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
  • C10L1/143—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
  • C10L1/16—Hydrocarbons
  • C10L1/1616—Hydrocarbons fractions, e.g. lubricants, solvents, naphta, bitumen, tars, terpentine
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/18—Organic compounds containing oxygen
  • C10L1/192—Macromolecular compounds
  • C10L1/198—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds homo- or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon to carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid
  • C10L1/1985—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds homo- or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon to carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid polyethers, e.g. di- polygylcols and derivatives; ethers - esters
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/22—Organic compounds containing nitrogen
  • C10L1/232—Organic compounds containing nitrogen containing nitrogen in a heterocyclic ring
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/22—Organic compounds containing nitrogen
  • C10L1/234—Macromolecular compounds
  • C10L1/238—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/22—Organic compounds containing nitrogen
  • C10L1/234—Macromolecular compounds
  • C10L1/238—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
  • C10L1/2383—Polyamines or polyimines, or derivatives thereof (poly)amines and imines; derivatives thereof (substituted by a macromolecular group containing 30C)

Definitions

• the present invention relates to additive formulations, in particular for fuels, comprising products having an ester function and a detergent-dispersant. These formulations can be used as multifunctional additives for fuels and in particular for fuels used in spark ignition engines.
• the accumulation of these deposits in the combustion chambers can lead to a reduction in the volume of the combustion zone, which then results in an increase in the compression ratio of the engine. This phenomenon also promotes the appearance of rattling.
• the deposits which form in the various parts of the engine in contact with the fuel can partially absorb a part of this fuel, thus contributing to a modification of the oxidizer-fuel mixture with a fuel depletion phase during absorption and an enrichment phase in the event of a desorption of this fuel. The modification of the richness of the fuel-air mixture no longer allows the engine to work in optimal conditions.
• the accumulation of deposits in the engines and in particular on the intake valves can also be reduced by the use of fuels containing certain additives, for example detergent-type additives possibly combined for example with anticorrosion additives or anti-deposit for room combustion.
• fuels containing certain additives for example detergent-type additives possibly combined for example with anticorrosion additives or anti-deposit for room combustion.
• Additives well known in the trade, for example those of the polyisobuteneamine type, are usually associated with a mineral or synthetic oil and are capable of causing increased fouling of the combustion chambers and therefore an increase in the octane requirement of the engine with greater sensitivity to the rattling phenomenon.
• Contamination of the combustion chambers occurs gradually during engine operation.
• the latter is characterized by its octane requirement which corresponds to the minimum octane level of fuel necessary for the engine to operate without rattling.
• the value of the octane requirement of the engine exceeds, in particular as a result of the fouling of the combustion chambers, the value of the octane number of the fuel used to supply this engine, the phenomenon of rattling is observed.
• the increase in engine octane requirements conventionally constitutes, for those skilled in the art, the ORI phenomenon according to the Anglo-Saxon abbreviation of "Octane Requirement Increase".
• Belgian patent BE 811678 describes fuel compositions containing a lubricant in the form of an ester and in particular of an ester of diacids and of alcohol or diols.
• diols are polyoxyalkylene glycols.
• the preferred diacids which can be used according to this application include adipic acid, azelaic acid and sebacic acid.
• US-A-3429817 describes lubricating compositions containing synthetic esters resulting from the reaction of 2 moles of a glycol having 2 to 5 carbon atoms and a diacid whose carboxylic groups are separated from one other by at least 9 carbon atoms.
• US-A-3836470 describes lubricant compositions and fuel compositions containing a dispersing additive resulting in particular from the reaction of a succinic acid, comprising a hydrocarbon side chain and having at least 30 carbon atoms in its molecule, on at least one polyoxyalkylene glycol or one polyoxyalkylene glycol ether. Mention may also be made of compositions such as those described for example in patent application EP-A-327097 which have good anti-ORI properties and good detergent properties at the inlet valve level, but detergent properties at the level of the relatively limited single point injector. Furthermore, these compositions are not described as having good anticorrosion properties.
