester, wherein the total comonomer content is between 9 and 21 mol%, preferably between 12 and 18 mol%.
  • copolymers contain, in addition to ethylene and 8 to 18 mol% of vinyl esters, 0.5 to 10 mol% of olefins such as propene, butene, isobutylene, hexene, 4-methylpentene, octene, diisobutylene and / or norbornene.
  • ethylene copolymers and terpolymers preferably have melt viscosities at 140 ° C. of from 20 to 10,000 mPas, in particular from 30 to 5,000 mPas, especially from 50 to 2,000 mPas.
  • the means of 1 H-NMR spectroscopy, certain degrees of branching are preferably between 1 and 9 CH 3/100 CH 2 groups, especially between 2 and 6 CH 3/100 CH 2 groups, which do not stem from the comonomers.
  • the mixing ratio between the terpolymers A) and ethylene copolymers B1) can vary within wide limits, the terpolymers A) often being the smaller fraction as crystal nucleating agents.
  • such additive mixtures contain 2 to 70 wt .-%, preferably 3 to 50 wt .-% and especially 5 to 20 wt .-% of component A and 30 to 98 wt .-%, preferably 50 to 97 wt .-% and especially 70 to 95 wt .-% of component B1.
  • Comb polymers as component B2) are generally characterized as containing a polymer backbone to which are attached at regular intervals long chain branches, such as hydrocarbon chains of about 8 to 50 carbon atoms. These side chains can be bonded directly to the polymer backbone via a C-C bond or via an ether, ester, amide or imide bond.
  • R ' preferably represents a hydrocarbon radical having 10 to 24 C atoms and in particular a hydrocarbon radical having 12 to 18 C atoms.
  • R ' is linear or predominantly linear, that is, R' contains at most one methyl or ethyl branch.
  • Suitable comb polymers are, for example, esterified copolymers of ethylenically unsaturated dicarboxylic acids such as maleic or fumaric acid or their reactive Derivatives with other ethylenically unsaturated monomers such as olefins or vinyl esters.
  • Particularly suitable olefins are ⁇ -olefins having 10 to 24 carbon atoms such as 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene and mixtures thereof.
  • olefins based on oligomerized C 2 -C 6 -olefins such as poly (isobutylene) with a high proportion of terminal double bonds are suitable as comonomers.
  • Copolymers of maleic acid or maleic anhydride and / or fumaric acid with hexadecene, octadecene and mixtures of these olefins are particularly preferred.
  • the copolymers contain up to 15 mol%, such as, for example, 1 to 10 mol% of poly (isobutylene) having a molecular weight Mw between 300 and 5,000 g / mol.
  • Vinyl esters which are particularly suitable as comonomers are derived from fatty acids having 1 to 12 C atoms and in particular 2 to 8 C atoms such as vinyl acetate, vinyl propionate, vinyl butyrate, 2-ethylhexanoic acid vinyl, neononanoic vinyl ester, vinyl neodecanoate and vinyl neoundecanoate. Also mixtures of different vinyl esters are suitable. Particularly preferred are copolymers of fumaric acid with vinyl acetate.
  • these copolymers are at least 50% esterified with alcohols having 10 to 24 carbon atoms such as with 12 to 18 carbon atoms.
  • Suitable alcohols include n-decan-1-ol, n-dodecan-1-ol, n-tetradecan-1-ol, n-hexadecan-1-ol, n-octadecan-1-ol, n-eicosan-1-ol and their mixtures. Particular preference is given to n-tetradecan-1-ol, n-hexadecan-1-ol and mixtures thereof.
  • comb polymers B2 are polymers and copolymers of ⁇ -olefins, and also esterified copolymers of styrene and maleic anhydride, and esterified copolymers of stryol and fumaric acid.
  • the above-mentioned alcohols having 10 to 24 carbon atoms are preferred for esterification.
