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
  • C10L1/18—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

Definitions

• the invention relates to the use of polymers which comprise an ⁇ -olefin, an ester of an ⁇ , ⁇ -unsaturated carboxylic acid and optionally an alkenyl ester of a carboxylic acid in copolymerized form, as an additive for turbine fuels and in particular as a cold flow improver for turbine fuels; the turbine fuels additized with these polymers; and additive packages containing such copolymers.
• Turbine fuels also referred to as jet fuels, jet fuels, jet fuel, aviation fuel or turbo fuel, must meet high demands on their cold properties due to their use in aviation and the associated temperature conditions.
• the freezing point of the turbine fuel must be so low that the fuel flow is not affected by the high temperature conditions prevailing at high altitudes and also fuel filters are easily passed.
• the freezing point is the temperature at which the hydrocarbon crystals previously formed and precipitated by cooling dissolve completely again.
• the freezing point in civil and military aviation may not exceed -40 ° C or approximately -50 ° C. If the freezing point falls below, longer-chain paraffins crystallize out and form large, platelet-shaped wax crystals.
• These wax crystals have a sponge-like structure and lead to the inclusion of other fuel constituents in the crystal composite.
• the appearance of these crystals causes the fuel to pass through small openings and filters only slowly.
• the viscosity of the fuel increases, whereby the fuel flow is deteriorated.
• PP pour point
• the freezing point of turbine fuels is adjusted primarily by distillation measures in the refineries, for example by reducing the proportion of high-boiling fractions, which also include wax fractions.
• the disadvantage here however, the consequent increase in the cost of turbine fuel.
• a turbine fuel composition comprising, in addition to a turbine fuel, at least one of the following additives: copolymers of ethylene with at least one unsaturated ester selected from vinyl esters of at least 5 carbon atoms, alkyl (meth) acrylates, dialkyl fumarates and dialkyl maleates; Ethylene / alkene copolymers; Ethylene / vinyl acetate copolymers with less as 15 mole percent vinyl acetate; nucleators; waxes; Alkylphenol / formaldehyde condensates; Comb polymers; and organic nitrogen compounds.
• additives are intended to ensure that turbine fuels additized thereby remain fluid even below the freezing point specified in their specification.
• the WO 01/62874 describes a composition containing, in addition to a turbine fuel, additives selected from the reaction products of alkanolamines with long chain substituted acylating agents; Phenol / aldehyde condensates; special aromatic systems; and ethylene / vinyl acetate copolymers. These additives are intended to lower the freezing point of the turbine fuel additized therewith.
• this object has been achieved by the unexpected observation that polymers containing an ⁇ -olefin, an ester of an ⁇ , ⁇ -unsaturated carboxylic acid and optionally a carboxylic alkenylester in copolymerized form, improve the cold properties, in particular the cold flow properties of turbine fuels and also a better Performance than the ethylene / vinyl acetate copolymers described in the prior art possess.
• a first aspect of the invention accordingly relates to the use of a polymer which comprises an ⁇ -olefin, an ester of an ⁇ , ⁇ -unsaturated carboxylic acid and optionally an alkenyl ester of a carboxylic acid in copolymerized form as an additive for turbine fuels.
• those polymers are used which contain in copolymerized form the ester of the ⁇ , ⁇ -unsaturated carboxylic acid and the optionally present alkenyl ester in random distribution.
• the polymer is a binary polymer composed essentially of the ⁇ -olefin and the ester of an ⁇ , ⁇ -unsaturated carboxylic acid or it Alternatively, it is preferably a terpolymer, which is composed essentially of the three aforementioned monomers.
• R 1 is H or C 1 -C 40 hydrocarbyl
• R 2 , R 3 and R 4 are independently H or C 1 -C 4 alkyl
• R 5 is C 1 -C 20 hydrocarbyl
• R 6 , R 7 and R 8 are independently H or C 1 -C 4 alkyl
• R 9 is C 1 -C 19 hydrocarbyl.
