CA2102893A1 - Lubricating compositions and concentrates - Google Patents

Abstract

A lubricating oil composition is described which comprises a major amount of an oil of lubricating viscosity and (A) at least about 1 % by weight of at least one carboxylic derivative composition produced by reacting (A-1) at least one substituted succinic acylating agent containing at least about 50 carbon atoms in the substituent with (A-2) from about 0.5 equivalent up to about 2 moles, per equivalent of acylating agent (A-1), of at least one amine compound characterized by the presence within its structure of at least one HN< group; and (B) an amount of at least one alkali metal overbased salt of a carboxylic acid or a mixture of a carboxylic acid and an organic sulfonic acid sufficient to provide at least about 0.002 equivalent of alkali metal per 100 grams of the lubricating oil composition provided that when the alkali metal salt comprises a mixture of overbased alkali metal salts of a hydrocarbyl-substituted carboxylic acid and a hydrocarbyl-substituted sulfonic acid, then the carboxylic acid comprises more than 50 %
of the acid equivalents of the mixture; and either (C-1) at least one magnesium overbased salt of an acidic organic compound provided that the lubricating composition is free of calcium overbased salts of acidic organic compounds; or (C-2) at least one calcium overbased salt of an acidic organic compound provided that the lubricating composition is free of magnesium overbased salts of acidic organic compounds.

Description

WO 93/23505 PCI ~VS~Z/0~737 ~ ~ 2 ~ 3 Title: LUBRlCATINC; COMPOSITIONS ANI~ CONCEhlTRATFS

Cross-Reference to Related A~P1iCatjOnS
This applicaticn is a contir~uation-~n-pa~t of pending U.S. Serial No.
07/688~195~ fi1ed APri1 19J 1991 ~nd pending U.5. 5erial Na. 07/690,1791 filed April 19, 1991. l`he disclos~res of said prior applications ar~ incorporated herein in their entirety.
f~-~L~t~
This invention relates to lubricating oil compositions and concentrates, and more particularly, to lubricating oil compositions containing alkali metal o~erbased salts of carboxylic acids and either magnesium or calciumoverbased salts of acidic compounds.
Back~round of the Invention As engines, specifically, spark-ignited and diesel engines have inc~eased power output and complexity, the performance requirements of lubricating oils have bee~a increased to require lubricating oils that exhibi~ areduced tendency t~ deteriorate under conditlons of use and thereby to reduce wear~ rust, cot'ro5ion and the forrnation of such undesirable deposits as varnish, sludge, carbonaceous materials and re inous materials which tend to adhere to 20 various engine parts:and reduce the efficiency of engines. Various materials .
- have been included in the ~ lubricating ~ oil compositions to enable ~he oil compositions to meet the various performance requirements, and ~hese include dispersants, detergents, friction modifiers, corrosion inhibitors, antioxidants,Yiscosity modif le~ s, e~c.

Wo 93/23505 PCrtUS92/08737 Dispersants are employed in lubricants to maintain impurities, particularly those formed during operation of an internal combustion engine, in suspension rather than allowing them to deposit as sludge. Dispersant additives for lubricants compr~sing the reaction produc~s of hydroxy comp~unds or amines S wi~h substituted ~uccinic acids or their derivatives have been described in the prior ar~, and typical disperslorls of this type are disclosed in, for example, U.S.
Patents 3,272,746; 3,522,179; 3,219,666; and 4,234,435. When incorporated into lubricating oils, the composi~ions described in the '435 patent func~ion primarily as dispersan~s/detergents and ~iscoslty-inde~ improvers.
Alkaline earth metal detergents have been included in lubricating oil compositions to suspend degradatlon products of a motor oil and to neutralize scid products within the oil in the en~ines. The alkaline earth m¢tals may be calcium, magnesium, barium or strontium, and mixtures of such metals can be used. The alkaline earth metal de~ergents generally are basic. Alkali metal detergents also have been used in lubricating oil compositio~s to provide improved detergency.
Alkali metal salts, including basic salts, have been described in the general literature and in patents. For example, Canadian Patent 1,05577pO
describes basic alkali metal sulfonate dispersions and processes. More particular-ly, ~he patent d~scrlbes s~lu~ions and/or stable dispersions of basic lithium sulfonates, basic sodium sulfonates and basic potassîum sulfonates having metal ratios jD ~he rsoge of from about 4 to about 40. In the procedure utilized for the prep~ration of these overbased sulfonates, the reaction mixture which is contacted with an acidic gaseous material such as carbon dioxide comprises in addition to one or more oil-soluble sulfonic acids or derivative~ thereof, one or more alkali metals or metal compounds, one or more lower aliphatic mono- or dihydric alcohols, and one or more oil-soluble carboxylic acids or derivatives thereof. These carboxylic acids include mono- and polycarboxylic acids.
U.S. Patent 3,271,31û (LeSuer) describes metal salts of an alkenyl succinic acid having at least about 50 aliphatic carbon atoms in the alkenyl ~ :

~VV 93/23505 PCr/US9~/08737 substituent. The salts include acidic salts, neutral salts or basic salts, and the metals are selec~ed from the class consisting of Group I metals, Group 11 metals, alurninum, lead, tin, cobalt and nickel. The metal salts of the alkenyl succinicacids are reported to be useful as lubricating addltives and may be included in lubrlcatlng oils in amounts of from about 0.1% to abuut 2û% by welght. Other additives whlch may be included Irl the lubricatiDg olls include, for ~xample, other detergents and dlspersants, oxidation-inhlbitlng agents, corrosion-inhiblting agents, extreme pressure agents, etc.
U.S. Patent 3,312,618 (LeSuer) descrlbes a process for preparing an oil-soluble highly basic metal salt of an org~nic acid utilizing anhydrous conditions a~d certain promoters. The organic acids may be sulfonic acids, phosphorus acids, carhoxylic acids or mixtures thereof. The carboxylic acids include f~tty aclds containing at leæt 12 carbon atoms such as palmitic acid, orcyclic acids such as those containing a benzenoid structure, for examplet .. benzene, an oil-soluble group or groups having a to~al of at least about 15 carbon atoms and preferably from about 15 to about 200 carbon a~oms. The metal compounds utilized to form the metal salts include alkali and alkaline earth metals.
U.S. Patent 4,283?294 (Clarke) describes lubricating oil composi-tions useful in marine diesel engines, and the compositions comprise in additionto oil, a mixture of a Group la metal overbased detergent, a Group lla metal overbased detergent, and an antioxidant provided that the weight ratio of the overbased detergent mixture to the antioxidant ~s between 7.5:1 and 50:1. The Group la and lla detergent additives include metal salts of pheno1$, phenol sulfides, phosphosulfurized polyolefins, organic sulfonates and carboxylic acids.
The carboxylic acids are: long chain, mono- or dicarboxylic acids such as those wherein the acid radical: contains at least 50 carbon atoms per molecule. Thus, the metal salts include salts of long chain :succinic acids such as those havingmolecular weights of 850 to 1200. The antioxidants described in this p~tent include alkylated hindered.phenols, organic amines, organic sulfur compounds, WO 93/23s0~ Pcr/US92/08737 1 nf ~ 'J ~-~

