DE102007015453A1 - Additives to minimize injector clogging and valve deposits and their applications - Google Patents

Abstract

The invention relates to compositions for use in minimizing injector clogging, such as in fuel injectors, and to preventing deposits in valves, such as injectors, comprising (a) a Mannich detergent and (b) a succinimide which includes a reaction product of (i) an alkenyl-substituted succinic anhydride having an average molecular weight of about 250 to about 3,000; and (ii) an amine-containing polyalkylene polymer having an average molecular weight of about 100 to about 750, wherein the alkenyl-substituted succinic anhydride and the amine-containing polyalkylene polymer in the reaction in a molar ratio of about 2.0: 1.0 to about 1.0: 1.3.

Description

BACKGROUND OF THE INVENTION

Field of the invention

The This invention relates to compositions for use in minimization injector clogging, as with fuel injectors, and prevention deposits in valves, such as intake valves, comprising (a) a Mannich detergent and (b) a particular succinimide.

State of the art

The Use of conventional Accelerated fuels without detergent and corrosion inhibiting additives the accumulation of deposits in the induction system in particular at the injectors, which clog, or even in the combustion chamber, what about the presence of polar aromatic compounds and traces derived from lubricants.

The Accumulation of deposits has a detrimental effect on the quality fuel evaporation, resulting in an increase in consumption, one Increase in the emission of pollutants and smoke during the Acceleration is much larger, and finally to a noise increase leads.

Around To solve this problem of clogging of the engine, it is possible that clogged components and in particular the injectors regularly from Time to time to clean. However, this procedure will be long-term very expensive.

One Another method for reducing clogging by deposits in engines, including Injectors, is the use of detergents that are able to be absorbed on the metal surfaces, to prevent the formation of deposits and / or already To remove deposits formed by cleaning the injectors. examples for Such detergents are the products of the condensation of polyalkenyl succinic anhydrides with polyamines, such as tetraethylenepentamine ("TEPA"), described in U.S. Patent No. 3,172,892.

BRIEF SUMMARY OF THE INVENTION

The Compositions of the invention can as detergents to prevent the formation of deposits and / or to remove already formed deposits in injectors, such as Fuel injectors, and / or in valves, including from Injectors, are used.

at In one aspect, the disclosure herein relates to novel fuel compositions, comprising or consisting essentially of (a) a Mannich detergent and (b) a succinimide which is a reaction product of (i) a Alkenyl-substituted succinic anhydride having an average molecular weight from about 250 to about 3,000 and (ii) an amine-containing polyalkylene polymer having an average molecular weight of about 100 to about 750, wherein the alkenyl-substituted succinic anhydride and the amine-containing Polyalkylene polymer in the reaction in a molar ratio of from about 2.0: 1.0 to about 1.0: 1.3.

at In another aspect, the disclosure herein 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 of (i) an alkenyl-substituted succinic anhydride having a middle one Molecular weight of about 250 to about 3,000 and (ii) an amine-containing Polyalkylene polymer having an average molecular weight of about 100 to about 750, wherein the alkenyl-substituted succinic anhydride and the amine-containing polyalkylene polymer in the reaction in a molar ratio from about 2.0: 1.0 to about 1.0: 1.3.

at In yet another aspect, the disclosure herein relates to gasoline additive compositions comprising or consisting essentially of (a) a Mannich detergent and (b) a succinimide which is a reaction product of (i) an alkenyl-substituted one Succinic anhydride having an average molecular weight of about 250 to about 3,000 and (ii) an amine-containing polyalkylene polymer having an average molecular weight of about 100 to about 750, wherein the alkenyl-substituted succinic anhydride and the amine-containing Polyalkylene polymer in the reaction in a molar ratio of from about 2.0: 1.0 to about 1.0: 1.3.

at In yet another aspect, the disclosure relates to a method for preventing injector clogging, such as 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 of (i) a Alkenyl-substituted succinic anhydride having an average molecular weight from about 250 to about 3,000 and (ii) an amine-containing polyalkylene polymer having an average molecular weight of about 100 to about 750, wherein the alkenyl-substituted succinic anhydride and the amine-containing Polyalkylene polymer in the reaction in a molar ratio of from about 2.0: 1.0 to about 1.0: 1.3.

at In another aspect, the disclosure relates to a method for preventing deposits in a valve, such as an inlet valve, comprising bringing the valve into contact with a new composition, comprising or consisting essentially of (a) a Mannich detergent and (b) a succinimide which is a reaction product of (i) a Alkenyl-substituted succinic anhydride having an average molecular weight from about 250 to about 3,000 and (ii) an amine-containing polyalkylene polymer having an average molecular weight of about 100 to about 750, wherein the alkenyl-substituted succinic anhydride and the amine-containing Polyalkylene polymer in the reaction in a molar ratio of from about 2.0: 1.0 to about 1.0: 1.3.

at In yet another aspect, the disclosure relates to one here An engine comprising a novel composition comprising or consisting consisting essentially of (a) a Mannich detergent and (b) a succinimide, a reaction product of (i) an alkenyl-substituted succinic anhydride with a average molecular weight from about 250 to about 3,000 and (ii) an amine-containing polyalkylene polymer having an average molecular weight from about 100 to about 750, wherein the alkenyl-substituted succinic anhydride and the amine-containing polyalkylene polymer in the reaction in a molar ratio from about 2.0: 1.0 to about 1.0: 1.3.

DETAILED DESCRIPTION OF THE INVENTION

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 of (i) a Alkenyl-substituted succinic anhydride having an average molecular weight from about 250 to about 3,000 and (ii) an amine-containing polyalkylene polymer having an average molecular weight of about 100 to about 750, wherein the alkenyl-substituted succinic anhydride and the amine-containing Polyalkylene polymer in the reaction in a molar ratio of from about 2.0: 1.0 to about 1.0: 1.3.

As As used herein, the singular forms include "a" or "an" or "the" multiple references unless it is because, it is clearly specified otherwise in the text. For example includes the reference to "an alkenyl-substituted Succinic anhydride "one Composition containing only a specific alkenyl-substituted succinic anhydride includes, and a composition containing a mixture of alkenyl-substituted ones Succinic anhydrides.

As used here, the term "about" includes the Range of experimental error that occurs with each measurement.

As As used herein, the term "present in the reaction" indicates that the starting materials, the be used to produce the succinimide that in the new Composition is included, mixed under conditions and / or are mixed, which lead to the formation of succinimide.

The Invention provides both a gasoline additive concentrate and a ready or additive offset gasoline fuel product.

