EP2516605A2 - Additifs de refroidissement ayant une meilleure aptitude à l'écoulement - Google Patents

Additifs de refroidissement ayant une meilleure aptitude à l'écoulement

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Publication number
EP2516605A2
EP2516605A2 EP10800881A EP10800881A EP2516605A2 EP 2516605 A2 EP2516605 A2 EP 2516605A2 EP 10800881 A EP10800881 A EP 10800881A EP 10800881 A EP10800881 A EP 10800881A EP 2516605 A2 EP2516605 A2 EP 2516605A2
Authority
EP
European Patent Office
Prior art keywords
alkyl
carbon atoms
cold
esters
radical
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP10800881A
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German (de)
English (en)
Other versions
EP2516605B1 (fr
Inventor
Matthias Krull
Werner Reimann
Stefan Dilsky
Sabine Goetzke
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Clariant Finance BVI Ltd
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Clariant Finance BVI Ltd
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Publication of EP2516605A2 publication Critical patent/EP2516605A2/fr
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • 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
    • C10L1/143—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
    • C10L1/196—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
    • C10L1/195—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
    • C10L1/1983—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
    • C10L1/18—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
    • 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
    • C10L1/198—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
    • C10L1/22—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
  • Paraffins containing middle distillates such as gas oil, diesel and fuel oil may crystallize as the temperature of the oil decreases 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, thereby preventing a safe metering of the fuels and under
  • cold flow improvers or flow improvers modify the crystal structure and Agglomerationsne instruct the precipitated paraffins, so that the so-additive oils still at
  • oil-soluble copolymers of ethylene and unsaturated esters are usually used.
  • oil-soluble copolymers of ethylene and vinyl acetate having a molecular weight between about 1,000 and 3,000 to.
  • Comb polymers are understood to mean a special form of the branched macromolecules which, at more or less regular intervals, are longer, more or less the same length, on a linear main chain
  • Copolymers of ethylene and unsaturated esters with comb polymers reported synergistically enhanced activities as cold additives, presumably due to a paraffin crystallization nucleating function of these comb polymers. These occur in particular when using comb polymers with very long side chains.
  • 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
  • DE-A-24 51 047 discloses light, low viscosity distillate fuel oils which contain no residues and are additized with ethylene copolymers and comb polymers having Ci8-C44 side chains.
  • comb polymers inter alia ester condensation polymers of alk (en) ylsuccinic anhydride with a Ci6-C4 4 -Alk (en) ylrest, a polyol having 2-6 OH groups and a C2o ⁇ C-44 monocarboxylic acid are used.
  • the three components of the polyester are preferably condensed in equimolar amounts, so that it is an im
  • polymer G is a polycondensate of equimolar amounts of C22-28 alkenyl succinic anhydride, trimethylolpropane and C20-22
  • Concentration of active substance in the concentrates should be as high as possible to increase the volume keep the additive concentrates to be transported and stored as low as possible.
  • organic solvents often have comparatively high eigenstock points of more than 20 ° C.
  • 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.
  • additives should also be soluble at low temperatures and easily soluble in the middle distillate to be added. In addition, they should not affect the filterability of the additized middle distillates or at least as little as possible.
