AU621856B2 - Fuel composition - Google Patents

Description

I i. 1 /7 'p OPI DATE 25/08/89 woF AOJP DATE 28/09/89 APPLN. ID 29461 89 PCT PCT NUMBER PCT/US89/00085 INTERNATIONAL APPLICATION PUBLISHED UNDER THE PATENT COOPERATION TREATY (PCT) (51) International Patent Classification 4 (11) Inl a I P ica Nu r: WO 89/ 07126 C1OL 1/14, 1/02, 1/24 Al V 1/18 (43) Interna l Pulicat Da ,A ugust 1989 (10.08.89) (21) International Application Number: PCT/US89/00085 (81) Designated States: AT (European patent), AU, BE (European patent), BR, CH (European patent), DE (Eu- (22) International Filing Date: 10 January 1989 (10.01.89) ropean patent), DK, FI, FR (European patent), GB (European patent), IT (European patent), JP, LU (European patent), NL (European patent), NO, SE (31) Priority Application Number: 148,784 (European patent).

(32) Priority Date: 27 January 1988 (27.01.88) Published (33) Priority Country: US With international search report.

Before the expiration of the time limit for amending the claims and to be republished in the event of the receipt (71) Applicant: THE LUBRIZOL CORPORATION [US/ of amendments.

US]; 29400 Lakeland Boulevard, Wickliffe, OH 44092

(US).

(72) Inventor: STOLDT, Stephen, H. 7390 Southmeadow Drive, Concord Township, OH 44077 (US).

(74) Agents: COLLINS, Forrest, L. et al.; The Lubrizol Corporation, 29400 Lakeland Boulevard, Wickliffe, OH 44092 (US).

(54) Title: FUEL COMPOSITION (57) Abstract This invention describes a water fix for an alcohol containing gasoline which has been formulated with a lead replacement,

.I

i r i i i WO 89/07126 PCT/US89/00085 FUEL COMPOSITION INTRODUCTION TO THE INVENTION This invention relates to fuel compositions for internal combustion engines which normally use low lead or unleaded gasoline. The fuels are further characterized as containing an alcohol.

The removal of lead additives, such as tetraethyl lead, from gasoline in order to reduce air pollution has led to several problems. It was found that the lead not only acted as an anti-knock agent, but was also effective in the prevention of valve seat recession. The exhaust valves in internal combustiox engines generally seat against the valve seat with a slight rotary motion. The rotary motion is imparted to the valve stem during its operation to shift the relative position of the valve and to prevent uneven wear on the valve tip. With the elimination of lead additives from gasoline, it was found that a dramatic increase in the wear of the valve seats occurs. For example, see Unleaded Versus Leaded Fuel Results in Laboratory Engine Tests, Z. J. Fuchs, The Lubrizol Corporation, presented at the Society of Automotive Engineers, National West Coast Meeting, Vancouver, British Columbia, August 16-19, 1971 (32 pages).

Because valve seat wear is a function of engine design, load, speed conditions and operating temperature it is highly desirae that a replacement forleadbe ol at as n a i n c a e ,b s a o e et e i i th prvnino av etrcsin h xas rj WO 89/07126 PCT/US89/0008 WO 89/07126 2employed. The use of a lead replacement for valve seat recession is complicated by the fact that a number of newer vehicles do not require lead additives. A number of fuels on the market contain lower levels of lead and still other fuels are essentially lead-free. It is further observed that alcohol-containing fuels such as gasohol or fuels containing alcohols used to boost octane rating are also widely marketed. It, therefore, becomes desirable to obtain a gasoline composition containing a lead replacement which is capable of functioning in a multitude of gasoline based fuels.

Set out below are various references to fuels containing lead replacements and gasoline additives. U.S.

Patent No. 2,764,548 to King et al, issued September 1956, describes motor oils and motor fuels containing various salts of dinonylnaphthalene sulfonic acid including the sodium, potassium, calcium, barium, airnionium and amine salts. The salts are reported to be effective rust inhibitors. U.S. Patent 3,506,416 to Patnkin, issued April 14, 1970, describes leaded gasolines containing gasoline soluble salts of a hydroxamic acid of the formula RC(O)NHOH where R is a hydrocarbon group containing up to 30 carbon atoms. The metal may be selected from the Group Ia, IIa, IIIa, Va, Ib, IIb, IIIb, IVb, Vb, VIb, VIIb, VIII and tin. U.S. Patent 3,182,019, issued to Wilks et al on May 4, 1965, describes lubricating aid fuel oils including complexes which contain an alkali or alkaline earth metal carbonate in colloidal form.

The use of sodium in lead-free gasoline compositions for inhibiting valve seat recession is suggested in U.S.

Patent 3,955,938 to Graham et al, issued on May 11, 1976.

The sodium may be incorporated into the fuel in a number of different forms such as sodiurr derivatives or organic compounds which are soluble, or dispersed in the gasoline.

For example, simple sodium salts of an organic acid such as sodium petroleum sulfonate can be utilized although the WO 89/07126 PCT/US89/00085 sodium preferentially is added in the form of a sodium salt of an inorganic acid such as sodium carbonate in a colloidal dispersion in oil. Other convenient forms for introducing sodium into the fuel which are described in U.S. Patent 3,955,938 include various sodium salts of sulfonic acids, sodium salts of saturated and unsaturated carboxylic acids, sodium salts of phospho-sulfurized hydrocarbons such as may be prepared by reacting P 2

S

5 with petroleum fractions such as bright stock, and sodium salts of phenols and alkylphenols. Various optional additives described by the Graham patent include corrosion inhibitors, rust inhibitors, anti-knock compounds, anti-oxidants, solvent oils, anti-static agents, octane appreciators, e.g. t-butyl acetate, dyes, anti-icing agents, e.g. isopropanol, hexyleneglycol, ashless dispersants, detergents, and the like. The amount of sodium additive included in the fuel is an amount to provide from about 0.5 to 20, preferably 0.5 to 10 lbs. of sodium per 1000 barrels of gasoline (2.86g/1000 liters is 1 lb/1000 bbl).

It also has been suggested that gasoline compositions can be improved by including certain detergents and dispersants. U.S. Patent 3,443,918 to Kautsky et al, issued May 13, 1969, describes the addition to gasoline of mono-, bis-, or tris-alkenyl succinimides of a bis- or tris-polymethylene polyamine. These additives are reported to minimize harmful deposit formation when the fuels are used in internal combustion engines.

U.S. Patent Nos. 3,172,892 to LeSuer, issued March 9, 1965; 3,219,666 to Norman, issued November 23, 1966; 3,272,746 to LeSuer, issued November 23, 1966; 3,281,428 also to LeSuer, issued October 25, 1966; and 3,444,170 to Norman et al, issued May 13, 1969 are directed to polyalkenyl succinic type ashless additives, and the Norman '170 patent teaches the use of the additive disclosed therein as a fuel detergent. U.S. Patent No.

3,347,645 to Pietsch et al, issued October 3 1 1967 also l' l

J

WO 89/07126 PCT/US89/00085 wo 89/07126 4 describes the use of alkenyl succinimides as dispersants in gasoline, but it is there noted that the dispersants promote aqueous emulsion formation during storage and shipping. U.S. Patent No. 3,649,229 to Otto, issued March 14, 1972, teaches a fuel containing a detergent amount-of a Mannich base prepared using, among other reactants, an alkenyl succinic compound. U.S. Patent 4,240,803 issued to Andress on December 23, 1980 also relates to hydrocarbon fuel compositions containing a detergent amount of a specific alkenyl succinimide wherein the alkenyl group is derived from a mixture of C16-28 olefins.

U.S. Patent 4,659,338 issued April 21, 1987 to Johnston et al discloses compositions containing a hydrocarbon-soluble alkali or alkaline earth metalcontaining composition and a hydrocarbon-soluble ashless dispersant. The Johnston compositions are useful for pr renting valve seat recession.

British published patent application 2,177,418A published January 21, 1987 discloses gasoline compositions containing a succinic acid derivative containing from to 200 carbon atoms.

U.S. Patent 4,708,809 issued November 24, 1987 to Davis discloses lubricants suitable for two-cycle engines.

It is further known from U.S. Patent 4,690,68.7 issued September 1, 1987 to Johnston et al that deposit formation within the cylinders may be avoided through a variety of means.

It has been observed that when hydrocarbon-soluble i" alkali matal or alkaline earth metal-containing compositions in an oxygenated fuel (alcohol-containing) are contacted with water that emulsions may form. The present invention deals with compositions hich are formulated to avoid emulsion/deemulsification problems arising from the presence of water in a gasoline composition.

Throughout the specification and claims, percentages and ratios are by weight, temperatures are in degrees WO 89/07126 PCT/US89/00085 Celsius and pressures are in KPascals gauge unless otherwise indicated. To the extent that the references cited herein are applicable, they are herein incorporated by reference. Percentages and ratios of components are considered exemplary and may be combined.

