CA1324151C - Titanium and zirconium complexes, and fuel compositions - Google Patents

Abstract

Title: TITANIUM AND ZIRCONIUM COMPLEXES, AND FUEL
COMPOSITIONS

Abstract of the Disclosure 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 wherein the fuel contains at least one titanium or zironcium complex, and certain novel titanium and zirconium complexes are described and claimed.

Description

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L-2335P~/B

Title: TITANIUM AND ZIRCONIVM COMPLEXES, AND FUEL
COMPOSITIONS

echnical F eld o~ th~ InY~tiQ~
This invention relates to a method of operating diesel engines equipped with an exhaust system particu-late 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 exhaus~ particulates collec~ed in the particulate traps of diesel exhaust systems. ; :
~ L~ g~ e` In~çn~i~n Diesel engines have ~een employed as engines for over-the-road vehicles because of relatively low ~uel costs and imprnved milaage~ ~owever~ because of their operating charactPristics~ dies~l engines discharge a larger amounk of carbon black particles or very fine condensate particles or agglomerates thereo~
as compared to the gasoline engine. These particles or condensates are sometimes referred to as ~diesel soot~
and the emission of such par~icles or soot res~llts in pollu~ion and is undesirable~ Moreover, diesel soot has been observed to be :rich in condensed, polynuclear --hydrocarbons~ and aome of these have been recognized as carcinoyenic. Accordingly/ particulate traps or filters have been designed for use wi~h diesel engines that are .::
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-2-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 o porou~ ceramic or metal fiber and an electric heater for heating and igniting carbon particulates collPcted by the filter elemen~. ~he heater is requiri3~d because the temperatures of the diesel exhau~t gas under normal operating conditions are insufficient to burn off the accumulated ~oot collected in the filter or trap. Generally, emperatures of about 450-600C are required, and the heater provides the nece~sary increase of ~he exhaust t~mperature in order to iynite the particles collec~ed in ~he trap and to regenerate the krap, Otherw:ise, there is an accumula-tlon of carbon black; and the trap is eventually plugged. The above-described heated traps do not provide a complete solution l:o the problem because ~he tempeLature o~ the exhaust gases is lower than the ignition temperature of carbon particulates while the vehicle runs under normal conditions~ and the h~a~
generated by the electric heater is withdrawn by the flowing exhaust gases when ~he 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.
t also has been suggested that the par~icle build-up in the traps can be controlled ~y lowering the ignition temperature of the particulates so that the particles begin burning at the lowes~t pQssihle tempera-tures. One method of lowering the ~ temperature involves the addition of a combustion improver to the , . ~.

1 3 2 ~ L

exhaust particulate, and the most practical way to effect the addition of the combustion improver to the exha~st 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 t~e treatment of lubricating oils and ~uels to improve various properties thereof~ When added to fuPls, the combustion characteristics of the fuels are improvedO The organic acids utillzed to make the tran~ition metal salts may be sulfonic acids; carboxylic acids, and phosphorus acids.
The addit:ion of transi~ion 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. Manclane~e soaps and fuels are described in U.S. Patent 3,762,8g0, and organic magnesium compounds as fuel c:onditioners are described in U.S. Patent 4~202,671. Various ~itanium containing organic ~alts have been desc:ribed as being useful .in fuels, lubricant~ etc., in, for example, U.S. Pa ents 4j093,614; 4,077~41; 3,355,270; and 3,493~508.

A method of operating a diesel engine equipped with an exhaust system particulate trap to reduce the build~up of ~xhaust particles collected in said trap is described. The method comprises operating said die~el engine with a fuel containing at lea~t one compound selected ~rom titanium or zirconium compounds e~fective to lower the ignition temperature of ~he exhaust par~iculates collected in said trap. Fuel compositions whi~h are useful particularly in the operation of diesel e~gines equipped with exhaus~ particulate traps and . ,''~' ~ ~ 2 '~

certain novel titanium and zirconium complexes are described and claimed.
~cri~tiQn ~f ~b~ efeL~e~_~m~5~i~n3~
In one embodiment, the invention relates to a method of op~ra~ing a di sel engine equipped with an exhaust system particulate trap to reduce the build-up of exhaust particles collected in the trap. The method comprises operating th~ 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~ organo-titanium and organo-zirconium compounds are the pre-ferred ti~anium and zirconium compounds of the present invention. In general, it has been observed thak the anionic portion of the titanium and zir~onium compound is not particularly critical to the present inven~ion.
It is preferred that the titanium and zirconium compound be hydrolytically stable in applications where ~ome water may be pre~ent~
The inorganic compounds of titanium and zir-conium include, for example, the oxides, hydroxides, chlorides~ sulfates r nitrates and carbonates.
; In one embodimentr the organo-titanium and organo-zirconiu~ compounds are titanium and zirconium salts ~f at least one acidic organic compound~ The most useful acidic organic compounds are sulfur acids, carbox~lic acids, organic phosphorus acids and phenols.
The salts can be neutral or basic, with the basic salts con~a1ning an excess amount of metal cation with respect to the amount of salt anion.

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The sulfur acids include sulfonic, sulfamic~
thiosulfonic~ sulfinic, sulfenicf 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 poly- :~
nuclear aromatic or cycloaliphatic compounds. The sulfonic acids can be repr~sented for th~ most part by the following formulae:

Rl(S03H)r (X) ~:
Ji . ' ~ R2 ) XT t so3 H ) y ( X I ) in which T is an aromatic nucleus such as, f~r example, ben~ene, naphthalene, anthracene, phenanthrene, diphen~
ylene oxide, thianthrene, phenothioxine, diphenylene sulfide, phenothiazine, diphenyl oxide, diphenyl sul-fide, diphenylamine, cyclohexane, petroieum naphthenes, decahydro~naphthalene, cyclopeltane, etc.; Rl and R2 are each independently aliphatic groups~ Rl contains at least about 15 carbon atoms, the sum of the carbon atoms in R2 and T is at least about 15~ and r, ~ and y are each independently 1 or greater. Specific examples of Rl are ~roups derived from petrolatum, saturated and unsaturated paraffin wax, and polyolefins, including polymPrized C2, C3l C4, C5, C6, etc., olefins containing from about 15 to 7000 or more carbon atoms~
The groups T, R1, and R~ in the above f~rmulae can also contain oth r inorganic or organic substituents in addition to those enumerated above such as, for example, hydruxy, mercapto, halogen, nitro, amino, nitroso, sulfide, disulfidieJ etc~ The subscript x is generally . ' i ~ 3 2 ~

