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
  • C10L1/22—Organic compounds containing nitrogen
• • 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
  • C10L1/198—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
  • C10L1/222—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond
  • C10L1/224—Amides; Imides carboxylic acid amides, imides
• • 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)
• • 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)
  • C10L1/2387—Polyoxyalkyleneamines (poly)oxyalkylene amines and derivatives thereof (substituted by a macromolecular group containing 30C)

Definitions

• the present invention relates to additive formulations which, when added, for example, to engine fuels, significantly reduce their tendency to deposit and corrode various parts of the engine.
• the use of conventional fuels very often leads to fouling of the different parts of the engine as a result of the incomplete vaporization and combustion of the fuel in the intake system and / or in the combustion chamber and as a result of the presence traces of lubricants.
• the accumulation of these deposits can be done at the injectors, the carburetor and the intake valves.
• Such an accumulation has harmful consequences both in terms of driving pleasure, with the appearance of unstable idling and misfires in spark-ignition engines, and in terms of optimal engine operation by changing the richness as a result. fuel adsorption-desorption phenomena on the deposits formed.
• 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 polyisobutene-amine 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 motor with greater sensitivity to the rattling phenomenon.
• condensation products of polyalkenylsuccinic anhydrides on hydroxyimidazolines, and in particular on 1- (2-hydroxyethyl) imidazolines substituted in position 2 by an alkyl or alkenyl group such as those described in the patent application EP-A-74724.
• the products described in this application are good additives (for engine fuels and have a significant anticorrosion action but are not very effective in terms of the detergency of the carburetor.
• the invention provides formulations of additives, in particular for engine fuels, which make it possible to substantially reduce the abovementioned drawbacks.
• the additive formulations of the present invention can be used in particular as multifunctional fuel additives; in particular for fuels used in spark ignition engines.
• the additive formulations of the invention have excellent detergent properties at the intake valves and the carburetor and have very good anti-corrosion properties.
• the additive formulations of the invention used in particular in fuels for positive-ignition engines make it possible to greatly reduce the formation of deposits on the intake valves, and the fouling of carburetors or injectors.
• these additive formulations reduce the corrosion of the various mechanical parts with which the fuel comes into contact.
• These additive formulations can be used without the addition of mineral oil, which makes it possible to overcome the drawbacks mentioned above and related to the use of a mineral oil.
• these additive formulations include: a component (A) and a component (B) said component (A) consisting of at least one nitrogenous compound resulting from the reaction of at least one succinic derivative chosen from the group formed by alkenylsuccinic acids and anhydrides and acids and polyalkenylsuccinic anhydrides on at least one polyamine corresponding to the general formula in which R1 represents a hydrogen atom or a hydrocarbon group having from 1 to 60 carbon atoms, Z is chosen from the groups -O- and -NR3- in which R3 represents a hydrogen atom or a hydrocarbon group having 1 to 60 carbon atoms, R1 and R3 can form together with the nitrogen atom to which they are linked a heterocycle, each R2 independently represents a hydrogen atom or a hydrocarbon group having from 1 to 4 carbon atoms, n is an integer from 2 to 6, m is an integer from 1 to 10 when Z is -NR3- and an integer from 2 to 10 when Z is
• the additive formulations according to the present invention further comprise at least one component (C) consisting of at least one polyglycol, soluble in said fuel, of molecular weight number 480 to 2100 and of general formula (III): (III) HO - R - (- O - R--) x -O - R - 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.
• component (C) consisting of at least one polyglycol, soluble in said fuel, of molecular weight number 480 to 2100 and of general formula (III): (III) HO - R - (- O - R--) x -O - R - 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.
• the constituent (C) is preferably a polyglycol of general formula (III) above in which each of the groups R independently represents an alkylene group, linear or branched, having from 2 to 4 atoms carbon and most often an ethylene or propylene group.
• each of the groups R independently represents an alkylene group, linear or branched, having from 2 to 4 atoms carbon and most often an ethylene or propylene group.
• the polyglycols, of general formula (III) which are particularly preferred, mention may be made of those in which each of the groups R represents a propylene group of formula: CH3-CH-CH2-
• Component (C) is preferably a polyglycol of number average molecular weight from 600 to 1800 and most often from 650 to 1250.
• the polydispersity index of the polyglycol, used as component (C), in the formulations according to the present invention, is usually about 1 to 1.25 and most often about 1 to 1.15.
• One of the characteristics of the invention relates to the synergistic effect observed when a constituent (A) and a constituent (B) are combined in a fuel.
• This synergistic effect is manifested in particular by a notable reduction in the tendency of the fuel to form deposits on the intake valves; one could not foresee such a significant reduction by considering the separate effects of constituents (A) and (B).