• formulations as described below, which can be used in particular as multifunctional additives for engine fuels, in particular for fuels used in spark-ignition engines.
• the formulations of the present invention have excellent detergent properties at the intake valves and the carburetor, and have very good anticorrosion properties.
• the subject of the present invention is an additive formulation, which can be used in particular as a multifunctional fuel additive, which comprises at least one constituent (A) and at least one constituent (B), said constituent (A) consisting of at least one composition comprising the products resulting from the reaction of at least one dicarboxylic compound (D), whose carboxylic functions are separated by at most 6 carbon atoms and preferably by at most 4 carbon atoms, on at least one glycol monoether or of polyoxyalkylene glycol (E) of general formula (I): (I) R1-O- (R2-O) n -H in which R1 represents a hydrocarbon group having from 1 to 30 carbon atoms, preferably an alkyl, alkaryl or aralkyl radical having from 1 to 25 carbon atoms, R2 represents a divalent hydrocarbon group having from 2 to 6 carbon atoms and n is a number from 1 to 60; and said component (B) consisting of at least one detergent-dispersant product.
• a multifunctional fuel additive
• formulations according to the present invention can be used in particular as additives in the fuels used in spark ignition engines in which they make it possible in particular to limit the increase in octane requirement (ORI) of these engines and therefore to limit, to delay or even to avoid, the appearance of the rattling phenomenon.
• ORI octane requirement
• These formulations also have an anti-corrosion action which can be observed both with the fuels used in spark ignition engines and in those used in auto ignition engines (Diesel engine).
• gasolines such as those which are defined by standard ASTM D-439, diesel or diesel fuels such as those defined by standard ASTM D-975.
• fuels can also contain other additives, such as for example, in particular in the case of fuels used for spark ignition engines, anti-knock additives such as lead compounds (for example tetraethyl lead), ethers such as methyltertiobutylether or methyltertioamylether or a mixture of methanol and tert-butyl alcohol and anti-icing additives.
• anti-knock additives such as lead compounds (for example tetraethyl lead), ethers such as methyltertiobutylether or methyltertioamylether or a mixture of methanol and tert-butyl alcohol and anti-icing additives.
• a non-hydrocarbon fuel such as for example an alcohol or a mixture of alcohols.
• Component (A) according to the present invention may result from the reaction of at least one compound (D) with at least one compound (E) under conventional conditions well known to those skilled in the art of product formation comprising functions esters.
• the preferred component (A) according to the present invention is usually obtained by carrying out the reaction at a temperature of from about 100 ° C to about 210 ° C and most often from about 120 ° C to about 200 ° C, with a ratio molar of compound (E) to compound (D) of approximately 1.5: 1 to approximately 5: 1 and for a sufficient time so that the products obtained have a corrected acid number of approximately 2000 to approximately 40,000, from preferably from about 3000 to about 30000 and most often from about 4000 to about 25000.
• the compounds (E) which are preferably used are those in which R2 represents an alkylene group, having 2 to 5 carbon atoms, of general formula (II): (II) -CH2-CR3H- in which R3 represents a hydrogen atom, a methyl group, an ethyl group or a propyl group.
• R3 represents a hydrogen atom, a methyl group, an ethyl group or a propyl group.
• R1 represents a linear or branched alkyl group.
• the compounds (E) those in which n is a number from 5 to 50 are most often used.
• polyoxyalkylene glycols of alkyl monoethers of glycol or of polyoxyalkylene glycols such as the alkyl monoethers of polypropylene glycol, the alkyl monoethers of polyethylene glycol and the alkyl monoethers of polypropylene glycol and of ethylene glycol.
• the alkyl group of these products most often contains at least 3 carbon atoms and is most often linear.
• These oxyalkylated products are commercial products sold by the company SHELL under the generic name OXYLUBE or by the company ICI.
• These compounds usually have a molecular mass of approximately 500 to approximately 2500 and most often approximately 600 to approximately 2000.
