Classifications

• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/18—Organic compounds containing oxygen
  • 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
  • C10L1/143—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
  • C10L1/196—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and a carboxyl group or salts, anhydrides or esters thereof homo- or copolymers of compounds having one or more unsaturated aliphatic radicals each having one carbon bond to carbon double bond, and at least one being terminated by a carboxyl radical or of salts, anhydrides or esters thereof
  • C10L1/1966—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and a carboxyl group or salts, anhydrides or esters thereof homo- or copolymers of compounds having one or more unsaturated aliphatic radicals each having one carbon bond to carbon double bond, and at least one being terminated by a carboxyl radical or of salts, anhydrides or esters thereof poly-carboxylic

Definitions

• the invention relates to copolymers which comprise, in addition to an ⁇ -olefin and an alkenyl ester of an aliphatic carboxylic acid or an ester of an ⁇ , ⁇ -unsaturated aliphatic carboxylic acid in copolymerized form a vinylaromatic. Moreover, the invention relates to the use of these copolymers as an additive for fuel oils and lubricants, and in particular as cold flow improvers in fuel oils; the fuel oils and lubricants additized with these copolymers; and additive packages containing such copolymers.
• Paraffinic wax-containing mineral oils such as middle distillates, e.g. Diesel and fuel oils show a significant deterioration of the flow properties when the temperature is lowered.
• the reason for this lies in the crystallization of longer-chain paraffins occurring from the temperature of the cloud point, which form large, platelet-shaped wax crystals.
• These wax crystals have a sponge-like structure and lead to the inclusion of other fuel constituents in the crystal composite. The appearance of these crystals quickly leads to the bonding of fuel filters both in tanks and in motor vehicles. At temperatures below the pour point (PP), finally, no more flow of fuel takes place.
• Cold flow improvers are added in amounts of about 50 to 500 ppm, depending on the nature of the base fuel and the additive.
• Various CFI products are known from the prior art (cf., for example, US Pat US-A-3,038,479 . 3,627,838 and 3,961,961 .
• Common CFI's are usually polymeric compounds, especially ethylene-vinyl acetate (EVA) copolymers, such as those disclosed in U.S. Pat. Trade name Keroflux products sold by BASF AG.
• EVA ethylene-vinyl acetate
• the WO 2004/106471 describes the use of terpolymers containing in copolymerized form ethylene, vinyl acetate and special acrylates as additives for fuel oils and lubricants, in particular as cold flow improvers for fuel oils.
• the WO 2004/106470 describes the use of terpolymers containing polymerized ethylene, vinyl acetate and heteroatom-functionalized vinyl compounds as additives for fuel oils and lubricants, especially as a cold flow improver for fuel oils.
• Another object of the invention is the use of these copolymers as an additive for fuel oils and lubricants and especially as a cold flow improver in fuel oils. Furthermore, the subject matter of the invention is the fuel oils and lubricants additized with these copolymers. Finally, the invention relates to additive packages containing such copolymers.
• C 1 -C 40 -hydrocarbyl is a hydrocarbon radical having 1 to 40 carbon atoms. It is preferably an aliphatic hydrocarbon radical, such as alkyl, alkenyl, alkadienyl or alkynyl.
• C 1 -C 40 -hydrocarbyl is C 1 -C 40 -alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, neopentyl, hexyl, heptyl , Octyl, 2-ethylhexyl, neooctyl, nonyl, neononyl, decyl, neodecyl, undecyl, neoundecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, hencosyl, docosyl, tricosyl, tetracosyl,
• C 1 -C 20 -hydrocarbyl radicals ie it is a hydrocarbon radical having 1 to 20 carbon atoms. It is preferably an aliphatic hydrocarbon radical, such as alkyl, alkenyl, alkadienyl or alkynyl.
• C 1 -C 20 hydrocarbyl is C 1 -C 20 alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, lsöbutyl, tert-butyl, pentyl, neopentyl, hexyl, heptyl , Octyl, 2-ethylhexyl, neo-octyl, nonyl, neononyl, Decyl, neodecyl, undecyl, neoundecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl and their constitutional isomers.