I

L WO 89/07126 PCT/US89/00085 -6 SUMMARY OF THE INVENTION The present invention describes a fuel composition comprising: at least one hydrocarbon-soluble or dispersible alkali metal or alkaline earth metal containing composition and, a hydrocarbyl substituted sulfonated phenol or salt thereof; (ii) an ethylene oxide/propylene oxide copolymer; gasoline, and at least one alcohol.

The present invention further describes a composition comprising: at least one hydrocarbon-soluble or dispersible alkali metal or alkaline earth metal containing composition, at least one member selected from the group consisting of a hydrocarbyl substituted sulfonated phenol or salt thereof; (ii) an ethylene oxide/propylene oxide copolymer, and (iii) a hydrocarbyl substituted phenol, and mixtures of any of (ii) and (iii), gasoline, and at least onealcohol.

A further embodiment of the invention is a fuel composition comprising: at least one member selected from the group consisting of: a hydrocarbon substituted sulfonated phenol or salt thereof; (ii) an ethylene oxide/propylene oxide copolymer; |t I i_ i -7- (iii) a hydrocarbyl substituted phenol,, and (iv) mixtures of any of (ii) and (iii); gasoline; an alcohol; and, at least one ashless dispersant selected from the group consisting of: at least one hydrocarbyl-substituted amine wherein the hydrocarbyl substituent is substantially aliphatic and contains at least 8 carbon atoms; (ii) at least one acylated, nitrogen-containing compound having a substituent of at least 10 aliphatic carbon atoms made by reacting a carboxylic acid acylating agent with at least one amino compound containing at least one -NH group, said acylating agent being linked to said amino compound through an imido, amido, amidine, or acyloxy ammonium linkage; "5 (iii) at least one nitrogen-containing condensate of a phenol or aldehyde and an amino compound having at least one NH (iv) at least one ester of a substituted carboxylic acid; at least one polymeric dispersant; 0 (vi) at least one hydrocarbon substituted phenolic dispersant; and (vii) at least one fuel soluble alkoxylated derivative of an alcohol, phenol, or amine.

Another embodiment of this invention is a fuel composition comprising: at least one member selected from the group consisting of: A. a hydrocarbyl substituted sulfonated phenol or salt thereof; B. an ethylene oxide/propylene oxide copolymer; C. a hydrocarbyl substituted phenol, and D. mixtures of any of (ii) and (iii); gasoline; at least one alcohol; and, at least one ashless dispersant selected from the group consisting of: at least one hydrocarbyl-substituted amine wherein the hydrocarbyl i Ir -8substituent is substantially aliphatic and contains at least 8 carbon atoms; (ii) at least one acylated, nitrogen-containing compound having a substituent of at least 10 aliphatic carbon atoms made by reacting a carboxylic acid acylating agent with at least one amino compound containing at least one NH group, said acylating agent being linked to said amino compound through an imido, amido, amidine, or acyloxy ammonium linkage; (iv) at least one ester of a substituted carboxylic acid; (vi) at least one hydrocarbon substituted phenolic dispersant; and (vii) at least one fuel soluble alkoxylated derivative of an alcohol, phenol, or amine.

A still further embodiment of the present invention is a process for delivering gasoline containing an alkali metal or alkaline earth metal containing composition with enhanced water tolerance to a vehicle fuel tank including the steps of combining with the gasoline: a hydrocarbon-soluble or dispersible alkali earth metal or alkaline earth Smetal containing composition, and S at least one member selected from the group consisting of: a hydrocarbon substituted sulfonated phenol or salt thereof; *I Ii (ii) an ethylene oxide/propylene oxide copolymer; (iii) a hydrocarbon substituted phenol, and (iv) mixtures of (ii) "5 and (iii) such that the weight ratio of to is sufficient to impart enhanced water tolerance to the mixture of and S Finally, another embodiment of the present invention is a fuel composition Scomprising: a mixture of two or more of a hydrocarbon substituted sulfonated phenol or salt thereof; (ii) an ethylene oxide/propylene oxide copolymer; or (iii) a hydrocarbyl substituted phenol; gasoline; 1 at least one alcohol; and,

C,,

I 1 -8a at least one ashless dispersant selected from the group :a t:ng of: at least one hydrocarbyl-substituted amine wherein the hydrocarbyl substituent is substantially aliphatic and contains at least 8 carbon atoms; (ii) at least one acylated, nitrogen-containing compound having a substituent of at least 10 aliphatic carbon atoms made by reacting a carboxylic acid acylating agent with at least one amino compound containing at least one -NHgroup, said acylating agent being linked to said amino compound through an imido, amido, amidine, or acyloxy ammonium linkage; (iii) at least one nitrogen-containing condensate of a phenol or aldehyde and an amino compound having at least one -NH- group; (iv) at least one ester of a substituted carboxylic acid; at least one polymeric dispersant; (vi) at least one hydrocarbon substituted phenolic dispersant; and (vii) at least one fuel soluble alkoxylated derivative of an alcohol, phenol, or amine.

S

*I

ON%

*idl comprising an ashless dispersant selected from the group consisting of; at least one hydrocarbyl-substituted amine 12

II

SWO 8907126 PCT/US89/000s85 DETAILED DESCRIPTION OF THE INVENTION The following describes the components, processing and use of the compositions of the present invention.

THE ALKALI or ALKALINE EA.RTH METAL-CONTAINING COMPOSITION =e v\ -ce Vt c W 3 vtfhe fuel compostion:i of the present invention contain a minor amount of at least one hydrocarbon-soluble alkali or alkaline earth metal-containing composition. The presence of such metal-containing compositions in the fuel compositions of the presen invention provides the fuel composition with a desirable ability to prevenc or minimize valve seat recession in internal combustion engines, particularly when the fuel is an unleaded or low-lead fuel. The choice of the metal does not appear to be particularly critical although alkali metals are preferred, with sodium or potassium being the preferred alkali metals.

The metal-containing composition may be alkali metal or alkaline earth metal salts of sulfur acids, carb'xylic ac-ids, phenols and phosphorus acids. These salts can be neutral or basic. The former contain an amount of metal cation just sufficient to neutralize the acidic groups present in salt anion; the latter contain an excess of metal cation and are often termed overbased.

These basic and neutral salts can be of oil-soluble organic sulfur acids such as s'lfonic, sulfamic, thiosulfonic, sulfinic, sulfenic, partial ester sulfuric, sulfurous and thiosulfuric acid. Generally they are salts of aliphatic or aromatic sulfonic acids.

The sulfonic acids include the mono- or poly-nuclear aromatic or cycloaliphatic compounds. .The sulfonic acids can be represented for the most part by the following formulae: R (SO 3 H) Formula I ?Aq (R T(SO 3) Yormula II at least one ashless dispersant selectea rrom uie ,iuuy xuv at least one hydrocarbyl-substituted amine wherein the hydrocarbyl substituent is substantially aliphatic and contains at least 8 carbon atoms; (ii) at least one acylated, nitrogen-containing compound having a i. /3 7* i; 1 PCT/US89/00085 WO 89/07126 10 in which T is an aromatic or cyclic nucleus such as, for example, benzene, naphthalene, anthracene, phenanthrene, diphenylene oxide, thiant.rene, phenothioxine, diphenylene sulfide, phenothiazine, diphenyl oxide, diphenyl sulfide, diphenylamine, cyclohexane, petroleum naphthenes, 1 2 decahydronaphthalene, cyclopentane, etc; R and R are each independently aliphatic groups, R contains at least 2 about 15 carbon atoms, the sum of the carbon atoms in R and T is at least about 15, and r, x and y are each independently 1 or greater.

Specific examples of R are groups derived from petrolatum, saturated and unsaturated paraffin wax, and polyolefins, including polymerized C 2

C

3

C

4

C

5

C

6 etc., olefins containing from about 15 to 7000 or more carbon atoms. The groups T, R and R 2 in the above formulae can also contain other inorganic or organic substituents in addition to those enumerated above such as, for example, hydroxy, mercapto, halogen, nitro, amino, nitroso, sulfide, disulfide, etc. The subscript x is generally 1-3, and the subscripts r y generally have an average value of about 1-4 per molecule.

The following are specific examples of oil soluble sulfonic acids coming within the scope of Formulae I and II above, and it is to be understood that such examples serve also to illustrate the salts.of such sulfonic acids useful in this invention. In other words, for every sulfonic acid enumerated it is intended that the corresponding neutral and basic metal salts thereof are also understood to be illustrated. sulfonic acids are mahogany sulfonic acids; bright stock sulfonic acids; sulfonic acids derived from lubricating oil fractions having a Saybolt viscosity from about 100 seconds at 100°F (37.7 0 C) to about 200 seconds at 210oF (99 0 petrolatum sulfonic acids; mono- and poly-wax substituted sulfonic and polysulfonic acids of, benzene, diphenylamine, thiophene, alpha-chloronaphthalene, etc.; o.ther substituted sulfonic acids such as alkyl benzene sulfonic 1 i, V.l L (vi) at least one hydrocarbon substituted phenolic dispersant; and (vii) at least one fuel soluble alkoxylated derivative of an alcohol, phenol, or amine.