metal tbiophosphates, etc. Optional additives in the lubricating oil compositions are dispersants such as polyisobutenyl succinic anhydride-tetraethylene pentamine reaction products.
Lubricating oll compositions containlng basic ~Ikali met~l salts of sulfonic or carboxylic acids, and carboxylic derivative ~ompositions obtained byreacting substitu~ed succlnic acylating agents with at least one amine compound are described in U.S. pateDts 4,~04,401; 4,938,881; and 4,952,238. The carbox~lic acids may be either mom)carboxylic acids or polycarboxylic acids including dicarboxylic acids such as substituted sucoinic aclds. Sui~able carboxylic acidsfrom which useful alkali me~al salts can be prepared include aliphatic, cycloaliphatic an~ aromatic morlo- and pol ycarboxyllc acids including naphthenic acids, alkenyl-substituted aromatic acid~, and alkenyl succinic aclds. Th~
aliphatic acids generally ~ontain frcm about 8 to about 50, ~nd pref~rably frornabout 12 to about 25 carbon atoms. These patents also describe basic alkali metal salts, mixtures of sulfonic aclds and carboxylic acids wherein the ratio of equivalents of the carboxylic acid when present to the organic sulfonic acid in the mixture geslerally is from about 1:1 to about 1:20 and preferably from about1:2 to about 1:10. The amount of the alkali metal overbased sulfonate,or carboxylate includ~d in these oil compositions may range from about 0.01 to about 2% by weight. The oil compositions may contain other desirable additives ; such as metal salts of dihydrocarbylphosphorodithioic acids, antioxidants~ friction modifiers, neutral and basic salts of phenol sulfides, sulfur-containing compounds useful in improving antiwear, exl:reme pressure antioxidant properties, and neutral or basic alkaiine earth metal salt detergents.

2~ U.K.~ Patent Application 2,062,672 (Zalar3 describes additi~e compositions for lubricating oils which comprise sulfurized alkyl phenol and high molecular weight dispersants. The dispersants are oil-soluble carboxylic dispersants containing a hydrocarbon-based radical having a number average molecular weight of at least 1300 attached to a polar group such as succinic acid or derivative thereof. Generally, the carboxylic dispersants are reaction ~VO 93/~350~ Pcr~usg2/08737 products of carboxylic acids ar derivatives thereof with (a) nit~ogen-containingcompourlds having at least one ~NH group, (b) organic hydroxy compounds such as phenols ~nd alcohols, and/or ~c~ reactive metals or metal-reactive compounds.The carboxylic dispersants may be post-treated with various reagents including sulfur and sulfur compounds, ureaJ thiourea, aldehydes, ke~ones, carboxylic acids, epoxides, boron compounds, phosphorus compounds, etc. The carboxylic acid which is u~ilized in the prep~ration of the dispersants are referred to as acylating agents. The acylating agent may be pr~pared by tbe alkylatlon of an acid such as maleic acid or anhydride. The alkylating agent may be a polymer containing at least one olefinic bond or ~ halogen. The number average molecular weight of the polymer is at least 1300 and usually ls in the range of about 1500 to about 5000. The ratic of Mw to Mn may be from about 1.5 to ahout 6 and is usually from 1.5 to about 4. Depending upon the ~nount of the reactants utilized to form the substituted succinic acids, and depending upon the type of dispersant desired~ the mole ratio of the polymer to the maleic acid or anhydride in the reaction mixture may be equal to, greater than or less than 1. In some applications, the dispersant is produced containing an average of at least 1.3 succinic moieties per polymer moiety. Arnong the reactive metal compour~ds which may be used to produce the dispersants are alkali met~l compounds such as alkali metal hydroxides, carbonates, alkoxides, oxides, etc. The patentees indicate that the lubricating oil compositions may also contain other additives including auxiliary detergents and dispersants, corrosion and oxidation-inhibi~ing agents, pour point depressing agents, extreme pressure agents, etc.
Summarv of the Invention 2~ A lubricating oil composition is described which comprises a major amount of an oil of lubricating ViSCGsity and (A) at least about 1% by weight of at least one carboxylic derivative composition produced by reacting (A-l) at least one substituted succinic acylating agent containing at least about 50 carbon atoms in the substituent with WO S33/~351)5 PCr/lJS92/08737 æ ~

(A-2~ from about 0.5 equivalent up to about 2 moles, per equivalent of acylating agent ~A-1), of at least one amine compound character-ized by the presence within its structure of at least one lHN~ group; and ~B~ an arnaunt of at least one alkali metal overbascd salt of a S carboxylic acid or a mixture of a carboxylic ~cid and an orgarlic sulfonic acld sufficient to provide at least about 0.002 equivalent of alkali metal per 100 grams of the lubrica~ing oil composition prnvlded tha~ when the alkali metal salt comprises a mixtu~e of overbased alkal~ me~a~ salts of a hydrocarbyl-substitutedcarboxylic acid and a hydrocarbyl-substituted sulfonic acid, then the carboxyllcacid comprises more than 50% of the acid equivalents of the mixture; and either (C-1) at least one magnesium overb~sed salt of an acidic organic compound provided that the lubricating compositiorl is free of calcium overbased salts of acidic organic compounds; or ~C:-2) st least onc calcium overbased salt of an acidic organic compound provided that ~he lubricating composition is free of magnesium overbased salts of acidic organic compnunds.
DescriDtion of the Preferred Embodiments Throughout this speclf ication and claims, refer~nces to percentag~s by weight of the various components are on a chemical basis urlless otherwise indicated. For example, when the oil compositions of the in~ention are describedas containing at leas~ 296 by weight of (A), the oil composition comprises at le~st 2% by weight of (A): on a chemical basls. Thus, if component (~) is available as~: ~ a 50% by weight oil solution, at least 4% by weight of the oil solu~ion would be included in the lubricant composition.
The number of equivalents of the acylating agent depends on the total nuzllber of carboxylic functlons present. In determining the number of equivalen~s for the acylating agents, those carboxyl functions which are not capable of reacting as a carboxylic acid acylating agent are excluded. In general, however, there :is one equivalent of acylating agent for each carboxy group in these acylating agents. For example~ there are two equivalents in an :

WO 93/2350~ PC~/US92/OB737 /' f i,',;',. ,, _~

anhydride derived from the reaction of one mole of olefin polymer and one mole of maleic anhydride. Conventional techniques are readily available for determin-ing the number of carboxyl functions (e.g., acid rlumber, saponification nurnber) and, thus, the number of equivalents of the acylating agent can be readily deter-mined by one skilled in the art.
An equivalent weigh~ of an amine or a polyamine is the molecular weight cf the amine or polyamirle divided by the total nurnber of nitrogens presen~ in the molecule. Thus, ethylene dlamlne has an equivalent weight equal to one-half of its molecular weight; diethylene triamine has an equivalent weight equa1 to one-third its molecular weight. The equivalent weight of a cornmer-cially avail~ble mixture of polyalkylene poly~nine can be dete~nined by dividingthe atomic weigbt of nitrogen (14) by the %N contained in the polyamine and multiplying by 100; thus, a polyarnlne mixture containing 34% nitrogen would have an equivalent weight of 41.2. An equi-valent weight of ammonia or a monoamine is the molecular weight.
An equivalent weight of a hydroxyl-substituted arnine to be reacted with the acylating ~gents to fo2~n the carboxylic derivative ~A~ is its molecular weight divided by the tol:al llwnber of nitrogen groups present in thP molecule.For the purpose of this invention in preparing component (A), the hydroxyl groups are ignored when calculating equivalent weight. l`hus, ethanolamine would have an equivalent weight equal to its molecular weight, and diethanolamine has an equivalent weight ~based on ni~rogen) equal to îts molecular weight.
The terms '1substituent", "acylating agent" and "substituted succinic acylating agent" are to be given their normal meanings. For example, a substituent is an atom or group of atoms that has replaced another atom or groupin a molecule as a result of a reaction. The terms acylating agent or substituted ~~ succinic acylating agent refer to the compound per se and does not include unreacted reactants used to form the acylating agent or substituted succinic acylating agent.

