EP2516605B1 - Additifs de refroidissement ayant une meilleure aptitude à l'écoulement - Google Patents

Additifs de refroidissement ayant une meilleure aptitude à l'écoulement Download PDF

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Publication number
EP2516605B1
EP2516605B1 EP10800881.4A EP10800881A EP2516605B1 EP 2516605 B1 EP2516605 B1 EP 2516605B1 EP 10800881 A EP10800881 A EP 10800881A EP 2516605 B1 EP2516605 B1 EP 2516605B1
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Prior art keywords
carbon atoms
alkyl
cold
esters
mol
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German (de)
English (en)
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EP2516605A2 (fr
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Matthias Krull
Werner Reimann
Stefan Dilsky
Sabine Goetzke
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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
    • C10L1/143—Organic compounds mixtures of organic macromolecular compounds with organic non-macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, 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
    • C10L1/1985—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
    • 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
    • C10L10/00—Use of additives to fuels or fires for particular purposes
    • C10L10/14—Use of additives to fuels or fires for particular purposes for improving low temperature properties
    • C10L10/16—Pour-point depressants
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, 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
    • C10L1/1608—Well defined compounds, e.g. hexane, benzene
    • 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
    • C10L1/1616—Hydrocarbons fractions, e.g. lubricants, solvents, naphta, bitumen, tars, terpentine
    • 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
    • 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
    • C10L1/1963—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 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
    • C10L1/1983—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 polyesters
    • 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

Definitions

  • the present invention relates to cold additives for middle distillates having improved low temperature handleability, their use for improving the cold properties of middle distillates, and the corresponding middle distillates.
  • paraffin-rich crude oils In the course of decreasing world oil reserves, increasingly heavier and thus paraffin-rich crude oils are extracted and processed, which consequently also lead to paraffin-rich fuel oils.
  • the paraffins contained in particular in crude oils and middle distillates such as gas oil, diesel and fuel oil can crystallize on lowering the temperature of the oil and agglomerate with the inclusion of oil. Due to this crystallization and agglomeration, blockages of the filters in engines and firing systems can occur, especially in winter, which prevents a safe metering of the fuels and may possibly lead to a complete interruption of the fuel or heating agent supply.
  • paraffin problem is further exacerbated by the environmental reasons to reduce the sulfur content to be carried out hydrogenating desulfurization of fuel oils, which leads to an increased proportion of cold-critical paraffins and a reduced proportion of the solubility of paraffins-improving mono- and polycyclic aromatic compounds in the fuel oil.
  • middle distillates are often added chemical additives, so-called cold flow improvers or flow improvers, modify the crystal structure and Agglomerationsne noticed the precipitated paraffins, so that the so-additive oils still pump or use at temperatures, often more than 20 ° C. lower than non-additized oils.
  • cold flow improvers oil-soluble copolymers of ethylene and unsaturated esters are usually used.
  • comb polymers For the addition of middle distillates with a high content of, in particular, longer-chain paraffins, these copolymers of ethylene and unsaturated esters are often used together with comb polymers.
  • Comb polymers is understood to mean a special form of the branched macromolecules which carry longer, more or less equally long alkyl side chains on a linear main chain at more or less regular intervals.
  • the co-use of copolymers of ethylene and unsaturated esters with comb polymers synergistically enhanced efficiencies are reported as cold additives, which are believed to be based on a paraffin crystallization nucleating function of these comb polymers. These occur in particular when using comb polymers with very long side chains.
  • U.S. 3,447,916 discloses condensation polymers of alkenyl succinic anhydrides, polyols and fatty acids to lower the pour point of hydrocarbon oils. These polymers have a high side chain density due to the almost complete esterification of the hydroxyl groups of the polyol. The font gives no indication of the common use with other additives.
  • DE-A-19 20 849 discloses condensation polymers of alkenyl succinic anhydrides, polyols having at least 4 OH groups and fatty acids for lowering the pour point of hydrocarbon oils.
  • the stoichiometry of the reactants used for the condensation is selected so that the number of moles of OH groups and carboxyl groups is the same, that is, there is essentially complete esterification. Because of the engagement Polyhydric alcohols and the associated further increase in the side chain density show these polymers according to the disclosure of the one of the additives U.S. 3,447,916 superior effectiveness. Also, this document gives no indication of the common use with other additives.
  • DE-A-24 51 047 discloses light, low viscosity distillate fuel oils which contain no residues and are additized with ethylene copolymers as well as comb polymers having C 18 -C 44 side chains.
  • comb polymers inter alia, ester condensation polymers of alk (en) ylsuccinic anhydride having a C 16 -C 44 -alk (en) yl radical, a polyol having 2-6 OH groups and a C 20 -C 44 monocarboxylic acid are used.
  • the three components of the polyester are preferably condensed in equimolar amounts, resulting in substantially complete esterification of both OH and COOH groups.
  • Exemplified (polymer G) is a polycondensate of equimolar amounts of C 22-28 alkenyl succinic anhydride, trimethylolpropane and C 20-22 fatty acids.
  • DE-A-103 49 859 discloses additive mixtures containing a waxy oligomeric ester based on glycerol monostearate and dimer acid and an ethylene-vinyl ester copolymer as a concentrate in a mineral oil middle distillate.
  • the additive mixtures improve the cold flow behavior of middle distillates such as diesel or heating oil.