1 i WO 89/07126 PCT/US89/00085 11 acids (where the alkyl group has at least 8 carbons), cetylphenol mono-sulfide sulfonic acids, dicetyl thianthrene disulfonic acids, dilauryl beta naphthyl sulfonic acids, and alkaryl sulfonic acids such as dodecyl benzene "bottoms" sulfonic acids.

The latter are acids derived from benzene which has been alkylated with propylene tetramers or isobutene trimers to introduce 1, 2, 3 or more branched-chain C 12 substituents on the benzene ring. Dodecyl benzene bottoms, principally mixtures of mono- and di-dodecyl benzenes, are available as by-products from the manufacturer of household detergents. Similar products obtained from alkylation bottoms formed during manufacture of linear alkyl sulfonates (LAS) are also useful in making the sulfonates used in this invention.

The production of sulfonates from detergent manufacture by-products by reaction with, SO3, is well known to those skilled in the art. See, for example, the article "Sulfonates" in Kirk-Othmer "Encyclopedia of Chemical Technology", Second dition, Vol. 19, pp. 291 et seq. published by John Wiley Sons, N.Y. (1969).

Other descriptions of neutral and basic sulfonate salts and techniques for making them can be found in the following U.S. Patents: 2,174,110; 2,174,506; 2,174,508; 2,193,824; 2,197,800; 2,202,781; 2,212,786; 2,213,360; 2,228,598; 2,223,676; 2,239,974; 2,263,312; 2,276,090; 2,276,097; 2,315,514; 2,319,121; 2,321,022; 2,333,568; 2,333,788; 2,335,259; 2,337,552; 2,347,568; 2,366,027; 2,374,193; 2,383,319; 3,312,618; 3,471,403; 3,488,2e4; 3,595,790 and 3,798,012. These are hereby incorporated by reference for their disclosures in this regard.

With respect to the sulfonic acids or salts thereof described herein and in the appended claims, it is intended herein to employ the term "petroleum sulfonic acids" or "petroleum sulfonates" to cover all sulfonic acids or the salts thereof deri ted from petroleum products. A particularly valuable group of petroleum

I

i I WO 89/07126 PCT/US89/00085 12 sulfonic acids are the mahogany sulfonic acids (so called because of their reddish-brown color) obtained as a by-product from the manufacturer of petroleum white oils by a sulfuric acid process.

The carboxylic acids from which suitable neutral and basic alkali metal and alkaline earth metal salts for use in this invention can be made include aliphatic, cycloaliphatic, and aromatic mono and polybasic carboxylic acids such as the naphthenic acids, alkyl- or alkenylsubstituted cyclopentanoic acids, the corresponding cyclohexanoic acids and the corresponding aromatic acids.

The aliphatic acids generally contain at least eight carbon atoms and preferably at least twelve carbon atoms.

Usually they have no more than about 400 carbon atoms.

Generally, if the aliphatic carbon chain is branched, the acids are more oil soluble for any given carbon atom content. The cycloaliphatic and aliphatic carboxylic acids can be saturated or unsaturated. Specific examples include 2-ethylhexanoic acid, alpha-linolenic acid, behenic acid, isostearic acid, pelargonic acid, capric acid, palmitoleic acid, linoleic acid, lauric acid, oleic acid, ricinoleic acid, undeeylic acid, dioctylcyclopentane carboxylic acid, myristic acid, dilauryldecahydronaphthalene carboxylic acid, stearyl-octahydroindene carboxylic acid, palmitic acid, commercially available mixtures of two or more carboxylic acids such as tall oils acids, rosin acids, and the like. A group of oil-soluble carboxylic acids useful in preparing the salts used in the present invention are ,he oil-soluble aromatic carboxylic acids. These acids are represented by the general formula: Ar*(CXXH) Formula III where R* is a hydrocarbyl (preferably aliphatic hydrocarbon-based) group of at least four carbon atoms, and no more than abo'. 400 aliphatic carbon atoms, a is an i _i "b ~K \l WO89/07126 PCT/US89/00085 WO 89/07126

PCT/US

13 integer of from one to four, Ar* is a polyvalent aromatic hydrocarbon nucleus of up to about 14 carbon atoms, each X is independently a sulfur or oxygen atom, and m is an integer of from one to four with the proviso that R* and a are such that there is an average of at least 8 aliphatic carbon atoms provided by the R* groups for each acid molecule represented by Formula III. Examples of aromatic nuclei represented by the variable Ar* are the polyvalent aromatic radicals derived from benzene, naphthalene, anthracene, phenanthrene, indene, fluorene, biphenyl, and the like. Generally, the radical represented by Ar* will be a polyvalent nucleus derived from benzene or naphthalene such as phenylenes and naphthlene, e.g., methyl-phenylenes, ethoxyphenylenes, nitrophenylenes, isopropyl-phenylenes, hydroxyphenylenes, mercaptophenylenes, N,N-diethylaminophenylenes, chlorophenylenes, dipropoxynaphthylenes, triethylnaphthylenes, and similar tri-, tetra-, pentavalent nuclei thereof, etc.

The R* groups are usually purely hydrocarbyl groups, preferably groups such as alkyl or alkenyl radicals.

However, the R* groups can contain a small number substituents such as phenyl, cycloalkyl cyclohexyl, cyclopentyl, etc.) and nonhydrocarbon groups such as nitro, amino, halo chloro, bromo, etc.) lower alkoxy, lower alkyl mercapto, oxo substituents thio groups interrupting groups such as -NH-, and the like provided the essentially hydrocarbon character of the R* group is retained. The hydrocarbon character is retained for purposes of this invention so long as any non-carbon atoms present in the R* group do not account for more than about 10% of the total weight of the R* groups.

Examples of R* groups include butyl, isobutyl, pentyl, octyl, nonyl, dodecyl, docosyl, tetracontyl, 5-chlorohexyl, 4-ethoxypentyl, 2-hexenyl, cyclohexyloctyl, 4-(p-chlorophenyl)-octyl, 2,3,5-trimethylheptyl, 2-ethyland substituents derived from polymerized Vancouver, britisn cuoiumoia, August 10- ±1/1 1 I..

pages).

Because valve seat wear is a function of engine design, load, speed conditions and operating temperature it is highly desirable that a replacement for lead be WO 89107126 PCT/US89/00085 14 olefins such as polychloroprenes, polyethylenes, polypropylenes, polyisobutylenes, ethylenepropylene copolymers, chlorinated olefin polymers, oxidized ethylene-propylene copolymers, and the like. Likewise, the group Ar may contain non-hydrocarbon substituents, for example, such diverse substituents as lower alkoxy, lower alkyl mercapto, nitro, halo, alkyl or alkenyl groups of less than four carbon atoms, hydroxy, mercapto and the like.

A group of particularly useful carboxylic acids are those of the formula: R* Ar* (CXXH) (XH) Formula IV a m p where X, Ar*, m and a are as defined in Formula III and p is an integer of 1 to 4, usually 1 or 2. Within this group, an especially preferred class of oil-soluble carboxylic acids are those of the formula: (COOH) (OH) c Formula V where in Formula V is an aliphatic hydrocarbon group containing at least 4 to about 400 carbon atoms, Ph is a phenyl group, a is an integer of from 1 to 3, b is 1 or 2, c is zero, 1, or 2 and preferably 1 with the proviso that and a are such that the acid molecules contain at least an average of about twelve aliphatic carbon atoms in the aliphatic hydrocarbon substituents per acid molecule.

And within this latter group of oil-soluble carboxylic acids, the aliphatic-hydrocarbon substituted salicylic acids wherein each aliphatic hydrocarbon substituent contains an average of at least about sixteen carbon atoms per substituent and one to three substituents per molecule are particularly useful. Salts prepared from such salicylic acids wherein the aliphetic hydrocarbon substituents are derived from polymerized olefins, particularly polymerized lower 1-mono-olefins such as of different forms such as sodium derivatives or organic compounds which are soluble, or dispersed in the gasoline.

For example, simple sodium salts of an organic acid such as sodium petroleum sulfonate can be utilized although the WO 89/07126 PCT/US89/00085 15 polyethylene, polypropylene, polyisobutylene, ethylene/ propylene co-polymers and the like and having average carbon contents of about 30 to 400 carbon atoms.

