AU8078687A

AU8078687A - Titanium and zirconium complexes, and fuel compositions

Info

Publication number: AU8078687A
Application number: AU80786/87A
Authority: AU
Inventors: Marvin Bradford Detar; Stephen A. Di Biase; George Robert Hill
Original assignee: Lubrizol Corp
Current assignee: Lubrizol Corp
Priority date: 1986-10-02
Filing date: 1987-09-25
Publication date: 1988-04-21
Anticipated expiration: 2007-09-25
Also published as: CA1324151C; EP0327559B1; DE3781557T2; WO1988002392A2; WO1988002392A3; DE3781557D1; JPH02504645A; ZA877370B; AU605193B2; EP0327559A1; ATE80175T1

Abstract

A method of operating a diesel engine equipped with an exhaust system particulate trap to reduce the build-up of exhaust particles collected in said trap. The method comprises operating said diesel engine with a fuel containing at least one compound selected from titanium or zirconium compounds effective to lower the ignition temperature of the exhaust particulates collected in said trap. Fuel compositions which are useful particularly in the operation of diesel engines equipped with exhaust particluate traps wherein the fuel contains at least one titanium or zirconium complex, and certain novel titanium and zirconium complexes are described and claimed.

Description

TITANIUM AND ZIRCONIUM COMPLEXES, AND FUEL COMPOSITIONS

Technical Field of the Invention This invention relates to a method of operating diesel engines equipped with an exhaust system particulate trap, to fuel compositions useful in operating diesel engines, and to certain titanium and zirconium complexes which are useful in the method and fuel of the invention. The fuels and titanium or zirconium compounds of the invention are useful in operating diesel engines and are effective in lowering the ignition temperature of exhaust particulates collected in the particulate traps of diesel exhaust systems.

Background of the Invention Diesel engines have been employed as engines for over-the-road vehicles because of relatively low fuel costs and improved mileage. However, because of their operating characteristics, diesel engines discharge a larger amount of carbon black particles or very fine condensate particles or agglomerates thereof as compared to the gasoline engine. These particles or condensates are sometimes referred to as "diesel soot", and the emission of such particles or soot results in pollution and is undesirable. Moreover, diesel soot has been observed to be rich in condensed, polynuclear hydrocarbons, and some of these have been recognized as carcinogenic. Accordingly, particulate traps or filters have been designed for use with diesel engines that are capable of collecting carbon black and condensate particles.

Conventionally, the particulate traps or filters have been composed of a heat-resistant filter element which is formed of porous ceramic or metal fiber and an electric heater for heating and igniting carbon particulates collected by the filter element. The heater is required because the temperatures of the diesel exhaust gas under normal operating conditions are insufficient to burn off the accumulated soot collected in the filter or trap. Generally, temperatures of about 450-600°C are required, and the heater provides the necessary increase of the exhaust temperature in order to ignite the particles collected in the trap and to regenerate the trap. Otherwise, there is an accumulation of carbon black, and the trap is eventually plugged. The above-described heated traps do not provide a complete solution to the problem because the temperature of the exhaust gases is lower than the ignition temperature of carbon particulates while the vehicle runs under normal conditions, and the heat generated by the electric heater is withdrawn by the flowing exhaust gases when the volume of flowing exhaust gases is large. Alternatively, higher temperatures in the trap can be achieved by periodically enriching the air/fuel mixture burned in the diesel engine thereby producing a higher exhaust gas temperature.

It also has been suggested that the particle build-up in the traps can be controlled by lowering the ignition temperature of the particulates so that the particles begin burning at the lowest possible temperatures. One method of lowering the addition temperature involves the addition of a combustion improver to the exhaust particulate, and the most practical way to effect the addition of the combustion improver to the exhaust particulate is by adding the combustion improver to the fuel. Manganese or copper compounds have been suggested as combustion improvers for fuels and fuel oils.

U.S. Patent 4,505,718 describes the treatment of lubricating oils and fuels to improve various properties thereof. When added to fuels, the combustion characteristics of the fuels are improved. The organic acids utilized to make the transition metal salts may be sulfonic acids, carboxylic acids, and phosphorus acids. The addition of transition metal salts of mixed organic carboxylic and sulfonic acids as anti-knock agents, combustion improvers and smoke suppressants is described in U.S. Patent 4,162,986. Manganese soaps and fuels are described in U.S. Patent 3,762,890, and organic magnesium compounds as fuel conditioners are described in U.S. Patent 4,202,671. Various titanium containing organic salts have been described as being useful in fuels, lubricants, etc., in, for example, U.S. Patents 4,093,614; 4,077,941; 3,355,270; and 3,493,508.

Summary of the Invention

A method of operating a diesel engine equipped with an exhaust system particulate trap to reduce the build-up of exhaust particles collected in said trap is described. The method comprises operating said diesel engine with a fuel containing at least one compound selected from titanium or zirconium compounds effective to lower the ignition temperature of the exhaust particulates collected in said trap. Fuel compositions which are useful particularly in the operation of diesel engines equipped with exhaust particulate traps and certain novel titanium and zirconium complexes are described and claimed.

Description of the Preferred Embodiments

In one embodiment, the invention relates to a method of operating a diesel engine equipped with an exhaust system particulate trap to reduce the build-up of exhaust particles collected in the trap. The method comprises operating the diesel engine with a fuel containing at least one compound selected from titanium or zirconium compounds effective to lower the ignition temperature of the exhaust particulates collected in said trap. The titanium and zirconium compounds may be either organic or inorganic compounds. It is preferred that the titanium and zirconium compounds be dispersible or soluble in the diesel fuel, and, accordingly, organotitanium and organo-zirconium compounds are the preferred titanium and zirconium compounds of the present invention. In general, it has been observed that the anionic portion of the titanium and zirconium compound is not particularly critical to the present invention. It is preferred that the titanium and zirconium compound be hydrolytically stable in applications where some water may be present.

The inorganic compounds of titanium and zirconium include, for example, the oxides, hydroxides, chlorides, sulfates, nitrates and carbonates.

In one embodiment, the organo-titanium and organo-zirconium compounds are titanium and zirconium salts of at least one acidic organic compound. The most useful acidic organic compounds are sulfur acids, carboxylic acids, organic phosphorus acids and phenols. The salts can be neutral or basic, with the basic salts containing an excess amount of metal cation with respect to the amount of salt anion. The sulfur acids include sulfonic, sulfamic, thiosulfonic, sulfinic, sulfenic, sulfurous and thiosulfuric acid. Generally, the sulfonic acid is an aliphatic or aromatic sulfonic acid, and aromatic sulfonic acids are preferred.

The sulfonic acids include the mono- or polynuclear aromatic or cycloaliphatic compounds. The sulfonic acids can be represented for the most part by the following formulae.

R¹(SO₃H)_r (X)

(R²)_xT(SO₃H)y (XI)

in which T is an aromatic nucleus such as, for example, benzene, naphthalene, anthracene, phenanthrene, diphenylene oxide, thianthrene, phenothioxine, diphenylene sulfide, phenothiazine, diphenyl oxide, diphenyl sulfide, diphenylamine, cyclohexane , petroleum naphthenes , decahydro-naphthalene, cyclopentane, etc.; R¹ and R² are each independently aliphatic groups, R¹ contains at least about 15 carbon atoms, the sum of the carbon atoms in R² and T is at least about 15, and r, x and y are each independently 1 or greater. Specific examples of R¹ are groups derived from petrolatum, saturated and unsaturated paraffin wax, and polyolefins, including polymerized C₂, C₃, C₄, C₅, C₆, etc., olefins containing from about 15 to 7000 or more carbon atoms. The groups T, R¹, and R² 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 X and XI 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 titanium and zirconium metal salts thereof are also understood to be illustrated. Such 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 to about 200 seconds at 210°F; petrolatum sulfonic acids; mono- and poly-wax substituted sulfonic and polysulfonic acids of, e.g., benzene, naphthalene, phenol, diphenyl ether, naphthalene disulfide, diphenylamine, thiophene, alpha-chloronaphthalene, etc.; other substituted sulfonic acids such as alkyl benzene sulfonic 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 C12 substituents on the benzene ring. Dodecyl benzene bottoms, principally mixtures of mono- and di-dodecyl benzenes, are available as by-products from the manufacture 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, e.g., SO3, is well known to those skilled in the art. See, for example, the article "Sulfonates" in Kirk-Othmer "Encyclopedia of Chemical Technology", Second Edition, Vol. 19, pp. 291 et seq. published by John Wiley & Sons, N.Y. (1969).

The carboxylic acids which are useful in preparing the titanium and zirconium compounds may be mono- or polycarboxylic acids. The monocarboxylic acids include lower carboxylic acids containing from 1 to 7 carbon atoms such as acetic acid, propionic acid, butyric acid, etc. Higher acids containing 8 or more carbon atoms such as octanoic acid, decanoic acid, dodecanoic acid, as well as fatty acids containing from about 12 to about 30 carbon atoms. The fatty acids are often mixtures of straight or branched chain acids containing, for example, from about 5 to about 30% straight chain acids, and about 70 to about 95% (mole) branched chain acids. Of the commercially available fatty acid mixtures containing higher proportions of straight chain acids also are useful in preparing the titanium and zirconium salts.