• the compounds (D) which are used are usually aliphatic, alicyclic or aromatic dicarboxylic compounds. These compounds can be saturated or unsaturated.
• the compounds (D) which are preferably used are chosen from the group formed by oxalic (ethanedioic), malonic (propanedioic), succinic (butanedioic), glutaric (pentanedioic), adipic (hexanedioic), pimelic (heptanedioic) acids.
• suberic octanedioic
• fumaric trans-butenedioic
• maleic cis-butenedioic
• glutaconic pentene-2 dioic
• muconic hexadiene-2,4 dioic
• citraconic cis-methylbutenedioic
• mesaconic trans-methylbutenedioic
• itaconic methylenebutanedioic
• phthalic or one of their derivatives and most often in the group formed by oxalic acid, maleic acid, phthalic acid or one of their derivatives.
• Acid anhydride and in particular phthalic anhydride or maleic anhydride are frequently used.
• Component (B) according to the present invention is usually chosen from the group formed by polyolefins, preferably polyisobutenes, polyisobutene-amines, mixtures of these types of compounds and the products which are described in particular in European patent application EP-A-349369 in the name of the applicant, as well as those described in patent US-A-4375974.
• the products described in application EP-A-349 369 result from the reaction in a first step of at least one succinic derivative chosen from the group formed by alkenylsuccinic acids and anhydrides and polyalkenylsuccinic acids and anhydrides on at least one 1 - (2-hydroxyethyl) imidazoline substituted in position 2 by an alkyl or alkenyl radical, linear or branched, having from 1 to 25 carbon atoms, the imidazoline / succinic derivative molar ratio being from 0.1: 1 to 0.9: 1, preferably from 0.2: 1 to 0.8: 1 and most often from 0.3: 1 to 0.7: 1, said step being carried out under conditions such that one forms and that the at least 0.15 mole of water is eliminated per mole of imidazoline used; and in a second stage of the reaction of the product resulting from the first stage with at least one polyamine corresponding to one of the following general formulas: in which R3 represents a hydrogen atom or a hydrocarbon group having from 1
• the succinic acid or anhydride used in the context of the present invention to prepare component (B) usually has a number average molecular weight of about 200 to 3000, preferably 500 to 2000 and most often 700 to 1500.
• These succinic derivatives are widely described in the prior art; they are for example obtained by the action of at least one alpha olefin or of a chlorinated hydrocarbon on maleic acid or anhydride.
• the alpha olefin or the chlorinated hydrocarbon used in this synthesis can be linear or branched, and usually contain from 10 to 150 carbon atoms, preferably from 15 to 80 carbon atoms and most often from 20 to 75 carbon atoms in their molecule.
• This olefin can also be an oligomer, for example a dimer, a trimer or a tetramer, or a polymer of a lower olefin, for example having 2 to 10 carbon atoms, such as ethylene, propylene, n -butene-1, isobutene, n-hexene-1, n-octene-1, methyl-2-heptene-1 or methyl-2-propyl-5-hexene-1. It is possible to use mixtures of olefins or mixtures of chlorinated hydrocarbons.
• succinic anhydrides used to prepare component (B) there may be mentioned n-octadecenylsuccinic anhydride, dodecenylsuccinic anhydride and polyisobutenyl succinic anhydrides, often called PIBSA, having a number-average molecular mass such as defined above.
• 1- (2-hydroxyethyl-) imidazolines substituted in position 2 by an alkyl or alkenyl radical having from 1 to 25 carbon atoms are usually commercial compounds or which can be synthesized for example by reaction of at least one organic acid with N- (2-hydroxyethyl) -ethylenediamine. The reaction proceeds by a first amidation step followed by cyclization.
• the organic acids used usually have from 2 to 26 carbon atoms; they are preferably aliphatic monocarboxylic acids.
• acetic acid propanoic acid, butanoic acid, caproic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, cerotic acid and the following unsaturated fatty acids:
• the first stage of preparation of component (B) according to the invention is usually carried out by progressive addition of the imidazoline derivative to a solution of the succinic derivative in an organic solvent, at ordinary temperature, then heating to a temperature usually between 65 ° C and 250 ° C and preferably between 80 ° C and 200 ° C.