Wo ~3/235V~ P~/USg~/08737 J ~ ~' The term "hydrocarbyl" include~s hydrocarbon, as well as substan-~ially hydrocarboll, groups. Substantially hydrocarbon describes groups which con~ain non-hydrocarbon substitùents Which do not alter the predominately hydrocarbon nature of the gruùp.
Examples of hydrocarbyl groups In~lude the fa}lowing:
~1) hydrocarbon substituents, that is, aliphatic (e.g., alkyl or alkenyl), alicyclic ~e.g., cycloallcyl, cycloalkenyl~ substituents, aromatic-, aliphatic- and alicyclic-substitu~ed aromatic substituents and the like as well as cyclic substituents wherein the ring is completed through another portion of themolecule ~that is, for exarnple, any two indic~ted substituents may together form an alicyclic rad;cal);
(2) substituted hydrocarbon sub~tituent~, that is, those substituents containlng non-hydrocarbon groups which, in the context of this in~ention, do no~ alter the predominantly hydrocarbon substituent; those skilledin the art will be aware of such groups ~e.g., halo (especially chloro and fluoro), hydroxy, alkoxy, r~ercapto, alkylmercapto, nitro, nitroso, sulfoxy, etc.);

(3) hetero substituents, that is, substituents which will, while having a predominantly hydrocarbon character within the contex~ of th,is inventlon, con~ain other than carbon present in a ring or chain otherwise composed of carbon~atoms. Suitable heteroatoms will be ~pparent to those of ordinary skill in the art and include, for exalmp}e, sulfur, oxygen, nitrogen and such substituents as, e.g., pyridyl, furyl, thienyl, imidazolyl, etc. In general, no more than about 2, preferably no more than one, non-hydrocarbon substituent will be present for eve~y lû carbon atoms in the hydrocarbyl group. Often, therewill be no such non-hydrocarbon~substituents in the hydrocarbyl group and the hydrocarbyl group is purely hydrocarbon.
.

:
~, :
~:

~/0 93/235û5 P~/US92/087~7 _9 Oil of Lubricatin~ ViscositY
The oil which is utilized in the preparation of the lubricants of the invention may be based on natural t)ils, synthetic oils, or mixtures thereof.
I~atural oils include animal oils ~nd vegctable oils ~e.g., castor oil, lard oil) as well as mineral lubricating oils such a~ liquid petroleum oils and sol-Yent treated or acid treated mineral lubricstlng oll~ of the paraffinic, naphthenic or mixed parafPinic-naphthenlc types. Oils of lubricating viscosity derlYed fromcoal or shale are also useful~ Synthetic lubricating oils include hydrocarbon oils and halo-substitute.i hydrocarbon oils such as polymerized and interpolymerized olefins ~e.g.) polybutylenes, polypropylenes, propylene-isobutylene copolymers, chlorinated polybu~ylenes, etc.); poly(l-hexenes), pnly(l~octenes), poly(l-dec-enes), etc. and mixtures thereof; alkylhenzenes (e.g., dodecylbenzenes, ~etradecylbenzenes, dinonylbenzeaes, di-(2-ethylhexy~)-benxcnes~ etc.);
polypherlyls (e.g., biphenyls, terphenyls, alkylated polyphenyls, etc.); alkylated diphenyl ethers and alkylated diphenyl sulfides snd the derivatives, analogs andhomologs thereof and the like.
Alkylene oxide polyrners and interpolymers and derivatives thereof where the terminal hydroxyl groups have been modified by esterificatio~, etherification, etc., constitute another class of known synthetic lubricating oils that can be used. These are exemplified by the oils prepared through polymer-ization of ethylene oxide or propylene oxide, the alkyl and aryl ethers of thesepolyoxyalkylene polymers (e.g., methylpolyisopropylene glycol ether having an average molecular weight of about 1000, diphenyl ether of po}yethylene glycol having a mo}ecular weight of abnat 500-1000, dlethyl ether of polypropylene '~ 25 glycQl having a molecular weigh~ of about 1000-1500, etc.) or mono- and polycar-boxylic es~ers thereof~ for example, the acetic acid esters, mixed C3-Cg fatty acid esters, or the C13 Oxo acid diester of tetraethylene ~Iycol.
Another saitable class of synthetic lubricating oils that can be used comprises the esters of dicarboxylic àcîds (e.g., phthalic acidl succinic acid, alkyl succinic ~cids, alkenyl succinic aeîds, maleic acid, azelaic acid, suberic acid, .

:

.

WO 93/23505 P~/US92/08737, ~" ~ r~ ?j 7~

sebacic acid, fumaric acid, adipic acid, linoleic acid dimer, malonic acid, alkyl malonic aclds, alkenyl malonic acids, etc.) with a variety of alcohols le.g., butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, ethylene glycol, diethylene glycol monoether, propylene glycol, etc.) Specific examples of these esters include dibutyl adipate, dl(2-ethylhexyl) sebacate, di-n-hexyl furnarate,dioctyl sebacate, diisooctyl azelate, diisodecyl azelate, dioctyl phthalate/ didecyl phthalate, dieicosyl sebacate, the 2-ethylhexyl diester of linoleic acid dimer, the complex ester formed by reacting one mole of sebacic acid with two moles of tetraethylene glycol snd two moles of 2-e~hylhexanoic acid and the like.
Esters useful as synthetic oils also include those made from Cs to C12monocarboxylic aci~s and polyols and polyol ethers such as neopentyl glycol, trime~hylol propaDe, pentaery~hritol, dipen~aerythritol, tripentaerythrltol, etc.
Silicon-based oils such a~ the polyalkyl-, polyaryl-, polyalkoxy-, or polyaryloxy-~iloxane oils and silicate oils ~ornprise another useful c:lass of synthetic lubrîcants ~e.g., tetraethyl silicate, tetraisopropyl silicate, tetra-(2-ethylhexyl)silicate, tetra-(4-methylhexyl)silicate, tetra-(p-tert-butylphenyl)sili-cate, hexyl-(4-methyl-2-pentoxy)disiloxane~ poly(methyl~siloxanes, poly-(methylphenyl)siloxanes, etc.). Other synthetic lubricating oils include liquid esters of phosphorus containing acids (e.g., tricresyl phosphate, trioctyl phos-phate, diethyl ester of decane phosphonic acid, etc~), polymeric tetrahydrofurans and the like.
Urlrefined? refined and rerefined oils, either na~ural or synthetic (as well as mixtures of two or more of any of these~ of the type disclosed hereinabove can be used in the concentrates of the present invention. Unrefined oils are those obtained directly from a natural or synthetic source without further purification treatment. For example, a shale oil obtained directly from retorting operations, a petroIeurn oil obtained directly from primary distillation or ester oil obtained directly from an esterification process and used without fur~her treatment would be an unrefined oil. Refined oils are similar to the unrefined oils excep~ they have been further treatecl in one or more purification 3/235V~ PCll /~lS92/0~737 ~,.. . , . " . .: ~

