Classifications

• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M145/00—Lubricating compositions characterised by the additive being a macromolecular compound containing oxygen
  • C10M145/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • C10M145/10—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate
  • C10M145/16—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate polycarboxylic
• • 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
  • C10L1/146—Macromolecular compounds according to different macromolecular groups, mixtures thereof
• • 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
• • 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
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
  • C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • C10M2209/08—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type
  • C10M2209/086—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type polycarboxylic, e.g. maleic acid
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
  • C10N2020/01—Physico-chemical properties
  • C10N2020/02—Viscosity; Viscosity index
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2070/00—Specific manufacturing methods for lubricant compositions
  • C10N2070/02—Concentrating of additives

Definitions

• the invention relates to the use of copolymers which, in addition to ethylenically unsaturated esters of dicarboxylic acids in copolymerized form contain at least one olefin and optionally the anhydride of an ethylenically unsaturated dicarboxylic acid in order to lower the CP value of fuel oils and lubricants.
• the invention relates to such copolymers and with these copolymers additiv convinced fuel oils and lubricants 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.
• CP Cloud Point
• WAT Wax Appearance Temperature
• CPD CP point depressants
• the WO 01/04238 describes the use of copolymers of C 14 -C 16 ⁇ -olefins and maleic imides or of terpolymers of ethylene, vinyl acetate and isobutene as CPD.
• the stated dosing rates are 500 ppm and are therefore very high.
• the EP-A-0214786 describes the use of copolymers which contain polymerized in addition to ⁇ -olefins with an alcohol esterified maleic anhydride, as a cold flow improver for fuels, eg for lowering the CP and the CFPP value.
• additives that more effectively decrease the CP value of fuel oils and lubricants, for example, by achieving the same effect as the additives of the prior art at lower dosage rates.
• the additives should have an improved formability and with other additives, which are usually added to the fuel oils and lubricants, not enter negative interactions. In particular, they should not adversely affect the effect of CFPP additives.
• this object has been achieved by the unexpected observation that copolymers containing esters of ethylenically unsaturated dicarboxylic acids, at least one olefin and optionally the anhydride of an ethylenically unsaturated dicarboxylic acid in copolymerized form, effectively lower the CP value of fuel oils and lubricants.
• Another object of the invention is such a copolymer.
• the invention further provides the fuel oils additized with these copolymers and Lubricants.
• the invention relates to additive packages containing such copolymers.
• hydrocarbyl radicals for example the alkyl, alkenyl, alkadienyl, alkatrienyl and alkatetraenyl radicals, or the unsaturated hydrocarbons, for example the alkenes, may be unsubstituted or monosubstituted or polysubstituted.
• Suitable substituents are, for example, OH, C 1 -C 4 -alkoxy, NR 15 R 16 (R 15 and R 16 are each independently H or C 1 -C 4 -alkyl) or carbonyl (COR 15 ). Preferably, however, they are unsubstituted.
• C 1 -C 4 alkoxy is a via an oxygen atom bonded C 1 -C 4 alkyl radical. Examples of these are methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, 2-butoxy, isobutoxy and tert-butoxy.
• C 18 -C 26 -alcohol represents a linear or branched saturated or unsaturated aliphatic hydrocarbon having 18 to 26 carbon atoms, which is substituted by one or more, preferably a hydroxy group.
• these are octadecanol, nonadecaol, eicosanol, octadecenol, nonadecenol, eicosenol, octadecadienol, nonadecadienol, eicosadienol, octadecatrienol, nonadecatrienol, eicosatrienol, positional and constitutional isomers thereof, the higher homologues having 21 to 26 carbon atoms and the associated positional and constitutional isomers.
