FI114991B - gasoline Compositions - Google Patents

Abstract

The invention provides a gasoline composition comprising a major amount of a gasoline suitable for use in spark-ignition engines, a minor amount of a polyalphaolefin having a viscosity at 100 DEG C in the range 2 x 10<-><6> to 2 x 10<-><5> m<2>/s (2 to 20 centistokes), being a hydrogenated oligomer containing 18 to 80 carbon atoms derived from at least one alphaolefinic monomer containing from 8 to 16 carbon atoms, and a minor amount of a polyoxyalkylene compound selected from glycols, mono- and diethers thereof, having number average molecular weight (Mn) in the range 400 to 3000, the weight ratio polyalphaolefin: polyoxyalkylene compound being in the range 1:10 to 10:1; a concentrate for the preparation of such gasoline composition and a method of operating a spark-ignition engine using such gasoline composition.

Description

114991

The present invention relates to gasoline compositions containing a major proportion of gasoline suitable for use in spark ignition engines and a minor amount of at least one additive. The invention also relates to additive concentrates suitable for incorporation in gasoline for the preparation of such gasoline compositions.

European Patent Application 290,088 discloses gasoline compositions containing a greater amount of gasoline suitable for use in spark ignition engines and a lower amount of polyalphaolefin having a viscosity at 100 ° C of between 2 x 10 6 and 2 x 10 5 m 2 / s. (2 to 20 centistokes), preferably a hydrogenated olefin containing from 15 to 18 carbon atoms derived from an alpha-olefinic monomer containing from 8 to 12 carbon atoms, and optionally small amounts of oil-soluble aliphatic polyamine and / or alkali metal or an alkaline earth metal salt of a succinic acid derivative having at least one of its carbon atoms a polyolefin substituent and / or a polyolefin derived from a C2-6 monomer having an average molecular weight (Mn) of between 500 and 1500 .

U.S. Patent 3,901,665 describes liquid hydrocarbon: T: fuel compositions characterized by improved antifreeze and carburetor purity comprising: v. A. Most liquid hydrocarbon fuel containing hydrocarbons boiling in the gasoline range and based on the weight of said fuel. B. from about 0.01% to about 0.06% by weight of 3 or 4 carbon ** olefins, preferably polyisobutene, having a molecular weight of from about 400 to about 1,400, preferably about 400 · · · · ·: About 900, and · · · · C. about 0.008 to about 0.016% by weight of a polyoxyalkyl, 1, lenene compound of formula 114991 2 CH3

R (OCH 2) x OH

Wherein R is alkyl of 1 to 20 carbon atoms, preferably 10 to 18 carbon atoms, and x has an average value of from 4 to 20; and additive compositions containing B and C as essential constituents.

U.S. Patent 3,658,494 discloses fuel compositions comprising a greater amount of at least one normally liquid fuel and a lesser amount of additives soluble in said fuel, the combination of which comprises (a) at least one oxy compound selected from the group consisting of glycol or polyglycol; and (b) at least one fuel-soluble dispersant selected from the group consisting of esters, amides, imides, amidines, and amine salts of at least one substantially saturated carboxylic acid, characterized in that its 20 acyl radicals have at least 30 aliphatic, the weight ratio of the oxy compound to the dispersant being from about 0.1: 1 to about 1: 0.1, but preferably from 0.1: 1 to about 2.5: 1. The oxy compounds used in the examples are ethylene glycol mono-n-butyl ether, dipropylene glycol monomethylene ether, triethylene glycol monoethyl ether, and ethylene glycol monophenyl ether.

EP-A-384 605 describes a motor fuel composition comprising a mixture of hydrocarbons boiling in the boiling range of gasoline, and additionally (1) a reaction product of 30 hydrocarbon-substituted dibasic acid and a specified polyoxyalkylene diamine. ) a polymeric component which is a polyolefin polymer, a copolymer or the like, aminated or hydrogenated, ·. a polymer or copolymer, or mixture thereof, of C2-10 hydrocarbon, said polyolefin polymer or copolymer having a molecular weight in the range of 500 to 10,000; (iii) polyalkyl 114991 3 ethylene glycol having a molecular weight in the range of 500-2000; and (iv) lubricating oil. With reference to (ii), it has been shown (page 9, lines 39, 40) that, generally, the olefin monomers from which the polyolefin polymer component is made are preferably unsaturated C 2-6 hydrocarbons. Polyalkylene glycol (iii) is said (page 10, lines 39, 40) to be preferably selected from the group consisting of polyethylene glycol, polypropylene glycol, and polybutylene glycol.

EP-A-526 129 (published February 3, 1993) discloses a fuel additive concentrate for controlling the increase in octane requirement in internal combustion engines, comprising a reaction product of (i) a polyamine and (ii) at least one acyclic hydrocarbon-substituted succinic acid, polyalphaolefin. Although EP Application No. 526,129 further and more specifically produces a fuel composition containing a greater proportion of hydrocarbons in the gasoline boiling range or hydrocarbon / oxygenate blends, or oxygenates containing a smaller but effective amount of (a) fuel additive. An agent comprising the reaction product of (i) a polyamine: ** and (ii) at least one acyclic hydrocarbon substituted succinyl acylating agent; (b) hydrogenated crude polyalphaolefin having a volatility of about 50% or less as determined by the test procedure described in the text; (c) and optionally (A) a mineral oil having a viscosity number of less than about 90 and a volatility of 50% or less as determined by the test procedure described in the text; (B) an- ··· thioxidant, or (C) an emulsion disintegrant, or a · · * (D) aromatic hydrocarbon solvent, or (E) a corrosion inhibitor, ···, or any combination of any two, three , four or all of the five components (A), (B), (C), (D) and (E) clearly have the essential property that the polyalphaolefin present is a non-hydrated polyalphaolefin. The emulsion disintegrating agent (c) comprises polyoxyalkylene glycols and oxyalkylated phenolic resins, and in particular mixtures thereof.

It has now surprisingly been found that petrols containing combinations of certain polyalphaolefins and certain polyoxyalkylene glycol derivatives can provide surprisingly improved engine performance in terms of a favorable combination of minimized engine intake system contamination and minimized valve.

According to the present invention, there is provided a gasoline composition containing a major portion of gasoline suitable for use in spark ignition engines with a reduced amount of poly-alpha olefin having a viscosity at 100 ° C of from 2 x 10 6 to 2 x 10 ~ 5 m 2 / s (2). 20 centistokes), being a 15 hydrogenated oligomer containing from 18 to 80 carbon atoms derived from at least one alpha-olefinic monomer containing from 8 to 16 carbon atoms and a lower amount of a polyoxyalkylene compound selected from glycols and their mono- and diethers having a number-average molecular weight (Mn) of from about 400 to about 3000, and a weight ratio of polyalphaolefin to polyoxyalkylene in the range of 1:10 to 10: 1.

The polyalphaolefins used are mainly trimers, tetramers and pentamers, and the synthesis of such materials, v, is outlined in the "Use of Synlubes" by Campen et al. , Hydrocarbon Processing, February> ► »1982, pages 75-82. Polyalefololines derived from 1-decene have been found to be very effective. The viscosity of the polyol aolefin at 100 ° C is preferably in the range 6 x 10 ~ 6 to 1 x 10 5 m 2 / s (6 to 10 centistokes). Polyalf aolefin having a viscosity at 100 ° C of 8 x 10 6 m 2 / s (8 centimeters * 35 ') has been found to be very effective.

I I M I * »114991 5

The polyoxyalkylene compound may be represented by the formula s R 1 -Q-fr-1 (I)

Wherein R 1 and R 2 each independently represent hydrogen or hydrocarbyl, preferably C 1-40, hydrocarbon, e.g. alkyl, cycloalkyl, phenyl or alkylphenyl, each R individually represents alkylene, preferably C 2-8 alkylene group. and n is such that the polyoxyalkylene compound has an Mn in the range of 400-3000, preferably 700-2000, more preferably 1000-1500.

Preferably R 1 represents a C 6-20 alkyl group and R 2 represents a hydrogen atom. Preferably R 1 represents a C 10 -C 15 alkyl group, more preferably a C 12 -C 15 alkyl group. R1 may preferably be a mixture of C12-C15 groups.

In Formula I, the groups R are preferably 1,2-alkylene groups.

Each R group individually preferably represents a C 2-4-20 alkylene group, e.g., ethylene or 1,2-propylene.

.. Very effective results have been achieved using • »*. polyalkylene compounds wherein each R group represents a 1,2-propylene group.

'· * * Polyalphaolefin and polyoxyalkylene compound may

I · I

Preferably present in the gasoline composition in total; In an amount ranging from 100 to 1200 ppmw, preferably · 100 to 600 ppmw, more preferably 150 to 500 ppmw, based on the total weight of the composition.

