FR2633637A1 - Compositions obtained from hydroxyimidazolines and polyamines and their use as fuel additives - Google Patents

Abstract

Composition resulting, in a first stage, from the reaction of at least one alkenyl- or polyalkenylsuccinic acid or anhydride with at least one 1-(2-hydroxyethyl)imidazoline substituted at position 2 by a linear or branched alkyl or alkenyl radical, containing from 1 to 25 carbon atoms in an imidazoline/succinic derivative molar ratio of 0.1:1 to 0.9:1 with removal of at least 0.15 mol of water per mole of imidazoline and then, in a second stage, from the reaction of the product originating from the first stage with at least one polyamine in a quantity representing at least 0.1 mol per mole of succinic derivative employed in the first stage. Use of these compositions as multifunctional additives in engine fuels based on hydrocarbons or a mixture of hydrocarbons and on at least one oxygen compound chosen from the group made up of alcohols and ethers.

Description

The present invention relates to compositions that can be used in particular as multifunctional additives for motor fuels, obtained by reacting at least one succinic acid or anhydride successively with at least one hydroxyimidazoline and at least one polyamine.

The use of conventional fuels very often leads to the fouling of the various 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 consequence of the presence traces of lubricants.

In the intake system, the accumulation of these deposits can be done at the injectors, carburetor and intake valves.

Such an accumulation has adverse consequences both in terms of driving pleasure, with the appearance of unstable idling and misfiring in spark-ignition engines, and at the level of optimal engine performance by modifying the wealth as follows. the adsorption-desorption phenomena of the fuel on the deposits formed.

In order to remedy the fouling, it is possible to carry out periodic cleaning, particularly expensive, of the organs concerned, in particular the valves.

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 or anti-settling additives for chamber of combustion.

The additives, well known in the art, for example those of the polyisobutene-amine type, are usually associated with a mineral or synthetic oil and are likely to cause increased fouling of the combustion chambers and therefore an increase in the octane requirement of the motor with a greater sensitivity to the phenomenon of rattling.

Among the numerous additives described in the prior art, mention may be made of the condensation products of polyalkenylsuccinic anhydrides on polyamines, such as, for example, tetraethylenepentanine, which are in particular described in US-A-3172892. These additives give good results in anti-corrosion properties, but are not effective as valve detergents.

Mention may also be made of the condensation products of polyalkenylsuccinic anhydrides on hydroxyimidazolines, and in particular on 1- (2-hydroxyethyl) imidazolines substituted in the 2-position 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 motor fuels and have a significant anticorrosion action but are not very effective at the level of carburetor detergency.

It has now surprisingly been found compositions, as described below, used in particular as multifunctional additives for motor fuels, in particular for fuels used in spark ignition engines.

The compositions of the present invention have excellent detergent properties at the intake valves and the carburetor, and have very good anticorrosive properties.

These compositions, used as multifunctional additives in motor fuels, and more particularly in fuels used for spark ignition engines, inhibit, or greatly reduce, the formation of deposits on the intake valves, as well as the fouling of carburetors. or injectors; in addition, they greatly reduce the corrosion of the various mechanical parts with which the fuel comes into contact.

dans lesquelles R représente un atome d'hydrogène ou un groupe hydrocarboné ayant de 1 à 60 atomes de carbone, Z est choisi parmi les groupes -0- et -NR3- dans lesquels R3 représente un atome d'hydrogène ou un groupe hydrocarboné ayant de 1 à 60 atomes de carbone, Rl et R pouvant former ensemble avec l'atome d'azote auquel ils sont liés un hétérocycle, chacun des R2 indépendamment représente un atome d'hydrogène ou un groupe hydrocarboné ayant de 1 à 4 atomes de carbone, n est un nombre entier de 2 à 6, m est un nombre entier de 1 à 10 lorsque z est -NR3- et un nombre entier de 2 à 10 lorsque Z est -O-, A, B, C et D, identiques ou différents, représentent chacun un groupe hydrocarboné divalent ayant de 2 à 6 atomes de carbone, a est un nombre entier de 1 à 60, b et c, identiques ou différents, sont chacun zéro ou un nombre entier de 1 à 50 et la somme a + b + c est un nombre entier de 1 à 60, la quantité de polyamine mise en réaction étant d'au moins 0,1 mole par mole de dérivé succinique introduit dans la première étape. La quantité totale d'imidazoline substituée et de polyamine est de préférence de 0,8 à 1,2 mole par mole de dérivé succinique.The subject of the present invention is a composition that can be used especially as a multifunctional additive for motor fuels, which results, in a first step, from the reaction of at least one succinic derivative chosen from the group formed by alkenylsuccinic acids and anhydrides and the polyalkenylsuccinic acids and anhydrides, on at least one l- (2-hydroxyethyl) -imidazoline substituted in the 2-position by a linear or branched alkyl or alkenyl radical 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 in conditions such that at least 0.15 moles of water are formed and removed per mole of imidazoline employed; and in a second stage of the reaction of the product resulting from the first stage on at least one polyamine corresponding to one of the general formulas