• C 16 -C 26 -alcohol represents a linear or branched saturated or unsaturated aliphatic hydrocarbon having 16 to 26 carbon atoms, which is substituted by one or more, preferably a hydroxy group.
• Examples include, in addition to the aforementioned C 18 -C 26 alcohols, hexadecanol, heptadecanol, hexadecenol, heptadecenol, hexadecadienol, heptadecadienol and the associated positional and constitutional isomers.
• C 16 -C 28 -Alcohol is a linear or branched saturated or unsaturated aliphatic hydrocarbon having 16 to 26 carbon atoms, which is substituted by one or more, preferably a hydroxy group.
• Examples include, in addition to the aforementioned C 18 -C 26 alcohols, the higher homologues having 27 or 28 carbon atoms and the associated position and constitution isomers.
• C 10 -C 26 -alcohol represents a linear or branched saturated or unsaturated aliphatic hydrocarbon having 10 to 26 carbon atoms, which is substituted by one or more, preferably a hydroxy group.
• Examples of these are, in addition to the abovementioned C 18 -C 26 -alcohols, decanol, undecanol, dodecanol, tridecanol, isotridecanol, tetradecanol, pentadecanol, hexadecanol, heptadecanol, decenol, undecenol, dodecenol, tridecenol, isotridecenol, tetradecenol, pentadecenol, hexadecenol, heptadecenol, Decadienol, undecadienol, dodecadienol, tridecadienol, iso
• C 10 -C 30 -Alcohol is a linear or branched saturated or unsaturated aliphatic hydrocarbon having 10 to 30 carbon atoms, which is substituted by one or more, preferably a hydroxy group. examples for this are in addition to the aforementioned C 10 -C 26 -alcohols, the higher homologues having 27 to 30 carbon atoms and the associated position and constitution isomers.
• C 8 -C 30 -alcohol represents a linear or branched saturated or unsaturated aliphatic hydrocarbon having 8 to 30 carbon atoms, which is substituted by one or more, preferably a hydroxy group.
• Examples include, in addition to the aforementioned C 10 -C 30 alcohols octanol, 2-ethylhexanol, nonanol, neononyl alcohol, octenol, 2-ethylhexenol, Nonenol and the associated position and constitution isomers.
• C 6 -C 30 -alcohol represents a linear or branched saturated or unsaturated aliphatic hydrocarbon having 6 to 30 carbon atoms which is substituted by one or more, preferably a hydroxy group.
• Examples include, in addition to the aforementioned C 8 -C 30 alcohols hexanol and heptanol and the associated position and constitution isomers.
• C 6 -C 40 -Alcohol is a linear or branched aliphatic hydrocarbon having 6 to 40 carbon atoms, which is substituted by one or more, preferably a hydroxy group.
• Examples include, in addition to the aforementioned C 6 -C 30 alcohols, the higher homologues having 31 to 40 carbon atoms and the associated position and constitution isomers.
• M2 and M3 preferably differ by the number of carbon atoms, the difference preferably being at least 6 carbon atoms. Most preferably, M3 contains a greater number of carbon atoms than M2. In particular, M3 contains at least 6 more carbon atoms than M2.
• the copolymer contains the monomers M1, M2, optionally M3 and optionally M4 randomly polymerized.
• the molar fraction of the monomer M3 is lower than that of the monomer M2.
• Monomer M1 is a mono- or diester of fumaric acid or maleic acid, optionally substituted on the C-C double bond.
• the copolymer used according to the invention may contain, as monomer M1, in copolymerized form monoesters and diesters of ethylenically unsaturated dicarboxylic acids.
• copolymer used as monomer M1 mono- and / or diesters of ethylenically unsaturated dicarboxylic acids in copolymerized form, which are derived from various alcohols.
• R 5 is preferably H or C 1 -C 40 -alkyl, more preferably H or C 6 -C 40 -alkyl, more preferably H or C 8 -C 30 -alkyl and especially H or C 10 -C 30 -Alkyl, for example for H or C 10 -C 26 -alkyl or C 18 -C 26 -alkyl.
• R 6 is preferably C 1 -C 40 -alkyl, more preferably C 6 -C 40 -alkyl, more preferably C 8 -C 30 -alkyl and in particular C 10 -C 30 -alkyl, for example C 10 - C 26 alkyl or C 18 -C 26 alkyl.
• the alcohol component of the ester monomer M1 (R 6 and optionally R 5 ) is derived correspondingly particularly preferably from relatively long-chain alcohols, for example from C 6 -C 40 -alcohols, preferably from C 8 -C 30 -alcohols and especially from C 10 - C 30 -alcohols, for example of C 10 -C 26 -alcohols or of C 18 -C 26 -alcohols. It can also be derived from mixtures of such alcohols, for example mixtures obtained from industrial processes, such as fatty alcohols or alcohols from hydroformylation processes.