• the organic solvent used in this preparation has a boiling point between 65 ° C and 250 ° C and is usually chosen so as to be able to allow the elimination of the water formed during the condensation of imidazoline on the derivative succinic, preferably in the form of a water-organic solvent azeotrope.
• An organic solvent will usually be used such as for example benzene, toluene, xylenes, ethylbenzene or a hydrocarbon cut such as for example the commercial cut SOLVESSO 150 (190-209 ° C) containing 99% by weight of aromatic compounds. It is possible to use mixtures of solvents, for example a mixture of xylenes.
• the duration of the heating after the end of the addition of imidazoline is usually 0.5 to 7 hours, preferably 1 to 5 hours. This first step will preferably be continued at the chosen temperature until the end of the evolution of the water formed during the reaction.
• the amount of water removed during this first step is usually about 0.15 to 0.6 moles and most often about 0.5 moles per mole of imidazoline involved in the reaction.
• At least one polyamine, preferably diluted in an organic solvent is preferably added gradually to the product or mixture resulting from this first step, after optional cooling, then it is usually heated to a temperature between 65 ° C. and 250 ° C. and preferably between 80 ° C and 200 ° C.
• the solvent used in the second step is preferably the same as that which is in the first step and the temperature is also the same during these two steps.
• the reactions are usually carried out at a temperature corresponding to the reflux temperature.
• the duration of this heating during this second stage is usually 0.1 to 7 hours and preferably 0.2 to 5 hours.
• the amount of polyamine used is at least 0.1 mole per mole of succinic anhydride introduced during the first step and it is preferably such that the total amount of substituted imidazoline and polyamine used in the preparation is 0.8 to 1.2 moles, preferably 0.9 to 1.1 moles per mole of succinic derivative.
• the substituted imidazoline to polyamine molar ratio is preferably from 1: 1 to 7: 1 and most preferably from 1: 1 to 3: 1.
• the amount of water removed during this second step is usually such that the amount of total water removed during the two successive reactions represents from 0.2 to 0.7 mole per mole of succinic derivative.
• the polyamines of formula (III) are preferably those in which R3 is a hydrogen atom or a hydrocarbon group having from 1 to 30 carbon atoms, Z is preferably a group -NR5- in which R5 preferably represents an atom of hydrogen or a hydrocarbon group having from 1 to 30 carbon atoms, each of R4 independently represents preferably a hydrogen atom or a methyl group, p is an integer from 2 to 4 and when Z is a group -NR5 - m is preferably an integer from 1 to 5.
• Z is -NR5-, R3, R4 and R5 each represent a hydrogen atom, p is equal to 2 and m is an integer from 1 to 5 or those in which R3 represents a hydrocarbon group preferably having from 5 to 24 carbon atoms, Z represents a group -NR5- in which R5 is a hydrogen atom, R4 represents a hydrogen atom, p is a number integer from 2 to 4, preferably 3, and m is an integer from 1 to 5, preferably 1.
• the hydrocarbon groups R3 and R5 are usually alkyl, alkenyl, linear or branched, aryl, aryl-alkyl (aralkyl), alkyl-aryl (alkaryl) or cycloaliphatic groups.
• the R3 and R5 groups are preferably alkyl or alkenyl groups, linear or branched.
• the hydrocarbon group R4 is usually a preferably linear alkyl group, for example methyl, ethyl, n-propyl or n-butyl.