Higher carboxylic acids include the well known dicarboxylic acids made by alkylating maleic anhydride or its derivatives. The products of such reactions are hydrocarbon-substituted succinic acids, anhydrides, etc. Lower molecular weight dicarboxylic acids such as glutaric acid, adipic acid, etc., also can be used to make the titanium and zirconium salts useful in the present invention. Specific examples of carboxylic acids useful in preparing the titanium and zirconium salts useful in the present invention include 2-ethylhexanoic acid, alphalinolenic acid, propylene-tetramer-substituted maleic acid, behenic acid, stearic acid, isostearic acid, pelargonic acid, capric acid, linoleic acid, lauric acid, oleic acid, myristic acid, palmitic acid, and commercially available mixtures of two or more carboxylic acids such as tall oil acids, rosin acids, etc.

Specific examples of the salts of the carboxylic acid compounds include titanium oleate, zirconium oleate, titanium stearate, zirconium stearate, etc.

Titanium and zirconium salts from phosphorus acids also are useful in the present invention. Pentavalent phosphorus acids useful in preparing the titanium and zirconium salts may be represented by the formula

wherein each of R¹ and R² is hydrogen or a hydrocarbon or essentially hydrocarbon group preferably having from about 4 to about 25 carbon atoms, at least one of R¹ and R² being hydrocarbon or essentially hydrocarbon; each of χ1, χ2, χ3 and χ4. is oxygen or sulfur; and each of a and b is 0 or 1. Thus, it will be appreciated that the phosphorus acid may be an organophosphoric, phosphonic or phosphinic acid, or a thio analog of any of these. Titanium and zirconium salts of the above- described organic acid compounds can be prepared by reacting the organic acid with titanium or zirconium in the form of the oxide, hydroxide, carbonate, etc.

The titanium and zirconium compounds useful in the fuels of. the present invention also may be titanium and zirconium alcoholates characterized by the general formula

M(OR)4

wherein M is titanium or zirconium and R is a hydrocarbyl group. Most often, the hydrocarbyl groups will contain up to about 30 carbon atoms, and examples of such hydrocarbyl groups include, ethyl, propyl, isopropyl, butyl, hexyl, 2-ethylhexyl , dodecyl , etc . These titanium and zirconium compounds can be prepared by methods well known in the art, and many such compounds are available commercially. Specific examples of such compounds include tetraisopropyl titanate, tetra-n-butyl titanate, tetraisopropyl zirconate, tetra-n-butyl zirconate, etc.

In another embodiment of the present invention, the titanium and zirconium compounds are titanium and zirconium complexes characterized by the formula

(RO)χM(Ch)_y (I)

wherein R is hydrogen or a hydrocarbyl group containing from 1 to about 30 carbon atoms; M is. titanium or zirconium; x is 1 or 2; y is 2 or 3; x + y is 4; and Ch is derived from at least one metal chelating agent. The metal chelating agents used in the preparation of the complexes (I) generally contain a hydrocarbon linkage and at least two functional groups on different carbon atoms. Generally, the functional groups are in vicinal or beta position to each other on the carbon skeleton of the hydrocarbon linkage. The hydrocarbon linkage may be aliphatic, cycloaliphatic or aromatic.

The term "metal chelating agent" is the accepted terminology for a well known class of chemical compounds which have been described in several texts including Chemistry of the Metal Chelate Compounds, by

Martell and Calvin, Prentice-Hall, Inc., N.Y. (1952). Examples of functional groups which may be present in the chelating agent include hydroxy groups, carboxy groups, carbonyl groups, amino groups, or mercapto groups. Generally, the chelating agent (Ch) may be aliphatic in nature and selected from the group consisting of glycols, dithiols, mercapto alcohols, amino alcohols, aminothiols, dicarboxylic acids, hydroxy carboxylic acids, mercapto carboxylic acids, amino carboxylic acids, diketones, ketocarbcxylic acids or esters, etc. Examples of general classes of aroxaatic chelating agents include dihydroxy benzenes, dimercapto benzenes, mercaptohydroxy benzenes, diamino benzenes, aminohydroxy benzenes, aiainomercapto benzenes, hydroxy-carboxy benzenes, aiainocarboxy benzenes and mercapto-carboxy benzenes having the two functional groups in vicinal or beta position to one another on the benzene nucleus.

The titanium and zirconium complexes represented by Formula I generally are prepared by reacting one or more chelating agents with a titanium or zirconium compound represented by the formula M (OR) 4

wherein M is titanium or zirconium and each R group is independently hydrogen or a hydrocarbyl group containing from 1 to about 30 carbon atoms. Generally, all of the R groups are hydrocarbyl groups. The number of chelate groups (Ch) which enter into the complex is dependent upon the relative amounts of the reactants, and generally, either two or three equivalents of the chelating group are reacted with two or one equivalents (respectively) of the compound of the formula M(OR)4. The mixtures generally are heated to accelerate the reaction and to remove the alcohol (ROH) formed in the reaction.

The preferred complexes represented by Formula I are soluble in fuel, and the chelating agents accordingly are selected to impart fuel-solubility to the complex. Generally, the chelating agents will contain a carbon skeleton of from 2 to about 18 carbon atoms.

Examples of suitable metal chelating agents within the above-described groups include vicinal- and beta-diols such as ethylene glycol and 2-ethyl-1,3-hexanediol; vicinal- and beta-dithiols such as ethylene mercaptan and 1,3-propanediol; vicinal- and beta-mercapto alcohols such as beta-mercaptoethanol, 3-mercapto-1-propanol; vicinal- and beta-diamines such as ethylene diamine and propylene diamine; vicinal- and beta-amino alcohols such as ethanolamine and 3-amino-1-propanol; vicinal- and beta-aminothiols such as thioethanolamine and 3-amine-1-mercaptopropane; vicinal- and beta-dicarboxylic acids such as oxalic acid and malonic acids yicinal- and beta-hydroxy carboxylic acids such as glycolic acid and beta-hydroxy butyric acid; vicinal- and beta-mercapto carboxylic acids such as thioglycolic acid and beta-mercapto butyric acid; vicinal- and beta-amino carboxylic acids such as glycine and beta-amino- butyric acid; beta-diketones such as acetylacetone and benzoyl acetone; beta-keto carboxylic acid esters such as ethylacetoacetate; etc.

As mentioned above, the metal chelating agents also may be alicyclic chelating agents or aromatic chelating agents such as represented by the structural formula

(IX) wherein R¹ is a hydrocarbyl group containing 1 to about 100 carbon atoms, n is an integer from 0 to 4, Y is in the ortho or meta positions relative to X, and X and Y are each independently functional groups such as OH, NH₂, NHR, SH, COOR, or C(O)H wherein R is hydrogen, or a hydrocarbyl group, preferably a lower aliphatic group. Specific examples of such aromatic compounds include hydrocarbyl-substituted and unsubstituted vicinal-di-hydroxy aromatic compounds such as pyrocatechol and 4-t-butyl-pyrocatechol; vicinal-dimercaptoaromatic compounds such as thiocatechol; vicinalmercapto-hydroxyaromatic compounds such as monothiocatechol or a mercaptohydroxy benzene; vicinal-diaminoaromatic compounds such as orthophenylenediamine; vicinal-amino-hydroxyaromatic compounds such as orthoaminophenol; vicinal-aminomercapto aromatic compounds such as orthoaminothiophenol; vicinal-hydroxycarboxy aromatic compounds such as salicyclic acid; vicinal- aminocarboxy aromatic compounds such as orthoaminobenzoic acid; vicinal-mercaptocarboxy aromatic compounds such as ortho-mercaptobenzoic acid, etc. Specific examples of alicyclic compounds include 1,2-dihydroxycyclohexane and, amino, 2-hydroxycyclohexane. The above-described alicyclic and aromatic chelating agents may have various other ring substituents including aromatic and substituted aromatic rings; hydroxy, alkoxy, and aryloxy groups, sulfhydryl, alkylthioether, arylthioether, alkylthioester, and arylthioester groups; acyl, aroyl, thioacyl and thioaroyl groups; amino, alkylamino, aryl- amino, acylamido and aroylamido groups; and nitro, halogen and sulfato groups.

In another embodiment of the present invention, the metal chelating agent (Ch) may be selected from the group consisting of:

(A) aromatic Mannich bases,

(B) amino acid compounds of the formula

(VI)

wherein R₁ is hydrogen or a hydrocarbyl group; R₂ is R₁ or an acyl group; R₃ and R₄ are each independently hydrogen or lower alkyl groups; and z is 0 or 1,

(C) beta diketones,

(D) phenolic compounds of the structure

(VIII) wherein each R is a hydrocarbyl group; and X is CH₂, S, or CH₂OCH₂, and

(E) an aromatic difunctional compound of the formula

(IX) wherein R¹ is a hydrocarbyl group containing 1 to about 100 carbon atoms, n is an integer from 0 to 4, Y is in the ortho or meta-position relative to X, and X and Y are each independently OH, NH₂, NHR, COOR, SH or

C(O)H groups wherein R is hydrogen or a hydrocarbyl group.

(A) : Aromatic Mannich Bases.

The Mannich reaction between active hydrogen compounds, aldehydes such as formaldehyde and amino compounds is well known. The Mannich condensation products utilized in the present invention are those which are derived from hydroxy aromatic compounds, amines or hydroxy amines, and aldehydes or ketones.