  • copolymers based on the abovementioned alkyl acrylates, methacrylates, alkyl vinyl ethers and / or vinyl esters for example copolymers of alkyl acrylates and vinyl esters.
  • mixtures of two or more comb polymers are suitable according to the invention.
  • the comb polymers of components B2) preferably have molecular weights Mw between about 2,000 and about 50,000 g / mol, preferably between 3,000 and 20,000 g / mol.
  • the mixing ratio between component A) and comb polymer B2) is usually in the range from 10: 1 to 1: 3, preferably between 6: 1 and 1: 2, for example between 5: 1 and 1: 1.
  • the mixing ratio between component B1) and comb polymer B2) is usually between 10: 1 to 1: 3, preferably between 6: 1 and 1: 2, for example between 5: 1 and 1: 1
  • the additive mixtures according to the invention are usually used for the purpose of better handling as concentrates in organic solvents.
  • Suitable solvents or dispersants are, for example, higher-boiling aliphatic hydrocarbons, aromatic hydrocarbons, alcohols, esters, ethers and mixtures thereof.
  • solutions or dispersions of the additive mixtures according to the invention contain from 10 to 90% by weight, in particular from 20 to 80% by weight and especially from 40 to 75% by weight, of solvent.
  • the solutions of the additive mixtures according to the invention have a lower ownstock point than corresponding mixtures based on terpolymers of ethylene, unsaturated esters and higher olefins according to the prior art.
  • they show improved efficacy in terms of the cold flow improvement of fuel oils, and in particular, improved solubility in fuel oils even at low temperatures.
  • these additives can also be used at low temperatures without prior heating of oil and / or additive, without filtration problems in the additized oil resulting from undissolved or recrystallized portions of the polymer A).
  • the additives according to the invention can be transported at the same temperature with a lower solvent content and processed as corresponding additives of the prior art, whereby transport and storage costs are reduced.
  • the additive mixtures according to the invention can also be added to middle distillates for improving the cold flowability in combination with other additives such as, for example, oil-soluble polar nitrogen compounds, alkylphenol resins, polyoxyalkylene compounds and / or olefin copolymers.
  • Suitable oil-soluble polar nitrogen compounds are preferably reaction products of fatty amines with compounds containing an acyl group.
  • the alkyl and alkenyl radicals can be linear or branched and contain up to two double bonds. They are preferably linear and substantially saturated, ie they have iodine numbers of less than 75 gl 2 / g, preferably less than 60 gl 2 / g and in particular between 1 and 10 gl 2 / g. Particular preference is given to secondary fatty amines in which two of the groups R 7 , R 8 and R 9 are C 8 -C 36 -alkyl, C 6 -C 36 -cycloalkyl, C 8 -C 36 -alkenyl, in particular C 12 -C 24 alkyl, C 12 -C 24 alkenyl or cyclohexyl.
  • Suitable fatty amines are, for example, octylamine, decylamine, dodecylamine, tetradecylamine, hexadecylamine, octadecylamine, eicosylamine, behenylamine, didecylamine, didodecylamine, ditetradecylamine, dihexadecylamine, dioctadecylamine, dieicosylamine, dibehenylamine and mixtures thereof.
  • the amines contain chain cuts based on natural raw materials such as coco fatty amine, tallow fatty amine, hydrogenated tallow fatty amine, dicocosfettamine, ditallow fatty amine and di (hydrogenated tallow fatty amine).
  • Particularly preferred amine derivatives are amine salts, imides and / or amides such as, for example, amide ammonium salts of secondary fatty amines, in particular dicocosfettamine, ditallow fatty amine and distearylamine.
  • Suitable carbonyl compounds for the reaction with amines are both monomeric and polymeric compounds having one or more carboxyl groups. In the case of the monomeric carbonyl compounds, preference is given to those having 2, 3 or 4 carbonyl groups. They can also contain heteroatoms such as oxygen, sulfur and nitrogen.