• N-alkyl diamino-propane for example N-dodecyldiamino-1,3 propane, N-tetradecyldiamino-1,3 propane, N-hexadecyldiamino-1,3 propane, N -octadecyldiamino-1,3 propane, N-eicosyldiamino-1,3 propane and N-docosyldiamino-1,3 propane; mention may also be made of N-alkyldipropylene triamines, for example N-hexadecyldipropylene triamine, N-o
• N, N diamines examples include N, N-diethyl diamino-1,2 ethane, N, N-diisopropyl diamino-1,2 ethane, N, N-dibutyl diamino-1, 2 ethane, N, N-diethyl-1,4-diamino butane, N, N-dimethyl diamino-1,3 propane, N, N-diethyl diamino-1,3 propane, N, N-dioctyl diamino- 1,3 propane, N, N-didécyl diamino-1,3 propane, N, N-didodécyl diamino-1,3 propane, N, N-dissetradécyl diamino-1,3 propane, N, N-dihexadécyl 1,3-diamino propane, N, N-dioctadecyl 1,3-d
• etheramines examples include N- (3-octyloxy-propyl) 1,3-diamino propane, N- (3-decyloxy-propyl) 1,3-diamino propane, N- [(trimethyl- 2,4,6 decyl) 3-oxy propyl] diamino-1,3 propane.
• the polyamines of formulas (IV) are preferably those in which R3 and R5 each represent a hydrogen atom, D, E, F and G, identical or different, each represent an alkylene group having 2 to 4 carbon atoms per example ethylene, trimethylene, methylethylene, tetramethylene, methyltrimethylene, 1-methyltrimethylene and 2-methyltrimethylene, a is an integer from 1 to 60 and b and c are zero or a is an integer from 1 to 59, c is zero or an integer such that the sum a + c is from 1 to 59 and b is an integer from 1 to 50, with in each case the sum a + b + c equal to an integer from 1 to 60.
• component (B) The products described by the applicant in US Pat. No. 4,375,974 and which can be used, in the context of the present invention, as component (B) are those resulting from the reaction of at least one polyamine, having at least one primary amino group and corresponding to the general formula (III) above, on at least one succinic derivative such as those described above, said reaction being carried out under conditions of formation and elimination of the water of reaction. Most often the reaction is carried out at a temperature of about 120 ° C to about 200 ° C with an amine to succinic derivative molar ratio of about 0.9: 1 to about 1.2: 1. This reaction can be carried out in the absence of solvent or in the presence of a solvent such as for example an aromatic hydrocarbon, a cut of hydrocarbons having a boiling point of about 70 ° C to about 250 ° C.
• a solvent such as for example an aromatic hydrocarbon, a cut of hydrocarbons having a boiling point of about 70 ° C to about 250 ° C.
• Component (B) according to the present invention can also be chosen from the group formed by polyisobutenes, polyisobuten-amines, mixtures of these two types of compounds.
• the polyolefins used can be polymers or copolymers or the corresponding amino or hydrogenated derivatives formed from hydrocarbons having from 2 to 10 carbon atoms in their molecule.
• These polymeric compounds are usually prepared from monoolefinic or diolefinic compounds and usually have a number average molecular weight of about 500 to 10,000 often about 500 to 3500 and preferably about 650 to 2600.
• the starting compounds used to manufacture these polymers are olefins having from 2 to 6 carbon atoms in their molecule, such as for example ethylene, propylene, isopropylene, butene, isobutene, amylene, l hexylene, butadiene and isoprene.
• Propylene, isopropylene, butene and isobutene are very frequently used.
• the other polyolefins which can also be used are that obtained by cracking of high molecular weight olefin polymers or copolymers into compounds having a molecular weight in the molecular weight range mentioned above.
• polypropylenes of average molecular weight in number from about 750 to 1000 and for example of about 800 polyisobutenes of average molecular weight in number of about 1000 to 1500 and for example of about 1300.
• component (B) is a mixture comprising a majority proportion of polyisobutene-ethylene diamine and a minority proportion of polyisobutene.
• This mixture is most often used dissolved in a hydrocarbon solvent so as to facilitate its incorporation into the fuel.
• the proportion of amino polymer in this mixture is usually from about 50% to about 80% by weight and for example from about 60% by weight and the proportion of hydrocarbon polymer is usually from about 5% to about 30% by weight and preferably from about 10% to about 25% by weight.
