FI113376B - gasoline - Google Patents

Abstract

The invention provides a gasoline composition comprising a major amount of a gasoline and from 5 ppmw to 1,000 ppmw based on the gasoline composition of a mixture of (a) an oil soluble polyamine selected from the group consisting of (i) a defined aliphatic alkylene polyamine, (ii) a defined Mannich polyamine, and (iii) mixtures of (i) and (ii); and (b) an oil soluble hydrocarbyl poly(oxyalkylene) aminocarbamate having a number average molecular weight in the range from 600 to 10,000 having at least one basic nitrogen atom wherein said hydrocarbyl group contains from 1 to 30 carbon atoms, and wherein the weight ratio of said polyamine (a) to said hydrocarbyl poly(oxyalkylene) aminocarbamate (b) ranges from 3:1 to 1:2; and a gasoline additive concentrate containing said mixture.

Description

1 113376

The present invention relates to a gasoline composition for use in an internal combustion engine and to a gasoline additive concentrate.

Petrol compositions have traditionally been formulated to improve the performance of the engines into which the fuel is injected by means of a carburetor and a throttle. Around 1984, automotive manufacturers have been introducing large-scale, 10-scale engines that electronically inject fuel into the intake manifold. Shortly thereafter, during the 1985 period, reports began to emerge that the suction valves of the electronically injected suction valves had precipitated 15 earth, indicating problems with starting, stopping, stalling when accelerating, and uneven engine idling.

Thus, it is desirable to provide fuel compositions that reduce or eliminate such harmful suction valve deposits in engines where fuel is injected electronically into the intake salt. In addition, as various fuel-injected * / carburettors and throttle engines will be in continuous use for the foreseeable future, it is · 25 desirable that these fuels also fit in with these | engines. Cleanliness of suction valves is generally defined in the BMW NA standard for cleanliness of suction valves * »· with unrestricted driving performance. Good runnability is then correlated in a generally accepted way 'i ;; 3O to an average deposition of suction valves of • · **; · 'by 100 milligrams per valve or less.

• M

f: O1-soluble olefinic polymer-containing polyalkylene polyamines are known to improve burn. material purification properties used in gas, 35, and throttle engines. These polyalkylethylene polyamines, especially when used in high concentrations, can lead to valve sticking and the need to increase octane rating. Various materials have been added to these polyalkylene polyamines to improve their performance. Thus, U.S. Patent No. 5,006,1305 discloses as a gasoline additive (a) a polyalkylene polyamine and (b) at least one component selected from the group consisting of (I) a C2-C6 mono-olefin, (II) C2-C6- a copolymer of mono-olefin, (III) the corresponding hydrogenated polymer or copolymer, and (IV) an oil-soluble polyoxyalkylene alcohol, glycol or polyol or a mono- or diethyl ether thereof.

U.S. Patent Nos. 4,197,409 and 4,191,537 disclose hydrocarbon polyoxyalkyleneaminocarbamates as an anti-precipitation additive that effectively suppresses precipitates in suction systems (carburetor, valves, etc.) in engines that use these containing fuels but do not increase the amount of combustion that burns. cause an increase in octane number.

Mannich polyamines formed by the condensation of a high molecular weight alkyl substituted hydroxy aromatic compound, an amine having at least one active hydrogen atom and an aldehyde condensation product are disclosed in U.S. Patent No. 4,231. 759 and: · they are said to be useful for transferring cleaning properties to vehicle fuel so that suction valves remain clean.

In accordance with the present invention, there is provided a gasoline composition comprising gasoline as the main component and 5-1000 weight ppm ···· 30% based on the gasoline composition of (a) oil-soluble polyamine selected »· '· ·· * from group (I) an aliphatic alkylene polyamine containing ··: at least one olefinic polymer chain linked to an nitrogen atom and / or a carbon atom of an alkyl, lene (s) linking the amino type and said polyamine;

I «· M

35 atoms, and said polyamine has a number average molar '·'! (II) Mannich poly-3 113376 amine formed from a high molecular weight, sulfur-free, alkyl-substituted hydroxy aromatic compound having an alkyl group or each alkyl group having a number average molecular weight of from 600 to 10,000, wherein an amino group containing an active hydrogen atom, and a condensation product of an aldehyde, wherein the respective molar ratios of reactants are from 1: 0.1 to 10: 0.1 to 10, and (III) mixtures of components (I) and (II); and (b) an oil-soluble hydrocarbon polyoxyalkylene aminocarbamate having a number average molecular weight of from 10 to 10,000 and having at least one basic nitrogen atom, wherein the weight ratio of said polyamine (a) to said hydrocarbon polyoxyalkylene amino carbamate (b) is 3: 1: 1.