in which R 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 R being able to form together with the nitrogen atom to which they are attached a heterocycle, each of 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 -O-, A, B, C and D, the same or different, each represents a divalent hydrocarbon group having 2 to 6 carbon atoms, a is an integer from 1 to 60, b and c, the same or different, are each zero or an integer from 1 to 50 and the sum of + b + c is an integer from 1 to 60, the amount of polyamine reacted being at least 0.1 mole per mole of succinic derivative introduced in the first step. The total amount of substituted imidazoline and polyamine is preferably 0.8 to 1.2 moles per mole of succinic derivative.

The succinic acid 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 succinic derivatives are widely described in the prior art; they are for example obtained by the action of at least one alpha olefin or a chlorinated hydrocarbon on the maleic acid or anhydride. The alpha olefin or the chlorinated hydrocarbon used in this synthesis may be linear or branched, and usually comprise from 10 to 150 carbon atoms, preferably from 15 to 80 carbon atoms and most often from 20 to 75 carbon atoms. This olefin may also be an oligomer, for example a dimer, a trimer or a tetramer, or a polymer of a lower olefin having, for example, from 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 olefin mixtures or chlorinated hydrocarbon mixtures.

As examples of succinic anhydrides, there may be mentioned n-octadecenylsuccinic anhydride, dodecenylsuccinic anhydride and polyisobutenylsuccinic anhydrides, often referred to as PIBSA, having a number average molecular weight as defined above. The 1- (2-hydroxyethyl) -imidazolines substituted in the 2-position 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 an organic acid with N- (2-hydroxyethyl) ethylenediamine. The reaction proceeds with a first amidification step followed by cyclization. The organic acids used usually have from 2 to 26 carbon atoms and are preferably aliphatic monocarboxylic acids.

By way of example, mention may be made of acetic acid, propanoic acid, butanoic acid, caprolate acid, capric acid, lauric acid, myristic acid, palmitic acid and the like. stearic acid, behenic acid, cerotic acid and unsaturated fatty acids
CH3-CH2-CH = CH- (CH2) 7COOH dodecylenic acid
CH3- (CH2-) 5CH = CH- (CH2-) 7COOH palmitoleic acid
CH3- (CH2-) 7CH = CH- (CH2-) 7COOH oleic acid
CH3- (CH2-) 5CHOH-CH2-CH = CH- (CH2-) 7COOH ricinoleic acid
CH3- (CH2-) 10CH = CH- (CH2-) aCOOH petroselenic acid
CH3- (CH2-) 5CH = CH- (CH2-) 9COOH vaccenic acid
CH, - (CH, -), CH = CH-CH, -CH = CH- (CH2-) 7COOH linoleic acid
CH3- (CH2-) 9CH = CH- (CH2-) 7COOH gadoleic acid
CH3- (CH2-) 9CH = CH- (CH2-) 9 COOH cetoleic acid
CH3- (CH2-) 7CH = CH- (CH2-) 11COOH erucic acid
CH3- (CH2-) 7CH = CH- (CH2-) 13COOH selacholeic acid
For example, 1- (2-hydroxyethyl) -2-heptadecenyl imidazoline, prepared for example from oleic acid and N- (2-hydroxyethyl) ethylenediamine, will be used. This preparation is for example described in US-A-2987515.

By way of example, mention may also be made of 1- (2-hydroxyethyl) -2-methyl imidazoline prepared, for example, from acetic acid and N- (2-hydroxyethyl) ethylenediamine.

1- (2-hydroxyethyl) -2-heptadecenylimidazoline is marketed by CIBA-GEIGY under the name "Amine-O" and by PROTEX under the name "Imidazoline-O".

The first step of preparation of the composition 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, and then heating at a temperature usually between 65 and 250. C and preferably between 80 and 200 OC.