  • WO-A-2007/015080 discloses esters of a substituted succinic acid with polyols, preparable by reaction of internal olefins having 3 to 80 carbon atoms and maleic anhydride, followed by the reaction of the substituted maleic anhydride with a polyol.
  • Additive compositions containing these esters have low viscosity and are useful for improving the lubricity of middle distillate fuels.
  • additive combinations of copolymers of ethylene and unsaturated esters and comb polymers used for improving the cold properties of middle distillates are usually used as concentrates in organic solvents. It is particularly important for the use of such additive concentrates in remote locations where there is often no way to heat the additive concentrates, important that they remain flowable at the lowest possible temperature and einmischbar in also cold fuel oils. At the same time, however, the concentration of active substance in the concentrates should be as high as possible, in order to increase the volume keep the additive concentrates to be transported and stored as low as possible.
  • the additive concentrates heated it is often not possible to store the additive concentrates heated. A dilution of the additives is undesirable for logistical reasons, since then the volumes to be transported and stored strongly increase.
  • the comb polymers derived from polyols having 3 or more OH groups often contain relatively high molecular weight fractions which impair the filterability of additized middle distillates.
  • one of the radicals R 1 to R 4 is a linear C 16 -C 40 -alkyl or alkenyl radical; together also referred to as C 16 -C 40 -Alk (en) ylrest, one for a methyl group and the remaining hydrogen.
  • one of the radicals R 1 to R 4 is a linear C 16 -C 40 -alkyl or alkenyl radical and the others are hydrogen.
  • R 5 is a CC single bond.
  • one of the radicals R 1 to R 4 is a linear C 16 -C 40 -alkyl or alkenyl radical, the remaining radicals R 1 to R 4 are hydrogen and R 5 is a C-C single bond.
  • the preparation of the dicarboxylic acids or their anhydrides bearing alkyl and / or alkenyl radicals can be carried out by known processes. For example, they can be prepared by heating ethylenically unsaturated dicarboxylic acids with olefins ("ene reaction") or with chloroalkanes. Preference is given to the thermal addition of olefins to ethylenically unsaturated dicarboxylic acids, which is usually carried out at temperatures between 100 and 250 ° C.
  • the resulting alkenyl radicals bearing dicarboxylic acids and dicarboxylic anhydrides can be hydrogenated to dicarboxylic acids and dicarboxylic anhydrides carrying alkyl radicals.
  • Preferred dicarboxylic acids and their anhydrides for the reaction with olefins are maleic acid and particularly preferably maleic anhydride. Also suitable are itaconic acid, citraconic acid, and their anhydrides and esters of the aforementioned acids, in particular with lower C 1 -C 8 alcohols such as methanol, ethanol, propanol and butanol.
  • linear olefins having 16 to 40 C atoms and especially having 18 to 36 C atoms, for example having 19 to 32 C atoms.
  • mixtures of olefins with different chain lengths are used.
  • olefins may also minor portions of shorter and / or contain longer-chain olefins, but preferably not more than 10 wt.% And in particular not more than 0.1 to 5 wt .-%.
  • Preferred olefins have a linear or at least substantially linear alkyl chain.
  • linear or largely linear is meant that at least 50 wt .-%, preferably 70 to 99 wt .-%, in particular 75 to 95 wt .-% such as 80 to 90 wt .-% of olefins a linear portion with 16 to 40 C atoms have.
  • Suitable olefins are preferably technical alkene mixtures.
  • These preferably contain at least 50% by weight, particularly preferably 60 to 99% by weight and in particular 70 to 95% by weight, for example 75 to 90% by weight, of terminal double bonds ( ⁇ -olefins).
  • olefin mixtures containing at least 75 wt .-% of linear ⁇ -olefins having a C chain length in the range of C 20 to C 24 .
  • Preferred polyesters A) are by reaction of a linear C 16 -C 40 alkyl or. Alkenyl radical bearing alkyl or alkenylsuccinic acids and / or their anhydrides with diols produced.
  • n is 1.
  • Preferred such diols have 2 to 10 C atoms, particularly preferably 2 to 6 C atoms and in particular 2 to 4 C atoms. They can be derived from aliphatic or aromatic hydrocarbons.
  • the hydrocarbon radicals preferably contain no further heteroatoms.
  • the hydroxyl groups are located on different C atoms of the hydrocarbon radical. They are preferably located on adjacent C atoms or on the terminal C atoms of an aliphatic hydrocarbon radical or in ortho and para position of an aromatic hydrocarbon radical.
  • Aliphatic hydrocarbon radicals are preferred.
  • the aliphatic hydrocarbon radicals can be linear, branched or cyclic. Favor are linear. Further preferably, they are saturated.
  • diols examples include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol and mixtures thereof. Particularly preferred is ethylene glycol.
  • n is from 2 to 100, more preferably from 3 to 50, and most preferably from 4 to 20, such as from 5 to 15.
  • the diols are preferably oligomers and polymers of C 2 -C 4 -alkylene oxides and in particular oligomers and polymers of ethylene oxide and / or propylene oxide.
  • the degree of condensation of these oligomers and polymers is preferably between 2 and 100, particularly preferably between 3 and 50 and in particular between 4 and 20, for example between 5 and 15.