Component (a) can be selected from aliphatic alkylene polyamine, Mannich polyamine or mixtures of aliphatic alkylene polyamine and Mannich polyamine.

(I) Aliphatic Alkylene Polyamine In an oil-soluble aliphatic alkylene polyamine component cleaner (a) (I), there is at least one polymer chain having an Mn (number average molecular weight) of 500-9,900, preferably an Mn of 550-4,900. *: 600 to 1300, and which may be a saturated or unsaturated and straight or branched chain attached to the nitrogen atom, and / or the carbon atom of the alkylene radicals connecting the amino nitrogen atoms.

* · * • ·

The aliphatic alkylene polyamine is preferably a compound of the general formula

R

RN-R '- (N-R') -NR "(I): wherein x is 0-5; R is selected from the group consisting of hydrogen and poly-, an olefinic group having an Mn of 500-9,900 and at least one of R 'is a polyolefin group; R' is independently C 113-C16, preferably C1-C4 alkylene; and R 'is independently a hydrogen atom or a lower alkyl group. Preferably, one of R groups is a branched olefin polymer and the other groups R are hydrogen. R has a number average molecular weight Mn in the range of 550 to 4900 and is particularly preferably in the range of 600-1300.

The olefinic polymers (R) which are reacted with the polyamines to be used as aliphatic alkylene polyamines for use in the present invention are olefinic polymers derived from straight or branched alkanes or alkenes, whether or not aromatic or cycloaliphatic. groups derived from polymers or copolymers of olefins, which may or may not have a double bond. Examples of unsubstituted alkenyl and alkyl groups are polyethylene groups, polypropylene groups, polybutylene groups, polyisobutylene groups, polyethylene-polypropylene groups and the like without double bonds. Examples of substituted alkenyl and alkyl groups include polyethylene poly-alpha-methyl-styrene groups and the like without double bond. Particularly preferred are polypropylene and especially poly (sobutylene) groups.

i !. The group "R" may be hydrogen, but is preferably lower, lower alkyl having, for example, up to seven carbon atoms, and is more preferably selected from the group consisting of methyl, ethyl, propyl and butyl.

The polyamines used to form the aliphatic alkylene polyamines used in the present invention are primary and secondary polyamines such as ethylenediamine, diethylenetriamine, triethylenetriamine, propylene triamine, butylenediamine, pentamethylenediamine, 35 hexamethylenediamine, heptamethylenediamine, diamino-3-octane, decamethylenediamine and higher homologues, 5,113,376 containing up to eighteen carbon atoms, N-methylethylenediamine, N-propylethylenediamine, N, N-dimethyloxy-1,3- -nidiamine, penta- (1-methylpropylene) hexamine, tetrabu-5-methylene pentamine, hexa- (1,1-dimethylethylene) heptane, di- (1-methylamylene) triamine, tetra- (1,3-dimethylpropylene) pentamine, penta- (1,5-dimethylamylene) hexamine, di- (1-methyl-4-ethylbutylene) triamine, penta- (1,2-dimethyl-1-isopropylethyl) lene) hexamine and tetraoctylene-10 pentamine.

Compounds containing triamine as well as tetramine and pentamine groups are useful because they can be prepared from technical blends of polyethylene polyamines, which may entail economic advantages.

The polyamine may be a cyclic polyamine, eg, cyclic polyamines formed by heating aliphatic polyamines having nitrogen atoms separated by ethylene groups in the presence of hydrogen chloride.

An example of a suitable process for the preparation of an aliphatic alkylene polyamine to be used according to the invention is the reaction of a halogenated polyhydrocarbon having at least one halogen atom substituted with tin and having the hydrocarbons ju, * ': as in R above. The halogen atom is replaced by a polyamine group and a hydrogen halide is formed. The hydrogen halide can then be removed by appropriate means, e.g. with an excess of polyamine as the forming salt. The reaction between the halogenated hydrocarbon and the polyamine is preferably carried out at an elevated temperature in the presence of a solvent, in particular a solvent having a boiling point of at least 160 ° C.

The reaction with polyhydrocarbon halide and polyamine having more than one nitrogen atom for this reaction is preferably carried out such that the crosslinking is minimized, e.g., by using an excess of polyamine.

• · 6 113376

The aliphatic alkylene polyamine has a number average molecular weight Mn in the range of 600 to 10,000, preferably Mn in the range of 600 to 5,000 and most preferably Mn in the range of 600 to 1500.