• alkyl such as methyl, ethyl,
• C 1 -C 10 -hydrocarbyl is a hydrocarbon radical having 1 to 10 carbon atoms. It is preferably an aliphatic hydrocarbon radical, such as alkyl, alkenyl, alkadienyl or alkynyl.
• C 1 -C 10 -hydrocarbyl is C 1 -C 10 -alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, neopentyl, hexyl, heptyl , Octyl, 2-ethylhexyl, neooctyl, nonyl, neononyl, decyl, neodecyl and their constitutional isomers.
• alkyl such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, neopentyl, hexyl, heptyl , Octyl, 2-ethylhexyl, n
• C 1 -C 4 -hydrocarbyl is a hydrocarbon radical having 1 to 4 carbon atoms. It is preferably an aliphatic hydrocarbon radical, such as alkyl, alkenyl, alkadienyl or alkynyl.
• C 1 -C 4 -hydrocarbyl is C 1 -C 4 -alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl and tert-butyl.
• C 1 -C 9 -alkyl represents a linear or branched alkyl radical having 1 to 9 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, neopentyl, hexyl , Heptyl, octyl, 2-ethylhexyl, neo-octyl, nonyl and neononyl and their constitutional isomers.
• C 1 -C 19 -alkyl is, for example, decyl, neodecyl, undecyl, neoundecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl and their constitutional isomers.
• the hydrocarbyl radicals may be unsubstituted or monosubstituted or polysubstituted.
• Suitable substituents are, for example, OH, C 1 -C 4 -alkoxy, NR 11 R 12 (R 11 and R 12 are each independently H or C 1 -C 4 -alkyl) or carbonyl (COR 11 ). Preferably, however, they are unsubstituted.
• Aryl represents an aromatic hydrocarbon radical having 6 to 14 carbon atoms, such as phenyl, naphthyl, anthracenyl or phenanthrenyl.
• the aryl radical can be unsubstituted or monosubstituted or polysubstituted.
• Suitable substituents are C 1 -C 10 alkyl, OH, C 1 -C 4 alkoxy and NO 2 .
• Preferred substituents are C 1 -C 10 -alkyl radicals, C 1 -C 4 -alkyl being particularly preferred.
• the substituents are ethyl or methyl and especially methyl.
• C 1 -C 4 alkoxy is a bonded via an oxygen atom C 1 -C 4 alkyl radical.
• Examples of these are methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, 2-butoxy, isobutoxy and tert-butoxy.
• C 1 -C 4 -alkanol represents a C 1 -C 4 -alkyl radical which is substituted by 1 to 3 hydroxyl groups on different carbon atoms.
• C 1 -C 10 -alkanol represents a C 1 -C 10 -alkyl radical which is substituted by 1 to 6 hydroxyl groups on different carbon atoms.
• C 1 -C 20 -alkanol is a C 1 -C 20 -alkyl radical which is replaced by 1 to 6 hydroxyl groups at different Carbon atoms is substituted.
• C 1 -C 40 -alkanol is a C 1 -C 40 -alkyl radical which is substituted by 1 to 6 hydroxyl groups on different carbon atoms.
• C 1 -C 4 -alkanols are methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, isobutanol, tert-butanol, ethylene glycol, propylene glycol and glycerol.
• C 1 -C 10 -alkanol is, for example, pentanol, hexanol, heptanol, octanol, 2-ethylhexanol, nonanol, decanol, their constitutional isomers, as well as erythritol, pentaerythritol and sorbitol.
• C 1 -C 20 -alkanol is, for example, undecanol, dodecanol, tridecanol, tetradecanol, pentadecanol, hexadecanol, heptadecanol, octadecanol, nonadecanol and eicosanol and also their constitutional isomers.
• C 1 -C 40 -alkanol is, for example, hencosanol, docosanol, tricosanol, tetracosanol, pentacosanol, hexacosanol, heptacosanol, octacosanol, nonacosanol, squalanol, the higher homologues and constitutional isomers thereof.
• the monomers M1 are preferably monoalkenes having a terminal double bond, such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, their constitution isomers and the higher monounsaturated homologs with up to 40 carbon atoms.
• R 1 is preferably H or C 1 -C 10 -alkyl, particularly preferably H or C 1 -C 4 -alkyl and in particular H, methyl or ethyl. Accordingly, monomer M1 is in particular ethylene, propylene or 1-butene. Specifically, M1 is ethylene.