  • Examples of preferred oligomers and polymers of C 2 -C 4 -alkylene oxides are diethylene glycol, triethylene glycol , Tetraethylene glycol, poly (ethylene glycol), poly (propylene glycol), poly (ethylene glycol-co-propylene glycol) and mixtures thereof.
  • the reaction of the dicarboxylic acids carrying the alkyl radicals or their anhydrides or their esters with the diol is preferably carried out in a molar ratio of 1: 2 to 2: 1, more preferably in a molar ratio of 1: 1.5 to 1.5: 1, in particular molar ratio of 1: 1.2 to 1.2: 1 and especially in the molar ratio of 1: 1.1 to 1.1: 1 such as equimolar.
  • the reaction is carried out with a slight excess of diol. In this case, molar excesses of 1 to 10 mol% and especially 1.5 to 5 mol% based on the amount of dicarboxylic acid used have proven particularly useful.
  • the condensation is preferably carried out by heating C 16 -C 40 -alkyl or alkenyl-substituted dicarboxylic acid or its anhydride or ester with the diol at temperatures above 100 ° C and preferably at temperatures between 120 and 320 ° C such as at temperatures between 150 and 290 ° C.
  • the acid number of the polyesters A) is preferably less than 40 mg KOH / g and particularly preferably less than 30 mg KOH / g, for example less than 20 mg KOH / g.
  • the acid value can be determined, for example, by titration of the polymer with alcoholic tetra-n-butylammonium hydroxide solution in xylene / isopropanol.
  • the hydroxyl number of the polyester A) is below 40 mg KOH / g, more preferably below 30 mg KOH / g and in particular below 20 mg KOH / g.
  • the hydroxyl number can be determined by reacting the free OH groups with isocyanate by means of 1 H NMR spectroscopy by quantitative determination of the urethane formed.
  • the hydroxyl value of the polymer is preferably less than 10 mg KOH / g and in particular less than 5 mg KOH / g, for example less than 2 mg KOH / g.
  • the polyesters A) are prepared in the absence of monocarboxylic acids.
  • the acid value of the polymer is preferably less than 10 mg KOH / g and in particular less than 5 mg KOH / g, for example less than 2 mg KOH / g.
  • the polyesters A) are prepared in the absence of monoalcohols.
  • the mean degree of condensation m of the polymers A1 according to the invention is preferably between 4 and 200, more preferably between 5 and 150 and especially between 7 and 100, for example between 10 and 50.
  • the weight-average molecular weight Mw of the polyester determined by GPC against poly (ethylene glycol) standard A) is preferably between 1,500 and 100,000 g / mol and in particular between 2,500 and 50,000 g / mol, for example between 4,000 and 20,000 g / mol.
  • Preferred copolymers of ethylene and olefinically unsaturated esters B) are, in particular, those which contain, in addition to ethylene, from 8 to 21 mol% and in particular from 10 to 19 mol% of olefinically unsaturated esters as comonomers.
  • the olefinically unsaturated esters are preferably vinyl esters, acrylic esters and / or methacrylic esters.
  • One or more esters may be included as comonomers in the polymer.
  • said alkyl groups may be substituted with one or more hydroxyl groups.
  • Particularly preferred vinyl esters are derived from secondary and especially tertiary carboxylic acids whose branching is in the alpha position to the carbonyl group.
  • R 12 in these vinyl esters is C 4 to C 16 alkyl and especially C 6 - to C 12 alkyl.
  • R 12 is a branched alkyl radical or a neoalkyl radical having 7 to 11 carbon atoms, in particular having 8, 9 or 10 carbon atoms.
  • 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.
  • these ethylene copolymers contain vinyl acetate and at least one further vinyl ester of the formula 2 in which R 12 is C 4 - to C 30 -alkyl, preferably C 4 - to C 16 -alkyl, especially C 6 - to C 12 -alkyl.
  • the further vinyl esters are particularly preferably branched in the alpha position.
  • Suitable acrylic esters include, for.
  • said alkyl groups may be substituted with one or more hydroxyl groups.
  • An example of such an acrylic ester is hydroxyethyl methacrylate.
  • the copolymers B) may contain other olefinically unsaturated compounds as comonomers in addition to olefinically unsaturated esters.
  • Preferred comonomers of this type are alkyl vinyl ethers and alkenes.
  • said alkyl groups may be substituted with one or more hydroxyl groups.
  • the alkenes are preferably monounsaturated 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.
  • terpolymers which, apart from ethylene, have from 3.5 to 20 mol%, in particular from 8 to 15 mol% of vinyl acetate and from 0.1 to 12 mol%, in particular from 0.2 to 5 mol%, of at least one longer-chain and preferably branched one Vinyl esters such as vinyl 2-ethylhexanoate, vinyl neononanoate or vinyl neodecanoate, wherein the total comonomer content of the terpolymers is preferably between 8.1 and 21 mol%, in particular between 8.2 and 19 mol%, for example between 12 and 18 mol%.
  • copolymers contain, in addition to ethylene and 8 to 18 mol% of vinyl esters of C 2 to C 12 carboxylic acids, from 0.5 to 10 mol% of olefins such as propene, butene, isobutylene, hexene, 4-methylpentene, octene, diisobutylene and / or norbornene wherein the total comonomer content is preferably between 8.5 and 21 mol% and in particular between 8.2 and 19 mol%.