• Polyisobutene ethylene diamine is a compound of general formula: in which z is a number from approximately 10 to approximately 40, preferably from approximately 30 to approximately 35 and for example approximately 33.
• Polyisobutene is a compound of general formula: in which t is a number from approximately 10 to approximately 40, preferably from approximately 30 to approximately 35 and for example approximately 33.
• the solvent used to dissolve the polymeric compounds and facilitate their incorporation into the fuel is most often a light aromatic distillate.
• ORONITE OGA-472 is a composition comprising approximately 60% by weight of polyisobutene-ethylene diamine, approximately 27% by weight of polyisobutene and approximately 13% by weight of light aromatic distillate comprising xylene and C9 alkylbenzenes.
• the formulations also contain at least one constituent (C) chosen from the group formed by mineral or synthetic lubricating oils and polyglycols, soluble in said fuel, of number-average molecular mass of 480 to 2,100 and of general formula (V): (V) HO-R - (- OR-) x -OR-OH wherein each of the R groups independently represents a hydrocarbon group having 2 to 6 carbon atoms and x represents the average degree of polymerization.
• C constituent chosen from the group formed by mineral or synthetic lubricating oils and polyglycols, soluble in said fuel, of number-average molecular mass of 480 to 2,100 and of general formula (V): (V) HO-R - (- OR-) x -OR-OH wherein each of the R groups independently represents a hydrocarbon group having 2 to 6 carbon atoms and x represents the average degree of polymerization.
• C constituent chosen from the group formed by mineral or synthetic lubricating oils and polyglycols, soluble in said fuel
• component C is a polyglycol, having a polydispersity index of approximately 1 to approximately 1.25 and preferably approximately 1 to 1.15, of general formula (V) in which each of the groups R independently represents an alkylene group, linear or branched, having from 2 to 4 carbon atoms, preferably an ethylene or propylene group.
• each of the groups R represents a propylene group of formula:
• the polyglycol used is preferably a polyglycol of average molecular mass in number from 600 to 1,800 and most often from 650 to 1,250.
• mineral or synthetic lubricating oils which can be used as constituent (C)
• mineral oils oil 600 NS, the main characteristics of which will be given below
• synthetic lubricating oils ethers and polyol esters and in particular polyoxyalkylene glycol ethers are examples of mineral oils, oil 600 NS, the main characteristics of which will be given below.
• the formulations according to the invention can in particular be used as an additive having good anti-corrosion activity for a fuel based on hydrocarbons or on a mixture of hydrocarbons and at least one oxygenated compound chosen from the group formed by alcohols and ethers.
• These formulations can also be used as a multifunctional additive having in particular good anti-ORI and detergent-dispersant properties for an engine fuel, for a spark-ignition engine, based on hydrocarbons or a mixture of hydrocarbons and at least minus an oxygenated compound chosen from the group formed by alcohols and ethers.
• these formulations are added to the fuel so as to obtain a mass concentration, of the additive composition in the engine fuel, of 10 to 10,000 ppm and most often of 100 to 2,000 ppm.
• the weight ratio of component (A) to component (B) [(A) / (B)] is usually from about 0.05: 1 to about 2: 1 and preferably from about 0.1: 1 to about 1: 1.
• the weight ratio of constituent (B) to constituent (C) [(B) / (C)] is usually about 0, 1: 1 to about 5: 1 and preferably from about 0.2: 1 to about 2: 1.
• the infrared spectrum shows two absorption bands (1740 cm ⁇ 1 and 1650 cm ⁇ 1) characteristic of the ester function on the one hand and of the residual unsaturation of the final product.
• Analysis by gel permeation chromatography shows that the product has a weight-average molecular weight of approximately 4,000.
• the acid number evaluated according to AFNOR T 60112 standard and corrected for molecular weight (IAc) is 18,000.
• PIBSA polyisobutenyl succinic anhydride
• polyisobutene polyisobutene of average molecular mass number 920
• maleic anhydride the assay of the anhydride functions of this product shows that one has 0, 7 anhydride function per theoretical mole of PIBSA
• 1018 g of xylene are loaded into a 2-liter reactor fitted with mechanical stirring, a Dean-Stark separator and a temperature regulation system.
