BE1017882A3 - ADDITIVE COMPOSITIONS FOR MINIMIZING ENJOYMENT OF INJECTORS AND DEPOSITS ON VALVES, AND FUEL COMPOSITIONS CONTAINING SAME. - Google Patents

Abstract

The invention provides compositions comprising (a) a Mannich detergent and (b) a succinimide comprising a reaction product (i) of an alkenyl-substituted succinic anhydride having an average molecular weight of about 250 to about 3000 and ii) an amine-functional polyalkylene polymer having an average molecular weight of about 100 to 750, the anhydride and the polymer being present in the reaction in a mole ratio of about 2.0: 1.0 to about about 1.0: 1.3. It also relates to fuel compositions using these additive compositions. Field of application: operation of engines with said compositions to prevent fouling of the engines.

Description

Additive compositions for minimizing fouling of injectors and valve deposits, and fuel compositions containing them.

The invention relates to compositions for use in minimizing fouling of injectors, for example in fuel injectors, and for preventing valve deposits, such as intake valves, comprising (a) a Mannich detergent and (b) a particular succinimide.

The use of conventional non-detergent fuels and corrosion inhibiting additives promotes the accumulation of deposits in the induction system, particularly at the injectors, which become fouled, or even in the combustion chamber, which results the presence of polar aromatic compounds and traces of lubricants.

The accumulation of deposits has a detrimental effect on the quality of the evaporation of fuel, which causes an increase in consumption, an increase in the emission of pollutants and smoke, which is significantly higher during the acceleration and, finally, an increase in noise.

To solve this problem of clogging of the engine, it is possible to periodically clean the dirty components and in particular the injectors. However, in the long run, this process becomes very expensive.

Another method for reducing fouling caused by deposits in engines, including injectors, is to use detergents that can be absorbed on metal surfaces to prevent the formation of deposits and / or to remove deposits already formed by injector cleaning. Examples of such detergents are the products resulting from the condensation of polyalkenylsuccinic anhydrides with polyamines, such as tetraethylenepentamine ("ΤΕΡΑ"), described in U.S. Pat. No. 3,172,892.

The compositions of the invention can be used as detergents to prevent the formation of deposits and / or to remove deposits already formed in injectors, such as fuel injectors, and / or on valves, including intake valves. .

In one aspect, the present disclosure relates to novel fuel compositions comprising or consisting essentially of (a) a Mannich detergent and (b) a succinimide which is a reaction product (i) of alkenyl substituted succinic anhydride having an average molecular weight of about 250 to about 3000 and (ii) an amine-functional polyalkylene polymer having an average molecular weight of about 100 to about 750, wherein alkenyl-substituted succinic anhydride and The amine-functional polyalkylene polymer is present in the reaction in a mole ratio of about 2.0: 1.0 to about 1.0: 1.3.

In another aspect, the present disclosure relates to novel gasoline compositions comprising, or consisting essentially of, (a) a hydrocarbon, (b) a Mannich detergent and (c) a succinimide which is a reaction product (i) an alkenyl-substituted succinic anhydride having an average molecular weight of about 250 to about 3000; and (ii) an amine-functional polyalkylene polymer having an average molecular weight of about 100 to about 750, wherein The alkenyl substituted succinic anhydride and the amine-functional polyalkylene polymer are present in the reaction in a mole ratio of about 2.0: 1.0 to about 1.0: 1.3.

In a further aspect, the present disclosure relates to additive compositions for gasoline, comprising, or consisting essentially of, (a) a Mannich detergent and (b) a succinimide which is a reaction product (i) of an alkenyl substituted succinic anhydride having an average molecular weight of about 250 to about 3000 and (ii) an amine-functional polyalkylene polymer having an average molecular weight of about 100 to about 750, wherein the anhydride The alkenyl substituted succinic and the amine-functional polyalkylene polymer are present in the reaction in a mole ratio of about 2.0: 1.0 to about 1.0: 1.3.

In a further aspect, the present disclosure relates to a method for preventing fouling of the injectors, for example in a fuel injector, comprising contacting the injector with a composition comprising, or consisting essentially of, (a) a Mannich detergent and (b) a succinimide which is a reaction product (i) of an alkenyl-substituted succinic anhydride having an average molecular weight of about 250 to about 3000 and (ii) a polyalkylene-type polymer to amine function having an average molecular weight of about 100 to about 750, wherein the alkenyl substituted succinic anhydride and the amine-functional polyalkylene polymer are present in the reaction in a mole ratio of about 2.0: 1 0 to about 1.0: 1.3.

In another aspect, the present disclosure relates to a method for preventing deposits on a valve, for example an intake valve, comprising contacting the intake valve with a novel composition comprising, or consisting essentially of, a) a Mannich detergent and (b) a succinimide which is a reaction product (i) of an alkenyl-substituted succinic anhydride having an average molecular weight of about 250 to about 3000 and (ii) a polymer of an amine-functional polyalkylene type having an average molecular weight of from about 100 to about 750, wherein the alkenyl-substituted succinic anhydride and the amine-functional polyalkylene polymer are present in the reaction in a molar ratio of about 2, 0: 1.0 to about 1.0: 1.3.

In a further aspect, the present disclosure relates to a .com engine comprising a novel composition comprising, or consisting essentially of, (a) a Mannich detergent and (b) a succinimide which is a reaction product (i) of a succinic anhydride alkenyl substituent having an average molecular weight of about 250 to about 3000 and (ii) an amine-functional polyalkylene polymer having an average molecular weight of about 100 to about 750, wherein the substituted succinic anhydride Alkenyl and the amine-functional polyalkylene polymer are present in the reaction in a mole ratio of about 2.0: 1.0 to about 1.0: 1.3.

The present disclosure relates to novel fuel compositions comprising or consisting essentially of (a) a Mannich detergent and (b) a succinimide which is a reaction product (i) of an alkenyl-substituted succinic anhydride having a molecular weight. average of about 250 to about 3000 and (ii) an amine-functional polyalkylene polymer having an average molecular weight of about 100 to about 750, wherein alkenyl-substituted succinic anhydride and polyalkylene-type polymer In the reaction, the amine function is present in a molar ratio of about 2.0: 1.0 to about 1.0: 1.3.

As used herein, the singular forms "a", "an", "the" and "the" include references to the plural, unless otherwise specified by context. For example, the reference to "alkenyl-substituted succinic anhydride" refers to a composition comprising a single alkenyl-substituted succinic anhydride, and also to a composition comprising a mixture of alkenyl-substituted succinic anhydrides.

As used herein, the term "about" includes the range of the experimental error that occurs in any measure.

As used herein, the phrase "present in the reaction" indicates that the starting materials used to generate the succinimide incorporated in the novel composition are mixed and / or mixed with each other under conditions which should result in the formation of succinimide.

The invention provides both an additive concentrate for gasoline and a product consisting of a fuel of the type of finished gasoline or with additives.

Detergents from Mannich

The Mannich detergents used in the novel compositions can be obtained by reacting an alkyl-substituted hydroxyaromatic compound, an aldehyde and an amine in a Mannich condensation reaction, as described herein.