  • olefins such as propene, butene, isobutylene, hexene, 4-methylpentene, octene, diisobutylene and / or norbornene
  • these ethylene-co- and terpolymers have melt viscosities at 140 ° C of from 20 to 2,500 mPas, especially from 30 to 1,000 mPas, especially from 50 to 500 mPas.
  • the determined by 1 H NMR spectroscopy 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 polymers underlying the mixtures differ in at least one characteristic.
  • they may contain different comonomers, have different comonomer contents, molecular weights and / or degrees of branching.
  • mixtures of ethylene copolymers having different comonomer contents have proven particularly useful, whose comonomer contents differ by at least 2 mol% and in particular more than 3 mol%.
  • the cold additives according to the invention contain from 25 to 95% by weight and preferably from 28 to 80% by weight, for example from 35 to 70% by weight of at least one organic solvent C).
  • Preferred solvents are higher-boiling, low-viscosity organic solvents.
  • these solvents contain only minor amounts of heteroatoms and especially they consist only of hydrocarbons. Further preferred is their measured at 20 ° C kinematic viscosity below 10 mm 2 / s and in particular below 6 mm 2 / s.
  • Particularly preferred solvents are aliphatic and aromatic hydrocarbons and mixtures thereof.
  • Aliphatic hydrocarbons preferred as solvents have 9 to 20 C atoms and in particular 10 to 16 C atoms. They can be linear, branched and / or cyclic. They may also be saturated or unsaturated, preferably they are saturated or at least largely saturated.
  • Aromatic preferred aromatic hydrocarbons have 7 to 20 carbon atoms and especially 8 to 16 such as 9 to 13 carbon atoms.
  • Preferred aromatic hydrocarbons are mono-, di-, tri- and polycyclic aromatics. In a preferred embodiment, these carry one or more, for example two, three, four, five or more substituents. With several substituents they may be the same or different.
  • Preferred substituents are alkyl radicals having 1 to 20 and in particular having 1 to 5 C atoms, such as, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl , n-pentyl, iso-pentyl, tert-pentyl and neo-pentyl.
  • suitable aromatics are alkylbenzenes and alkylnaphthalenes. For example, aliphatic and / or aromatic hydrocarbons or hydrocarbon mixtures, for.
  • kerosene, decane, pentadecane, toluene, xylene, ethylbenzene or commercial solvent mixtures such as solvent naphtha, Shellsoll ® AB, Solvesso ® 150, Solvesso ® 200, Exxsol ® , ISOPAR ® and Shellsol ® D types particularly suitable.
  • the specified solvent mixtures contain different amounts of aliphatic and / or aromatic hydrocarbons.
  • the solvent C) and polar solubilizers such.
  • alcohols organic acids, ethers and / or esters of organic acids.
  • Preferred solubilizers have 4 to 24 carbon atoms, particularly preferably 6 to 18 and in particular 8 to 16 carbon atoms.
  • solubilizers examples include butanol, 2-ethylhexanol, decanol, iso-decanol, iso-tridecanol, nonylpenol, benzoic acid, oleic acid, dihexyl ether, dioctyl ether, 2-ethylhexyl acid butyrate, ethyl octanoate, ethylhexanoate, butyl 2-ethylhexylate and 2-ethylhexyl butyrate and higher Ethers and / or higher esters such as di (2-ethylhexyl) ether, 2-ethylhexyl acid 2-ethylhexyl ester and 2-ethylhexyl stearate.
  • the proportion of polar solubilizers on the solvent C) is preferably from 5 to 80% by weight and in particular from 10 to 65% by weight.
  • Mineral oils based solvents are also based on renewable raw materials solvents such.
  • the cold additives according to the invention contain from 1.5 to 73.5, in particular from 15 to 70 and especially from 25 to 60% by weight of constituent B).
  • the cold additives according to the invention contain from 0.1 to 50, in particular from 0.5 to 30 and especially from 1 to 20,% by weight of constituent A).
  • the cold additives according to the invention are preferably added to middle distillates in amounts of from 0.001 to 1.0% by weight, more preferably from 0.002 to 0.5% by weight, for example from 0.005 to 0.2% by weight.
  • the cold additives according to the invention can be used together with one or more further cold flow improvers. They are preferably used together with one or more of the cold flow improvers III) to VII):
  • oil-soluble polar nitrogen compounds are suitable. These are preferably reaction products of fatty amines with compounds containing an acyl group.
  • the preferred amines are compounds of the formula NR 6 R 7 R 8 , in which R 6 , R 7 and R 8 may be identical or different, and at least one of these groups is 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, and the other groups are either hydrogen, C 1 -C 36 -alkyl, C 2 -C 36 alkenyl, cyclohexyl, or a group of the formulas - (AO) x -E or - (CH 2 ) k -NYZ, where A is an ethyl or propyl 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. Particularly preferred are secondary fatty amines in which two of the groups R 6 , R 7 and R 8 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 and the third stand for hydrogen.
  • 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.
  • 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 -alkenylic, 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 to be particularly preferred, copolymers of maleic anhydride are particularly preferred.
  • 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 in each case 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, more preferably between 500 and 10,000, for example between 1,000 and 5,000.
  • 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. U.S. 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-A-0 398 101 ).