• the copolymer also contains, in addition to M 1, M 2 and optionally also M 3, copolymerized monomer M 4.
• the molar ratio of copolymerized M1 to copolymerized M4 is preferably 20: 1 to 1.5: 1, more preferably 10: 1 to 2: 1, more preferably 8: 1 to 2: 1, in particular 5: 1 to 2: 1 and especially 4: 1 to 2: 1.
• one of the radicals R 1 or R 2 is preferably H, while the other is -COOR 5 .
• one of R 3 or R 4 is H while the other is -COOR 6 .
• M1 is preferably an unsubstituted mono- or diester of fumaric acid or maleic acid.
• R 1 and R 3 are H, while R 2 is -COOR 5 and R 4 is -COOR 6 , ie M1 is particularly preferably a maleic acid mono- or diester.
• the copolymer used according to the invention preferably also contains monomer M 4 in copolymerized form.
• M1 may be both a symmetric and a mixed ester (ie, R 5 and R 6 may be the same or different).
• R 5 is not H.
• the copolymer can of course also contain monomer M4 in copolymerized form. Preferably, however, it does not contain any copolymerized M4 in this case.
• M1 here is preferably a maleic acid or in particular fumaric diester.
• ester monomers M1 are the monoesters or the symmetrical or mixed diesters of fumaric acid or maleic acid with methanol, ethanol, propanol, isopropanol, butanol, sec-butanol, isobutanol, tert-butanol, pentanol, hexanol, heptanol, octanol, 2- Ethylhexanol, nonanol, decanol, undecanol, dodecanol, tridecanol, tetradecanot, pentadecanol, hexadecanol, heptadecanol, octadecanol, nonadecanol, eicosanol, hencosanol, docosanol, tricosanol, tetracosanol, pentacosanol, hexacosanol,
• preferred ester monomers M1 are the monoesters or the symmetrical or mixed diesters of fumaric acid or maleic acid with longer-chain alcohols, for example with C 6 -C 40 -alcohols, particularly preferably with C 8 -C 30 -alcohols and in particular with C 10 -C 30 -alcohols, for example with C 10 -C 26 -alcohols or with C 18 -C 26 -alcohols.
• M2 and M3 differ by at least 6 carbon atoms, with M3 being particularly preferred as the longer-chain monomer. Accordingly, M3 in such a terpolymer most preferably contains at least 6 carbon atoms more than M2.
• R 9 and R 13 are C 8 -C 48 -alkyl, particularly preferably C 10 -C 48 -alkyl, in particular C 14 -C 38 -alkyl, for example C 16 -C 28 -alkyl.
• R 9 and R 13 differ by at least 6 carbon atoms, it being preferred that R 13 is the longer chain, ie that R 13 contains at least 6 more carbon atoms than R 9 .
• R 10 , R 11 , R 12 , R 14 , R 15 and R 16 may be the same or different and are preferably C 1 -C 4 alkyl, and more preferably H or methyl. It is preferred that at least one and in particular at least two of the radicals R 10 , R 11 or R 12 in monomer M 2 or at least one and in particular at least two of the radicals R 14 , R 15 or R 16 in monomer M 3 stand for H. Specifically, all three radicals R 10 , R 11 and R 12 in monomer M2 or all three radicals R 142 , R 15 and R 16 in monomer M3 for H.
• the monomers M2 and M3 are preferably longer-chain linear or branched alkenes, for example C 6 -C 50 -alkenes, preferably C 10 -C 50 -alkenes and in particular C 12 -C 50 -alkenes, for example C. 12 -C 40 -alkenes or C 18 -C 30 -alkenes.
• the double bond can be arranged both terminally ( ⁇ -olefin) and internally ( ⁇ -, ⁇ -, ⁇ -olefin, etc.).
• the alkenes may also be oligomers or polymers of alkenes, for example of C 2 -C 8 -alkenes, such as ethylene, propylene, 1- or 2-butene, isobutene, pentene, hexene or heptene, or in particular of C 3 -C 8 alkenes.
• C 2 -C 8 -alkenes such as ethylene, propylene, 1- or 2-butene, isobutene, pentene, hexene or heptene, or in particular of C 3 -C 8 alkenes.
• the monomers M2 and M3 are alkenes having the C-C double bond in the ⁇ - or ⁇ -position (relative to the main chain of the molecule) and in particular in the ⁇ -position (terminal alkenes, ⁇ -alkenes).
• the monomers M2 and M3 may also be alkene mixtures, for example mixtures obtained from industrial processes. This is the case in particular when the olefins used are olefin oligomers or polymers, such as polypropylene, polybutene or polyisobutene.
• copolymers used according to the invention are preferably obtainable by, preferably free-radical, polymerization, in particular solution polymerization, of the monomers M1, M2, optionally M3 and optionally M4.