Mannich detergents

The Mannich detergents used in new compositions can, can by reaction of 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 may be used in the formation of the Mannich detergents include, but are not limited to, polypropylphenol (formed by alkylation of phenol with polypropylene), polybutylphenols (formed by alkylation of Phenol with polybutenes and / or polyisobutylene), polybutyl-co-polypropylphenols (formed by alkylating phenol with a copolymer of butylene and / or butylene and propylene), polypropyl cresol (formed by alkylating cresol with polypropylene), polybutyl cresols (formed by alkylation of Cresol with polybutenes and / or polyisobutylene), polybutyl-co-polypropyl cresols (formed by alkylation of cresol with a copolymer of butylene and / or butylene and propylene). Other comparable long-chain alkylphenols can also be used. Examples include, but are not limited to, phenols or cresols which are alkylated with copolymers of butylene and / or isobutylene and / or propylene, and one or more monoolefinic copolymers copolymerizable therewith (eg, ethylene, 1-pentene, 1-). Hexene, 1-octene, 1-decene, etc.), wherein the copolymer molecule contains at least 50% by weight of butylene and / or isobutylene and / or propylene units. The comonomers polymerized with propylene or the butenes may be aliphatic and may also contain non-aliphatic groups, eg styrene, o-methylstyrene, p-methylstyrene, divinylbenzene and the like. Thus, the resulting polymers and copolymers used in forming the alkyl-substituted hydroxyaromatic compounds are essentially aliphatic hydrocarbon polymers.

at an embodiment the alkyl-substituted hydroxyaromatic compound is polybutylphenol (formed by alkylation of phenol with polybutylene). At a another embodiment the alkyl-substituted hydroxyaromatic compound is polybutylcresol (formed by alkylation of cresol with polybutynes). Unless otherwise stated herein, the term "polybutylene" is used in a generic sense that polymers prepared from "pure" or "substantially pure" 1-butene or isobutene and polymers consisting of mixtures of 2 or all 3 of 1-butene, 2-butene and isobutene are included. Commercially available qualities of such Polymers can also contain not appreciable amounts of other olefins. So-called highly reactive polybutylenes with relatively high levels of polymer molecules a terminal vinylidene group formed by methods such as For example, in U.S. Pat. No. 4,152,499 and in the West German Publication 29 04 314 described are also for use in the formation of the long-chain alkylated phenol or cresol reactant suitable.

The alkylation of the hydroxyaromatic compound may be carried out in the presence of an alkylation catalyst, such as BF ₃ , at a temperature in the range of from about 50 to about 200 ° C. The long-chain alkyl substituent groups on the benzene ring of the phenol or cresol molecule are derived from the polyolefin having an average molecular weight of from about 500 to about 3,000, as determined by gel permeation chromatography ("GPC"). In one embodiment, the polyolefin has an average molecular weight of from about 500 to about 2,000.

at an embodiment has the ability to derive the long-chain alkyl substituent groups polyolefin used on the benzene ring of the phenol or cresol molecule polydispersity (Weight average molecular weight / average molecular weight) from about 1 to about 4 as determined by GPC. With another embodiment has the ability to derive the long-chain alkyl substituent groups polyolefin used on the benzene ring of the phenol or cresol molecule polydispersity from about 1 to about 2.

The Mannich detergent can be selected from a long chain alkylphenol or a long-chain alkylcresol are produced. However, more can be done phenolic compounds are used, including, however not limited high molecular weight alkyl-substituted derivatives of resorcinol, hydroquinone, Catechin, xylenol, hydroxydiphenyl, benzylphenol, phenethylphenol, Naphthol and tolylnaphthol.

at an embodiment the Mannich detergent is prepared from a polyalkylphenol or a Polyalkylcresol synthesized, such as polypropylphenol, polybutylphenol, Polypropyl cresol and polybutyl cresol, but is not limited thereto. at another embodiment is the Mannich detergent from a polyalkylphenol or polyalkyl cresol, containing an alkyl substituent group having an average molecular weight from about 650 to about 1,500, synthesized. In another embodiment is the Mannich detergent from a polyalkylphenol or polyalkyl cresol, containing an alkyl substituent group having an average molecular weight from about 800 to about 1,300, synthesized.

at an embodiment For example, the Mannich detergent is prepared from a polyalkyl cresol such as polypropyl cresol and polybutylcresol, but not limited to, synthesized. At a Another embodiment will the Mannich detergent of a polyalkyl cresol containing one Alkyl substituent group having an average molecular weight of about 650 to about 1,500, synthesized. At another one embodiment becomes the Mannich detergent from a polyalkylphenol or a polyalkylcresol containing an alkyl substituent group having an average molecular weight of about 800 to about 1,300, synthesized.

at an embodiment The Mannich detergent is synthesized from polybutyl cresol. at another embodiment The Mannich detergent is made of polybutyl cresol containing one Alkyl substituent group having an average molecular weight of about 650 to about 1,500, synthesized. At another one embodiment becomes the Mannich detergent of polybutylcresol containing an alkyl substituent group with an average molecular weight of about 800 to about 1,300.

suitable Amines used in the reaction to produce the Mannich detergent used include, but are not limited to, Alkylenepolyamines with at least one expediently reactive primary or secondary Amino group in the molecule. Other substituents, such as hydroxy, cyano and amido, may also be used be present in the polyamine.

In one embodiment, the alkylene polyamine used in the reaction that produces the Mannich detergent is a polyethylene polyamine. Suitable alkylenepolyamine reactants include, but are not limited to, ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, hexaethyleneheptamine, heptaethyleneoctamine, octaethylenemoneamine, nonaethylene decamine, decaethyleneundecamine, and mixtures of such amines with nitrogen contents corresponding to alkylene polyamines of the formula H ₂ N- (CH ₂ -CH ₂ -NH-) _n H, where n is an integer from 1 to 10. Corresponding propylene polyamines are also suitable reactants. The alkylene polyamines can be obtained by the reaction of ammonia and dihaloalkanes, such as dichloroalkanes. Thus, the alkylene polyamines obtained from the reaction of 2 to 11 moles of ammonia with 1 to 10 moles of dichloroalkanes of 2 to 6 carbon atoms and the chlorine atoms on different carbon atoms are suitable alkylene polyamine reactants.

at another embodiment is the amine used in the reaction to produce the Mannich detergent is used, an aliphatic diamine having a primary or secondary Amino group and a tertiary one Amino group in the molecule. examples for suitable polyamines include, but are not limited to, N, N, N '', N '' - -tetraalkyldialkylenetriamines (two terminal tertiary Amino groups and a central secondary amino group), N, N, N ', N "-tetraalkyltrialkylenetetramine (a terminal tertiary Amino group, two internal tertiary Amino groups and a terminal primary amino group), N, N, N ', N' ', N' '' - pentaalkyltrialkylenetetramine (a terminal tertiary Amino group, two internal tertiary Amino groups and a terminal secondary amino group), N, N-dihydroxyalkyl-alpha, omega-alkylenediamines (a terminal tertiary Amino group and a terminal primary amino group), N, N, N'-trihydroxyalkyl-alpha, omega-alkylenediamine (a terminal tertiary Amino group and a terminal secondary amino group), tris (dialkylaminoalkyl) aminoalkylmethane (three terminal tertiary Amino groups and a terminal primary amino group), and the like Compounds wherein the alkyl groups are the same or different and not more than about 12 carbon atoms each, and which preferably each contain 1 to 4 carbon atoms. at an embodiment the alkyl groups are methyl and / or ethyl groups. With another embodiment are the polyamine reactants N, N-dialkyl-alpha, omega-alkylenediamine, 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 particularly preferably the same, but different could be. Again, another embodiment is the polyamine reactant N, N-dimethyl-1,3-propanediamine.