• radicals R 2 , R 3 , R 4 or R 5 in the comonomer M2 is -COOR 10 , this is, for example, an ester of an ⁇ , ⁇ -ethylenically unsaturated carboxylic acid.
• one of the radicals R 2 , R 3 , R 4 or R 5 in M2 is -OCOR 10 , this is, for example, the alkenyl ester, for example the vinyl or propenyl ester of an aliphatic carboxylic acid, which may be unsaturated or preferably saturated.
• two radicals R 2 , R 3 , R 4 or R 5 stand for -COOR 10 , then M2 is the diester of an ethylenically unsaturated dicarboxylic acid.
• ⁇ , ⁇ -unsaturated carboxylic acids are acrylic acid, methacrylic acid and crotonic acid.
• esters of ⁇ , ⁇ -unsaturated carboxylic acids are the esters with C 1 -C 40 -alkanols, preferably with C 1 -C 20 -alkanols, in particular with C 1 -C 10 -alkanols.
• esters with C 1 -C 40 -alkanols preferably with C 1 -C 20 -alkanols, in particular with C 1 -C 10 -alkanols.
• examples these are the methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl -, nonyl or decyl esters of acrylic acid, methacrylic acid or crotonic acid. Preference is given to the esters of acrylic or methacrylic
• diesters of unsaturated dicarboxylic acids are the diesters with C 1 -C 40 -alkanols, preferably with C 1 -C 20 -alkanols, in particular with C 1 -C 10 -alkanols.
• Unsaturated dicarboxylic acids are, for example, maleic acid, fumaric acid and citraconic acid.
• esters are the methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, nonyl or decyl esters of maleic acid, fumaric acid or citraconic acid, it being possible for the carboxyl groups of the dicarboxylic acids to be esterified with identical or different alkanols.
• radicals R 2 , R 3 , R 4 or R 5 are -COOR 10 or -OCOR 10 and particularly preferably -OCOR 10 .
• the other three radicals are preferably H or C 1 -C 10 -alkyl, more preferably H or C 1 -C 4 -alkyl.
• Two of the radicals are preferably H and the third radical is H or C 1 -C 4 -alkyl.
• all three remaining radicals are H or methyl, it being preferred that two of the radicals is H and the third is H or methyl.
• all three remaining radicals are H.
• R 10 is C 1 -C 20 alkyl, preferably C, more preferably C 1- C 10 alkyl.
• R 10 is C 1 -C 19 alkyl, preferably C, particularly preferably C 1 -C 9 alkyl, in particular methyl or ethyl and especially methyl.
• the monomer M2 is the vinyl ester of an aliphatic saturated C 1 -C 20 carboxylic acid.
• the monomer M2 is the vinyl ester of an aliphatic saturated C 1 -C 10 carboxylic acid.
• the monomer M2 is vinyl acetate or vinyl propionate.
• the monomer M2 is vinyl acetate.
• R 6 , R 7 and R 8 independently of one another are H or C 1 -C 4 -alkyl. Preferably, they stand for H or methyl. More preferably, at most one of these radicals is methyl and the other two are H. Specifically, all three radicals R 6 , R 7 and R 8 are H.
• R 9 is preferably optionally substituted phenyl.
• Preferred substituents are OH and C 1 -C 4 -alkyl, with methyl and ethyl and especially methyl being particularly preferred.
• R 9 particularly preferably represents phenyl, methylphenyl, such as 2-, 3- or 4-methylphenyl, or dimethylphenyl, such as 2,3-, 2,4-, 2,5- or 2,6-dimethylphenyl. Specifically, R 9 is unsubstituted phenyl.
• the monomer M3 is styrene (vinylbenzene).
• the copolymers according to the invention have a number-average molecular weight M n in the range from preferably 1000 to 20 000, more preferably from 1000 to 10000 and in particular from 1500 to 7000.
• the copolymers may also have a weight-average molecular weight M w of from 1000 to 30 000, in particular 1500 to 20 000 and / or an M w / M n ratio of 1.5 to 5.0, in particular 1.8 to 3.0.
• the copolymer according to the invention is particularly preferably an ethylene / vinyl acetate / styrene terpolymer.