• 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.
• esterification of the maleic anhydride is carried out so that a part of the anhydride used and copolymerized remains unchanged. It is also possible to use in the polymerization reaction instead of the actually desired monomers M1 the corresponding esters with shorter-chain alcohols, for example the methyl or ethyl esters of maleic acid or fumaric acid, and to convert these after polymerization by reaction with longer-chain alcohols in the desired ester.
• the copolymers of the invention obtainable by the polymerization process are preferably composed essentially of the above-defined monomers M1, M2, optionally M3 and optionally M4.
• monomers M1, M2, optionally M3 and optionally M4 For manufacturing purposes, e.g. if maleic anhydride is used as a precursor for M1 or as monomer M4, it may contain, if appropriate, small amounts of maleic acid hydrolytically removed from the anhydride, e.g. caused by traces of water. The same applies when using other monomers M4.
• Low proportions means that the copolymer contains at most 2 mol%, preferably at most 1 mol%, more preferably at most 0.5 mol%, in particular at most 0.1%, of the acid, based on the other monomers.
• the copolymer may also contain minor amounts of other compounds, e.g. Regulator, included.
• the copolymers are used to lower the CP of fuel oils.
• copolymers according to the invention are used alone or in combination with other coadditives in amounts such that they have an effect as CP depressants in the additized fuel oil or lubricant.
• Another object of the invention are the copolymers described above. With regard to preferred embodiments of these copolymers, reference is made to the above statements.
• 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 weight fraction of a conventional lubricant and a smaller weight fraction of at least one copolymer of the invention.
• fuel oils 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, with diesel fuel and heating oil being 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 also Ullmann's Encyclopedia of Industrial Chemistry, 5th edition, Vol. A12, pp. 617 et seq., To which reference is expressly made).
• 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 .-%.
• diesel fuels are those produced by coal gasification or gas liquefaction (GTL) or biomass liquefaction (biomass to liquid). (BTL) fuels) are available. Also suitable are mixtures of the abovementioned diesel fuels with regenerative fuels, such as biodiesel.
• 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 oils are selected from diesel fuels, kerosene and fuel oil, which 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 copolymer 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 CP value of the fuel oil compositions.
• the additive is added in an amount of from 0.001 to 1% by weight, more preferably from 0.005 to 0.1% by weight, and especially from 0.01 to 0.05% by weight, based on the total amount of the fuel oil composition, used.
• 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 oil compositions of this invention besides the copolymer of the present invention, especially for diesel fuels and fuel 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, flow improvers (“MDFI"), paraffin dispersants (“WASA”) and the combination of the last two additives (“WAFI”) (cf. Ullmann's Encyclopedia of Industrial Chemistry, 5th Edition, Vol. A16, p.719 ff; or the patents cited at the outset for flow improvers).
• detergents corrosion inhibitors, dehazers, demulsifiers, antifoams, antioxidants, metal deactivators, multifunctional stabilizers, cetane improvers,
• 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 is linear or can be 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.
• 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.
• 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 polyoxyalkylenes c) are, for example, polyoxyalkylene esters, ethers, - ester / 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 a 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 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 R 19 [O- (CH 2 ) y ] x OR 20 (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.