The carboxylic acids corresponding to Formulae III and IV above are well known or can be prepared according to procedures known in the art. Carboxylic acids of the type illustrated by the above formulae and processes for preparing their neutral and basic metal salts are well known and disclosed, for example, in such U.S. Patents as 2,197,832; 2,197,835; 2,252,662; 2,252,664; 2,714,092; 3,410,798 and 3,595,791.

Another type of neutral and basic carboxylate salt used in this invention are those derived from alkenyl succinates of the general formula:

R*CH(COOH)CH

2 COOH Formula VI wherein R* is as'defined above in Formula III. Such salts and means for making them are set forth in U.S. Patents 3,271,130; 3,567,637 and 3,632,610. Generally, the molecular weight of the polybasic carboxylates (polycarboxylates) will be about 400 to about 2000, preferably about 500 to about 1500. Such molecular weights will correspond to about 28 to about 145, preferably abdut 35 to about 110 carbon atoms in the hydrocarbon chain of the molecule. One such acid is propylene tetramer-substituted maleic acid. Other patents specifically describing techniques for making basic salts of the hereinabove-described sulfonic acids, carboxylic acids, and mixtures of any two or more of these include U.S. Patent Nos. 2,501,731; 2,616,904; 2,616,905; 2,616,906; 2,616,911; 2,616,924; 2,616,925; 2,617,049; 2,777,874; 3,027,325; 3,256,186; 3,282,835; 3,384,585; 3,373,108; 3,368,396; 3,342,733; 3,320,162; 3,312,618; 3,318,809; 3,471,403; 3,488,284; 3,595,790 and 3,629,109.

Neutral and basic salts of phenols (generally known as phenates) are also useful in the compositions of this polyalkenyl succinic type ashless additives, and the Norman '170 patent teaches the use of the additive disclosed therein as a fuel detergent. U.S. Patent No.

3,347,645 to Pietsch et al, issued October 1967 also i WO 89/07126 PCT/US89/00085 16 invention and well known to those skilled in the art. The phenols from which these phenates are formed are of the general formula: Formula VII a m wherein a, Ar*, and m have the same meaning and preferences as described hereinabove with reference to -i 1 1 Formula III. The same examples described with respect to Formula III also apply.

The commonly available class of phenates are those made from phenols of the general formula: (R4) Ph(OH)b Formula VIII wherein a is an integer of 1-3, b is of 1 or 2, z is 0 or 1, Ph is a phenyl group R' in Formula VIII is a substantially saturated hydrocarbon-based substituent having an average of from about 30 to about 400 aliphatic carbon atoms and R 4 is selected from the group consisting of lower alkyl, lower alkoxyl, nitro, and halo groups.

One particular class of phenates for use in this invention are the basic overbased, etc.) alkali and alkaline earth metal sulfurized phenates made by sulfurizing a phenol and described hereinabove with a sulfurizing agent such as sulfur, a sulfur halide, or sulfide or hydrosulfide salt. Techniques for making these sulfurized phenates are described in U.S. Patents 2,680,096; 3,036,971 and 3,775,321.

Other phenates that are useful are those that are made from phenols that have been linked through alkylene methylene) bridges. These are made, by reacting single or multi-ring phenols with aldehydes or ketones, typically, in the presence of an acid or basic catalyst.

Such linked phenates as well as sulfurized phenates are described in detail in U.S. Patent 3,350,038; particularly columns 6-8 thereof.

formulated to avoid emulsion/deemulsification problems arising from the presence of water in a gasoline composition.

Throughout the specification and claims, percentages and ratios are by weight, temperatures are in degrees W0O89/07126 PCT/US89/00085 17 Alkali and alkaline earth metal salts of phosphorus acids also are useful in the fuel compositions of the invention. For example, the normal and basic salts of the phosphonic and/or thiophosphonic acids prepared by reacting inorganic phosphorus reagents such as P2S5 with petroleum fractions such as bright stock or polyolefins obtained from olefins of 2 to 6 carbon atoms. Particular examples of the polyolefins are polybutenes having a molecular weight of from 700 to 100,000. Other phosphorus-containing reagents which have been reacted with olefins include phosphorus trichloride or phosphorus trichloride-sulfur chloride mixture, U.S. Patent Nos. 3,001,981 and 2,195,517), phosphites and phosphite chlorides U.S. Patent Nos. 3,033,890 and 2,863,834), and air or oxygen with a phosphorus halide U.S. Patent No. 2,939,841).

Mixtures of two or more neutral and basic salts of the hereinabove described organic sulfur acids, carboxylic acids, phosphorus acids and phenols can be used in the compositions of this invention. As mentioned above, the amount of alkali or alkaline earth metal containing composition included in the fuel composition will be an amount which is sufficient to provide from about 1 to about 100 parts per million of the alkali metal or alkaline earth metal in the fuel composition. When utilized in lead free or low lead fuels, the amount of alkali metal or alkaline earth metal-containing composition included in the fuel is an amount which is sufficient to reduce valve seat recession when the fuel is used in an internal combustion engine.

The following specific illustrative examples describe the preparation of exemplary alkali and alkaline earth metal compositions useful in the fuel compositions of this invention.

Example A-1 A mixture of 1000 parts of a primary branched monoalkyl benzene sulfonic acid approximately 522) K_ r i, WO 89/07126 PCT/US89/00085 18 in 637 parts of mineral oil is neutralized with 145.7 parts of a 50% caustic soda solution and the excess water and caustic remove. The product containing the sodium salt obtained in this manner contains 2.5% sodium and 3.7% sulfur.

Example A-2 The procedure of Example A-1 is repeated except that the caustic soda is replaced by a chemically equivalent amount of Ca(OH) 2 Example A-3 The procedure of Example A-1 is repeated except that the caustic soda is replaced by a chemically equivalent amount of KOH.

Example A-4 A mixture of 906 parts of an alkyl phenyl sulfonic acid (having an average molecular weight of 450, vapor phase osmometry), 564 parts mineral oil, 600 parts toluene, 98.7 parts magnesium oxide and 120 parts water is blown with carbon dioxide at a temperature of 78-85°C for seven hours at a rate of about 3 cubic feet of carbon dioxide per. hour (85 1/hr) The reaction mixture is constantly agitated throughout the carbonation. After carbonation, the reaction mixture is stripped to 165 0 torr (2.65 KPa) and the residue filtered. The filtrate is an oil solution of the desired overbased magnesium sulfonate having a metal ratio of about 3.

Example A mixture of 323 parts of mineral oil, 4.8 parts of "0 water, 0.74 parts of calcium chloride, 79 parts of lime, and 128 parts of methyl alcohol is prepared, and warmed to a temperature of about 50 0 C. To this mixture there is added with mixing, 1000 parts of an alkyl phenyl sulfonic acid having an average molecular weight (vapor phase osmometry) of 500. The mixture then is blown with carbon dioxide at a temperature of about 50°C at the rate of about 5.4 lbs. per hour (40.8g/mirute) for about hours. After carbonation, 102 additional parts of oil are i WO 89/07126 PCT/US89/00085 19 19 added and the mixture is stripped of volatile materials at a temperature of about 150-155 0 C at 55 mm (7.3 KPa) pressure. The residue is filtered and the filtrate is the desired oil solution of the overbased calcium sulfonate having calcium content of about 3.7% and a metal ratio of.

about 1.7.

THE WATER FIX The second component of the invention is at least one member selected from the group consisting of: a hydrocarbyl substituted sulfonated phenol or salt thereof; (ii) an ethylene oxide/propylene oxide copolymer, and (iii) a hydrocarbyl substituted phenol, or (iv) mixtures of (ii) and (iii).

Component may be obtained by preparing the sulfonic acid of (B)(iii) or the salt of the sulfonic acid of B (iii). An ample disclosure of the sulfonic acids and sulfonates is found in the description of component The cationic portion of is preferably ammonium.

When a phenol is employed as the aromatic nucleus in (A) the hydrocarbyl substituted phenol sulfonic acid or salt is obtained.

The second item under is an ethylene oxide/propylene oxide copolymer. Such materials are well known in the art and are obtained by reacting ethylene oxide or a polymer of ethylene oxide with propylene oxide or a polymer of propylene oxide. It is first possible to obtain a random polymer of ethylene oxide and propylene oxide by simply charging the desired quantities of each material and conducting the polymerization as is known in i the art. It is also possible to prepolymerize ethylene oxide to a desired chain length and then to further react the ethylene oxide by capping with propylene oxide.

It is further possible to polymerize the propylene oxide to the desired molecular weight and to ,then terminate the propylene oxide polymer with ethylene dxide. i IIt WO 89/07126 PCT/US89/00085 20 Of course, the propylene oxide may be polymerized and then reacted with an ethylene oxide polymer. The molecular weight of (ii) is conveniently about 400 to 10,000, preferably 600 to 5,000.

It is desirable that the weight percent of the ethylene oxide in the copolymer is from 10 to 90 percent, preferably 15 to 90 percent by weight of the copolymer.