Examples for polyamines with a reactive primary or secondary Amino group participating in the Mannich condensation reaction can, and with at least one sterically hindered amino group, the at the Mannich condensation reaction not directly in a significant Participate in extent may 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.

at an embodiment is the amine included in the reaction to synthesize the Mannich detergent is, dibutylamine. Also here are for the synthesis of the Mannich detergent dimethylamine, diethylamine, and dipropylamine. Also here are mixed alkylamines, such as ethylpropylamine, propylbutylamine and mixtures of mono- and Dialkylamines suitable. Monoamines are also suitable here.

Examples of aldehydes that may be used in the preparation of the 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 yet another embodiment, the aldehyde is a heterocyclic aldehyde, such as furfural or thiophene aldehyde. In yet another embodiment, a formaldehyde generator is used reagent such as paraformaldehyde or an aqueous formaldehyde solution such as formalin. In another embodiment, the aldehyde is formaldehyde or formalin.

The Condensation reaction between an alkyl-substituted hydroxy-aromatic Compound, an amine and an aldehyde may be at a temperature in the range of about 40 ° C up to about 200 ° C carried out become. The reaction may be carried out in bulk (without diluent or solvent) or in a solvent or diluents carried out become. Water is developed and can be produced by azeotropic distillation while the course of the reaction are removed. In one embodiment become the Mannich detergents by reaction of an alkyl-substituted hydroxyaromatic compound, an amine and an aldehyde in the molar ratio of 1.0: 0.5-2.0: 1.0-3.0, respectively educated.

succinimides

(i) alkenyl-substituted succinic anhydride

The Alkenyl-substituted succinic anhydrides containing an amine-containing Polyalkylene polymer are reacted to the reaction product included in the compositions disclosed herein is generally of average molecular weight about 250 to about 3,000. In one embodiment, the mean is Molecular weight of the alkenyl-substituted succinanide about 500 to about 2,500. In a further embodiment, the mean is Molecular weight of the alkyl-substituted succinic anhydride about 600 until about 2,000. In yet another embodiment, the mean is Molecular weight of the alkenyl-substituted succinic anhydride, for example 750 to about 1,500. Again, another embodiment is the average molecular weight of the alkenyl-substituted succinic anhydride about 900 to about 1,200. In another embodiment, the mean is Molecular weight of the alkenyl-substituted succinic anhydride, for example 1050.

at an embodiment the alkenyl-substituted succinic anhydride comprises an alkenyl-substituted group, containing on average at least about 30 carbon atoms. at another embodiment contains the alkenyl substituent group averages at least about 40 carbon atoms. Again, another embodiment For example, the alkenyl substituent group has an average of at least about 50 carbon atoms. In yet another embodiment contains the alkenyl substituent group averages at least about 60 carbon atoms. In another embodiment, the alkenyl substituent group contains an average of at least about 75 carbon atoms. at again another embodiment contains the alkenyl substituent group averages at least 100 Carbon atoms.

at an embodiment contains the alkenyl substituent group has an average number of carbon atoms from about 30 to about 150. In another embodiment, the alkenyl substituent group contains an average number of carbon atoms of about 40 to about 100. In yet another embodiment, the alkenyl substituent group contains an average number of carbon atoms of about 50 to about 90. In yet another embodiment, the alkenyl substituent group contains an average number of about 80 carbon atoms.

at an embodiment the alkenyl substituent group has an average molecular weight of about 200 to about 2,950. In another embodiment, the alkenyl substituent group an average molecular weight of about 450 to about 2,450. at again another embodiment the alkenyl substituent group has an average molecular weight from about 550 to about 1,950. Again, another embodiment the alkenyl substituent group has an average molecular weight from about 700 to about 1,450. In another embodiment the alkenyl substituent group has an average molecular weight from about 850 to about 1,150. In another embodiment form the alkenyl substituent group has an average molecular weight from about 950.

Possibly For example, the alkenyl substituent group may have one or more carbon-carbon double bonds lock in.

Non-limiting examples of suitable alkenyl substituent groups include polyethylene, polypropylene, polybutene, poly (1-hexene), polyisobutene or q-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 consist of a mixture of any of these substituent groups, and may optionally contain molecules having different numbers of carbon atoms and / or Include molecular weights. In addition, the alkenyl substituent groups may be optionally substituted.

at an embodiment the alkenyl substituent group is poly (isobutene). With another embodiment the alkenyl substituent group is poly (isobutene) having a middle one Molecular weight of about 200 to about 2,950. At another one embodiment the alkenyl substituent group is poly (isobutene) having a middle one Molecular weight of about 450 to about 2,450. At another one embodiment the alkenyl substituent group is poly (isobutene) having a middle one Molecular weight of about 550 to about 1,950. With another embodiment the alkenyl substituent group is poly (isobutene) having a middle one Molecular weight of about 700 to about 1450. At another one embodiment the alkenyl substituent group is poly (isobutene) having a middle one Molecular weight of about 850 to about 1150. At another one embodiment the alkenyl substituent group is poly (isobutene) having a middle one Molecular weight of about 950.

One special example of is a suitable alkenyl-substituted succinic anhydride but not limited on, polyisobutylene succinic anhydride ("PIBSA"). In one embodiment, PIBSA has a middle one Molecular weight from about 250 to about 3,000. With another embodiment PIBSA has an average molecular weight of about 500 to about 2500. In yet another embodiment, PIBSA has one average molecular weight of about 600 to about 2,000. At again another embodiment has PIBSA an average molecular weight of about 750 to about 1,500. at another embodiment PIBSA has an average molecular weight of about 900 to about 1,200. Again, another embodiment PIBSA has an average molecular weight of about 1,050.

at an embodiment PIBSA has a polyisobutylene group that averages at least about Contains 30 carbon atoms. In another embodiment PIBSA has a polyisobutylene group that averages at least Contains 40 carbon atoms. Again, another embodiment has PIBSA is a polyisobutylene group that averages at least contains about 50 carbon atoms. at again another embodiment PIBSA has a polyisobutylene group that averages at least contains about 60 carbon atoms. In another embodiment PIBSA has a polyisobutylene group that averages at least contains about 75 carbon atoms. Again, another embodiment PIBSA has a polyisobutylene group that averages at least Contains 100 carbon atoms.

at an embodiment PIBSA has a polyisobutylene group which has an average Number of carbon atoms from about 30 to about 150 contains. at another embodiment PIBSA has a polyisobutylene group which has an average Number of carbon atoms from about 40 to about 100 contains. at again another embodiment PIBSA has a polyisobutylene group which has an average Number of carbon atoms from about 50 to about 75 contains. at again another embodiment PIBSA has a polyisobutylene group which has an average Number of carbon atoms of about 60 contains.

method for the preparation of the alkenyl-substituted succinic anhydride well known to those skilled in the art. For example, alkenyl-substituted Succinic anhydrides using a thermal process, the as "ene-chemistry" (see, for example, US Pat No. 3,361,673), and a chlorination process (see z. U.S. Patent No. 3,172,892).

(ii) Amine-containing polyalkylene polymer

The Amine-containing polyalkylene polymer is a molecule having a straight or branched chain with at least one tertiary amine. The polyalkylene group of the amine-containing Polyalkylene polymer is preferably relatively free of aliphatic Unsaturation d. H. an ethylenic and acetylenic, especially acetylenic Unsaturation. The polyalkylene group of the amine-containing polyalkylene polymer is generally a straight chain.