  • the invention provides cold additives for middle distillates, containing A) at least one polyester of the formula
  • one of the radicals R 1 to R 4 is a linear C 6 -C 40 -alkyl or alkenyl radical and
  • radicals R 1 to R 4 independently of one another represent hydrogen or an alkyl radical having 1 to 3 C atoms
  • R 5 is a CC bond or an alkylene radical having 1 to 6 C atoms
  • R 16 is a hydrocarbon group having 2 to 10 carbon atoms
  • n is a number from 1 to 100
  • Another object of the invention is a method for improving the cold flow properties of fuel oils by adding a cold additive to a middle distillate, the at least one polyester of the formula
  • radicals R to R 4 independently of one another represent hydrogen or an alkyl radical having 1 to 3 C atoms
  • R 5 is a C-C bond or an alkylene radical having 1 to 6 C atoms
  • R 16 is a hydrocarbon group having 2 to 10 carbon atoms
  • n is a number from 1 to 00
  • Another object of the invention are fuel oils containing
  • radicals R 1 to R 4 independently of one another represent hydrogen or an alkyl radical having 1 to 3 C atoms
  • R 5 is a CC bond or an alkylene radical having 1 to 6 C atoms
  • R 16 is a hydrocarbon group having 2 to 10 carbon atoms
  • n is a number from 1 to 100
  • Preferred dicarboxylic acids suitable for the preparation of the polyesters A) correspond to the general formula 1
  • radicals R 1 to R 4 for a linear C 6 -C 4 o-alkyl or alkenyl radical and the remaining of the radicals R 1 to R 4 independently of one another represent hydrogen or an alkyl radical having 1 to 3 C atoms, and
  • R 5 is a CC bond or an alkylene radical having 1 to 6 C atoms.
  • one of the radicals R to R 4 is a linear C 16 -C 4 o-alkyl or alkenyl radical; together also referred to as Ci 6 -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 one
  • Ci6-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 6 -C 40 -alkyl or alkenyl radical, the remaining radicals R 1 to R 4 are hydrogen and R 5 is a
  • the preparation of the dicarboxylic acids or their anhydrides bearing alkyl and / or alkenyl radicals can be carried out by known processes.
  • they can be prepared by heating ethylenically unsaturated dicarboxylic acids with olefins ("ene reaction") or with chloroalkanes
  • ene reaction ethylenically unsaturated dicarboxylic acids
  • chloroalkanes Preferred is the thermal addition of olefins to ethylenically unsaturated dicarboxylic acids, which is usually carried out at temperatures between 100 and 250.degree.
  • Dicarboxylic acid anhydrides can be hydrogenated to dicarboxylic acids bearing dicarboxylic acids and dicarboxylic acid anhydrides.
  • 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 its anhydrides and the esters of the aforementioned acids in particular with lower C-i-Ce 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. Under linear
  • olefins preferably technical alkene mixtures. These preferably contain at least 50 wt .-%, particularly preferably 60 to 99 wt .-% and in particular 70 to 95 wt .-% such as 75 to 90 wt .-% terminal double bonds ( ⁇ -olefins). In addition, they may contain up to 50% by weight, preferably 1 to 40% by weight and especially 5 to 30% by weight, for example 10 to 25% by weight of olefins having an internal double bond, for example vinylidene double bonds with the structural element
  • R 17 - CH C (CH 3 ) 2 , where R 17 is an alkyl radical having 2 to 36 carbon atoms and especially having 14 to 32 carbon atoms, such as having 15 to 28 carbon atoms. Furthermore, minor amounts of technical reasons
  • olefin mixtures containing at least 75 wt .-% of linear ⁇ -olefins having a C chain length in the range of C 2 o to C 2 .
  • Preferred polyesters A) are transmitted by reacting a linear C 6 -C 4 o-alkyl or alkenyl alkyl or alkenyl succinic acids and / or anhydrides thereof with diols to produce.
  • 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. Preferably contain the
  • Hydrocarbon radicals 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 ones
  • Hydrocarbon radicals are preferred.
  • the aliphatic hydrocarbon radicals can be linear, branched or cyclic. Favor are linear. Further preferably, they are saturated.
  • Examples of preferred diols are 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 a number from 2 to 100, more preferably from 3 to 50, and most preferably from 4 to 20, such as from 5 to 15. In this
  • 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 Preferably, the
  • oligomers and polymers between 2 and 100, more preferably between 3 and 50, and especially between 4 and 20, for example between 5 and 15.
  • 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 of Ci 6 -C 4 o-alkyl or
  • Alkenylsubstituierter dicarboxylic acid or its anhydride or ester with the diol to temperatures above 100 ° C and preferably to temperatures between 120 and 320 ° C such as at temperatures between 150 and 290 ° C.