1-3, and the subscripts r ~ y generally have an average value of about 1-4 per molecule.
The following are sp~cific examples of oil-soluble sulfonic acids coming within the scope of Formulae X and XI above, and it is to be understood that such example~ 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 al~o understood to be illustrated~
Such sulfonic acids are mahogany sulfonic acids; bri~ht stock sulfonic acids; sulfonic acids derived from lubricating oil fractions havin~ a Saybolt viscosity from about 100 seconds at 100F to about 200 seconds at 210F; petrolatum ~ulfonic acids; mono- and poly~wax substituted sulfonic and polysulfonic acids ofl e.g., benzene, naphthalene, phenol, diphenyl ether, naphtha-lene disulfide, diphenylamine, thiophene, alpha-chloro-naphthalene, etc~; other substituted sulfonic acids such as alkyl benzene sul~onic 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"
~ulfonic acids.
The latter are acids derived from benzene which has been alkylated with propylene tPtramers or isobutene rimer~ to introduce 1~ 2, 3, or more branched-chain Cl~ substituents on the benzene ring. Dodecyl benzene bottoms, principally mixtures of mono- and di-dodecyl benzenes, are available as by-products from the manufac~
ture of household detergents. ~imilar products obtained from alkylation bottoms formed dur~ng manufacture of ~ '1 ~ 3 ~

linear alkyl sulfonates (LAS) are also useful in making the sulonates used in this invention.
The production of sulfonates from detergent manuacture by-products by reaction with, e.g., S03, is well known to those skilled in the art. See, for example, the article 'ISulfonatesn in Rirk-Othmer Encyclopedia of Chemical Technology"; Second Edition, Vol. 19, pp. 291 et seq. published by John Wiley ~ Sons, N.Y. (1369~.
~ he carboxylic acids which are useful in preparing the titanium and zirconium compounds may be mono- or polycarboxylic acids. The monocarboxylic acids include :Lower carboxylic a~ids containing from 1 to 7 carbon atoms such as acetic acid, propionic acid, butyric acid, etcO Eligher 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 at:oms. 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% ~molej branched chain acids. Of the commercially available fat~y acid mixtures containirlg higher proportions of ~ ~ s~raight chain acids also are useul in preparing the 7 ; ~ titanium and zirconium salts.
¦ ~ Higher carboxylic acids include the well known dicarboxylic acids made by alkylatiny maleic anhydride ~ or its derivatives. The products of such reactions are j` ~hydrocarbon substituted succinic acids, anhydrides, etc. Lower molecular weight dicarboxylic a ids such as glutaric acid; adipic acid, etc., also can be used to :make the titanium and zirconium salts useful in the present invention.
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Specific examples of carboxylic acid~ useful in preparing the ititanium and zirconium salts useful in the present invention include 2-ethylhexanoic acid, alpha-linolenic acid, propylene-tetramer-substituted maleic .acid, behenic acid, stearic acid, isostearic acid, pelargonic acid, capric acid, linoleic acid, lauric j acid, oleic acid/ myristic acid, palmitic acid, and commercially available mixtures of two or more carboxylic acids ~uch as tall oil acids, rosin acids, ~tc.
Specific examples of the salts of the carboxylic acid compounds include titanium oleate 9 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 xD~
Rl(Xl)a\ll R2 ( x2 ) b wherein each of Rl and R2 is hydrogen or a hydro~
carbon or essentially hydrocarbon yroup pre~erably having from about 4 to about 25 carbon atoms, at least one of Rl and R2 being hydrocarbon or essentially hydrocarbon; each of xl r X2, X3 and X4 is oxygen or sulfur; and each o a and b is O or 1~ Thus, it will be appreciated that the phosphorus acid may be an organ-ophosphoric, phosphonic or phosphinic acid, or a thio analog of any o~ ~hese.

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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 inve~tion also may be titanium and zirconium alcoholates characterized by the general formula :, .
M(OR)4 wherein M is titanium or æirconium and R is a hydro-carbyl group~ Most often, the hydrocarbyl groups will . contain up to about 30 carbon atoms, and examples o I such hydrocarbyl groups include, ethyl, propyl, j isopropyl, butyl, hexyl, 2-ethylhexyl, dodecyl, etc~
J These titanium and zirconium compounds can be prepared I, by methods well known in t:he art, and many such ¦ compounds are available commercially. Specific examples ¦ of such compounds include tetraisopropyl titanate, tetra-n-~utyl titanate, te~kraisopropyl zirconate, tetra-n--butyl 2irconate, etc.
In another embodiment of the present invention~
~he titanium and zirconium compounds are titanium and , ~irconium complexes characterized by the formula .1 , (RO)~M~Ch)y ~I) ~ wherein R is hydrogen or a hydrocarbyl group containing i ~rom 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 ch~lating agent~ The metal chelating agents used in the preparat1on of the '.. .
. .
' ~