It is, of course, recognized that as ethylene oxide has a lower molecular weight than propylene oxide that a greater number of equivalents of ethylene oxide will 'be utilized on a equivalent basis than of the propylene oxide.

Component (iii) is a hydrocarbyl substituted phenol.

The hydrocarbon su1 .tituted phenol generally corresponds to component the hydrocarbyl substituted sulfonated phenol or salt thereof. Thus, component (iii) is usually the raw material for component and is commercially available. When mixtures of and (B) (iii) are desired, it is possible to under-sulfonate the hydrocarbon substituted phenol. Either of components or (iii) will typically contain about 10 to about carbon atoms on the hydrocarbyl chain on average, preferably about 14 to about 26 carbon atoms.

The hydrocarbyl substituted phenol may also be crosslinked through the use of formaldehyde to give a polymeric structure. That is, the hydrocarbyl substituted phenol is crosslinked at the ortho (and often para position) to the hydroxyl groups. It is further possible to alkoxylate the phenol. In this regard, the reader's attention is directed to the discussion of ethylene oxide and propylene oxide given above. Each of the foregoing materials may be condensed onto the hydroxyl group of the phenol whether polymeric or monomeric.

It is further possible, as compcnent (iv) to utilize a mixture of any of the foregoing components 5 designated as component A preferred species of component is, in fact, such a mixture.

I i I L (iii) a hydrocarbyl substituted phenol; gasoline; 1(D) at least one alcohol; and, WO 89/07126 PCT/US89/00085 21 When component is it is desired that the weight ratio of component to (ii) is from about 10:1 to about 1:10, preferably about 5:1 to about 1:5. The weight ratio of to (iii) is typically from about 8:1 to about 1:8, preferably about 5:1 to about 1:5. The desired ratio of component (ii) to (iii) is typically about 7:1 to about 1:7, preferably 4:1 to about 1:4. When two of the three individual components of are employed, the ratios are also as described above.

THE GASOLINE COMPONENT The gasoline component useful in the present invention is obtained as a hydrocarbon distillate.

Gasolines are supplied in a number of different grades depending on the type of service for which they are intended. The gasolines utilized in the present invention include those designed as motor and aviation gasolines.

Motor gasolines include those defined by ASTM specification D-439-73 and are composed of a mixture of various types of hydrocarbons including aromatics, olefins, paraffins, isoparaffins, naphthenes and occasionally diolefins. Motor gasolines normally have a boiling range within the limits of about 20 0 C to 230C while aviation gasolines have narrower boiling ranges, usually within the limits of about 37 0 C to 165 0

C.

The gasoline may have any of the typically added ingredients provided that there are no adverse effects to obtaining performance for valve seat recession, obtaining the desired water *fix, and which do not cause a substantial reduction of the octane value of the gasoline, One such ingredient which is typically included in gasoline is lead in the form of a compound such as tetraethyl lead or tetramethyl lead. It is first noted that lead is being regulated out of gasoline in many countries. Those countries still allowing some amounts of lead in the gasoline allow "low-lead" formulations.

Typically, a low-lead gasoline contains less than about b rane w n te l s o WO 89/07126 PCT/US89/00085 22 gram of lead per gallon of fuel. This invention is concerned in one aspect with low-lead fuels containing as little as 0.1 gram of lead per gallon (0.0264 g/liter) of gasoline.

It is further preferred in the present invention that the gasoline be lead-free. By lead-free it is meant that small trace amounts of lead, significantly less than the amounts in a low-lead fuel, are tolerated. That is, no-lead or lead-free gasoline compositions occasionally contain trace amounts of lead due to contamination by leaded fuels. Thus, the term no-lead or lead-free gasolines includes very small amounts of lead; however, it is preferred that the end gasoline product be completely lead-free.

A further typical ingredient which is included with gasoline is a scavenger to remove or reduce engine deposits. Typically, the scavenger will be ethylene dichloride or ethylene dibromide or mixtures thereof. For a further discussion of scavengers useful in the compositions of the present invention, the reader is directed to U.S. Patent 4,690,687 issued September 1, 1987 to Johnston et al which is herein incorporated by reference.

THE ALCOHOL Alcohols which are used in the present invention are typically those which are normally added to gasoline.

The use of alcohols in gasolines is primarily for three purposes. The first purpose is as a partial fuel substitute for the hydrocarbons present in the gasoline to extend the supply of the petroleum hydrocarbons. In this regard, methanol and ethanol are typically utilized as partiil replacements for the hydrocarbon source in gasoline.

The second group of alcohols often used in fuels are those alcohols which have utility as an octane enhancer, Typically, the octane enhancer alcohols will be materials WO 89/07126 PCT/US89/00085 -23 such as methanol, ethanol, isopropanol, t-amyl alcohol and t-butanol. Such alcohols aid in the combustion of the hydrocarbon source and promote the clean burning of the fuel in the internal combustion engine cylinders, thereby increasing power output.

The third use of alcohols in gasoline is to reduce levels of certain emissions. Such emissions include evaporative or exhaust emissions which lead to photochemical smog. The alcohols described immediately above have sach uses.

Overall, the alcohols which are typically employed in the present invention contain u'p to Lbout 8 carbon atoms, preferably from about 1 to about 6 carbon atoms. The preferred alcohols for gasahol production are methanol and ethanol. The preferred alcohols for octane enhancement are tertiary alcohols. Thus, t-butanol is a preferred octane enhancer. An especially preferred combination of alcohols for use in octane enhancement is a mixture of t-butanol and methanol, particularly in a weight ratio to one another of 10:1 to 1:10, preferably about 5:1 to abo;t The le/el of usage of the alcohols in the present invention is typically from about 0.1 percent to about percent by weijht of the total gasoline composition. More typically, the amount of alcohol present will be from about 0.5 percent to about 15 percent by weight of the total gasoline composition.

The preferred alcohols for use in gasoline cc .positions of the present invention are monohydric alcohols.

THE DISPERSANT The fuel compositions of the present invention desirably also contain a minor amount of at least one hydrocarbon soluble ashless dispersant. compounds useful as cchless dispersants generally are characterized by a "polar" group attached to a relatively high molecular I I j SL L-L--tu suironic and polysulfonic acids of, benzene, diphenylamine thiophene, alpha-chloronaohthalene, etc.; other substituted sulfonic acids such as alkyl benzene sulfonic PCT/US89/00085 WO 89/07126 24 weight hydrocarbon chain. The "polar" group generally contains one or more of the elements nitrogen, oxygen and phosphorus. The solubilizing chains are generally higher in molecular weight than those employed with the metallic types, but in some instances they may be quite similar.

In general, any of the ashless detergents which are known in the art for use in lubricants and fuels can be utilized in the fuel compositions of the present invention.

In one embodLment of the present invention, the dispersant is selected from the group consisting of at least one hydrocarbyl-substituted amine wherein the hydrocarbyl substituent is substantially aliphatic and contains at least 8 carbon atoms; (ii) at least one acylated, nitrogen-containing compound having a substituent of at least 10 aliphatic carbon atoms made by reacting a carboxylic acid acylating agent with at least one amino compound containing at least one

-NH-

group, said acylating agent being linked to said amino compound through an imido, amido, amidine, or acyloxy ammonium linkage; (iii) at least one nitrogen-containing condensate of a phenol, aldehyde and amino compound having at least one

-NH-

group; (iv) at least one ester of a substituted carboxylic acid; at least one polymeric dispersant; (vi) at least one hydrocarbon substituted phenolic dispersant; and (vii) at least one fuel soluble alkoxylated derivative of an alcohol, phenol or amine.

The following specific examples illustrate the preparation of exemplary dispersants useful in the fuel compositions of this invention.

UUi< L D LAU -L J.Iic LCt:b LU UUV .L dCLJ. bU L UI I L acids or the salts thereof derived from petroleum products. A particularly valuable group of petroleum WO 89/07126 PCT/US89/00085

N

Example E-l A mixture of 1500 parts of chlorinated poly- (isobutene) having a molecular weight of about 950 and a chlorine content of 285 parts of an alkylene polyamine having an average composition corresponding stoichiometrically to tetraethylene pentamine and 1200 parts of benzene is heated to reflux. The temperature of the mixture is then slowly increased over a 4-hour period 0 to 170 C while benzene is removed. The cooled mixture is diluted with an equal volume of mixed hexanes and absolute ethanol The mixture is heated to reflux and 1/3 volume of 10% aqueous sodium carbonate is added to the mixture. After stirring, the mixture is allowed to cool and phase separate. The organic phase is washed with water and stripped to provide the desired polyisobutenyl poly-amine having a nitrogen content of 4.5% by weight.