  • To set the important for the effectiveness of molecular weight of the polyester A) is usually the removal of water of reaction or alcohol
  • Suitable catalysts are known acidic, basic as well as organometallic compounds.
  • 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
  • the hydroxyl number can after reacting the free OH groups with! Socyanat by means of 1 H NMR spectroscopy
  • C3o-monocarboxylic acids particularly preferably C2- to Cie-monocarboxylic acids, in particular C2- to C16-monocarboxylic acids and especially C3- to
  • Ci4 monocarboxylic acids such as C4 to Ci2 monocarboxylic acids or their esters replaced with lower alcohols. However, at most 20 mol% and preferably 0.1 to 10 mol% such as 0.5 to 5 mol% of the alk (en) ylreste bearing dicarboxylic acids or their anhydrides or their esters are replaced by a monocarboxylic acid or its esters , Also mixtures of different carboxylic acids are suitable.
  • the hydroxyl value of the polymer is preferably less than 10 mg KOH / g, and more preferably less than 5 mg KOH / g, such as less than
  • the polyesters A) are prepared in the absence of monocarboxylic acids. Furthermore, minor amounts such as up to 10 mol% and in particular 0.01 to 5 mol% of the alkyl radicals carrying dicarboxylic acids whose anhydrides or their esters are also replaced by other dicarboxylic acids such as succinic acid, glutaric acid, maleic acid and / or fumaric acid.
  • minor amounts of the diol by Cr to C 30 monohydric alcohols more preferably C 2 to C 2 4 monoalcohols and especially C3 to C-ie monoalcohols such as C4 bis Replaced Ci2 mono alcohols.
  • 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.
  • at most 20 mol% and particularly preferably 0.1 to 10 mol%, for example 0.5 to 5 mol% of the polyol, are replaced by one or more monoalcohols.
  • 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.
  • Mw of the polyester A) is preferably between 1,500 and 100,000 g / mol and in particular between 2,500 and 50,000 g / mol as
  • 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 in alpha position to
  • R 12 is 6 -alkyl and especially C 6 these Vinylestern C for 4 to Ci - to Ci2 alkyl.
  • R 12 is 6 -alkyl and especially C 6 these Vinylestern C for 4 to Ci - to Ci2 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,
  • Ci 2 alkyl The further vinyl esters are particularly preferably branched in the alpha position.
  • (meth) acrylic esters For the acrylic and methacrylic esters, hereinafter referred to as (meth) acrylic esters
  • CH 2 CR 13 - COOR 14 (3)
  • R 3 is hydrogen or methyl and RC to C 3 o-alkyl, preferably C 4 - to C 6 -alkyl, especially C 6 - to C-
  • 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.
  • alkyl vinyl ethers are preferably compounds of the formula 4
  • CH 2 CH - OR 15 (4) wherein R 15 is C 3 to C 3 o-alkyl, preferably C 4 to C-1 6 alkyl, especially C6 bis
  • Ci2-alkyl examples which may be mentioned are methyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether.
  • said alkyl groups may be substituted with one or more hydroxyl groups.
  • the alkenes are preferably monounsaturated
  • Suitable alkenes include propene, butene, isobutylene, pentene, hexene, 4-methylpentene, octene, diisobutylene and norbornene and its derivatives such as methylnorbornene and vinylnorbornene.
  • the mentioned alkenes include propene, butene, isobutylene, pentene, hexene, 4-methylpentene, octene, diisobutylene and norbornene and its derivatives such as methylnorbornene and vinylnorbornene.
  • Alkyl groups substituted with one or more hydroxyl groups.
  • terpolymers which except Ethyleh 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 at least one long-chain and preferably branched Vinyl esters such as vinyl 2-ethylhexanoate,
  • 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%.
  • Ci 2 carboxylic acids 0.5 to 10 mol% olefins, such as propene, butene, isobutylene, hexene, 4-methylpentene, octene, diisobutylene -
  • olefins such as propene, butene, isobutylene, hexene, 4-methylpentene, octene, diisobutylene -
  • Further particularly preferred copolymers contain, in addition to ethylene and from 8 to 18 mol% of C 2 Vinylestern 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%.