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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 a.romatic.
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~ h~ I~SI~tal ~hela~e_C.~m~Q~nds, by Martell and Calvin, Prentice-Hall, Inc , N.Y. (195~3"
Examples of functional groups which may be present in the chelating agent include hydroxy groups, car~oxy yroups, carbonyl groups, amino groups, or mercapto groups~ Generally, the chelating agen~ (Ch) may be aliphatic in nature and S3ielected from ~he group consisting of ~lycols, dithiols, mercapto alcohols, amino alcohols, aminothiols, dicarboxylic acids, hydroxy carboxylic acids, mercapto carboxylic acids, amino carboxylic acids, diketones, ketocarboxylic cid~ or ester~i, etc. Examples of general classes of aromatic chelating agents include dihydroxy benzenes, dimercapto benzenes, mercaptohydroxy benzenes, diamino benzenes, aminohydroxy benzenes, aminomercapto benzenes, hydroxy-carboxy benzenes, aminocarboxy benzenes and mercapto-carboxy benzenes haviny the two ~unctional groups in vicinal or beta position to one ano~her on ~he benzene nucleus..
~ he titanium and zirconium complexes repre-sented 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 atomsO Çenerallyr 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 ~enerally, either two or three equivalents of the chelating group are reacted with two or one equivalents (respectively) of the compound of t.he forrnula M50R)~.
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 9 and ~he chelating agents accordingly are selected to impart fuel-solubility to the complexO Generally, the chelating agents will contain a carbon skeleton of from 2 to about lB carbon atomsO
Examples of suitable metal chelating agents within the above~described groups include vicinal--and beta-diols such as ethylene glycol and ~-ethyl-1,3-hexanediol,o vicinal- and beta-dithiols such as ethylene mercaptan and ~ ~ r-yr~l; vicinal- and beta-mercapto alcohols such as ~ mercaptoethanolJ 3-mer capto~ propanol; vicinal~ and beta-diamines such as ethylene diamine and propylene diamine; vicinal- and beta-amino alcoholi such as iethanolamine and 3-amino-1-propanol, vicinal- and beta-aminothiols such as thio-ethanolamine and 3-amine~l-mercaptopropane; vicinal- and beta~dicarboxylic acids such as oxalic acid and malonic acids~ vicinal- and beta-hydroxy carboxylic acids such ' ~:

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as glycolic acicl 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-diketon~S such as acetylacetone and benzoyl acetone; beta-keto carboxylic acid esters such as ethylacetoacetate; etcO
As mentioned above~ the metal chelating agents also may be alicyclic chelating agents or aromatic chelating agents such as represented by the structural formula X
Rln ~ (IX) wherein Rl 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 relatlve to X, and X
and Y are each independently functional groups surh as OH, NH2, NHR, SH, COOR, or C~O)H wherein R is hy~rogen or a hydrocarbyl group~ pre:Eerably a lower aliphatic group. Specific examples o;E such aromatic compounds include hydrocarbyl-substituted and unsubstituted vicinal-di-hydroxy aromatic compounds such a~ pyrocate-chol and 4-t-butyl~pyrocatechol; vicinal-dimercapto-aromatic eompounds such as thiocatechol, vicinal-mercapto~hydroxyaromatic eompounds such as monothio-eakeehol or a mercaptohydroxy benzenP; vicinal-diamino-aromatic compounds such as orthophenylenediamine;
vicinal~amino-hydroxyaromatic compounds sueh as ortho-aminophenol; vieinal~aminomereapto aromatie eompounds such as orthoamino hiophenol; vieinal~hydroxyearboxy aromatic compounds such as salicyclie acid; vicinal-: .

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~minocarboxy aromatic compounds such as orthoamino-benzoic acid; vicinal-mercaptocarboxy aromatic compounds such as ortho-mercaptobenzoic acid, etc. Specific examples of alicyclic compounds include 1,2-dihydroxy-cyclohexane 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 Man~ich ~ases~
(B) amino acid compounds of the formula RlR2NCH-(CH)zCOOH (VI) wherein Rl i5 hydrogen or a hydrocarbyl group; R2 is Rl or an acyl gLOUp; R3 and R4 are each independently hydro~en or lower alkyl groups; and z is 0 or 1~ ~
~C) beta diketones, -(D) phenolic compounds of the structure :
OH OH
- X ~ (VIII) R ~ i ~

132dt~

wherein each ~ is a hydrocarbyl group; and X is CH2, Sl or CH20CH2, and (E) an aromatic difunctional compoun~ of the formula X - .
Rln~-y ( IX3 wherein Rl is a hydrocarbyl group containing 1 to about 100 carbon atoms, n is an integer from O to 4, Y
is in the ortho or meta-position relative to X, and X ~:~
and Y are each independently OHy NH2, NHR, COOR, SH or C(O)H groups wherein R is hydrogen or a hydrocarbyl group.
romatic Mannich ~a~:
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 inven~ion are those which are derived from hydroxy aromatic compounds, amines or ~ydroxy amines, and aldehydes or ketones~
In one embodiment, the metal chelating agent gCh) is an aromatic Mannich base which is the reaction product ~ A-l) a compound having the formula RD
(Rl)n Ar - (XH~m wherein Ar is an aromatic ~roup or a coupled aromatic group; wherein m is 1~ 2 or 3; wherein n is an integer from 1 to 4; wherein Rl independently is hydrogen or a hydrocarbyl having from 1 to about 100 carbon atoms; and .

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~ 3 2 f -15-wherein R is hydrogenf, amino, or carboxyl; and wherein X is o, S, or both when m is 2 or greaterl (A-2) a compound having the formula l, 1l I R2 - C~-- R3

3 or a precursor thereof; wherein R2 and R3 indepen-dently are hydrogen, a saturated hydrocarbon group I having from l to about 18 carbon atom3; or wherein R3 is a carbonyl-containing hydrocarbon group having from 1 J~ to about 18 carbon atoms; and t (A-3) an amine which contains at least one primary or secondary amino group The iA-l) hydrocarbyl-substitutPd hydroxyl and/or thiol-containing aromatic compound o the present invention generally has the formula (Rl)n-Ar-(xH~m wherein Ar is an aromatic qroup such as phenyl or polyaromatic group such as naphthyl, and the like.
Moreover D Ar can be coupled aromatic compounds such as i ~ naphthyl, phenyl, etc " wheriein the coupling agent is O, f ~ S, ~H2, a lower alkylenfe group having from l to about 6 carbon atoms, N~, and the ].ike with Rl and XH gener-¦~ : : : ally being pendant from each aromatic group. Examples t:~ : of speciic: coupled aromatic compounds include diphen-yIamine, diphenylmethylene ~nd~the like. The number of i'm" XH groups;is usually from:l to 3, desirably l or 2, f~ with l being preferredO The number of "n" substituted Rl groups is usually from 1 :to 4, desirably 1 or 2 wi~h a sinigle substituted:group being preferred. X is 0:
and/or S with 0 being preferred. That is, if m is ~ff X
can be both 0, both S, or one 0 and one S. Rl can be f~ a hydr~gen or a hydrocarbyl-based substituent having t f ~ ) ~ 3 2 ~