• the monomers M1, M2 and M3 may be present in the polymer in the following molar proportions (Mx / (M1 + M2 + M3)):
• 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 20 hydrocarbyl, more preferably H or C 1 -C 10 hydrocarbyl, and more preferably H or C 1 -C 4 hydrocarbyl.
• Hydrocarbyl is preferably alkyl.
• R 1 is H, methyl or ethyl.
• monomer M1 is in particular ethylene, propylene or 1-butene.
• R 1 is H, ie M1 is specifically ethylene.
• the radicals R 2 , R 3 and R 4 are preferably H or methyl. Particularly preferably, two of the radicals R 2 , R 3 and R 4 are H and the other radical is H or methyl. In particular, all three radicals R 2 , R 3 and R 4 are H.
• the monomer M2 is preferably the esters of ⁇ , ⁇ -unsaturated carboxylic acids which are selected from acrylic acid, methacrylic acid, crotonic acid and isocrotonic acid, more preferably from acrylic acid and methacrylic acid and especially acrylic acid.
• Examples of such preferred ⁇ , ⁇ -unsaturated carboxylic acid esters M2 are: acrylic esters of C 1 -C 20 -alkanols, such as methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, acrylic acid n-pentyl ester, nylropenyl acrylate, acrylate hexyl ester, heptyl acrylate, octyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, acrylonyl acrylate, acrylonyl neonate, acrylic acid decylate, acryloylacrylate, acryloylacrylate, acryloylammonium ester and a stearylacrylate; also the corresponding methacrylic, crot
• R 5 is C 1 -C 20 hydrocarbyl.
• R 5 is a hydrocarbyl radical having at least 5 carbon atoms, for example C 5 -C 20 -hydrocarbyl.
• R 5 particularly preferably represents a hydrocarbyl radical having at least 6 carbon atoms, for example C 6 -C 20 -hydrocarbyl, preferably C 6 -C 16 -hydrocarbyl or particularly preferably C 6 -C 14 -hydrocarbyl.
• R 5 is a hydrocarbyl radical having at least 8 carbon atoms, for example C 8 -C 20 -hydrocarbyl, preferably C 8 -C 16 -hydrocarbyl and particularly preferably C 8 -C 14 -hydrocarbyl.
• Hydrocarbyl is preferably alkyl.
• R 5 is C 8 -C 12 hydrocarbyl.
• R 5 is C 4 -C 20 -hydrocarbyl, for example C 5 -C 20 -hydrocarbyl, particularly preferably C 4 -C 16 -hydrocarbyl, for example for C 6 -C 16 -hydrocarbyl, and in particular for C 4 -C 14 -hydrocarbyl, for example for C 6 -C 14 -hydrocarbyl.
• Hydrocarbyl is preferably alkyl.
• R 5 is in particular 2-ethylhexyl or lauryl.
• the monomer M2 is selected from 2-ethylhexyl acrylate and acrylic acid lauryl ester. Specifically, it is 2-ethylhexyl acrylate.
• the monomer M3 is the alkenyl ester, e.g. the vinyl or propenyl ester, an aliphatic carboxylic acid which may be unsaturated or preferably saturated.
• alkenyl esters in particular the vinyl or propenyl esters of an aliphatic carboxylic acid, which may be unsaturated or preferably saturated
• R 6 , R 7 and R 8 independently of one another are preferably H or methyl and particularly preferably H.
• R 9 is preferably C 1 -C 9 -hydrocarbyl. Hydrocarbyl is preferably alkyl. More preferably R 9 is ethyl or methyl and especially methyl.
• the monomer M3 is vinyl acetate.
• the copolymer used according to the invention contains the monomer M3 in copolymerized form and is thus composed of monomers comprising the monomers M1, M2 and M3
• the polymers used according to the invention are preferably composed essentially of the above-defined monomers M1, M2 and optionally M3. Depending on the manufacturing process, small amounts of a compound used as regulator (chain terminator) may possibly be present.
• the polymers of the invention also have a number average molecular weight M n in the range of about 1000 to 20,000, more preferably from 1000 to 10,000, in particular from 1500 to 6000 and especially from 1500 to 5000 on.