· * · The weight ratio of polyalphaolefin to polyoxyalkylene in the gasoline composition is preferably in the range of 1: 8 to 8: 1, more preferably 1: 5 to 5: 1. Weight ratios that are

IltM

in the range of 1: 4 to 4: 1, have been found to be very effective * *.

The gasoline compositions of the present invention preferably also contain a small amount of at least one hydrocarbon soluble ash-free dispersant. Compounds useful as ash dispersants have a characteristic "polar" group attached to a relatively high molecular weight hydrocarbon chain. This "polar" group generally contains one or more of the al-5 moieties nitrogen, oxygen and phosphorus. Cell-stabilizing chains are generally of higher molecular weight than those used with metal types, but in some cases may be quite similar.

In general, any ash-free dispersants known in the art for use in lubricants and fuels may be used in the gasoline compositions of this invention.

In one embodiment of the present invention, the dispersant is selected from the group consisting of (i) at least one hydrocarbon substituted amine wherein the hydrocarbon substituent is substantially aliphatic and contains at least 8 carbon atoms; (ii) at least one acylated nitrogenous compound having a hydrocarbon-based substituent having at least 20 aliphatic carbon atoms and prepared by reacting a carboxylic acid acylating agent with at least one amino compound containing at least one •> A -NH- group, said acylating agent being bound to said amino compound by an imido, amido, amidine or acyloxyammonium bond; (Iii) at least one nitrogen-containing condensate of a phenol, an aldehyde and an amino compound having at least one, -NH-. ' Chapter 35; (Iv) at least one substituted carboxylic acid ester; (v) at least one polymeric dispersant; (vi) at least one fuel-soluble alkoxylated derivative of an alcohol, phenol or amine.

The hydrocarbon substituted amines used in the gasoline compositions of this invention are known to those skilled in the art and are described in numerous patents. Among these, U.S. Patents 3,275,554, 10,343,8757, 3,454,555, 3,565,804, 3,575,433 and 3,822,209.

These patents disclose hydrocarbon substituted amines suitable for use in the present invention and processes for their preparation.

A typical hydrocarbon-substituted amine 15 has the general formula: [AXN] x [-N ([UN-] a [-UQ] b)] yR3cHi + 2y + ay-c (II) wherein A is hydrogen, a hydrocarbon group having from 1 to 10 a carbon atom of 20 m, or a hydroxy hydrocarbon group having from 1 to 10 carbon atoms; X is hydrogen, a hydrocarbon group having from 1 to 10 carbon atoms. or a hydroxy hydrocarbon group having from 1 to 10 carbon atoms and may be taken together with A and N to form a ring. . having 5 to 6 ring members and up to 12 carbon atoms; U is an alkylene group having from 2 to 10 carbon atoms, this includes hydrocarbons for the generation of trivalent nitrogen atoms, R 3 is an aliphatic hydrocarbon having from 30 to 400 carbon atoms; Q is a piperazine structure; a is an integer from 0 to 10; b is an integer ·· - 30 from 0 to 1; a + 2b is an integer from 1 to 10; c is * · * an integer from 1 to 5 and is on average in the range 1 ..., j to 4, and is less than or equal to the number of nitrogen atoms in the molecule; x is an integer from 0 to 1; y is an integer from 0 to 1; jax + y is equal to 1.

'·' '35 In interpreting this formula, it is required that R 3 and' * 'H atoms be attached to the nitrogen valences of the unsaturated tower within the parentheses of the formula. Thus, the formula encompasses, for example, the resulting formulas wherein R 3 is attached to the terminal nitrogen atoms, and the isomeric derived formulas wherein it is attached to the nitrogen atoms which are not in the terminal position. Nitrogen atoms that are not attached to R 3 may have hydrogen or an AXN substituent.

The hydrocarbon-substituted amines useful in the present invention of Formula II above are monoamines such as poly (propylene) amine, N, N-dimethyl-n-poly (ethylene / propylene) amine (monomer molar ratio 50: 50), poly (isobutene) amine, N, N-di (hydroxyethyl) -N-poly (isobutene) amine, poly (isobutene / 1-butene / 2-butene) amine (50:25 monomer ratio): 25), N- (2-15 hydroxyethyl) -N-poly (isobutene) amine, N- (2-hydroxypropyl) -N-poly (isobutene) amine, N-poly (1-butene) aniline , and N-poly (isobutene) morpholine; as well as polyamines such as N-poly (isobutene) ethylenediamine, N-poly (propylene) trimethyldiamine, N-poly (1-butene) di-20-ethylenetriamine, Ν ', N'-poly (isobutene) tetraethylene pentamine, N , N-dimethyl-N'-poly (propylene), and 1,3-propylene diamine.

In the gasoline compositions of this invention,; · Useful hydrocarbon-substituted amines are also; 25 certain N-amino hydrocarbon morpholines of general formula: R 3 N (A) UM (III); * 30 wherein R 3 is an aliphatic hydrocarbon group having 30 to 400 carbons, A is hydrogen, a hydrocarbon group having 1 to 10 carbon atoms -: a atom, or a hydroxy hydrocarbon group having from 1 to 10 carbon atoms, U is an alkylene group having from 2 to 10 carbon atoms and M is a morpholine structure. These hydrocarbon-substituted amino hydrocarbon morpholines, as well as the polyamines of formula II, are among the typical hydrocarbon-substituted amines used in the preparation of the present invention.

A person skilled in the art is familiar with a number of acylated nitrogen-containing compounds having a hydrocarbon-based substituent having at least 10 aliphatic carbon atoms, prepared by reacting a carboxylic acid acylating agent with an amino compound. The acylating agent binds to the amino compound via an imido, amido, amidine or acyloxyammonium bond. The hydrocarbon-based subs-10 substituent having at least 10 aliphatic carbon atoms may be present in either a portion of the molecule derived from a carboxylic acid acylating agent or a moiety derived from an amino compound. However, it is preferably present in the moiety derived from the acylating agent. The acylating agent may range from formic acid and its acylating derivatives to acylating agents having high molecular weight aliphatic substituents up to 5,000, 10,000 or 20,000 carbon atoms. Amino compounds can range from ammonia itself to amines having aliphatic substituents up to 30 carbon atoms.

A typical class of acylated nitrogen-containing compounds useful in the compositions of this invention are those prepared by the administration of an acylating agent having at least 10 carbon atoms! an aliphatic substituent, and a nitrogen compound having *,! characterized by the presence of at least one -NH group, react * »· '·' 'with one another. Typically, the acylating agent is a mono- or polycarboxylic acid (or a reactive equivalent thereof), such as substituted succinic or propionic acid, and the amino compound is a polyamine or a mixture of polyamines, most typically a mixture of ethylene polyamines. The amine may also be a hydroxyalkyl-substituted polyamine. Such acylating agents preferably have an aliphatic substituent having an average of at least 30 or 50 and up to 400 "carbon atoms.

114991 10

Illustrative hydrocarbon-based substituent groups containing at least ten aliphatic carbon atoms include n-decyl, n-dodecyl, tetrapropenyl, n-octa-decyl, oleyl, chlorooctadecyl, and tri -contanyl.

Generally, hydrocarbon-based substituents are prepared from homo- or interpolymers of mono- and diolefins having from 2 to 20 carbon atoms, such as ethylene, propylene, 1-butene, isobutene, butadiene, isoprene, 1-hexene and 1-octene (e.g. copolymers, terpolymers). Typically, these olefins are mono-olefins. The substituent may also be derived from halogenated (e.g., chlorinated, brominated) analogs of such homo- and interpolymers. However, the substituent may be prepared from other sources, such as monomeric high molecular weight alkanes (e.g. -20 of alkenes, such as those produced by the Zieg-ler-Natta process (e.g., polyethylene fats) and others. from sources familiar to those skilled in the art. Any unsaturation in the substituent may be reduced or eliminated by hydrogenation according to methods known in the art.

!. As used herein, the term "hydrocarbon-based, icy" refers to a group having a carbon atom directly "*" attached to the remainder of the molecule and having a predominant hydrocarbon character in the context of the present invention. for every ten: for carbon atoms, provided that this non-hydrocarbon group does not significantly alter the predominant hydrocarbon nature of the group, and those skilled in the art are aware of such groups as, for example, hydroxyl, halogen (especially chlorine and fluorine), however, usually the hydrocarbon-based substituents are purely hydrocarbons and do not contain such non-hydrocarbon groups.