Examples of suitable alkyl-substituted hydroxyaromatic compounds which can be used in the formation of Mannich detergents include, but are not limited to, polypropylphenol (formed by alkylating phenol with polypropylene), polybutylphenols (formed by alkylating phenol with polybutenes and / or polyisobutylene), polybutyl-copolypropylphenols (formed by alkylating phenol with a butylene and / or butylene-propylene copolymer), polypropylcresol (formed by alkylating cresol with polypropylene), polybutylamines, cresols (formed by alkylating cresol with polybutenes and / or polyisobutylene), polybutyl-copolypropyl-cresols (formed by alkylating cresol with a copolymer of butylene and / or butylene and propylene). Other long chain alkylphenols may also be used. Examples include, but are not limited to phenols or cresols alkylated with butylene and / or isobutylene and / or propylene copolymers, and one or more mono-olefin comonomers copolymerizable therewith (e.g., ethylene). , 1-pentene, 1-hexene, 1-octene, 1-decene, etc.), the copolymer molecule containing at least 50% by weight of butylene and / or isobutylene and / or propylene units. Comonomers polymerized with propylene or said butenes may be aliphatic and may also contain non-aliphatic groups, for example styrene, o-methylstyrene, p-methylstyrene, divinylbenzene, and the like. Thus, the resulting polymers and copolymers used to form alkyl-substituted hydroxyaromatic compounds are substantially aliphatic hydrocarbon polymers.

In one embodiment, the alkyl-substituted hydroxy-aromatic compound is polybutylphenol (formed by alkylating phenol with polybutylene). In another embodiment, the alkyl substituted hydroxyaromatic compound is polybutylcresol (formed by alkylating cresol with polybutylene). Unless otherwise specified herein, the term "polybutylene" is used in a general sense to include polymers prepared from "pure" or "substantially pure" 1-butene or isobutene, and polymers prepared from from mixtures of two or all of the three monomers consisting of 1-butene, 2-butene and isobutene. Commercial grades of these polymers may also contain insignificant amounts of other olefins. Polybutylenes referred to as high reactivity polybutylenes comprising relatively high proportions of polymer molecules having a terminal vinylidene group, formed by processes such as those described, for example, in U.S. No. 4,152,499 and W. German Offenlegungsschrift 29 04 314 may also be suitably used in the formation of the long chain alkylated phenol or cresol reactant.

The alkylation of the hydroxyaromatic compound can be carried out in the presence of an alkylation catalyst such as BF3 at a temperature in the range of about 50 to about 200 ° C. Long-chain alkyl groups substituted on the benzene ring of the phenol or cresol molecule are derived from a polyolefin having an average molecular weight of from about 500 to about 3000, as determined by gel permeation chromatography. ( "GPC"). In one embodiment, the polyolefin has an average molecular weight of about 50 to about 2000.

In one embodiment, the polyolefin used to obtain the long-chain alkyl groups as substituents on the benzene ring of the phenol or cresol molecule has a polydispersity (weight average molecular weight / average molecular weight) of about 1 to about 4, as determined by GPC. In another embodiment, the polyolefin used to obtain the long-chain alkyl groups as substituents on the benzene ring of the phenol or cresol molecule has a polydispersity of from about 1 to about 2.

The Mannich detergent can be prepared from a long chain alkylphenol or a long chain alkylcresol. However, it is possible to use other phenolic compounds including, but not limited to, alkyl-substituted high molecular weight derivatives of resorcinol, hydroquinone, catechol, xylenol, hydroxydiphenyl, and the like. benzylphenol, phenethylphenol, naphthol and tolylnaphthol.

In one embodiment, the Mannich detergent is synthesized from a polyalkylphenol or a polyalkylcresol, such as, but not limited to, polypropylphenol, polybutylphenol, polypropylcresol and polybutylcresol. In another embodiment, the Mannich detergent is synthesized from a polyalkylphenol or polyalkylcresol containing a substituent alkyl group, having an average molecular weight of about 650 to about 1500. In another embodiment, the Mannich detergent is synthesized from Mannich detergent is synthesized from a polyalkylphenol or polyalkylcresol containing a substituent alkyl group, having an average molecular weight of about 800 to 1300.

In one embodiment, the Mannich detergent is synthesized from a polyalkylcresol such as, but not limited to, polypropylcresol and polybutylcresol. In another embodiment, the Mannich detergent is synthesized from a substituted alkyl group-containing polyalkylcresol having an average molecular weight of from about 650 to about 1500. In a further embodiment, the detergent of Mannich is synthesized from a polyalkylphenol or polyalkylcresol containing a substituent alkyl group, having an average molecular weight of from about 800 to about 1300.

In one embodiment, the Mannich detergent is synthesized from polybutylcresol. In another embodiment, the Mannich detergent is synthesized from a substituted alkyl group-containing polybutylcresol having an average molecular weight of about 650 to about 1500. In a further embodiment, the detergent of Mannich is synthesized from a polybutylcresol containing a substituent alkyl group, having an average molecular weight of from about 800 to about 1300.

Suitable amines used in the reaction to generate the Mannich detergent include, but are not limited to, alkylene polyamines having at least one primary or secondary amino group suitably reactive in the molecule. Other substituents such as hydroxyl, cyano and amido substituents may also be present in the polyamine.

In one embodiment, the alkylene polyamine used in the Mannich detergent generating reaction is a polyethylene polyamine. Suitable alkylenepolyamine reactants include, but are not limited to, ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, hexaethyleneheptamine, heptaethylene octamine, octaethylenenonamine, nonaethylenecamine, decaethyleneundecamine and mixtures of these amines having nitrogen contents corresponding to alkylene polyamines of the formula H 2 N- (CH 2 -CH 2 -NH) nH, wherein n represents an integer of 1 to 10. The corresponding propylenepolyamines are also suitable reactants. The alkylene polyamines can be obtained by reacting ammonia and dihaloalkanes, such as dichloroalkanes. Thus, the alkylene polyamines obtained by reacting 2 to 11 moles of ammonia with 1 to 10 moles of dichloroalkanes having 2 to 6 carbon atoms and the chlorine atoms on different carbon atoms are suitable alkylenepolyamine reactants.

In another embodiment, the amine used in the reaction to generate the Mannich detergent is an aliphatic diamine having a primary or secondary amino group and a tertiary amino group in the molecule. Examples of suitable polyamines include, but are not limited to, N, N, N '', N '' - tetraalkyldialkylene triamines (two terminal tertiary amino groups and one central secondary amino group), N, N, N ' , N '' - tetraalkyl-trialkylenetetramines (a terminal tertiary amino group, two internal tertiary amino groups and a terminal primary amino group), N, N, N ', N' ', N' '' - pentaalkyltrialkylene tetramines (a terminal tertiary amine group, two tertiary amino groups and a terminal secondary amino group), N, N-dihydroxyalkyl-alpha, omega-alkylenediamines (terminal tertiary amino group and terminal primary amino group), N, N, N tri-hydroxyalkyl-alpha, omega-alkylenediamines (a terminal tertiary amino group and a terminal secondary amino group), tris- (dialkylaminoalkyl) aminoalkylmethanes (three terminal tertiary amino groups and a terminal primary amino group) and similar compounds, wherein the groups alkyl are the same or different and may contain not more than about 12 carbon atoms each, and preferably contain 1 to 4 carbon atoms each. In one embodiment, the alkyl groups are methyl and / or ethyl groups. In another embodiment, the polyamine reactants are N, N-dialkyl-alpha, omega-alkylenediamines, such as those having 3 to about 6 carbon atoms in the alkylene group and 1 to about 12 carbon atoms. in each of the alkyl groups, which are preferably identical but which may be different. In a further embodiment, the polyamine reactant is N, N-dimethyl-1,3-propanediamine.

Examples of polyamines having a reactive primary or secondary amino group which may participate in the Mannich condensation reaction, and at least one hindered amino group which can not participate directly in the Mannich condensation reaction to any appreciable degree, include, but are not limited to, N- (tert-butyl) -1,3-propanediamine, N-neopentyl-1,3-propanediamine, N- (tert-butyl) -1-methyl-1,2-ethanediamine, N- (tert-butyl) -1-methyl-1,3-propanediamine and 3,5-di- (tert-butyl) aminoethylpiperazine.