  • these ethylene-co- and terpolymers have melt viscosities at 140 ° C from 20 to 2,500 mPas, in particular from 30 to 1, 000 mPas, especially from 50 to 500 mPas.
  • melt viscosities at 140 ° C from 20 to 2,500 mPas, in particular 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 Chb groups, in particular 2-6 CH3 / IOO CHFE-groups which are not from the
  • the polymers underlying the mixtures differ in at least one
  • Characteristic may contain different comonomers, have different comonomer contents, molecular weights and / or degrees of branching.
  • mixtures of ethylene copolymers having different comonomer contents have proved particularly suitable, the comonomer contents of which are at least 2 mol% and
  • the cold additives of the invention preferably contain 25 to 95 wt .-% and preferably 28 to 80 wt .-%, such as 35 to 70 wt .-% 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.
  • solvent preferred aromatic aromatic solvents are aliphatic hydrocarbons preferred as solvents.
  • 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. These carry in one
  • 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 examples of suitable aromatics.
  • Benzine fractions 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 as 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
  • 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 of the invention preferably contain from 1, 5 to 73.5, in particular 15 to 70 and especially 25 to 60 wt .-% of component B).
  • the cold additives according to the invention preferably contain 0.1 to 50, in particular 0.5 to 30 and especially 1 to 20 wt .-% of the component A).
  • the cold additives according to the invention are preferably added to middle distillates in amounts of 0.001 to 1.0% by weight, more preferably 0.002 to 0.5% by weight, for example 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
  • 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 g / g, preferably less than 60 gb / g and in particular between 1 and 10 g / g. Particular preference is given to 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 2 4-alkenyl or cyclohexyl and the third are hydrogen.
  • Suitable fatty amines are, for example, octylamine, decylamine, dodecylamine,
  • Tetradecylamine Tetradecylamine, hexadecylamine, octadecylamine, eicosylamine, behenylamine, didecylamine, didodecylamine, ditetradecylamine, dihexadecylamine,
  • the amines contain chain cuts based on natural raw materials such. Cocosfettamine, tallow fatty amine, hydrogenated tallow fatty amine, dicocosfettamine, ditallow fatty amine and di (hydrogenated tallow fatty amine). Especially preferred
  • Amine derivatives are amine salts, imides and / or amides such as amide ammonium salts of secondary fatty amines, especially dicocosfettamine, ditallow fatty amine and distearylamine.
  • acyl group is meant here a functional group of the following formula:
  • Carbonyl compounds suitable for 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.
  • suitable carboxylic acids are maleic, fumaric, crotonic, itaconic, succinic, C 1 -C 40 -alk (en) ylsuccinic, adipic, glutaric, sebacic, and malonic acids
  • Ethylenediaminetetraacetic acid and its reactive derivatives such as esters, anhydrides and acid halides.
  • polymeric carbonyl compounds have in particular copolymers of ethylenically unsaturated acids such as acrylic acid, methacrylic acid, maleic acid, fumaric acid and
  • Suitable comonomers are those which are the
  • Oil-soluble is understood here to mean that the copolymer, after reaction with the fatty amine, becomes practically relevant
  • 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 0,000, 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 (compare US Pat. No. 4,211,534).
  • the same are amides and ammonium salts of
  • Aminoalkylenpolycarbon Acid such as nitrilotriacetic acid or
  • Ethylenediaminetetraacetic acid with secondary amines suitable as oil-soluble polar nitrogen compounds (see EP-A-0 398 101).
  • Other oil-soluble polar nitrogen compounds are copolymers of maleic anhydride with ⁇ , ⁇ -unsaturated compounds, optionally with primary
  • Monoalkylamines and / or aliphatic alcohols can be reacted (see, EP-A-0 154 177, EP-A-0 777 712), the reaction products of
  • EP-A-0 606055 A2 Reaction products of terpolymers based on
  • 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 from 0.1 to 10 parts by weight, preferably from 0.2 to 10 parts by weight, based on the active compounds
  • phenol-formaldehyde resins the oligo- or polymers having a repetitive structural unit of the formula
  • R 11 is CC 2 oo-alkyl or alkenyl, OR 10 or OC (O) -R 10 , R 0 is
  • Ci-C2oo-alkyl or alkenyl and h is a number from 2 to 100 contained.