These hydrocarbon-based substituents are substantially saturated, i.e. contain no more than one carbon-carbon-unsaturated bond for every ten simple carbon-carbon bonds present. Typically, they contain no more than one non-aromatic unsaturated carbon-carbon bond per lane of 50 present carbon-carbon bond.

The hydrocarbon-based substituents are also substantially aliphatic in nature, i.e., they contain no more than one non-aliphatic group (cycloalkyl, cycloalkenyl, or aromatic) having six or less 15 carbon atoms for every ten carbon atoms of the substituent. Usually, however, the substituents do not contain more than one such non-aliphatic group for every fifty carbon atoms, and in many cases do not contain any such non-aliphatic groups; in other words, typical substituents are purely aliphatic. Typically these tel -: * '. again the aliphatic substituents are alkyl or alkynyl.

Particular examples of substantially saturated hydrocarbon-based substituents containing an average of more than 30 carbon atoms include the following: a mixture of poly (ethylene / propylene) groups having from 35 to 70 carbon atoms, a mixture of oxidized or mechanically degraded poly (ethylene / propylene) from 35 to 70 carbon atoms, a mixture of poly (propylene / 1-hexene) groups having from 80 to 150 carbon atoms, and a mixture of polyisobutene groups having an average of 50 to 75 carbon atoms.

; A preferred source of substituents are polyisobutenes obtained by polymerization of a C4 refinery stream having a 35 to 75 weight percent butene content and a 30 to 60 weight percent isobutene content, a Lewis acid catalyst such as alumina 11499112 or trichloride boron. in the presence of. These polyisobutenes contain predominantly (more than 80% of all repeating units) repeating isobutene units having the structure: 5 -C (CH 3) 2CH 2 -.

Examples of amino compounds useful in the preparation of these acylated compounds include the following: (1) polyalkylene polyamines of general formula: (R4) 2N [PN (R4)] mR4 (IV) wherein each R4 is independently a hydrogen atom, a hydrocarbon group, or a hydroxy substituted hydrocarbon group; containing up to 30 carbon atoms, provided that at least one of R 4 is hydrogen, m is an integer from 1 to 10 and P is a C 1-8 alkylene group; (2) hydroxyalkyl-substituted polyamines wherein the polyamines are as described above; · '·, (3) heterocyclic substituted polyamines wherein the polyamines are as described above and the heterocyclic substituent. the support is derived, for example, from piperazine, imidazoline, pyrimidine or morpholine; and λ (4) aromatic polyamines having the general formula: t

Ar (NR42) z (V). Wherein Ar is an aromatic ring having 6 to 20 carbon atoms, each R 4 is as described above and z is 2 to 8.

: Specific examples of the polyalylene polyamine polyamines of formula IV are ethylenediamine, tetra (ethylene) pentaamine, tri (trimethylene) tetraamine, and 1,2-v * 35 propylene diamine.

»? i 114991 13

Specific examples of hydroxyalkyl-substituted polyamines include N- (2-hydroxyethyl) ethylenediamine, N, N'-bis- (2-hydroxyethyl) ethylenediamine and N- (3-hydroxybutyl) tetramethylenediamine.

Specific examples of heterocyclic-substituted polyamines include N-2-aminoethylpiperazine, N-2- and N-3-aminopropylmorpholine, N-3- (dimethylamino) -propylpiperazine, 2-heptyl-3- (2-aminopropyl) imidazoline. , 1,4-bis (2-aminoethyl) piperazine, 1- (2-hydroxyethyl) piperazine, and 2-heptadecyl-1- (2-hydroxyethyl) imidazoline.

Specific examples of aromatic polyamines are the various isomeric phenylenediamines and the various isomeric naphthalenediamines.

Many patents have described useful acylated nitrogen compounds, including U.S. Patent Nos. 3,172,892, 3,219,666, 3,272,746, 3,310,492, 3,341,542, 3,444,170, 3,455,831, 3,455,832, 3,576 743, 3 630 904.

3,632,511; 3,804,763; and 4,234,435. A typical acylated nitrogenous compound of this class 20 is that prepared by the administration of a polyisobutene-substituted succinic acid anhydride acylating agent having a polyisobutene-substituent of 50-400 carbon atoms, reacting with a mixture of ethylene polyamines having from 3 to 7 liters *; 25 nitrogen atoms per ethylene polyamine.

Another type of acylated nitrogen compounds belonging to this class is that prepared by reacting the above alkylene amines with the aforementioned substituted succinic or anhydrides 30 and aliphatic monocarboxylic acids having 2 to 12 carbon atoms. In these acylated nitrogen compounds *: *; In the types, the molar ratio of succinic acid to monocarboxylic acid is in the range of 1: 0.1 to 1: 1. Typical monocarboxylic acids include formic acid, acetic acid, dodecanoic acid, · butanoic acid, oleic acid, sterile acid, a commercial mixture of stearic acid isomers known as iso- 114991 14 stearic acid, and tolylic acid. Such materials are more fully described in U.S. Patents 3,216,936 and 3,250,715.

Another type of acylated nitrogen compounds useful in the benzene compositions of this invention is the product of the reaction of a fatty monocarboxylic acid of 12 to 30 carbon atoms with alkylene amines, typically ethylene, propylene or trimethylene polyamines, containing 2-8 amino acids. , or 10 between these mixtures. Fatty monocarboxylic acids are generally mixtures of straight and branched chain fatty carboxylic acids containing from 12 to 30 carbon atoms. The widely used type of acylated nitrogen compounds is prepared by reacting the above alkylene polyamine 15 with a fatty acid mixture of 5 to 30 mol% of straight chain acid and 70 to 95 mol% of branched chain fatty acids. Commercially available mixtures include those widely known in the art as iso-stearic acid. These mixtures are prepared as a by-product of the dimerization of unsaturated fatty acids as described in U.S. Patent Nos. 2,812,342 and 3,260,671.

• '·. Branched Fatty Acids may also contain • 4 non-alkyl branched moieties found in phenyl and cyclohexyl steroic acids | V; 25 and chloro stearic acid. The products of the branched chain fatty carboxylic acids / alkylene polyamines are described, for example, in U.S. Patent Nos. 3,101,673, 3,251,853, 3,326,801, 3,337,459, 3,405,064, 3,429,674, 3,468,639 and 3,857,791.

;;; Phenol / aldehyde / amino compound condensates which '··' are useful as dispersants in the gasoline compositions of this invention include those which are · generally referred to as Mannich condensates. Generally, they are prepared by reacting at the same time At least one active hydrogen compound, sequentially or sequentially,

<> M

such as a hydrocarbon substituted phenol (e.g. alkylphenol, 114991 wherein the alkyl group has at least an average of 12-400, preferably 30-400 carbon atoms) having at least one hydrogen atom bonded to an aromatic carbon, at least one aldehyde or aldehyde-producing material (typically formaldehyde). and at least one amino or polyamino compound having at least one NH group. Amino compounds include primary or secondary monoamines having hydrocarbon substituents from 1 to 30 carbon atoms or hydroxyl substituted hydrocarbon substituents from 1 to 30 carbon atoms. Another type of typical amino compounds are the polyamines described during the presentation on acylated nitrogenous compounds.

Examples of monoamines are methylethylamine, methyloctadecylamines, aniline, diethylamine, diethanolamine and dipropylamine. The following patents contain extensive descriptions of Mannich condensates: U.S. Patents 2,459,112, 3,413,347, 3,558,743, 2,962,442, 3,442,808, 3,586,629, 2,984,550, 3,448,047, 3,591,598, 3,036. 003, 3,454,497, 3,600,372, 3,166,516, 3,459,661, 20,363,515, 3,236,770, 3,461,172, 3,649,229, 3,555,270, 3,493,520, 3,697,574, 3,368,972 and 3,539,633.

• '** Condensates made from sulfur

• I

These reagents may also be used in the gasoline compositions of this invention. Such sulfur-containing condensates are described in U.S. Patents 3,368,972, 3,649,229, 3,600,372, 3,649,659, and 3,741,896. . titers also describe sulfur-containing Mannich condensates.

In general, the condensates used in the preparation of the compositions of this invention are made from phenol ;;;; 30 having an alkyl substituent of 6 to 400 carbon atoms, more typically 30 to 250 carbon atoms. These typical condensates; tit is made from formaldehyde or C2-7 aliphatic ···; aldehyde as well as an amino compound such as those used in the preparation of the acylated nitrogen-containing compounds described above.

.1 (»114991 16) These preferred condensates are prepared by reacting one molar portion of a phenolic compound with 1-2 molar aldehyde and 1-5 equivalents amino compound (one equivalent amino compound being 5 molar masses divided by the number of -NH groups therein). wherein such condensation reactions are performed are known to those skilled in the art.