Example E-2 A mixture of 140 parts of toluene and 400 parts of a polyisobutenyl succinic anhydride (prepared from the poly(isobutene) having a molecular weight of about 850, vapor phase osmometry) having a saponification number 109, and 63.6 parts of an ethylene amine mixture having an average composition corresponding in stoichiometry to tetraethylene pentamine, is heated to 150 C while the water/toluene azeotrope is removed. The reaction mixture is then heated to 150 0 C under reduced pressure until toluene ceases to distill. The residual acylated polyamine has a nitrogen content of 4.7% by weight.

i j WO 89/07126 PCT/US89/00085 26 Example E-3 To 1,133 parts of commercial diethylene triamine heated at 110-150 0 C is slowly added 6820 parts of isostearic acid over a period of two hours. The mixture is held at 150°C for one hour and then heated to 180 0

C

over an additional hour. Finally, the mixture is heated to 205 0 C over 0.5 hour; throughout this heating, the mixture is blown with nitrogen to remove volatiles. The mixture is held at 205-2300C for a total of 11.5 hours; and the stripped at 230°C/20 torr (2,65KPa) to provide the desired acylated polyamine as residue containing 6.2% nitrogen by weight.

Example E-4 To a mixture of 50 parts of a polypropyl-substituted phenol (having a molecular weight of about 900, vapor phase osmometry) 500 parts of mineral oil (a solvent refined paraffinic oil having a viscosity of 100 SUS at 100 0 F) and 130 parts of 9.5% aqueous dimethylamine solution (equivalent to 12 parts amine) is added dropwise, over an hour, 22 parts of a 37% aqueous solution of formaldehyde (corresponding to 8 parts aldehyde). During the addition, the reaction temperature is slowly increased to 100°C and held at that point for three hours while the mixture is blown with nitrogen. To the cooled reaction, mixture is added 100 parts toluene and 50 parts mixed butyl alcohols. The organic phase is washed three times with water until neutral to litmus paper and the organic phase filtered and stripped to 200°C/5-10 (0.66-1.33KPa) torr. The residue is an oil solution of the final product containing 0.45% nitrogen by weight.

Example A mixture of 140 parts of a mineral oil, 174 parts of a poly(isobutene)-substituted succinic anhydride (molecular weight 1000) having a saponification number of 105 and 23 parts of isostearic acid is prepared at To this mixture there is added 17.6 parts of a mixture of polyalkylene amines having an overall composition IV 1 1 B. 5-chlorohexyl, 4-ethoxypentyl, 2-hexenyl, cyclohexyloctyl, 4- (p-chlorophenyl) -octyl, 2,3,5-trimethylheptyl, 2-ethyland substituents derived from polymerized WO 89107126 PCT/US89/00085 -27 corresponding to that of tetraethylene pentamine at 0 -100 0 C throughout a period of 1.3 hours. The reaction is exothermic. The mixture is blown at 225 0 C with nitrogen at a rate of 5 pounds (2.27 Kg) per hour for 3 hours whereupon 47 parts of an aqueous distillate is obtained. The mixture is dried at 2250C for 1 hour, cooled to 100 0 C and filtered to provide the desired final product in oil solution.

Example E-6 A substantially hydrocarbon-substituted succinic anhydride is prepared by chlorinating a polyisobutene having a molecular weight of 1000 to a chlorine content of and then heating the chlorinated polyisobutene with 1.2 molar proportions of maleic anhydride at a temperature of 150 0 -220 0 C. The succinic anhydride thus obtained has an acid number of 130. A mixture of 874 grams (1 mole) of the succinic anhydride and 104 grams (1 mole) of neopentyl glycol is mixed at 240°-250 0 C/30 mm (4 KPa) for 12 hours.

The residue is a mixture of the esters resulting from the esterification.of one and/or both hydroxy radicals of the glycol. It has a saponification number of 101 and an alcoholic hydroxyl content of 0.2% by weight.

Example E-7 The dimethyl ester of the substantially hydrocarbon-substituted succinic anhydride of Example B-2 is prepared by heating a mixture of 2185 grams of the anhydride, 480 grams of methanol, and 1000 cc. of toluene at 50°-65 C while hydrogen chloride is bubbled through' the reaction mixture for 3 hours. The mixture is then heated at 60 0 -65°C for 2 hours, dissolved in benzene, washed with water, dried and filtered. The filtrate is heated at 150°C/60 mm (8 KPa) to rid it of volatile components. The t residue is the defined dimethyl ester.

Example E-8 A carboxylic acid ester is prepared by slowly adding 3240 parts of a high molecular weight carboxylic acid (prepared by reacting chlorinated polyisobutylen and h.i WO 89/07126 PCT/US89/00085 28 acrylic acid in a 1:1 .equivalent ratio and having an average molecular weight of 982) to a mixture of 200 parts of sorbitol and 100 parts of diluent oil over a period while maintaining a temperature of 115 0 -125 0

C.

Then 400 parts of additional diluent oil are added and the mixture is maintained at about 195 0 -205 0 C for 16 hours while blowing the mixture with nitrogen. An additional 755 parts of oil are then added, the mixture cooled to 140 0 C, and filtered. The filtrate is an.oil solution of the desired ester.

Example E-9 An ester is prepared by heating 658 parts of a carboxylic acid having an average molecular weight of 1018 (prepared by reacting chlorinated polyisobutene with acrylic acid) with 22 parts of pentaerythritol while maintaining a temperature of about 180 0 -205 0 C for about 18 hours during which time nitrogen is blown through the mixture. The mixture is then filtered and the filtrate is the desired ester.

Further information on dispersants may be obtained from U.S. Patent 4,690,687 issued September 1, 1987 which is herein incorporated by reference.

AMOUNT OF THE COMPONENTS The amount of the hydrocabon-soluble or dispersible alkali metal or alkaline earth metal-containing composition to the water fix is typically about 1:2 to about 50:1, preferably 1:1 to about 40:1. The weight ratio of the water fix to the ashless dispersant is typically from about 2:1 to about 1:50, preferably about 1:1 to about 1:40.

The amount of the ashless dispersant to the gasoline is typically about 25 parts to about 500 parts, more preferably about 35 parts to 400 parts by weight of the dispersant per million parts of fuel. The weight ratio of the hydrocarbon-soluble or dispersible alkali metal or alkaline earth metal-containing composition (A) I I I 3,318,809; 3,471,403; 3,488,284; 3,595,790 and 3,629,109.

Neutral and basic salts of phenols (generally known as phenates) are also useful in the compositions of this 4a 1 PCT/US89/00085 WO 89/07126 PT/US89/00085 S29 to the ashless dispersant is typically from about 4:0.1 to about 1:4.

The amount of the hydrocarbon soluble alkali or alkaline earth metal-containing composition included in the fuel compositions of the present invention may vary over a wide range although it is preferrednot to include unnecessarily large excesses of the metal composition.

The amount included, in the fuel should be an amount sufficient to improve the desired properties such as the reduction of valve seat recession when the fuel is burned in internal combustion engines which are not designed for use with unleaded gas. For example, older engines which were designed for leaded fuels were not constructed with specially hardened valve seats. Accordingly, the amount of metal composition to be included in the fuel will depend in part on the amount of lead in the fuel. For unleaded fuels, large amounts of the metal composition are required to provide the desirable reduction in valve seat recession. When low-lead fuels are treated in accordance with the present invention, lesser amounts of the metal-containing composition generally are required.

In summary, the amount of component included in the fuel compositions of the present invention will be an amount which is sufficient to reduce valve seat recession when such fuels are utilized in an internal combustion engine. Generally, the fuel will contain less than about gram, preferably less than 1.0 gram of the alkali or alkaline earth metal compound per liter of fuel. In another embodiment, the fuel composition of the present invention will contain from about 1 to about 100 parts of the alkali metal or alkaline earth metal per million parts of fuel although amounts of from 5 to about 60 parts per million appear to be adequate for most applications.

The amount of the hydrocarbon-soluble ashless dispersant optionally included in the fuel compositions of this invention also can vary over a wide range.

Typically, the weight ratio of the water fix o (E) r? ii; 1, ir~L:-f WO 89/07126 PCT/US89/00085 30 the dispersant will be 2:1 to 1:50, preferably 1:1 to 1:40. The amount of will depend in part on the amount of the metal-containing composition Typically the ashless dispersant is used at about 4:0.1 to about 1:10 by weight to The amount of the ashless dispersant to be included in the particular fuel composition can be determined readily by one skilled in the art and, obviously, the amount of dispersant contained in the fuel should not be so high as to have deleterious effects such as forming deposits on engine parts when the engine is cooled.

The following is an exemplification of the present invention.

Example 1 48.8 parts of mineral oil are added to a mixing vat having stirring capacity. A mixture of 0.6 parts of a C 24 alkylphenol sulfonate ammonium salt and 0.3 parts of a polyethylene glycol/polypropylene glycol copolymer having a molecular weight of 600 is added to the mixture. The copolymer is approximately 1:1 weight ratio of the monomers. A C24 substituted phenol is added at 0.3 parts by weight.