  • R 11 is preferably -C 2 o alkyl or alkenyl and especially C4-Ci 6 alkyl or alkenyl such as, for example, C6-Ci2 alkyl or alkenyl.
  • R 11 is C 1 -C 20 -alkyl or alkenyl and in particular C 4 -C- 6 - alkyl or alkenyl such as for C6-C-i2-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.
  • hydrocarbon radicals as defined below may be the same or different in the alkylphenol-aldehyde resins used in the process according to the invention, they may be saturated or unsaturated and have 1 - 200, preferably 1 - 20, especially 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 may be the same or different in the alkylphenol
  • 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 with 1 to
  • G is H, R ", R" -COOR ', an aryl radical or a heterocyclic radical;
  • R ' is a hydrocarbon chain of 8 to 50 carbon atoms
  • R is a hydrocarbon chain of 1 to 10 carbon atoms
  • a is a number between 0.4 and 1, 0;
  • b is a number between 0 and 0.6.
  • 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.
  • longer-chain olefins based on oligomerized C2-C6 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. Particularly preferred are mixtures of n-tetradecane-1-ol and n-hexadecan-1-ol.
  • Also suitable as comb polymers are poly (alkyl acrylates),
  • homopolymers and copolymers of olefins having 2 to 30 C atoms are also suitable as further cold flow improvers.
  • these can be derived directly from monoethylenically unsaturated monomers or indirectly by
  • polymers derived from polyunsaturated monomers such as isoprene or butadiene can be prepared.
  • 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 cc-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%, more 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. B. non-terminal olefins or non-conjugated olefins. Particularly preferred are ethylene-propylene copolymers. Further preferred are 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
  • 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.
  • Polyoxyalkylene compounds such as esters, ethers and ethers / esters of polyols bearing at least one alkyl radical having 12 to 30 carbon atoms.
  • the oil-soluble ones such as esters, ethers and ethers / esters of polyols bearing at least one alkyl radical having 12 to 30 carbon atoms.
  • Polyoxyalkylenharmen at least 2, such as 3, 4 or
  • these radicals are the oil-soluble
  • Polyoxyalkylene compounds 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,
  • oil-soluble polyoxyalkylene compounds are derived from polyols having 3 or more
  • OH groups preferably from polyols having from 3 to about 50 OH groups, for example from 4 to 10 OH groups, in particular from neopentyl glycol,
  • Glycerol trimethylolethane, trimethylolpropane, sorbitan, pentaerythritol, as well as the resulting from condensation oligomers with 2 to
  • 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.
  • Fatty acids are, for example, lauric, tridecane, myristic, pentadecane,
  • Preferred fatty acid mixtures contain more than 50 mol% of fatty acids having at least 20 carbon atoms.
  • 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 of I 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 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
  • 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 6 to 26 carbon atoms polyoxyalkylene esters according to the invention are likewise obtained.
  • Preferred fatty alcohols or fatty alcohol mixtures contain more than
  • 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.
  • 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 are transferred.
  • the preferred fatty alcohols are linear and
  • 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 as far as possible
  • Ci7-C24 fatty acids are completely esterified with largely saturated Ci7-C24 fatty acids.
  • Behenic acid esterified polyethylene glycols having molecular weights between 350 and 800 g / mol; Neopentyl glycol 14-ethylene oxide distearate (with 14 mol
  • 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 inventive cold additives improve in particular the
  • middle distillates obtained by distillation of crude oil and boiling in the range of about 150 to 410 ° C and in particular in the range of about 170 to 380 ° C or consist mainly of these, such as kerosene, jet fuel, diesel and heating 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 according to the invention are particularly advantageous in middle distillates with a high content of cold-critical constituents with an n-alkyl chain with one
  • C chain length of 16 and more C atoms 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.