In one embodiment, the metal chelating agent (Ch) is an aromatic Mannich base which is the reaction product

(A-1) a compound having the formula

m wherein Ar is an aromatic group or a coupled aromatic group; wherein m is 1, 2 or 3; wherein n is an integer from 1 to 4; wherein R¹ independently is hydrogen or a hydrocarbyl having from 1 to about 100 carbon atoms; and wherein R° is hydrogen, amino, or carboxyl; and wherein X is O, S, or both when m is 2 or greater,

(A-2) a compound having the formula

or a precursor thereof; wherein R² and R³ independently are hydrogen, a saturated hydrocarbon group having from 1 to about 18 carbon atoms; or wherein R³ is a carbonyl-containing hydrocarbon group having from 1 to about 18 carbon atoms; and

(A-3) an amine which contains at least one primary or secondary amino group.

The (A-1) hydrocarbyl-substituted hydroxyl and/or thiol-containing aromatic compound of the present invention generally has the formula (R¹) n-Ar-(XH)m wherein Ar is an aromatic group such as phenyl or polyaromatic group such as naphthyl, and the like. Moreover, Ar can be coupled aromatic compounds such as naphthyl, phenyl, etc., wherein the coupling agent is 0, S, CH₂, a lower alkylene group having from 1 to about 6 carbon atoms, NH, and the like with R¹ and XH generally being pendant from each aromatic group. Examples of specific coupled aromatic compounds include diphenylamine, diphenylmethylene and the like. The number of "m" XH groups is usually from 1 to 3, desirably 1 or 2, with 1 being preferred. The number of "n" substituted R¹ groups is usually from 1 to 4, desirably 1 or 2 with a single substituted group being preferred. X is 0 and/or S with 0 being preferred. That is, if m is 2, X can be both 0, both S, or one 0 and one S. R¹ can be a hydrogen or a hydrocarbyl-based substituent having from 1 to about 100 carbon atoms. As used herein and throughout this specification, the term "hydrocarbyl-based substituent" or "hydrocarbyl" denotes a substituent having carbon atoms directly attached to the remainder of the molecule and having predominantly hydrocarbyl character within the context of this invention. Such substituents include the following:

(1) Hydrocarbon substituents, that is, aliphatic (for example alkyl or alkenyl), alicyclic (for example cycloalkyl or cycloalkenyl) substituents, aromatic-, aliphatic- and alicyclic-substituted aromatic nuclei and the like, as well as cyclic substituents wherein the ring is completed through another portion of the molecule (that is, any two indicated substituents may together form an alicyclic radical).

(2) Substituted hydrocarbon substituents, that is, those containing non-hydrocarbon radicals which, in the context of this invention, do not alter the predominantly hydrocarbyl character of the substituent. Those skilled in the art will be aware of suitable radicals (e.g., halo, (especially chloro and fluoro), amino, alkoxyl, mercapto, alkylmercapto, nitro, nitroso, sulfoxy, etc.)

(3) Hetero substituents, that is, substituents which, while predominantly hydrocarbon in character within the context of this invention, contain atoms other than carbon present in a chain or ring otherwise composed of carbon atoms.

As noted above, R¹ is hydrogen, or a hydrocarbyl group. The hydrocarbyl groups may contain from 1 to about 100 carbon atoms such as an alkyl, or alkyl groups may be mixtures of alkyl groups having from 1 up to an average of about 70 carbon atoms, more desirably from about 7 to about 20 carbon atoms, an alkenyl having 2 to about 30 carbon atoms, more desirably from about 8 to about 20 carbon atoms, a cycloalkyl having from 4 to about 10 carbon atoms, an aromatic group having from about 6 to about 30 carbon atoms, an aromatic-substituted alkyl or alkyl-substituted aromatic having a total of from about 7 to about 30 carbon atoms and more desirably from about 7 to about 12 carbon atoms. The hydrocarbyl-based substituent preferably is an alkyl having from 7 to about 20 carbon atoms with from about 7 to about 14 carbon atoms being highly preferred. Examples of suitable hydrocarbyl-substituted hydroxylcontaining aromatics include the various naphthols, and more preferably, the various alkyl-substituted catechols, resorcinols, and hydroquinones, the various xylenols, the varous cresols, aminophenols, and the like. Examples of various suitable (A) compounds include heptylphenol, octylphenol, nonylphenol, decylphenol, dodecylphenol, tetrapropylphenol, eicosylphenol, and the like. Dodecylphenol, tetrapropylphenol and heptylphenol are especially preferred. Examples of suitable hydrocarbyl-substituted thiol-containing aromatics include heptylthiophenol, octylthiophenol, nonylthiophenol, dodecylthiophenol, tetrapropylthiophenol, and the like. Examples of suitable thiol and hydroxyl-containing aromatics include dodecylmonothioresorcinol.

The aldehyde or ketone (A-2) used in the present invention has the formula

or a precursor thereof, wherein R² and R³ independently can be hydrogen, a hydrocarbon such as an alkyl having from 1 to about 18 carbon atoms and more preferably 1 or 2 carbon atoms. The hydrocarbon can also be a phenyl or an alkyl-substituted phenyl having from 1 to about 18 carbon atoms and more preferably from 1 to about 12 carbon atoms. Examples of suitable (A-2) compounds include the various aldehydes and ketones such as formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, valeraldehyde, benzaldehyde, and the like, as well as acetone, methyl ethyl ketone, ethyl propyl ketone, butyl methyl ketone, glyoxal, glyoxylic acid, and the like. Precursors of such compounds which react as aldehydes under reaction conditions of the present invention can also be utilized and include paraformaldehyde, formalin, trioxane and the like. Formaldehyde and its polymers, for example, paraformaldehyde are preferred. Mixtures of the various (A-2) reactants also can be utilized.

The third reactant used in preparing the Mannich base is (A-3) an amine which contains at least one primary or secondary group. Thus the amine is characterized by the presence of at least one -N-H group. The remaining valences of the above nitrogen atom preferably are satisfied by hydrogen, amino, or organic groups bonded to said nitrogen atom through direct carbon-to-nitrogen linkages. The amine (A-3) may be represented by the formula

(IV) wherein R¹ is a hydrocarbyl group, amino-substituted hydrocarbyl, hydroxy-substituted hydrocarbyl, or alkoxy-substituted hydrocarbyl group, and R² is hydrogen or R¹. Thus, the compounds from which the nitrogen-containing group may be derived include principally ammonia, aliphatic amines, aliphatic hydroxy or thioamines, aromatic amines, heterocyclic amines, or carboxylic amines. The amines may be primary or secondary amines and may also be polyamines such as alkylene amines, arylene amines, cyclic polyamines, and the hydroxy-substituted derivatives of such polyamines.

Specific amines of these types are methylamine, N-methyl-ethylamine, N-methyl-octylamine, N-cyclohexylaniline, dibutylamine, cyclohexylamine, aniline, di(p-methyl) amine, dodecylamine, octadecylamine, o-phenylenediamine, N,N'-di-n-butyl-p-phenylenediamine, morpholine, piperazine, tetrahydropyrazine, indole, hexahydro-1,3,5-triazine, 1-H-1,2,4-triazole, melamine, bis-(p-aminophenyl) methane, phenyl-methylenimine, menthanediamine, cyclohexamine, pyrrolidine, 3-amino-5,6-diphenyl-1,2,4-triazine, ethanolamine, diethanolamine, quinonediimine, 1,3-indandiimine, 2-octadecylimidazoline, 2-phenyl-4-methyl-imidazolidine, oxazolidine, and 2-heptyl-oxazolidine.

The hydroxyl-containing amines can be characterized by the formula

χ (V) wherein each of the R¹ groups is independently a hydrogen atom or a hydrocarbyl, hydroxyhydrocarbyl, aminohydrocarbyl, or hydroxyaminohydrocarbyl group provided that at least one of R¹ is a hydroxyhydrocarbyl or a hydroxyaminohydrocarbyl group, R² is an alkylene group, and x is an integer from 0 to about 5.

Examples of specific hydroxyl-containing amines include ethanolamine, 2-amino-1-butanol, 2-amino-2-methyl-1-propanol, di-(3-hydroxypropyl)-amine, 3-hydroxybutyl-amine, 4-hydroxybutyl-amine, 2-amino-1-butanol, 2-amino-2-methyl-1-propanol, 2-amino-1-propanol, 3-amino-2-methyl-1-propanol, 3-amino-1-propanol, 2-amino-2-methyl-1,3-propanediol, 2-amino-2-ethyl-1,3-propanediol, diethanolamine, di-(2-hydroxypropyl)-amine, N-(hydroxypropyl) -propylamine, N-(2-hydroxyethyl) -cyclohexylamine, 3-hydroxycyclopentylamine, N-hydroxyethyl piperazine, and the like.

The amine (A-3) also may be a polyamine conforming for the most part to the formula

wherein n is an integer preferably less than about 10, A is a substantially hydrocarbon or hydrogen group, and the alkylene group is preferably a lower alkylene group having less than about 8 carbon atoms. The alkylene amines include principally methylene amines, ethylene amines, butylene amines, propylene amines, pentylene amines, hexylene amines, heptylene amines, octylene amines, other polymethylene amines, and also the cyclic and the higher homologues of such amines such as piperazines and amino-alkyl-substituted piperazines. They are exemplified specifically by: ethylene diamine, triethylene tetramine, propylene diamine, decamethylene diamine, octamethylene diamine, di(heptamethylene) tri amine, tripropylene tetramine, tetraethylene pentamine, trimethylene diamine, pentaethylene hexamine, di(trimethylene)-triamine, 2-heptyl-3-(2-aminopropyl)imidazoline, 4-methyl-imidazoline, 1,3-bis(2-aminoethyl)imidazoline, pyrimidine, 1-(2-aminopropyl) piperazine. 1,4- bis(2-aminoethyl)piperazine, and 2-methyl-1-(2-aminobutyl)piperazine. Higher homologues such as are obtained by condensing two or more of the above- illustrated alkylene amines likewise are useful.