A particularly preferred class of nitrogen-containing condensation products for use in the gasoline compositions of this invention are those prepared by (1) administering at least one hydroxy aromatic compound containing an aliphatic or cycloaliphatic substituent having at least 30 carbon atoms and up to 400 carbon atoms With C 1-7 aldehyde or a reversible polymer thereof in the presence of a basic reagent such as an alkali metal hydroxide at a temperature not exceeding 150 ° C; (2) substantially neutralizing the reaction mixture thus formed intermediate product; and (3) reacting the neutralized intermediate with at least one amino-containing compound containing at least one -NH group.

More preferably, these condensates are prepared from (a) phenols having a hydrocarbon-based substituent of 30 to 250 carbon atoms, said substituent being pe-N. 25 of a polymer of propylene, 1-butene, 2-butene or isobutene, and (b) formaldehyde or its reversible polymer (e.g., trioxane, paraformaldehyde) or a functional equivalent thereof (e.g., methylol) and (c), an alkylene polyamine such as ethylene having from 30 to 10 nitrogen atoms.

* ·· 'In the gasoline compositions of this invention, the esters useful as dispersants are derivatives of substituted carboxylic acids having a substantially aliphatic, substantially' · * '35-membered saturated hydrocarbon group containing at least 30, preferably at least 50 and up to 750 114991 17 aliphatic carbon atoms. As used herein, the term "hydrocarbon-based group" refers to a group having a carbon atom directly attached to the remainder of the molecule and having the predominant hydrocarbon nature of the present invention. Such groups include: (1) Hydrocarbon groups; that is, aliphatic groups, aromatic and alicyclic substituted aliphatic groups, and the like, which are known to those skilled in the art.

(2) Substituted hydrocarbon groups; that is, groups containing non-hydrocarbon substituents which, in the context of this invention, do not alter the predominant hydrocarbon nature of the group. Those skilled in the art will be aware of suitable substituents; examples include halogens, nitro, hydroxy, alkoxy, carbalkoxy and alkylthio.

(3) Hetero groups; in other words, groups which are predominantly hydrocarbons in the context of this invention contain non-carbon atoms present in a chain or ring otherwise composed of carbon atoms. Suitable heteroatoms will be apparent to those skilled in the art and include, for example, nitrogen, oxygen and sulfur.

• '·. Generally, no more than about three substituents or heteroatoms, and preferably no more than one, are present for each 10 carbon atoms based on hydrocarbons. 25 sa group.

Substituted carboxylic acids are prepared by standard alkylation of nor -, -; - t with an unsaturated acid or the like. a derivative such as anhydride at the source of the desired hydrocarbon based group. Suitable unsaturated acids and derivatives thereof include acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid; : acid, itaconic acid anhydride, citraconic acid, citric acid, · acid anhydride, mesaconic acid, glutaconic acid, chloremaleic acid, aconitic acid, crotonic acid, methylcrotonic acid, 2-dicarboxylic acid, sorbic acid, , 3,5-tricarboxylic acid. Particularly preferred 11499118 are unsaturated dicarboxylic acids and their derivatives, in particular maleic acid, fumaric acid and maleic anhydride.

Suitable alkylating agents include homopolymers and interpolymers of polymerizable olefinic monomers containing from 2 to 10 and usually from 2 to 6 carbon atoms, and derivatives thereof containing polar substituents. Such polymers are substantially saturated (i.e., contain no more than about 5% olefinic linkages) and substantially aliphatic (i.e., contain at least 80% and preferably at least 95% by weight of units derived from aliphatic monoolefins). Illustrative monomers that may be used to prepare such polymers include ethylene, propylene, 1-butene, 2-butene, isobutene, 1-octene, and 1-decene. Possible unsaturated units may be derived from conjugated dienes such as 1,3-butadiene and isoprene; unconjugated dienes such as 1,4-hexadiene, 1,4-cyclohexadiene, 5-ethylidene-2-norbornene and 1,6-octadiene; and trienes such as 1-isopropylidene-3a, 4,7,7a-tetrahydro-indene, 1-isopropylidene-dicyclopentadiene and 2: *; (2-Methylene-4-methyl-3-pentenyl) [2.2.1] -bicyclo-5-heptene.

A first preferred class of polymers comprises those derived from terminal olefins such as propene, 1-butene, isobutene and 1-hexene. Particularly preferred in this class are polybutenes, which mainly contain isobutene units. Another preferred class consists of ethylene, C3-8 alpha-mono-olefin and polyene selected from the group consisting of conjugated dienes (which are particularly preferred) and trienes, terpolymers. An illustrative such terpolymer is "Ortholeum 2052" manufactured by E.I. duPont de Nemours 35 & Company, which is a terpolymer containing about 48 '1 mol% ethylene groups, 48 mol% propylene groups and 4 mol% 1 14991 19 1,4-hexadiene groups and having a specific viscosity of 1.35 ( 8.2 g of polymer in 10 ml of carbon tetrachloride at 30 ° C).

Methods for preparing substituted carboxylic acids and derivatives thereof are well known in the art and need not be described in detail. Reference is made, for example, to U.S. Patent Nos. 3,272,746, 3,522,179, and 4,234,435. The molar ratio of polymer to unsaturated acid or derivative thereof may be equal to, greater than or equal to 10, depending on the type of product desired.

Esters are esters of the substituted carboxylic acids described above with hydroxy compounds which may be aliphatic compounds such as monohydric and polyhydric alcohols or aromatic compounds such as phenols or naphthols. Examples of aromatic hydroxy compounds include phenol, beta-naphthol, alpha-naphthol, cresol, resoscinol, catechol, p, p1-dihydroxybiphenyl, 2-chlorophenol, 2,4-dibutylphenol, propylene tetramer substituted phenol, 4-didodecylphenol, , 4'-methylene-bisphenol, alpha-Decyl-beta-naphthol, polyiso-; · .. phenol substituted with butene (molecular weight 1000) * * | the product of heptylphenol and formaldehyde, the condensation product of octylphenol and acetone, di (hydroxy-2-phenyl) oxide, di (hydroxyphenyl) sulfide, di (hydroxyphenyl) di sulfide and 4-cyclohexyl phenol. Phenol and alkylated phenols having up to three alkyl substituents are preferred. Each of the alkyl substituents may contain 100 or more carbon atoms.

The aliphatic alcohols from which the esters may be derived preferably contain up to 40 aliphatic carbon atoms. They may be monohydric alcohols, such as methanol, ethanol, iso-octanol, dodecanol, cyclohexanol, cyclopentanol, behenyl alcohol, hexatri- * acontanol, neopentyl alcohol, isobutyl alcohol, benz 'xyl alcohol, beta-methyl alcohol, beta - 114,491 lohexanol, beta-chloroethanol, diethylene glycol mono-methyl ether, diethylene glycol mono-butyl ether, triethylene glycol monododecyl ether, ethylene glycol mono-oleate, diol, li and glycerol dioleate. The polyhydric alcohols preferably contain from 2 to 10 hydroxy radicals. They are exemplified by, for example, ethylene glycol, diethylene glycol, tri-ethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, dibutylene glycol, tributylene glycol, and other alkylene glycols containing alkylene radicals. Other useful polyhydric alcohols include glycerol, glycerol mono-15-oleate, glycerol monostearate, glycerol monomethyl ether, pentaerythritol, 9,10-dihydroxystearic acid, 9,10-dihydroxystearic acid methyl ester, 1,2-butane, 2,4-hexanediol, penacol, erythritol, arabitol, sorbitol, mannitol, 1,2-cyclohex-20 -anediol, and xylene glycol. Carbohydrates such as sugars, starches and cellulose may also be; *, to obtain esters useful in the present invention. Of these: '· * carbohydrates may be exemplified by glucose, fruc-. tose, sucrose, rhamnose, mannose, glyceraldehyde and galactose.

A particularly preferred class of polyhydric alcohols are those having at least three hydroxy radicals, some of which have been esterified with a monocarboxylic acid of 8 to 30 carbon atoms, such as octanoic acid, oleic acid, stearic acid, linoleic acid, dodecanoic acid. Examples of such partially esterified polyhydric alcohols are sorbitol mono-oleate, sorbitol distearate, glycerol mono-oleate, glycerol monostearate, erythritol diode-35 canoate.