(II) Mannich Polyamine Oil-soluble Mannich Polyamine Component Cleanser (a) (II) is formed from a high molecular weight alkylamino substituted hydroxy aromatic moiety of the amine having at least one active hydrogen atom and aldehyde. Such condensation products may be prepared by conventional condensation under Mannich reaction conditions: (1) an alkyl substituted hydroxy aromatic compound wherein the alkyl substituent or each alkyl substituent has an Mn of from 600 to 10,000, preferably from 600 to 3,000, more preferably from 740 to 1,200, and most preferably 1,000 1100, preferably polyalkylphenol, the polyalkyl substituent of which is derived from 1-mono-olefin polymers, preferably having an Mn in the range of 600-3000, more preferably 740-2020, and most preferably 1000-1100; (2) an amine, preferably a polyamine, containing at least one = NH group, preferably an alkylene polyamine of the formula NK 2 - (AN) n H (il) i: where: are independently a divalent alkylene radical of 2 to 6 carbon atoms and n is an integer from 1 to 10; and (3) an aldehyde, preferably formaldehyde.

*. 30 S »* I» useful in the present invention

Examples of Mannich polyamines are described in U.S. Patent No. 4,231,759. The aforementioned high molecular weight products useful in the present invention are preferably prepared by methods that have hitherto been conventional in the preparation of Mannich condensation products. , 7 113376 using the above reactants, i.e., high molecular weight alkyl substituted hydroxy aromatic compound (1), amine (2) and aldehyde (3) respectively in a molar ratio of 1: 0.1 to 10: 0.1-10. A suitable condensation-5 product is obtained by adding the aldehyde reagent (3) in the temperature range from ambient temperature (20 ° C) to 93 ° C, e.g.

formaldehyde, in a mixture of the reactants (1) and (2) in a solvent-free or in any easily removable organic solvent such as benzene, xylene or toluene or in a solvent-free neutral oil and then heating the reaction mixture to elevated temperature (120-175 ° C) stripping agents such as nitrogen or carbon dioxide until completion of dehydrogenation. The product thus obtained is completed, if desired, by filtration and dilution.

Preferred cleaning additives for use in the present invention are high molecular weight Mannich condensation products formed by reacting (1) an alkyl phenol having an alkyl group Mn of 600 to 3000; 20 (2) ethylene polyamine or amine reactant and (3) formal dehyde forming reactant, respectively, in molar ratio; 1: 0.5-2.0: 1.0-3.0.

High Molecular Weight, Alkyl - Substituted # *. : hydroxy aromatic compounds are represented by polypropyl • phenol, polybutyl if enol and other polyalkyl phenols.

: These polyalkylphenols can be obtained by alkylating phenol with a high molecular weight polypropylene, polybutylene and other polyalkylene compounds in the presence of an alkylation catalyst such as BF3, whereby the phenol is benzene-ring; One or more alkyl substituents are formed and each alkyl substituent has an Mn of from 600 to 10,000.

; Hydroxy aromatic compounds having an Mn of 600 or more alkyl substituents can be derived from high molecular weight, polyalkylenic polypropylenes, polybutenes and other polymers of mono-olefins, in principle 1-mono-olefins. Also useful are copolymers of mono-olefins and monomers copolymerized therewith, wherein the copolymer contains at least 90% by weight of mono-olefin units. Selected examples are copolymers of propylene or butenes (butene-1, butene-2 and isobutylene) and monomers copolymerized therewith, wherein the copolymer contains at least 90% by weight of propylene and butene units, respectively. Said monomers which are copolymerized with propylene or said butenes include monomers containing a small proportion of unreacted polar groups such as chlorine, bromine, keto, ether, aldehyde, which significantly reduce the oil solubility of the polymer. The co-monomers polymerizable with propylene or said butenes may be aliphatic and may also contain non-aliphatic groups such as styrene, methyl styrene, p-dimethylstyrene and divinylbenzene. The foregoing limitations on the monomer copolymerizable with propylene or said butenes make it clear that said polymers and copolymers of propylene and said butenes are substantially aliphatic hydrocarbon polymers. Thus, the formulated alkylated phenols contain substantially 'alkyl hydrocarbon substituents with Mn greater than 600.

These high molecular weight hydroxy aromatic; In addition to these compounds, other compounds which are sulfurized derivatives other than resorsinol, hydroquinone, cresol, catechol, xylenol, hydroxydiphenyl, benzylphenol, phenethylphenol, >> d 30 naphthol and tolylnaphthol, high molecular weight, alkylstyridine, may be used. derivatives. For the preparation of such preferred Manich niche condensation products, polyalkylphenol reactants are preferred, e.g., polypropyl phenol and '1' polybutylphenol, wherein the alkyl groups have an Mn of from 600 to 3000, with more preferred alkyl groups having Mn of 740 to 1200 and most preferred 9 113376 alkyl group is a polypropyl group having an Mn of 800-850, in particular 825.