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 imidazoline with the succinic derivative, preferably in the form of a water-organic solvent azeotrope. An organic solvent such as, for example, benzene, toluene, xylenes, ethylbenzene or a hydrocarbon cut such as, for example, the commercial cutlery SOLVESSO 150 (190-209 OC) containing 99% by weight of compounds, will usually be used. aromatics. It is possible to use solvent mixtures, for example a mixture of xylenes. The duration of the heating after the end of the addition of the imidazoline is usually from 0.5 to 7 hours, preferably from 1 to 5 hours. This first step will preferably be continued at the chosen temperature until the end of the release of the water formed during the reaction.

The amount of water removed in this first step is usually about 0.15 to 0.6 mole and most often about 0.2 to 0.5 mole per mole of imidazoline involved in the reaction. . To the product or mixture resulting from this first stage, after optional cooling, at least one polyamine, preferably diluted in an organic solvent, is preferably gradually added, and then the mixture is then heated to a temperature of between 65 and 250.degree. C. and preferably between 80.degree. and 200 OC. The solvent employed in this second step is preferably the same as that used 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 from 0.1 to 7 hours and preferably from 0.2 to 5 hours.

The amount of polyamine employed is at least 0.1 mole per mole of succinic anhydride introduced in the first step and is preferably such that the total amount of substituted imidazoline and polyamine employed in the preparation is 0.8 to 1.2 moles, preferably 0.9 to 1.1 moles per mole of succinic derivative. The polyamine-substituted imidazoline 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 stage is usually such that the total amount of water removed during the two successive reactions is 0.2 to 0.7 moles per mole of succinic derivative.

The polyamines of formula (I) are preferably those in which R 1 is a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms, Z is preferably a group -NR 3 - in which R 3 is preferably an atom of hydrogen or a hydrocarbon group having 1 to 30 carbon atoms, each of R 2 independently is preferably a hydrogen atom or a methyl group, n is an integer of 2 to 4 and when Z is a group -NR 3 m is preferably an integer of 1 to 5.

Among the compounds of formulas (I) above, those in which Z is -NR 3 -, R 1, R 2 and R 3 each represent a hydrogen atom, n is equal to 2 and m is an integer of 1 to Or wherein R 1 is a hydrocarbon group preferably having 5 to 24 carbon atoms, Z is -NR 3 wherein R 3 is hydrogen, R 2 is hydrogen, n is an integer of 2 to 4, preferably 3, and m is an integer of 1 to 5, preferably 1.

The hydrocarbon groups R 1 and R 3 are usually alkyl, alkenyl, linear or branched, aryl, aryl-alkyl (aralkyl), alkyl-aryl (alkaryl) or cycloaliphatic groups. The groups R 1 and R 3 are preferably linear or branched alkyl or alkenyl groups. The hydrocarbon group R2 is usually a preferably linear alkyl group and for example methyl, ethyl, n-propyl or n-butyl.

Specific compounds that may be mentioned include: ethylenediamine, propylenediamine, triethylenetetramine, tripropylenetetramine, tetraethylenepentamine, trimethylenediamine, hexamethylenediamine, di (trimethylene) triamine, N-alkyl-1,3-diaminopropane, for example N 1,3-1,3-dodecyl-1,3-propane, N-tetradecyl-1,3-diamine-propane, N-hexadecyldiamino-1,3 propane, 1,3-N-octadecyl-1,3-propane, N-eicosyldiamino-1,3 propane and N-docosyldiamino-1,3 propane: there may also be mentioned
N-alkyldipropylene tri amines, for example N-hexadecyldipropylene triamine, N-octadecyldipropylene triamine, N-eicosyldipropylene triamine and N-docosyldipropylene triamine; N-alkenyldiamino-1,3 propane and N-alkenyldipropylene triamines, for example N-octadecenyldiamino-1,3 propane, N-hexadecenyldiamino-1,3 propane, N-dodecylenyldiamino-1,3 propane may also be mentioned; 1,3-N-octadecadienadienino-1,3-propane and 1,3-N-docosenyldiamino are exemplified by N, N-diethyl-1,2-diaminoethane, N, N-disubstituted diamines. N, N-diisopropyl-1,2-diaminoethane, N, N-dibutyl-1,2-diaminoethane, N, N-diethyl-1,4-diaminobutane, N, N-dimethyl-1,3-diaminopropane, the
N, N-diethyl-1,3-diaminopropane, N, N-dioctyl-1,3-diaminopropane, N, N-didecyl-1,3-dimethylpropane, N, N-didodecyl-1,3-diaminopropane N, N-ditetradecyl-1,3-diaminopropane, N, N-dihexadecyl-1,3-diaminopropane, N, N-dioctadecyl-1,3-diaminopropane, N, N-didodecyldipropylenetriamine, N , N-diketadecylpropyl triamine, N, N-dihexadecylpropyl triamine, N, N-dioctadecyl dipropylene triamine, N-methyl, N-butyl-1,2-diaminoethane,
N-methyl N-octyl-1,2-diaminoethane, N-ethyl, N-octyl-1,2-diaminethane, N-methyl, N-decyl-1,2-diaminoethane, N-methyl-N-dodecyl 1,3-diamino propane, N-methyl, N-hexadecyl-1,3-dianopropane and N-ethyl N-octadecyl-1,3-diaminopropane.