  • 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. Particularly advantageous are the inventive
  • Refrigeration additives continue in such oils, which are only a very small proportion of very long-chain n-paraffins with 28 or more carbon atoms that are considered natural
  • 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.
  • Special advantages of the inventive cold additives in particular in such oils containing a high content of cold-critical constituents with an n-alkyl chain having 16 or more carbon atoms and at the same time a very small proportion of very long-chain n-paraffins with 28 or more carbon atoms The content of n-paraffins and optionally other components critical to refrigeration, such as, for example, fatty acid methyl esters, is usually determined by means of
  • 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., and of
  • middle distillates the boiling ranges between 20 and 90% distillation volume of less than 120 ° C and in particular 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 like for example
  • 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 for improving the low-temperature properties of fuels based on renewable raw materials
  • 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 with 10 to 24 carbon atoms as well as those from them 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 cooking 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.
  • the also widespread oils of sunflower, palm and soybeans and their mixtures with rapeseed oil are preferred.
  • Particularly suitable as biofuels are lower alkyl esters of fatty acids.
  • commercially available mixtures of the ethyl, propyl, butyl and especially methyl esters of fatty acids having 14 to 22 carbon atoms for example of lauric acid, myristic acid, palmitic acid, palmitoleic acid, stearic acid, oleic acid, elaidic acid, petroselinic acid, ricinoleic acid,
  • 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. B. with others
  • pour point depressants or dewaxing aids with detergents, Antioxidants, cetane improvers, dehazers, demulsifiers, dispersants, defoamers, dyes, corrosion inhibitors, lubricity additives,
  • Tetra-n-butylammonium hydroxide solution in xylene / isopropanol determined.
  • the hydroxyl numbers were after reaction of the free OH groups of the polymers with Isocyanate determined by H-NMR spectroscopy by quantitative determination of the urethane formed. The values given refer to the solvent-free polymers.
  • the molecular weights were determined by means of lipophilic
  • A1 copolymer of equimolar amounts of C 2 O / 24-alkenylsuccinic anhydride prepared by thermal condensation of maleic anhydride with technical C 2 o / 24-olefin containing as main constituents 43% C 2 o-, 35% C 22 - and 17% C 24 - Olefin, with 90% ⁇ -olefins and 7.5% linear internal
  • Example A1 In analogy to Example A1) produced copolymer of equimolar proportions C3o + alkenylsuccinic anhydride (prepared by thermal condensation of maleic anhydride with technical C3o + olefin containing as main constituents 9% olefin in the range C 24 -C 2 8 and 90% with C chain lengths of at least C 3 o. wherein 82% were ⁇ -olefins, 3% linear internal olefins and 14% branched olefins) and ethylene glycol.
  • the acid number of the polymer was 11.6 mg KOH / g, the hydroxyl number 11 mg KOH / g and the weight-average molecular weight 7,400 g / mol.
  • the acid value of the polymer was 9.4 mg KOH / g, the hydroxyl value was 10 mg KOH / g and the weight-average molecular weight was 9,400 g / mol.
  • the acid number of the polymer was 15 mg KOH / g, the hydroxyl number 6 mg KOH / g and the weight average molecular weight 8,300 g / mol (comparative example).
  • Acid number of the polymer was 9 mg KOH / g, the hydroxyl number
  • Solvesso ® 150 high-boiling aromatic mixture (about 98% aromatics, 0.7% naphthalene, boiling range 175 - 205 ° C, flash point 65 ° C)
  • Boiling range 182 - 212 ° C, flash point 63 ° C) To determine the cold properties of the cold additives, their pour points were determined in accordance with DIN ISO 3016. A low pour point indicates a good flowability and thus good handling in the cold. The percentages given for the additives are based on the used
  • solvent C optionally solvent-based components contained in the polymers are indicated as solvent C).