• This synergy is also manifested by a noticeable improvement in the cleanliness of the carburetor after a fixed operating time, an improvement which could not have been foreseen by considering the separate effects of the constituents (A) and (B).
• the molar ratio of the constituent (A) to the constituent ( B) or from 0.2: 1 to 5: 1, preferably from 0.2: 1 to 1: 1, most preferably from 0.3: 1 to 0.9: 1 and better still from 0, 4: 1 to 0.8: 1.
• the succinic acid and / or anhydride used to form component (A) and component (B) may be the same or different. It is possible to use a single succinic derivative or a mixture of several succinic derivatives.
• the succinic acid and / or anhydride used in the context of the present invention usually has a number average molecular weight of about 200 to 3000, preferably 500 to 2000 and most often 700 to 1500.
• These derivatives succinics 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 may 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 mention may be made of n-octadecenylsuccinic anhydride, dodecenylsuccinic anhydride and polyisobutenyl succinic anhydrides, often called PIBSA, having a number-average molecular mass as defined above.
• the polyamines of formula (I) are preferably those in which R1 is a hydrogen atom or a hydrocarbon group having from 1 to 30 carbon atoms, Z is preferably a group -NR3- in which R3 preferably represents an atom of hydrogen or a hydrocarbon group having from 1 to 30 carbon atoms, each of the R2 independently represents preferably a hydrogen atom or a methyl group, n is an integer from 2 to 4 and when Z is a group -NR3- m is preferably an integer from 1 to 5.
• Z is -NR3-, R1, R2 and R3 each represent a hydrogen atom, n is equal to 2 and m is an integer from 1 to 5 or those in which R1 represents a hydrocarbon group preferably having from 5 to 24 carbon atoms, Z represents a group -NR3-in which R3 is a hydrogen atom, R2 represents a hydrogen atom, n is a number integer from 2 to 4, preferably 3, and m is an integer from 1 to 5, preferably 1.
• the hydrocarbon groups R1 and R3 are usually alkyl, alkenyl, linear or branched, aryl, aryl-alkyl (aralkyl), alkyl-aryl (alkaryl) or cycloaliphatic groups.
• the R1 and R3 groups are preferably alkyl or alkenyl groups, linear or branched.
• the hydrocarbon group R2 is usually an alkyl group, preferably linear, and for example methyl, ethyl, n-propyl or n-butyl.
• N-alkyl diamino-1,3 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-octadecyldipropylene triamine, N-eicosy
• N, N diamines examples include N, N-diethyl-1,2-diamino ethane, N, N-diisopropyl diamino-1,2 ethane, N, N-dibutyl diamino-1,2 ethane, N, N-diethyl diamino-1,4 butane, N, N-dimethyl diamino-1,3 propane, N, N 1,3-diethyl diamino-1,3 propane, N, N-dioctyl diamino-1,3 propane, N, N-didecyl diamino-1,3 propane, N, N-N-didodecyl diamino-1,3 propane, N , N-dissetradécyl diamino-1,3 propane, N, N-dihexadécyl diamino-1,3 propane, N, N-dioctadécyl di
• etheramines examples include N- (octyloxy-3-propyl) diamino-1,3 propane, N- (decyloxy-3 propyl) diamino-1,3 propane, N- (trimethyl- 2,4,6 decyl) oxy-3 propyl diamino-1,3 propane.
• the polyamines of formulas (II) are preferably those in which R1 and R3 each represent a hydrogen atom A, B, C and D identical or different each represent an alkylidene group having 2 to 4 carbon atoms, for example ethylidene , propylidene, isopropylidene, butylidene and isobutylidene, 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.
• the reaction for the formation of component (A) is usually carried out by progressive addition of the polyamine to a solution or to a dispersion of the succinic derivative in an organic solvent, at ordinary temperature, then heating to a temperature usually between 65 and 250 ° C. and preferably between 80 and 200 ° C.
• the organic solvent used in this preparation has a boiling point of between 65 and 250 ° C. and is usually chosen so as to allow the elimination of the water formed during the condensation of the polyamine on the succinic derivative, 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.
• the duration of the heating after the end of the addition of the polyamine is usually 0.5 to 7 hours, preferably 1 to 5 hours.
• the heating is usually continued, at the chosen temperature, most often at reflux, until the end of the evolution of the water formed during the reaction.
• the product obtained is then optionally isolated by removing, for example by vacuum distillation, the solvent used in the preparation.
• the amount of water removed during the reaction is usually about 0.8 to 1.2 moles and most often about 1 mole of water per mole of succinic derivative.
• the polyamine is preferably diluted in an organic solvent, for example one of those mentioned above and preferably the same as that used to form the solution or dispersion of the succinic derivative; this dilution facilitates the gradual addition of the polyamine.