• the viscosity of such copolymers is about 5 - 25000 mm 2 / s, in particular about 10 to 2000 mm 2 / s, each at a temperature of about 120 ° C.
• the copolymers used according to the invention are preferably obtainable by, preferably free-radical, polymerization, in particular high-pressure polymerization, of the monomers M1, M2 and M3.
• Suitable polymerization processes are well known.
• processes for the direct radical high-pressure copolymerization of unsaturated compounds for example in Ullmann's Encyclopedia of Industrial Chemistry 5th edition, keyword: Waxes, Vol. A 28, p. 146 ff., VCH Weinheim, Basel, Cambridge, New York, Tokyo, 1996 to which reference is hereby incorporated by reference.
• suitable methods are for example in DE-A-2515805 . DE-A-3141507 .
• EP-A-0007590 and US 3,627,838 which is also incorporated herein by reference in its entirety.
• copolymers of the invention obtainable by the polymerization process are preferably composed essentially of the above-defined monomers M1, M2 and M3. Depending on the manufacturing process, small amounts of a compound used as regulator (chain terminator) may possibly be present.
• copolymers according to the invention are preferably prepared in stirred high-pressure autoclaves or in high-pressure tubular reactors or combinations of the two. For them, the ratio of length / diameter in the range from 5: 1 to 30: 1, preferably 10: 1 to 20: 1, predominantly.
• Suitable pressure conditions for the polymerization are 1000 to 3000 bar, preferably 1500 to 2000 bar.
• the reaction temperatures are e.g. in the range of 160 to 320 ° C, preferably in the range of 200 to 280 ° C.
• a regulator for adjusting the molecular weight of the copolymers used for example, an aliphatic aldehyde or an aliphatic ketone of the general formula I. or mixtures thereof.
• R a and R b may also be covalently linked together to form a 4- to 13-membered ring.
• R a and R b may together form the following alkylene groups: - (CH 2 ) 4 -, - (CH 2 ) 5 -, - (CH 2 ) 6 , - (CH 2 ) 7 -, -CH (CH 3 ) -CH 2 -CH 2 -CH (CH 3 ) - or -CH (CH 3 ) -CH 2 -CH 2 -CH 2 -CH (CH 3 ) -.
• Suitable regulators are unbranched aliphatic hydrocarbons, for example propane or branched aliphatic hydrocarbons having tertiary H atoms, for example isobutane, isopentane, isooctane or isododecane (2,2,4,6,6-pentamethylheptane).
• unbranched aliphatic hydrocarbons for example propane or branched aliphatic hydrocarbons having tertiary H atoms, for example isobutane, isopentane, isooctane or isododecane (2,2,4,6,6-pentamethylheptane).
• higher olefins such as propylene, can be used.
• the amount of regulator used corresponds to the amounts customary for the high-pressure polymerization process.
• di-tert-butyl peroxide, tert-butyl peroxypivalate, tert-butyl peroxyisononanoate, tert-amyl peroxypivalate or dibenzoyl peroxide or mixtures thereof are particularly suitable.
• azo compound azobisisobutyronitrile ("AIBN") is exemplified.
• AIBN azobisisobutyronitrile
• the free-radical initiators are metered in amounts customary for polymerizations.
• the copolymers of the present invention are prepared by reacting a mixture of monomers M1, M2 and M3 in the presence of the regulator at a temperature in the range of about 20 to 50 ° C, e.g. of 30 ° C, preferably continuously passed through a stirred autoclave, which at a pressure in the range of about 1500 to 2000 bar, such. of about 1700 bar, is maintained.
• a suitable solvent e.g. Isododecane
• the temperature in the reactor at the desired reaction temperature such as. at 200 to 250 ° C, held.
• the resulting after the relaxation of the reaction mixture polymer is then isolated in a conventional manner.
• Another object of the present invention is the use of the copolymers of the invention as an additive for fuel oils and lubricants.
• the copolymers are used as cold flow improvers, preferably for fuel oils.
• copolymers of the invention are used alone or in combination with other co-additives in amounts to show an effect as a cold flow improver in the additized fuel oil or lubricant.