As examples of etherarines mention may be made of N- (3-octyloxypropyl) 1,3-diaminopropane, N- (3-decyloxypropyl) 1,3-diaminopropane, N- [(trimethyl) -2,4,6 decyl) 3-oxypropyl-1,3-diamino propane.

It should be understood that it is possible to use as polyamine compound one or more compounds of formula (I) and / or (II).

As specific examples of mixtures of compounds corresponding to formula (I), mention may be made of fatty diamine cuts corresponding to the formula R 1 -NH- (CH 2) 3 NH 2, the R 1 groups of which are aliphatic hydrocarbon radicals in the form of
C8, C10, C12, C14, C16, C18, C20 and C22, in approximate molar proportions given in Table I below.

TABLE I

<tb> chains <SEP> alkyls <SEP> *
<tb> Cut <SEP> C8 <SEP> C10 <SEP> C12 <SEP> C14 <SEP> C16 <SEP> C18 <CEN> C18-1 <SEP> C20 <SEP> C22
<tb> A <SEP> 0 <SEP> 0 <SEP> 0 <SEP> 1% <SEP> 28% <SEP> 71% <SEP> 0 <SEP> 0 <SEP> 0
<tb> B <SEP> 0 <SEP> 0 <SEP> 0 <SEP> 1% <SEP> 5% <SEP> 42% <SEP> 0 <SEP> 12% <SEP> 40%
<tb> C <SEP> 3% <SEP> 6% <SEP> 56% <SEP> 18% <SEP> 10% <SEP> 2% <SEP> 5% <SEP> 0 <SEP> 0
<tb> D <SEP> 0 <SEP> 0 <SEP> 0 <SEP> 0 <SEP> 16% <SEP> 4.9% <SEP> 79.1% <SEP> 0 <SEP> 0
<tb> E <SEP> 0 <SEP> 0 <SEP> 0 <SEP> 2.3% <SEP> 31.8% <SEP> 24.2% <SEP> 39% <SEP> 2.7% <SEP> 0
<Tb>
* C18-1 chain containing ethylenic unsaturation.

The polyamines of formulas (II) are preferably those in which R1 and R3 each represent a hydrogen atom A, B, C and D, which may be identical or different, each represent an alkylidene group having 2 to 4 carbon atoms, for example ethylidene, propylidene, isopropylidene, butylidene, 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 of + c is 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 of 1 to 60.

Specific compounds of formula (II) that may be mentioned are those corresponding to formulas (II) NH 2 -CH 2 -CH 2 - (O-CH 2 -CH 2 -) aNH 2 (II 2) NH 2 -CH-CH 2 - (OCH 2 -CH-) aNH 2
CH3 CH3 wherein a is 2, 3, 5, 6 or about 33 (II3) NH2-CH-CH2- (OCH-CH2 -) (OCH2CH2) (O-CH2CH-) NH2
ABC
Wherein b is about 8, 9, 15, 16 or 40 and a + c is about 2 or 3.

These products are in particular marketed by the company TEXACO
Chemical in non Jeffamine EDR 148 for the product of formula (II1) wherein a = 2, Jeffamine D-230 for a product of formula (II2) of number average molecular weight of 230, Jeffamine D-400 for a product of formula (II2) having a number average molecular weight of 400, Jeffamine D-2000 for a product of formula (II2) of average molecular weight in number of 2000, Jeffamine ED-600 for a product of formula (II3) of molecular weight number average of 600, Jeffamine ED-900 for a product of formula (II3) of number average molecular weight of 900 and Jeffamine ED-2001 for a product of formula (II3) of number average molecular weight of 2000.

The compositions of the present invention may be used as a solution in the reaction medium or it may be evaporated and optionally replaced with another solvent or solvent mixture or with a diluent.