The alkyl-substituted hydroxy aromatic compound preferably has the same configuration as the parasubs-5-substituted monoalkyl phenol. However, any alkyl phenols which are readily reactive in Mannich condensation can be used. Thus, ortho-monoalkylphenols and diaicylphenols are useful in the present invention.

Various amine reactants may be used, including mono- and polyamines. Preferred amine reactants are alkylene polyamines, mainly polyethylene polyamines. Other representative organic compounds containing at least one = NH group which may be used in the preparation of Mannich condensation compounds are known and include mono- and diaminoalkanes and substituted analogs thereof such as ethylamine, dimethylamine, dimethylaminopropylamine and diethanolamine; aromatic diamines such as phenylenediamine, diaminonaphthalenes; heterocyclic amines such as morpholine, pyrrole, pyrrolidine, imidazole, imidazoline and piperidine; melamine and its substituted analogs.

Suitable alkylene-polyamine reactants include ethyl: ethylenediamine, diethylenetriamine, triethylenetetramine, *, · tetraethylenepentamine, pentaethylene hexamine, hexaethylene octamine, heptaethylene octamine, decaethylamine, * provide nitrogen in the alkylene polyamines of the above formula (II) H2N- (A-NH) nH, where A is divalent ethylene and n is an integer from 1 to 10. Suitable reactants are also the corresponding propylene polyamines such as propy. lenediamine and di-, tri-, tetra-, pentapropylene-tri-, tetra-, penta- and hexa-amines Alkylenepolyamines can be (usually obtained by reacting ammonia with dihalo * * * * * 35 gene alkanes such as dichloroalkanes). · The alkylene polyamine reactants are thus alkylene polyamine reactants obtained by reacting 2-11 moles of ammonia. and 1 to 10 moles of dichloroalkanes having 2 to 6 carbon atoms and the chlorine atoms being on different carbon atoms.

Representative aldehydes useful in the preparation of the high molecular weight products used in this invention include aliphatic aldehydes such as formaldehyde (including paraformaldehyde), acetaldehyde and aldol (b-hydroxybutyraldehyde). Formaldehyde or a formaldehyde-forming reactant is preferred.

(III) Mixtures of aliphatic alkylene polyamine and Mannich polyamine

Mixtures of components (a) (I) and (a) (II) may also be conveniently combined with component (b) in the preparation of gasoline compositions of the present invention.

Component (b) - Aminocarbamate

Preferably, the amine portion of the hydrocarbon terminated polyoxyalkylene aminocarbamate is derived from a polyamine having 2 to 12 amine nitrogen atoms and 2 to 40 carbon atoms. The poly-20 amine is preferably reacted with hydrocarbon polyoxyalkylene chloroformate to form the hydrocarbon polyoxyalkylene: aminocarbamate component (b). The chloroformate itself is derived from the hydrocarbon polyoxyalkylene alcohol in the reaction. j with phosgene. A polymer comprising diamines yields .25 polyoxyalkyleneaminocarbamate having an average color,. at least one basic nitrogen atom per carbamate molecule, i.e. a nitrogen atom which can be titrated with a strong acid.

The ratio of carbon to nitrogen in the polyamine is preferably in the range of 1: 1-10: 1. The polyamine may be substituted with substituents selected from the group consisting of 1-10 carbon atoms, acyl groups containing 2 to 10 carbon atoms, and monocarboxy groups of 1 to 10 carbon atoms. , monohydroxy, mononitro, monocyano, alkyl and alkoxy derivatives. Advantageously, at least one of the basic nitrogen atoms of the poly * 35 amine is a primary or secondary nitrogen atom. Examples of suitable polyamines are described in U.S. Patent No. 4,191,537.