• the polymers may also have a weight-average molecular weight M w of from 1000 to 30 000, in particular 2000 to 20 000 and / or an M w / M n ratio of from 1.5 to 5.0, preferably from 1.8 to 4.0 and in particular of 1.9 to 3.5.
• the viscosity of such polymers is about 5 to 25,000 mm 2 / s, preferably about 10 to 1000 mm 2 / s, in particular about 50 to 700 mm 2 / s, each at a temperature of about 120 ° C.
• Preferably used polymers are selected from ethylene / acrylic acid 2-ethylhexyl ester polymers, ethylene / acrylic acid 2-ethylhexyl ester / vinyl acetate polymers and ethylene / acrylic acid lauryl ester / vinyl acetate polymers.
• the polymers are used as cold flow improvers. They are particularly preferably used for lowering the pour point (PP) of the turbine fuel additized therewith.
• the above-described polymers are used alone or in combination with other such polymers in amounts which are sufficient to have an effect on the cold properties, in particular on the cold flow behavior of the turbine fuel additized therewith.
• the polymers used according to the invention can also be used in combination with other conventional cold flow improvers and / or other turbine fuel additives.
• the polymers according to the invention are prepared by processes known per se. They are preferably prepared by free-radical polymerization, in particular high-pressure polymerization, of the monomers M1, M2 and optionally M3. Such processes for direct radical high-pressure copolymerization of unsaturated compounds are known from the prior art (cf., for example Ullmann's Encyclopedia of Industrial Chemistry 5th edition, keyword: Waxes, Vol. A 28, p. 146 ff., VCH Weinheim, Basel, Cambridge, New York, Tokyo, 1996 ; Furthermore US 3,627,838 ; DE-A 2515805 ; DE-A 3141507 ; EP-A 0007590 ).
• copolymers of the invention obtainable by the polymerization process are preferably composed essentially of the above-defined monomers M1, M2 and optionally M3. Depending on the manufacturing process, small amounts of a compound used as regulator (chain terminator) may possibly be present.
• the polymers 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 for example, an aliphatic aldehyde or an aliphatic ketone of the general 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.
• Another object of the invention relates to turbine fuel compositions containing a greater weight fraction of a turbine fuel and a smaller weight fraction of at least one polymer used in the invention according to the above definition.
• the polymers used according to the invention can be used in combination with other conventional cold flow improvers and / or other turbine fuel additives.
• the turbine fuel composition contains a major amount of liquid turbine fuel, which may be a conventional turbine fuel in civil or military aviation. These include, for example, fuels named Jet A, Jet A-1, Jet B, JP-4, JP-5, JP-7, JP-8 and JP-8 + 100. Jet A and Jet A-1 are commercially available turbine fuel specifications based on kerosene. The associated standards are ASTM D 1655 and DEF STAN 91-91. Jet A and Jet A-1 have maximum freezing points of -40 ° C and -47 ° C, respectively, according to their specifications. Jet B is a further cut fuel based on naphtha and kerosene fractions. JP-4 is equivalent to Jet B.
• JP 4, JP-5, JP-7, JP-8 and JP-8 + 100 are military turbine fuels such as those used by the Navy and Air Force. In part, these standards designate formulations which already contain other additives, such as corrosion inhibitors, anti-icing agents, static dissipators, etc.
• Preferred turbine fuels are Jet A, Jet A-1 and JP 8.
• the polymer used in the invention is preferably used in a proportion based on the total amount of the turbine fuel composition, which in itself has a substantially sufficient influence on the cold flow properties of the turbine fuel composition.
• the polymer is preferably used in an amount of from 10 to 10000 mg / l, particularly preferably from 50 to 7000 mg / l, in particular from 100 to 5000 mg / l, based on 1 l of the turbine fuel composition.
• the polymers according to the invention can be added to the turbine fuel compositions individually or as a mixture of such polymers and optionally in combination with other additives known per se.