The compositions of the present invention are mainly used as multifunctional additives for a motor fuel for example a fuel based on hydrocarbons or based on a mixture of hydrocarbons and at least one oxygenated compound selected from the group formed by the alcohols and ethers, or a non-hydrocarbon fuel such as for example an alcohol or a mixture of alcohols.

The compositions of the present invention are particularly well suited for use as additives for fuels used in spark ignition engines.

Examples of motor fuels include gasolines such as for example those defined by ASTM D-439, gas oils or diesel fuels such as, for example, those defined by ASTM D-975. These fuels may also contain other additives than the compositions of the present invention, for example antiknock additives such as lead compounds (for example tetraethyl lead), methyl tert-butyl ether, methyl tert-amyl ether or a mixture of methanol and methanol. tert-butyl alcohol, antifreeze additives and octane requirement reducers.

The compositions of the present invention are used in sufficient quantity to obtain a significant reduction in the deposits on the various engine components, in particular at the level of the intake valves and the carburettor. Usually, amounts representing from 10 to 1000 ppm by weight of composition (active ingredient) relative to the weight of the motor fuel, preferably from 50 to 700 ppm and most often from 100 to 500 ppm, are used.

The following examples illustrate the invention without limiting its scope. Examples 9 to 11 are given for comparison.

Example 1 1018 g of polyisobutenyl succinic anhydride (PIBSA), resulting from the condensation of polyisobutene (polyisobutene of number average molecular weight 920), on maleic anhydride (the anhydride function assay of this product shows that we have 0.7 anhydride function per theoretical mole of PIBSA) and 1018 g of xylene are charged to a 2-liter reactor equipped with mechanical agitation, a Dean-Stark and a temperature control system.

148 g (0.423 mol) of 1- (2-hydroxyethyl) -2-heptadecenyl imidazoline diluted in 148 g of xylene are then added dropwise at room temperature and with stirring.

The addition is carried out in 30 minutes and accompanied by a rapid increase in the temperature of the reaction mixture by about 5 ° C.

The mixture is then refluxed for 3 hours with removal of water by azeotropic distillation. The amount of water collected is 2.3 ml. The progress of the reaction can also be monitored by infrared spectrometry at the imine absorption band at 1660 cm which disappears progressively during the reaction.

The temperature of the reactor is decreased to 50 OC then maintained at this value during the time of the progressive addition (drop by drop) of 56 g (0.297 mole) of tetraethylempentamine diluted in 49 g of xylene. At the end of this addition the mixture is refluxed again for 15 minutes. There is again a removal of water. The total amount of water collected during these two reaction steps is 7.2 ml. The infrared spectrum shows two absorption bands (1710 cm and 1770 cm) characteristic of the succinic function with a shoulder (lisp cn-1) characteristic of the ester function.

A solution of 50% by weight of active material in xylene of a composition according to the invention is thus obtained.

Elemental analysis of the composition shows a nitrogen content of 2.55% by weight.

Example 2
A composition according to the invention is prepared in the same manner as in Example 1, replacing the tetraethylenepentanine with diethylenetriamine. 102 g (0.1 mole) of PIBSA at 0.68 anhydride function per 1000 g of product and 102 g of xylene are charged into the reactor and 14 g (0.04 mole) of 1 g are added dropwise (dropwise). - (2-hydroxyethyl) -2-heptadecenyl imidazoline diluted in 14 g of xylene. The mixture is then refluxed for 3 hours with removal of 0.2 ml of water by azeotropic distillation.

This removal of water occurs essentially during the first 170 minutes of reaction. After cooling to 50 ° C., 2.9 g (0.028 mol) of diethylenetriamine diluted in 2 g of xylene are gradually added, followed by refluxing for 3 hours. Water removal occurs (essentially during the first 170 minutes of reaction). The total amount of water removed in both steps is 0.65 ml. A solution of 50% by weight of active material in xylene is thus obtained of a composition according to the invention.

Example 3
The procedure described in Example 2 is repeated by replacing the diethylenetriamine with a tallow diamine such as that marketed under the tradename Dinoram S by the company CECA and corresponding to the section E, the characteristics of which have been mentioned in Table I below. before. 10.1 g (0.028 mol) of
Dinoram S were added in the second stage. In total, the removal of 0.85 ml of water was observed. A solution of 50% by weight of active material in xylene is thus obtained of a composition according to the invention.

Example 4
The procedure described in Example 2 is repeated replacing diethylenetriamine with 1.68 g (0.028 mol) of ethylenediamine and using toluene as the reaction solvent instead of xylene. A 50% solution by weight of active ingredient in toluene of a composition according to the invention is thus obtained.