• Another object of the invention relates to fuel oil compositions containing a greater weight fraction of a boiling in the range of about 120-500 ° C middle distillate fuel and a smaller proportion by weight of at least one copolymer of the invention.
• Another object of the invention relates to lubricant compositions containing a greater proportion by weight of a conventional lubricant and a smaller proportion by weight of at least one cold flow improver as defined above.
• fuel oil compositions is meant according to the invention preferably fuels.
• Suitable fuels are gasolines and middle distillates, with middle distillates being preferred.
• Suitable middle distillates are, for example, diesel fuels, heating oil or kerosene; wherein diesel fuel and heating oil are particularly preferred.
• the fuel oils are, for example, low-sulfur or high-sulfur petroleum refines or stone or lignite distillates, which usually have a boiling range of 150 to 400 ° C.
• the fuel oils may be standard fuel oil according to DIN 51603-1, which has a sulfur content of 0.005 to 0.2 wt .-%, or it is low sulfur fuel oils having a sulfur content of 0 to 0.005 wt.
• heating oil is in particular heating oil for domestic oil firing systems or heating oil called EL.
• the quality requirements for such heating oils are specified, for example, in DIN 51603-1 (cf. Ullmann's Encyclopedia of Industrial Chemistry, 5th edition, Vol. A12, p. 617 ff ., which is hereby incorporated by reference).
• the diesel fuels are, for example, petroleum raffinates, which usually have a boiling range of 100 to 400 ° C. These are mostly distillates with a 95% point up to 360 ° C or even beyond. However, these may also be so-called "ultra low sulfur diesel” or "city diesel", characterized by a 95% point of, for example, a maximum of 345 ° C and a maximum sulfur content of 0.005 wt .-% or by a 95% point of, for example 285 ° C and a maximum sulfur content of 0.001 wt .-%.
• GTL coal gasification or gas liquefaction
• BTL biomass to liquid
• mixtures of the abovementioned diesel fuels with regenerative fuels such as biodiesel or bioethanol.
• the additive according to the invention is particularly preferred for the addition of low-sulfur diesel fuels, that is to say having a sulfur content of less than 0.05% by weight, preferably less than 0.02% by weight, in particular less than 0.005% by weight. % and especially less than 0.001% by weight of sulfur or for the addition of heating oil with a low sulfur content, for example with a sulfur content of at most 0.2% by weight, preferably of at most 0.05% by weight, more preferably of at most 0.005 Gew., Used.
• Such fuel oil compositions may further comprise as fuel component biodiesel (from animal and / or vegetable production) in proportions of 0-30% by weight.
• Preferred fuel oil compositions are selected from diesel fuels, kerosene and fuel oil, wherein the diesel fuel may be obtainable by refining, coal gasification, gas liquefaction or biomass liquefaction, may be a mixture of such products and optionally mixed with regenerative fuels.
• diesel fuel may be obtainable by refining, coal gasification, gas liquefaction or biomass liquefaction, may be a mixture of such products and optionally mixed with regenerative fuels.
• Such fuel oil compositions are preferred in which the sulfur content of the mixture is at most 500 ppm.
• the additive of the present invention is preferably used in a proportion based on the total amount of the fuel oil composition, which in itself has a substantially sufficient influence on the cold flow properties of the fuel oil compositions.
• the additive is used in an amount of 0.001 to 1 wt .-%, in particular from 0.01 to 0.1 wt .-%, based on the total amount of the fuel oil composition.
• the copolymers according to the invention can be used in combination with other conventional cold flow improvers and / or further lubricating and fuel oil additives.
• copolymers according to the invention can be added to the fuel oil compositions individually or as a mixture of such copolymers and optionally in combination with other additives known per se.
• Suitable additives which may be included in the fuel oils of this invention besides the copolymer of the present invention, especially for diesel fuels and heating oils include detergents, corrosion inhibitors, dehazers, demulsifiers, antifoams, antioxidants, metal deactivators, multifunctional stabilizers, cetane improvers, combustion improvers, dyes, Markers, solubilizers, antistatic agents, lubricity improvers, and other additives which improve the cold properties of the fuel, such as nucleators, other conventional flow improvers (“MDFI"), paraffin dispersants (“WASA”) and the combination of the last two additives (“WAFI”) (cf. . also Ullmann's Encyclopedia of Industrial Chemistry, 5th Edition, Vol. A16, p. 719 ff ; or the patents cited at the outset for flow improvers).