Hydroxyalkyl-substituted alkylene amines, i.e., alkylene amines having one or more hydroxyalkyl substituents on the nitrogen atoms, likewise are contemplated for use herein. The hydroxyalkyl-substituted alkylene amines are preferably those in which the alkyl group is a lower alkyl group, i.e., having less than about 6 carbon atoms. Examples of such amines include N-(2-hydroxyethyl) ethylene diamine, N,N'-bis(2-hydroxyethyl) ethylene diamine, 1-(2-hydroxyethyl)piperazine, mono- hydroxypropyl-substituted diethylene triamine, 1,4-bis- (2-hydroxypropyl) piperazine, di-hydroxypropyl-substi- tuted tetraethylene pentamine, N-(3-hydroxypropyl) tetramethylene diamine, and 2-heρtadecyl-1(2-hydroxyethyl)-imidazoline.

Higher homologues such as are obtained by condensation of the above-illustrated alkylene amines or hydroxyalkyl-substituted alkylene amines through amino groups or through hydroxy groups are likewise useful. It will be appreciated that condensation through amino groups results in a higher amine accompanied with removal of ammonia and that condensatioα through the hydroxy groups results in products containing ether linkages accompanied with removal of water. The preparation of the Mannich compounds can be carried out by a variety of methods known in the art. One method involves adding the (A-1) hydroxyl containing aromatic compound, the (A-2) saturated aldehyde or ketone, and the (A-3) amine compound to a suitable vessel and heating to carry out the reaction. Reaction temperatures from about ambient to about the decomposition temperature of any component or the Mannich product can be utilized. During reaction, water is drawn off as by sparging. Desirably, the reaction is carried out in solvent such as an aromatic type oil. The amount of the various reactants utilized is desirably on a mole to mole basis of (A-1) and (A-2) for each (A-3) secondary amino group or on a two-mole basis of (A-1) and (A-2) for each (A-3) primary amino group, although larger or smaller amounts can also be utilized.

In another method of preparing Mannich products, the hydroxyl containing aromatic compound (A-1) and the amine compound (A-3) are added to a reaction vessel. The aldehyde or ketone (A-2) is generally rapidly added and the exothermic reaction generated is supplemented by mild heat such that the reaction temperature is from about 60°C to about 90°C. Desirably the addition temperature is less than the boiling point of water, otherwise, the water will bubble off and cause processing problems. After the reaction is essentially complete, the water by-product is removed in any conventional manner as by evaporation thereof which can be achieved by applying a vacuum, applying a sparge, heating or the like. A nitrogen sparge is often utilized at a temperature of from about 100°C to about 130°C. Naturally, higher or lower temperatures can be utilized. The reaction is generally carried out in a solvent. Any conventional solvent can be utilized such as toluene, xylene or propanol. Oftentimes various oils are utilized such as an aromatic type oil, 100 neutral oil, etc.

Some examples of the amounts of the various (A-1), (A-2) and (A-3) components are set forth above. However, other amounts and ratios can be utilized. For example, for each primary amino group of (A-3) from about 0.5 to about 6 moles of (A-1) and (A-2) can be utilized and more desirably from about 1.8 to about 2.2 moles of (A-1) and (A-2). For each secondary amino group of (A-3), from about 0.2 to about 2 moles of (A-1) and (A-2) can be utilized and more desirably from about 0.9 to about 1.1 moles of (A-1) and (A-2). (B) : Amino Acid Compounds

The metal chelating agent (Ch) also may be at least one amino acid compound of the formula

(VI)

wherein R₁ is hydrogen or a hydrocarbyl group; R₂ is R₁ or an acyl group; R₃ and R₄ are each independently hydrogen or lower alkyl groups; and z is 0 or 1. The hydrocarbyl groups R₁ and R₂ may be any one of the hydrocarbyl groups as broadly defined above. In particular, R₁ and R₂ are alkyl, cycloalkyl, phenyl, alkyl-substituted phenyl, benzyl or alkylsubstituted benzyl groups.

In one preferred embodiment, R₁ and R₂ of Formula VI are each independently alkyl groups containing from 1 to about 18 carbon atoms, cyclohexyl. phenyl, phenyl groups containing alkyl substituents containing from 1 to about 12 carbon atoms at the 4-position of the phenyl ring, benzyl or benzyl having an alkyl group of from 1 to about 12 carbon atoms at the 4-position of the phenyl ring. Generally, R₁ in Formula VI is a lower alkyl such as a methyl group, and R₂ is an alkyl group having from about 4 to about 18 carbon atoms.

In another embodiment, R₁ is as defined above and R₂ is an acyl group. Although a variety of acyl groups may be utilized as R₂, the acyl group generally can be represented by the formula

R₂'C(O)-

wherein R₂' is an aliphatic group containing up to about 30 carbon atoms. More generally, R₂' contains from about 12 to about 24 carbon atoms. Such acylsubstituted amino carboxylic acids are obtained by reaction of an amino carboxylic acid with a carboxylic acid or carboxylic halide. For example, a fatty acid can be reacted with an amino carboxylic acid to form the desired acyl-substituted amino carboxylic acid. Acids such as dodecanoic acid, oleic acid, stearic acid, linoleic acid, etc., may be reacted with amino carboxylic acids such as represented by Formula VI wherein R₂ is hydrogen.

The groups R₃ and R₄ in Formula VI are each independently hydrogen or lower alkyl groups. Generally, R₃ and R₄ will be independently hydrogen or methyl groups, and most often, R₃ and R₄ are hydrogen. In Formula VI, z may be 0 or 1. When z is 0, the amino acid compound is glycine, alpha-alanine and derivatives of glycine and alpha-alanine. When z is 1, the amino carboxylic acid (VI) is beta-alanine or derivatives of beta-alanine.

The amino acid compounds of Formula VI which are useful as metal chelating agents in the present invention can be prepared by methods described in the prior art, and some of these amino acids are available commercially. For example, glycine, alpha-alanine, beta-alanine, valine, arginine, and 2-methyl-alanine. The preparation of amino acid compounds represented by Formula VI where z is 1 is described in, for example, U.S. Patent 4,077,941. For example, the amino acids can be prepared by reacting an amine of the formula

R₁R₂NH

wherein R₁ and R₂ are as previously defined, with a compound of the formula

R₃CH=C(R₄)-CO₂R₅

wherein R₃ and R₄ are as defined previously with respect to Formula VI, and R₅ is a lower alkyl, preferably methyl or ethyl, followed by hydrolysis of the ester with a strong base and acidification. Among the amines which can be reacted with the unsaturated ester are the following: dicyclohexylamine, benzylmethylamine, aniline, diphenylamine, methylethylamine, cyclohexylamine, n-pentylamine, diisobutylamine, diisopropylamine, dimethylamine, dodecylamine, octadecylamine, N-n-octylamine, aminopentane, sec-butylamine, propylamine, etc. Amino acid compounds of Formula VI wherein R₂ is methyl or an acyl group can be prepared by reacting a primary amine of the formula

R₁NH₂

wherein R₁ is as defined previously with a compound of the formula

R₃CH=C(R₄)-CO₂R₅

wherein R₃, R₄ and R₅ are as defined above. Subsequently, this intermediate is converted to the methyl derivative by N-methylation and hydrolysis of the ester followed by acidification. The corresponding acyl derivative is formed by reacting the intermediate with an acid or acid halide such as stearic acid, oleic acid, etc. Specific amino acids of the type represented by Formula VI are illustrated in the following Table I.

(C); Beta-piketones

The metal chelating agent (Ch) also may be at least one beta-diketone. Generally, the beta-diketone is characterized by the formula

R-C(O)-CH₂-C(O)-R₁ (VII)

wherein R and R₁ are each independently hydrocarbyl groups. The hydrocarbyl groups may be aliphatic or aromatic hydrocarbyl groups as defined above. Among the aliphatic hydrocarbyl groups, the lower hydrocarbyl groups containing up to about 7 carbon atoms are preferred. Specific examples of R₁ and R₂ groups include methyl, ethyl, phenyl, benzyl, etc., and specific examples of beta-diketones include acetyl acetone and benzoyl acetone.

(P): Phenolic Compounds

The metal chelating agent (Ch) also may be at least one phenolic compound of the formula

(VIII) wherein each R is a hydrocarbyl group; and X is CH₂, S, or CH₂OCH₂. In one embodiment, each R is independently an aliphatic group which generally contains from about 4 to about 20 carbon atoms.

Examples of typical R groups include butyl, hexyl heptyl, 2-ethyl-hexyl, octyl, nonyl decyl, dodecyl, etc. The phenolic compounds represented by Formula VIII can be prepared by reacting the appropriate substituted phenol with formaldehyde or a sulfur compound such as sulfur dichloride. When one mole of formaldehyde is reacted with two moles of the substituted phenol, the bridging group X is CH₂. When a molar ratio of formaldehyde to substituted phenol is 1:1, bis-phenolic compounds bridged by the group CH₂OCH₂ can be formed as a result of the reaction. When two moles of a substituted-phenol are reacted with one mole of sulfur dichloride, a bis-phenolic compound is formed which is bridged by a sulfur atom. (E): Aromatic Difunctional Compounds

The metal chelating agent (Ch) may be an aromatic difunctional compound of the formula

(IX) wherein R¹ is a hydgrocarbyl group containing 1 to about 100 carbon atoms, n is an integer from 0 to 4, Y is in the ortho or meta position relative to X, and X and Y are each independently OH, NH₂, NR₂, COOR, SH, or C(O)H wherein R is hydrogen or a hydrocarbyl group. Specific examples of useful aromatic difunctional compounds represented by Formula IX have been given above.