from 1 to about 100 carbon atoms As used herein and throughout this specification, the term "hydrocarbyl-based substituent" or ~Ihydrocarbyl7~ denotes a substi- :
tuent having carbon atoms directly attached to the remainder of the molecule and having predominantly hydrocarbyl character within the context of this inv~ntion, 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 thro~gh another portion of the molecule (that is, any two indicated substituents may together form an alicyclic radical). -~
(2) Substikuted 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 skille~ in the art will be aware of suitable radicals (e.g., halo, (especially chloro and fluoro), amino, alkoxyl, mercapto~ alkylmercapto, nitro, nitroso, ~ulfoxy, etcc) - -[3) ~letero 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, Rl is hydrogen, or a hydro-carbyl 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 abou~ 70 carbon atoms, more desirably :::
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~32~
~17-from about 7 to about 20 carbon atoms~ an alkenyl having 2 to about 30 carbon atomis, 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-substi-tuted alkyl or alkyl-substituted aromatic having a total of from abou~ 7 to about 30 carbon atoms and more desirably from absut 7 to about 12 carbon atoms. The hydrocarbyl-baised substituent preferably is an alkyl having from 7 to about 20 carbon atom~ with from about 7 to about 14 carbon atoms being highly preferredr Examples of suitable hydrocarbyl~substituted hydroxyl-containing aromatic~ include the various naphthols, and more pre:Eerably, the various alkyl-isubstituted cate-chols, resorcinols, and hydroquinones, the various xylenols, the varous cresols, aminophenols, and the like. Example~ ¢f various suitable (A) compounds include heptylphenol, octylphenol, nonylphenol, decyl-phenol~ dodecylphenol, tetraprs~pylphenol, eicosylphenol, and the like~ Dodecylpheno:L, tetrapropylphenol and heptylphenol are especially preferred. Examples of suitable hydrocarbyl-substii:uted thiol-con~aining aromatics include heptylthiophenol, octylthiophenol~
nonylthiophenol, dodecylthiophenol, tetrapropylthio-phenol~ and he like. Examples of suitable thiol and : hydroxyl-containing aromatics include dodecylmonothio-r~esorcinol.
The aldehyde or keto~e (A-2) used in the pxesent invention has the formula ~ . .

R2 - C _ R3 i.

, ", ", ;." ~ " ; f ~ " ~ " ~ " " j ~ ~ "

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or a precursor ~hereof, wherein R2 and R3 indepen-dently 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 akoms. Examples of suitable ~A-2~
compounds include the various aldehydes and ketones such as formaldehyde, acetaldehyde, propionaldehyde, bukyr-aldehyde, valeraldehyde, benzàldehyde, and the like, as well as acetone, methyl ethyl ketone, ethyl propyl ketoner 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 paraform-aldehyde, formalin, trioxane and the like. Formaldehyde and its polymers, for example, paraformaldehyde are preferred. Mixtures of the various ~A-2) reactants also I 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 lea~t one -N-H
groupO The remaining valences of the above nitrogen atom preferably ar~ satisfied by hydrogen, amino~ or organic g~oup~ bonded to said nitrogen atom through direct carbon~to~nitrogen linkages. The amine (A-3) may be represented by the formula 1:
~l-N-H -R2 ~IV) :::
~, -19- ~32~

wherein Rl is a hydrocarbyl group~ amino-substituted hydrocarbyl, hydroxy-substituted hydrocarbyl, or alkoxy-substituted hydrocarbyl group, and R2 is hydrogen or Rl. 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 amine~ may be primary or secondary amine~ and may also be polyamines such as alkylene an~ines, arylene amines, cyclic polyaminesl and the hydroxy-substituted derivatives of such polyamines.
Specific amines of these types are methylamine, N-methyl-ethylamine, N-methyl-octylamine, N-cyclohexyl-aniline, dibutylamine, cyclohexylamine, aniline, di~p-methyl)amine, dodecylamine, octadecylamine, o-phenyl-enediaminet NtN'-di-n-butyl-p-phenylenediamine, morpho-line, piperazine, tetrahydropyrazine, indole, hexahydro-1,3,5-triazine, 1-H-1,2,4-triazole, melamine, bis-(p-aminophenyl)methane, phenyl-methylenimine, menthane-diamine, cyclohexamine, pyrrolidine, 3-amino-5,6-diphen-yl-1,2,4-triazine, ethanolamine, diethanolamine, ~uin-onediimine, 1~3-indandiimine, 2-octadecylimidazoline, 2-phenyl-4-methyl-imidazolidiner oxazolidine, and 2-heptyl-oxazolidine.
The hydroxyl-containing amines can be charac-terized by the formula ~.
Rl - .
RlNH-~R2N)XRl ~V) ~ .