  • carboxylic acids examples include maleic, fumaric, crotonic, itaconic, succinic, C 1 -C 40 -alkenylsuccinic, adipic, glutaric, sebacic, and malonic acids and benzoic, phthalic, trimellitic and pyromellitic acid, nitrilotriacetic acid , Ethylenediaminetetraacetic acid and their reactive derivatives such as esters, anhydrides and acid halides.
  • Copolymers of ethylenically unsaturated acids such as, for example, acrylic acid, methacrylic acid, maleic acid, fumaric acid and itaconic acid, have proven particularly suitable as polymeric carbonyl compounds, particular preference is given to copolymers of maleic anhydride.
  • Suitable comonomers are those which impart oil solubility to the copolymer. Oil-soluble means here that the copolymer dissolves without residue in the middle distillate to be additive after reaction with the fatty amine in practice-relevant metering rates.
  • Suitable comonomers are, for example, olefins, alkyl esters of acrylic acid and methacrylic acid, alkyl vinyl esters and alkyl vinyl ethers having 2 to 75, preferably 4 to 40 and in particular 8 to 20 carbon atoms in the alkyl radical.
  • the carbon number refers to the alkyl radical attached to the double bond.
  • the molecular weights of the polymeric carbonyl compounds are preferably between 400 and 20,000, particularly preferably between 500 and 10,000, for example between 1,000 and 5,000 g / mol.
  • Oil-soluble polar nitrogen compounds which have been obtained by reaction of aliphatic or aromatic amines, preferably long-chain aliphatic amines, with aliphatic or aromatic mono-, di-, tri- or tetracarboxylic acids or their anhydrides have proven particularly suitable (cf. US 4 211 534 ).
  • amides and ammonium salts of aminoalkylene polycarboxylic acids such as nitrilotriacetic acid or ethylenediaminetetraacetic acid with secondary amines are suitable as oil-soluble polar nitrogen compounds (cf. EP 0 398 101 ).
  • oil-soluble polar nitrogen compounds are copolymers of maleic anhydride with ⁇ , ⁇ -unsaturated compounds which can be reacted, if appropriate, with primary monoalkylamines and / or aliphatic alcohols (cf. EP-A-0 154 177 . EP 0 777 712 ), the reaction products of Alkenylspirobislactonen with amines (see. EP-A-0 413 279 B1) and after EP-A-0 606 055 A2 reaction products of terpolymers based on ⁇ , ⁇ -unsaturated dicarboxylic acid anhydrides, ⁇ , ⁇ -unsaturated compounds and polyoxyalkylene ethers of lower unsaturated alcohols.
  • the mixing ratio between the additive mixtures according to the invention and oil-soluble polar nitrogen compounds may vary depending on the application.
  • Such mixtures preferably contain 0.1 to 10 parts by weight, preferably 0.2 to 5 parts by weight, based on the active ingredients, of at least one oil-soluble polar nitrogen compound per part by weight of the additive mixture according to the invention.
  • Suitable alkylphenol-aldehyde resins are in particular those alkylphenol-aldehyde resins which are derived from alkylphenols having one or two alkyl radicals in ortho and / or para position to the OH group.
  • Particularly preferred as starting materials are alkylphenols which carry at least two hydrogen atoms capable of condensation with aldehydes on the aromatic and in particular monoalkylated phenols.
  • the alkyl radical is in the para position to the phenolic OH group.
  • the alkyl radicals (which are generally understood as hydrocarbon radicals as defined below for the alkylphenol resins) may be identical or different in the alkylphenol-aldehyde resins which can be used with the additive mixtures according to the invention.
  • the alkyl radicals can be saturated or unsaturated. They can be linear or branched, preferably they are linear. They have 1 to 200, preferably 1 to 24, especially 4 to 16 such as 6 to 12 carbon atoms.
  • mixtures of alkylphenols having different alkyl radicals are used for the preparation of the alkylphenol resins.