• Suitable additives which may be included in the turbine fuel compositions of the present invention include other low temperature fuel additives, refrigerants, detergents, corrosion inhibitors, antioxidants such as hindered tert-butylphenols or N-butylphenylenediamines, metal deactivators such as N, N'-disalicylidene 1,2-diaminopropane, solubilizers, antistatic agents such as Stadis 450, biocides, anti-icing agents such as diethylene glycol methyl ether, and mixtures thereof.
• the monomer is preferably selected from alkenylcarboxylic acid esters, (meth) acrylic acid esters, fumaric acid esters, maleic acid esters and olefins.
• Suitable olefins are, for example, those having 3 to 20 carbon atoms and having 1 to 3, preferably 1 or 2, in particular having one, carbon-carbon double bond.
• the carbon-carbon double bond can be arranged both terminally ( ⁇ -olefins) and internally.
• ⁇ -olefins particularly preferably ⁇ -olefins having 3 to 20, more preferably 3 to 10 and in particular 3 to 6 carbon atoms, such as propene, 1-butene, 1-pentene and 1-hexene.
• Suitable (meth) acrylic esters are, for example, esters of (meth) acrylic acid with C 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.
• the notation "(meth) acrylic acid” is meant to include that both acrylic acid and methacrylic acid are included.
• Suitable alkenylcarboxylic esters are, for example, the vinyl and propenyl esters of carboxylic acids having 2 to 20 carbon atoms, the hydrocarbon radical of which may be linear or branched. Preferred among these are the vinyl esters.
• carboxylic acids with a branched hydrocarbon radical preference is given to those whose branching is in the ⁇ -position to the carboxyl group, the ⁇ -carbon atom being particularly preferably tertiary, ie the carboxylic acid being a so-called neocarboxylic acid.
• alkenylcarboxylic esters examples include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl neopentanoate, vinyl hexanoate, vinyl octanoate, vinyl 2-ethylhexanoate, vinyl neononanoate, vinyl neodecanoate and the corresponding propenyl esters, 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 1000 to 20 000, more preferably from 1000 to 10000 and in particular from 1000 to 6000.
• Such ethylene copolymers (a) are, for example, in WO 01/62874 or EP-A-1357168 to which reference is hereby incorporated by reference.
• Comb polymers (b) are for example those described in " Comb-like polymers. Structure and Properties ", NA Platé and VP Shibaev, J. Poly. Sci. Macromolecular Revs., 8, pp. 117-253 (1974) are described.
• comb polymers of the formula II are suitable wherein D is R 17 , COOR 17 , OCOR 17 , R 18 , OCOR 17 or OR 17 , E is H, CH 3 , D or R 18 , G is H or D, J is H, R 18 , R 18 COOR 17 , aryl or heterocyclyl, K is H, COOR 18 , OCOR 18 , OR 18 or COOH, L is H, R 18 , COOR 18 , OCOR 18 , COOH or aryl, in which R 17 is a hydrocarbon radical having at least 10 carbon atoms, preferably having 10 to 30 carbon atoms, R 18 is a hydrocarbon radical having at least one carbon atom, preferably having 1 to 30 carbon atoms, m for a mole fraction in the range of 1.0 to 0.4 and n represents a mole fraction in the range of 0 to 0.6.
• 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, and subsequent esterification of the anhydride or acid function with an alcohol of 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.
• Suitable nucleators (c) are in particular polyoxyalkylenes, for example polyoxyalkylene esters, ethers, esters / ethers and mixtures thereof.
• the polyoxyalkylene compounds preferably contain at least one, particularly preferably at least two, linear alkyl groups having from 10 to 30 carbon atoms and at least one polyoxyalkylene group having a molecular weight of up to 5,000.
• the alkyl group of the polyoxyalkylene radical preferably contains from 1 to 4 carbon atoms.
• Such polyoxyalkylene compounds are for example in the EP-A-0 061 895 , in the EP-A-1357168 as well as in the US 4,491,455 which is incorporated herein by reference in its entirety.
• Preferred polyoxyalkylene esters, ethers and esters / ethers have the general formula III wherein R 19 and R 20 are each independently R 21 , R 21 is -CO-, R 21 is -O-CO (CH 2 ) z - or R 21 is -O-CO (CH 2 ) z CO-, where R 21 is linear C 1 -C 30 -alkyl, y is a number from 1 to 4, x is a number from 2 to 200, and z is a number from 1 to 4.