  • oil-soluble polar nitrogen compounds are copolymers of maleic anhydride with ⁇ , ⁇ -unsaturated compounds, which can optionally be reacted with primary monoalkylamines and / or aliphatic alcohols (cf. EP-A-0 154 177 . EP-A-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 cold additives of the present invention and oil-soluble polar nitrogen compounds as component III may vary depending on Use case vary.
  • Such additive mixtures preferably contain 0.1 to 10 parts by weight, preferably 0.2 to 5 parts by weight, of at least one oil-soluble polar nitrogen compound (constituent III) per part by weight of the additive combination of A) and B) according to the invention.
  • phenol-formaldehyde resins which are oligomers or polymers having a repeat structural unit of the formula wherein R 11 is C 1 -C 200 -alkyl or -alkenyl, OR 10 or OC (O) -R 10 , R 10 is C 1 -C 200 -alkyl or -alkenyl and h is a number from 2 to 100, contain.
  • R 10 is 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 11 is 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.
  • h is a number from 2 to 50 and especially a number from 3 to 25, for example a number from 5 to 15.
  • constituent IV are those resins which are derived from alkylphenols having one or two alkyl radicals in ortho and / or para position to the OH group.
  • Particularly preferred 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.
  • alkyl radicals may be identical or different in the alkylphenol-aldehyde resins which can be used in the process according to the invention, they may be saturated or unsaturated and have 1 to 200, preferably 1 to 20, in particular 4-16, such as 6-12 carbon atoms; it is preferably n-, iso- and tert-butyl, n- and iso-pentyl, n- and iso-hexyl, n- and iso-octyl, n- and iso-nonyl-, n and iso-decyl, n- and iso-dodecyl, tetradecyl, hexadecyl, octadecyl, tripropenyl, tetrapropenyl, poly (propenyl) and poly (isobutenyl) radicals.
  • mixtures of alkylphenols having different alkyl radicals are used for the preparation of the alkylphenol resins.
  • resins based on butyphenol on the one hand and octyl, nonyl and / or dodecylphenol in a molar ratio of 1:10 to 10: 1 on the other hand have proven particularly useful.
  • Resins suitable as constituent IV may also contain or consist of structural units of other phenol analogs, such as salicylic acid, hydroxybenzoic acid, aminophenol and derivatives thereof, such as esters, amides and salts.
  • Suitable aldehydes for the preparation of the 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 suitable 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 1500-3,000 g / mol.
  • a prerequisite here is that the resins are oil-soluble at least in application-relevant concentrations of 0.001 to 1% by weight.
  • Suitable comb polymers are, for example, copolymers of ethylenically unsaturated dicarboxylic acids such as maleic or fumaric acid with other ethylenically unsaturated monomers such as olefins or vinyl esters such as vinyl acetate.
  • Particularly suitable olefins are ⁇ -olefins having 10 to 36 carbon atoms and especially having 12 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.
  • these copolymers are at least 50% esterified with alcohols having 10 to 22 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.
  • comb polymers are poly (alkyl acrylates), poly (alkyl methacrylates) and poly (alkyl vinyl ethers) derived from alcohols having 12 to 20 carbon atoms and poly (vinyl esters) derived from fatty acids having 12 to 20 carbon atoms ,
  • homopolymers and copolymers of olefins having 2 to 30 C atoms are also suitable as further cold flow improvers.
  • olefins having 2 to 30 C atoms 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 propylene, butene, isobutene, n-hexene, isohexene, n-octene, isooctene, n-decene, isodecene.
  • the comonomer content of olefins is preferably between 15 and 50 mol%, particularly preferably between 20 and 35 mol% and especially between 30 and 45 mol%. These copolymers can also be small amounts, for. B. up to 10 mol% of other comonomers such.
  • copolymers of various olefins having 5 to 30 carbon atoms such as poly (hexene-co-decene).
  • the olefin homo- and copolymers can be prepared by known methods, e.g. B. 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) c A and (AB) d , where c is a number between 1 and 10 and d is a number between 2 and 10.
  • oil-soluble polyoxyalkylene compounds such as, for example, esters, ethers and ethers / esters of polyols which carry at least one alkyl radical having 12 to 30 carbon atoms.
  • the oil-soluble polyoxyalkylene compounds have at least 2, such as, for example, 3, 4 or 5 aliphatic hydrocarbon radicals.
  • these radicals independently of one another have 16 to 26 C atoms, for example 17 to 24 C atoms.
  • these radicals of the oil-soluble polyoxyalkylene compounds are linear. Further preferably, they are largely saturated, in particular, these are alkyl radicals. Esters are especially preferred.
  • Particularly suitable polyols according to the invention are polyethylene glycols, polypropylene glycols, polybutylene glycols and their copolymers having a molecular weight of about 100 to about 5,000 g / mol, preferably 200 to 2,000 g / mol.
  • the oil-soluble polyoxyalkylene compounds are derived from polyols having 3 or more OH groups, preferably from polyols having 3 to about 50 OH groups, for example 4 to 10 OH groups, in particular neopentyl glycol, glycerol, trimethylolethane, trimethylolpropane , Sorbitan, pentaerythritol, as well as the resulting from condensation oligomers having 2 to 10 monomer units such as.
  • polyglycerol As polyglycerol.
  • polystyrene resin such as sorbitol, sucrose, glucose, fructose and their oligomers such as cyclodextrin are suitable as polyols, provided that their esterified or etherified alkoxylates are oil-soluble at least in application-relevant amounts.