In one preferred embodiment, the metal chelating agent (Ch) is an amino phenol. Preferably, the amino phenol is an ortho-amino phenol which may contain other substituent groups such as hydrocarbyl groups. The following examples illustrate the preparation of several exemplary metal chelating agents which are useful in preparing the titanium or zirconium complexes of the present invention. Unless otherwise indicated in the following examples and elsewhere in the specification and claims, all parts and percentages are by weight, and all temperatures are in degrees centigrade.

Example A

A mixture of 157 parts of dodecylphenol and 296 parts of mineral oil is prepared, and to this mixture there is added with stirring, 20.6 parts of a commercial polyamine mixture by responding to diethylenetriamme over a period of 30 minutes. To this mixture at about 60°C, there is added 20.6 parts of formalin solution (37% paraformaldehyde) dropwise over a period of one hour while maintaining the reaction temperature below about 96°C. The mole ratio of phenol to formaldehyde to amine is 3:3:1. After complete addition of the formalin solution, the reaction mixture is maintained at a temperature of about 96-99°C for 3.5 hours. The water formed in the reaction is removed by distillation under vacuum and thereafter cooled to room temperature. The product that is obtained is a red oil.

Example B

Dodecylphenol (1000 parts) is charged to a reaction vessel and the temperature is adjusted to 38-55°C whereupon 290 parts of sulfur dichloride is added at a rate to maintain the temperature of the reaction mixture below about 66°C. The mixture is blown with nitrogen while heating to 143-149°C, and the mixture is maintained at this temperature until the direct acid number is less than 1.5 acid. The mixture is cooled to about 95-100°C while adding about 788 parts of diluent oil. The reaction mixture is filtered, and the filtrate is the desired sulfur-coupled phenol.

Example C

A mixture of 526 parts (2.01 mole) of dodecylphenol, 44.1 parts (1.34 moles) of paraformaldehyde flakes, 60 parts of toluene, 90 parts of isopropyl alcohol and 3 parts of caustic soda and 12 parts of water is prepared with stirring. The mixture is heated to a temperature of about 115°C over a period of about 20 minutes to remove solvent. The mixture then is maintained at 145°C while sparging with nitrogen until no additional solvent can be removed from the mixture. The residue is the desired methylene-coupled phenolic product.

Example D

A reaction flask is charged with 3240 parts of dodecyl phenol, 2772 parts of hydro-refined naphthenyl oil and 380 parts of ethanolamine. The mixture is stirred and heated to 72°C, and 372 parts paraformaldehyde are rapidly charged thereto. The reaction temperature is increased to a maximum of 147°C over a 3-hour period while water is removed by sparging with nitrogen. A total of 218 parts of water is collected versus a theoretical amount of 230 parts. The mixture is cooled and the product is removed.

The titanium and zirconium complexes which are particularly useful in the invention are represented by the formula wherein R is hydrogen or a hydrocarbyl group containing from 1 to about 30 carbon atoms; M is titanium or zirconium; x is 1 or 2; y is 2 or 3; x + y is 4; and Ch is derived from at least one metal chelating agent may be prepared by the reaction of one or more titanium or zirconium compounds represented by the formula

M(OR) 4

wherein M and R are as described above, with one or more of the metal chelating agents (Ch) described above. The metal chelating compound (Ch) displaces one or more of the R groups depending upon the number of equivalents of metal chelating agent utilized per equivalent of titanium or zirconium compound. For example, if one equivalent of the metal compound M(OR)4 is reacted with two equivalents of the metal chelating agent, then x and y in Formula I are each 2. Similarly, if one equivalent of the metal compound M(OR)4 is reacted with three equivalents of the metal chelating agent, then x is 1 and y is 3 in Formula I.

The reaction between the metal compound M(OR)4 and the metal chelating agent is affected by mixing the reactants. In many instances, the reaction is exothermic and external heating of the mixture is unnecessary. The alcohol (ROH) formed in the reaction may be left in the reaction product or removed by distillation. Alternatively, the reaction mixture can be heated to an elevated temperature to increase the rate of reaction and/or to remove the alcohol found. Generally, the reaction mixture is heated at an elevated temperature (optionally under reduced pressure) until substantially no additional alcohol can be recovered by distillation. The reaction mixture may be purged with nitrogen or other inert gas in order to facilitate the removal of the alcohol.

The following examples illustrate the preparation of the titanium complexes or the type represented by Formula I above.

Example 1 To the reaction product obtained in Example A, there is added 56 parts of tetra-n-butyl titanate. This mixture is heated to 110°C at 25-30 mm. Hg. and thereafter at 150°C at 16 mm. Hg. while removing n-butanol. The residue is cooled to 60° and filtered through a filter aid. The filtrate is the desired product.

Example 2 A mixture is prepared containing 107 parts of tetra-i-propyl titanate and 520.2 parts of a 50% xylene solution of the Mannich base prepared as in Example A except that the dodecylphenol is replaced by an equivalent amount of heptylphenol and the reaction is conducted in xylene. Upon addition of the titanium compound, the mixture turns red, and an exotherm to about 42°C in five minutes is observed. The mixture is stirred for 1.3 hours at a temperature of 35-40°C.

Example 3 A mixture of 100 parts of isopropyl alcohol, 47.4 parts of a commercial alcohol mixture containing an average of about 9 to about 11 carbon atoms (Neodol 91, Shell Chemical), and 85.2 parts of tetraisopropyl titanate is prepared, and 30 parts of 2,4-pentanedione is added with stirring. An exothermic reaction occurs, and after a period of about several minutes, the solvent is removed by stripping. The residue, a yellow oil, is the desired titanium complex. Example 4

A mixture of 163 parts of tetraisopropyl titanate and 406 parts of Sarkosyl O (N=oleoyl sarkosine available from Ciba Geigy) is prepared, purged with nitrogen, and heated with stirring under vacuum to a temperature of about 55°C (about 80 mm. Hg.). The mixture then is heated to about 100ºC at 70-90 mm. Hg. over a period of about 1.6 hours until no further distillate is obtained. The mixture is vacuum stripped at 100°C at about 10-20 mm. Hg. The residue is filtered at about 100°C through a filter aid. The filtrate is the desired titanium complex.

Example 5

Into a reaction vessel there is added 604 parts of the product of Example B, and the product is stirred and heated to about 160°C in a nitrogen atmosphere. After cooling to about 60°C, 101 parts of tetraisopropyl titanate is added over a period of 5 minutes. The mixture is heated to 145°C for one hour, and 80 parts of a colorless liquid is removed by distillation. A residue is the desired titanium complex.

Example 6

To the methylene-coupled phenolic product prepared in Example C, there is added 138 parts of a diluent oil followed by the addition of 152 parts of tetraisopropyl titanate dropwise over a period of about 6 minutes. The temperature of the reaction mixture is maintained at about 150°C for about one hour while removing about 128 parts of isopropanol. The residue is the desired titanium complex containing 20% diluent oil.

Example 7

A mixture of 363 parts of butyl diethanolamine and 388 parts of a diluent oil is prepared and heated to about 100°C at 120 mm. Hg. whereupon 100 parts of tetraisopropyl titanate and 225 parts of tetra-n-butyl titanate are added in three portions with stirring. After reducing the pressure to 20-25 mm. Hg. at 65°C, the mixture is stirred for 1.2 hours as butyl and isopropyl alcohols are removed by distillation. The residue is filtered, and the light red-orange filtrate is the desired titanium complex containing 10.6% titanium (theory, 10.2).

The above-described titanium and zirconium compounds, and in particular, the titanium and zirconium complexes described above are particularly useful in fuel compositions which comprise a major proportion of a normally liquid fuel, usually a hydrocarbonaceous petroleum distillate fuel such as diesel fuels, distillate fuels, heating oils, residual fuels, transfer fuels, and motor gasoline as defined by ASTM Specification D-439. Diesel fuels may be defined broadly as fuels having a suitable boiling range and viscosity for use as a fuel in a diesel-type engine. Fuels containing alcohols and esters also are included within the definition of a diesel fuel. The boiling range of a diesel fuel can vary from about an ASTM boiling range of about 120°C to about 425°C, more desirably from about 140°C to about 400°C, and most often between about 200°C to about 370°C. Generally, diesel fuels are within grades ID, 2D and 4D, and usually, the diesel fuels have viscosities of from about 1.3 to about 24.0 centistokes at 40°C.

The diesel fuel compositions which, are treated in accordance with the present invention will contain an amount of the titanium and zirconium compounds described above which is effective in lowering the ignition temperature of exhaust particulates formed on burning of the diesel fuel. Thus, the fuel compositions generally will contain from 1 to about 5000 parts of titanium or zirconium per million parts of fuel, and most often, the diesel fuels will contain from about 1 to about 500 parts of titanium or zirconium per million parts of fuel.