• Preferred polyoxyalkylene compounds of the formula III in which both R 19 and R 20 are R 21 are polyethylene glycols and polypropylene glycols having a number average molecular weight of 100 to 5,000.
• Preferred polyoxyalkylenes of the formula III in which one of the radicals R 19 is R 21 and the other is R 21 -CO- are polyoxyalkylene esters of fatty acids having 10 to 30 carbon atoms, such as stearic acid or behenic acid.
• Preferred polyoxyalkylene compounds in which both R 19 and R 20 are R 21 -CO- are diesters of fatty acids having 10 to 30 carbon atoms, preferably stearic or behenic acid.
• Suitable nucleators (c) are block copolymers, as described, for example, in US Pat EP-A-1357168 is described, the contents of which are hereby incorporated by reference.
• Suitable block copolymers comprise at least one crystallizable block and at least one non-crystallizable block.
• the copolymers may be diblock, triblock or higher block polymers.
• Preferred triblock polymers have a crystallizable block on both polymer ends.
• such block copolymers are composed of butadiene and isoprene units.
• the polar nitrogen compounds (d) are also referred to as wax anti-settling additives (WASA). They are suitably oil-soluble, may be both ionic and non-ionic, and preferably have at least one, more preferably at least 2, substituents of the formula> NR 22 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 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 with long-chain hydrocarbon radicals.
• polar nitrogen compounds are ring systems bearing at least two substituents of the formula -A-NR 23 R 24 wherein A is a linear or branched aliphatic hydrocarbon group optionally substituted by one or more groups selected from O, S , NR 35 and CO, is interrupted, and R 23 and R 24 are a C 9 -C 40 -hydrocarbon radical, which is optionally interrupted by one or more groups selected from O, S, NR 35 and CO, and / or substituted by one or more substituents selected from OH, SH and NR 35 R 36 , wherein R 35 is 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
• 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 diphenyl sulfide, non-aromatic or partially saturated ring systems such as decalin, and three-dimensional structures such as a- 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 , of the EP-A-1357168 or the EP-B-398 101 described, to which reference is hereby made.
• Suitable sulfocarboxylic acids / sulfonic acids or their derivatives are, for example, those of the general formula IV wherein Y is SO 3 - (NR 25 3 R 26 ) + , SO 3 - (NHR 25 2 R 26 ) + , SO 3 - (NH 2 R 25 R 26 ), SO 3 - (NH 3 R 26 ) or SO 2 NR 25 R 26 , X for Y, CONR 25 R 27 , CO 2 - (NR 25 3 R 27 ) + CO 2 - (NHR 25 2 R 27 ) + R 28 -COOR 27 NR 25 COR 27 , R 28 OR 27 , R 28 OCOR 27 , R 28 R 27 , N (COR 25 ) R 27 or Z - (NR 25 3 R 27 ) + , in which R 25 is a hydrocarbon radical, R 26 and R 27 are alkyl, alkoxyalkyl or polyalkoxyalkyl having at least 10 carbon atoms in the main chain,
• Suitable poly (meth) acrylic esters (f) are both homo- and copolymers of acrylic and methacrylic acid esters. Preference is given to acrylic acid ester homopolymers derived from C 1 -C 40 -alcohols. Also preferred are copolymers of at least two different (meth) acrylic acid esters, which differ with respect to the fused alcohol. Optionally, the copolymer contains a further, different of which olefinically unsaturated monomer copolymerized. The weight average molecular weight of the polymer is preferably from 50000 to 500000.
• a particularly preferred polymer is a copolymer of methacrylic acid and methacrylic esters of saturated C 14 - and C 15 alcohols, wherein the acid groups are neutralized with hydrogenated tallow amine.
• Suitable poly (meth) acrylic esters are for example in the WO 00/44857 which is incorporated herein by reference in its entirety.