These esters may also be derived from unsaturated alcohols such as allyl alcohol, Kinnamyl alcohol, propargyl alcohol, 1-cyclohexen-3-ol and oleyl alcohol. Yet another class of alcohols-5 and capable of providing esters useful in the present invention are ether alcohols and amino alcohols including, for example, oxyalkylene, oxiarylene, aminoalkylene and aminoarylene substituted alcohols having one or more oxyalkylene, oxo-10 siarylene, aminoalkylene or aminoarylene radicals. Examples of these are Cellosolve, carbitol, phenoxyethanol, heptylphenyl (oxypropylene) 6-H, octyl (oxyethylene) 30-H, phenyl (oxyoctylene) 2-H, mono (heptylphenyl-oxypropylene) substituted glycerol, poly (sty-15 rhenium oxide), aminoethanol, 3-aminoethylpentanoyl, di- (hydroxyethyl) amine, p-aminophenol, tri (hydroxypropyl) amine, N-hydroxyethylethylenediamine, and N, N, N ', N' -tetrahydroksitrimetyleenidiamiini. Mostly ethereal alcohols having up to about 150 oxyalkylene radicals having an alkylene radical containing from 1 to 8 carbon atoms are preferred.

; Esters may be diesters of succinic acids; or acidic esters, i.e. partially esterified polyhydric. alcohols or phenols, i.e. esters with 25 free alcoholic or phenolic hydroxyl radicals.

Mixtures of the above esters are also intended to be included within the scope of this invention.

Esters of succinic acid can be prepared by any of several methods. The process, which is advantageous due to the good properties of the help and the esters it produces, comprises the reaction of a suitable alcohol or phenol with substantially hydrocarbon substituted succinic acid hydride. The esterification is usually carried out at a temperature above about 100 ° C, preferably between about 150 ° C and 300 ° C.

• »114991 22

The by-product water is removed by distillation as the esterification progresses. The solvent can be used in esterification to facilitate mixing and temperature control. It also facilitates the removal of water from the reaction mixture. Useful solvents include xylene, toluene, diphenyl ether, chlorobenzene and mineral oil.

A variation of the above method involves replacing the substituted succinic anhydride with the corresponding succinic acid. However, succinic acids readily dehydrate at temperatures above about 100 ° C and thus convert to anhydrides which are then esterified by reaction with an alcohol reagent. In this respect, succinic acids appear to be substantially equivalent to their anhydrides in this process.

The relative proportions of succinic acid reagent and hydroxy reagent to be used will largely depend on the type of product desired and the number of hydroxyl groups present in the hydroxy reagent molecule. For example, the formation of a semi-ester of succinic acid, i.e. one in which only one of the two acid radicals is esterified, comprises one mole of monohydric al. use of alcohols per mole of substituted succinic acid, while the succinic acid diester »«. formation involves the use of two moles of alcohol, v. 25 for each mole of acid. On the other hand, one mole of hexahyd! this alcohol may be combined with up to six moles of succinic acid to form an ester in which each of the six hydroxyl radicals of the alcohol is esterified with one of the two acid radicals of succinic acid. Thus, the maximum proportion of succinic acid, used with po-30 short hydrate alcohol, is determined by the number of hydroxyl groups present in the hydroxy-reagent molecule. This biscuit; for the purpose of the invention, it has been found that the esters obtained by the reaction of equimolar amounts of amber acid reagent and hydroxy reagent have superior properties and are therefore preferred.

114991 23

In some cases, it is preferable to carry out the esterification using a catalyst such as sulfuric acid, pyridine hydrochloride, hydrochloric acid, benzenesulfonic acid, p-toluenesulfonic acid, phosphoric acid or any other known esterification catalyst. The amount of catalyst in the reaction can be as low as 0.01% (by weight of the reaction mixture), most often 0.1% to 5%.

Alternatively, the succinic esters may be obtained by reaction of the substituted succinic acid or anhydride with an epoxide or a mixture of epoxide and water. Such a reaction is similar to an acid or anhydride and glycol. For example, the product may be prepared by the reaction of substituted succinic acid with one mole of ethylene oxide. Similarly, the product can be obtained by reaction of substituted succinic acid with two moles of ethylene oxide. Other epoxides commonly available for use in such a reaction include, for example, propylene oxide, styrene oxide, 1,2-butylene oxide, 2,3-butylene oxide, epichlorohydrin, cyclohexene oxide, 1,2-octylene oxide, epoxidized soybean oil, 9,10-epoxide methyl ester and Buta-I 1. dieenimonoepoksidi. Mostly, the epoxides are alkylene and oxides having from 2 to 8 carbon atoms in the alkylene radical. mia; or epoxidized fatty acid esters with 25 fatty acid radicals having up to 30 carbon atoms and an ester ring (the dical is derived from a lower alcohol having up to 8 carbon atoms.

Instead of succinic acid or its anhydride, lactonic acid or substituted succinic acid halide may be used in the methods described above. Such halides may be acid dibromides, acid dichlorides, acidic monochlorides and acid monobromides. Substituted succinic anhydrides and acids can be prepared, for example, by reaction of maleic anhydride with a high molar mass of 35 olefin or a halogenated hydrocarbon such as that obtained by chlorination of the previously described 114991 24 olefin polymer. This reaction involves merely heating the reagents to a temperature, preferably between 100 ° C and 250 ° C. The product of such a reaction is alkenyl succinic anhydride. The alkenyl group may be hyd-5-alkylated. The anhydride can be hydrolyzed by treatment with water or steam to the corresponding acid. Another method useful for the preparation of succinic acids or anhydrides involves the reaction of itaconic acid or its anhydride with an olefin or a chlorinated hydrocarbon at a temperature usually in the range of 100 ° C to 250 ° C. Succinic acid halides can be prepared by reaction of acids or their anhydrides with a halogenating agent such as phosphorus tribromide, phosphorus pentachloride or thionyl chloride. These and other methods for preparing succinic acid compounds are well known in the art and need not be described in further detail herein.

Still other processes for preparing the esters 20 useful in the gasoline compositions of this invention are available. For example, these esters may be obtained by reaction of maleic acid or its anhydride with the alcohol described above, whereby: a mono- or di-ester of maleic acid is formed, and then 1: | ; ester reaction with an olefin or a chlorinated hydrocarbon,. 25 described above. They can also be obtained by first esterifying itaconic anhydride or acid and then reacting the ester intermediate with an olefin or a chlorinated hydrocarbon under similar conditions as described above.

; A large number of different types of polymeric dispersants have been proposed as useful in lubricating oil; ; compositions, and such polymeric dispersants; they are useful in the gasoline compositions of this invention. Such additives have often been found to be useful in lubricating compositions as viscosity improving agents having dispersant properties. These polymeric dispersants are generally polymers or copolymers having a long carbon chain and having "polar" groups to give them dispersing properties. Examples of polar groups include amino, amido, imino, imido, hydroxyl and ether groups. Polymeric dispersants can be, for example, copolymers of methacrylates or acrylates containing polar groups, ethylene / propylene copolymers containing polar groups, or vinyl acetate / fumaric acid ester copolymers.

Many such polymeric dispersants have been previously described in the art, for example in U.S. Patents 4,402,844, 3,356,763 and 3,891,721.

A number of these polymeric dispersants can be prepared by grafting polar monomers onto polyolefinic backbones. For example, U.S. Patents 3,687,849 and 3,687,905 describe the use of maleic anhydride as a grafting monomer on a polyolefinic backbone. Maleic acid 20 or its anhydride is a particularly good graft monomer because this monomer is relatively inexpensive and provides economical; , a further route to the addition of dispersing nitrogen compounds to the polymers by the following reaction with maleic acid or. carboxyl groups of an anhydride and, for example, nitrogen compounds, pathways or hydroxy compounds. U.S. Patent J ·, ·, 4,160,739 discloses graft copolymers obtained by grafting a monomer system containing maleic acid or its anhydride and at least one other monomer which is additive polymerizable thereto, and : The grafted monomer system is reacted with * * = '· ... · da polyamine. The monomers which copolymerize with maleic acid or its anhydride are any; alpha-beta-monoethylenically unsaturated monomers which are sufficiently soluble in the reaction medium '35 and reactive with maleic acid or its anhydride to allow substantially higher amounts of maleic acid 114991 26 or its anhydride to be incorporated into the grafted polymeric product. Accordingly, suitable monomers include esters, amides and nitriles of acrylic and methacrylic acids, and monomers which do not contain free acid groups. Incorporation of heterocyclic monomers in graft copolymers has been described by a process comprising the first step of graft polymerizing an alkyl acrylic acid or methacrylic acid ester, alone or in combination with styrene, to a backbone copolymer of hydrat-10, styrene and conjugated to form a graft polymer. In a second step, the polymerizable heterocyclic monomer, alone or in combination with a hydrophobising vinyl ester, is copolymerized with the first graft copolymer to form a second graft copolymer.

Other patents describing graft polymers useful as dispersants in the gasoline compositions of this invention are U.S. Patents 20,343,481, 3,475,514, 3,723,575, 4,026,167, 4,085,055, 4,181,618, and 4,476,283.