  • Preferred polyoxyalkylene compounds thus have a branched polyoxyalkylene nucleus attached to the multiple oil-solubilizing alkyl radicals are.
  • the polyols are generally reacted with from 3 to 70 mol of alkylene oxide, preferably from 4 to 50, in particular from 5 to 20, mol of alkylene oxide per hydroxyl group of the polyol.
  • Preferred alkylene oxides are ethylene oxide, propylene oxide and / or butylene oxide.
  • the alkoxylation is carried out by known methods.
  • the fatty acids which are suitable for the esterification of the alkoxylated polyols preferably have 12 to 30 and in particular 16 to 26 C atoms.
  • Suitable fatty acids are, for example, lauric, tridecane, myristic, pentadecane, palmitic, margarine, stearic, isostearic, arachic and behenic, oleic and erucic acids, palmitoleic, myristoleic, ricinoleic acid, as well as natural fats and oils derived fatty acid mixtures.
  • Preferred fatty acid mixtures contain more than 50 mol% of fatty acids having at least 20 carbon atoms.
  • the fatty acids used for the esterification contain double bonds, in particular less than 10 mol%; specifically, they are largely saturated.
  • the esterification can also be carried out starting from reactive derivatives of the fatty acids such as esters with lower alcohols (for example methyl or ethyl esters) or anhydrides.
  • the term "iodine number" of the fatty acid or of the fatty alcohol used is understood to be largely saturated by up to 5 g / l per 100 g of fatty acid or fatty alcohol.
  • Polyol and fatty acid are used for the esterification based on the content of hydroxyl groups on the one hand and carboxyl groups on the other hand in a ratio of 1.5: 1 to 1: 1.5, preferably in the ratio of 1.1: 1 to 1: 1.1 and in particular equimolar.
  • the acid number of the esters formed is generally below 15 mg KOH / g, preferably below 10 mg KOH / g, especially below 5 mg KOH / g.
  • the OH number of the esters is preferably below 20 mg KOH / g and especially below 10 mg KOH / g.
  • the terminal hydroxyl groups are converted, for example by oxidation or by reaction with dicarboxylic acids into terminal carboxyl groups.
  • fatty alcohols having 8 to 50, in particular 12 to 30, especially 16 to 26 carbon atoms polyoxyalkylene esters according to the invention are likewise obtained.
  • Preferred fatty alcohols or fatty alcohol mixtures contain more than 50 mol% of fatty alcohols having at least 20 carbon atoms.
  • less than 50 mol% of the fatty alcohols used for the esterification contain double bonds, in particular less than 10 mol%; specifically, they are largely saturated.
  • esters of alkoxylated fatty alcohols with fatty acids which contain the abovementioned proportions of poly (alkylene oxides) and whose fatty alcohol and fatty acid have the abovementioned alkyl chain lengths and degrees of saturation are suitable according to the invention.
  • the above-described alkoxylated polyols can be converted by etherification with fatty alcohols having 8 to 50, in particular 12 to 30, especially 16 to 26 C-atoms in accordance with the invention suitable polyoxyalkylene compounds.
  • the preferred fatty alcohols are linear and largely saturated.
  • the etherification takes place completely or at least largely completely.
  • the etherification is carried out by known methods.
  • Particularly preferred polyoxyalkylene compounds are derived from polyols having 3, 4 and 5 OH groups, which carry about 5 to 10 mol of structural units derived from ethylene oxide per hydroxyl group of the polyol and are largely completely esterified with largely saturated C 17 -C 24 fatty acids.
  • Further particularly preferred polyoxyalkylene compounds are polyethylene glycols which have been esterified with largely saturated C 17 -C 24 -fatty acids and have molecular weights of about 350 to 1,000 g / mol.
  • polyoxyalkylene compounds examples include stearic and especially behenic acid esterified polyethylene glycols having molecular weights between 350 and 800 g / mol; Neopentyl glycol 14-ethylene oxide distearate (neopentyl glycol alkoxylated with 14 moles of ethylene oxide and then esterified with 2 moles of stearic acid), and especially neopentyl glycol 14-ethylene oxide dibehenate; Glycerol 20-ethylene oxide tristearate, glycerol 20-ethylene oxide dibehenate, and especially glycerol 20-ethylene oxide tribehenate; Trimethylolpropane tribehenate 22-ethylene oxide; Sorbitan 25-ethylene oxide tristearate, sorbitan 25-ethylene oxide tetrastearate, sorbitan 25-ethylene oxide tribehenate, and especially sorbitan 25-ethylene oxide tetrabehenate; Pentaerythritol-30-ethylene oxide tribehenate, pentaerythri
  • the mixing ratio between the cold additives according to the invention and the other cold flow improvers IV, V, VI and VII is generally between 50: 1 and 1: 1, preferably between 10: 1 and 2: 1 by weight, based on the weights (A + B ): (IV, V, VI and VII).
  • the cold additives according to the invention improve the cold properties of such middle distillates which are obtained by distillation of crude oil and boil in the range of about 150 to 410 ° C and especially in the range of about 170 to 380 ° C or consist predominantly of these, such as kerosene, Jet-fuel, diesel and fuel oil.
  • middle distillates typically contain about 5 to 50 wt .-%, such as about 10 to 35 wt .-% n-paraffins, of which the longer-chain crystallize on cooling and can affect the flowability of the middle distillate.