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

at an embodiment is the average number of nitrogen atoms per molecule of the amine-containing Polyalkylene polymer about 3.0 to about 18.0. In another embodiment is the average number of nitrogen atoms per molecule of amine-containing Polyalkylene polymer about 3.5 to about 17.5. At another one embodiment is the average number of nitrogen atoms per molecule of the amine-containing Polyalkylene polymer about 3.0 to about 7.0. At another one embodiment is the average number of nitrogen atoms per molecule of the amine-containing Polyalkylene polymer about 8.0 to about 16.0. In another embodiment is the average number of nitrogen atoms per molecule of the amine-containing polyalkylene polymer about 8.5 to about 15.5. In yet another embodiment, the average Number of nitrogen atoms per molecule of the amine-containing polyalkylene polymer about 9.0 to about 15.0.

at an embodiment is the average number of nitrogen atoms per molecule of the amine-containing Polyalkylene polymer about 8.5 to about 9.5. In another embodiment is the average number of nitrogen atoms per molecule of the amine-containing Polyalkylene polymer about 9.5 to about 10.5. At another one embodiment is the average number of nitrogen atoms per molecule of the amine-containing Polyalkylene polymer about 14.5 to about 15.5.

at an embodiment For example, the amine-containing polyalkylene polymer is a mixture in which the predominant amine-containing polyalkylene polymer at least about 3 nitrogen atoms per molecule contains. at another embodiment For example, the amine-containing polyalkylene polymer is a mixture in which the predominant amine-containing polyalkylene polymer at least about 4 nitrogen atoms per molecule contains. at another embodiment For example, the amine-containing polyalkylene polymer is a mixture in which the predominant amine-containing polyalkylene polymer at least about 5 nitrogen atoms per molecule contains. at again another embodiment For example, the amine-containing polyalkylene polymer is a mixture in which the predominant amine-containing polyalkylene polymer at least about Contains 6 nitrogen atoms per molecule. at another embodiment For example, the amine-containing polyalkylene polymer is a mixture in which the predominant amine-containing Polyalkylenpolymer contains at least about 7 nitrogen atoms per molecule. at again another embodiment For example, the amine-containing polyalkylene polymer is a mixture in which the predominant amine-containing polyalkylene polymer at least about 8 nitrogen atoms per molecule contains. Again, another embodiment For example, the amine-containing polyalkylene polymer is a mixture in which the predominant amine-containing Polyalkylenpolymer contains at least about 9 nitrogen atoms per molecule. at another embodiment For example, the amine-containing polyalkylene polymer is a mixture in which the predominant amine-containing polyalkylene polymer at least contains about 10 nitrogen atoms per molecule. At another one embodiment is the amine-containing Polyalkylene polymer is a mixture in which the predominant amine-containing Polyalkylenpolymer contains at least about 11 nitrogen atoms per molecule. at again another embodiment For example, the amine-containing polyalkylene polymer is a mixture in which the predominant amine-containing polyalkylene polymer at least contains about 12 nitrogen atoms per molecule. In another embodiment For example, the amine-containing polyalkylene polymer is a mixture in which the predominant amine-containing polyalkylene polymer is at least about 13 nitrogen atoms per molecule contains. Again, another embodiment For example, the amine-containing polyalkylene polymer is a mixture in which the predominant amine-containing polyalkylene polymer at least contains about 14 nitrogen atoms per molecule. At another one embodiment For example, the amine-containing polyalkylene polymer is a mixture in which the predominant amine-containing polyalkylene polymer at least contains about 15 nitrogen atoms per molecule. In another embodiment For example, the amine-containing polyalkylene polymer is a mixture in which the predominant amine-containing polyalkylene polymer at least contains about 16 nitrogen atoms per molecule.

Examples for suitable Amine-containing polyalkylene polymers include, but are not limited tetraethylenepentamine ("TEPA"), triethylenetetramine ("TETA"), pentaethylenehexamine ("PEHA") and diethylenetriamine ( "DETA"). In one embodiment is the amine-containing polyalkylene polymer TEPA.

Process for the preparation the succinimide

The novel compositions described herein are more effective than other detergents in minimizing injector clogging and preventing deposits in valves. One possible rationale for these results is that the new compositions are more polar than these other detergents. The polarity of a detergent composition can be affected by various factors, including which starting materials are used, and the ratio of starting components, such as the ratio of the alkenyl-substituted succinic anhydride and the Amine-containing polyalkylene polymer used in the production of the succinimide.

The Alkenyl-substituted succinic anhydride and the amine-containing polyalkylene polymer can in a molar ratio from about 2.0: 1.0 to about 1.0: 1.3. In one embodiment For example, the alkenyl-substituted succinic anhydride and the amine-containing Polyalkylene polymer reacted in a molar ratio of about 1.0: 1.0 become.

compositions

The novel compositions of the invention contain (a) a Mannich detergent and (b) a succinimide, the a reaction product of (i) an alkenyl-substituted succinic anhydride having an average molecular weight of about 250 to about 3,000 and (ii) an amine-containing polyalkylene polymer having a middle one Molecular weight of about 100 to about 750, wherein the alkenyl-substituted Succinic anhydride and the amine-containing Polyalkylene polymer in the reaction in a molar ratio of from about 2.0: 1.0 to about 1.0: 1.3. In one embodiment is the new composition that is (a) a Mannich detergent and (b) contains a succinimide, a reaction product of (i) an alkenyl-substituted succinic anhydride having an average molecular weight of about 250 to about 3,000 and (ii) an amine-containing polyalkylene polymer having a middle one Molecular weight of about 100 to about 750, wherein the alkenyl-substituted Succinic anhydride and the amine-containing polyalkylene polymer in the reaction in a molar ratio from about 2.0: 1.0 to about 1.0: 1.3, in a fuel composition locked in. In another embodiment, the Mannich detergent and the succinimide, a reaction product of (i) an alkenyl-substituted succinic anhydride having an average molecular weight of about 250 to about 3,000 and (ii) an amine-containing polyalkylene polymer having a middle one Molecular weight of about 100 to about 750, wherein the alkenyl-substituted Succinic anhydride and the amine-containing polyalkylene polymer in the Reaction in a molar ratio from about 2.0: 1.0 to about 1.0: 1.3, of the fuel composition individually added to give a new composition. at again another embodiment is the new composition, which (a) a Mannich detergent and (b) contains a succinimide, a reaction product of (i) an alkenyl-substituted succinic anhydride having an average molecular weight of about 250 to about 3,000 and (ii) an amine-containing polyalkylene polymer having a middle one Molecular weight of about 100 to about 750, wherein the alkenyl-substituted Succinic anhydride and the amine-containing polyalkylene polymer in the Reaction in a molar ratio from about 2.0: 1.0 to about 1.0: 1.3, as an additive composition formulated as a concentrate, and may optionally be a fuel composition be added before the fuel composition with a Engine, like an engine that uses spark ignition fuels, including an injector a fuel injector, and / or a valve, such as an injection valve, is brought into contact.