The term hydrocarbon used to describe all components of this invention refers to an or-5 organic radical consisting of carbon and hydrogen, which may be aliphatic, alicyclic, aromatic or a combination thereof, e.g., aralkyl. Preferably, the hydrocarbon group has relatively low aliphatic unsaturation, i.e. ethylene and acetylene, particularly acyl-10-ethylenic unsaturation. A more preferred polyamine of the aminocarbamate component is a polyalkylene polyamine including alkylenediamine and including substituted polyamines, e.g., alkyl- and hydroxyalkyl-substituted polyalkylene polyamine. The alkylene group preferably has 2 to 6 carbon atoms and the nitrogen atoms preferably has 2 to 3 carbon atoms. Examples of such polyamines are ethylenediamine, diethylenetriamine, triethylenetetramine, dipropylene triamine and tetraethylene pentamine. Of the polyalkylene polyamines, polyethylene-20 -ene-polyamines and polypropylene-polyamines having from 2 to 12 amine nitrogen atoms and from 2 to 24 carbon atoms are particularly preferred, and lower polyethylene / polypropylene polyamines are most preferred; such as ethylenediamine and di-propylene triamine.

. : The hydrocarbon terminated polyoxyalkylene polymers used in the preparation of aminocarbamates are monohydric; roxy compounds, e.g. alcohols, often referred to as monohydroxy polyethers or polyalkylene glycol monocarbyl ethers or "terminated" polyoxyalkylene glycols, and must be distinguished from polyoxyalkylene glycols (diols) or polyols which are not. they have no end groups. Hydrocarbon-terminated polyoxyalkylene alcohols are prepared by the addition of lower alkylene oxides such as ethylene oxide, propylene oxide and butylene oxide to the hydroxy compound R6H under polymerization conditions where R is a polyoxyalkylene chain. : concluding hydrocarbon group. In the polyoxyalkyl moiety of the aminocarbamate, R 11 is from 1 to 30 carbon atoms, preferably from 2 to 20 carbon atoms, and the group is aliphatic or aromatic, i.e. alkyl or alkylphenyl, wherein the alkyl is straight or branched and has 1-24 carbon atoms. The oxyalkylene units of the polyoxyalkylene component preferably have from 2 to 5 carbon atoms, but may also include one or more units containing more carbon atoms. Each polyoxyalkylene polymer has at least 5 oxyalkylene units, preferably 8-100 oxyalkylene units, more preferably 10-100 units, and most preferably 10-25 units. The polyoxyalkylene component is further described and illustrated by examples in U.S. Patent Nos. 4,191,537 and 4,197,409. The hydrocarbon polyoxyalkylene amino-15 carbamate used in the compositions of the present invention is obtained by combining an amine component and a polyoxyalkylene component with a C (O) bond , whereby the oxygen can be considered as the terminal hydroxylic acid of the polyoxyalkylene alcohol component and the carbonyl group -C (O) - is obtained from the coupling agent, eg phospho: ·. gene. In a preferred preparation method, the carbon: hydrogen polyoxyalkylene alcohol is reacted with phosgene to form chloroformate and the chloroformate is reacted with polyamine. Carbamate bonds are formed by the bonding of the polyoxy 's-alkylene chains to the nitrogen of the polyamine via an oxycarbonyl group of chloroformate. Because the polyamine may have more than one nitrogen atom that is capable of reacting with chloroformate, the aminocarbamate: has at least one hydrocarbon polyoxyalkylene polymer chain ti <i; bonded via an oxycarbonyl group to the ... nitrogen atom of the polyamine, and the carbamate may have 1, 2 or more »» »* such chains. The hydrocarbon polyoxyalkylene amino carbamate preferably contains an average of one polyoxyalkyl 35 carbonene chain per molecule (i.e., is a monocarbamate), although it is clear that this pathway can lead to mixtures of 13,133,376 polyamines with multiple reactive nitrogen atoms. or a higher polyoxyalkylene chain substitution. Particularly preferred individual amino carbamates are butyl polyoxyalkylene N- (2-aminoethyl) carbamate and alkylphenyl polyoxyalkylene N- (2-aminoethyl) carbamate. A particularly preferred carbamate can be represented by the following formula: I / N-NH2-CH2-CH2-NC-O-CC- [O-CC-] aO ----- <^ - y> H C2 H5 C2 K5 wherein R has a hydrogen atom or an alkyl group and is greater than 5. The aminocarbamates useful in the present invention may be obtained from the Oronite Additives Division of the Chevron Chemical Company.

Methods of synthesizing the aminocarbamates used as component (b) to prevent excessive substitution, methods of preparation, and other characteristics are described in more detail and exemplified in U.S. Patent Nos. 4,191,537 and 4,197,409.

; t

The aminocarbamate has a number average molecular weight of 20 to about 10,000, preferably between 600 and 5,000 and most preferably between 600 and 2,000.

f Total amount of component (a) plus component (b): The petrol compositions of the invention have in the range of 5 to 1000, preferably 50 to 1000, more preferably 50 to 500, even more preferably 100 to 400 and most preferably 200 to 300 ) based on the petrol composition.