  • the cold additives of the invention in middle distillates with a high content of cold-critical constituents with an n-alkyl chain having a C-chain length of 16 and more carbon atoms.
  • These include, for example, n-paraffins of fossil origin, but also n-paraffins obtained by hydrogenation or co-hydrogenation of animal and / or vegetable fats and esters of saturated fatty acids with lower alcohols such as methanol or ethanol.
  • middle distillates with a content of more than 4 wt .-% and especially with 6 to 20 wt .-%, such as with 7 to 15 wt .-% of these cold-critical constituents the cold additives of the invention have proven particularly useful.
  • the cold additives of the invention are particularly advantageous in oils which are only a very small proportion of very long-chain n-paraffins containing 28 or more carbon atoms, which act as natural nucleators for paraffin crystallization.
  • the cold additives according to the invention have proven particularly useful in oils which contain less than 1% by weight and especially less than 0.5% by weight, for example less than 0.3% by weight of long-chain n-paraffins with 28 or more C Contain atoms.
  • compositions according to the invention are furthermore particularly advantageous in low boiling end middle distillates, ie in middle distillates which have 90% distillation points below 360 ° C., in particular 350 ° C. and in special cases below 340 ° C.
  • the boiling ranges have between 20 and 90% distillation volume of less than 120 ° C and in particular of less than 110 ° C.
  • the middle distillates may also contain minor amounts, for example up to 40% by volume, preferably 1 to 20% by volume, especially 2 to 15, for example 3 to 10% by volume of the oils of animal and / or vegetable origin described in more detail below such as fatty acid methyl esters.
  • the middle distillates contain no residues from the distillation of mineral oils such as residues from atmospheric distillation and / or vacuum distillation.
  • the cold additives of the invention are also suitable for improving the low-temperature properties of fuels based on renewable raw materials (biofuels).
  • biofuels is meant oils obtained from animal and preferably vegetable material or both, and derivatives thereof, which can be used as fuel and especially as diesel or fuel oil.
  • biofuels oils obtained from animal and preferably vegetable material or both, and derivatives thereof, which can be used as fuel and especially as diesel or fuel oil.
  • These are in particular triglycerides of fatty acids having 10 to 24 carbon atoms and from them by Transesterification of accessible fatty acid esters of lower alcohols such as methanol or ethanol.
  • biofuels examples include rapeseed oil, coriander oil, soybean oil, cottonseed oil, sunflower oil, castor oil, olive oil, peanut oil, corn oil, almond oil, palm kernel oil, coconut oil, mustard seed oil, beef tallow, bone oil, fish oils and used edible oils.
  • Other examples include oils derived from wheat, jute, sesame, shea tree, arachis oil and linseed oil.
  • the fatty acid alkyl esters, also referred to as biodiesel can be derived from these oils by methods known in the art.
  • Rapeseed oil which is a mixture of glycerol esterified fatty acids, is preferred because it is available in large quantities and is readily available by squeezing rapeseed.
  • sunflower, palm and soybeans and their mixtures with rapeseed oil are preferred.
  • esters of fatty acids are particularly suitable as biofuels.
  • Preferred esters have an iodine value of from 50 to 150 and in particular from 90 to 125.
  • Mixtures with particularly advantageous properties are those which are principally, i. H. to contain at least 50 wt .-% of methyl esters of fatty acids having 16 to 22 carbon atoms and 1, 2 or 3 double bonds.
  • the preferred lower alkyl esters of fatty acids are the methyl esters of oleic, linoleic, linolenic and erucic acids.
  • the cold additives of the invention can be used alone or together with other co-additives, for.
  • pour point depressants or dewaxing aids with detergents, Antioxidants, cetane improvers, dehazers, demulsifiers, dispersants, defoamers, dyes, corrosion inhibitors, lubricity additives, sludge inhibitors, odorants, and / or cloud point depressants.
  • the advantages of the cold additives according to the invention and of the process which uses them lie in a significantly improved inherent flowability in the cold compared to corresponding additive combinations of the prior art, with simultaneously improved effectiveness.
  • these cold additives can be used at the same active ingredient content even at lower temperatures than the additives of the prior art without having to be heated.
  • higher concentrated additives can be used, so that the cost of transport and storage is reduced.
  • the cold additives of the invention surprisingly show improved effectiveness in improving the cold flow properties of middle distillates. This is all the more unexpected since the side chain density of the comb polymers B) according to the invention is markedly lower than in the case of the additionally combed esterified comb polymers of the prior art ( DE-A-1 920 849 . DE-A-2 451 047 ).
  • the filterability of the fuel oils treated with the inventive cold additives is surprisingly significantly less affected than in the case of additization with additives of the prior art under the same conditions.
  • Table 2 Characterization of the test oils Test oil 1 Test oil 2 Test oil 3 Initial boiling point [° C] 179 171 173 Final boiling point [° C] 348 355 331 Boiling range (20-90)% [° C] 94 93 89 density [g / cm 3 ] .8437 .8555 .8409 Cloud point [° C] -15.6 -11.7 -22.0 CFPP [° C] -15 -12 -22 sulfur content [Ppm] ⁇ 10 ⁇ 10 ⁇ 10 Components with n-alkyl radical ⁇ C 16 [Wt .-%] 9.8 11.1 8.3 n paraffins ⁇ C 28 [Wt .-%] 0.11 0.04 0.01 example additive CFPP [° C] (according to Tab.