• the reactor temperature is reduced to 50 ° C. and then maintained at this value during the time of the gradual addition (dropwise) of 56 g (0.297 mole) of tetraethylenepentamine diluted in 49 g of xylene. At the end of this addition the mixture is again brought to reflux for 15 minutes. Water elimination again occurs. The total amount of water collected during these two reaction stages is 7.2 ml.
• the infrared spectrum shows two absorption bands (1710 cm ⁇ 1 and 1770 cm ⁇ 1) characteristic of the succinimide function with a shoulder ( 1740 cm ⁇ 1) characteristic of the ester function.
• compositions F1 to F5 comprising various weight quantities of the constituents (A), (B) and (C) defined below.
• Component (A) is formed by one of the compositions obtained in Examples 1 and 2.
• Component (B) is formed by the composition obtained in Example 3 or by a composition of the polymeric type and, preferably, that of the polyisobutene-ethylene diamine and polyisobutene type such as one of those described in the documents.
• constituent (B) will be designated below by the initials PBA; this constituent is then the composition sold by the company CHEVRON CHEMICAL under the name ORONITE OGA -472 comprising approximately 60 parts by weight of polyisobutene-ethylene diamine, 13 parts by weight of polyisobutene and 27 parts by weight of a distillate light aromatic comprising xylene and alkylbenzenes having 9 carbon atoms in their molecule.
• the formulation F1 according to the present invention contains the constituent (A) formed by the composition obtained in Example 1, the constituent (B) formed by the composition obtained in Example 3 and the constituent (C) formed by the polypropylene glycol described above. These constituents are used in a weight ratio, in terms of active material, A: B: C of 1: 5: 5.
• the formulation F2 (comparison formulation) contains the constituent (B) formed by the composition obtained in Example 3 as well as the constituent (C) formed by the polypropylene glycol described above, but no constituent (A).
• the weight ratio of active ingredient B: C is 1: 1.
• the formulation F3 (comparison formulation) contains the constituent (B) designated by the initials PBA as well as the constituent (C) formed by the mineral oil 600 NS in a weight ratio of active material B: C of 1: 3.
• the formulation F4 according to the present invention contains the constituent (A) formed by the composition obtained in Example 1, the constituent (B) designated by the initials PBA and the constituent (C) formed by the mineral oil 600 NS, in a weight ratio of active ingredient A: B: C of 1: 2: 6.
• the formulation F5 according to the present invention contains the constituent (A) formed by the composition obtained in Example 2, the constituent (B) formed by the composition obtained in Example 3 and the constituent (C) formed by the polypropylene glycol, in a weight ratio of active ingredient A: B: C of 1: 5: 5.
• the duration of each test is 200 hours.
• the engine is conditioned with new valves and the combustion chambers are free of any deposits.
• the octane requirements of each cylinder are then determined at the start of the test as follows: the richness of the air-fuel mixture admitted is adjusted to the manufacturer's reference value for the measurement regime under consideration (2,000 rpm) / min and 3,500 rpm).
• the octane requirement of each cylinder is successively determined by supplying them with reference fuels made up of mixtures isooctane and n-heptane.
• the value of the octane requirement of a cylinder corresponds to the octane number of the reference fuel which shows the knock phenomenon.
• the cyclic procedure described above is then applied by supplying the engine with test fuel containing or not containing additive.
• a new measurement of the octane requirements of each cylinder is carried out as above.
• the average of the calculated differences between the octane requirement at the end of the test and the octane requirement at the start of the test for each cylinder constitutes, for the measurement regime considered, the value of the increase in octane requirement (ORI).
• the additives are added to the fuel so as to obtain a concentration, by weight of active material in the additive fuel, specified for each example in Table II below which gives the results obtained.
• This fuel with an engine octane rating of 86 and a research octane rating of 99, has an initial distillation point of 34 ° C and a final distillation point of 185 ° C.