wherein each of the Rl groups is independently a hydrogen atom or a h~droca.rbyl, hydroxyhydrocarbyl, aminohydrocarbyl, or hydroxyamirlohydrocarbyl group , . , ' '' '' ,, .'' ~ ' ' .. '.. , ,' ' , , ' " ., . ~ . , ,. ',' ' " , . ' ',, ,, , ., . , :, ' , ~ 3 ~

provided that at least one of Rl is a hydroxyhydro-carbyl or a hydroxyaminohydroCarbYl group9 R2 is an alkylene group~ and x is an integer rom 0 ~o about 5.
Examples o~ specific hydroxyl-containing amines include ethanolamine, 2-amino-1-butanol, 2-amino-2-methyl-l~propanol, di-(3-hydroxypropylJ-amine, 3-hy-droxyb~tyl-am.ine, 4-hydroxybutyl-amine~ 2-amino-1-buta-nol r 2-amino-2-methyl-1-propanol, 2-amino-1-propanol~
3-ami~o-2-methyl l-propanol, 3-amino-1-propanol, 2-ami-no~-2-methyl-1,3-propanediol, 2-amino-2-ethyl-1,3-pro-panediol, dieth~nolamine, di-(2-hydroxypropyl)-amine, N~(hydroxypropyl) propylamine, N-(2-hydroxyethyl)-cyclo-hexylamine, 3-hydroxycyclopentylamine, N-hydroxyethyl piperaæine, and the like~
The amine tA-3) also may be a polyamine conforming for the most part to the formula H~N(alkylene--N~H
A A

wherein n is an integer prefer;lbly less than about 10, A
is a substantially hydrocarbon or hydrogen group; and the alkylene group is preferahly a lower alkylene group having lei~is than about 8 carbon atoms. The alkylene amines include principally methylene amines, ethylene amines, butylene amines, pr~pylene a~ines, pentylene amine~i, hexylene amine~, hep~ylene amines~ octylene amine~, o~her polymethylene amines, and also the cycli~
and the higher hom~logues of such amines such as piperazines and amino-alkyl-substituted piperazines~
They are exemplified specifically by: ethylene diamine, triethylene tetramine9 propylene diamine, decamethylene diamine, oc~amethylene diamine, ditheptamethylene)tri ;."

. .

~ ) ~ 3 2 ~

amine, tripropylene tetraminey tetr~ethylene pentamine, trimethylene diamlne, pentaethylene hexamine, di(tri-methylene)-triamine, 2 hep-tyl 3-(2-aminopropyl)imidazo-line, 4-methyl-imidazoline, 1,3 bis~2-aminoethyl)imida-zoline, pyrimidine, l-t2-aminopropyl)piperazine. 1,4-bis~2-aminoethyl)piperazine, and 2~methyl-1-(2-amino-butyl)piperazine. Higher homologues such as are obtained by condensing two or more of the above-illustrated alkylene amines likewise are wseful.
Hydroxyalkyl-substituted alkylene amines, i.eO, alkylene amines having one or more hydroxyalkyl ~iubsti-tuents 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, l,4-bis-(2-hydroxypropyl~piperazine, di-hydroxypropyl-substi-tuted tetraethylene pentamine, N-(3-hydroxypropyl)tetra-methylene diamine, and 2-hept:adecyl-1(2-hydroxyethyl)-imidazoline.
Higher hornologues such as are obtained by condensation of the above~illustra ed alkylene amines or hydroxyalkyl-subi~tituted 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 a~monia and that condensation through the hydroxy groups results in products containing ether linkages accompAnied with removal of water~

t'. ,......... , ,' . '' , , . . '' ' : . . ' ' ~ 3 2 ~

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~l) 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 reactionO Reaction temperatures ~rom about ambient to about the d~composi-tion temperature of any component OE the Mannich product can be u~llized. During reaction, water is drawn off as by sparging. Desirablyt the reaction is carried out in solvent such as an aromatic type oil~ The amount of the various reactants utili~ed is desirably on a mole to mole basis of (A-l) and (A~2~ for each ~A 3~ secondary amino group or on a two-mole basis of ~A-l) and (~-2) for each (A~3) primary amino group, although larger or smaller amounts can also be uti:lized.
In another method of preparing Mannich ¦ products/ the hydroxyl containing aromatic compound (A-l) and the amine compound (A-3) are added to a reaction vessel~ The aldehyde or ketone ~A-2) is 'I generally rapidly added and the exothermic reaction generated is supplemented by mild heat such that the reaction temperature is from about 60C to about 90C.
j Desirably the ~ddi~ion temperatur~ is less than the I boiling point of water, otherwise, the water will bubble I of and cause proce~sing problems. After ~he reaction is essentially complete, the water by-product is removed t~ 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 I utilized at a temperature of from about 100C to about 130C. Naturally, higher or lower temperatures can be utilized.

,:~

~ ?

~ ~ 2 ~

J The reaction is generally carried out in a solven~. 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 I oil, etc.
Some examples o the amounts of the various tA-l), (A-2) and (A-3) components are set forth above.
However, other amounts and ratios can ~e utilized. ~or example, for each primary amino group of (A~3~ from about 0.5 to about 6 moles of (A-13 and (A-2) can be utilized and more desirably from about 1.8 to about 2.2 ~, moles of ~A-l) and ~A-2). For each secondary amino --group of (A-3), from about 0.2 ~o about 2 moles of (A~l) and (A-2) can be u~ilized and more desirably from about 0.9 to about 1~1 moles of (A-l) and (A-2).

The m~tal chelating agent (Ch) also may be at least one amino acid compound oE the formula RlR~NCH-(CH~zCOOH (VI) `

:
;~ wherein Rl is h~drogen or a hydrocarbyl group; R2 is , Rl or an acyl ~roup; R3 and R4 are each ,~ independently hydrogen or lower alkyl 9LOUpS; and z is 0 or 1~ The hydrocarbyl groups Rl and R~ may be any one o~ the hydrocarbyl groups as broadly defined above.
In particiular, Rl and R2 are alkyl, cycloalkyl, phenyl r alkyl-substituted phenyl, benzyl or alkyl--'l~ substituted benzyl groups. ~;
In one preferred embodimPnt, Rl and R2 Of ~ Formula VI are each independently alkyl groups ! : containing from 1 to about 18 carbon atomsl cyclohexyl, '~