Another class of polymeric dispersants useful in the gasoline compositions of this invention are so-called "star 25" polymers and copolymers. There are such polymers! described, for example, in U.S. Patent Nos. 4,346,193, 4,141,847, 4,358,565, 4,409,120, and 4,077,893.

The hydrocarbon-substituted phenolic dispersants useful in the gasoline compositions of this invention are hydrocarbon-substituted phenolic compounds wherein the hydrocarbon substituents have molecular weights sufficient to convert the phenolic compound into a fuel. Generally, the hydrocarbon substituent is a substantially saturated hydrocarbon V '35 nitrogen-based group having at least 30 carbon atoms. These phenolic compounds may be represented generally by the following formula: (R5) e-Ar1- (OH) f (VI) 5 wherein R5 is a substantially saturated hydrocarbon-based substituent having an average of 30 to 400 aliphatic carbon atoms, and e and f are each 1, 2 or 3. Ar 1 is an aromatic group such as a benzene ring, a naphthalene group, or linked benzene rings. Optionally, the above-described phenates of formula VI may contain other substituents such as lower alkyls, lower alkoxy, nitro, amino and halogen groups. Preferred examples of optional substituent supports include nitro and amino groups.

A substantially saturated hydrocarbon-based group R5 in Formula VI may contain up to 750 aliphatic carbon atoms, although it typically has a maximum average of 400 carbon atoms. In some cases, 20 R5 has a minimum of 50 carbon atoms. As noted, the phenolic compound may contain more than one aromatic core of the aromatic moiety of the aromatic moiety of R5-i ··· m.

Generally, hydrocarbon-based groups R5 are derived. 25 homo- or interpolymers (e.g., copolymers, terpolymers) of mono- and diolefins having from 2 to 10 carbon atoms, such as ethylene, propylene, 1-butene, isobutene, butadiene, isoprene, 1-hexene, n -okteenista. Typically, these olefins are ···· 30 1-mono-olefins. The groups R5 may also be derived from the halogenated * · * ··· 'of such homo- or interpolymers; (e.g., chlorinated or brominated) analogs. However, the R5 groups may also be prepared from other sources, such as monomeric high molecular weight alkenes (e.g., 1-tetraconene) and their chlorinated and '' chlorinated analogs, aliphatic petroleum fractions, in particular paraffin waxes and their Kraka chlorinated as well as hydrochlorinated analogs, white oils, synthetic alkenes such as those produced by the Ziegler-Natta process (e.g., polyethylene fats) and other sources known to those skilled in the art. Any unsaturation in the R5 groups may be reduced or eliminated by hydrogenation according to methods known in the art prior to the nitration step described below.

Particular examples of substantially saturated hydrocarbon-based groups R5 are: tetracontanyl group, henpentacontanyl group, mixture of 35-70 carbon atoms of poly (ethylene / propylene), mixture of 35-70-15 carbon atoms of oxidised or mechanically decomposed poly (propylene), a mixture of poly (propylene / l-hexene) groups of 80 to 150 carbon atoms, a mixture of polyisobutene groups of 20 to 32 carbon atoms, and a mixture of polyisobutene groups having an average of 50 to 75 carbon atoms.

A preferred source of R5 groups is polyisobutenes obtained by polymerization of a C4 refinery stream having a buenium content of 35-75% by weight and an isobutene content of 30-60% by weight of a Lewis acid catalyst such as aluminum tri-; in the presence of chloride or boron trifluoride. These polyisobutenes contain predominantly (> 80% of all repeating units) repeating isobutene units having a t * structure of: i> • -C (CH 3) 2 CH 2 - 30 * t e.

The attachment of hydrocarbon-based group R to the aromatic *; ··· aromatic group Ar1 can be accomplished by a variety of methods known to those skilled in the art.

In a preferred embodiment, petrol compositions useful in the gasoline compositions of this invention are

Mil + 'dispersants are hydrocarbon-substituted 114991 29 nitrophenols represented by Formula VI wherein the optional substituent is one or more nitro groups. These nitrophenols can be readily prepared by nitration of suitable phenols, and typically these nitrophenols are prepared by nitration of alkyl phenols having at least 30 carbon atoms, and preferably at least 50 carbon atoms. The preparation of a number of hydrocarbon-substituted nitro-phenols useful in the gasoline compositions of this invention is described in U.S. Patent 4,347,148. In another preferred embodiment, the hydrocarbon-substituted amino groups. These amino-15 phenols are most readily prepared by nitration of the appropriate hydroxy aromatic compound as described above and subsequent reduction of the nitro groups to amino groups. Typically useful aminophenols are formed by nitration and reduction of alkyl phenols having 20 alkyl or alkenyl groups having at least 30 and preferably at least 50 carbon atoms. A wide variety of hydrocarbon-substituted aminophenols that are useful; · As dispersants in the present invention. . is described in U.S. Patent 4,320,021.

Also useful as dispersants in the gasoline compositions of this invention are fuel soluble alkoxylated derivatives of alcohols, phenols and amines. A wide variety of such derivatives can be used as long as these derivatives are soluble in 30 fuels. More preferably, in addition to being fuel-soluble, these derivatives should ... | they must be water insoluble. Accordingly, in the preferred embodiment, the fuel-soluble alkoxylated t1 »'*' 35 useful as dispersants are characterized by HLB values ranging from 1 to 13.

30

As is known to those skilled in the art, the fuel solubility and water insolubility of alkoxylated derivatives can be adjusted by the choice of alcohol, phenol or amine, the choice of alkoxy reagent to be used, and the amount of alkoxy reactive with the alcohol, phenol or amine. Accordingly, the alcohols used in the preparation of these alkoxylated derivatives are hydrocarbon-based alcohols, while the amines are the hydrocarbon-substituted amines described above. Phenols may be phenols or hydrocarbon-substituted phenols, and the hydrocarbon substituent may have as little as 1 carbon atom.

The alkoxylated derivatives are obtained by reacting an alcohol, a phenol or an amine with a mixture of epoxide or epoxy and water. For example, the derivative may be prepared by reaction of an alcohol, phenol or amine with an equal molar or excess amount of ethylene oxide. Other epoxides which may be reacted with an alcohol, phenol, or amine include, for example, pro-20 pylene oxide, styrene oxide, 1,2-butylene oxide, 2,3-butylene oxide, epichlorohydrin, cyclohexene oxide and. .. 1,2-octylene oxide. Preferably, these epoxides are alkyl: oxides having 2-8 carbon atoms in the alkylene group; mia. As mentioned above, it is desirable and preferred that the amount of alkylene oxide reacting with the alcohol, phenol or amine is insufficient to render the derivative water-soluble.

The following are examples of commercially available alkylene oxide derivatives which may be used as dispersants in the gasoline compositions of this invention; Ethomeen S / 12, ethylene oxide condensation products of tertiary amines from primary fatty amines (HLB 4.15; Armak Industries); and Plurafac A-24, an oxyethylated straight chain alcohol available from BASF Wyandotte Industries (HLB 5.0). Other suitable fuel soluble alkoxylated derivatives 114991 31 from alcohols, phenols and amines are readily apparent to those skilled in the art.

In a particularly preferred embodiment, in addition to the polyalphaolefin and the polyoxyalkylene compound, the gasoline composition of this invention may further comprise, as an ashless dispersant, a small amount of a polyolefin substituted succinimide derivative wherein the polyolefin has an Mn of from 800 to 5000, preferably more preferably at least 1,750, 1,800 or 1,850 and 10 at most 400, 3500, 3000 or 2500. The amine from which this succinimide is formed is preferably a C 1-30 amine, especially C 4-12 amine containing 7 nitrogen atoms, e.g., diethylenetriamine, triethylene tetraamine, tetramethylenepentaamine, pentaethylene hexaamine, hexa-ethylene heptamine, tripropylene tetraamine, or mixture I of any two or more thereof.

Preferably, the hydrocarbon soluble ash-free dispersant is present in an amount of from 30 to 500 ppm, more preferably from 100 to 300 ppm, based on the total weight of the composition.

The petrol composition may further comprise (e.g.

i as an alternative to the addition of a succinimide derivative) oil; a soluble polyamine as disclosed in EP Application Publication No. 290 088; or an N-substituted carbamate, one described in EP Application Publication No. 414 963, in each case in amounts similar to those described in r '.

The gasoline composition may further contain an alkali metal or alkaline earth metal salt of a succinic acid derivative as a flame retardant, as described in EP-A-290 088, in the same amounts as described therein.