In one embodiment, the amine incorporated in the reaction to synthesize the Mannich detergent is dibutylamine. Amines also useful herein for synthesizing Mannich detergent are dimethylamine, diethylamine and dipropylamine. Amines also useful herein are mixed alkylamines such as ethylpropylamine, propylbutylamine and mixtures of mono- and dialkylamines. Monoamines are also useful here.

Examples of aldehydes that can be used in the preparation of Mannich detergents include, but are not limited to, aliphatic aldehydes. In one embodiment, the aldehyde is formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, valeraldehyde, caproaldehyde, heptaldehyde or stearaldehyde. In another embodiment, the aldehyde is an aromatic aldehyde, such as benzaldehyde or salicylaldehyde. In a further embodiment, the aldehyde is a heterocylic aldehyde, such as furfural or thiophenealdehyde.

In a further embodiment, a formaldehyde producing reagent, such as paraformaldehyde or an aqueous formaldehyde solution, such as formalin, is used. In another embodiment, the aldehyde is formaldehyde or formaldehyde.

The condensation reaction between an alkyl substituted hydroxy-aromatic compound, an amine and an aldehyde may be conducted at a temperature in the range of about 40 ° C to about 200 ° C. The reaction can be conducted in bulk (no diluent or solvent) or in a solvent or diluent. Water is evolved and can be removed by azeotropic distillation during the reaction. In one embodiment, the Mannich detergents are formed by reacting an alkyl-substituted hydroxyaromatic compound, an amine and an aldehyde in a molar ratio of 1.0: 0.5-2.0: 1.0, respectively. -3.0. Succinimides (i) Alkenyl substituted succinic anhydride

The alkenyl substituted succinic anhydrides which are reacted with an amine-functional polyalkylene polymer to provide the reaction product incorporated in the compositions described herein generally have an average molecular weight of about 250 to about 3000. In one embodiment the average molecular weight of the alkenyl substituted succinic anhydride is from about 500 to about 2500. In another embodiment, the average molecular weight of the alkenyl substituted succinic anhydride is from about 600 to about 2000. In a further embodiment, the average molecular weight of the alkenyl substituted succinic anhydride is from about 750 to about 1500. In a further embodiment, the average molecular weight of the alkenyl substituted succinic anhydride is about 900 to about 1200. In another embodiment, the average molecular weight of the anhydride is uccinic alkenyl substituent is about 1050.

In one embodiment, the alkenyl substituted succinic anhydride comprises an alkenyl substituent group containing an average number of at least about 30 carbon atoms. In another embodiment, the alkenyl substituent group contains an average number of at least about 40 carbon atoms. In a further embodiment, the alkenyl substituent group contains an average number of at least about 50 carbon atoms. In another embodiment, the alkenyl substituent group contains an average number of at least about 60 carbon atoms. In another embodiment, the alkenyl substituent group contains an average number of at least about 75 carbon atoms. In a further embodiment, the alkenyl substituent group contains an average number of at least 100 carbon atoms.

In one embodiment, the alkenyl substituent group contains an average number of carbon atoms of from about 30 to about 150. In another embodiment, the alkenyl substituent group contains an average number of carbon atoms. in a further embodiment, the alkenyl substituent group contains an average number of carbon atoms of from about 50 to about 90. In a further embodiment, the alkenyl group serving Substituent contains an average number of about 80 carbon atoms.

In one embodiment, the alkenyl substituent group has an average molecular weight of about 200 to about 2950. In another embodiment, the alkenyl substituent group has an average molecular weight of about 450 to about 2450. In a further embodiment, the alkenyl substituent group has an average molecular weight of about 550 to about 1950. In a further embodiment, the alkenyl substituent group has an average molecular weight of about 700 to about 1450. In another embodiment, the alkenyl substituent group has an average molecular weight of about 850 to about 1150. In a further embodiment, the alkenyl substituent group has an average molecular weight of about 950.

Optionally, the alkenyl substituent group may include one or more carbon-carbon double bonds.

Non-limiting examples of alkenyl groups as suitable substituents include polyethylene, polypropylene, polybutene, poly (1-hexene), polyisobutene or poly (1-butene) or mixtures of poly (ethylene / propylene), poly (ethylene / butene), poly (propylene / 1-hexene), poly (isobutene) or poly (1-butene). The alkenyl substituent groups may be a mixture of any of these substituent groups and may optionally include molecules having different numbers of carbon atoms and / or different molecular weights. In addition, alkenyl substituent groups may be optionally substituted.

In one embodiment, the alkenyl substituent group is a poly (isobutene) group. In another embodiment, the alkenyl substituent group is a poly (isobutene) having an average molecular weight of about 200 to about 2950. In a further embodiment, the alkenyl substituent group is a poly (isobutene). ) in a further embodiment, the alkenyl substituent group is a poly (isobutene) having an average molecular weight of about 550 to about 1950. In another form In one embodiment, the alkenyl substituent group is a poly (isobutene) having an average molecular weight of about 700 to about 1450. In a further embodiment, the alkenyl substituent group is a poly (isobutene) having a weight. molecular weight of about 850 to about 1150. In another embodiment, the alkenyl substituent group is a poly (isobutene) having a weight average molecular weight of about 950.

A specific example of a suitable alkenyl substituted succinic anhydride includes, but is not limited to, polyisobutylenesuccinic anhydride ("PIBSA"). In one embodiment, the PIBSA has an average molecular weight of about 250 to about 3000. In another embodiment, the PIBSA has an average molecular weight of about 500 to about 2500. In a further embodiment, the PIBSA has an average molecular weight of about 600 to about 2000. In another embodiment, the PIBSA has an average molecular weight of about 750 to about 1500. In another embodiment, the PIBSA has a molecular weight averaging from about 900 to about 1200. In another embodiment, the PIBSA has an average molecular weight of about 1050.

In one embodiment, the PIBSA has a polyisobutenyl group containing an average number of at least about 30 carbon atoms. In another embodiment, the PIBSA has a polyisobutenyl group containing an average number of at least about 40 carbon atoms. In a further embodiment, the PIBSA has a polyisobutenyl group containing an average number of at least about 50 carbon atoms. In a further embodiment, PIBSA has a polyisobutenyl group containing an average number of at least about 60 carbon atoms. In another embodiment, the PIBSA has a polyisobutenyl group containing an average number of at least about 75 carbon atoms. In a further embodiment, PIBSA has a polyisobutenyl group containing an average number of at least 100 carbon atoms.

In one embodiment, the PIBSA has a polyisobutenyl group containing an average number of carbon atoms of from about 30 to about 150. In another embodiment, the PIBSA has a polyisobutenyl group containing an average number of carbon atoms. in a further embodiment, the PIBSA has a polyisobutenyl group containing an average number of carbon atoms of from about 50 to about 75. In a further embodiment, the PIBSA has a polyisobutenyl group containing an average number of carbon atoms of about 60.

Methods for the preparation of alkenyl substituted succinic anhydride are well known to those skilled in the art. For example, alkenyl-substituted succinic anhydrides can be prepared using a thermal process known as a "chemical process" (see, for example, US Pat. No. 3,361,673) and a chlorination process (see, for example, US Pat. U.S. Patent No. 3,172,892).