• MDFI nucleators
• WASA paraffin dispersants
• WAFI last two additives
• the monomer is preferably selected from alkenylcarboxylic esters, (meth) acrylic esters and olefins.
• Suitable olefins are, for example, those having 3 to 10 carbon atoms and having 1 to 3, preferably 1 or 2, in particular having one, carbon-carbon double bond. In the latter case, the carbon-carbon double bond can be arranged both terminally ( ⁇ -olefins) and internally.
• ⁇ -olefins more preferably ⁇ -olefins having 3 to 6 carbon atoms, such as propene, 1-butene, 1-pentene and 1-hexene.
• Suitable (meth) acrylic esters are, for example, esters of (meth) acrylic acid with C 1 -C 10 -alkanols, in particular with methanol, ethanol, propanol, isopropanol, n-butanol, sec-butanol, isobutanol, tert-butanol, pentanol, hexanol, Heptanol, octanol, 2-ethylhexanol, nonanol and decanol.
• Suitable alkenylcarboxylic esters are, for example, the vinyl and propenyl esters of carboxylic acids having 2 to 20 carbon atoms, the hydrocarbon radical of which may be linear or branched. Preferred among these are the vinyl esters.
• carboxylic acids having a branched hydrocarbon radical preferred are those whose branch is in the ⁇ -position to the carboxyl group, the ⁇ -carbon atom being particularly preferably tertiary, ie. H. the carboxylic acid is a so-called neocarboxylic acid.
• the hydrocarbon radical of the carboxylic acid is linear.
• alkenylcarboxylic esters examples include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl 2-ethylhexanoate, vinyl neopentanoate, vinyl hexanoate, vinyl neononanoate, vinyl neodecanoate and the corresponding propenyl esters, with vinyl esters being preferred.
• a particularly preferred alkenyl carboxylic acid ester is vinyl acetate.
• the ethylenically unsaturated monomer is selected from alkenylcarboxylic esters.
• copolymers which contain two or more mutually different alkenylcarboxylic acid esters in copolymerized form, these differing in the alkenyl function and / or in the carboxylic acid group. Also suitable are copolymers which, in addition to the alkenylcarboxylic ester (s), contain at least one olefin and / or at least one (meth) acrylic acid ester in copolymerized form.
• the ethylenically unsaturated monomer is copolymerized in the copolymer in an amount of preferably from 1 to 50 mol%, particularly preferably from 10 to 50 mol% and in particular from 5 to 20 mol%, based on the total copolymer.
• the copolymer a) preferably has a number-average molecular weight M n of from 1,000 to 20,000, more preferably from 1,000 to 10,000 and in particular from 1,000 to 6,000.
• Preferred comb polymers are obtainable, for example, by the copolymerization of maleic anhydride or fumaric acid with another ethylenically unsaturated monomer, for example with an ⁇ -olefin or an unsaturated ester, such as vinyl acetate, followed by esterification of the anhydride or acid function with an alcohol having at least 10 carbon atoms.
• Other preferred comb polymers are copolymers of ⁇ -olefins and esterified comonomers, for example, esterified copolymers of styrene and maleic anhydride or esterified copolymers of styrene and fumaric acid.
• mixtures of comb polymers are suitable.
• Comb polymers may also be polyfumarates or polymaleinates.
• homopolymers and copolymers of vinyl ethers are suitable comb polymers.
• Preferred polyoxyalkylene compounds of the formula III in which both R 19 and R 20 are R 21 are polyethylene glycols and polypropylene glycols having a number average molecular weight of 100 to 5000.
• Preferred polyoxyalkylenes of the formula III in which one of the radicals R 19 is R 21 and the other is R 21 -CO- are polyoxyalkylene esters of fatty acids having 10 to 30 carbon atoms, such as stearic acid or behenic acid.
• Preferred polyoxyalkylene compounds in which both R 19 and R 20 are R 21 -CO- are diesters of fatty acids having 10 to 30 carbon atoms, preferably stearic or behenic acid.