In applications where the fuel contains some water or where the fuel may come in contact with water, it is desirable and preferable that the titanium and zirconium compounds be complexes that are hydrolytically stable. In such applications, it is preferred to use the titanium and zirconium complexes of the formula

(RO)χH(Ch)y (I)

as defined above. Any of the metal chelating agents described above can be included provided that the complex is hydrolytically stable. Preferably the Ch group is one or more of the chelate groups identified as A, B, C, D or E above.

The fuel compositions can contain, in addition to the compositions of this invention, other additives which are well known to those of skill in the art. These include antiknock agents such as tetraalkyl lead compounds, lead scavengers such as haloalkanes (e.g., ethylene dichloride and ethylene dibromide), deposit preventers or modifiers such as triaryl phosphates, dyes, cetane improvers, antioxidants such as 2,6-di- tertiary-butyl-4-methyl-phenol, rust inhibitors such as alkylated succinic acids and anhydrides, bacteriostatic agents, gum inhibitors, metal deactivators, demulsifiers, upper cylinder lubricants and anti-icing agents. In certain preferred fuel compositions the compositions of this invention are combined with an ashless dispersant in gasoline. Suitable ashless dispersants include esters of mono- or polyols and high molecular weight mono- or polycarboxylic acid acylating agents containing at least 30 carbon atoms in the acyl moiety. Such esters are well known to those skilled in the art. See, for example, French Patent 1,396,645; British Patents 981,850; 1,055,337 and 1,306,529; and U.S. Patents 3,255,108; 3,311,558; 3,331,776; 3,346,354; 3,522,179; 3,579,450; 3,542,680; 3,381,022; 3,639,242; 3,697,428; and 3,708,522. These patents are expressly incorporated herein by reference for their disclosure of suitable esters and methods for their preparation. Generally, the weight ratio of the composition of this invention to the aforesaid ashless dispersant is between about 0.1:1 and about 10:1, preferably between about 1:1 and about 10:1.

The titanium and zirconium compositions of this invention can be added directly to the fuel, or they can be diluted with a substantially inert, normally liquid organic diluent such as naphtha, benzene, toluene, xylene or a normally liquid fuel as described above, to form an additive concentrate. These concentrates generally contain from about 20% to about 90% by weight of the composition of this invention and may contain, in addition one or more other conventional additives known in the art or described hereinabove.

The following examples illustrate the fuel compositions of the invention and fuel compositions useful in this invention. Fu el A

Titanium Complex of Ex. 1 2100 ppm No. 2 Fuel Oil remainder Fuel B

Titanium Complex of Ex. 2 4400 ppm

Fuel C

Titanium acetonylacetonate 100 ppm (Ti) No. 1 Fuel Oil remainder

Fuel D

Titanium Complex of Ex. 4 125 ppm (Ti) No. 2 Fuel Oil remainder

While the invention has been explained in relation to its preferred embodiments, it is to be understood that various modifications thereof will become apparent to those skilled in the art upon reading the specification. Therefore, it is to be understood that the invention disclosed herein is intended to cover such modifications as fall within the scope of the appended claims.

PCT TUAL PROPER Y ANIZAT International Bureau

INTERNATIONAL APPLICATION PUBLISHED UNDER THE PATENT COOPERATION TREATY (PCT

(51) International Patent Classification ⁴ (11) International Publication Number: WO 88/ 0

C10L 1/18, 1/26, 1/30 A3 C07F 7/00, C10L 10/06 (43) International Publication Date: 7 April 1988 (07.

(21) International Application Number : PCT/US87/02495 (74) Agents: POLYN, Denis, A. et al.; The Lubrizol poration, 29400 Lakeland Blvd., Wickliffe, OH

(22) International Filing Date: 25 September 1987 (25.09.87) (US).

(31) Priority Application Number: 914,382 (81) Designated States: AT (European patent), AU, BE ropean patent), CH (European patent), DE (

(32) Priority Date: 2 October 1986 (02.10.86) pean patent), FR (European patent), GB (Euro patent), IT (European patent), JP, LU (Europea

(33) Priority Country : US tent), NL (European patent), SE (European pat

(71) Applicant: THE LUBRIZOL CORPORATION [US/ Published

US]; 29400 Lakeland Blvd., Wickliffe, OH 44092 With international search report. (US). Before the expiration of the time limit for amendin claims and to be republished in the event of the rece

(72) Inventors: HILL, George, Robert ; 104 Countryside amendments.

Drive, Chagrin Falls, OH 44022 (US). DI BIASE, Stephen, A. ; 504 East 266th Street, Euclid, OH 44132 (US). DETAR, Marvin, Bradford ; 1880 Ridgewick, (88) Date of publication of the international search report Wickliffe, OH 44092 (US). 21 April 1988 (21.0

(54) Title: TITANIUM AND ZIRCONIUM COMPLEXES, AND FUEL COMPOSITIONS

(57) Abstract

A method of operating a diesel engine equipped with an exhaust system particulate trap to reduce the build-up o haust particles collected in said trap. The method comprises operating said diesel engine with a fuel containing at least compound selected from titanium or zirconium compounds effective to lower the ignition temperature of the exhaust ticulates collected in said trap. Fuel compositions which are useful particularly in the operation of diesel engines equi with exhaust particluate traps wherein the fuel contains at least one titanium or zirconium complex, and certain novel nium and zirconium complexes are described and claimed.

FOR THE PURPOSES OF INFORMATION ONLY

Codes used to identify States party to the PCT on the frontpages of pamphlets publishing international applications under the PCT.

AT Austria FR France ML Mali

AU Australia GA Gabon MR Mauritania

BB Barbados GB United Kingdom MW Malawi

BE Belgium HU Hungary NL Netherlands

BG Bulgaria IT Italy NO Norway

BJ Benin P Japan RO Romania

BR Brazil KP Democratic People's Republic SD Sudan

CF Central African Republic ofKorea SE Sweden

CG Congo KR Republic ofKorea SN Senegal

CH Switzerland LI Liechtenstein su Soviet Union

CM Cameroon LK Sri Lanka TD Chad

DE Germany, Federal Republic of LU Luxembourg TG Togo

DK Denmark MC Monaco US United States of America

El Finland MG Madagascar

PCT WORLD INTELLECTUAL PROPERTY ORGANIZATION International Bureau

INTERNATIONAL APPLICATION PUBLISHED UNDER THE PATENT COOPERATION TREATY (PC

(51) International Patent Classification 4 (11) International Publication Number : WO 88/ 0

(21) International Application Number: PCT/US87/02495 (74) Agents: POLYN, Denis, A. et al.; The Lubrizol poration, 29400 Lakeland Blvd., Wickliffe, OH

(22) International Filing Date: 25 September 1987 (25.09.87) (US).

(31) Priority Application Number : 914,382 (81) Designated States: AT (European patent), AU, B ropean patent), CH (European patent), DE (

(32) Priority Date: 2 October 1986 (02.10.86) pean patent), FR (European patent), GB (Eur patent), IT (European patent), JP, LU (Europea

(33) Priority Country: US tent), NL (European patent), SE (European pat

(71) Applicant: THE LUBRIZOL CORPORATION [US/

US]; 29400 Lakeland Blvd., Wickliffe, OH 44092 Published (US). With international search report

(72) Inventors: HILL, George, Robert ; 104 Countryside With amended claims .

Date of publication of the amended claims:

05 May 1988 (05.05.8

(54) Title: TITANIUM AND ZIRCONIUM COMPLEXES, AND FUEL COMPOSITIONS

(57) Abstract

FOR THE PURPOSES OFINFORMAπON ONLY

Codes used to identify States party to the PCT on the front pages of pamphlets publishing international applications under the PCT.

AT Austria FR France ML Mali

AU Australia GA Gabon MR Mauritania

BB Barbados GB United Kingdom M Malawi

BE Belgium HU Hungary NL Netherlands

BG Bulgaria IT Italy NO Norway

BJ Benin JP Japan RO Romania

BR Brazil KP Democratic People's Republic SD Sudan

CF Centra] African Republic ofKorea SE Sweden

CG Congo KR Republic ofKorea SN Senegal

CH Switzerland LI Liecbtenstein SU Soviet Union

CM Cameroon LK Sri anJca TD Chad

DE Germany, Federal Republic or LU Luxembourg TG Togo

DE Denmark MC Monaco US United States of America

Fl Finland MG Madagascar

Claims

1. A method of operating a diesel engine equipped with an exhaust system particulate trap to reduce the build-up of exhaust particles collected in said trap comprising operating said diesel engine with a fuel containing at least one compound selected from titanium or zirconium compounds effective to lower the ignition temperature of the exhaust particulates collected in said trap.

2. The method of claim 1 wherein the titanium and zirconium compounds are dispersible or soluble in the diesel fuel.

3. The method of claim 1 wherein the titanium and zirconium compounds are organo-titanium or organo-zirconium compounds.

4. The method of claim 1 wherein the titanium and zirconium compounds are titanium and zirconium salts of at least one organic acid, said organic acid being selected from the group consisting of carboxylic acids, phosphoric acids, sulfonic acids, and mixtures thereof.

5. The method of claim 4 wherein the salts are basic metal salts.

6. The method of claim 4 wherein the metal salts are salts of carboxylic acids, sulfonic acids, or mixtures thereof.

7. The method of claim 4 wherein the metal salts are titanium salts.

8. The method of claim 1 wherein the titanium and zirconium compounds are titanium and zirconium complexes characterized by the formula

(RO)_xM(Ch)_y (I) wherein R is hydrogen or a hydrocarbyl group containing from 1 to about 30 carbon atoms; M is titanium or zirconium; x is 1 or 2; y is 2 or 3; x + y is 4; and Ch is derived from at least one metal chelating agent.