  • resins based on Butylphenol on the one hand and octyl, nonyl and / or dodecylphenol in a molar ratio of 1:10 to 10: 1 on the other hand particularly proven.
  • Suitable alkylphenol resins may also contain or consist of structural units of other phenol analogs such as salicylic acid, hydroxybenzoic acid and derivatives thereof such as esters, amides and salts.
  • Suitable aldehydes for the alkylphenol-aldehyde resins are those having 1 to 12 carbon atoms and preferably those having 1 to 4 carbon atoms such as formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, 2-ethylhexanal, benzaldehyde, glyoxalic acid and their reactive equivalents such as paraformaldehyde and trioxane.
  • Particularly preferred is formaldehyde in the form of paraformaldehyde, and especially formalin.
  • the molecular weight of the alkylphenol-aldehyde resins measured by gel permeation chromatography against poly (styrene) standards in THF is preferably 500-25,000 g / mol, more preferably 800-10,000 g / mol, and especially 1,000-5,000 g / mol such as 1,500-3,000 g / mol.
  • the prerequisite here is that the alkylphenol-aldehyde resins, at least in application-relevant concentrations of 0.001 to 1 wt .-% are oil-soluble.
  • these are alkylphenol-formaldehyde resins, the oligo- or polymers having a repetitive structural unit of the formula wherein R 10 is C 1 -C 200 alkyl or alkenyl, OR 11 or OC (O) -R 11 , R 11 is C 1 -C 200 alkyl or alkenyl and n is a number from 2 to 100 stand.
  • R 11 stands preferably C 1 -C 20 -alkyl or -alkenyl and in particular C 4 -C 16 -alkyl or -alkenyl, for example C 6 -C 12 -alkyl or -alkenyl.
  • R 10 particularly preferably represents C 1 -C 20 -alkyl or -alkenyl and in particular C 4 -C 16 -alkyl or -alkenyl, for example C 6 -C 12 -alkyl or -alkenyl.
  • n is a number from 2 to 50 and especially a number from 3 to 25, such as a number from 5 to 15.
  • alkylphenol-aldehyde resins having C 2 -C 40 -alkyl radicals of the alkylphenol, preferably having C 4 -C 20 -alkyl radicals such as, for example, C 6 -C 12 -alkyl radicals.
  • the alkyl radicals can be linear or branched, preferably they are linear.
  • Particularly suitable alkylphenol-aldehyde resins are derived from linear alkyl radicals having 8 and 9 C atoms.
  • alkylphenol-aldehyde resins whose alkyl radicals carry 4 to 50 carbon atoms, preferably 10 to 30 carbon atoms.
  • the degree of polymerization (n) here is preferably between 2 and 20, preferably between 3 and 10 alkylphenol units.
  • alkylphenol-aldehyde resins are, for example, by condensation of the corresponding alkylphenols with formaldehyde, ie with 0.5 to 1.5 moles, preferably 0.8 to 1.2 moles of formaldehyde per mole of alkylphenol.
  • the condensation can be carried out solvent-free, but preferably it is carried out in the presence of a non or only partially water-miscible inert organic solvent such as mineral oils, alcohols, ethers, and the like.
  • Particularly preferred are solvents which can form azeotropes with water.
  • solvents in particular aromatics such as toluene, xylene diethylbenzene and higher-boiling commercial solvent mixtures such as ® Shellsol AB, and solvent naphtha are used.
  • fatty acids and their derivatives such as esters with lower alcohols having 1 to 5 carbon atoms such as ethanol and especially methanol are suitable as solvents.
  • the condensation is preferably carried out between 70 and 200 ° C such as between 90 and 160 ° C. It is usually catalysed by 0.05 to 5 wt .-% bases or preferably by 0.05 to 5 wt .-% acids.