• the polar nitrogen compounds d), suitably oil-soluble, may be both ionic and nonionic, and preferably have at least one, more preferably at least 2, substituents of the formula> NR 22 wherein R 22 is a C 8 -C 40 hydrocarbon radical.
• the nitrogen substituents may also be quaternized, that is in cationic form.
• An example of such nitrogen compounds are ammonium salts and / or amides obtainable by reacting at least one amine substituted with at least one hydrocarbyl radical with a carboxylic acid having 1 to 4 carboxyl groups or with a suitable derivative thereof.
• the amines preferably contain at least one linear C 8 -C 40 -alkyl radical.
• Suitable primary amines are octylamine, nonylamine, decylamine, undecylamine, dodecylamine, tetradecylamine and the higher linear homologs.
• Suitable secondary amines are, for example, dioctadecylamine and methylbehenylamine.
• amine mixtures in particular industrially available amine mixtures, such as fatty amines or hydrogenated tallamines, as used, for example, in US Pat Ullmann's Encyclopedia of Industrial Chemistry, 6th edition, 2000 electronic release, chapter "Amines, aliphatic".
• Suitable acids for the reaction are, for example, cyclohexane-1,2-dicarboxylic acid, cyclohexene-1,2-dicarboxylic acid, cyclopentane-1,2-dicarboxylic acid, naphthalenedicarboxylic acid, phthalic acid, isophthalic acid, terephthalic acid and succinic acids substituted by long-chain hydrocarbon radicals.
• polar nitrogen compounds are ring systems bearing at least two substituents of the formula -A-NR 23 R 24 wherein A is a linear or branched aliphatic hydrocarbon group optionally substituted by one or more groups selected from O, S , NR 35 and CO, and R 23 and R 24 are a C 9 -C 40 hydrocarbon radical optionally interrupted by one or more groups selected from O, S, NR 35 and CO, and / or or substituted by one or more substituents selected from OH, SH and NR 35 R 36 , wherein R 35 is C 1 -C 40 alkyl optionally substituted by one or more moieties selected from CO, NR 35 , O and S, interrupted, and / or substituted by one or more radicals selected from NR 37 R 38 , OR 37 , SR 37 , COR 37 , COOR 37 , CONR 37 R 38 , aryl or heterocyclyl, wherein R 37 and R 38 each una depending on one another, are selected from H or C 1 -
• A is a methylene or polymethylene group having 2 to 20 methylene units.
• suitable radicals R 23 and R 24 are 2-hydroxyethyl, 3-hydroxypropyl, 4-hydroxybutyl, 2-ketopropyl, ethoxyethyl and propoxypropyl.
• the cyclic system can be either homocyclic, heterocyclic, condensed polycyclic or non-condensed polycyclic systems.
• the ring system is carbo- or heteroaromatic, in particular carboaromatic.
• polycyclic ring systems examples include condensed benzoic structures, such as naphthalene, anthracene, phenanthrene and pyrene, condensed non-benzoidic structures, such as azulene, indene, hydrindene and fluorene, uncondensed polycycles, such as diphenyl, heterocycles, such as quinoline, indole, dihydroindole, benzofuran, Coumarin, isocoumarin, benzthiophene, carbazole, diphenylene oxide and diphenylene sulfide, non-aromatic or partially saturated ring systems such as decalin, and three-dimensional structures such as ⁇ -pinene, camphene, bornylene, norborane, norbornene, bicyclooctane and bicyclooctene.
• condensed benzoic structures such as naphthalene, anthracene, phenanthrene and pyrene
• Suitable polar nitrogen compounds are condensates of long-chain primary or secondary amines with carboxyl group-containing polymers.
• Suitable polar nitrogen compounds are also in the DE-A-198 48 621 of the DE-A-196 22 052 or the EP-B-398 101 described, to which reference is hereby made.
• Suitable poly (meth) acrylic esters f) are both homo- and copolymers of acrylic and methacrylic acid esters. Preferred are copolymers of at least two mutually different (meth) acrylic acid esters, which differ with respect to the fused alcohol. Optionally, the copolymer contains a further, different of which olefinically unsaturated monomer copolymerized. The weight average molecular weight of the polymer is preferably from 50000 to 500000.