• the acylating agents used are preferably those which contain a hydrocarbon radical having 8 to 50 carbon atoms. Examples are a C 8 -C 50 - substituted, preferably C 12 -C 35 alkyl or alkenyl succinic acids and succinic acid derivatives.
• the alkanolamines are, for example, diethanolamine, dipropanolamine, dibutanolamine, N-methylethanolamine or N-ethylethanolamine. Such compounds are for example in the WO 01/62874 described, which is incorporated herein by reference.
• the hydroxyaromatics used for the preparation of the condensation products of hydroxyaromatics with aldehydes (h) are those which are substituted by a linear or branched hydrocarbon radical.
• the hydroxyaromatic can be either a substituted phenol or any other hydroxy group-containing aromatic such as naphthol.
• aldehyde component both the aldehydes themselves and suitable aldehyde sources can be used.
• aldehydes examples include formaldehyde (which can be used, for example, as paraldehyde or trioxane), acetaldehyde, propanal, butanal, isobutyraldehyde, heptanal, 2-ethylhexanal and glyoxylic acid.
• formaldehyde which can be used, for example, as paraldehyde or trioxane
• acetaldehyde propanal
• butanal isobutyraldehyde
• heptanal 2-ethylhexanal
• 2-ethylhexanal 2-ethylhexanal
• glyoxylic acid examples include glyoxylic acid.
• Suitable waxes (i) are both linear and non-linear paraffins.
• the n-paraffins are preferably C 8 -C 35 -, more preferably C 8 -C 30 - and in particular C 8 -C 25 -alkanes.
• the non-linear paraffins preferably comprise amorphous solids having a melting point of 10 to 60 ° C and a molecular weight of 150 to 500.
• Such waxes are for example in the EP-A-1357168 described, which is incorporated herein by reference.
• a final subject of the invention also relates to additive packages comprising at least one polymer used according to the invention as defined above and at least one further conventional turbine fuel additive and optionally at least one diluent.
• Suitable conventional turbine fuel additives are the coadditives described above.
• Preferred co-additives are anti-icing additives; in addition, the said conventional cold flow improvers, those of group (a) being preferred; Corrosion inhibitors; detergents; antioxidants; Antistatic agents and metal deactivators.
• the additive package contains, in addition to at least one of the polymers described above, at least one anti-icing agent and optionally at least one of the following coadditives: Conventional cold flow improvers, those of group (a) being preferred; Corrosion inhibitors; detergents; antioxidants; Antistatic agents and metal deactivators.
• the polymer used according to the invention is present in an amount of preferably from 0.1 to 99% by weight, more preferably from 1 to 95% by weight and in particular from 5 to 90% by weight.
• the additive package may optionally contain at least one diluent.
• Suitable diluents are, for example, fractions obtained in petroleum processing, such as kerosene, naphtha or bright stock.
• aromatic hydrocarbons such as Solvent Naphtha heavy, Solvesso ® or Shellsol ®, and aliphatic hydrocarbons.
• the polymer used according to the invention is preferably present in the concentrates in an amount of from 0.1 to 90% by weight, more preferably from 1 to 80% by weight and in particular from 10 to 70% by weight. %, based on the total weight of the concentrate.
• the inventive use of the described polymers improves the cold flow properties of turbine fuels additized therewith. Above all, the freezing point, the cloud point (CP) and in particular the pour point (PP) are lowered.
• a total of 28 different polymers according to the invention were prepared by high-pressure polymerization of ethylene and 2-ethylhexyl acrylate (AEH) or of ethylene, 2-ethylhexyl acrylate (AEH) or acrylic acid lauryl ester (AL) and vinyl acetate (VAC).
• AEH 2-ethylhexyl acrylate
• AAC acrylic acid lauryl ester
• VAC vinyl acetate
• Table 1 summarizes the properties of the polymers used in the following test examples.
• the jet A turbine fuel additized with the copolymers used according to the invention has a significantly lower pour point than the non-additized fuel, while the conventional ethylene-vinyl acetate copolymer has no effect on the pour point.

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• 2005
  • 2005-09-28 EP EP05021172A patent/EP1770150A1/fr not_active Withdrawn

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