(ii) Amine Function Polyalkylene Polymer

The amine-functional polyalkylene polymer is a molecule having a straight or branched chain with at least one tertiary amine. The polyalkylene group of the amine-functional polyalkylene polymer is preferably relatively free of aliphatic unsaturation, i.e., ethylenic and acetylenic unsaturation, particularly acetylenic unsaturation. The polyalkylene group of the amine-functional polyalkylene polymer will generally be an unbranched chain.

In one embodiment, the amine-functional polyalkylene polymer has an average molecular weight of about 100 to about 750. In one embodiment, the amine-functional polyalkylene polymer has an average molecular weight of about 150. at about 650. In another embodiment, the amine-functional polyalkylene polymer has an average molecular weight of about 150 to about 500. In a further embodiment, the amine-functional polyalkylene polymer has a weight average molecular weight of about 400 to about 600.

In one embodiment, the average number of nitrogen atoms per molecule of the amine-functional polyalkylene polymer is from about 3.0 to about 18.0. In another embodiment, the average number of nitrogen atoms per molecule of the amine-functional polyalkylene polymer is from about 3.5 to about 17.5. In a further embodiment, the average number of nitrogen atoms per molecule of the amine-functional polyalkylene polymer is from about 3.0 to about 7.0. In a further embodiment, the average number of nitrogen atoms per molecule of the amine-functional polyalkylene polymer is from about 8.0 to about 16.0. In another embodiment, the average number of nitrogen atoms per molecule of the amine-functional polyalkylene polymer is from about 8.5 to about 15.5. In a further embodiment, the average number of nitrogen atoms per molecule of the amine-functional polyalkylene polymer is from about 9.0 to about 15.0.

In one embodiment, the average number of nitrogen atoms per molecule of the amine-functional polyalkylene polymer is from about 8.5 to about 9.5. In another embodiment, the average number of nitrogen atoms per molecule of the amine-functional polyalkylene polymer is from about 9.5 to about 10.5. In a further embodiment, the average number of nitrogen atoms per molecule of the amine-functional polyalkylene polymer is from about 14.5 to about 15.5.

In one embodiment, the amine-functional polyalkylene polymer is a mixture wherein the predominant amine-functional polyalkylene polymer contains at least about 3 nitrogen atoms per molecule. In another embodiment, the amine-functional polyalkylene polymer is a mixture wherein the predominant amine-functional polyalkylene polymer contains at least about 4 nitrogen atoms per molecule. In a further embodiment, the amine-functional polyalkylene polymer is a mixture in which the predominant amine-functional polyalkylene polymer contains at least about 5 nitrogen atoms per molecule. In a further embodiment, the amine-functional polyalkylene polymer is a mixture in which the predominant amine-functional polyalkylene polymer contains at least about 6 nitrogen atoms per molecule. In another embodiment, the amine-functional polyalkylene polymer is a mixture in which the predominant amine-functional polyalkylene polymer contains at least about 7 nitrogen atoms per molecule. In a further embodiment, the amine-functional polyalkylene polymer is a mixture wherein the predominant amine-functional polyalkylene polymer contains at least about 8 nitrogen atoms per molecule. In a further embodiment, the amine-functional polyalkylene polymer is a mixture wherein the predominant amine-functional polyalkylene polymer contains at least about 9 nitrogen atoms per molecule. In another embodiment, the amine-functional polyalkylene polymer is a mixture wherein the predominant amine-functional polyalkylene polymer contains at least about 10 nitrogen atoms per molecule. In a further embodiment, the amine-functional polyalkylene polymer is a mixture wherein the predominant amine-functional polyalkylene polymer contains at least about 11 nitrogen atoms per molecule. In a further embodiment, the amine-functional polyalkylene polymer is a mixture wherein the predominant amine-functional polyalkylene polymer contains at least about 12 nitrogen atoms per molecule. In another embodiment, the amine-functional polyalkylene polymer is a mixture wherein the predominant amine-functional polyalkylene polymer contains at least about 13 nitrogen atoms per molecule. In a further embodiment, the amine-functional polyalkylene polymer is a mixture wherein the predominant amine-functional polyalkylene polymer contains at least about 14 nitrogen atoms per molecule. In a further embodiment, the amine-functional polyalkylene polymer is a mixture wherein the predominant amine-functional polyalkylene polymer contains at least about 15 nitrogen atoms per molecule. In another embodiment, the amine-functional polyalkylene polymer is a mixture wherein the predominant amine-functional polyalkylene polymer contains at least about 16 nitrogen atoms per molecule.

Examples of suitable amine-functional polyalkylene polymers include, but are not limited to, tetraethylenepentamine ("ΤΕΡΑ"), triethylenetetramine ("TETA"), pentaethylenehexamine ("PEHA") and diethylenetriamine ("DETA "). In one embodiment, the amine-functional polyalkylene polymer is ΤΕΡΑ.

Process for the preparation of succinimides

The novel compositions described herein are more effective in minimizing fouling of the injectors and preventing valve deposits compared to other detergents. One possible reason for obtaining these results is that the novel compositions are more polar than these other detergents. The polarity of a detergent composition can be influenced by various factors, including the starting materials that are used, as well as the ratio of starting constituents, for example the ratio of alkenyl-substituted succinic anhydride and the polymer of the type amino-functional polyalkylenes used in the production of succinimide.

The alkenyl substituted succinic anhydride and the amine-functional polyalkylene polymer can be reacted in a molar ratio of from about 2.0: 1.0 to about 1.0: 1.3. In one embodiment, the alkenyl substituted succinic anhydride and the amine-functional polyalkylene polymer can be reacted in a molar ratio of about 1.0: 1.0.

compositions

The novel compositions of the invention contain (a) a Mannich detergent and (b) a succinimide which comprises a reaction product (i) of an alkenyl-substituted succinic anhydride having an average molecular weight of about 250 to about 3000 and (ii) an amine-functional polyalkylene polymer having an average molecular weight of from about 100 to about 750, wherein the alkenyl substituted succinic anhydride and the amine-functional polyalkylene polymer are present in the reaction. a molar ratio of from about 2.0: 1.0 to about 1.0: 1.3. In one embodiment, the novel composition contains (a) a Mannich detergent and (b) a succinimide which comprises a reaction product (i) of an alkenyl-substituted succinic anhydride having an average molecular weight of about 250 to about 3000 and (ii) an amine-functional polyalkylene polymer having an average molecular weight of about 100 to about 750, wherein the alkenyl substituted succinic anhydride and the amine-functional polyalkylene polymer are present in the Reaction in a mole ratio of about 2.0: 1.0 to about 1.0: 1.3 is incorporated in a fuel composition. In another embodiment, the Mannich detergent and succinimide which comprises a reaction product (i) of an alkenyl-substituted succinic anhydride having an average molecular weight of about 250 to about 3000 and (ii) a an amine-functional polyalkylene polymer having an average molecular weight of about 100 to about 750, wherein the alkenyl-substituted succinic anhydride and the amine-functional polyalkylene polymer are present in the reaction in a mole ratio of about 2 , 0: 1.0 to about 1.0: 1.3, are added individually to the fuel composition to obtain a novel composition. In a further embodiment, the novel composition contains (a) a Mannich detergent and (b) a succinimide which comprises a reaction product (i) of an alkenyl substituted succinic anhydride having an average molecular weight of about 250 at about 3000 and (ii) an amine-functional polyalkylene polymer having an average molecular weight of about 100 to about 750, wherein the alkenyl substituted succinic anhydride and the amine-functional polyalkylene polymer are present in the reaction in a mole ratio of about 2.0: 1.0 to about 1.0: 1.3, is formulated as an additive composition, such as a concentrate, and may be optionally added to a fuel composition prior to contacting the fuel composition with an engine, such as an engine that uses spark ignition fuels, an injector, including a fuel injector, and / or a valve, such as 'a soup admission.