The weight ratio of component (a) to component (b) is in the range of 3: 1 to 1: 1 and preferably 2: 1 to 1: 1. In a particularly preferred embodiment, the weight ratio is 1: 1.

Suitable liquid hydrocarbon fuels in the boiling range of gasoline include mixtures of hydrocarbons boiling in the range of 25 ° C to 232 ° C and comprising saturated hydrocarbons, olefinic hydrocarbons and aromatic hydrocarbons. Preferred are gasoline blends having a content of saturated hydrocarbons in the range of 40 to 80% by volume and aromatic hydrocarbons in the range of 10 to 60% by volume. aromatic hydrocarbon mixtures obtained from synthetically thermally or catalytically reformed hydrocarbons or catalytic cracked or thermally cracked petroleum feedstocks, or mixtures thereof. The hydrocarbon composition and octane number of this base fuel are not critical, M) / 2, generally greater than 85. Any conventional motor reference fuel may be used in the practice of this invention. In petrol, for example, hydrocarbons can be replaced to a considerable extent with conventional alcohols or ethers known to be used in fuels. Base fuels are essentially anhydrous because water can prevent uniform combustion.

The petrols used in the present invention are preferably unleaded but may contain small amounts of dopants such as methanol, ethanol and methyl tert-butyl ether, e.g., 0.1-15 vol. : cents from the base fuel. Petrols may also contain antioxidants such as phenols, eg, 2,6-di-tert-butylphenol, or phenylenediamines, e.g.

! .. * N, N '-di-sec-butyl-p-phenylenediamine, colorants, metal deactivators and dehumidifiers such as polyester-type ethoxylated alkylphenol-formaldehyde hydro-resins and corrosion inhibitors such as succinic acid, an ester of a derivative and a polyhydric alcohol having at least one alpha-substituted carbon atom containing an unsubstituted or substituted aliphatic hydrocarbon group having from 20 to 500 carbon atoms, e.g., polyisobutylene-substituted-35-succinic acid pentaerythritol, *. 1; the number average molecular weight of the silyl group is 950, 15 113376 in an amount of 1 to 1000 ppm by weight. Petrols may also contain anti-knock compounds, such as methylcyclopentadienyl manganese tricarbonyl and orthoazidophenol, and co-antifouling compounds such as benzoylacetone.

The additive mixture (a) plus (b) used in the present invention can be added to gasoline as such or as a concentrate. For example, the agent may be added separately or mixed with other additives. The present invention thus further provides a concentrate of petrol additive-10 which is mainly composed of a mixture of (a) an oil soluble polyamine selected from group (I), an aliphatic alkylene polyamine containing at least one olefinic polymer chain linked to a nitrogen atom and / or carbon atom in an alkylene radical (s) wherein said polyamine has a number average molecular weight of from 600 to 10,000, (II) a Mannich polyamine consisting of a high molecular weight, sulfur-free, alkyl-substituted hydroxy , from the condensation: product of an amine having an amino group containing at least one active hydrogen atom and an aldehyde such that the molar ratio of reactants is 1: 0.1 to 10: 0.1 to 01 and (III) respectively for components (I) and · ; · 25 (II) mixtures thereof; and (b) an oil-soluble hydrocarbon polyoxyalkylene-aminocarbamate having a number average molecular weight in the range of 600 to 10,000 and having at least one * 1 basic nitrogen atom and said hydrocarbon group having from 1 to 30 carbon atoms and said polyamine (a) and said carbon; The weight ratio of 30 hydrocarbons of polyoxyalkylene alkylene aminocarbamate (b) is in the range "·· *" from 3: 1 to 1: 1 and to a small extent from a petrol compatible diluent having a boiling range of 50 to 232 ° C. The additive mixture (a) plus (b) can be added to gasoline 'at any point before distribution to the consumer.

The present invention further provides the use of 5-1000 ppm by weight of a total composition of a mixture of (a) an oil soluble polyamine selected from (I) an aliphatic alkylene polyamine containing at least one olefinic polymer chain attached to a nitrogen atom and / or a carbonene in the alkylene radical (s) linking the amino nitrogen atoms, wherein said polyamine has a number average molecular weight in the range of 600 to 10,000, (II) a Mannich polyamine formed by a high molecular weight, sulfur-free, alkyl-substituted hydroxy each alkyl group having a number average molecular weight of 600-10,000, from the condensation product of an amine having at least one active hydrogen atom with an aldehyde such that the molar ratio of reactants is 1: 0.1-10: 0.1-0.1: 10, respectively; and (III) of the components of com-15 (I) and (II) mixtures; and (b) an oil-soluble hydrocarbon polyoxyalkyleneaminocarbamate having a number average molecular weight of from 600 to 10,000 and having at least one basic nitrogen atom and said hydrocarbon group having from 1 to 30 carbon atoms and said polyamine 20 (a) and said hydrocarbon polyoxyalkylene having in the range of 3: 1 to 1: 1, in a petrol composition containing petrol as the main component, to reduce the suction valve.