steps to improve one or more properties. Many such purification techniques are known to those skilled in ~he art such as solvent extraction, hydrotreating, secondary distillation, acid or base extraction, filtration, percolation, etc~
Rerefined oils ar~ obtained by proces~es simllar to those used to obtain refinedoils applied to refined olls whi h have been already used in ~ervice. Such rerefined oils are also known as reclaimed, recycled or reprocessed olls and often are additionally processed by techniques dlrected to removal of spent additives,oil contaminan~ such as water and fuel, ~nd oil breakdown products.
(A) : ~1!~1~
Component (A) which is utllized in the lubricating oils of the present invention is at lea~t one carboxyl~c deriva~ive composltion produced by reacting (A-l) at least one substituted succinic acylating agent containing at ~east about 50 carbon atoms in the substituent with (A-2) at least one amine compound containing at least one HN~ group. Generally the reaction involves about 0.5 equivalent up to about 2 moles of the amine compourld per equivalent of acylating agent. In one preferred embodiment, the a~ylating agent (A-1) consists of substituent groups and ~uccinic groups wherein the substituent groups are derived from a polyalkene characterized by an Mn value of about 1300 to about 5000 and an Mw/Mn ratio of about 1.5 to about 4.5, and said acylating ~0 agents are further characteri~ed by the presence within their structure of an average of a~ least about 1.3 succinic groups for each equivalent weight of substituent groups.
The carboxylic derivatives ~A) are included in the oil compositions to improve dispersancy and Vl properties of the oil cornpositions. ln ~eneral from about 1% and more often from about 1.5% or 2% to about 10 or 15% by weight of component (A) can be included in the oil compositions, although the oil compositions preferably will contain at least 2.5% and often at least 3% by weight of component (A).
The substi~uted succinic acylating agent (A-1 ) utilized in the preparation of the carboxylic derivative (A) can be characterized by the presence WV g3/~35~ PCr/US9~ 737~.
, 8 ~ ~

within its structure of two ~oups or moieties. The first group or moiety is referred to hereinafter, for convenience, as the ~7substituent group(s)" and is dcrived from a polyalkene. The polyalkene from which the substituted groups are derived is characterized in one embodiment as containing at lcast about 50 S carbon atoms and by an Mn (number average mo}ecular weight) value of from sbout 900 to ~bout 5000 or even 10,000 or higher. In one preferred embodiment the Mn is from about 1300 to about 5000, and an ~w/Mn value of at least about 1.5 or at least 2.0 up to about 4.0 or ~.5. The abbreviation Mw ls the conven-tional syrnbol represen~ing the w~ight average molecular weight. Gel pe~neation chromatography (GPC) is a meth~d which provides both weight average and nurnber average molecular weights as well as the entire molecular weight dls-tribution of the polymers. For purpose of tbis invention a series of fractionated polymers of isobutene, polyisobutene, is used as the calibration standard in theGPC.
The techniques for detel mining Mn and Mw values of pol~ners are well known ~nd are described in numerous books and articles. For example, methods for the dete~nination of Mn and molecular weight distribution of poly-mers is described in W.W. Yan1 J~J. Kirkland and D.D. Bly, "Modern Size Exclusion Liquid Chromatographs", J.Wiley & Sons, Inc., 1979.
The second group or moiety in the acylating agent is referred to herein as the ~Isuccinic group(s)". The succinic groups are those groups characterized by the structure :' O O
ll I I 11 X~C-C-C-C-~
~` I I
wherein X and X' are the same or di~ferent provided at least one of X and ~C' issuch that the substituted succinic acylating agent can function as carboxylic acylating agent. That is, at least one of X and X' must be such that the substituted acylating agent can form amides or amine salts with amino U/O ~3/235~)~ P~/VS92/~8737 f, J

compounds, and otherwise function as a conventional carboxylic acid acylating agent. Transesterification and transamidation reactions are considered, for purposes of this invention, as conYentional acylating reactions.
Thus, X and/or X' is usually -OH, -O-hydrocarbyl, -O-M+ where M~
represents cne equivalent of a metal, ammoniurn or amine cation, -NH2, -Cl, -Br,and together, X and X' can be -O- so as to form the anhydride. The specific identlty of any X or X' group which ls not one of ~he above is not critical so long as its presence does not prevent the remaining group from entering int~ acylation reactions. Preferably, howeYer, X and X' are each such that both carboxyl functions of the succinic group (i.e., both -C~O)X ~nd -C(O)X' can enter into acylation reactions.
One of the unsatisfied valences in the grouping -C-~-of Folmula I fonns a carbon bond with a carbon atom in the substituent group.
While other such unsatisfied Yalence may be satisfied by a simllar bond with thesame or different substituent group, all but the said one such valence is usua~ly satisfied by hydrogen; i.e., -H.
In one embodiment, the substituted succinic acylating agents are characterized by the presence within their structure of at least one succinic group (~hat is, groups corresponding to Formula 1) for each equivalent weight ofsubstituent groups. In a preferred embodiment ~the substituted succinic acylating agents ~re characterized by the presence of an average of at least 1~3 succinic groups for each equivalent weight of substituent groups. For purposes of this invention, the equivalent weight of substituent groups is deemed to be the -number obtained by dividing the ~ln value of the polyalkene from which the substituent is derived into the totai weight of the substituent groups present in the substituted succinic acylating agents. Thus, if a substituted succinic acylating agent is cbaracterlzed by a total weight of substituent group of 5000 W~ ~3/23~05 ~ PCr/US92/0873 æ~ 3~3 -and the Mn value for the polyalkene from which the substituent ~roups are derived is 2000, then that substituted succinic acylating agent is characterizedby a total of 2.5 (S00012000=2 5) equivalent weights of substituent groups.
Therefore, that particular succinic ~cylating agent must also be characterized by the pregence within its structure of at least 3.25 succinlc groups to meet one of the req~Jirements of the succinic acylating agen~s used in this invention~
Ancther requirement for the substltuted succinic acylating agents in a preferred embodiment is that the substituent groups must have been derived from a polyalkene characterized by an Mlw/Mn value of at least about 1.5 or 2ØThe upper llmit of Mw/Mn will generally be sbout 4.0 or 4.5. Values of from 1.5 to about 4.5 are useful, and a ratio of 2 to about 4.5 is particularly useful.
Polyallcenes having the Mn and Mw values discussed aboYe are known in the art and can be prepared ~ccording to conve~tional procedures. For ex~nple, some of these polyalkenes are described and exemplified in U.S. Patent 4,234,435, and the disclosure of this pa~ent relative to such polyalkenes is hereby incorporated by reference. Several such polyalkenes, especially polybl~tenes, are comrnercially available.
In one preferred embodiment, the succinic groups will norrna,lly correspond to the formula , -CH--C(O~R
CH2-C(O)R' (II) wherein R and R' are each independently selected from the group consisting of -OH, -Cl, -O-lower alkyl, and when taken together, R and R' are -O-. In the latter case, the succinic group is a succinic anhydride group. All the succînic groups in a particular succinic acylating agent need not be the same, but they can be the same. Preferably, the succinic groups will correspond to WO ~3/23~0:. P~/US92/08737 -lS-~0 ~0 -CH--C--(:)H -CH--C ~
~` O CH2 C~ (111), (A) (B) and mixtures of ~III(A)) and (III(B)). Prov~ding stlbstituted succinic acylatingagents wherein the succinic groups are the s~ne or different is wi~hin the ordinary sklll of the art and can be accomplished through conventional procedures such as treating the subs~ituted succinic acylating agents themselve~s (for example, hydrolyzing the ~nhydride to the free acid or conver~ing the free acid to an acid chlorlde with thionyl cbloride) and/or selecting the appropriatemaleic or fumaric reac~ants.
As previously mentioned, the minimum number of succinic groups for each equivalent weight of subs~ituent grollp is ~t least 1 and preferably 1.3.
The maximum number generally will not exceed 4.5. In ~nother preferred embodiment, the minimum will be about 1.4 succinic groups for each equivale,nt weight of substituent group. A range based on this minimum is at least 1.4 to ab~ut 3~5, and more specifically about 1.4 to about 2.5 succinic groups per :: 20 equivalent weigh~ of substituen~ groups.
In addition to preferred substituted succinic groups where the preference depends~ on ~the number and identity of succinic groups for each ea,uivalen~ weight of substituent groups,~ still further pref~rences are based on the identity and charscterization of the polyalkenes From which the substituent groups are deri~red.~ ~ ~
~ ~ ~ With respect to the value~of~ Mn for ex~ple, a minimum of about : ~ ~ 1300 and a:maximwn of about 5000 are preferred with an Mn value in the range ~ of from about 15û0 to about 5000 also being preferred. A rnore preferred Mn WO ~3/2350~ PCl /lJS92/08737 J ~