• the amount of polyamine employed is usually at least 0.5 mole per mole of succinic derivative, for example from 0.5: 1 to 2: 1 and preferably from 0.8: 1 to 1.2: 1. most often uses an amount of about 1 mole of polyamine per mole of succinic derivative.
• the constituent (A) used can be a commercial compound, for example the compound sold by the company OCTEL under the reference 0MA 41OG, which is based on a condensation product of tetraethylene pentamine on a PIBSA.
• the 1- (2-hydroxyethyl -) - imidazolines substituted in position 2 by an alkyl or alkenyl radical having from 1 to 25 carbon atoms used for the preparation of component (B) can be commercial compounds or 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.
• component (B) 1- (2-hydroxyethyl) -2 heptadecenylimidazoline is marketed by the company CIBA-GEIGY under the name "Amine-O" and by the company PROTEX under the name "Imidazoline-O".
• the preparation of component (B) is usually carried out by progressive addition of imidazoline, for example diluted in an organic solvent to a solution or to a dispersion of the succinic derivative in an organic solvent.
• the solvents used are preferably identical and they are, for example, chosen from those mentioned above in the description of the preparation of component (A).
• the addition of imidazoline to the succinic derivative is usually carried out at room temperature; after the end of the addition, the mixture is heated to a temperature usually around 65 to 250 ° C, preferably around 80 to 200 ° C.
• 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. Heating is usually continued, at the chosen temperature, most often at reflux, until the end of the evolution of the water formed during the reaction.
• the product obtained is then optionally isolated by removing, for example by vacuum distillation, the solvent used in the preparation.
• the amount of water removed during the reaction is usually about 0.2 to 0.8 moles and most often about 0.3 to 0.6 moles of water per mole of succinic derivative.
• the amount of imidazoline used in the reaction is usually at least 0.5 mole per mole of succinic derivative, for example from 0.5: 1 to 1.5: 1 and preferably from 0.9: 1 a 1.1: 1. Most of the time, approximately 1 mole of imidazoline is used per mole of succinic derivative.
• the formulations of the present invention can be used in the form of a solution in the reaction medium having served for the preparation of each of the constituents.
• the formulations can also be added directly to the fuel or be previously diluted in a solvent chosen, for example, from those mentioned above for the preparation of each of the constituents.
• the formulations of the present invention are mainly used as multifunctional additives for a fuel for engines, for example a fuel based on hydrocarbons or based on a mixture of hydrocarbons and at least one oxygenated compound chosen from the group formed. by alcohols and ethers, or a non-hydrocarbon fuel such as for example an alcohol or a mixture of alcohols.
• the formulations of the present invention are particularly well suited for use as additives for fuels used in spark ignition engines. Examples of fuels that may be mentioned include gasolines such as, for example, those defined by standard ASTM D-439, gas oils or diesel fuels, such as, for example, those defined by standard ASTM D-975.
• These fuels may also contain other additives as the formulations of the present invention for example anti-knock additives such as lead compounds (for example tetraethyl lead), methyltertiobutylether, methyl-tertioamylether or a mixture of methanol and tert-butyl alcohol, anti-freeze additives and octane reducers.
• anti-knock additives such as lead compounds (for example tetraethyl lead), methyltertiobutylether, methyl-tertioamylether or a mixture of methanol and tert-butyl alcohol, anti-freeze additives and octane reducers.
• the formulations of the present invention are used in an amount sufficient to obtain a significant reduction in deposits on the various components of the engine, in particular at the level of the intake valves and of the carburetor.
• amounts are used representing from 10 to 3000 ppm by weight of active material relative to the weight of the fuel, preferably from 10 to 1000 ppm and most often from 50 to 700 ppm.
• the amount of the constituent (C) is usually from 10 to 2000 ppm, most often from 10 to 900 ppm so preferred from 30 to 800 ppm.
• Examples 1 to 5 describe the preparation of constituents (A) and (B) used for the preparation of the formulations according to the invention.
• the progress of the reaction can also be followed by infrared spectrometry at the level of the absorption band of the imine function at 1660 cm ⁇ 1 which gradually disappears during the reaction, while two bands appear (1710 cm ⁇ 1 and 1770 cm ⁇ 1) characteristics of the succinimide function.
• a solution, at 50% by weight of active material, in xylene, of component 81 is thus obtained.
• the infrared spectrum shows an imine band at 1660 cm ⁇ 1 and in nuclear magnetic resonance spectrometry we detect the presence of the two methylene groups of the imidazoline cycle and the presence of the methyl group in position 2 on the imidazoline cycle. Elemental analysis provides a percentage of nitrogen of 22.1% by weight for a calculated percentage of 21.8%.