• a particularly preferred polymer is a copolymer of methacrylic acid and methacrylic esters of saturated C 14 - 15 alcohols and C, wherein the acid groups are neutralized with hydrogenated tallow amine.
• Suitable poly (meth) acrylic esters are, for example, in WO 00/44857 which is incorporated herein by reference in its entirety.
• Another object of the invention is the use of the copolymers according to the invention for improving the action of cold flow improvers of the prior art.
• the copolymers of the invention are used in such an amount that they alone have no significant effect on the cold flow properties of the fuel oil thus additized.
• the copolymers according to the invention and the conventional cold flow improvers are employed in a weight ratio of from 1: 5 to 1:50, more preferably from 1: 7 to 1:20, in particular from 1: 8 to 1:15, especially about 1: 9.
• the conventional cold flow improvers are preferably those the group a) of the co-additives, among which ethylene (meth) acrylic acid ester copolymers and in particular ethylene-vinyl ester copolymers, for example ethylene-vinyl acetate copolymers, are particularly preferred.
• the conventional cold flow improvers are used in conventional amounts, for example in an amount of 0.001 to 1 wt .-%, preferably 0.01 to 0.1 wt .-%, based on the total weight of the fuel oil composition.
• the subject of the present application is an additive concentrate containing at least one copolymer of the invention and at least one diluent and optionally at least one further additive, in particular selected from the above co-additives.
• Suitable diluents are, for example, fractions obtained in petroleum processing, such as kerosene, naphtha or bright stock. Also suitable are aromatic and aliphatic hydrocarbons and alkoxyalkanols. Dilutants preferred for middle distillates, especially for diesel fuels and fuel oils, are naphtha, kerosene, diesel fuels, aromatic hydrocarbons, such as Solvent Naphtha heavy, Solvesso® or Shellsol®, and mixtures of these solvents and diluents.
• the copolymer according to the invention is preferably present in the concentrates in an amount of from 0.1 to 80% by weight, more preferably from 1 to 70% by weight and in particular from 20 to 60% by weight, based on the total weight of the concentrate, in front.
• Another object of the invention is an additive composition
• a copolymer of the invention and a conventional cold flow improver.
• Suitable cold flow improvers are the aforementioned.
• cold flow improvers from group (a) in particular ethylene / vinyl ester copolymers, e.g. to EVA copolymers.
• the copolymers according to the invention and the conventional cold flow improvers are present in a weight ratio of preferably from 1: 5 to 1:50, more preferably from 1: 7 to 1:20, in particular from 1: 8 to 1:15 and especially from about 1: 9 before.
• the composition may also contain other conventional cold flow improvers and other coadditives as well as diluents. With regard to suitable co-additives and diluents, reference is made to the above statements.
• the copolymers of the invention show improved performance compared to conventional fuel additives.
• they improve the cold flow properties of additive fuel oils more effectively than comparable additives of the prior art.
• they are capable of significantly increasing the effect of conventional cold flow improvers when used in combination with them.
• they increase the effect of conventional cold flow improvers in fuel oils. It is sufficient if they are used in amounts that have no effect on the cold flow properties have additive-fuel oils.
• they are characterized by a good formability. So they have an improved solubility in fuels and lubricants and in the diluents of additive packages and can be handled well (eg metering) due to their relatively low viscosity.
• a total of seven different copolymers of the invention were prepared by high pressure polymerization of ethylene, styrene and vinyl acetate.
• the Cloud Point was determined according to ASTM D 2500, the Cold Filter Plugging Point (CFPP) to DIN EN 116 and the Pour Point (PP) to ASTM D 97.
• copolymers of the invention are also useful as impact modifiers for cold flow improvers of the prior art.
• 10% solutions of the polymers 6 and 7 were prepared in solvent naphtha.
• test results summarized in Tables 2 to 5 demonstrate a surprisingly good performance of the copolymers according to the invention as cold flow improvers in middle distillate fuel compositions.
• additives according to the invention it is now possible on the one hand to set comparable CFPP values as with conventional MDFIs, but at a lower metering rate, or to achieve improved (higher) CFPP values for the same metering.
• test results summarized in Tables 6 and 7 demonstrate that the copolymers according to the invention are also capable of significantly increasing the effect of conventional MDFI on the CFPP value.

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• 2005
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