In formulating a gasoline composition of the invention, the Mannich detergent and succinimide which comprises a reaction product (i) of an alkenyl-substituted succinic anhydride having an average molecular weight of about 250 to about 3000 and (ii) an amine-functional polyalkylene polymer having an average molecular weight of about 100 to about 750, wherein the alkenyl substituted succinic anhydride and the amine-functional polyalkylene polymer are present in the reaction in a mole ratio of about 2.0: 1.0 to about 1.0: 1.3, are each used in an amount sufficient to minimize fouling of the injectors, for example in a fuel injector, or to prevent deposits on valves, for example on intake valves. Thus, the fuel composition contains a small amount of the reaction product to control, or reduce, the formation of deposits and a dominant amount of a base fuel, such as a hydrocarbon.

The basic fuels used in the formulation of the fuel compositions of the invention include any of the basic fuels that can be suitably used in the operation of internal combustion and spark-ignition engines, such as leaded or unleaded gasolines. lead for engines and for aviation and gasolines termed reformulated gasolines which may contain both hydrocarbons in the boiling range of gasoline and oxygenating agents soluble in fuels, such as alcohols, ethers and other suitable oxygenated organic compounds. Oxygen compounds suitable for use in the invention include methanol, ethanol, isopropanol, t-butanol, mixed C 1 -C 5 alcohols, tert-butyl methyl ether, tert-butyl ethyl ether and mixed ethers. Oxygenates, when used, are usually present in the base fuel in an amount of less than about 25% by volume, and preferably in an amount that provides an oxygen content in the total fuel that is within the range of range from about 0.5 to about 5% by volume.

In one embodiment, the base fuel comprises a hydrocarbon. In another embodiment, the hydrocarbon comprises spark ignition fuel. In a further embodiment, the spark ignition fuel comprises gasoline. In a further embodiment, the spark ignition fuel comprises a mixture of hydrocarbons in the boiling range of gasoline and a fuel-soluble oxygenate compound.

In another embodiment, the fuel composition contains, based on the active ingredients, an amount of the reaction product of about 1.42 to about 1426.5 grams per cubic meter (g / m 3) of each ingredient. In a further embodiment, the fuel composition contains, based on the active ingredients, about 5.7 to about 285.3 g / m 3 of each ingredient. In a further embodiment, the fuel composition contains, based on the active ingredients, about 8.56 to about 257 g / m 3 of each ingredient.

In one embodiment, the fuel composition contains about 142.6 to 427.9 g / m 3 of the Mannich detergent and about 2.85 to about 28.53 g / m 3 of the succinimide which comprises a reaction product (i) an alkenyl-substituted succinic anhydride having an average molecular weight of about 250 to about 3000; and (ii) an amine-functional polyalkylene polymer having an average molecular weight of about 100 to about 750, where Alkenyl substituted succinic anhydride and the amine-functional polyalkylene polymer are present in the reaction in a mole ratio of about 2.0: 1.0 to about 1.0: 1.3. In another embodiment, the fuel composition contains about 213.9 to about 285.3 g / m 3 of the Mannich detergent and about 5.7 to about 19.97 g / m 3 of the succinimide which comprises a reaction product ( i) an alkenyl-substituted succinic anhydride having an average molecular weight of about 250 to about 3000 and (ii) an amine-functional polyalkylene polymer having an average molecular weight of about 100 to about 750, where the alkenyl substituted succinic anhydride and the amine-functional polyalkylene polymer are present in the reaction in a mole ratio of about 2.0: 1.0 to about 1.0: 1.3.

In another embodiment, the Mannich detergent and succinimide which comprises a reaction product (i) of an alkenyl-substituted succinic anhydride having an average molecular weight of about 250 to about 3000 and (ii) a an amine-functional polyalkylene polymer having an average molecular weight of about 100 to about 750, wherein the alkenyl-substituted succinic anhydride and the amine-functional polyalkylene polymer are present in the reaction in a mole ratio of about 2 , 0: 1.0 to about 1.0: 1.3, may be formulated as an additive composition, such as a concentrate, and may be optionally added to a fuel composition prior to contacting. with the engine, such as an engine that uses spark ignition fuels, an injector, including a fuel injector, and / or a valve, such as an intake valve. Mannich detergent and succinimide which comprises a reaction product (i) of an alkenyl-substituted succinic anhydride having an average molecular weight of about 250 to about 3000 and (ii) an amine-functional polyalkylene polymer having an average molecular weight of from about 100 to about 750, wherein the alkenyl substituted succinic anhydride and the amine-functional polyalkylene polymer are present in the reaction in a molar ratio of about 2.0: 1.0 to about about 1.0: 1.3, can be formulated into the additive composition with a carrier. In one embodiment, the support is a liquid fluid serving as a vehicle.

In one embodiment, the additive composition contains about 20 to about 80% by weight of each of the Mannich detergent agents and the succinimide which comprises a reaction product (i) of alkenyl substituted succinic anhydride having an average molecular weight of about 250 to about 3000 and (ii) an amine-functional polyalkylene polymer having an average molecular weight of about 100 to about 750, wherein the alkenyl-substituted succinic anhydride and the polymer Amine-functional polyalkylene compounds are present in the reaction in a mole ratio of about 2.0: 1.0 to about 1.0: 1.3. In one embodiment, the additive composition contains about 30 to about 50% by weight of each of the Mannich detergent agents and the succinimide which comprises a reaction product (i) of alkenyl substituted succinic anhydride having an average molecular weight of about 250 to about 3000 and (ii) an amine-functional polyalkylene polymer having an average molecular weight of about 100 to about 750, wherein the alkenyl-substituted succinic anhydride and the polymer Amine-functional polyalkylene compounds are present in the reaction in a mole ratio of about 2.0: 1.0 to about 1.0: 1.3.

In another embodiment, the additive composition may contain about 20 to about 70% by weight of the carrier. In a further embodiment, the additive composition may contain about 30 to about 50% by weight of the liquid vehicle fluid.

In general, the weight ratio of the carrier to each of the Mannich detergent and succinimide agents which comprises a reaction product (i) of an alkenyl substituted succinic anhydride having an average molecular weight of about 250 to about 3000 and (ii) an amine-functional polyalkylene polymer having an average molecular weight of from about 100 to about 750, wherein the alkenyl substituted succinic anhydride and the amine-functional polyalkylene polymer are present in the reaction. a molar ratio of from about 2.0: 1.0 to about 1.0: 1.3, based on the active ingredients, is usually from about 1.6: 1 to about 2: 1. In one embodiment, the weight ratio of the carrier to each of the Mannich detergent agents and succinimide which comprises a reaction product (i) of an alkenyl-substituted succinic anhydride having an average molecular weight of about 250 at about 3000 and (ii) an amine-functional polyalkylene polymer having an average molecular weight of about 100 to about 750, wherein the alkenyl substituted succinic anhydride and the amine-functional polyalkylene polymer are present in the reaction in a molar ratio of from about 2.0: 1.0 to about 1.0: 1.3, based on the active ingredients, is usually from about 1.6: 1 to about 1: 1. The active ingredient base excludes the weight (i) of the unreacted alkenyl substituted succinic anhydride or the amine-functional polyalkylene polymer associated with and remaining in the product as produced and used, and (ii) the solvent (s), if any, used in the production of Mannich detergent and / or succinimide which comprises a reaction product (i) of an alkenyl substituted succinic anhydride having a weight of average molecular weight of about 250 to about 3000 and (ii) an amine-functional polyalkylene polymer having an average molecular weight of about 100 to about 750, wherein alkenyl-substituted succinic anhydride and polyalkylene-type polymer The amino functional groups are present in the reaction in a mole ratio of about 2.0: 1.0 to about 1.0: 1.3, during or after formation but before the addition of the carrier.