To the foregoing mixture is added 8.4 parts of the ashless dispersant obtained from Example E-2. A fluidizing oil (high viscosity mineral oil) is added at 8 parts by weight. Lastly, 33.6 parts by weight of the active ingredient obtained from Example A-i are added to the mixture with stirring.

The foregoing mixture is added at 250 PTB (pounds per thousand barrels or 0.71 to oxygenated gasoline as described below. The hydrocarbon component of the gasoline is 93.8%. The methanol is 3.89% and the tbutanol is 2.4% by weight. The respective volume ratio is 95:3:2.

I

of w.

broke The gasoline fuel is observed to have a high degree ater tolerance, any emulsification is quickly n with substantially complete saeparaticn into an

I-

S

I

L

this invention.

Example A-1 A mixture of 1000 parts of a primary branched monoalkvl benzene sulfonic acid approximately 522) WO 89/07126 PCT/US89/00085 31 organic and a water phase. The product also functions to protect exhaust valve seats.

Example 2 This composition is formulated identically to Example 1, however, replacement of the sodium alkylbenzene sulfonate salt with an equivalent amount (on a sodium basis) of the neutral sodium salt of polyisobutylene succinic acid is employed. The molecular weight of the anionic portion of the succinic acid salt is 950 and is obtained according to U.S. Patent 3,271,370 issued to Le Suer, September 6, 1966.

The product is otherwise obtained as previously described in Example 1 and blended at the same level in gasoline. The product functions as an aid against valve seat recession and is observed to break aqueous emulsions rapidly.

I-

1

Claims (27)

1. A fuel composition comprising: at least one hydrocarbon-soluble or dis- persible alkali metal or alkaline earth metal containing composition, at least one member selected from the group consisting of a hydrocarbyl substituted sulfonated pnenol or salt thereof; (ii) an ethylene oxide/propylene oxide 'I copolymer, and (iii) a hydrocarbyl substituted phenol, and (iv) mixtures of any of (ii) and (iii), gasoline, and at least one alcohol.

2. The composition of claim 1, wherein is an aromatic sulfonate.

3. The composition of claim 1, wherein is a polycarboxylate salt.

4. The compositiol of claim 1, wherein the hydrocarbyl chain on the hydrocarbyl substituted sulfonated phenol contains an average of aboeI 10 to ab;e carbon atoms.

5. The composition of claim 1, additionally comprising: an ashless dispersant selected from the group consisting of; at least one hydrocarbyl-substituted amine wherein the hydrocarbyl substituent is substantially aliphatic and contains at least 8 carbon atoms; (ii) at least one acylated, nitrccen-containincq compound having a substituent of at least 10 aliphatic carbon atoms made by reacting a carboxylic acid acylating ii/C-, s i Ps 1 i i~ rr WO 89/07126 PCT/US89/00085 33 agent with at least one amino compound containing at least one -NH- group, said acylating agent being linked to said amino compound through an imido, amido, amidine, or acyloxy ammonium linkage; (iii) at least one nitrogen-containing condensate of a phenol or aldehyde, and an amino compound having at least one -NH- group; (iv) at least one ester of a substituted carboxylic acid; at least one polymeric dispersant; (vi) at least one hydrocarbon substituted phenolic dispersant; and (vii) at least one fuel soluble alkoxylated deriva- tive of an alcohol, phenol, or amine.

6. The composition of claim 1, wherein the weight percent of the ethylene oxide in the copolymer is from to

7. The composition of claim 1 wherein the alcohol is at least one monohydric alcohol.

8. The composition of claim 2, wherein the aromatic sulfonate is the sodium salt.

9. The composition of claim 3, wherein the polycarboxylate salt is a hydrocarbyl substituted alkali metal succinate. 1C. The composition of 'claim I, wherein the hydrocarbyl group of is polyisobutylene.

11. The composition of claim 1 Wherein B(iii) is hydrocarbyl substituted phenol wherein the hydrocarbvl groups contain a total of 10 to 30 carbon atoms.

12. The composition of claim I, wherein the is a neutral salt.

13. The composition of claim 7, wherein the ^IA' monohvdric alcohol is a mixture of t-butanol and methanol. SP i PCT/US89/0005 WO 89/07126 34

14. The composition of claim 1, wherein is unleaded gasoline. The composition of claim 14 additionally comprising: an ashless dispersant selected from the group consisting of; at least one hydrocarbyl-substituted amine wherein the hydrocarbyl substituent is substantially aliphatic and contains at least 8 carbon atoms; (ii) at least one acylated, nitrogen-containing compound having a substituent of at least 10 aliphatic carbon atoms made by reacting a carboxylic acid acylating agent with at least one amino compound containing at least one -NH- group, said acylating agent being linked to said amino compound through an imido, amido, amidine, or acyloxy ammonium linkage; (iii) at least one nitrogen-containing condensate of a phenol or aldehyde, and an amino compound having at least one -NH- group; (iv) at least one ester of a substituted carboxylic acid; at least one polymeric dispersant; (vi) at least one hydrocarbon substituted phenolic dispersant; and (vii) at least one fuel soluble alkoxylated deriva- tive of an alcohol, phenol, or amine; and at least one monohydric alcohol;

16. The composition of claim 15 wherein the is a mixture of (ii) and (iii)

17. The composition of claim 1, wherein is the ammonium salt thereof. L_ i i I _i_

18. The composition of claim 15, wherein the hydrocarbon soluble or dispersible alkali metal or alkaline earth metal salt is the sulfonate salt.

19. The composition of claim 15, wherein the woeight ratio ,f to the ashless dispersant is 2:1 to 1:50. The composition of claim 19, wherein the molecular weight of is 400 to 10,000.

21. A fuel composition comprising: at least one member selected from the group consisting of: a hydrocarbon substituted sulfonated phenol or salt thereof; (ii) an ethylene oxide/propylene oxide copolymer; (iii) a hydrocarbyl substituted phenol, and (iv) mixtures of any of (ii) and (iii); gasoline; at least one alcohol; and, at least one ashless dispersant selected from the group consisting of: at least one hydrocarbyl-substituted amine wherein the hydrocarbyl substituent is substantially aliphatic and contains at least 8 carbon atoms; S(ii) at least one acylated, nitrogen-containing compound having a substituent of at least 10 aliphatic carbon atoms made by reacting a carboxylic acid acylating agent with at least one amino compound containing at least one -NH group, said acylating agent being linked to said amino compound through an imido, amido, amidine, or acyloxy ammonium linkage; (iv) at least one ester of a substituted carboxylic acid; (vi) at least one hydrocarbon substituted phenolic dispersant; and (vii) at least one fuel soluble alkoxylated derivative of an alcohol, phenol, or amine.

22. The composition of claim 21, additionally comprising at least one monohydric alcohol.

23. The composition of claim 21, wherein the weight percent ethylene oxide in the copolymer is 10% to

24. The composition of claim 21, wherein the ashless dispersant is /*is^ nycirocaron soluble ashless dispersant. T1.' compounds useful as ashless dispersants generally are characterized by a "polar" group attached to a relatively high molecular S :i 1 1- 36 The composition of claim 21, additionally contaiiing a hydrocarbyl substituted phenol wherein the hydrocarbyl groups contain a totil of 10 to carbon atoms.

26. A fuel composition comprising: at least one hydrocarbon-soluble or dispersible alkali metal or akaline earth metal containing composition and, a hyd: carbyl substituted sulfonated pL.:nol or salt thereof; an ethylene oxide/propylene oxide copolymer; gasoline, and at least one alcohol.