Example 5
The procedure described in Example 2 is repeated replacing the diethylenetriamine by the polyoxyalkyleneamine marketed by TEXACO under the name Jeffamine D-230 with a number average molecular weight of 230. 6.44 g (0.028 mol) of Jeffamine D- 230 were added in the second step. In total it was found the removal of 0.7 ml of water. This gives a solution, at EO> by weight of active material, in xylene, of a composition according to the invention.

Example 6
Example 5 is repeated using 11.2 g (0.028 mol) of Jeffamine
D-400 sold by TEXACO and having a number average molecular weight of 400. In total it was found the removal of 0.4 ml of water. A solution of 50% by weight of active material in xylene is thus obtained of a composition according to the invention.

Example 7
In a 2-liter reactor equipped with mechanical agitation, a
Dean-Stark and a temperature control system is charged 15.6 g (0.15 mole) of N-hydroxyethylethylenediamine diluted in 15.6 g of toluene. 9 g (0.15 mole) of glacial acetic acid diluted in 9 g of toluene are then added gradually (dropwise). The mixture is then refluxed for 16 hours during which 4.8 ml of water are removed by azeotropic distillation. The product of the reaction is isolated after evaporation of toluene in vacuo. A pale yellow oily product is thus obtained which has been characterized by the conventional means of analysis as 1- (2-hydroxyethyl) -2-methyl imidazoline.

-l
The infrared spectrum shows an imine band at 1660 cm 2 and in nuclear magnetic resonance spectrometry the presence of the two -methylene groups of the imidazoline ring and the presence of the methyl group at the 2-position on the imidazoline ring are detected.

Elemental analysis provides a nitrogen percentage of 22.1% by weight for a calculated percentage of 21.8%.

Example 8
The procedure described in Example 1 is repeated replacing 1- (2-hydroxyethyl) -2-heptaecenylimidazoline with 1- (2-hydroxyethyl) -2-methylimidazoline prepared in Example 7. 4 g (0.12 mol) of PIBSA diluted in 22.4 g of xylene and 6.1 g (0.048 mol) of imidazoline prepared in Example 7 diluted in 6.1 g of xylene. During the first stage reflux is maintained for 3 hours and 0.9 ml of water is removed. After cooling to 50 ° C., 6.36 g (0.034 mol) of tetraethylenepentamine diluted in 5 g of xylene are added, followed by refluxing for 15 minutes.

A total of 1.3 ml of water are collected in the two stages. A solution of 50% by weight of active material in xylene of a composition according to the invention is thus obtained.

Example 9
In a 2-liter reactor equipped with mechanical agitation, a
Dean-Stark and a temperature control system are introduced 306 g (0.3 mol) of PIBSA, equivalent to 0.7 anhydride function per theoretical mole of PIBSA, diluted in 306 g of xylene, and then added gradually ( dropwise) 39.7 g (0.21 mol) of tetraethylenepentamine diluted in 34 g of xylene. The mixture is then refluxed for 5 hours.

The amount of water removed during the reaction is 5.7 ml. A 50% by weight solution of active material in xylene is thus obtained with a composition which is not in accordance with those of the present invention.

Example 10 (comparative)
In a 2-liter reactor equipped with mechanical agitation, a
Dean-Stark and a temperature control system is charged 586g (0.40 mole) of PIBSA, equivalent to 0.7 anhydride function per theoretical mole of PIBSA, diluted in 500 g of xylene and then added gradually (drop to drop) at room temperature 145 g (0.41 mol) of 1- (2-hydroxyethyl) -2-heptadecenyl imidazoline diluted in 231 g of xylene. The mixture is then refluxed for 195 minutes. The amount of water removed during the reaction is 3.5 ml.

A 50% by weight solution of active material in xylene is thus obtained with a composition which is not in accordance with those of the present invention.

Example 11 (comparative)
In a 2-liter reactor equipped with mechanical agitation, a
Dean-Stark and a temperature control system are introduced 1018 g of PIBSA, equivalent to 0.7 anhydride function per theoretical mole of PIBSA, diluted in 1018 g of xylene and then added gradually (dropwise) at room temperature a mixture of 148 g (0.423 mol) of 1- (2-hydroxyethyl) -2-heptadecenyl imidazoline and 56 g (0.297 mol) of tetraethylenepentamine diluted in 190 g of xylene. The mixture is then refluxed for 195 minutes. The amount of water collected is 13.5 ml.