• the procedure described in Example 1 is repeated, replacing 1- (2-hydroxyethyl) -2-heptadecenylimidazoline with 1- (2-hydroxyethyl) -2-methylimidazoline prepared above.
• Example 1 The procedure described in Example 1 is repeated, replacing the imidazoline with a tallow diamine such as that sold under the brand Dinoram S by the company CECA and corresponding to cut E, the characteristics of which have been mentioned in table I below. -before. 306 g (0.3 mole) of PIBSA diluted in 306 g of xylene and 108 g (0.3 mole) of Dinoram S diluted in 108 g of xylene were used. The reflux is maintained for 5 hours. The reaction water is eliminated as it is formed; this elimination mainly occurs during the first 4 hours of reaction. A solution is thus obtained, adjusted to 50% by weight of active material, in xylene, of component A2.
• Example 3 The procedure of Example 3 is repeated, replacing Dinoram S with 0.3 mole of tetraetriylenepentamine (56 g) diluted in 56 g of xylene. The reflux is maintained for 5 hours. The reaction water is eliminated as it is formed; this elimination mainly occurs during the first 4 hours of reaction. A solution is thus obtained, at 50% by weight of active material, in xylene, of the constituent A3.
• Example 2 The procedure described in Example 1 is repeated, replacing the imidazoline with the polyoxyalkyleneamine sold by the company TEXACO under the name Jeffamine D-400 with a number average molecular mass of 400.
• the Jeffamine D-400 is added in the form of a solution in xylene containing 164 g (0.41 mole) of Jeffamine D-400.
• the reflux is maintained throughout the elimination of the reaction water by azeotropic distillation, then for an additional hour.
• a solution is thus obtained, adjusted to 50% by weight of active material, in the xylene of the constituent A4.
• the tests consist in determining the extent of the corrosion produced on samples of polished ordinary steel, in the presence of synthetic seawater, by following the modified ASTM D 665 standard (temperature 32.2 ° C, duration 20 hours) .
• the tests are carried out using some of the fuels described in Example 6.
• the results obtained are presented in Table IV below; they are expressed as percentages (%) of the surface of the corroded test piece after hours.
• Table IV Fuel % of corroded surface C1 100% C2 0% C8 0% C10 0%
• Formula F1 contains the component (A3) described in Example 4, component (B1) described in Example 1 and polypropylene glycol (component (C)) described above; the molar ratio of the number of moles of the constituent (A3) to the number of moles of the constituent (B1) is 0.7: 1; the quantity of polypropylene glycol contained in this formulation is such that the molar ratio of the sum of the number of moles of constituent (A3) and of constituent (B1) which it contains to the number of moles of polypropylene glycol which it contains ((A3) + (B1)) / (C) is 0.7: 1.
• the formulation F2 contains the constituent (A3) described in Example 4, the constituent (B1) described in Example 1 and the poylpropylene glycol (constituent ( C)) described above; the molar ratio of the number of moles of the constituent (A3) to the number of moles of the constituent (B1) is 2: 1; the quantity of polypropylene glycol contained in this formulation is such that the molar ratio of the sum of the number of moles of constituent (A3) and of constituent (B1) which it contains to the number of moles of polypropylene glycol which it contains ((A3) + (B1)) / (C) is 0.73: 1.
• Formulation F3 includes polypropylene glycol and contains neither component (A3) nor component (B1).
• the formulation F4 comprises each of the constituents (A3) and (B1) in a molar ratio of 2: 1 and does not contain polypropylene glycol.
• a series of tests is carried out in order to assess the detergency properties of valves of various formulations.
• the tests were carried out on a Mercédes M102E engine test bench, without additives in the case of examples 11 to 14 inclusive.
• the test procedure is a standard procedure comprising the use of an engine having 4 cylinders, of the Mercedes M102E type, having a displacement of 2299 cc and a compression ratio of 9/1.
• the test procedure is a cyclic procedure, each cycle comprising four successive periods of operation: - 30 s (seconds) at 800 rpm (revolutions per minute) under zero load, - 60 s at 1300 rpm under a load of 31 newtons (mxkgxs-2), - 120 s at 1850 rpm under a load of 34 newtons and - 60 s at 3000 rpm under a load of 37 newtons.
• the duration of each test is usually 40 to 150 hours; in examples 10 to 14 the duration of the test was fixed at 40 hours.
• 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 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.
• each valve intake side: tulip
• CRC Coordinating Research Council
• the fuel used in these assessments is an unleaded premium fuel, comprising 2% by volume of a mixture of methanol and tert-butanol in a volume ratio of 1.5: 1.
• This premium fuel with an octane rating of 85 and octane distillation search of 227 ° C; it includes in volume: - 49% aromatics - 11% olefins - 40% of saturated compounds (paraffins + naphthenics)

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