The following illustrative examples make kek-> · easier. 25 understanding.

EXAMPLE 1 This example illustrates the beneficial effects of the petrol additive on the suction valve precipitate additive. consisting of a mixture of aliphatic alkylene-polyamine and hydrocarbon "" 30 -tolyloxyalkyleneaminocarbamate.

i »* ··· * The suction valve precipitation tests used a BMW 325 ·; · branded car with a 2.7-liter six-cylinder engine equipped with a fuel suction injection.

•, The car was driven 8,050 kilometers with test fuel. Prior to the start of the '35 test, the precipitates were removed from the cylinder head, the intake manifold, and the top of the pistons and weighed and 17,133,376 new suction valves installed. The oil and filter were replaced, new spark plugs were installed and the flow of fuel injectors checked. The driving performance took place on a dynamometer simulating road driving. A four minute 5 test period was used. It consisted of two minutes acceleration from 54 km / h to 75 km / h, one minute acceleration to 112 km / h and one minute deceleration to 54 km / h. The average speed was 79 km / h and the cycle was repeated until the driving distance was 8 050 km (almost 102 hours). Table 1 lists the additive compositions A-C, 1 and 2 used in unleaded premium base gasoline and the average weight of the (six) suction valve deposits at the end of the test (8,050 kilometers). Compositions A, B and C are reference compositions and Compositions 1 and 2 are in accordance with the present invention.

table 1

Total Component Component Ratio Results by car 20 tent nent tent (a) / (b) BMW 325. Precipitation (a) (I) 1 (b) 2 Avg. weight mg weight ppm weight ppm A 200 0 200: 0 39.0 25 1 150 50 3: 1 34.3. ' 2 100 100 1: 1 34.6 B 50 150 1: 3 148.6 / C 0 200 0: 200 153.6 30 ^ Component (a) (1) is N-polyisobutenyl-N ', N-dimethyl-1. , 3-diaminopropane, Mn = 1050 component (b) is a hydrocarbon polyoxyalkyleneaminocarbatyl; The results of these tests show that the gasoline compositions of the invention provide a synergistic effect in reducing suction valve deposition while allowing the aliphatic alkylene polyamine content of 113376 to be reduced. , so that they reduce the known ability of the polyamine to cause the valves to engage.

Example II

5 BMW was used for sedimentation test of suction valves

A 318i car with a 1.8-liter four-cylinder engine run at 10,000 miles (16,093.4 kilometers) on test fuel. Prior to the start of the test, the sediment was removed from the cylinder head, intake manifold and upper piston surface of the pistons, and new suction valves were weighed and installed. The oil and filter were replaced, new spark plugs were installed and the flow of fuel injectors checked. The driving took place on public roads using accustomed drivers. The Tes tire was composed of about 10% city-15 lanes, 20% sideways and 70% motorways (maximum speed 65 mph (104.6 km / h)).

The primary test value was the weight of the suction valve sediment (IVD) at the end of the 10,000 mile (16,093.4 km) test. BMW's acceptance criteria are: an average sediment weight of 100 mg / valve or less at the end of the test meets BMW's requirements for unlimited running performance; average sediment weight of 250 mg / valve / or less at the end of the test meets BMW requirements! 50,000 miles (80,467 miles) for maintenance.

25 Table 2 lists the additive compositions 3 and; 'j 4 used in conventional unleaded base gasolines and the average weight of the suction valve at the end of the test (10,000 miles / 16,093.4 kilometers). Compositions 3 and 4 were according to the present invention; 3 0 kaisia.