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Claims (12)

  1. Additifs de tenue au froid pour distillats moyens, contenant
    A) 0,1 à 50% en poids d'au moins un polyester de formule
    Figure imgb0011
     dans laquelle un des radicaux R1 à R4 représente un radical C16-C40-alkyle ou C16-C40-alcényle linéaire et les autres des radicaux R1 à R4 représentent, indépendamment les uns des autres, hydrogène ou un radical alkyle comprenant 1 à 3 atomes de carbone,
    R5 représente une liaison C-C ou un radical alkylène comprenant 1 à 6 atomes de carbone,
    R16 signifie un radical hydrocarboné comprenant 2 à 10 atomes de carbone,
    n vaut un nombre de 1 à 100,
    m vaut un nombre de 3 à 250,
    p vaut 0 ou 1, et
    q vaut 0 ou 1,
    B) 1,5 à 73,5% en poids d'au moins un copolymère d'éthylène et d'au moins un ester éthyléniquement insaturé, le copolymère présentant une viscosité en masse fondue mesurée à 140°C d'au plus 5000 mPa.s et
    C) 25 à 95% en poids d'au moins un solvant organique.
  2. Additifs de tenue au froid selon la revendication 1, dans lesquels R1 représente un radical C16-C40-alkyle ou C16-C40-alcényle, R2, R3 et R4 représentent hydrogène et R5 représente une simple liaison.
  3. Additifs de tenue au froid selon la revendication 1 et/ou 2, dans lesquels R16 représente un groupe éthylène.
  4. Additifs de tenue au froid selon la revendication 1 et/ou 2, dans lesquels R16 représente un groupe C2-C4-alkylène et n vaut un nombre de 2 à 100.
  5. Additifs de tenue au froid selon l'une ou plusieurs des revendications 1-4, dans lesquels le polymère B) est un copolymère d'éthylène et de 8 à 21% en mole d'au moins un composé oléfiniquement insaturé choisi parmi les esters de vinyle, les esters d'acryle et/ou les esters de méthacryle.
  6. Additifs de tenue au froid selon l'une ou plusieurs des revendications 1-5, dans lesquels le solvant C) est choisi parmi les hydrocarbures aliphatiques comprenant 9 à 20 atomes de carbone et les hydrocarbures aromatiques comprenant 7 à 20 atomes de carbone.
  7. Additifs de tenue au froid selon l'une ou plusieurs des revendications 1-6, dans lesquels le solvant C) contient en outre un promoteur de solubilisation, qui contient 4 à 24 atomes de carbone et qui est choisi parmi les alcools, les acides organiques, les éthers et les esters d'acides organiques ou leurs mélanges.
  8. Additifs de tenue au froid selon l'une ou plusieurs des revendications 1-7, contenant en plus au moins un autre agent d'amélioration de l'écoulement à froid, qui est choisi dans le groupe constitué par
    III) les composés azotés polaires solubles dans l'huile,
    IV) les résines de dérivés de phénol portant des radicaux alkyle avec des aldéhydes,
    V) les polymères en peigne de formule
    Figure imgb0012
     où
    A signifie R', COOR', OCOR', R"-COOR', OR' ;
    D signifie H, CH3, A ou R" ;
    E signifie H, A ;
    G signifie H, R", R"-COOR', un radical aryle ou un radical hétérocyclique ;
    M signifie H, COOR", OCOR", OR", COOH ;
    N signifie H, R", COOR", OCOR, un radical aryle ;
    R' signifie une chaîne hydrocarbonée comprenant 8 à 50 atomes de carbone ;
    R" signifie une chaîne hydrocarbonée comprenant 1 à 10 atomes de carbone ;
    a vaut un nombre entre 0,4 et 1,0 ; et
    b vaut un nombre entre 0 et 0,6,
    VI) les homopolymères et les copolymères d'oléfines comprenant 2 à 30 atomes de carbone,
    VII) les esters, les éthers et les esters/éthers de polyols alcoxylés, qui portent au moins un radical alkyle comprenant 12 à 30 atomes de carbone.
  9. Procédé pour améliorer les propriétés d'écoulement à froid de fuel-oils, dans lequel un additif de tenue au froid selon l'une ou plusieurs des revendications 1 à 8 est ajouté à un distillat moyen.
  10. Fuel-oil, contenant un distillat moyen et au moins un additif de tenue au froid selon l'une ou plusieurs des revendications 1 à 8.
  11. Fuel-oil selon la revendication 10, dans lequel le distillat moyen présente une teneur en constituants présentant une chaîne n-alkyle de 16 atomes de carbone ou plus supérieure à 4% en poids.
  12. Fuel-oil selon la revendication 10 et/ou 11, le distillat moyen présentant une proportion de n-paraffines à longue chaîne comprenant 28 atomes de carbone et plus inférieure à 1% en poids.
EP10800881.4A 2009-12-24 2010-12-07 Additifs de refroidissement ayant une meilleure aptitude à l'écoulement Expired - Fee Related EP2516605B1 (fr)

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CA2785463A1 (fr) 2011-06-30
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CN102639682A (zh) 2012-08-15
CN102639682B (zh) 2014-09-10
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