  • sour Catalysts are in addition to carboxylic acids such as acetic acid and oxalic acid in particular strong mineral acids such as hydrochloric acid, phosphoric acid and sulfuric acid and sulfonic acids common catalysts.
  • Particularly suitable catalysts are sulfonic acids which contain at least one sulfonic acid group and at least one saturated or unsaturated, linear, branched and / or cyclic hydrocarbon radical having 1 to 40 C atoms and preferably having 3 to 24 C atoms.
  • aromatic sulfonic acids especially alkylaromatic monosulfonic acids having one or more C 1 -C 25 -alkyl radicals and, in particular, those having C 3 -C 22 -alkyl radicals.
  • Suitable examples are methanesulfonic acid, butanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, xylenesulfonic acid, 2-mesitylenesulfonic acid, 4-ethylbenzenesulfonic acid, isopropylbenzenesulfonic acid, 4-butylbenzenesulfonic acid, 4-octylbenzenesulfonic acid; Dodecylbenzenesulfonic acid, didodecylbenzenesulfonic acid, naphthalenesulfonic acid.
  • polyoxyalkylene compounds are, for example, esters, ethers and ethers / esters of polyols which carry at least one alkyl radical having 12 to 30 carbon atoms.
  • the alkyl groups are derived from an acid, the remainder is derived from a polyhydric alcohol; If the alkyl radicals come from a fatty alcohol, the remainder of the compound derives from a polyacid.
  • Suitable polyols are polyethylene glycols, polypropylene glycols, polybutylene glycols and their copolymers having a molecular weight of about 100 to about 5000, preferably 200 to 2000 g / mol.
  • alkoxylates of polyols for example of glycerol, trimethylolpropane, pentaerythritol, neopentyl glycol, and the oligomers having from 2 to 10 monomer units obtainable therefrom by condensation, such as, for example, polyglycerol.
  • Preferred alkoxylates are those having from 1 to 100, in particular from 5 to 50, mol of ethylene oxide, propylene oxide and / or butylene oxide per mole of polyol. Esters are especially preferred.
  • Fatty acids containing 12 to 26 carbon atoms are preferred for reaction with the polyols to form the ester additives, more preferably C 18 to C 24 fatty acids, especially stearic and behenic acid.
  • the esters can also be prepared by esterification of polyoxyalkylated alcohols. Preference is given to completely esterified polyoxyalkylated polyols having molecular weights of from 150 to 2,000, preferably from 200 to 600. Particularly suitable are PEG-600 dibehenate and glycerol-ethylene glycol tribehenate.
  • Olefincopolymers which are suitable as further constituent of the additive according to the invention can be derived directly from monoethylenically unsaturated monomers or can be prepared indirectly by hydrogenation of polymers derived from polyunsaturated monomers such as isoprene or butadiene.
  • preferred copolymers contain structural units which are derived from ⁇ -olefins having 3 to 24 carbon atoms and have molecular weights of up to 120,000 g / mol.
  • Preferred ⁇ -olefins are propene, butene, isobutene, n-hexene, isohexene, n-octene, isooctene, n-decene, isodecene.
  • the comonomer content of ⁇ -olefins having 3 to 24 C atoms is preferably between 15 and 50 mol%, more preferably between 20 and 35 mol% and especially between 30 and 45 mol%. These copolymers may also contain minor amounts, eg up to 10 mol% of other comonomers, such as non-terminal olefins or non-conjugated olefins.
  • Preferred are ethylene-propene copolymers.
  • the olefin copolymers can be prepared by known methods, for example by Ziegler or metallocene catalysts.
  • olefin copolymers are block copolymers containing blocks of olefinically unsaturated aromatic monomers A and blocks of hydrogenated polyolefins B.
  • Particularly suitable are block copolymers of the structure (AB) n A and (AB) m , where n is a number between 1 and 10 and m is a number between 2 and 10.
  • the mixing ratio between the additive mixtures according to the invention and alkylphenol resins, polyoxyalkylene compounds or olefin copolymers can vary depending on the application.