The proportion of the carrier used relative to each of the Mannich detergent and succinimide agents which comprises a reaction product (i) of an alkenyl substituted succinic anhydride having an average molecular weight of about 250 to about 3000 and (ii) an amine-functional polyalkylene polymer having an average molecular weight of from about 100 to about 750, wherein the alkenyl substituted succinic anhydride and the amine-functional polyalkylene polymer are present in the reaction in one reaction. molar ratio of about 2.0: 1.0 to about 1.0: 1.3, in the additive formulations of the invention, is such that the fuel composition containing the diluted additive composition, when its consumption in an engine, such as an engine that uses fuels for spark ignition, results in improved cleanliness, compared to the cleanliness of the same engine operating with the same composition of bus except for the lack of support with the new composition.

The carrier fluid component of the fuel compositions and fuel additive compositions described herein may also include a first base oil derived from a gaseous source. Gaseous sources include a wide variety of materials such as natural gas, methane, C1 to C3 alkanes, household waste gases and the like. These gases can be converted into liquid hydrocarbon products which can be suitably used as vehicles by a gas-to-liquid process (GTL), such as the process described in U.S. Pat. No. 6,497,812, the specification of which is incorporated herein by reference. For purposes of this specification, a "gas" or "gaseous source" is a material that is in a gaseous state at ambient temperature and at atmospheric pressure. A "liquid" consists of a material which is primarily in the liquid or fluid state at ambient temperature and at atmospheric pressure.

Gaseous source derived fluids or oils, hereinafter referred to as "GTL base oils", usually have a viscosity number greater than about 130, a sulfur content of less than about 0.3% by weight, contain greater than about 90% by weight of saturated hydrocarbons (isoparaffins), usually about 95 to about 100% by weight of branched aliphatic hydrocarbons, have a pour point of 15 to -20 ° C, and have volatility NOACK less than about 15% by weight and, in another embodiment, a NOACK volatility of less than about 10% by weight. The carrier oil used as a component of the fuel composition, as described herein, may comprise from about 5 to about 100% by weight of the GTL oil with the remainder of the carrier oil being a conventional base oil. .

Conventional base oils that may optionally be combined with the GTL base oil to provide a fuel composition include natural and synthetic Group I to V basic and base oils as specified in the base oil interchangeability indications. ("Base Oil Interchangeability Guidelines") of the American Petroleum Institute (API).

Alternatively, the proportion of carrier used relative to each of the detergent agents of

Mannich and succinimide which comprises a reaction product (i) of an alkenyl-substituted succinic anhydride having an average molecular weight of about 250 to about 3000 and (ii) an amine-functional polyalkylene polymer having a weight average molecular weight of from about 100 to about 750, wherein the alkenyl substituted succinic anhydride and the amine-functional polyalkylene polymer are present in the reaction in a mole ratio of about 2.0: 1.0 to about 1, 0: 1.3, in the additive formulations of the invention, is such that the fuel composition containing the diluted additive composition, when consumed in an injector, such as a fuel injector, has as its result improved cleanliness, compared with the cleanliness of the same injector operating with the same fuel composition, with the exception of the lack of support with the new composition.

Furthermore, the proportion of the carrier used relative to each of the Mannich detergent and succinimide agents which comprises a reaction product (i) of an alkenyl substituted succinic anhydride having an average molecular weight of about 250 to about 3000 and (ii) an amine-functional polyalkylene polymer having an average molecular weight of about 100 to about 750, wherein the alkenyl substituted succinic anhydride and the amine-functional polyalkylene polymer are present in the reaction in a mole ratio of about 2.0: 1.0 to about 1.0: 1.3, in the additive formulations of the invention, is such that the fuel composition containing the diluted additive composition when consumed at a valve, such as an intake valve, results in improved cleanliness compared to the cleanliness of the same valve operating with the same fuel composition, with the exception of n of the absence of the support with the new composition.

The additive compositions used in the formulation of the preferred fuels of the invention may be blended with the fuel, such as spark ignition fluid, individually, or in the form of various sub-combinations. In one embodiment, all the components are mixed together using an additive concentrate as this allows to take advantage of the mutual compatibility offered by the combination of ingredients when it is in the form of a concentrate of additives. . In addition, the use of a concentrate reduces mixing time and reduces the possibility of mixing errors.

In addition to the Mannich detergent and succinimide which comprises a reaction product (i) of an alkenyl-substituted succinic anhydride having an average molecular weight of about 250 to about 3000 and (ii) a polyalkylene-type polymer having an amine function having an average molecular weight of from about 100 to about 750, wherein the alkenyl substituted succinic anhydride and the amine-functional polyalkylene polymer are present in the reaction in a mole ratio of about 2.0: 1, 0 to about 1.0: 1.3, the fuel compositions and / or additive concentrates may optionally contain additional components. For example, the fuel compositions and / or additive concentrates may include one or more vehicle fluids, friction modifiers, detergents, dispersants, valve seat shrinkage reducing agents, combustion, antioxidants, thermal stabilizers, anti-icing additives, anti-knock additives, corrosion inhibitors, anti-theft agents, metal deactivators, anti-foaming agents, biocides, cosolvents, formulation compatibilizers, additives lubricity, antistatic additives, friction reducing agents, colorants, labels, cold flow improving additives, demulsifiers, etc. Similarly, the fuel compositions and / or additive concentrates may contain suitable amounts of conventional fuel blend components, such as methanol, ethanol, dialkyl ethers and the like.

One embodiment of the invention includes a method for reducing the amount of deposits in an engine, which comprises contacting the engine with a fuel composition comprising a dominant amount of a hydrocarbon and a small proportion or a small amount of each of the Mannich detergent and succinimide agents which comprises a reaction product (i) of an alkenyl substituted succinic anhydride having an average molecular weight of about 250 to about 3000 and (ii) a polymer amine-functional polyalkylene type having an average molecular weight of about 100 to about 750, wherein the alkenyl-substituted succinic anhydride and the amine-functional polyalkylene polymer are present in the reaction in a molar ratio of about 2, 0: 1.0 to about 1.0: 1.3. In another embodiment, the invention includes a method for reducing the amount of deposits in an engine that uses a spark ignition fuel, which comprises contacting the engine with a fuel composition comprising a dominant amount of fuel. a hydrocarbon and a small proportion or a small amount of each of the Mannich detergent and succinimide agents which comprises a reaction product (i) of an alkenyl substituted succinic anhydride having an average molecular weight of about 250 to about 3000 and (ii) an amine-functional polyalkylene polymer having an average molecular weight of about 100 to about 750, wherein the alkenyl substituted succinic anhydride and the amine-functional polyalkylene polymer are present in the reaction in a molar ratio of from about 2.0: 1.0 to about 1.0: 1.3.