27. The composition of claim 26 containing less than 0.5 g/liter of lead.

28. A fuel composition comprising: (B a mixture of two or more of a hydrocarbon substituted sulfonated phenol or salt thereof; (ii) an ethylene oxide/propylene oxide copolymer; or (iii) a hydrocarbyl substituted phenol; gasoline; at least one alcohol; and, at least one ashless dispersant selected from the group consisting of: at least on( hydrocarbyl-substituted amine wherein the hydrocarbyl substituent is substantialiy aliphatic and contains at least 8 carbon atoms; at lea. one acyiated, nitrogen-containing compound having a substituent of at least 10 aliphatic carbon atoms made by reacting a carboxylic acid aacylating agent 1 ith ct least one anmino compound containing at least one -NH- group, said acylating agent being linked to said amino compound through an Siimido, amido, amidine, or acyloxy ammonium linkage; (iii) at least ,te nitrogen-containing condensate of a phenol or aldehyde and an amino compound having at least one -NH- group; (iv) at least one ester of a substituted carboxylic acid; at least one polymeric dispersant;= (vi) at least one hydrocarbon substituted phenolic dispersant; and (vii) at least one fuel soluble alkoxylated derivative of an alcohol, phenol, U I S The following specific examples illustrate the preparation of exemplary dispersants useful in the fuel compositions of this invention. Example 1 or Example 2. A process for delivering gasoline containing an alkali metal or alkaline earth metal containing composition with enhanced water tolerance to a vehicle fuel tank including the steps of combining with the gasoline: a hydrocarbon-soluble or dispersible alkali earth metal or alkaline earth metal containing composition, and at least one member selected from the group consisting of: a hydrocarbon substituted sulfonated phenol or salt thereof; (ii) an ethylene oxide/propylene oxide copolymer; (iii) a hydrocarbyl substituted phenol, and (iv) mixtures of (ii) and (iii) such that the weight ratio of to is sufficient to impart enhanced water tolerance to the mixture of and

31. The process of claim 30, comprising the steps of adding an ashless f: dispersant selected from the group consisting of: at least one hydrocarby1-substituted amine wherein the hydrocarbyi substituent is substantially aliphatic and contains at least 8 carbon atoms; (ii) at least one acylated, nitrogen-containing compound having a substituent of at least 10 aliphatic carbon atoms made ?y reacting a carboxylic acid acylating agent with at least one amino compound containing at least one -NH- group, said acylating agent being linked to said amino compound through an imido, amido, amidine, or acyloxy ammonium linkage; Yea (iii) at least one nitrogen-containing condensate of a phenol or aldehyde and an amino compound having at least one -NH- group; (iv) at least one ester of a substituted carboxylic acid; at least one polymeric dispersant; (vi) at least one hydrocarbon substituted phenolic dispersant; and Sxre ofi iadi (vii) at least one fuel, soluble aikoxylated derivative of an alcohol, phenol, or amine.

32. A process for delivering gasoline containing an alkali or alkaline earth metal containing composition with enhanced water tolerance to a vehicle fuel tank which process is substantially as herein described with reference to any one of the Examples. DATED this 9th day of January 1992. THE LUBRIZOL CORPORATION By their Patent Attorneys: CALLINAN LAWRIE *S. go 32 rcs o eieiggsln otann nakl rakieerhm a A carboxylic acid ester is prepared by slowly adding 3240 parts of a high molecular weight carboxylic acid (prepared by reacting chlorinated polyisobutylene and *t INTERNATIONAL SEARCH REPORT International Application No PCT/US 89/00085 1. CLASSIFICATION OF SUBJECT MATTER (If several clasilfication symbols apply, Indicate all) According to International Patent Classlfication (IPC) or to both National Claosification and IPC IPC4: C 10 L 1/14; C 10 L 1/02; C 10 L 1/24; C 10 L 1/18 II. FIELDS SEARCHED Minimum Documentation Searched 7 Classification System Classification Symbols 4 I C C 10 L Documentation Searched other than Minimum Documentation to the Extent that such Documents are Included In the Flelds Searched I III. DOCUMENTS CONSIDERED TO BE RELEVANT' Category I Citation of Document, with ind!Patlon, where appropriate, of the relevant passages 12 Relevant to Claim No. X US, A, 4083698 (WENZEL et al.) 1,3,28 11 April 1978 see claims Y 5-9,12,14, 15,18,29 Y WO, A, 87/01126 (LUBRIZOL) 26 February 1987 5,7-9,12, see the whole document 14,15,18, cited in the application 29 X US, A, 3930810 (GATTUSO) 21-23 6 January 1976 see the whole document Y 6 X US, A, 4398921 (RIFKIN et al.) 21-23,25 16 August 1983 see the whole document X GB, A, 2021144 (NL INDUSTRIES INC.) 1,17 28 November 1979 see the whole document Special categories of cited documents: 10 later document published after the international filing date document defining th. general state ol the art which in not or priority date and not In conflict with the application but con t cular relevance cited to Understand the prlnciple or theory underlying the considered to be of particular relevance invention earlier document but published on or after the international document of particular relevance; the claimed invention filing date cannot be considered novel or cannot be conitdered to document which may throw doubts on priority claim(s) or involve an inventive step which is cited to establish the publication date of another document of particular relevance;' the claimed invention citation or other special roason (as specified) cannot be considered to involve an Inventive steo when the document referring to an oral disclosure, use, exhibition or document is combined with one or more other such docu- other means ments, such combinatio, being obyviou to a person skilled document published priof to the international filino date but In the art. later than the priority date claimed document member of the same patent family IV. CERTIFICATION Date of the Actual Complatlcn of the International Search Date of Malling of this International Search Report 22nd April 1989 3 0, 05, 89 International Searching Authority Slgnature of Authorized Ofct EUROPEAN PATENT OFFICE M. AN MCL Form PCT/ISA/210 (tecond shoot) (January 1985) I _i CLI-Y F Intornatlonal ApplIcation No. -2- POT/US 89.100085

111. DOCUMENTS CONSIDERED TO BE RELEVANT (CONTINIED PRMOM THE SECOND SHEET) Category' i Citation of Document, with indicoatin, where appropriate, of tri rotavant passages IRoloyant to Claim No A' A A A A Chemical Abstracts, volume 93, no. 8, August 1980, (Columbus, Ohio, US) see page 224, abstract 75551j, SU, A, 722938 (ROGACHEVSKAYA, T.A. et al.) 25 March 1980 GB, A, 2147005 (SANDOZ) 1 May 1985 see the whole document EP, A, 0078249 (LANG CO.) 4 May 1983 see claims; examples US, A, 3328284 (GODAR) 27 June 1967 see the whole document US, A, 2995427 (SIGWORTH et al.) 8 August 1961 see the whole document FR, A, 2372224 (BEROL KEMI AB) 23 June 1978 see claim 1 1-29 1-29 1-29 1-29 17 ,27 6, 24 EP, A, 0086049 (LUBRIZOL) 17 August 1983 see claims Form, PCT ISA 210 (extra shoot) (January 1985) dispersant optionally included in the fuel compjositions of this invention also can vary over a wide range. Typically, the weight ratio of the water -fLix toc ANNEX TO THE INTERNATIONAL SEARCH REPORT ON INTERNATIONAL PATENT APPLICATION NO. US 8900085 SA 26397 This annex lists the patent family members relating to the patent documents, cited in the above-mentioned international search report. The members are as contained in the wropean Patent Office EI)P file on 23/05/89 Th Vuropean Patent Office is in no way liable for thesc particulars which are merely given for the purpose of information. Patent document Publication Patent family I Publication cited in search report date member(s) Idate US-A- 4083698 11-04-78 US-A- 4002435 11-01-77 WO-A- 8701126 26-02-87 AU-A- 6192986 10-03-87 US-A- 4659338 21-04-87 EP-A- 0233250 26-08-87 US-A- 4690687 01-09-87 JP-T- 63500602 03-03-88 AU-A- 8253087 31-03-88 US-A- 3930810 06-01-76 FR-A,B 2280703 27-02-76 DE-A- 2531000 12-02-76 CA-A- 101194,' 14-06-77 GB-A- 1511748 24-05-78 JP-A- 51049204 28-04-76 US-A- 4398921 16-08-83 None GB-A- 2021144 28-11-79 None GB-A- 214700S 01-05-85 AU-A- 3345184 28-03-85 FR-A- 2552444 29-03-85 DE-A- 3433554 11-04-85 JP-A- 60092394 23-05-85 BE-A- 900593 18-03-85 EP-A- 0078249 04-05-83 AT-A,B 373274 10-01-84 CA-A- 1188891 18-06-85 DE-A- 3277537 03-12-87 US-A- 3328284 None US-A- 2995427 None FR-A- 2372224 23-06-78 NL-A- 7713095 31-05-78 DE-A- 2753027 20-07-78 JP-A- 53082504 19-07-78 GB-A- 1591398 24-06-81 CA-A- 1098699 07-04-81 SE-A- 7623355 30-05-78 MFor more details about this annex~ see Official Journal of the Luropean P'atent Office, No. 1 2/8. 9 5:3 :2. The gasoline fuel is observed to have a high degree of watcr tolerance, any emulsification is quickly broken with substLantially complete separation into ar, ~4IA Page ANNEX TO THE INTERNATIONAL SEARCH REPORT ON INTERNATIONAL PATENT APPLICATION NO. US 8900085 SA 26397 This annex lists the patent family members relating to the patent documents cited in the abovc-ientioncd international search report. IThe members are as contained in the European Patent Office ED], ile onl 23/05189 The European Patent Office is in no way liable for these particulars which are merely given for the purpose of information. Patent document Publication Patent family Publication cited in search report date memiber(s) date FR-A- 2372224 SE-B- 404702 23-10-78 EP-A- 0086049 17-08-83 JP-A- 58134192 10-08-83 AU-A- 1082583 11-08-83 GA-A- 1208236 22-07-86 AU-B- 563150 02-07-87 w kor more dotilils about this; annex see Official Journal of thc 1-mropeain Patent office, ,so. i2/s2