value is one in the range of from about 1500 to about 2800. A most preferred range of Mn values is from about 1500 to about 2400.
Before proceeding to a further discussion of the polyalkenes from which the substituent groups are derived, it should be pointed out that these preferred characteristios of the succinic acylating agents are intended to be understood as being both indepe~dent and dependent. They ~re intended to be independent ~n the sense that, for example, a preference for a minimum of 1.4 or 1.5 succinic groups per equivalent weight of substltuent groups is not tied to a more prPferred value uf Mn or Mw/Mn. Th~r are intended to be dependent In the sense that, for example, when ~ preference for a minirnum of 1.4 or 1.5 succinic groups is combined with more preferred ~alues of Mn ~nd/or Mw/Mn, the combination of preferences does ln fact describe still further more preferred e~bodimer~ts of ~he invention. Thus, the various parameters aFe intended to stand alone with respect to the particular parameter being discussed but can also be combined with other parameters to identify further preferences. This same concept is intended to apply throughout the specification with respect to the description of preferred values~ ranges, ratios, reactan(ts, and the like unless a contrary intent is clearly demonstrated or apparent.
In one embodiment, when the Mn of a polyalkene is at the lower end of ~he range, e~g., about 1300, the ratio of succinic groups to subst~tuent groups derived from said polyalkene in the acylating agen~ is preferably higher than ~he ratio when the Mn is, for example, 1500. Conversely when the Mn of the polyalkene is hlgher, e.g., 2000, the ratio may be lower than when ~he Mn ofthe polyalkene is, e.g., 1500.
I The polyalkenes from which the substituent groups are derived are homopolymers and interpolymers of polymerizable olefin monomers of 2 to about 16 carbon atoms, usually 2 to about 6 carbon atoms. The interpolymers are those in which two or more olefin monomers are in~erpolymerized according to well-known conventional procedures to form polyalkenes having units within their 3~ structure derived from each of sald two or more ole~in monomers. Thus, 5 ~CI`/US92/08737 "interpolymer(s)" as used herein Is inclusive of copolymers, terpolyrners, tetrapolymers, and the like. As wlll be apparent to those of ordinary skill in the art, the polyalkenes from which the substituent groups are derived are often conventionally referred to as "polyolefin(s)".
The olefin monomers from which the polyalkenes are derived are polymerizable olefin monomers characterized by the presence of one or more eth~lenically unsaturated groups (i.e."C=C~); that is, they are monoolefinic monomers such as ethylene7 propylene, butene-1, isobutene, and octene-1 or polyolefinic monomers ~ususlly diol~finic monomers) such as butadiene-1,3 and isoprene.
These oiefin monomers are usually polyrnerizable terminal olefins;
that is, olefins characterized by ths presence in their structure of the group ~C=CH ~. HoweYer, polymerizable internsl olefin monomers ~sometimes referred to in the literature as medial olefins) characterized by the presence withln thelr structure of the group -C-C=C-C-can also be used to form the polyalkenes. When internal olefin monomers a~e employed, they normally will be employed with terminal olefins to produce polyalkenes which are interpolymers. For purposes of this invention, when a particular polymerized olefin monomer can be classified as both a terminal olefin and an internal olefin, it will be deemed to be a terminal olefln. Thus, 1 ,3-pen~a-diene (i.e., piperylene) is deemed to be 8 terminal olefin for purposes of this invention.
`, . I ~ ! j Some af the substltuted succinic acylating agents (A-l) useful in 25 ~ preparing the carboxylic derivatives (A) are known in the art and are described ~~ in, for exarnple, IJ.S. Patents 3,0~7,936 (LeSuer), 3,219,666 (Norman) and 4,234,435 (Meinhardt~, the disclosures of which are hereby incorporated by reference. The acylating agents described in the '435 patent are characterized WO 93/~3505 PCr/US~2/08737 ~f ~ J ,~

as containing substituent groups derived from polyalkenes having an Mn value of about 1300 to about 5000, and an Mw/Mn value of about 1.5 to about 4.
There is a general preference for aliphatic, hydrocarbon polyalk-enes free from aromatic and cycloaliphatic groups. Wi~hin this gcneral preference, there is a further prcference for polyalkenes which are derived fromthe group consisting of homopolymers and interpolylxlers of termillal hydrocarbon olefins of 2 to about 16 carbon atoms. This further preference is qualified by the proviso that, while interpolymers of terminal olefins are usually preferred, interpolymers optlonally containing up to about 40% of pulyrner units derived from internal olefins of up to about 16 carbon atoms are also withirl a preferred group. A more preferred class of polyalkenes are those selected from the group consistlng of homopolymers and Interpolymers of ~erminal olefins of 2 ~o about 6 carbon atoms, more preferably 2 to 4 carb~n atoms. However, anothe.
prefe~red class of polyalkenes ~e the latter more preferred polya}kenes optionally containing up to about Z5% of pol~er units derived from internal olefins of up to about 6 carbon atoms.
Obviously, preparing polyalkenes as described above which meet the various criteria for l~ln and Mw/Mn is within the skill of the art and does not comprise part of the present invention. Techniques readily apparent to those in ~0 the art include controlling polymerization temperatures, regulating the amoun~
and type of polymeriza~ion initiator and/or cata!yst, employing chain ~erminating groups in the palymerization ~procedwe, and the like. Other conventional techniques such as stripping (including vacuurn stripping) a very light end and/or oxidatively or mechanically degrading high molecular weight polyalkene to i` 25 produce lower molecular weight polyalkenes can also be used.
In preparing the substituted succinic acylating agents of this invention, one or more of the above-described polyalkenes ~or halogenated derivatives thereof)is reacted with one or more acidic reac~ants selected from the group consisting of maleic or fumaric reactants of the general formula Vvo ~3/23505 PCI /US92/08737 ,, ", .,v, .,~