  • Table 1 Determination of pour points

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Abstract

L'invention concerne des additifs de refroidissement pour des distillats moyens, contenant A) au moins un polyester représenté par la formule (A1) dans laquelle un des radicaux R1 à R4 est un radical C16-C40-alkyle ou alcényle linéaire, et les autres radicaux R1 à R4 sont indépendamment l'un de l'autre hydrogène ou un radical alkyle portant 1 à 3 atomes de C, R5 est une liaison C-C ou un radical alcényle, R6 est un groupe hydrocarbure portant 2 à 10 atomes de carbone, n est un entier de 1 à 100, m est un entier de 3 à 250, p est 0 ou 1 et q est 0 ou 1; B) au moins un copolymère choisi parmi éthylène et au moins un ester à insaturation éthylénique, le copolymère ayant une viscosité de fusion maximale de 5000 mPas mesurée à 140 °C; et C) au moins un solvant organique.
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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FR2991992B1 (fr) * 2012-06-19 2015-07-03 Total Raffinage Marketing Compositions d'additifs et leur utilisation pour ameliorer les proprietes a froid de carburants et combustibles
CN103773522A (zh) * 2012-10-26 2014-05-07 戴伟 大比例催化燃烧甲醇汽油添加剂
BR112015013261A2 (pt) * 2012-12-18 2017-07-11 Basf Se processo para produzir uma formulação de polímero, formulação de polímero, e, uso de uma formulação de polímero
US9574146B2 (en) 2012-12-18 2017-02-21 Basf Se Polymeric compositions composed of ethylene-vinyl ester copolymers alkyl (meth)acrylates, processes for production thereof and use thereof as pour point depressants for crude oils, mineral oils or mineral oil products
BR112015013238B1 (pt) * 2012-12-18 2021-05-25 Basf Se composição polimérica, e, uso de uma composição polimérica
KR102262320B1 (ko) 2013-03-15 2021-06-07 캘리포니아 인스티튜트 오브 테크놀로지 회합성 폴리머 및 관련 조성물 및 방법 및 시스템
WO2016044810A1 (fr) * 2014-09-18 2016-03-24 California Institute Of Technology Polymères associatifs, et compositions, procédés et systèmes associés
US10428286B2 (en) 2015-09-18 2019-10-01 California Institute Of Technology Associative polymers for use in a flow and related compositions, methods and systems
US11180949B2 (en) 2017-11-27 2021-11-23 Thermo Traks Inc Sealing system for overhead door
WO2023180263A1 (fr) * 2022-03-21 2023-09-28 Schill + Seilacher Struktol Gmbh Composition de caoutchouc contenant un additif et son utilisation

Family Cites Families (27)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2993773A (en) * 1959-02-02 1961-07-25 Petrolite Corp Ester additives
US3048479A (en) 1959-08-03 1962-08-07 Exxon Research Engineering Co Ethylene-vinyl ester pour depressant for middle distillates
GB1215214A (en) 1968-05-09 1970-12-09 Exxon Research Engineering Co Fuel or oil compositions
US3447916A (en) 1965-11-10 1969-06-03 Exxon Research Engineering Co Acylated polyesters,polyesteramides,or polyamides
FR2108164B1 (fr) * 1970-09-18 1973-04-27 Inst Francais Du Petrole
US3966428A (en) 1973-10-31 1976-06-29 Exxon Research And Engineering Company Ethylene backbone polymers in combination with ester polymers having long alkyl side chains are low viscosity distillate fuel cold flow improvers
US4211534A (en) 1978-05-25 1980-07-08 Exxon Research & Engineering Co. Combination of ethylene polymer, polymer having alkyl side chains, and nitrogen containing compound to improve cold flow properties of distillate fuel oils