...: In addition to the components described above, the gasoline composition may contain other additives. Thus, it may • contain a lead compound as an anti-knock additive, and '35 thus the gasoline composition of this invention comprises *' * both leaded and unleaded gasoline. This benzylic acid composition may also contain antioxidants such as phenolics, e.g., 2,6-di-tert-butylphenol, or phenylenediamines, e.g., N, N'-di-sec-butyl-p-phenylene-. diamine, or anti-knock agents other than lead compounds, or polyether amino additives, e.g., as described in U.S. Patent 4,477,261 and European Patent Application 151,621.

The gasoline composition of this invention contains a major portion of gasoline (base fuel) suitable for use in spark ignition engines. This includes hydrocarbon-based fuels that boil substantially in the range of 30 to 230 ° C for gasoline. These basic fuels may consist of mixtures of saturated, olefinic and aromatic hydrocarbons. They can be derived directly from distilled gasoline, synthetically produced aromatic hydrocarbon blends, thermally or catalytically cracked hydrocarbon feed streams, hydrocracked petroleum fractions or catalytically reformed hydrocarbons. The base fuel octane number of 20 is not a critical factor and is generally above 65. In gasoline, hydrocarbons can be substituted in significant amounts: up to alcohols, ethers, ketones or esters. Naturally, these base fuels are * * substantially free of water, as water may give rise to slow combustion.

The polyalphaolefin and the polyoxyalkylene compound can be easily added in admixture with other selected additives. An easy way to prepare a gasoline composition is therefore to make a concentrate of polyalfaole-30 and a polyoxyalkylene compound together with other additives, and then to add this concentrate to gasoline in the amount required to achieve the required final additive concentrations.

. Accordingly, the present invention further provides a V * 35 concentrate suitable for addition to gasoline, which comprises 114991 33 diluents compatible with gasoline, a polyalphaolefin as defined above, a polyoxyalefin: 1 to 10: optionally at least one ash-free ash-dispersant in carbon-5 hydrocarbon.

Preferably, the polyalphaolefin and the polyoxyalkylene compound are present together in an amount ranging from 20 to 80% by weight, and the ash-free dispersant, if present, is present in an amount ranging from 5 to 30% by weight, all percentages being based on dilution. in relation to them.

Suitable diluents compatible with gasoline include hydrocarbons, e.g. heptane, alcohols or ethers such as methanol, ethanol, propanol, 2-butoxy-15 ethanol or methyl tert-butyl ether. Preferably, the diluent is an aromatic hydrocarbon solvent such as toluene, xylene, a mixture thereof, or a mixture of toluene or xylene with an alcohol. Preferably, the solvent is toluene. Optionally, the concentrate may contain an anti-clouding agent, in particular a polyether-type ethoxylated alkylphenol-formaldehyde resin. This anti-clouding; The substance, if used, may conveniently be present in the concentrate in an amount of from 0.01 to 2% by weight, based on the diluent.

In yet another aspect, the present invention provides a method for operating a spark ignition engine comprising feeding a gasoline composition of the present invention as defined above to the combustion chambers of said engine.

The present invention will be better understood by reading the following illustrative examples. In these examples, various li · ·; · | the agents are named as follows: (a) "PGHE" is a polyoxypropylene glycol hemeether (monoether) prepared using a mixture of C12-15- '* 35 alcohols as initiator, having an Mn in the range of 1200' * to 1500 and a kinematic viscosity in the range of 72 82 114991 at 34 mm2 / s at 40 ° C as measured by ASTM D 445, available as "SAP 949" from member companies of the Royal Dutch / Shell Group; (b) "PAO" is a polyalphaolefin which is a hydrogenated oligomer of 5-decene and has a viscosity at 100 ° C of 8 x 10 6 m 2 / s (8 centistokes).

(c) "PMP" is a 40% by weight solution in xylene of polyisobutylene succinimide prepared by reaction of maleic acid anhydride with polyisobutylene having a number average molecular weight (Mn) of 2470 10 (determined by quantitative reaction with ozone), reaction of the polyisobutylene succinic anhydride product with a mixture of tetraethylene pentaamine, pentaethylene hexaamine and hexamethylene hepttaamine (molar ratio 1: 2: 1) in anhydride: amine 2: 1 molar ratio.

In the following examples, amounts of PMP are expressed as amounts of solution, and when amounts of xylene are stated, they do not include the amount of xylene associated with 40% by weight solutions of PMP.

In the examples, additive concentrates were prepared by sampling PMP and adding with stirring. At 20 ° C, amounts of PAO (plus xylene added) followed by addition of PGHE. Then samples of these li-. . of the concentrate concentrates were added to gasoline compositions; , 25 in amounts which gave the desired concentrations of the components. This reflects true industry practice, and is important both for complete additive concentrates and for petrol containing additives to provide good performance with respect to engine cleanliness and valve sticking.

; Examples 1-8. : Additive concentrates were prepared according to the present invention and comparative examples as described above * 35 and stored for 6 weeks at 20 ° C to 114991 ° C and -20 ° C, after which the stability was determined visually. The results are shown in Table I.

Table I

5 Quantities (g) Ratio Storage

Pre-Additive Oil Added PHGE: (6 weeks) brand PMP PGHE PAO xylene PAO at 20 ° C and -20 ° C 10 Vert.A 2025 - 105 1: 0 precipitated 1 20 12.5 12.5 40 1: 1 clear

Vert.B 30 30 - 100 1: 0 Slightly cloudy + 2 30 15 15 40 1: 1 Bright 15

Vert.C 30 40 - 90 1: 0 phase difference + 3 30 20 20 60 1: 1 clear 4 30 25 15 80 1.67: 1 clear 20 Vert.D 40 40 - 100 phase difference + 5 40 20 20 70 1 : 1 clear: j 6 4010 30 40 1: 3 clear •, 25 7 20 17.5 17.5 50 1: 1 clear j _ 8 25 20 20 60 1: 1 clear + = storage at 20 ° C only » . As can be easily seen, the additive concentrates of this invention containing both: PGHE and PAO had good storage stability, while the comparative examples containing only PGHE were insufficiently stable.

»* 114991 36

Examples 9-10

A standard VW Polo car equipped with a single-throttle, 4-cylinder engine with a displacement of 1.043 liters was used to assess the purity of the intake valves in a standard road test (Volkswagen Polo Road Test).

Prior to the test, the intake manifold parts and combustion chambers were cleaned, and the engine was fitted with new pre-weighed intake valves and new spark plugs, a new oil-10 line filter was installed and the engine was filled with new engine oil. A small windshield was attached to the roof of the test vehicle to increase air resistance and thus engine load. The fuel tank was emptied and filled with the gasoline composition to be tested before being used for a 5,000 km test run. 37 minute test cycles were used in which the vehicle was driven at 4500 rpm for 30 minutes at 4 (105 km / h) and then idle for 7 minutes. 12 cycles were performed daily for 8 consecutive days to complete the 5,000 km test run. At the end of the test, the suction valves were removed and weighed to determine the average weight of the suction valves.

The gasoline compositions of the present invention were subjected to comparative tests using 25 unleaded gasoline (95 ULG) without additives (base gasoline) or containing PMP and either of PGHE and PAO. The results are shown below! See Table II.

»*»% 114991 37

Table II

Concentrations (ppmw) Average Suction-Additive Oil for Valve Deposition

Experience No. PMP PGHE PAO Weight (mg) 5

Vert E 387

E.g. 9 250 250 250 31

Vert F 250 500 - 54

Vert G 250 - 500 82 10 Ex. 10 300 200 200 20

Vert H 300 300 - 44

The results in Table II show that in the cases (Examples 9 and 10) where the additive oil contains 15 combinations of PGHE and PAO, the weights of the suction valves are significantly and surprisingly lower when compared to cases where the corresponding amount of additive oil consists solely of either PGHE. . or PAO.

Examples 11 - 23 20 A regular Opel Ascona 1.6 car equipped with a standard 4-cylinder 1.6 liter; “'· With a 16SH engine, was used to evaluate the adhesion of the valves using the standard test procedure.

This test procedure involved driving a vehicle using the petrol composition to be tested on ordinary city crystals for a total distance of 130 km at low speeds (50 km / h maximum). The vehicle was then stored overnight at -20 ° C, and the maximum compression pressure of each cylinder was measured and averaged over these four; 3 0 of value. The higher the pressure value, the better the • »'*' * pi was.