Becomes a gasoline composition according to the invention formulated, the Mannich detergent and the succinimide which is a reaction product of (i) an alkenyl-substituted one Succinic anhydride having an average molecular weight of about 250 to about 3,000 and (ii) an amine-containing polyalkylene polymer having an average molecular weight of about 100 to about 750, wherein the alkenyl-substituted succinic anhydride and the amine-containing Polyalkylene polymer in the reaction in a molar ratio of about 2.0: 1.0 to about 1.0: 1.3, each in an amount used to minimize injector clogging, as in a fuel injector, or to prevent deposits in valves, such as in injectors, sufficient. Thus, the fuel composition contains a small amount of the reaction product to the formation of deposits to control or minimize, and a large amount a basic fuel, such as a hydrocarbon.

The basic fuels used in formulating the fuel compositions of the present invention include any of the base fuels suitable for use in the operation of internal spark-ignition internal combustion engines, such as a leaded or unleaded engine, and aviation gasolines and so-called reformulated gasolines, both Gasoline boiling range hydrocarbons as well as fuel-soluble oxygenated mixing agents, such as alcohols, ethers, and other suitable oxygen-containing organic compounds. Oxigenates suitable for use in the present invention include methanol, ethanol, isopropanol, t-butanol, mixed C ₁ to C ₅ alcohols, methyl tertiary butyl ether, tertiary amyl methyl ether, ethyl tert. butyl ether and mixed ethers. Oxigenates, when used, will normally be present in the base fuel in an amount below about 25% by volume and preferably in an amount containing an oxygen content in the total fuel in the range of about 0.5 to about 5% by volume. provides.

at an embodiment the base fuel comprises a hydrocarbon. In another embodiment For example, the hydrocarbon comprises a spark ignition fuel. At again another embodiment includes the spark ignition fuel Petrol. In yet another embodiment, the spark ignition fuel comprises a mixture of hydrocarbons of the gasoline boiling range and a fuel-soluble oxygenated compound.

at another embodiment contains the fuel composition, based on an active ingredient, an amount of the reaction product of from about 0.5 to about 500 pounds per 1,000 barrels ("PTB") of each ingredient. Again, another embodiment contains the fuel composition, based on an active ingredient, from about 2 to about 100 PTB of each component. At another one another embodiment contains the fuel composition, based on an active ingredient, from about 3 to about 90 PTB of each component.

at an embodiment contains the fuel composition is about 50 to about 150 PTB of the Mannich detergent and about 1 to about 10 PTB of the succinimide which is a reaction product of (i) an alkenyl-substituted succinic anhydride having a middle one Molecular weight of about 250 to about 3,000 and (ii) an amine-containing Polyalkylene polymer having an average molecular weight of about 100 to about 750, where the alkenyl-substituted Succinic anhydride and the amine-containing polyalkylene polymer in the Reaction in a molar ratio from about 2.0: 1.0 to about 1.0: 1.3. In another embodiment contains the fuel composition is about 75 to about 100 PTB of Mannich detergent and from about 2 to about 7 PTB of succinimide, which is a reaction product of (i) an alkenyl-substituted succinic anhydride having a middle one Molecular weight of about 250 to about 3,000 and (ii) an amine-containing Polyalkylene polymer having an average molecular weight of about 100 to about 750, where the alkenyl-substituted Succinic anhydride and the amine-containing polyalkylene polymer in the Reaction in a molar ratio from about 2.0: 1.0 to about 1.0: 1.3.

at another embodiment can the Mannich detergent and succinimide, which is a reaction product of (i) an alkenyl-substituted succinic anhydride having a middle one Molecular weight of about 250 to about 3,000 and (ii) an amine-containing Polyalkylene polymer having an average molecular weight of about 100 to about 750, wherein the alkenyl-substituted succinic anhydride and the amine-containing Polyalkylene polymer in the reaction in a molar ratio of from about 2.0: 1.0 to about 1.0: 1.3, as an additive composition, like a concentrate, can be formulated and possibly before Contacting the engine, such as an engine, the spark ignition fuels used an injector, including a fuel injector, and / or a valve, such as an injector, of a fuel composition be added. The Mannich detergent and succinimide, the a reaction product of (i) an alkenyl-substituted succinic anhydride having an average molecular weight of about 250 to about 3,000 and (ii) an amine-containing polyalkylene polymer having a middle one Molecular weight of about 100 to about 750, wherein the alkenyl-substituted succinic anhydride and the amine-containing polyalkylene polymer in the reaction in a molar ratio of about 2.0: 1.0 to about 1.0: 1.3 are present be formulated in the additive composition with a carrier. At a embodiment is the carrier a liquid Carrier fluid.

at an embodiment contains the additive composition is about 20 to about 80 weight percent each of the Mannich detergent and succinimide, which is a reaction product of (i) an alkenyl-substituted succinic anhydride having an average molecular weight of about 250 to about 3,000 and (ii) an amine-containing polyalkylene polymer having a middle one Molecular weight of about 100 to about 750, wherein the Alkenyl-substituted succinic anhydride and the amine-containing polyalkylene polymer in the reaction in a molar ratio of about 2.0: 1.0 to about 1.0: 1.3 are present. In one embodiment, the additive composition contains from about 30 to about 50 weight percent of each of the Mannich detergent and the succinimide, the one A reaction product of (i) an alkenyl-substituted succinic anhydride with a average molecular weight from about 250 to about 3,000 and (ii) an amine-containing polyalkylene polymer having an average molecular weight from about 100 to about 750, wherein the alkenyl-substituted Succinic anhydride and the amine-containing polyalkylene polymer in the Reaction in a molar ratio from about 2.0: 1.0 to about 1.0: 1.3.

at another embodiment For example, the additive composition may contain from about 20 to about 70 percent by weight of the carrier. Again, another embodiment For example, the additive composition may be about 30 to about 50 weight percent of the liquid carrier fluid contain.

In general, the weight ratio of carrier to each of the Mannich detergent and the succinimide comprising a reaction product of (i) an alkenyl-substituted succinic anhydride having an average molecular weight of about 250 to about 3,000 and (ii) an amine-containing polyalkylene polymer having an average molecular weight of about 100 to 750 wherein the alkenyl-substituted one Succinic anhydride and the amine-containing polyalkylene polymer are present in the reaction in a molar ratio of about 2.0: 1.0 to about 1.0: 1.3, based on an active ingredient, usually about 1.6: 1 to about 2 :1. In one embodiment, the weight ratio of carrier to each of the Mannich detergent and the succinimide which is a reaction product of (i) an alkenyl-substituted succinic anhydride having an average molecular weight of about 250 to about 3,000 and (ii) an amine-containing polyalkylene polymer an average molecular weight of about 100 to about 750, wherein the alkenyl-substituted succinic anhydride and the amine-containing polyalkylene polymer are present in the reaction in a molar ratio of about 2.0: 1.0 to about 1.0: 1.3, based on an active ingredient, generally about 1.6: 1 to about 1: 1. The active ingredient base includes the weight of (i) the unreacted alkenyl-substituted succinic anhydride or the amine-containing polyalkylene polymer associated with and remaining in the thus prepared and used product, and (ii) solvent (s), if present ) used in the preparation of the Mannich detergent and / or succinimide, which is a reaction product of (i) an alkenyl-substituted succinic anhydride having an average molecular weight of from about 250 to about 3,000 and (ii) an amine-containing polyalkylene polymer having an average molecular weight of about 100 to about 750, wherein the alkenyl-substituted succinic anhydride and the amine-containing polyalkylene polymer in the reaction in a molar ratio of about 2.0: 1.0 to about 1.0: 1.3, either during or after its formation, but before the addition of the carrier.