Another embodiment of the invention includes a method for minimizing fouling of the injectors, comprising contacting an injector with a fuel composition comprising a major amount of a hydrocarbon and a small amount of each Mannich detergent and succinimide agents which comprises a reaction product (i) of an alkenyl-substituted succinic anhydride having an average molecular weight of about 250 to about 3000 and (ii) a polymer of the type amine-functional polyalkylene having an average molecular weight of from about 100 to about 750, wherein the alkenyl-substituted succinic anhydride and the amine-functional polyalkylene polymer are present in the reaction at a molar ratio of about 2.0: 1.0 to about 1.0: 1.3. In a further embodiment, the invention includes a method for minimizing fouling of the injectors, comprising contacting a fuel injector with a fuel composition comprising a dominant amount of a hydrocarbon and a small amount of fuel. amount of each of the Mannich detergent and succinimide agents which comprises a reaction product (i) of an alkenyl substituted succinic anhydride having an average molecular weight of about 250 to about 3000 and (ii) a an amine-functional polyalkylene polymer having an average molecular weight of about 100 to about 750, wherein the alkenyl-substituted succinic anhydride and the amine-functional polyalkylene polymer are present in the reaction in a mole ratio of about 2 0: 1.0 to about 1.0: 1.3. In a further embodiment, the invention comprises a method for minimizing fouling of the injectors, comprising contacting a fuel injector with a fuel composition comprising a dominant amount of a fuel for ignition by fuel. and a small amount of each of the Mannich detergent and succinimide agents which comprises a reaction product (i) of an alkenyl-substituted succinic anhydride having an average molecular weight of about 250 to about 3000 and (ii) ) an amine-functional polyalkylene polymer having an average molecular weight of from about 100 to about 750, wherein the alkenyl-substituted succinic anhydride and the amine-functional polyalkylene polymer are present in the reaction in a molar ratio from about 2.0: 1.0 to about 1.0: 1.3.

One embodiment of the invention comprises a method for preventing deposits on a valve, comprising contacting a valve with a fuel composition comprising a major amount of a hydrocarbon and a small amount of each of the agents. Mannich detergent and succinimide which comprises a reaction product (i) of an alkenyl-substituted succinic anhydride having an average molecular weight of about 250 to about 3000 and (ii) a polyalkylene-type polymer having an amine function having an average molecular weight of from about 100 to about 750, wherein the alkenyl substituted succinic anhydride and the amine-functional polyalkylene polymer are present in the reaction in a mole ratio of about 2.0: 1, 0 to about 1.0: 1.3. In a further embodiment, the invention comprises a method for preventing deposits on an intake valve, comprising contacting an intake valve with a fuel composition comprising a major amount of a hydrocarbon and a small amount of each of the Mannich detergent and succinimide agents which comprises a reaction product (i) of an alkenyl-substituted succinic anhydride having an average molecular weight of about 250 to about 3000 and (ii) an amine-functional polyalkylene polymer having an average molecular weight of from about 100 to about 750, wherein the alkenyl substituted succinic anhydride and the amine-functional polyalkylene polymer are present in the reaction in a molar ratio of about 2.0: 1.0 to about 1.0: 1.3. In a further embodiment, the invention comprises a method for preventing deposits on an intake valve, comprising contacting a fuel injector with a fuel composition comprising a dominant amount of a fuel for fuel. spark ignition and a small amount of each of the Mannich detergent and succinimide agents which comprises a reaction product (i) of an alkenyl-substituted succinic anhydride having an average molecular weight of about 250 to about 3000 and (ii) an amine-functional polyalkylene polymer having an average molecular weight of from about 100 to about 750, wherein the alkenyl substituted succinic anhydride and the amine-functional polyalkylene polymer are present in the reaction in one molar ratio of about 2.0: 1.0 to about 1.0: 1.3.

In certain embodiments, the reaction between alkenyl substituted succinic anhydride having an average molecular weight of about 250 to about 3000 and the amine-functional polyalkylene polymer having an average molecular weight of about 100 to about 750, wherein the alkenyl substituted succinic anhydride and the amine-functional polyalkylene polymer are present in the reaction in a molar ratio of from about 2.0: 1.0 to about 1.0: 1.3, may occur in the liquid serving as a vehicle. The Mannich detergent may then be added to the carrier liquid before or after the reaction of the alkenyl substituted succinic anhydride and the amine-functional polyalkylene polymer.

In some embodiments, the preformed succinimide is mixed with a suitable amount of the carrier liquid. The Mannich detergent may be mixed with the carrier liquid before or after the addition of the succinimide. If desired, the product of the reactants may be formed in a suitable solvent or a suitable vehicle liquid and may then be mixed with an additional amount of the same carrier liquid or a different liquid.

In some embodiments, the Mannich detergent may be mixed with the succinimide prior to mixing the one or the other component with the carrier liquid.

All of the patents and publications cited herein are incorporated herein by reference in their entirety.

EXAMPLES EXAMPLE 1

Synthesis of a PIBSA

178 g of maleic anhydride and 1435 g of a polyisobutylene (molecular weight equal to 950) were introduced into a reactor. The reaction mixture was heated to 235 ° C and refluxed for 5 hours.

A sample of the mixture was taken and a driving acid number was determined. The target range was 1.03 to 1.07. If the drive acid value was below the target range, a small amount of maleic anhydride (17-18 g) was added and the reaction was continued until the target value was reached.

Then, excess maleic anhydride was removed from the reactor by stripping for 2 hours at 230-235 ° C under a vacuum of 7999-9332 Pa.

EXAMPLE 2

Synthesis of a succinimide

The PIBSA of Example 1 was charged to a reactor under a nitrogen atmosphere and heated to 167 ° C. Then, approximately 300 g of ΤΕΡΑ were added, so that the molar ratio of PIBSA to ΤΕΡΑ was 1.0: 1.0. The rate of addition of ΤΕΡΑ to the mixture of PIBSA depends on the degree of foaming.

The vacuum was slowly brought to 9332 Pa. The water was then removed by stripping the reaction mixture for approximately 2.5 hours.

The substance was then filtered at 150 ° C.

Nitrogen content ranged from 6.2 to 6.4% and total basicity ranged from 140 to 160. Infrared analysis and 13C-NMR showed peaks. carbonyl groups.

The viscosity of the product at 100 ° C was usually above 2300 cSt.

EXAMPLE 3

Results of the FPI frame test

The results of various additive formulations are shown below in Table 1.

TABLE 1

The Mannich detergent formulation contained 4.56 g / m 3 of a succinimide which was the reaction product obtained by reaction of PIBSA and ΤΕΡΑ in a molar ratio of 1.6: 1.0.

The succinimide used was the reaction product obtained by reaction of PIBSA and ΤΕΡΑ in a molar ratio of 1.0: 1.0.

It goes without saying that the present invention has been described for explanatory purposes, but in no way limiting, and that many modifications can be made without departing from its scope.

Claims (53)