·; : In a similar manner to Table II, the compositions of the tested *; · · gasoline compositions and the results obtained are shown in the following Table III, where "additive oil" ♦ · '] 35 consisted of PGHE and PAO: 38 114991

Table III

Concentrations Ratio Compression _ (ppmw) _ PGHE: PAO pressure

Experience Additive (w / w) li- (bar) 5 No. PMP oil in binder oil (x105 Pa)

Example 11 600 1050 1: 1 13.1

Vert.I 600 1500 1: 0 3.3 10 Ex.12 600 1500 4: 1 13.3

Ex. 13,600 1,500 1,5: 1,13,5

Ex.14 600 1500 1: 1.5 12.1

Ex.15 600 1500 1: 4 13.8

Vert.J 600 1500 0: 1 10.3 15

Ex.16 750 1200 1: 1 11.1

Vert.K 750 1500 1: 0 3.8

Ex.17 750 1500 4: 1 7.4 | 20 Ex.18 750 1500 1.5: 1 12.9) Ex.19 750 1500 1: 1.5 10.4; * ·· Example.20 750 1500 1: 4 13.3

Vert.L 750 1500 0: 1 13.5 • V. 25 Vert.M 900 900 1: 0 0.5

Ex.21,900,900 1.5: 1,13.3. *,; Ex.22,900,900 1: 1 13.8

Vert.N 900 900 0: 1 13.4 30 Vert.o 900 1200 1: 0 3.5 * ·· - 'Eg.23 900 1200 1: 1 13.0 »·; * * Vert.P 900 1200 0 : 1 11.8 • t ». · *

Those skilled in the art will recognize that the concentrations used above represent three times the normal commercial concentrations to increase the differences in the assay.

114991 39

The above results show that when the additive oil is a combination of PGHE and PAO, the compression pressure result is very good, always significantly better than PGHE alone, significantly better than what PGHE alone and PAO alone would predict. values, and generally comparable, and sometimes even better, than PAO alone.

Examples 24-47

The effect of the fuel composition on the precipitates of the engine intake-10 system was evaluated by the intake manifold precipitation simulation test (ISD). In this test procedure, the gasoline composition was dispensed into a spray nozzle, from which it was blown as a flat mist pattern on a surface of an aluminum tube heated to 250 ° C. The base petrol used contained thermally kra-15 gasoline to increase the formation of precipitates. Under these experimental conditions, such base naphtha alone will form a central carbon deposit on the tube surface. The purity enhancers prevent mid-range precipitation and lead to annular precipitation in the tube. The formation of residue 20 was visually evaluated on the following scale: 1 hr! 0 - clean '| 1 - 2 - almost clean; 3 - 4 - slightly carded 25 5 - 6 - moderately carded 7 - 8 - more than average carded i t 9 - 10 - badly carded • »♦ over 10 - very badly carded» 1 · ;;; 30 As in Table III, the results of the ISD tests are shown in the following Table IV: ♦ 1 * t 114991 40

Table IV

Concentrations Ratio

(ppmw) PGHE: PAO

Test Additive (w / w) Add-on ISD-5 No. PMP Oil in Resin Oil Value

Example 24 100 175 1: 1 6

Ex.25 100 200 1: 1 4 10 Vert.Q 100 250 1: 0 5

Example.26 100 250 4: 16

Example.27 100 250 1.5: 17

Example 28 100 250 1: 1.5 6

Example.29 100 250 1: 4 6 15 Vert.R 100 250 0: 1 14

Vert.S 125 250 1: 0 3

Ex.30 125 250 4: 1 3

Example 311 125 250 1.5: 1 4 20 Example.32 125 250 1: 1.5 7

Example 33 125 250 1: 4 6

Vert.T 125 250 0: 1 14

Vert.U 150 150 1: 0 2 25 Example.34 150 150 1: 1 3

Vert.V 150 150 0: 1 12

Vert.w 150 200 1: 0 4

Ex.35 150 200 1: 1 3 30 Vert.X 150 200 0: 1 12

Ex.36 200 350 1: 1 3

Vert.Y 200 500 1: 0 2 [· 35 Ex.37 200 500 4: 1 1

Example 38 200 500 1.5: 1 2 • Example 39 200 500 1: 1.5 3

Ex.40 200 500 1: 4 4: it; * 40 Vert.Z 200 500 0: 1 9 • »· • · ·

Ex.41 250 400 1: 1 3

Vert.AA 250 500 1: 0 1 45 Example 42 250 500 4: 1 1

Ex. 43 250 500 1.5: 1 2

Ex.44 250 500 1: 1.5 3 ·: ·: Ex.45 250 500 1: 4 3

Vert.BB 250 500 0: 1 6 50 Vert.CC 300 300 1: 0 1

Ex.46 300 300 1: 1 2 V · 'Vert.DD 300 300 0: 1 7

Vert.EE 300 400 1: 0 1 * 'Ex: 47 300 400 1: 1 3 55 Vert.FF 300 400 0: 1 7 114991 41

The results in Table IV show that when the additive oil is a combination of PGHE and PAO, the ISD value is generally good, always better than that of PAO alone, and significantly better than what could be predicted by PGHE alone and between PAO values alone, and generally comparable to PGHE alone.

In summary, additive concentrates containing both PGHE and PAO had good storage stability compared to similar concentrates containing PGHE but not PAO; suction valve precipitates were found to be lower for gasolines containing the additive oil in the form of a combination of PGHE and PAO compared to those where the additive oil was PGHE or PAO alone; avoiding valve sticking, as demonstrated by compression pressure measurements, was significantly better for PGHE and PAO combinations than for PGHE alone and generally comparable to PAO alone; and the avoidance of precipitation, as demonstrated by the ISD experiments, was significantly better than the combinations of PGHE and PAO than PA0 alone and generally comparable to PGHE alone.

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Claims (14)

1. Gasoline composition, characterized in that it contains for the most part gasoline suitable for use in spark ignition engines, a small part of polyphenolefin, whose viscosity at 100 ° C is in the range 2 x 10 6 - 2 x 10 10 m 2 / s (2-20 centistokes), being a hydrogenated oligomer containing 18-80 carbon atoms and derived from at least one alpha olefin monomer containing 8-16 carbon atoms, and a small amount of a polyoxyalkylene compound, selected from glycols and their mono- and dieters, and whose number average molar mass (Mn) is in the range of 400-3000, the weight ratio of poly-alpha olefin: polyoxyalkylene compound being in the range of 1: 10-10: 1. 2. A composition according to claim 1, characterized in that the polyalphaolefin is derived from an alpha-olefin monomer containing from 8 to 12 carbon atoms. 3. A composition according to claim 1 or 2, characterized in that the viscosity of the polyalphaolefin at 100 ° C is in the range 6 x 10 4. A composition according to any one of claims 1-3, characterized in that the polyoxyalkylene compound has: / FormeIn * · · V. R 2 -Or R-O - R 2 (I): n <II where R 1 and R 2 are each separately represents hydrogen atoms or C 1-40 hydrocarbon groups, each R separately represents, ··. a C 2-8 alkylene group and n is such that the polyoxyalkylene compound Mn is in the range 700-2000. Composition according to claim 4, characterized in that R 1 represents a C 8-20 alkyl group and R 2 represents a hydrogen atom. Composition according to claim 4 or 5, characterized in that each R is separately designated 114991 a C2-4 alkyl group. Composition according to any of claims 1-6, characterized in that the polyalphaolefin and the polyoxyalkylene compound together are present in an amount that is in the range 100-1200 ppm based on the total weight of the composition. Composition according to any of claims 1-7, characterized in that it also contains a small amount of at least one hydrocarbon-soluble ash-free dispersant. Composition according to claim 8, characterized in that the dispersant comprises a polyolefin-substituted succinimide derivative, wherein the Mn of the polyolefin is in the range 800-5000. 10. A composition according to claim 8 or 9, characterized in that the ashless dispersant is present in an amount in the range of 30-500 ppm based on the total weight of the composition. Composition according to any one of claims 1-10, characterized in that the weight ratio of polyalphaolefin: polyoxyalkylene compound is in the range of 1: 5-5: 1. Concentrate suitable for addition to petrol, characterized in that it contains a gasoline-compatible diluent, a polyalphaolefin which. As defined in claim 1, a polyoxyalkylene compound which was defined in claim 1, wherein the weight ratio of poly-alpha-olefin: polyoxyalkylene compound is in the range of 1: 10-10: 1,> · 'and optionally, at least one hydrocarbon-soluble ash-free dispersant. . .: 3 0 13. Concentrate according to claim 12, characterized in that the polyalphaolefinet and the polyoxyalkylene foil purification together are present in an amount in the range 20-80% by weight, and the ashless dispersant, if present, is present in an amount. in the range 5-30% by weight, with all percentages calculated in proportion to the diluent. 11 4 9 S1 A method of operating a spark ignition combustion engine, characterized in that it comprises supplying a gasoline composite island according to any of claims 1-11 to said combustion chamber of said engine. t »t 1 | * t