X(O)C-CH=CH-C(O)X' ~IV~

wherein X and X' are as defined hereinbefore in Formula I. Preferably the malelc and fumaric reactants w~ll be one or more campounds corresponding to the formula I~CtO) CH-CH C(O)R' (V) wherein R and R' are as preYiously defined in Formula 1I herein. Ordinarily, themaleic or fumaric reactants will be maleic acid, fwnaric acid, maleic anhydride,or a mLlcture of two or more of these. The maleic reactants are; usually pref~Ted o~rer the fumaric reac~ants because the former are ~ore readily available ~nd are, in general, more readlly reac~ed with the polyalkenes (or derivatives thereof) ~o prepare the substituted succinic acylating ~gents of thepresen~ invention~ The especially preferred reac~nts are maleic acld, maleic anhydride, and mixtures oî these~ Due to availability and ease of reaction, maleic anhydride will usually be employed.
lS: Examples of patents describing various procedures for prepari,ng useful acylating agents include U.S. Patents 3,215,707 (Rense); 3,219,66~
(Norman et al); 3,2319587 (Rense); 3,912,764 ~Palmer); 4,110,349 (Cohen); and 4,234,435 ~Meinhardt et al);: and U.K. 1,440,219~ The disclosures of these patents ~: are hereby incorporated by reference.
~ The relative amount of the polyalkene and maleic reactant used in preparing the hydrocarbyl-substituted succinic acids will vary according to the proportion of the succinic acid groups ~esired in the product. Thus, for each mole of the polymer :employed, one or more moles of maleic reactant may be used depending upon: whether one or more ~succinic acid groups are ~o be :~ 25 incorporated in each~polymer molecule. In ~eneral, the higher the molecular weight of the polymer,~ the greater the proportion of maleic reactant which may be used. On the other hand, if a molar excess of the polymer reactant is used, WO 93~235~5 PCr/US92/08737 the excess polymer will simply remain in the product as diluent without adverse effect.
For convenience and brevity, the term "maleic reactant" is often used hereinafter. When used, it should be understood that the term ls generic toacidic reactants selected from maleic and fumaric reactants corresponding ~o Formulae (IV) and (V) ~bove including a mlxture of such reactants.
The acylating reagents described above are interrnediates in processes for preparing the carboxyllc derivative compositions (A) comprising reacting (A-l) one or more acylating reagents with (A-~) at least one amino compound characterized by the presence within i~;s structure of at least one HN~
group.
The amino compound ~A-2) characterize~ by ~he presence within its structure of at least one HN~ group can be a monoamine or poly~Tline compound. Mixtures of two or more amino compounds can be used in the reaction with one or more acylating reagents of this invention. Preferably, the amino compound contains at least one primary amino group (i.e., -NH2) and more preferably the amine is a polyamine, especially a polyamine containing at least two -NH- groups, either or bo~h of which are primary or secondary amines. The amines may be aliphati~, cycloaliphatic, aromatic or heterocyclic amines. The polyamines not only result in c~rboxylic acid derivative compositions which are usually more effective as dispersant/detergent additives, relative to derivativecompositions derived from monoamines, but these preferred polyamines result in carboxylic derivative compositions which exhibit more pronounced Vl improving properties.
A~nong the preferred amines are the alkylene polyamines, including the polyalkylene polyamines. The alkylene polyamines include those conforming to the foImula R3N-(U-N)n-R3 (Vl) , ,., I ,~
r>J DJ
~ I~

WO 93/2350~ P~/US92/08737 ~ u! / / !, ,~ rJ

wherein n is from 1 to about 10; each ~3 i5 independently a hydrogerl atorn, a hydrocarbyl group or a hydroxy-substituted or amine-substituted hydrocarbyl group having up to about 30 atorns, or two R3 groups on different nitrogen atomscan be joined together ~o form a U group, wi~h the proviso ~hat at least one R3 S group is a hydrogen atom and U is an alkylene group of about 2 to about 10 carbon atoms. Preferably U is ethylene or propylene. Especlally preferred are the alkylene polyarnines where each R3 is hydrogen or an amin~substituted hydrocarbyl group w~th the ethylene polyamine~ and mixtures of ethylene polyamines bein~ the most preferred. Usually n wlll ha~ve an a~erage value of from about 2 ta about 7. Such alkylene polyamines include methylene polyamine, ethylene polyamines, butylene polya~nines, propylene polyamines, pentylene polyamines, hexylene polyamines, heptylene polyarnines, etc. The higher homo-logs of such amines snd related amino alkyl-substituted piperazines are also included.
Alkylene polyamines useful in preparing the carboxylic derivative compositions (A~ include ethylene dlamine, triethylene tetramine, propylene diamine, trirnethylene diamine, hexamethylene diamine, decamethylene diamineJ
hexamethylene diamine, decamethylene diamine, octamethylene diamin,e, di~heptamethylene) triamine, tripropylene tetramine, tetraethylene pentarnine, trimethylerle diarnine, peMaethylene hexamine, di~trimethylene)triamine, N-(2 ~minoethyl3piperazine, 1 ,4-bis(2~aminoethyî)piperazlne, and the like. Higher homologs as are obtained by condensing two or more of the above-illustrated alkylene amines ar~ useful, as are mixtures of two or more of any of the afore-described polyamines.
1' ' I ~ ~ ' . ~
2S Ethylene polyamines9 such as ~hose men~ionedabove, are especially useful for reasons of cost and effectiveness. Such polyamines are describecl in dètail under the heading "Diamines and Higher A minesl'in The Encyclopedia of Chemîcal Techn~logy7 Second Edition, Kirk and Othmer, Volume 7, pages 27-3~, In~erscience Publishers, Division o~ John Wiley and Sons,1965, which is hereby incorporated by reference for the disclosure of useful polyamines. Such WO 93/2350~ PCI /IJS92/~8737 21~12'U

compounds are prepared rnost conveniently by the reaction of an alkylene chloride with amrnonia or by reaction of an ethylene imine with a ring-opening reagent such as ammonia, etc. These reactiorls result in the production of the somewhat complex mixtures of alkylene polyamines, including cyclic conden-sation products such as piperazines. The mixtures are par~icularly useful in preparing carboxylic derivative (A3 useful In this invention. On the other hand,quite satisfactory produ~ts can al50 be obtained by the use of pure alkylene polyamines.
Other useful types of polya~ine mixtures are tho~e resulting from stripping of the above-described polyamine mixtures. In this instance, lower molecular weight polyamines and volatile co~ltaminants are removed from an alkylene polyamine mixture to leave 8S re~sidue what is often termed "polyamine bottoms". In general, alkylene polyamine bottoms can be characterized as having less than two, usually less than 1% ~by weight) material boiling below about 200C. In the instance of e~hylene polyamine bo~toms, which are readily available and fcund to be quite useful, the bottoms contain less than about 2g~
(by weight) total diethylene triamine (DETA) or triethylene tetramine ~TErA3.
A typical sample of such ethylerle polyamine bottoms obtained from the Dow (::hemical Company of Freeport, Texas designated "E-100" showed a specific gravity at 15.6C of 1.0168, a percent nitrogen by weight of 33.15 and a viscosity at 40~C of 121 centistokes. Gas chromatography analysis of such a sample showed it to contain about 0.93% "Light Ends" (most probably DETA), 0.72%
TETA, 21.74% tetrae~hylene pentamine and 76.61% pentaethylene hexamine and higher (by weight). These alkylene polyarnine bottoms include cyclic ~ondensa-tion products such as piperazlne and higher anal~gs of diethylenetriamine, triethylenete~ramine` and the like.
These alkylene polyamine bottoms can be reacted solely with the acylating agent, in which case the amino reactant consists essentially of alkylene polyamine bottoms, or they can be used with other amines and polyamines, or ~0 93/2350~ PCr/US92/0~737 alcohols or mixtures thereof. In these latter cases at least one amino reactant comprises alky}ene polyamine bo~toms.
Other polyamines which can be reacted with the acylating agents ~A-l) in accordance with this inYention are described in, for examp~e, U.S.
Patents 3,219,666 and 4,234~435, and these patents are hereby incorporated by reference f~r their disclosures of amines whlch ca~ be reacted with the acylatlng agents described above to form the carboxylic derivatives ~B) of thls invention.ln another embodiment, the amine may be a hydroxyamine.
T3rplcally, the hydroxyamines are primary or secondary alkanol amines or mixtures thereof. Such amines can be represented by the formulae:

H2N~R'-OH, (VII) and R'1N~H3-R'-OH (Vlll) . , whereln each Rll is independently a hydrocarbyl group of one to about eight carbon atorns or hydroxyhydrocarbyl group of two to about eight carbon atoms, preferably one to about four, and R' is a divalent hydrocarbyl group of about ttyo to about 18 carbon atoms, preferably two to about four. The group -R'-OH in such formulae repr~sents the hydroxyhydrocarbyl group, R' can be an acyclic, alicyclic or aromatic group Typically, R' is an acyclic straight or branched alkylene group such as an ethylene, 1,2-propylene, 1,2-butylene, 1,2-octadecyl-enet etc. group. Where two R'~ grollps are present in the same molecule they can be j~ined by a direct carbon-to-carbon bond orthrough a heteroatom ~e g, oxygen, nitrogen or sulfur) to forrn a 5-, 6-, 7- or 8-mernbered ring structure ~amples of such heterocyclic amines include N-(hydroxyl lower al-kyi)-morpholines,-~hiomorpholines, -piperidines, -oxazolidines, -thiazolidines and the like Typically, however, each R'l is independently a methylj ethyl, propyl, bu~yl, pentyl or hexyl group.