  • Such mixtures preferably contain 0.1 to 10 parts by weight, preferably 0.2 to 5 parts by weight, based on the active compounds at least one alkylphenol resin, a polyoxyalkylene compound and / or an olefin copolymer per part by weight of the additive mixture according to the invention.
  • the additive mixtures according to the invention can be used alone or together with other additives, e.g. with other pour point depressants or dewaxing aids, with antioxidants, cetane number improvers, dehazers, demulsifiers, detergents, dispersants, defoamers, dyes, corrosion inhibitors, lubricity additives, sludge inhibitors, odorants and / or cloud point depressants.
  • other additives e.g. with other pour point depressants or dewaxing aids, with antioxidants, cetane number improvers, dehazers, demulsifiers, detergents, dispersants, defoamers, dyes, corrosion inhibitors, lubricity additives, sludge inhibitors, odorants and / or cloud point depressants.
  • the additive mixtures according to the invention are suitable for improving the cold flow properties of animal, vegetable mineral and / or synthetic fuel oils.
  • these additive blends and their concentrated formulations in mineral oil based solvents have low levels of inherent stickiness. This allows a problem-free use of these additive mixtures at lower temperatures or in higher concentrations than is possible with additives of the prior art.
  • the additive mixtures can be dosed due to their good solubility in cold oils, without causing filter blockages by undissolved or recrystallized portions of the additive mixtures.
  • Additive mixtures containing components A and B1 are particularly suitable for middle distillates with cloud points below + 5 ° C such as between -15 ° C and + 3 ° C. They are particularly suitable for those oils which have a high content of particularly cold-critical paraffins with a carbon chain length of 20 or more carbon atoms of more than 3.0 area% and in particular more than 4.0 area%.
  • Additive mixtures containing components A and B2 are particularly suitable for middle distillates with cloud points above -4 ° C such as above -2 ° C.
  • oils which have a high content of particularly cold-critical paraffins with a carbon chain length of 20 or more carbon atoms of more than 3.5 area% and in particular more than 4.5 area%.
  • the paraffin content is determined by gas chromatographic separation of the oil under detection by a FID detector and calculation of the integral of n-paraffins with a chain length of at least 20 C atoms in relation to the total integral of the oil.
  • they have often been subjected to hydrogenation refining and preferably contain less than 350 ppm sulfur, and more preferably less than 100 ppm sulfur, such as less than 50 ppm or 10 ppm sulfur.
  • the fuel oils according to the invention preferably contain 5 to 5,000 ppm, particularly preferably 10 to 2,000 ppm and especially 50 to 1,000 ppm of the additive mixtures according to the invention.
  • the middle distillate is in particular those mineral oils which are obtained by distillation of crude oil and boil in the range of 120 to 450 ° C, for example kerosene, jet fuel, diesel and fuel oil.
  • the additive mixtures according to the invention are particularly advantageous in those middle distillates which have 90% distillation points according to ASTM D86 above 340 ° C., in particular above 360 ° C. and in special cases above 370 ° C.
  • Middle distillates also include synthetic fuel oils boiling in the temperature range of about 120 to 450 ° C and mixtures of these synthetic and mineral middle distillates.
  • Examples of synthetic middle distillates are, in particular, fuels produced from coal, natural gas or even biomass by the Fischer-Tropsch process. Synthesis gas is first produced and this is converted into normal paraffins via the Fischer-Tropsch process. The normal paraffins thus prepared can then be modified, for example, by catalytic cracking, isomerization, hydrocracking or hydrosiomerization.
  • the additive mixtures according to the invention are also particularly effective in middle distillates which contain minor amounts, for example up to 30% by volume, of oils of animal and / or vegetable origin.
  • oils of animal and / or plant origin are both triglycerides and esters derived therefrom with lower alcohols having 1 to 5 carbon atoms such as ethyl and especially methyl esters, for example, from cotton, palm kernels, rapeseed, soy, sunflower, tallow and the like are accessible.