9. The method of claim 8 wherein the metal chelating agent contains a hydrocarbon linkage and at least two functional groups on different carbon atoms.

10. The method of claim 9 wherein the chelating agent contains at least two functional groups which are in vicinal or beta-position to each other on the hydrocarbon linkage.

11. The method of claim 9 wherein the functional groups are selected from hydroxy, carboxy, carbonyl, amino or mercapto groups.

12. The method of claim 8 wherein the chelating agent (Ch) is a diol, a dithiol, a mercapto alcohol, a diamine, an amino alcohol, an amino thiol, a dicarboxylic acid, a hydroxy carboxylic acid, a mercapto carboxylic acid, an amino carboxylic acid, a diketone, a ketocarboxylic acid, or ester, or mixtures thereof.

13. The method of claim 8 wherein the complex is a titanium complex.

14. The method of claim 8 wherein R in Formula I is an aliphatic group containing from about 1 to about 30 carbon atoms.

15. The method of claim 8 wherein x and y in Formula I are each 2.

16. The method of claim 8 wherein the metal chelating agent (Ch) is selected from the group consisting of:

(A) aromatic Mannich bases, (B) amino acid compounds of the formula

(VI) wherein R₁ is hydrogen or a hydrocarbyl group; R₂ is R₁ or an acyl group; R₃ and R₄ are each independently hydrogen or lower alkyl groups; and z is 0 or 1,

(C) beta diketones,

(D) phenolic compounds of the structure

(VIII)

wherein each R is a hydrocarbyl group; and X is CH₂, S, or CH₂OCH₂, and

(E) an aromatic difunctional compound of the formula

(IX) wherein R¹ is a hydrocarbyl group containing 1 to about 100 carbon atoms, n is an integer from 0 to 4, Y is in the ortho or meta-position relative to X, and X and Y are each independently OH, NH₂, NHR, COOR, SH or C(O)H groups wherein R is hydrogen or a. hydrocarbyl group.

17. The method of claim 16 wherein the aromatic Mannich base (A) is the reaction product of (A-1) a hydrocarbon-substituted aromatic phenol or thiol phenol, (A-2) an aldehyde or ketone, and (A-3) an amine which contains at least one primary or secondary amino group.

18. The method of claim 17 wherein the aromatic phenol or thiophenol compound (A-1) is represented by the formula

(R¹)n (XH)m (II)

wherein Ar is an aromatic group or a coupled aromatic group, m is 1, 2 or 3, n is an integer from 1 to 4, R¹, independently, is hydrogen or a hydrocarbyl group having from 1 to about 100 carbon atoms, R° is hydrogen, amino, or carboxy1, and X is 0, S, or both when m is 2 or greater.

19. The method of claim 17 wherein the aldehyde or ketone (A-2) is characterized by the formula

(III)

or a precursor thereof wherein R² and R³, independently, are hydrogen, a hydrocarbyl group having from 1 to about 18 carbon atoms, or R³ is a carbonyl containing hydrocarbon group having from 1 to 18 carbon atoms.

20. The method of claim 18 wherein R¹ of said (A-1) compound is hydrogen, an alkyl group having from 1 up to an average of about 70 carbon atoms, a cycloalkyl group having from 4 to about 10 carbon atoms, an alkenyl group having from 2 to about 30 carbon atoms. an aromatic or an alkyl-substituted aromatic having from about 7 to about 30 carbon atoms, an aromatic-substituted alkyl group having from about 7 to about 30 carbon atoms, and said coupling agent of said coupled Ar group is O, S, NH or a lower alkylene group.

21. The method of claim 17 wherein said (A-3) compound is a hydrocarbyl amine containing from zero to about 10 hydroxyl and thiol groups and from 1 to about 10 amine groups.

22. The method of claim 17 wherein the amine (A-3) is characterized by the structural formula

(IV)

wherein R¹ is a hydrocarbyl, amino-substituted hydrocarbyl, hydroxy-substituted hydrocarbyl, or alkoxy- substituted hydrocarbyl group, and R² is hydrogen or R¹.

23. The method of claim 17 wherein the amine (A-3) is at least one aliphatic or aromatic monoamine or polyamine containing at least one primary and/or secondary amino group, polyalkylene polyamine, or heterocyclic amine or polyamine.

24. The method of claim 17 wherein the amine (A-3) is a polyalkylene polyamine.

25. The method of claim 17 wherein (A-3) is a hydroxylhydrocarbyl amine having the formula

(V) wherein each of R¹ is independently a hydrogen atom or a hydrocarbyl, hydroxyhydrocarbyl, aminohydrocarbyl, or hydroxyaminohydrocarbyl group, provided that at least one of R¹ is a hydroxyhydrocarbyl or hydroxyaminohydrocarbyl group, R² is an alkylene group, and x is an integer from 0 to about 5.

26. The method of claim 18 wherein Ar of said (A-1) compound is phenyl, m is 1 or 2, n is 1 or 2, R° is H, R¹ is an alkyl group containing from about 4 to about 20 carbon atoms, a cycloalkyl group having from about 5 to 7 carbon atoms, an alkenyl group having from about 8 to about 20 carbon atoms or an alkyl-substituted aromatic group containing from 7 to about 12 carbon atoms.

27. The method of claim 26 wherein m of said (A-1) compound is 1, n is 1 or 2, R¹ is an alkyl group containing from about 4 to about 20 carbon atoms, X is 0, and R² and R³ of said (A-2) compound is hydrogen.

28. The method of claim 16 wherein Ch of Formula I is

(B) at least one amino acid compound of the formula

(VI) wherein R₁ is a hydrocarbyl group; R₂ is an acyl group; R₃ and R₄ are each independently hydrogen or lower alkyl; and z is 0 or 1.

29. The method of claim 28 wherein R¹ is an alkyl, cycloalkyl, phenyl, alkyl-substituted phenyl, benzyl or alkyl-substituted benzyl group.

30. The method of claim 28 wherein R₃ and R₄ are hydrogen.

31. The method of claim 28 wherein z is 0.

32. The method of claim 28 wherein R₂ is an acyl group represented by the formula

R₂'C(O)-

wherein R₂' is an aliphatic group containing up to about 30 carbon atoms.

33. The method of claim 32 wherein R₂' contains from about 12 to about 24 carbon atoms.

34. The method of claim 16 wherein Ch is

(C) at least one beta-diketone characterized by the formula

R-C(O)-CH₂-C(O)-R₁ (VII)

wherein R and R₁ are each independently hydrogen or hydrocarbyl groups.

35. The method of claim 34 wherein R and R₁ are lower hydrocarbyl groups.

36. The method of claim 16 wherein Ch is

(D) at least one phenolic compound of the formula

(VIII)

wherein each R is independently a hydrocarbyl group; and X is CH₂, S, or CH₂OCH₂.

37. The method of claim 36 wherein X is CH₂.

38. The method of claim 36 wherein each R is a hydrocarbyl group containing from about 4 to about 20 carbon atoms.

39. The method of claim 8 wherein Ch is at least one aromatic Mannich base

(A) which is the reaction product of (A-1) a compound of the formula

wherein R¹ is an alkyl group containing from about 4 to about 20 carbon atoms,

(A-2) formaldehyde or a precursor of formaldehyde, and

(A-3) a polyalkylene polyamine.

40. The method of claim 8 wherein Ch is a beta-diketone characterized by the formula

R-C(O)-CH₂-C(O)-R₁ (VII)

wherein R and R¹ are each independently lower alkyl groups.

41. The method of claim 40 wherein the diketone is 2,4-pentanedione.

42. The method of claim 16 wherein Ch is (E) an amino phenol.

43. The method of claim 42 wherein Ch is ortho-aminophenol.

44. A fuel composition comprising a major amount of a normally liquid fuel and a minor, property- improving amount of at least one titanium or zirconium complex charaxterized by the formula

(RO)_xM(Ch)_y (I)

wherein R is an aliphatic group containing from 1 tp about 30 carbon atoms; M is titanium or zirconium; x is 1 ot 2; y is 2 or 3; x + y is 4; and Ch is derived from at least one metal chelating agent.

45. The fuel composition of claim 44 wherein the metal chelating agent contains a hydrocarbon linkage and at least two functional groups on different carobn atoms.

46. The fuel composition of claim 45 wherein the chelating agent contains at least two functional groups which are in vicinal or beta-position to each other on the hydrocarbon linkage.

47. The fuel composition of claim 45 wherein the functional groups are selected from hydroxy, carboxy, carbonyl, amino or mercapto groups.

48. The fuel composition of claim 42 wherein the chelating agent (Ch) is a diol, a dithiol, a mercapto alcohol, a diamine, an amino alcohol, an amino thiol, an ortho-aminophenol, a dicarboxylic acid, a hydroxy carboxylic acid, a mercapto carboxylic acid, an amino carboxylic acid, a diketone, a ketocarboxylic acid, or ester, or mixtures thereof.

49. The fuel composition of claim 44 wherein the complex is a titanium complex.

50. The fuel composition of claim 44 wherein R in Formula I is an aliphatic group containing from about 1 to about 30 carbon atoms.