`, .
, -, -24- ~ 32~ 7 phenyl, phenyl groups containiny alkyl substituents containin~ from 1 to about 12 carbon atoms at the 4-position of the phenyl ring, benzyl or benzyl having an alkyl group of froJn 1 to about 12 carbon atoms at the 4-position of the phenyl ring. Generally, Rl in Formula VI is a lower alkyl such as a methyl group, and R~ is an alkyl group having from about 4 to about 18 carbon atoms.
In another embodiment, Rl is as defined above and R2 is an acyl group. Although a variety of acyl groups may be utilîzed 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 acyl-substituted amino carboxylic acids are obtained by reac~ion of an amino carboxylic acid with a car~oxylic acid or carboxylic halide. For e~ample, a fatty acid can be reacted with an amino carboxylic acid to form the desired acyl-substituted amino carboxylic acidO ~cids such as dodecanoic acid, oleic acid, stearic acid, linoleic acîd, etc., may be reacted with amino carboxylic acids such as represeinted by Formula VI
wherein R2 is hydrogen. .A
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.
: '' ~'' ~2~

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 æ is 1, the amino carboxylic acid (VI) is beta-alanine or derivatives of be~a-alanine.
The amino acid compounds of Formula VI which are useful as metal chelating agents in the present invention can be prepared by me~hods described in ~he prior art~ and some of these amino acids are available commerciallyO 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 describ~d in, for example, U~Sr Patent ~,077,941. For example, ~he arnino acids can :~
be prepared by reacting an amine of the formula :
RlR2MH

¦ wherein Rl and R~ are as previously defined, with a compound o the formula R3 CH=C ~ R4 )--C02R5 ~

wherein R3 and R4 are as defined previously with i respect to Formula VI~ and Rs 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, benzyl~
methylamine, aniline, diphenylamine~ methylethylamine~ -cyclohexylamine, n-pentylamine, dii~obutylamine, diiso-propylamine, dimethylamine, dodecylamine, octadecyl-amine, N~n-octylaminep aminopentane~ sec-butylamine, prop~lamine, etc.

:, ~32~
-26~

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 ~.
RlNH2 wherein R1 is as defined previously with a compound of the formula R3CH=C(R4)-C02Rs .:~

wher~in R3, R4 and R5 are as defined above~ ~
Subse~uent.ly, this intermediate is converted to the : .
mekhyl derivative by N-methylat~on and hydrolysis o~ the ~:
ester followed by acidi~ication. 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 oX the type represented by Formula VI are illustrated in th~ following Table I~ :~

.~.:'-: ~ .
: .-.'.
: , :

,:

,; , ' , ~ ' !. . ; . ~,. . ' ~ , , , ' i -27- ~ 3~

~;L

RlR2N-CEI-(CH)zCOOH -Rl R2R3 z R4 CH3 isoamyl H 1 H
CH3 octadecyl H 1 H
CH3 octadecyl H 1 CH3 . .
CH3 n-butyl C2E~5 1 H
n-octyl n-octyl n-propyl 1 CH3 cyclohexyl cyclohexyl H 1 H
CH3 n-octadecyl CH3 1 ~ .
CH3 isopropyl H 1 H
CH3 oleyl H 1 H
CH3 CH3 H ~~
~ H CH3 0 --CH3 ~ CH3 CH3 0 -- ~::
H oleoyl H 0 .
: :: oleoyl H
: H stearoyl H 0 --Me ~ stéaroyl ;H 0 --H oleoyl H ~ 1 ~ H
Me stearoyl H 1 H - .

' , ,:
~: . ,' .,'' ~32~ 3~ :
-2%-( C ) ~ ~Q~=~
~he 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)-Rl (VII) wherein R and Rl are each independently hydrocarbyl groups~ The hy~rocarbyl groups may be aliphatic or , aromatic hydrocarbyl groups as defined above. Among the f aliphatic hydrocarbyl groups, thP lower hydrocarbyl , groups containing up to about 7 carbon atoms are I preferred7 Specific exampl~s of Rl and R2 groups I include methyl, ethyl, phenyl, benzyl, etc., and specific examples of beta-diketones include acetyl acetone and benzoyl acetone.
~ Phenolic Com~unds ¦ The metal chelating agent (Ch) also may be at least one phenolic compound of t:he formula OH OH
X - ~ ~VIII) R

, wherein ea~h R is a hydrocarbyl ~roup; and X is CH2, ,1 S, or S~20GH2. In one embodiment, each R is independently an aliphatic group which generally contains ~rom about 4 to about 20 carbon atoms.
, Examples of typical R groups include butyl, j hexyl heptyly 2-ethyl-hexyl, octyl, nonyl decyl, dodecyl, etc.

!

~ 3 2 '~

The phenolic compounds represented by Formula VIII can be prepared by reacting the appropriate substituted phenol with ~ormaldehyde or a sulfur compound s~ch as sulfur dichlorideO When one mole of formald~hy~e is reacted ~ith two moles of the substi~uted phenol, the ~ridging group X is CH~, Wh~n a molar ratio of formaldehyde to substi~uted phensl is 1:1, bis-phenolic compounds bridg~d by the group CH20C~ can be formed as a r~sult of the reaction.
When two moles of a substituted-phenol are reacted with one mole of sulfur dichloride, a bis-phPnolic csmpound is formed which is bridged by a sulfur atom.
(E~7 A~ nc~iQn~l ~om~ound~
The metal chelating agent (Ch) may be an aromatic difunctional compound of the ~ormula Rln ~ (IX) .

wherein Rl is a hydrocarbyl group containing 1 to about 100 carbon atoms, n i~ 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~ N~2, NR2, COOR, S~, or C~O~H wherein R is hydrogen or a hydrocarbyl group.
Speci~ic 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. Preerably; :
the amino phenol is an ortho-amino phenol which may contain other sub~tituent groups such as hydrocarbyl groups.
- :