A gasoline additive composition, characterized in that it comprises (a) a Mannich detergent and (b) a succinimide which is a reaction product (i) of an alkenyl-substituted succinic anhydride having a molecular weight from about 250 to about 3000 and (ii) an amine-functional polyalkylene polymer having an average molecular weight of from about 100 to about 750, alkenyl substituted succinic anhydride and polyalkylene functional polymer. amine being present in the reaction in a mole ratio of about 2.0: 1.0 to about 1.0: 1.3. 2. A composition according to claim 1 characterized in that the alkenyl-substituted succinic anhydride has an average molecular weight of about 600 to about 2000. 3. A composition according to claim 1, characterized in that the alkenyl substituent group of the alkenyl substituted succinic anhydride has an average molecular weight of about 200 to about 2950. 4. A composition according to claim 1, characterized in that the alkenyl-substituted succinic anhydride is polyisobutylenesuccinic anhydride. 5. The composition of claim 4, wherein the polyisobutylene succinic anhydride has an average molecular weight of about 600 to about 2000. The composition of claim 4, wherein the alkenyl substituent group of polyisobutylene succinic anhydride has an average molecular weight of about 200 to about 2950. The composition of claim 1 wherein the amine-functional polyalkylene polymer has an average molecular weight of about 125 to about 650. 8. A composition according to claim 1, characterized in that the amine-functional polyalkylene polymer is a mixture in which the predominant amine-functional polyalkylene polymer contains at least about 4 nitrogen atoms per molecule. The composition of claim 1 wherein the average number of nitrogen atoms per molecule of the amine-functional polyalkylene polymer is from about 3.0 to about 18.0. 10. Composition according to claim 1, characterized in that the polyalkylene-amine-functional polymer is tetraethylenepentamine. 11. Composition according to claim 1, characterized in that the alkenyl-substituted succinic anhydride is polyisobutylenesuccinic anhydride and the amine-functional polyalkylene polymer is tetraethylenepentamine. The composition of claim 1 wherein the alkenyl substituted succinic anhydride and the amine-functional polyalkylene polymer are present in the reaction at a molar ratio of about 1.6: 1.0 to about 1 , 0: 1.0. 13. A composition according to claim 1, characterized in that the Mannich detergent comprises the reaction product of at least one alkyl-substituted hydroxyaromatic compound, an aldehyde and at least one amine. 14. A composition according to claim 13, characterized in that the alkyl-substituted hydroxyaromatic compound is an alkyl-substituted cresol. 15. Composition according to claim 14, characterized in that the alkyl-substituted cresol is polybutylphenol. 16. A composition according to claim 15, characterized in that the polybutylphenol has an average molecular weight of about 750 to about 1200. 17. Composition according to claim 13, characterized in that the amine comprises at least one aliphatic diamine having a primary or secondary amino group and a tertiary amino group in the molecule. 18. Composition according to Claim 17, characterized in that the amine comprises dibutylamine. 19. Composition according to claim 13, characterized in that the aldehyde is formaldehyde. 20. Composition according to claim 13, characterized in that the alkyl-substituted hydroxyaromatic compound is an alkyl-substituted cresol, the aldehyde is formaldehyde and the amine is dibutylamine. 21. A composition according to claim 1 further comprising at least one additive selected from the group consisting of vehicle fluids, friction modifiers, detergents, dispersants, reducing agents, valve seats, combustion improvers, antioxidants, heat stabilizers, anti-icing additives, anti-knock additives, corrosion inhibitors, anti-theft agents, metal deactivators, defoamers, biocides, co-solvents, formulation compatibility agents, lubricity additives, antistatic additives, friction reducing agents, dyes, labels, cold flow improvers and demulsifiers. 22. Fuel composition of the gasoline type, characterized in that it comprises (a) a hydrocarbon, (b) a Mannich detergent and (c) a succinimide which comprises a reaction product (i) of a succinic anhydride with alkenyl substituent having an average molecular weight of about 250 to about 3000 and (ii) an amine-functional polyalkylene polymer having an average molecular weight of about 100 to about 750, alkenyl-substituted succinic anhydride and the like. The amine-functional polyalkylene polymer is present in the reaction in a mole ratio of about 2.0: 1.0 to about 1.0: 1.3. 23. Fuel composition according to claim 22, characterized in that Mannich detergent and succinimide are each present in a small amount. 24. Fuel composition according to claim 22, characterized in that the hydrocarbon comprises a fuel for ignition by spark. 25. Fuel composition according to claim 24, characterized in that the fuel for spark ignition comprises gasoline. Fuel composition according to claim 25, characterized in that the spark ignition fuel comprises a mixture of hydrocarbons in the boiling range of the gasoline and a fuel-soluble oxygen compound. 27. Fuel composition according to claim 22, characterized in that the alkenyl-substituted succinic anhydride has an average molecular weight of about 600 to about 2000. 28. Fuel composition according to claim 22, characterized in that the alkenyl substituent group of the alkenyl substituted succinic anhydride has an average molecular weight of about 200 to about 2950. 29. Fuel composition according to claim 22, characterized in that the alkenyl-substituted succinic anhydride is polyisobutylenesuccinic anhydride. 30. Fuel composition according to claim 29, characterized in that the polyisobutylene succinic anhydride has an average molecular weight of about 600 to about 2000. 31. The fuel composition according to claim 29, characterized in that the alkenyl substituent group of polyisobutylene succinic anhydride has an average molecular weight of about 200 to about 2950. 32. Fuel composition according to claim 22, characterized in that the amine-functional polyalkylene polymer has an average molecular weight of about 125 to about 650. 33. Fuel composition according to claim 22, characterized in that the amine-functional polyalkylene polymer is a mixture in which the predominant amine-functional polyalkylene polymer contains at least about 4 nitrogen atoms per molecule. 34. Fuel composition according to claim 22, characterized in that the average number of nitrogen atoms per molecule of the amine-functional polyalkylene polymer is from about 3.0 to about 18.0. 35. Fuel composition according to claim 22, characterized in that the amine-functional polyalkylene polymer is tetraethylenepentamine. 36. Fuel composition according to claim 22, characterized in that the alkenyl-substituted succinic anhydride is polyisobutylenesuccinic anhydride and the amine-functional polyalkylene polymer is tetraethylenepentamine. 37. Fuel composition according to claim 22, characterized in that the alkenyl-substituted succinic anhydride and the amine-functional polyalkylene polymer are present in the reaction in a molar ratio of about 1.6: 1.0 to about about 1.0: 1.0. 38. Fuel composition according to claim 22, characterized in that the Mannich detergent comprises the reaction product of at least one alkyl-substituted hydroxyaromatic compound, an aldehyde and at least one amine. 39. Fuel composition according to claim 38, characterized in that the alkyl-substituted hydroxyaromatic compound is an alkyl-substituted cresol. 40. Fuel composition according to claim 39, characterized in that the alkyl-substituted cresol is polybutylphenol. 41. Fuel composition according to claim 40, characterized in that the polybutylphenol has an average molecular weight of about 750 to about 1200. 42. Fuel composition according to claim 38, characterized in that the amine comprises at least one aliphatic diamine having a primary or secondary amino group and a tertiary amino group in the molecule. 43. Fuel composition according to claim 42, characterized in that the amine comprises dibutylamine. 44. Fuel composition according to claim 38, characterized in that the aldehyde is formaldehyde. 45. Fuel composition according to claim 38, characterized in that the alkyl substituted hydroxyaromatic compound is an alkyl-substituted cresol, the aldehyde is formaldehyde and the amine is dibutylamine. 46. Fuel composition according to claim 22, characterized in that the succinimide and the Mannich detergent are each present in an amount of about 0.5 to about 500 millionths. 47. Fuel composition according to claim 22, characterized in that it further contains an additive selected from the group consisting of vehicle fluids, friction modifiers, detergents, dispersants, reducing agents, valve seats, combustion improvers, antioxidants, heat stabilizers, anti-icing additives, anti-knock additives, corrosion inhibitors, anti-theft agents, metal deactivators, defoamers, biocides, co-solvents, formulation compatibility agents, lubricity additives, antistatic additives, friction reducing agents, dyes, labels, cold flow improvers and demulsifiers. 48. Engine, characterized in that it comprises the composition of claim 1. 49. An engine, characterized in that it comprises the fuel composition of claim 22. 50. A method for preventing the fouling of injectors of gasoline engines, characterized in that it comprises contacting an injector with the composition of claim 1. 51. A method for preventing the fouling of the injectors, characterized in that it comprises contacting an injector with the fuel composition of claim 22. 52. Process for preventing deposits on the valves, characterized in that it comprises the step of providing the composition of claim 1. A method of preventing valve deposits, characterized in that it comprises the step of providing the fuel composition of claim 22.