• compositions are added to the fuel so as to obtain a concentration, by weight of the active material in the additive fuel specified for each example in Table III below which gives the results obtained:
• the carburetor detergency properties of the formulations F1 and F2 prepared in Example 4 are evaluated.
• the engine test procedure is carried out according to European standard R5-CEC-F03-T-81.
• the results are expressed in terms of merit from zero to 10.
• a merit 10 corresponds to a clean carburetor and a merit 0 to a very dirty carburetor.
• the formulations are added to the fuel so as to obtain a concentration by weight of active ingredient in the additive fuel. specified for each example in Table IV below which gives the results obtained:
• the fuel used in these assessments is an unleaded premium fuel with an engine octane rating of 85.3 and a research octane rating of 96.7.
• This premium fuel has an initial distillation point of 36 ° C and a final distillation point of 203 ° C.
• This engine octane fuel of 86 and research octane fuel of 96 has an initial distillation point of 31 ° C and a final distillation point of 202 ° C.
• the engine test procedure is carried out by following the IFP-TAE 187 method established by the French Petroleum Institute as described below.
• the flow rate of each injector is measured at the start and end of the test in order to assess the percentage of flow restriction induced by fouling of the injectors.
• This engine octane fuel of 85.7 and research octane of 97.5 has an initial distillation point of 33 ° C and a final distillation point of 197 ° C.
• the tests are carried out on a Hyundai generator equipped with a generator (240 Volt, 5500 Watt) driven by a twin-cylinder 359 cc 4-stroke engine with tumbled valves.
• the engine is conditioned with new valves that are weighed.
• the valves are dismantled, washed with hexane, dried, then weighed after physical removal (by scraping) of the deposits formed on the valve on the combustion chamber side.
• the results presented below give the average of the deposits by weight relative to a valve, calculated from the weight of deposits measured, on the tulip of each intake valve, by difference between the weight of said new valve and the weight of said valve at the end of each test after removal of deposits on the combustion chamber side.
• the fuel used in these assessments is an unleaded premium fuel identical to that described in Example 5.
• the formulations are added to the fuel so as to obtain a concentration, by weight of active material in the additive fuel, specified for each example in Table VII below giving the results obtained.
• Formulations F1 to F4 prepared in Example 4 are evaluated. The tests consist in determining the extent of the corrosion produced on samples of polished ordinary steel, in the presence of water, following the modified ASTM D 665 standard (temperature 32.2 ° C, duration 20 hours).
• the results are expressed as a percentage (%) of the surface of the corroded test piece after 20 hours.
• the fuel is the same as that used in Example 5.
• composition is added to the fuel so as to obtain a concentration, by weight of active material in the additive fuel, specified for each example in Table VIII below giving the results obtained:
• Tests are carried out so as to evaluate the anti-corrosion properties of the formulations according to the invention prepared in Example 4.
• the tests are carried out in a similar manner to that described in Example 11 (temperature 60 ° C, duration 20 hours) in Diesel fuel.
• the main characteristics of the diesel fuel used are: The amount of composition is added to the fuel so as to obtain a concentration, by weight of active material in the additive fuel, specified for each example in Table IX below summarizing the results obtained:
• compositions used in a diesel fuel also have anti-corrosion properties.

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• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Lubricants (AREA)
• Liquid Carbonaceous Fuels (AREA)
• Detergent Compositions (AREA)
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• 1991
  • 1991-08-30 FR FR919110851A patent/FR2680796B1/fr not_active Expired - Fee Related
• 1992
  • 1992-08-24 ES ES92402335T patent/ES2103910T3/es not_active Expired - Lifetime
  • 1992-08-24 EP EP92402335A patent/EP0530094B1/de not_active Expired - Lifetime
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  • 1992-08-28 CA CA002077148A patent/CA2077148A1/fr not_active Abandoned
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  • 1992-08-31 US US07/936,410 patent/US5433755A/en not_active Expired - Fee Related
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• 1997
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