A 50% by weight solution of active material in xylene is thus obtained with a composition which is not in accordance with those of the present invention.

Example 12
The "carburettor" detergency properties of the compositions prepared in Examples 1, 3, 4, 8, 9 and 10 are evaluated.

The engine test procedure is carried out following the European standard R5-CEC-F03-T-81. The results are expressed in terms of merit from zero to ten. A merit 10 is a clean carburetor and a merit O has a very dirty carburetor. The compositions are added to the fuel so as to obtain a concentration of 300 ppm by weight of active material in the additive fuel.

<Tb>

Fuel <SEP> Merit
<tb> I <SEP> Fuel <SEP> only <SEP> t <SEP> 1,9 <SEP> - <SEP> 2,3
<tb> Fuel <SEP> + <SEP> composition <SEP> example <SEP> 1 <SEP> 1 <SEP> 8.5 <SEP> - <SEP> 8.6
<tb>(<SEP> Fuel <SEP> + <SEP> composition <SEP> example <SEP> 3 <SEP> I <SEP><SEP> 8.3 <SEP> - <SEP> 8.5
<tb> Fuel <SEP> + <SEP> composition <SEP> example <SEP> 4 <SEP> 1 <SEP> 8.4 <SEP> - <SEP> 8.6
<tb> Fuel <SEP> composition <SEP> example <SEP> 8 <SEP> t <SEP> 8.5 <SEP> - <SEP> 8.7
<tb> 1 <SEP> Fuel <SEP> + <SEP> composition <SEP> example <SEP> 9 <SEP> 1 <SEP><SEP> 7.6 <SEP> - <SEP> 7.8
<tb> I <SEP> Fuel <SEP> + <SEP> composition <SEP> example <SEP> 10 <SEP> 1 <SEP><SEP> 3,7 <SEP> - <SEP> 3,3
<Tb>
The fuel used in these assessments is a conventional premium gasoline additive in lead alkyl containing 0.4 g of lead per liter (fuel only).

This super-fuel contains 48.1% paraffin by volume 15.4% olefins 29.2% aromatics and 4.3% naphthenics
Example 13
The valve detergency properties of the compositions prepared in Examples 1, 3, 4, 8, 9, 10 and 11 are evaluated.

The tests were carried out on a Renault 25 GTX vehicle by preventive treatment on a 5000 km route. At the start of each test the engine is conditioned with new valves that are weighed. At the end of the test, the valves are disassembled, washed with hexane, dried, and weighed after physical removal (by scraping) of the deposits formed on the valve on the combustion chamber side.

The results presented below give the weight of deposits measured, on the tulip of each intake valve, by difference between the weight of the new valve and the weight of the valve at the end of each test after removal of deposits on the chamber side. of combustion.

The amount of composition added in the premium gasoline is 300 ppm by weight of active material, this fuel is that already used in Example 12.

<Tb>

Fuel <SEP> Weight <SEP> of <SEP> depots
<tb> Fuel <SEP> only <SEP> 360 <SEP> mg
<tb> Fuel <SEP> + <SEP> composition <SEP> example <SEP> 1 <SEP> | <SEP> I <SEP> 19 <SEP> mg <SEP> t <SEP>
<tb> Fuel <SEP> + <SEP> composition <SEP> example <SEP> 3 <SEP> 1 <SEP> 18 <SEP> mg
<tb> t <SEP> Fuel <SEP> + <SEP> composition <SEP> example <SEP> 4 <SEP> | <SEP> 20 <SEP> mg
<tb> Fuel <SEP> + <SEP> composition <SEP> example <SEP> 8 <SEP> | <SEP> 17 <SEP> mg
<tb> Fuel <SEP> + <SEP> composition <SEP> example <SEP> 9 <SEP> I <SEP> 160 <SEP> mg <SEP> I
<tb> Fuel <SEP> + <SEP> composition <SEP> example <SEP> 10 <SEP> 1 <SEP> 108 <SEP> mg <SEP> t <SEP>
<tb> Fuel <SEP> + <SEP> composition <SEP> example <SEP> 11 <SEP> 1 <SEP> 177 <SEP> mg
<Tb>
Example 14
The anti-corrosion properties of the compositions prepared in Examples 1 and 8 are evaluated.

The tests consist in determining the extent of the corrosion produced on polished ordinary steel samples in the presence of synthetic seawater according to ASTM D 665 modified (temperature 32.2 OC, duration 20 hours).