51. The fuel composition of claim 44 wherein x and y in Formula I are each 2.

52. The fuel composition of claim 44 wherein the metal chelating agent (Ch) is selected from the group consisting of:

(A) aromatic Mannich bases,

(B) amino acid compounds of the formula

(VI) wherein R₁ is hydrogen or a hydrocarbyl group; R₂ is R₁ or an acyl group; R₃ and R₄ are each independently hydrogen or lower alkyl groups; and z is 0 or 1, (C) beta diketones,

(D) phenolic compounds of the structure

(VIII)

wherein each R is a hydrocarbyl group; and X is CH₂, S, or CH₂OCH₂, and

(E) an aromatic difunctional compound of the formula

(IX) wherein R¹ is a hydrocarbyl group containing 1 to about 100 carbon atoms, n is an integer from 0 to 4, Y is in the ortho or meta-position relative to X, and X and Y are each independently OH, NR₂, COOR, SH or C(O)H groups wherein R is hydrogen or a hydrocarbyl group.

53. The fuel composition of claim 52 wherein the aromatic Mannich base (A) is the reaction product of (A-1) a hydrocarbon-substituted aromatic phenol or thiol phenol, (A-2) an aldehyde or ketone, and (A-3) an amine which contains at least one primary or secondary amino group.

54. The fuel composition of claim 53 wherein the aromatic phenol or thiophenol compound (A-1) is represented by the formula

(II)

wherein Ar is an aromatic group or a coupled aromatic group, m is 1, 2 or 3, n is an integer from 1 to 4, R¹, independently, is hydrogen cr a hydrocarbyl group having from 1 to about 100 carbon atoms, R° is hydrogen, amino, or carboxyl, and X is 0, S, or both when m is 2 or greater.

55. The fuel composition of claim 53 wherein the aldehyde or ketone (A-2) is characterized by the formula

(III)

56. The fuel composition of claim 52 wherein R¹ of said (A-1) compound is hydrogen, an alkyl group having from 1 to an average of about 70 carbon atoms, a cycloalkyl group having from 4 to about 10 carbon atoms, an alkenyl group having from 2 to about 30 carbon atoms, an aromatic or an alkyl-substituted aromatic having from about 7 to about 30 carbon atoms, an aromatic-substituted alkyl group having from about 7 to about 30 carbon atoms, and said coupling agent of said coupled Ar group is 0, S, NH or a lower alkylene group.

57. The fuel composition of claim 53 wherein said (A-3) compound is a hydrocarbyl amine containing from zero to about 10 hydroxyl and thiol groups and from 1 to about 10 amine groups.

58. The fuel composition of claim 53 wherein the amine (A-3) is characterized by the structural formula

(IV) wherein R¹ is a hydrocarbyl, amino-substituted hydrocarbyl, hydroxy-substituted hydrocarbyl, or alkoxysubstituted hydrocarbyl group, and R² is hydrogen or R¹.

59. The fuel composition of claim 53 wherein the amine (A-3) is at least one aliphatic or aromatic monoamine or polyamine containing at least one primary and/or secondary amino group, polyalkylene polyamine, or heterocyclic amine or polyamine.

60. The fuel composition of claim 53 wherein the amine (A-3) is a polyalkylene polyamine.

61. The fuel composition of claim 53 wherein (A-3) is a hydroxylhydrocarbyl amine having the formula

62. The fuel composition of claim 54 wherein Ar of said (A-1) compound is phenyl, m is 1 or 2, n is 1 or 2, R° is H, R¹ is an alkyl group containing from about 4 to about 20 carbon atoms, a cycloalkyl group having from about 5 to 7 carbon atoms, an alkenyl group having from about 8 to about 20 carbon atoms or an alkyl-substituted aromatic group containing from 7 to about 12 carbon atoms.

63. The fuel composition of claim 62 wherein m of said (A-1) compound is 1, n is 1 or 2, R¹ is an alkyl group containing from about 4 to about 20 carbon atoms, X is 0, and R² and R³ of said (A-2) compound is hydrogen.

64. The fuel composition of claim 52 wherein Ch of Formula I is

(B) at least one amino acid compound of the formula

65. The fuel composition of claim 64 wherein R¹ is an alkyl, cycloalkyl, phenyl, alkyl-substituted phenyl, benzyl or alkyl-substituted benzyl group.

66. The fuel composition of claim 64 wherein R₃ and R₄ are hydrogen.

67. The fuel composition of claim 64 wherein z is 0.

68. The fuel composition of claim 64 wherein R₂ is an acyl group represented by the formula

R₂'C(O)-

wherein R₂' is an aliphatic group containing up to about 30 carbon atoms.

69. The fuel composition of claim 68 wherein R₂' contains from about 12 to about 24 carbon atoms.

70. The fuel composition of claim 52 wherein Ch is

(C) at least one beta-diketone characterized by the formula

R-C(O)-CH₂-C(O)-R₁ (VII)

wherein R and R₁ are each independently hydrocarbyl groups.

71. The fuel composition of claim 70 wherein R and R₁ are lower hydrocarbyl groups.

72. The fuel composition of claim 52 wherein Ch is (D) at least one phenolic compound of the formula

(VIII)

73. The fuel composition of claim 72 wherein X is CH₂.

74. The fuel composition of claim 72 wherein each R is a hydrocarbyl group containing from about 4 to about 20 carbon atoms.

75. The fuel composition of claim 44 wherein Ch is an aminophenol.

76. The fuel composition of claim 44 wherein Ch is ortho-aminophenol.

77. The fuel composition of claim 44 wherein Ch is at least one

(A) aromatic Mannich base which is the reaction product of

(A-1) a compound of the formula

wherein R¹ is an alkyl group containing from about 4 to about 20 carbon atoms,

(A-2) formaldehyde or a precursor of formaldehyde, and (A-3) a polyalkylene polyamine.

78. The fuel composition of claim 44 wherein Ch is a beta-diketone characterized by the formula

R-C(O)-CH₂-C(O)-R₁ (VII)

wherein R and R₁ are each independently lower alkyl groups.

79. The fuel composition of claim 78 wherein the diketone is 2,4-pentanedione.

80. A titanium or zirconium complex characterized by the formula

(RO)χM(Ch)y (I)

wherein R is a hydrocarbyl group containing from 1 to about 30 carbon atoms; M is titanium or zirconium; x is 1 or 2; y is 2 or 3; x + y is 4; and Ch is derived from a metal chelating agent selected from the group consisting of:

(A) aromatic Mannich bases,

(B) at least one amino acid compound of the formula

(VI) wherein R₁ is hydrogen or a hydrocarbyl group; R₂ is R₁ or an acyl group; R₃ and R₄ are each independently hydrogen or lower alkyl groups; and z is 0 or 1, (D) phenolic compounds of the structure (VIII)

wherein each R is a hydrocarbyl group, and X is CH₂, S, or CH₂OCH₂, and

(E) an ortho-aminophenol.

81. The complex of claim 80 wherein M is titanium.

82. The complex of claim 80 wherein R in Formula I is an aliphatic group containing from about 1 to about 30 carbon atoms.

83. The complex of claim 80 wherein x and y in Formula I are each 2.

84. The complex of claim 80 wherein Ch of Formula I is (A) is the reaction product of (A-1) a hydrocarbon-substituted aromatic phenol or thiol phenol, (A-2) an aldehyde or ketone, and (A-3) an amine which contains at least one primary or secondary amino group.

85. The complex of claim 84 wherein (A-1) is represented by the formula

m (II)

wherein Ar is an aromatic group or a coupled aromatic group, m is 1, 2 or 3, n is an integer from 1 to 4, R¹, independently, is hydrogen or a hydrocarbyl group having from 1 to about 100 carbon atoms R° is hydrogen, amino, or carboxyl, and X is 0, S, or both when m is 2 or greater.

86. The complex of claim 84 wherein (A-2) is characterized by the formula

R (III)

87. The complex of claim 84 wherein (A-3) is characterized by the formula

(IV)

88. The complex of claim 80 wherein Ch of Formula I is

(B) at least one amino acid compound of the formula

89. The complex of claim 88 wherein R¹ in Formula VI is an alkyl, cycloalkyl, phenyl, alkyl- substituted phenyl, benzyl or alkyl-substituted benzyl group.

90. The complex of claim 88 wherein R₃ and R₄ in Formula VI are hydrogen.

91. The complex of claim 88 wherein z in Formula VI is 0.

92. The complex of claim 88 wherein R₂ in Formula VI is an acyl group represented by the formula

R₂'C(O)-

wherein R₂' is an aliphatic group containing up to about 30 carbon atoms.

93. The complex of claim 92 wherein R₂' contains from about 12 to about 24 carbon atoms.

94. The complex of claim 80 wherein Ch in Formula I is

(D) at least one phenolic compound of the formula

(VIII)

95. The complex of claim 94 wherein X is CH₂.

96. The complex of claim 94 wherein each R is a hydrocarbyl group containing from about 4 to about 20 carbon atoms.

97. A fuel additive concentrate comprising a normally liquid organic diluent and from about 10% to about 99% by weight of the complex of claim 80.

98. A fuel additive concentrate comprising a normally liquid organic diluent and from about 10% to about 99% by weight of the complex of claim 84.

99. A fuel additive concentrate comprising a normally liquid organic diluent and from about 10% to about 99% by weight of the complex of claim 88.

100. A fuel additive concentrate comprising a normally liquid organic diluent and from about 10% to about 99% by weight of the complex of claim 94.