Of the Proportion of the carrier used relative to each of the Mannich detergent and succinimide, the a reaction product of (i) an alkenyl-substituted succinic anhydride having an average molecular weight of about 250 to about 3,000 and (ii) an amine-containing Polyalkylene polymer having an average molecular weight of about 100 to about 750, wherein the alkenyl-substituted succinic anhydride and the amine-containing polyalkylene polymer in the reaction in a molar ratio of about 2.0: 1.0 to about 1.0: 1.3 is present in the additive packages of this invention so that the fuel composition containing the diluted additive composition contains at consumption in an engine, such as an engine, the spark ignition fuels used, for improved cleanliness compared to cleanliness of the same engine, operated with the same fuel composition, except that the carrier with the new composition is missing.

The carrier fluid component of the fuel and fuel additive compositions described herein may also include a first base oil derived from a gas source. Gas sources include a wide variety of materials such as natural gas, methane, C ₁ -C ₃ alkanes, landfill gases, and the like. Such gases may be converted to liquid hydrocarbon products suitable for use as carrier fluids by a gas-to-liquid (GTL) process, such as the process described in US Pat. No. 6,497,812, the disclosure of which is incorporated herein by reference is. For purposes of this disclosure, a "gas" or "gas source" means a material that is gaseous at room temperature and atmospheric pressure. A "liquid" means a material that is predominantly in a liquid or fluid state at room temperature and atmospheric pressure.

carrier fluids or oils, derived from a gas source, hereafter referred to as "GTL base oils", typically have a viscosity index greater than about 130, a sulfur content of less than about 0.3 wt%, contain more than about 90% by weight of saturated hydrocarbons (isoparaffins), typically about 95 to about 100 weight percent branched aliphatic Hydrocarbons, have a pour point below 15 to -20 ° C and have a NOACK volatility less than about 15% by weight, and in another embodiment a NOACK volatility less than about 10% by weight. The carrier oil component of the fuel composition, as described herein may include from about 5 to about 100 weight percent of the GTL oil, wherein the remainder of the carrier oil component a conventional one base oil is.

conventional Base oils which may optionally be combined with the GTL base oil To provide a fuel composition include natural and synthetic base oils in Groups I-V, as in the American Petroleum Institute (API) Base Oil Interchangeability Guidelines specified.

Alternatively, the proportion of carrier used is relative to the Mannich detergent and succinimide which is a reaction product of (i) an alkenyl-substituted succinic anhydride having an average molecular weight of from about 250 to about 3,000 and (ii) an amine-containing polyalkylene polymer an average molecular weight of about 100 to about 750, wherein the alkenyl-substituted succinic anhydride and the amine-containing polyalkylene polymer in the reaction in a molar ratio of about 2.0: 1.0 to about 1.0: 1.3 are present in the additive packages of the invention such that the fuel composition containing the dilute additive composition when consumed in an injector, such as a fuel injector, results in improved cleanliness in the air Comparing to the cleanliness of the same injector operated with the same fuel composition, except that the carrier with the new composition is missing.

Besides that is the proportion of the carrier used relative to the Mannich detergent and the succinimide, respectively a reaction product of (i) an alkenyl-substituted succinic anhydride having an average molecular weight of about 250 to about 3,000 and (ii) an amine-containing polyalkylene polymer having a middle one Molecular weight of about 100 to about 750, wherein the alkenyl-substituted succinic anhydride and the amine-containing polyalkylene polymer in the reaction in a molar ratio of about 2.0: 1.0 to about 1.0: 1.3 are present in the additive packages according to the invention so that the fuel composition containing the diluted additive composition contains when consumption in a valve, such as an injection valve, to a improved cleanliness compared to the cleanliness of the same Valve leads, operated with the same fuel composition, except that the carrier with the new composition is missing.

The in the formulation of the preferred fuels of the invention used additive compositions can the fuel as a Spark ignition fluid, individually or mixed in different sub-combinations. In one embodiment be all components simultaneously using an additive concentrate mixed, since it takes advantage of mutual compatibility, which is supplied by the combination of components, if they are in the form of an additive concentrate. Also reduced the use of a concentrate reduces the mixing time and reduces the possibility of mixed mistakes.

In addition to Mannich detergent and succinimide, which is a reaction product of (i) an alkenyl-substituted succinic anhydride having a middle one Molecular weight of about 250 to about 3,000 and (ii) an amine-containing Polyalkylene polymer having an average molecular weight of about 100 to about 750, wherein the alkenyl-substituted succinic anhydride and the amine-containing Polyalkylene polymer in the reaction in a molar ratio of about 2.0: 1.0 to about 1.0: 1.3, the fuel compositions and / or additive concentrates optionally contain additional components. For example, you can the fuel compositions and / or additive concentrates or more carrier fluids, Friction modifiers, detergents, dispersants, antistain press-fit reducing agents, Combustion improvers, antioxidants, heat stabilizers, deicing additives, Anti-knock additives, corrosion inhibitors, demisters, metal deactivators, Antifoam agents, biocides, cosolvents, Package compatibilizer, lubricity additives, antistatic additives, drag reducing agents, dyes, markers, Cold flow additives, demulsifiers and the like include. Similarly, the Fuel compositions and / or additive concentrates suitable Quantities of conventional Mixed fuel components such as methanol, ethanol, dialkyl ethers and the same.

A embodiment The invention includes a method for reducing the amount of deposits an engine, which is the bringing together of the engine with a fuel composition that includes a large one Amount of a hydrocarbon and a small proportion of a small one Each comprising Mannich detergent and succinimide, a reaction product of (i) an alkenyl-substituted succinic anhydride having an average molecular weight of about 250 to about 3,000 and (ii) an amine-containing polyalkylene polymer having a middle one Molecular weight of about 100 to about 750, wherein the alkenyl-substituted Succinic anhydride and the amine-containing polyalkylene polymer in the Reaction in a molar ratio from about 2.0: 1.0 to about 1.0: 1.3. With another embodiment For example, the invention includes a method of reducing the amount of deposits an engine that uses a spark ignition fuel used, which involves bringing the engine into contact with a fuel composition, the one big one Amount of a hydrocarbon and a small proportion of a small one Each comprising Mannich detergent and succinimide, a reaction product of (i) an alkenyl-substituted succinic anhydride having an average molecular weight of about 250 to about 3,000 and (ii) an amine-containing polyalkylene polymer having a middle one Molecular weight of about 100 to about 750, wherein the alkenyl-substituted Succinic anhydride and the amine-containing polyalkylene polymer in the reaction in a molar ratio from about 2.0: 1.0 to about 1.0: 1.3.