~y3~

The following examples illustrate the prepara-tion of several exemplary metal chelating agents which are useful in preparing the titanium or zirconium com-plexes of the present invention. Unless otherwise indicated in the ~ollowing examples and elsewhere in the specification and claims, all parts and percentages are by weight~ and all temperatures are in degrees centi-grade.
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 oE a commercial polyamine mixture by responding to diethylenetriamine over a period of 30 minutes. To this mixture at about 60C, there i~ added 20.6 parts of formalin solution (37% paraformaldehyde) dropwise over a period of one hour while maintaining the reaction temperature below about 36C. 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 96-9gC for 3.5 hours. ThP water ~ormed in the reaction is removed b~- distillation under vacuum and therea~ter cooled to room temperature. The product that is obtained is a red oilc Example B
Dodecylphenol ~1000 parts) is charged to a reaction vessel and the temperature i~ adjusted to 38-55C whereupon 290 parts of sulfur dichloride is added at a rate to maintain the temperature of the reaction mixture below about 66C. The mixture is blown with nitrogen while heating to 143-149C, and the mixture is maintained at this temperature until the direct acid number is less than 1.5 acid~ The mixture ~::
~ ~ .
' ~

~3 ~

~ ~ 2 '~

is cooled to about 95-100C while adding about 788 parts of diluent oil. The reaction mixture is filtered, and the filtrate is the desired sulfur-coupled pheno].
Example C
A mixture of 526 parts (2.01 mole) of dodecyl-phenol, 44.1 parts (1~34 moles7 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 s~irriny. The mixture is heated to a temperature of about 115C over a period of about minutes to remove solvent~ The mixture then is maintained at 145C while sparging with nitrogen until no additi.onal solvent can be remo~ed 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 ethanolamin~. The mixture is stirred ~nd heated to 72C, and 372 parts paraformalde-hyde are rapidly charged thereto, The reaction temper-ature is increased to a maximum of 147C over a 3-hour period while water is removed by sparging with nitro-gen. A total of 218 parts of wat~r is colla~.ted 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 inven~ion are represented by the formula (RO)xMtch~y tI) ".

.:: - . , , , .,. , , . . ,: . . " ., ., ~ , . ... . . ... . . .

~2~

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 37 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 ti~anium or zirconium compounds represent~d by the formula M(OR)4 wherein M and R are as described abovey with one or more of the metal chelating agents ~Ch) described aboveO 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 e~uivalent of the metal compound M(3R)4 is reacted with two equivalents of thP metal chelating agent, then x and y in Formula I are each 2. Similarly, if one e~uivalent of the metal compound M(OR)~ is reacted with three equivalents of thle metal chelating agent, then x is 1 and y is 3 in Formula I, ~ he reaction between the metal compound M~OR~ and the metal chelatin agent is affected by mixing the reactants. In many in~tances, tbe reaction i~ exothermic and external heating of the mixture is unnecessary. '~he alcohol (RO~) 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 foundO
General~y, he reaction mixture is heated at an elevated temperature (optionally under reduced pressure~ until substantiall~ no additional alcohol can be recovered by , ..

-33- ~2~

distillation. The reaction mixture may be purged with nitrogen or other inert gas in order to facilitate the removal of the alcohol.
The follo~ing exampl~s illustrate the prepar-ation 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 t~ 110C at 25-30 mm. ~g. and there-after at 150C at 16 mm. Hg. while removing n-butanol.
The residue is cooled to 60 and filtered through a ~ilter aid. The filtrate is the desired product.
Example 2 A mixture is prepared containing 107 parts of tetra-i-propyl titanate and 5'20.2 parts of a 50% xylene solution of the Mannich base prepared as in Example A
except that the dodecylphenol is replaced by an eguivalent amount of heptylp~henol and the reaction is conducted in xyleneO Upon addition of the titanium compound, the mix ure ~urns red, and an exotherm to about 42C in five minutes is ob~erved. The mixture is stirred for 1.3 hours at a temperature of 35-40C.
Example 3 A mixture of 100 parts of isopropyl alcohol, 47~4 parts of a c~mmercial alcohol mixture containing an average of about 9 to about 11 carbon atoms (Neodol 91, Shell Chemical) r and 85.2 part~ of tetraisopropyl titanate is prepared, and 30 parts of 2~4-pentanedione is added with stirring. An exothermic reaction occurs, and af~er a period of about several minutes, the solvent is remvved by stripping. The residue, a yellow oil, is the desired titanium co~plex7 .
i, , -.
.~ .

1 3 2 ~

Example 4 A mixture of 163 parts of tetraisopropyl titanate and 406 parts of Sarkosyl O ~N-oleoyl sairkosine available from Ciba Geigy) is prepar~d, purged with nitrogen, and heated with stirring under vacuum to a temperature of about 55C (about 80 mm. Hg.). The mixture then is heated to about lOO~C at 70-90 mmO Hg~
over a period of ~bout 1.6 hours until no further distillate is obtained~ The mixture i5 vacuum stripped at lOO~C at about 10-20 mm~ Hg. The residue is filtered at about 100C through a filter aidO 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 160C in a nitrogen atmosphere.
After cooling to about 60Ct lOl parts of tetraisopropyl titanate is added over a pe~riod of 5 minutes. The mixture is heated to 145C 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, ~here ~s added 138 parts of a :
diluent oil followed by the addition of 152 parts of tetraiisiopropyl titanate dropwise over a period of about 6 minutes. The temperature of the reaction mixture is maintained at ahouk 150C fGr 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 diethanolamîne and 388 parts of a diluent oil is prepared and heated to :;, .