»·» I9 1 13376

Table 2

Component Component Ratio Results by car dark index (a) / (b) BMW 325. Precipitation 5 (a) (I) 1 (b) Avg. weight mg ppm by weight ppm by weight ppm 3 12 51 1252 1: 1 0 4 1253 1252 1: 1 44 10 1 Component (a) is an Amoco Mannich amine known as "Amoco 596" and described in U.S. Pat. No. 4,231,759, Mn = 1,000 - 1,100 2 Component (b) is a hydrocarbon polyoxyethylene amino carbamate 15, Mn = 1,400-1,800, sold by Oronite Additives

Component (a) of the Division of Chevron Chemical Company under the name OGA 480 is N-polyisobutylene-N ', N'-dimethyl-1,3-diaminopropane, Mn = 1050 » * * i ·

• »I

· I

2 I ·

Claims (9)

A gasoline composition characterized in that it comprises a greater amount of a gasoline and from 5 ppm 5 to 1,000 ppm, by weight, based on the gasoline composition, of a mixture of (a) an oil-soluble polyamine selected from the group consisting of (I) ) an aliphatic alkylene polyamine containing at least one olefin polymer chain attached to a nitrogen atom and / or a carbon atom of the alkylene radical (s), linking the amino nitrogen atoms and said polyamine with a number average molecular weight in the range of 600 to 10,000; Mannich polyamine comprising the condensation product of a high molecular weight sulfur-free alkyl-substituted hydroxy aromatic compound in which the alkyl group or each alkyl group has a molecular weight number in the range of 600 to 10,000, an amine containing an amino group having at least one active hydrogen atom , and an aldehyde, the respective molar ratio of the reactants being 1: 0.1 - 10: 0.1 - 10, and (III) mixtures of (I) and (II); and (b) an oil-soluble hydrocarbon poly (oxyalkylene) aminocarbamate having a number average molecular weight in the range from 600 to 10,000 with at least one basic nitrogen atom, said hydrocarbon group containing from, 1 to 30 carbon atoms, and the weight of the ratio of said · *. Polyamine (a) to said hydrocarbon poly (oxyalkylene) amino carbamate (b) is in the range of 3: 1 to 1: 1. Composition according to claim 1, characterized in that the aliphatic alkylene polyamine has a molecular weight in the inlet. the tervail from 600 to 5,000, the alkyl group or each ;;; The alkyl group in the Mannich polyamine has a molecular weight in the range of 600 to 3,000, and the amino carbamate has a molecular weight in the range of 600 to 5,000. 3. A composition according to claim 1 or 2. wherein the aliphatic alkylene polyamine has a molecular weight in the range of 600 to 1,500, the alkyl group or each alkyl group in the Mannich polyamine has a molecular weight in the range of 1000 to 1 100, and the amino carbamate has a molecular weight in the range from 600 to 2,000. Composition according to any one of claims 1 to 3, characterized in that the amount of the polyamine and aminocarbamate mixture ranges from 50 ppm to 500 ppm, by weight based on the gasoline composition. Composition according to claim 4, characterized in that the amount of the mixture of polyamine and aminocarbamate 10 ranges from 100 ppm to 400 ppm, by weight based on the gasoline composition. 6. Composition according to claim 5, characterized in that the amount of the mixture of polyamine and aminocarbamate ranges from 200 ppm to 300 ppm, by weight based on the gasoline composition. Composition according to any of the preceding claims, characterized in that the weight ratio of polyamine to aminocarbamate ranges from 2: 1 to 1: 1. Composition according to claim 7, characterized in that the weight ratio of polyamine to aminocarbamate is 1: 1. 9. Gasoline additive concentrate, characterized in that (it comprises a substantial amount of a mixture of · · (a) an oil-soluble polyamine selected from the group consisting of ··· 25 of (I) an aliphatic alkylene polyamine containing ethyl acetate). an olefin polymer chain attached to a nitrogen atom and / or, a carbon atom of the alkylene radical (s), which binds the amino nitrogen atoms and said polyamine with a number average molecular weight in the range of 600 to 10,000, to 30 ( II) a Mannich polyamine comprising the condensation product of a high molecular weight sulfur-free substituted hydroxy aromatic compound in which the alkyl group or each alkyl group has a number average molecular weight in the range of 600 to 10,000, a amine containing an amino group having at least one active hydrogen atom, and an aldehyde, respectively, whose respective molar ratio of the reactants is 1: 0.1 - 10: 0.1 - 10, and (III) mixtures of (I) and (II); and (b) an oil-soluble hydrocarbon poly (oxyalkylene) aminocarbamate having a number average molecular weight in the range of 600 to 10,000 having at least one basic nitrogen atom, wherein said hydrocarbon group is contains from 1 to 30 carbon atoms, and the weight ratio of said polyamine (a) to said hydrocarbon poly (oxyalkylene) aminocarbamate (b) is in the range of 3: 1 to 1: 1, and a smaller amount of a diluent compatible with a gasoline . ««> · * S * * t · (* »» '' * · <· 1 t · * * · • · · »M it •» ti · * $ • · · * · · »· 0 •• 00 * 0 »00 • ·