Another embodiment of the invention includes a method of minimizing injector plugging comprising contacting an injector with a fuel composition comprising a large amount of a hydrocarbon and a small amount of each of the Mannich detergent and the suc comprising a reaction product of (i) an alkenyl-substituted succinic anhydride having an average molecular weight of from about 250 to about 3,000 and (ii) an amine-containing polyalkylene polymer having an average molecular weight of from about 100 to about 750, wherein the alkenyl substituted succinic anhydride and the amine-containing polyalkylene polymer are present in the reaction in a molar ratio of about 2.0: 1.0 to about 1.0: 1.3. In yet another embodiment, the invention includes a method of minimizing injector clogging, comprising contacting a fuel injector with a fuel composition comprising a large amount of a hydrocarbon and a small amount of each of the Mannich detergent and succinimide, which is a reaction product of (i ), an alkenyl-substituted succinic anhydride having an average molecular weight of from about 250 to about 3,000, and (ii) an amine-containing polyalkylene polymer having an average molecular weight of from about 100 to about 750 wherein the alkenyl-substituted succinic anhydride and the amine-containing polyalkylene polymer are included the reaction in a molar ratio of about 2.0: 1.0 to about 1.0: 1.3 are present. In yet another embodiment, the invention includes a method of minimizing injector clogging, comprising contacting a fuel injector with a fuel composition comprising a large amount of a spark ignition fuel and a small amount of each of the Mannich detergent and succinimide, which is a reaction product of (i) an alkenyl-substituted succinic anhydride having an average molecular weight of from about 250 to about 3,000; and (ii) an amine-containing polyalkylene polymer having an average molecular weight of from about 100 to about 750, wherein the alkenyl-substituted succinic anhydride and the amine-containing polyalkylene polymer are disclosed in U.S. Pat Reaction in a molar ratio of about 2.0: 1.0 to about 1.0: 1.3 are present.

A another embodiment The invention includes a method for preventing deposits in a valve comprising contacting a valve with a fuel composition containing a large amount of a hydrocarbon and a small amount of each of Mannich detergent and succinimide comprising a reaction product of (i) an alkenyl-substituted one Succinic anhydride having an average molecular weight of about 250 to about 3,000 and (ii) an amine-containing polyalkylene polymer having an average molecular weight of about 100 to about 750, where the alkenyl-substituted Succinic anhydride and the amine-containing polyalkylene polymer in the Reaction in a molar ratio from about 2.0: 1.0 to about 1.0: 1.3. At another one another embodiment The invention includes a method for preventing deposits in an injector, comprising contacting an injector with a fuel composition containing a large amount of a hydrocarbon and a small amount of each of the Mannich detergent and succinimide which is a reaction product of (i) a Alkenyl-substituted succinic anhydride having an average molecular weight from about 250 to about 3,000 and (ii) an amine-containing polyalkylene polymer having an average molecular weight of about 100 to about 750, wherein the alkenyl-substituted succinic anhydride and the amine-containing Polyalkylene polymer in the reaction in a molar ratio of from about 2.0: 1.0 to about 1.0: 1.3. At another one embodiment The invention includes a method for preventing deposits in an injector, comprising contacting a fuel injector with a fuel composition containing a large amount a spark ignition fuel and a small amount of each of Mannich detergent and succinimide comprising a reaction product of (i) an alkenyl-substituted one Succinic anhydride having an average molecular weight of about 250 to about 3,000 and (ii) an amine-containing polyalkylene polymer having an average molecular weight of about 100 to about 750, wherein the alkenyl-substituted succinic anhydride and the amine-containing Polyalkylene polymer in the reaction in a molar ratio of from about 2.0: 1.0 to about 1.0: 1.3.

at some embodiments may be the reaction between the alkenyl-substituted succinic anhydride having an average molecular weight of about 250 to about 3,000 and the amine-containing polyalkylene polymer having a middle one Molecular weight of about 100 to about 750 in the carrier liquid occur, wherein the alkenyl-substituted succinic anhydride and the Amine-containing polyalkylene polymer in the reaction in a molar ratio of from about 2.0: 1.0 to about 1.0: 1.3. The Mannich detergent can then be the carrier liquid either before or after the reaction of the alkenyl-substituted succinic anhydride and of the amine-containing polyalkylene polymer.

at some embodiments is the preformed succinimide with a suitable amount of the carrier liquid mixed. The Mannich detergent can be used with the carrier liquid either before or are mixed after addition of the succinimide. If desired, can the reactant product in a suitable solvent or suitable carrier fluid formed and then with an additional Amount of the same or a different carrier liquid be mixed.

In some embodiments, the Mannich detergent may be mixed with the succinimide, before mixing both components with the carrier liquid.

All Patents and publications, which are cited herein are fully incorporated by reference including their entirety.

EXAMPLES

EXAMPLE 1

Synthesis of PIBSA

178 g maleic anhydride and 1,435 g of polyisobutylene (molecular weight 950) were in a Submitted reactor. The reaction was heated to 235 ° C and refluxed for 5 h heated.

A Sample of the mixture was taken out and the acid value after stripping became determined. The target range was between 1.03 and 1.07. If the stripped acid number lower than the target area, was a small amount of maleic anhydride (17-18 g) and the reaction was prolonged until the target was reached has been.

Subsequently was the excess maleic anhydride by 2 h stripping at 230-235 ° C at 60-70 mmHg vacuum removed from the reactor.

EXAMPLE 2

Synthesis of succinimide

The PIBSA of Example 1 was added to a reactor under nitrogen and at 167 ° C heated. Subsequently were approximately 300 g of TEPA was added so that the molar ratio of PIBSA to TEPA was 1.0: 1.0. The rate of addition of the TEPA to the PIBSA mixture depends on the extent of foaming.

The Vacuum is slowly changed to 70 mmHg. Subsequently, will the water is withdrawn from the reaction for about 2.5 hours.

Subsequently, will the material at 150 ° C filtered.

The nitrogen content ranged from 6.2-6.4% and the total base number ranged from 140 to 160. Both infrared and carbon ¹³ -NMR showed the expected carbonyl peaks.

The viscosity of the product at 100 was typically above 2,300 cSt.

EXAMPLE 3

Results of the PFI drilling equipment test

• * Das Mannich-Detergenzpaket enthielt 1,6 PTB eines Succinimids, das das Reaktionsprodukt einer Reaktion von PIBSA und TEPA in einem Molverhältnis von 1,6:1,0 war.
• + Das verwendete Succinimid war das Reaktionsprodukt einer Reaktion von PIBSA und TEPA in einem Molverhältnis von 1,0:1,0.

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

• * The Mannich detergent package contained 1.6 PTB of a succinimide which was the reaction product of a reaction of PIBSA and TEPA in a molar ratio of 1.6: 1.0.
• + The succinimide used was the reaction product of a reaction of PIBSA and TEPA in a molar ratio of 1.0: 1.0.