The amount of composition added is 300 ppm by weight of active ingredient. Fuel. is the same as that used in Example 12.

The results are expressed as a percentage (%) of the surface of the corroded test piece after 20 hours.

<Tb>

Fuel <SEP>% <SEP> of <SEP> Surface <SEP> Corroded
<tb> I <SEP> Fuel <SEP> only <SEP> I <SEP> 100 <SEP>
<tb> Fuel <SEP> + <SEP> compcsiticn <SEP> example <SEP> 1 <SEP> | <SEP> O
<tb> I <SEP> Fuel <SEP> + <SEP> composition <SEP> example <SEP> 81 <SEP> 0 <SEP>
<Tb>

Claims (8)

1. Composition, used in particular as a multifunctional additive for motor fuels, characterized in that it results in a first step of the reaction of at least one succinic derivative selected from the group consisting of alkenylsuccinic acids and anhydrides and acids. and the polyalkenylsuccinic anhydrides on at least one 1- (2-hydroxyethyl) imidazoline substituted in the 2-position by a linear or branched alkyl or alkenyl radical having from 1 to 25 carbon atoms, the imidazoline / succinic derivative molar ratio being from 0.1: 1 to 0.9: 1, said step being carried out under such conditions that at least 0.15 moles of water are removed per mole of imidazoline employed; and in a second step of the reaction of the product resulting from the first step on at least one polyamine corresponding to one of the general formulas in which R represents a hydrogen atom or a hydrocarbon group having from 1 to 60 carbon atoms, Z is selected from the groups -O- and -NR3- wherein R3 represents a hydrogen atom or hydrocarbon group having 1 to 60 carbon atoms, R1 and R3 may together form with the nitrogen atom to which they are bonded to a heterocycle, each of R2 independently represents a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms, n is an integer of 2 to 6, m is an integer of 1 to 10 when Z is -NR3- and an integer of 2 to 10 when Z is -O-, A, B, C and D, identical or different, each represent a divalent hydrocarbon group having 2 to 6 carbon atoms, a is a whole number from 1 to 60, b and c, identical or different, are each ze or an integer from 1 to 50 and the sum a + b + c is an integer from 1 to 60, the amount of polyamine reacted being at least 0.1 mole per mole of succinic derivative introduced into the first step 2. Composition according to claim 1 wherein the succinic derivative is an alkenylsuccinic anhydride or polyalkenylsuccinic anhydride having a number average molecular weight of 200 to 3000. 3. Composition according to claim 1 or 2 wherein the polyamine has the general formula (I)

 wherein R 1 is a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms, Z is a group -NR 3 - in which R3 represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms, each of R2 independently represents a hydrogen atom or a methyl group, n is an integer of 2 to 4 and m is a whole number from 1 to 5. 4. Composition according to one of claims I to 3 wherein the polyamine corresponds to the general formula (I)

 wherein R1 and R2 are each hydrogen, Z is -NR3- wherein R3 is hydrogen, n is 2 and m is an integer of 1 to 5. 5. Composition according to one of claims 1 to 3 wherein the polyamine corresponds to the general formula (I)

 in which R 1 represents a hydrocarbon group having from 5 to 24 carbon atoms, Z represents a group -NR 3 - in which R 3 is a hydrogen atom, R 2 represents a hydrogen atom, n is equal to 3 and m is equal to to 1. The composition of claim 1 or 2 wherein the polyamine has the general formula (II):

 in which R1 and R3 each represent a hydrogen atom, A, B, C and D, identical or different, each represents a divalent hydrocarbon group having 2 to 4 carbon atoms, 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, the sum a + b + c being in all cases an integer from 1 to 60 . 7. Composition according to one of claims 1 to 6 wherein the imidazoline substituted is selected from the group consisting of 1- (2-hydroxyethyl) -2-heptadecenylimidazoline and 1- (2-hydroxyethyl) -2-methylimidazoline .  e. Composition according to one of Claims 1 to 7, characterized in that the reactions are carried out at a temperature of 65 to 250 OC. 9. Composition according to one of claims 1 to 8 characterized in that the reactions are carried out in the presence of a solvent having a boiling point of about 65 to 250 OC for the azeotropic removal of water, the said reactions being carried out at the reflux temperature. 10. Use of a composition according to one of claims 1 to 9 as a multifunctional additive for a hydrocarbon-based fuel or a mixture of hydrocarbons and at least one oxygenated compound selected from the group consisting of alcohols and ethers. 11. Use according to claim 10 for a fuel used in spark ignition engines.