  • a terpolymer of ethylene, vinyl acetate and propene according to EP 0 190 553 a terpolymer of ethylene, vinyl acetate and 4-methylpentene-1 according to EP 0 807 642 and a terpolymer of ethylene, vinyl acetate and isobutylene.
  • the vinyl acetate content is determined by means of pyrolysis of the polymer freed from residual monomers at 150 ° C./100 mbar.
  • 100 mg of the polymer are thermally split with 200 mg of pure polyethylene in a pyrolysis flask for 5 minutes at 450 ° C in a closed system under vacuum and collected the fission gases in a 250 ml round bottom flask.
  • the cleavage product acetic acid is reacted with a NaJ / KJO 3 solution and titrated with Na 2 S 2 O 3 solution, the liberated iodine.
  • the determination of the content of methyl groups derived from propene is carried out by means of 13 C-NMR spectroscopy at a measurement frequency of 125 MHz at also 10 to 15% solutions in C 2 D 2 Cl 4 at 300 K.
  • the integral of the Propene-derived methyl groups between 19.3 and 20.2 ppm are proportioned to that of the aliphatic carbon atoms of the polymer backbone between 22 and 44 ppm.
  • 1 H and 13 C NMR measurements are carried out on the same sample.
  • the number of chain ends is determined by subtracting the number of methyl groups derived from propene by 13 C-NMR from the total number of methyl groups determined by 1 H-NMR. Both values are to be treated as dimensionless numbers.
  • Table 1 Characterization of the ethylene copolymers A used polymer Polymerization method / moderator Vinyl acetate in the polymer [mol%] Propene-CH 3 per 100 aliph.
  • the polymers described in Table 1 were dissolved in a predominantly aliphatic solvent mixture having a boiling range of 175-260 ° C. and a flash point of 66 ° C., 35% strength by weight.
  • the polymer and solvent were heated with stirring to 80 ° C and cooled after homogenization to room temperature.
  • the Filterverstopfungstendenz a treated with additives of the invention test oil was determined according to IP 387/97.
  • 300 ml of an additive diesel fuel at a defined temperature and a pump capacity of 20 ml / min are filtered through a 1.6 micron glass fiber filter.

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Claims (14)

  1. Mélanges d'additifs, qui comportent
    A) au moins terpolymère d'éthylène, de propène et d'au moins un ester à insaturation éthylénique, qui
    i) comporte 6,0 à 12,0 % en moles d'au moins un ester à insaturation éthylénique comportant des motifs structuraux dérivés d'un radical alkyle en C1-C3,
    ii) comporte 0,5 à 4,0 groupes méthyle liés au squelette polymère et dérivés du propène pour 100 atomes de carbone aliphatiques,
    iii) a moins de 8,0 groupes méthyle provenant d'extrémités de chaînes pour 100 groupes CH2, et
    B) 0,5 à 20 parties en poids, par rapport à A), d'au moins un autre composant efficace en tant additif pour l'amélioration des propriétés à froid pour huiles minérales, choisi parmi
    B1) des copolymères d'éthylène et de composés à insaturation éthylénique, dont la teneur en composés à insaturation éthylénique est supérieure d'au moins 2 % en moles à la teneur en esters à insaturation éthylénique du terpolymère défini en A),
    B2) des polymères en peigne, et
    B3) des mélanges de B1) et B2).
  2. Mélange d'additifs selon la revendication 1, dans lequel l'ester à insaturation éthylénique du composant A) est l'ester vinylique d'un acide carboxylique ayant de 1 à 4 atomes de carbone.