Wo 93t235~)5 PCI`/US92/0~737~

Examples of these alkanolamines include mono-, di-, and triethanol amine, diethylethanolamine, ethylethanolarnine, butyldiethanolamine, etc.
The hydroxyamines can also be an ether N-(hydroxyhydrocarbyl-)amine. These are hydroxypoly~hydrocarbyloxy) analogs of the above-described hydroxy amines ~these analogs also include hydroxyl-substituted oxyalkylene analogs). Such N~(hydroxyhydrocarbyl) amines can be conveniently prep~red by reaction of epoxides with afore-described amines and can be represented by the forrnulae:

H2N-~R )x~ (IX) 10 and R'lN(H)-(R C))XH

wherein x is a mLmber from about 2 to about 15 and Rl and R' are as described above. R'l may also be a hydroxypoly(hydrocarbyloxy) group.
The carboxylic deriYative composi~ions (A) produced frorn the 15 acylating reagents (A-1) and the amino compounds ~A-2) described hereinbeforecomprise acylated amines which include amine salts, amides7 imides, amidines, amidic acidst amidi~ salts and imidazolines as well as mixtures thereof. To .
prepare the carboxylic acid deriva~ives from the acylating reagents and the amino compounds, one or more acylating reagents and one or more amino 20 compounds are heated~ optionally in the presence of a normally liquid, substan-tially inert organic liquid solventldiluent, at temperatures in the range of a~out 80C up to the decomposition point of either the reactants or the carboxylic derivative but' normally at temperatures in the range of about 100C up to abou~300C provided 300C does not exceed~ the decomposition point. Temperatures 25 of ~bout 125C to about 250C are norrnally used. The acylating reagent and ~he amino compound are; reacted in amounts sufficient to provide from about one-half equivalent up to about 2 moles of amino compound per equivalent of acylating reagent. ~;

::

WO '33/23505 ~CI`/US9~f08737 Because the acylating reagents (A-l) can be reacted with the arnine compounds (A-2) in the same manner as the high molecular weight acylating agents of the prior art are reacted wilth amines7 U.S. P~tents 3,172,892;
3,2197666; 3,272,746; and 4,Z34,435 are expressly incorporated hexein by reference for tbeir disclosures with respect ~n the procedures applicable to reacting the acylating reagents with the amino compounds as described above.
In order to produce carboxylic derlvatlve compositions ext~ibiting viscosity index improving capabilitles, it h~s besn found gen~rally necessa~7 toreact the acylating reagents witb polyfunc~ional amine reac~ants. For ex~nple, polyamines having two or more primary and/or secondary amino groups are preferred. Obviously, however, it is not necessary that all of the amino com-pound reac~ell with the acylating reag~nts be polyfunctional. Thus, combinationsof mono and polyfunctional amino compounds be used.
The acylating agent is reacted wlth from about 0.5 e~uivalent up to about 2 n oles of the amine compound per equivalent of acylating agent. In another embodiment, the amount of amine m~y range from 0~7 up to about 1.5 equivalents per equivalent of acylatlng age~lt.
In another embodiment, the acylatlng agent is reacted w~th fro,m about 0.5 and more often 0.7 equivalent up to less than 1 equivalent (e.g., about 0.95 equivalent) of amine compound, per equiva1ent of acylating agent. The lower limit on the equivalents of amine compound may be 0.75 or even 0.80 up t.o about 0.90 or 0.95 equlvalent, per equivalent of acylating agent. Thus narrower ranges of equivalents of acyla~lng agents (A-1) to amlne compounds (A-2) may be from about 0.70 to about 0.90 or about 0.75 to abvut 0.90 or about 0.75 to about 0.85. It appears, at least ln some situations, that when the equivalent of amine compound is about 0.75 or less, per equivalent of acylating agent, the effectiveness of the carboxylic derivative as a dispersant is reduced.
In yet another embodiment, the acylating agent is reacted with from about 1~0 equivalent up to 2 moles of amine per equivalent of acylating WO ~3/~350~ PCl/US92/08737"~,, agent. More often the acylating agent is reacted with from abou~ 1.0 or 1.1 up to 1.5 equivalents of amine per equivalent of acylating agent.
The arnaunt of amine compound (A-2) within the above ranges that is reacted ~vith the acylating agent (A-l~ may also depend in part on the numberand type of nitrogen atoms present. For example, a smaller amount of a polyamine containing one or more -NH2 grQups is required to react wi~h a given acylating agent than a polyamlne having the same numiber of nitrogen atoms and fe,wer or no -NHi2 groups. One -~H2 group can react with two -COOH groups to form an imide. If only secondary ni~rogens are present in the amine compound, each ~NH group can react with only one -COO~I group. Accordlngly, the amount of polyamine within the above ranges to be reacted with the acylating agent to form the carboxylic derivatives of the inYention can be readlly determined from a consideration of the nwnber and types of nitrogen atoms ln the polyamin~i ~l.e., -NH2, ~NH, and ~N-).
In addition to the relative amounts of acylating agent and amine compound used to formi the carboxyl~c derivative composition (A), other fea~uresof the carboxylic derivative compositions used in this invention are the Mn and the Mw/Mn valu~ of the polyalkene as well as the presence wlthin the acylating agents of an average pf a~ least I and preferably at least 1.3 succinic groups for 2~ each equivalent weight of substituent groups. When all of these features are present in ~he carboxylic derivative compositions (A), the lubricating oil compositions of the present invention are characterized by improved perfor-mance in combustion engines.
The ratio of succinic groups to the equivalent weight of substituen~
group present in the acylating agent can be determined from the saponification number of the reacted mixture corrected to account for unreacted polyalkene present in the reaction mixture at the end of the reaction (generally referred to as filtrate or residue in the following examples3. Saponification nwnber is determined using the ASTM D-94 procedure~ The formula for calculating the ratio from the saponification number is as follows:

` ~:

WO ~3/23S05 PClr/US92/08737 ",",.

Ra~io = (Mn)(SaD No.~corrected?
112,200-98(Sap No.,corrected) The corrected saponifica~ion number is obtained by dividing the saponific~tiun nurnber by the percent of the polyalkene ~hat has reacted. For example, if 10% of the polyalkene dld not react and the saponification number of the filtrate or residue is 95, the corrected saponificatlon number is 95 divided by 0.90 or 105.5.
The preparation of the acylatlng agents is Illus~rated in the following Examples 1-6 and the prepara~ion of the carboxylic acid derivative lû compositions ~A) is illus~ated by the following Examples A-1 to ~-29. In the following ex~nples, and elsewhere in the speciflca~on and clalms, all percentag~es and par~s are by weight~ temperatures are in degrees centi~rade and pressuresare atInospheric unless ntherwise clearly indicated. The deslred ~cylating agents are some~imes referred to in the examples as "residue" without specific determination or mention of other materials present or the amounts thereof~
Acy~atin~ents Example 1 A mixture of 510 parts (0.28 mole) of polyisobutene (Mn=1845;
Mw=5325) and S9 par~s (0.59 mole) of maleic anhydride is heated to 110C. This mixture is heatcd to 190~C in 7 hours durin~ which 43 parts (0.6 mole) of gaseous chlorineisaddedbeneaththesurface. At 190-192Canadditional 11 parts(0,16 mole) of chlorine Is addcd over 3.5 hours. Thc reaction mi~ture is stripped by hea~ing at 190-193~C with nitrogen blowing for 10 hours. The residue is the desired polyisobutene-substi~uted succinic acylating agent having a saponification equivalent nwnber of 87 as~ determined by ASTM procedure D-94.
Example 2 A mixture of 1000 parts ~0.495 mole) of polyisobutene ~Mn=2020;
Mw=6049) and 115 parts (1.17 moles) of maleic anhydride is heated to 110C.
This mixture is heated to 184C in 6 hours during which 85 parts (1.2 moles) of :