Claims (53)

Gasoline additive composition comprising (a) a Mannich detergent and (b) a succinimide which is a reaction product comprising (i) an alkenyl-substituted succinic anhydride an average molecular weight of about 250 to about 3,000 and (ii) an average molecular weight amine-containing polyalkylene polymer from about 100 to about 750, wherein the alkenyl-substituted succinic anhydride and the amine-containing polyalkylene polymer in the reaction in a molar ratio from about 2.0: 1.0 to about 1.0: 1.3. A composition according to claim 1, wherein the alkenyl-substituted Succinic anhydride has an average molecular weight of about 600 to about 2,000. A composition according to claim 1, wherein the alkenyl substituent group of the alkenyl-substituted succinic anhydride has an average molecular weight from about 200 to about 2,950. A composition according to claim 1, wherein the alkenyl-substituted Succinic anhydride is polyisobutylene succinic anhydride. A composition according to claim 4, wherein the polyisobutylene succinic anhydride has an average molecular weight of about 600 to about 2,000. A composition according to claim 4, wherein the alkenyl substituent group of the polyisobutylene succinic anhydride has an average molecular weight from about 200 to about 2,950. A composition according to claim 1, wherein the amine-containing Polyalkylene polymer has an average molecular weight of about 125 to about 650 has. A composition according to claim 1, wherein the amine-containing Polyalkylenpolymer is a mixture in which the predominant amine-containing Polyalkylenpoly mer contains at least about 4 nitrogen atoms per molecule. A composition according to claim 1, wherein the middle one Number of nitrogen atoms per molecule of the amine-containing polyalkylene polymer is about 3.0 to about 18.0. A composition according to claim 1, wherein the amine-containing Polyalkylene polymer is tetraethylenepentamine. A composition according to claim 1, wherein the alkenyl-substituted Succinic anhydride is polyisobutylene succinic anhydride and the amine-containing Polyalkylene polymer is tetraethylenepentamine. A composition according to claim 1, wherein the alkenyl-substituted Succinic anhydride and the amine-containing polyalkylene polymer in the Reaction in a molar ratio from about 1.6: 1.0 to about 1.0: 1.0. The composition of claim 1, wherein the Mannich detergent the reaction product of at least one alkyl-substituted hydroxyaromatic Compound, an aldehyde and at least one amine. A composition according to claim 13, wherein the alkyl-substituted Hydroxy-aromatic Compound is an alkyl-substituted cresol. The composition of claim 14, wherein the alkyl-substituted Cresol is polybutylphenol. A composition according to claim 15, wherein the polybutylphenol has an average molecular weight of about 750 to about 1,200. A composition according to claim 13, wherein the amine at least one aliphatic diamine having a primary or secondary Amino group and a tertiary one Amino group in the molecule includes. A composition according to claim 17, wherein the amine Dibutylamine includes. A composition according to claim 13, wherein the aldehyde Formaldehyde is. A composition according to claim 13, wherein the alkyl-substituted Hydroxy-aromatic Compound is an alkyl-substituted cresol, the aldehyde is formaldehyde and the amine is dibutylamine. A composition according to claim 1, wherein the composition additionally contains at least one additive, selected from the group consisting of carrier fluids, Antifriction agents, detergents, dispersants, antistain press-fit reducing agents, Combustion improvers, antioxidants, heat stabilizers, deicing additives, Anti-knock additives, corrosion inhibitors, defoggers, metal deactivators, Antifoams, biocides, cosolvents, Package compatibilizers, lubricity additives, antistatic additives, drag reducing agents, dyes, Markers, cold flow additives and demulsifiers. A gasoline fuel composition comprising (a) a hydrocarbon, (b) a Mannich detergent and (c) a succinimide, which comprises a reaction product of (i) an alkenyl-substituted one Succinic anhydride having an average molecular weight of about 250 to about 3,000 and (ii) an amine-containing polyalkylene polymer having an average molecular weight of about 100 to about 750, where the alkenyl-substituted Succinic anhydride and the amine-containing polyalkylene polymer in the Reaction in a molar ratio from about 2.0: 1.0 to about 1.0: 1.3. A fuel composition according to claim 22, wherein the Mannich detergent and succinimide each in a minor amount available. A fuel composition according to claim 22, wherein the hydrocarbon is a pilot fuel includes. A fuel composition according to claim 24, wherein the pilot fuel Gasoline included. A fuel composition according to claim 25, wherein the pilot fuel a mixture of hydrocarbons of the gasoline boiling range and a fuel-soluble one oxygenated compound. A fuel composition according to claim 22, wherein the alkenyl-substituted succinic anhydride has an average molecular weight from about 600 to about 2,000. A fuel composition according to claim 22, wherein the alkenyl substituent group of the alkenyl-substituted succinic anhydride has an average molecular weight from about 200 to about 2,950. A fuel composition according to claim 22, wherein the alkenyl-substituted succinic anhydride polyisobutylene succinic anhydride is. A fuel composition according to claim 29, wherein the polyisobutylene succinic anhydride has an average molecular weight from about 600 to about 2,000. A fuel composition according to claim 29, wherein the alkenyl substituent group of the polyisobutylene succinic anhydride has an average molecular weight from about 200 to about 2,950. A fuel composition according to claim 22, wherein the amine-containing polyalkylene polymer has an average molecular weight from about 125 to about 650. A fuel composition according to claim 22, wherein the amine-containing polyalkylene polymer is a mixture in which the predominant amine-containing polyalkylene polymer at least about 4 nitrogen atoms per molecule contains. A fuel composition according to claim 22, wherein the average number of nitrogen atoms per molecule of amine-containing Polyalkylene polymer is about 3.0 to about 18.0. A fuel composition according to claim 22, wherein the amine-containing polyalkylene polymer is tetraethylenepentamine. A fuel composition according to claim 22, wherein the alkenyl-substituted succinic anhydride polyisobutylene succinic anhydride and the amine-containing polyalkylene polymer is tetraethylenepentamine is. A fuel composition according to claim 22, wherein the alkenyl-substituted succinic anhydride and the amine-containing Polyalkylene polymer in the reaction in a molar ratio of from about 1.6: 1.0 to about 1.0: 1.0. A fuel composition according to claim 22, wherein the Mannich detergent is the reaction product of at least one Alkyl-substituted hydroxyaromatic compound, an aldehyde and at least one amine. A fuel composition according to claim 38, wherein the alkyl-substituted hydroxyaromatic compound is an alkyl-substituted one Cresol is. A fuel composition according to claim 39, wherein the alkyl-substituted cresol is polybutylphenol. A fuel composition according to claim 40, wherein the polybutylphenol has an average molecular weight of about 750 until about 1,200 has. A fuel composition according to claim 38, wherein the amine is at least one aliphatic diamine having a primary or secondary Amino group and a tertiary one Amino group in the molecule includes. A fuel composition according to claim 42, wherein the amine comprises dibutylamine. A fuel composition according to claim 38, wherein the aldehyde is formaldehyde. A fuel composition according to claim 38, wherein the alkyl-substituted hydroxyaromatic compound is an alkyl-substituted one Cresol, the aldehyde is formaldehyde and the amine is dibutylamine is. A fuel composition according to claim 22, wherein the succinimide and the Mannich detergent each in an amount that are about 0.5 to about 500 parts per million is. A fuel composition according to claim 22, wherein the fuel composition additionally contains an additive selected from the group consisting of carrier fluids, friction modifiers, detergents, dispersants, anti-extrusion press-fit reducing agents, combustion improvers, antioxidants, heat stabilizers, anti-icing additives, anti-knock additives, corrosion inhibitors, defoggers, metal deactivators, anti-foaming agents, Biocides, cosolvents, package compatibilizers, lubricity additives, antistatic additives, drag reducing agents, dyes, markers, cold flow additives and demulsifiers. A motor comprising the composition of claim 1. Engine having the fuel composition according to claim 22 includes. Method for preventing gasoline engine injector clogging, comprising contacting an injector with the composition according to claim 1. Method for preventing injector clogging, comprising contacting an injector with the fuel composition according to claim 22. Method for preventing valve deposits, comprising providing the composition of claim 1. Method for preventing valve deposits, comprising providing the fuel composition according to Claim 22.