  3. Mélange d'additifs selon la revendication 2, dans lequel l'ester insaturé est l'acétate de vinyl.
  4. Mélange d'additifs selon une ou plusieurs des revendications 1 à 3, dans lequel la somme G de la teneur molaire en ester insaturé i) et du nombre des groupes méthyle dérivés du propène pour 100 atomes de carbone aliphatiques du polymère ii) G = % en moles dʹester insatué + CH 3 de propène
    Figure imgb0006
    est comprise entre 8,0 et 14,0.
  5. Mélange d'additifs selon une ou plusieurs des revendications 1 à 4, dans lequel le composant A) contient également 0,3 à 5,0 % en poids d'au moins une unité structurale dérivée d'un modérateur contenant des groupes carbonyle.
  6. Mélange d'additifs selon une ou plusieurs des revendications 1 à 5, dans lequel la teneur du copolymère B1) de composés éthyléniquement insaturés est supérieure d'au moins trois % en moles à celle du terpolymère A) en esters éthyléniquement insaturés.
  7. Procédé de fabrication du terpolymère A), dans lequel un mélange d'éthylène, de propène et d'au moins un ester de vinyle est mis en réaction sous pression élevée et température élevée en présence d'un initiateur formant des radicaux, et dans lequel le poids moléculaire du terpolymère A) est ajusté par un modérateur contenant des groupes carbonyle.
  8. Utilisation d'un mélange d'additifs selon une ou plusieurs des revendications 1 à 6, pour l'amélioration de l'aptitude à l'écoulement à froid d'huiles combustibles.
  9. Procédé pour l'amélioration de l'aptitude à l'écoulement d'huiles combustibles, dans lequel on ajoute à l'huile combustible un mélange d'additifs selon une ou plusieurs des revendications 1 à 6.
  10. Composition, contenant au moins un mélange d'additifs selon une ou plusieurs des revendications 1 à 6 et au moins un composé d'azote polaire soluble dans l'huile.
  11. Composition, contenant au moins un mélange d'additifs selon une ou plusieurs des revendications 1 à 6 et au moins une résine d'alkylphénol-aldéhyde.
  12. Composition, contenant au moins un mélange d'additifs selon une ou plusieurs des revendications 1 à 6 et au moins un polymère d'oléfine.
  13. Composition selon une ou plusieurs des revendications précédentes, contenant au moins un mélange d'additifs selon une ou plusieurs des revendications 1 à 6 et au moins un composé de polyoxyalkylène.
  14. Composition d'huile combustible, contenant un distillat moyen et au moins un mélange d'additifs selon une ou plusieurs des revendications 1 à 6.
EP07011538A 2006-07-18 2007-06-13 Additif destiné à l'amélioration des propriétés à froid d'huiles combustibles Active EP1881053B1 (fr)

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DE102006033150A DE102006033150B4 (de) 2006-07-18 2006-07-18 Additive zur Verbesserung der Kälteeigenschaften von Brennstoffölen

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EP1881053A2 EP1881053A2 (fr) 2008-01-23
EP1881053A3 EP1881053A3 (fr) 2011-02-02
EP1881053B1 true EP1881053B1 (fr) 2012-03-28

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EP (1) EP1881053B1 (fr)
JP (1) JP5348861B2 (fr)
KR (1) KR101412451B1 (fr)
CA (1) CA2593940C (fr)
DE (1) DE102006033150B4 (fr)
ES (1) ES2381371T3 (fr)

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DE102006033150B4 (de) 2008-10-16
JP2008024928A (ja) 2008-02-07
CA2593940A1 (fr) 2008-01-18
KR20080008285A (ko) 2008-01-23
KR101412451B1 (ko) 2014-06-30
JP5348861B2 (ja) 2013-11-20
US8968428B2 (en) 2015-03-03
DE102006033150A1 (de) 2008-01-31
ES2381371T3 (es) 2012-05-25
EP1881053A3 (fr) 2011-02-02
CA2593940C (fr) 2014-02-11
US20080016754A1 (en) 2008-01-24
EP1881053A2 (fr) 2008-01-23

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