about 100C at 120 mmO Hg. whereupon 100 parts of tetraisopropyl titanate and 225 parts of tetra-n~butyl titanate are added in three portions wi~h stirring.
After reducing the pressure to 20-25 mm. Hg. at 65C, 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 compo~ncls, and in particular, the titanium and ~irconium complexes described above are particularly useful in fuel compositions which comprise a major proportion of a normally liquid ~uel, usually a hydrocarbonaceous p~troleum distillate fuel such as diesel fuels, distil-lake fuel~, heating oils, residual fuels, transfer fuels J and motor gasoline as defined by ASTM
Specification D-439. Diesel fuels may be defined broadly as fuels having a ~;uitable boiling range and viscosity for use as a fuel in a diesel~type engine.
Fuels containing alcohols ancl 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 120C to about 42~C, more desirably from about 140CC to about 400C, and mGst often between about 200C to about 370C. Generally, diesel fuels are within grades lDI 2D and 4D, and usually, the diesel fuel~ have viscosities of from about 1,3 to about ~4 7 0 centistokes at 40C~
The diesel fuel composition~ which are treated in accordance with the present invention will contain an amount of the titanium and zirconium compounds described above which lS efective in lowering the ignition ternpexature of exhaust particulakes formed on burning of the diesel fuel. Thus, the fuel compositions generally will contain from 1 to about 5000 parts of titanium or zirconiurn per million parts of fuel, and most often, the diesel fuels will contain ~rom about 1 to about 500 parts o~ 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 ~hat the titanium and zirconium compounds be complexes that are hydrolytically stable. In such applications, it is preferred to use the titanium and zirconium complexe~ of the formula (~O)x~(ch)~ (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 identifi~d 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.y,, ethylene dirhloride and ethylene dibromide), deposit preventers or modifiers such as triaryl phosphates, dyes t ce~ane improvers, antioxidants such as 2,6-di-tertiary-butyl-4-methyl-p~henol, rust inhibitors such as alkylated succinic acids and anhydrides, bac~eriostatic agents, gum inhibitors, metal deactivators, demulsifi-ers, upper cylinder lubricants and anti~icing agents, .

:
:. ' .

~ ,6~ ~ L'lA ~_ r~ ~

In certain pr~ferred 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 of relevance for theîr disclosure of suitable est~rs and methods ~or their preparation. Generally, the weight ratio of the composition of this invention to the aforesaid asAless dispersant is between about 0.1:1 and about lO:1, preerably b~tween about 1:1 and about 10:1.
The titanium and zirconium compositions o~ this invention can be added directly to ~he fuel, or they can be dilut~d with a substantially iner.t, normally liquid organic diluent ~uch as naphkha, benzene, toluene, xylene or a normally liquid fuel as described above, to form an additive concentrate. The~e concentrates generally contain ~rom about 20% to about gO~ by weight of the composition o~
this in~antion and may contain, in addition one or more other conventional additives ~nown in the art or described ~-her ina~ove. :~
~he following examples illustrate the fuel ~:
compositions of the invention and fuel composition~ u3eful in this invention. ~

~ .
;'~'' ' ~'.
.: .

~ 3 2 ~
-3~-Fuel A
Titanium Complex of Ex. 1 2100 ppm :
No. 2 Fuel Oil remainder Fu~l ~
Titanium Complex of Ex. 2 4400 ppm ''~
Titanium acetonylacetonate 100 ppm (Ti~
No. 1 Fuel Oil remainder .
~uel ~
Titanium Complex of Ex. 4 125 ppm (Ti) Mo. 2 Fuel Oil remainder While the invention has been explained in relation to i~s 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.

-: ~ : ', ~
.. .

:

Claims (93)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

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 (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.

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, indepen-dently, 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-substi-tuted 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,

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 hydro-carbyl, 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 hydroxyamino-hydrocarbyl 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 x 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-pentanediene.

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 diesel fuel and a minor, property improving amount of at least one titanium or zirconium complex characterised by the formula (RO)xM(Ch)y (I) wherein R is an aliphatic 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, excepting a diol which is not an aromatic Mannich base.

45. The fuel composition of claim 44 wherein the metal chelating agent contains a hydrocarbon linkage and at least two functional groups on different carbon 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 44 wherein the chelating agent (Ch) is 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, and (D) 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, X is NR2, COOR, SH or C(O)H, and Y is OH, NR2, COOR, SH or C(O)H groups wherein 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 or a hydrocarbyl group having from 1 to about 100 carbon atoms, R° is hydrogen, amino, or carboxyl, and X is O, 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) or a precursor thereof wherein R2 and R3, indepen-dently, 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.

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-substi-tuted 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.

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 hydro-carbyl, hydroxy-substituted hydrocarbyl, or alkoxy-substituted hydrocarbyl group, and R2 is hydrogen or R1.

53. 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 (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 hydroxyamino-hydrocarbyl group, R2 is an alkylene group, and x is an integer from 0 to about 5.

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 (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,

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 R23 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 44 wherein Ch is an aminophenol.

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

74. 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.

75. 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.

76. The fuel composition of claim 75 wherein the diketone is 2,4-pentanedione.

77. A titanium or zirconium complex characterized by the formula (RO)XM(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, and (C) an ortho-aminophenol.

78. The complex of claim 77 wherein M is titanium.

79. The complex of claim 77 wherein R in Formula I is an aliphatic group containing from about 1 to about 30 carbon atoms.

80. The complex of claim 77 wherein x and y in Formula I are each 2.

81. The complex of claim 77 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.

82. The complex of claim 81 wherein (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 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.

83. The complex of claim 81 wherein (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.

84. The complex of claim 81 wherein (A-3) is characterized by the formula (IV) wherein R1 is a hydrocarbyl, amino-substituted hydrocarbyl, hydroxy-substituted hydrocarbyl, or alkoxy-substituted hydrocarbyl group, and R2 is hydrogen or R1.

85. The complex of claim 77 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.

86. The complex of claim 85 wherein R1 in Formula VI is an alkyl, cycloalkyl, phenyl, alkyl-substituted phenyl, benzyl or alkyl-substituted benzyl group.

87. The complex of claim 85 wherein R3 and R4 in Formula VI are hydrogen.

88. The complex of claim 85 wherein z in Formula VI is 0.

89. The complex of claim 85 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.

90. The complex of claim 89 wherein R2' contains from about 12 to about 24 carbon atoms.

91. A fuel additive concentrate comprising a normally liquid organic diluent and from about 10% to about 99% by weight of the complex of claim 77.

92. A fuel additive concentrate comprising a normally liquid organic diluent and from about 10% to about 99% by weight of the complex of claim 81.

93. A fuel additive concentrate comprising a normally liquid organic diluent and from about 10% to about 99% by weight of the complex of claim 85.