• the polar nitrogen compounds d), 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 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 described, for example, in 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, is interrupted, and R 23 and R 24 are a C 9 -C 40 hydrocarbon radical, optionally by one or more groups selected from O, S, NR 35 and CO, interrupted 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 interrupted by one or more groupings selected from CO, NR 35 , O and S, and / or by one or more radicals selected from NR 37 R 38 , OR 37 , SR 37 , COR 37 , COOR 37 , CONR 37 R38, aryl or heterocyclyl, wherein R 37 and R 38 are each independently selected from H or C 1 -C 4 alkyl; and R 36 is H
• 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 sulfocarboxylic acids / sulfonic acids or their derivatives e) 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
• 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 - and C 15 alcohols, 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.
• the fuel oil composition according to the invention preferably comprises at least one of the abovementioned conventional cold flow improvers and in particular at least one of the calf flow improvers the group a). These cold flow improvers are used in particular for lowering the CFPP value of fuel oil compositions additized therewith.
• the subject of the present application is an additive package comprising at least one copolymer according to the invention and at least one further additive, preferably selected from the above co-additives and optionally at least one diluent.
• the additive package contains at least one of the aforementioned conventional cold flow improvers, and more particularly at least one of the cold flow improvers of group a).
• 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. When middle distillates, especially in diesel fuels and heating oils preferably used diluents are naphtha, kerosene, diesel fuels, aromatic hydrocarbons such as Solvent Naphtha heavy, Solvesso ® or Shellsol ®, as well as mixtures of these solvents and diluents.
• the copolymer according to the invention is preferably present in the additive packages in an amount of from 0.1 to 99% by weight, more preferably from 1 to 90% by weight and in particular from 10 to 80% by weight, based on the total weight of the additive package, in front.
• copolymers of the invention show improved performance compared to conventional cold flow improvers. In particular, they lower the CP value of fuel oils additized therewith more effectively than comparable additives of the prior art. Another advantage is that they have no negative impact on other additives contained in fuel oils, especially on cold flow improvers and especially on those that are intended to lower the CFPP value.
• a total of four different copolymers of the invention were prepared by solution polymerization.
• an ⁇ -C 20 -C 24 olefin (178 g) and an ⁇ -C 12 olefin (152 g) were added and heated to 150 ° C with stirring under a nitrogen atmosphere. These were then added with maleic anhydride (148 g) together with di-tert-butyl peroxide (24 g) over 6 h.
• the content of the individual comonomers was determined by IR spectroscopy. To determine the molar masses, the K value was determined. Determination of the K value (relative viscosity)
• the Cloud Point was determined according to ASTM D 2500 and the Cold Filter Plugging Point (CFPP) according to DIN EN116.
• CP of additized fuel oils copolymer Dosing rate [ppm] CP [° C] (H ⁇ 1) Dosing rate [ppm] CP [° C] (H ⁇ 2) Dosing rate [ppm] CP [° C] (H ⁇ 3) - - 2.9 - 0.1 - 3 1 100 2.6 100 -0.1 500 2.4 500 -0.8 2 100 2.6 100 -0.7 100 2.1 500 1.8 500 -0.7 500 1.4 3 100 2.2 100 -0.8 100 1.9 500 1.7 500 -1.3 500 1.3 4 100 2.4 100 -0.6 500 2.0 500 -0.9 500 1.8 copolymer Dosing rate [ppm] CP [° C] (DK1) Dosing rate [ppm] CP [° C] (DK2) - - -7 - -7.2 1 100 -9 100 -8.3 500 -9.2 500 -8.9

Landscapes

• Chemical & Material Sciences (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Engineering & Computer Science (AREA)
• Health & Medical Sciences (AREA)
• Emergency Medicine (AREA)
• Lubricants (AREA)

Priority Applications (2)

Applications Claiming Priority (1)

Publications (1)

Family

ID=35160031

Family Applications (1)

Country Status (1)

Cited By (1)

Citations (13)

• 2005
  • 2005-07-22 EP EP05015991A patent/EP1746146A1/fr not_active Withdrawn

Patent Citations (13)

Non-Patent Citations (1)

Similar Documents

Legal Events