DE3405843A1 (de) 1984-02-17 1985-08-29 Bayer Ag, 5090 Leverkusen Copolymere auf basis von maleinsaeureanhydrid und (alpha), (beta)-ungesaettigten verbindungen, ein verfahren zu ihrer herstellung und ihre verwendung als paraffininhibitoren
JPS6218493A (ja) * 1985-02-20 1987-01-27 Lion Corp 流動性向上剤
JPH0710982B2 (ja) * 1986-06-30 1995-02-08 ライオン株式会社 流動性向上剤
DE3916366A1 (de) 1989-05-19 1990-11-22 Basf Ag Neue umsetzungsprodukte von aminoalkylenpolycarbonsaeuren mit sekundaeren aminen und erdoelmitteldestillatzusammensetzungen, die diese enthalten
DE3926992A1 (de) 1989-08-16 1991-02-21 Hoechst Ag Verwendung von umsetzungsprodukten von alkenylspirobislactonen und aminen als paraffindispergatoren
GB9204709D0 (en) * 1992-03-03 1992-04-15 Exxon Chemical Patents Inc Additives for oils
US5266084A (en) 1992-09-17 1993-11-30 Mobil Oil Corporation Oligomeric/polymeric multifunctional additives to improve the low-temperature properties of distillate fuels
DK0606055T3 (da) 1993-01-06 1998-04-14 Clariant Gmbh Terpolymerer på basis af alfa,beta-umættede dicarboxylsyreanhydrider, alfa-beta-umættede forbindelser og polyoxyalkylenethere af lavere umættede alkoholer
GB9301119D0 (en) * 1993-01-21 1993-03-10 Exxon Chemical Patents Inc Fuel composition
DE4430294A1 (de) 1994-08-26 1996-02-29 Basf Ag Polymermischungen und ihre Verwendung als Zusatz für Erdölmitteldestillate
DE69730709T2 (de) * 1996-05-31 2005-09-22 The Associated Octel Co. Ltd. Brennstoffzusätze
DE10000649C2 (de) * 2000-01-11 2001-11-29 Clariant Gmbh Mehrfunktionelles Additiv für Brennstofföle
US7256242B2 (en) * 2003-06-27 2007-08-14 Chevron Oronite Company, Llc Esterified copolymers of polyalkenes/unsaturated acidic reagents useful as lubricant and fuel additives
DE10349859B4 (de) 2003-10-22 2006-12-07 Leuna Polymer Gmbh Additivmischung als Bestandteil von Mineralölzusammensetzungen
KR20080012831A (ko) * 2005-03-21 2008-02-12 벤-구리온 유니버시티 오브 더 네게브 리서치 앤드 디벨럽먼트 어쏘러티 식물성 또는 동물성 오일로부터 디젤 연료의 제조
DE102005035277B4 (de) * 2005-07-28 2007-10-11 Clariant Produkte (Deutschland) Gmbh Mineralöle mit verbesserter Leitfähigkeit und Kältefließfähigkeit
GB0515998D0 (en) * 2005-08-03 2005-09-07 Ass Octel Fuel additives
DE102006022720B4 (de) * 2006-05-16 2008-10-02 Clariant International Limited Kaltfließverbesserer für pflanzliche oder tierische Brennstofföle
US8349033B2 (en) 2007-05-31 2013-01-08 The Penray Companies, Inc. Diesel fuel, diesel fuel additive, and associated method for using the same
CN101910379B (zh) * 2008-07-10 2013-09-18 株式会社Adeka 用于生物柴油的低温流动性改进剂

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2011076337A2 *

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KR101650292B1 (ko) 2016-08-23
KR20120123261A (ko) 2012-11-08
RU2012131475A (ru) 2014-01-27
US9150808B2 (en) 2015-10-06
ES2494591T3 (es) 2014-09-15
RU2540279C2 (ru) 2015-02-10
JP2013515792A (ja) 2013-05-09
JP5709321B2 (ja) 2015-04-30
CA2785463A1 (fr) 2011-06-30
CA2785463C (fr) 2016-12-13
US20120304532A1 (en) 2012-12-06
EP2516605B1 (fr) 2014-07-09
CN102639682A (zh) 2012-08-15
CN102639682B (zh) 2014-09-10
WO2011076337A3 (fr) 2011-09-01
WO2011076337A2 (fr) 2011-06-30
DE102009060389A1 (de) 2011-06-30

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