WO 93/23505 PiCr/US9~518737 .
3 ;LJ e~

gaseous chlorine is added beneath the surface. At 184-189C an additional 59 parts (0.83 mole) of chlorine is added over 4 hours. The reaction m~cture is stripped by heating at 186-190C with nitrogen blowing for 26 hours. The residueis the deslred polyisobutene~ubstituted succinic acylating agent having a sapon~fication e~ulvalent number of 87 aS deterrïlined by ASTM procedwe D 94.
Example 3 A mixture of 3251 par~s of polyisobutene chloride, prepared by the , addition of 251 parts of gaseous chlorlne to 3000 parts of polyis~butene (Mn=1696; Mw=6594) at 80C in 4.66 hours, and 345 parts of malelc anl~ydride is heated to 200C in Oi,5 hour. The reaction mixture is held at 200 224C f~ 6.33 hours, stripped at 210C under vacuum and fil~ered. The filtrate is tbe desired polyisobutene-substituted succinic acylating agent having a saponifica~ion equivalent number of 94 as determined by ASTM procedure D-94.
Example 4 A polyisobutenyl succinic ~nhydride is prepared by the reaction of 1 mole of a chlorinated polyisobutyleDe wlth 1 mole of maleic anhydride at 200C. The polyisobutenyl group has an average molecular weight of 8~0, and the resulting substi~uted succinic anhydride is found to have an acid n~nber pf 113 ~corresponding to an equlvalent weight of 500).
Example 5 A polyisobutenyl succi~lic anhydride having an acid nurnber of 105 and an eguivalent weight of 540 is prepared by the reaction of 1 mole of a chlorinated polyisobutylene ~having an Mn of about 1050 and a chlorjne conten~
of 4.3%) and 1 mole of maleic anhydride at a temperature of about 20QC.
Example 6 A substituted succin~ic anhydride is prepared by reacting 1 mole o~
maleic anhydride with 1 mole of 8 chlorinated copolymer of isobutylene and styrene. The copolymer consists of 94 parts by weight of isobutylene units and 6 parts by weight of styrene unit~s,~ has an Mn of about 1200, and is chlorinated : `

WO 93/2350~ PCI /US92/08737 to a chlorine content of 2.8% by weight. The resulting substituted succinic anhydride has an acid number of 40.
Carboxvlic Derivative Compositions (AL
E:xample A-1 A mixtllre is prepared by the addltion of 10.2 parts ~0.25 equiva-lent) of a con~nercial mixture of ethylene polyamin~ having frnm about 3 to about 10 nitrogen atoms permolecule tu 113 parts of mineral oll and 161 par~s (0.25 equivalent) of the substltu~ed SUCCilliC acylatlng agent prepared in Exarnple I at 138G The reaction ml~ture is heated to 150C in 2 hours and stripped by blowing with nitrogen. The reaction rnixture is filtered ~o yield the flltrate as an oil solution of the desired product.
E:xample A-2 A mixture is prep~red by the addition of 57 parts (1.38 equivalents) of a commercial mixture of ethylene polyamines having from about 3 to 10 nitrogen atoms per molecule ~o 10~7 parts of mineral oil and 8~3 parts (1.38 equivalents) of the subs~ituted succinic acylating agent prepared in Exarnple 2 at 140-145~C. The reaction mixture is heated to 155C in 3 hours and stripped by blowin~ with nitrogen. The reaction mixture is filtered to yield ~he filtr~teas an oil solution of the desired produ~t.
E:xample A-3 A mixture of 1132 parts of mineral oil and 7a9 parts (1.2 equiva-lents) of a substituted succinic acylating agent prepared as in Example 1 is prepared, and a solution of 56.8 parts of piperazine (1.32 equivalents) in 200 parts of water is added slowly from a dropping funnel to the above mixture at 13û-140~C over approximately 4 hours. Heating is continued to 160C as water is removed. The mixture is maintained at 160-165C for one hour and cooled o~erni~ht. After reheatlng the mixture tO 160C, the mixture is main~ained at this temperature for 4 hours. Mineral oil ~270 parts) is added, and the mixture is filtered at 150C through a filter aid. The filtrate is an oil solution of the desired product (6S% oil) containing 0.65% nitrogen (theory, 0.86%).

W~ 93/~3505 Pcr/US9~/0~737 ~f ~, ,')$ ,i ,,~, ~ ,.;

Example A-4 A mixture of 1968 parts of mineral oil and 1508 parts ~2.5 equivalents) a substituted succinic acylating agent prepared as in Exarnple 1 ishested to 145C whereupon 125.6 parts ~3.0 equivalents~ of a commercial mixture of ethylene polyamines as used in Ex~nple ~-1 are ~dded over a period of 2 hours while maintaining the reaction temperature at 145--150C. The reaction rnixture ls stirred for 5.5 hours at 150-152C while b}owlng wlth nitrogen. The mixture is filtered at 150C with a filter aid. The filtrate is an oil solution of thei desired product (55g6 oil) contalning l.Z09~ nitrogen (thearyl 1.17).
Example A-5 A mixture of 4082 parts of mineral oil and 250.8 partQi (6.24 equivalents) of a commercial mixture of ethylene polyamine of the ~rpe utilized in E:xample A-} is heated tu 110C whereiupon 3136 parts (5.2 equivalents) of a substituted succinic acylating agent prepared as itl E:xample 1 are added over aperlod of 2 hours. During the addition, the temperature is maintained at 110-120C while blowing wlth nitrogen. When all of the amine has been added, the mixture is heated to 160C and maintained at this temperature for about 6.5 hours while removing water. The mixture is filtered at 140C with a filter aid, ~nd the filtrate is sn oil solution of the desired product (55% oil) containing l.I7% ni~ragen (theory, 1.18).
Example A-6 A mixture of 4158 parts of mineral oil and 3136 parts ~5.2 equivalents) of a substituted succinic acylating agent prepared as in Example 1 is heated to 140C whereupon 312 parts (7.26 equivalents) of a commercial 2S mix~ure of ethylene polyam(nes as used in Example A-1 are added over a period of one hour as the temperature increases to 140-150G. The mixture is maintained at 150C for 2 h~urs while blowing with nitrogen and at 160C for 3 hours. The mixture is filtered at 140C wlth a filter aid. The filtrate is an oil solution of the desire~ product ~55% oil) containing 1.44% nitrogen ~theory, 1.34).
: ~:

WO ~3/2350~ PCr/US92/û8737 ~,, , . ~

Example A-7 A mixture of 4053 parts of rnineral oil and 287 parts (7.14 equivalents~ of a eommercial mixture of ethylene polyamines as used in Example A~l is heat~d to 110C whereupon 3075 parts (5.1 equivalents) of a substituted succlnic acylating agent prepared as ~n Example 1 are added over a period of onehour while maintaining the ~emperature at about 110C. The mixturP is heated to 160C over~ a period of 2 hours and held at th~s temperature for an addîtional 4 hours. The reaction mixture then is filtered at 150C with filter aid, and thefiltra~e is an oil solution of the desired produc~ (55% oll) co2~aining 1.33%
nitrogen (theory, 1.36).
E:xample A-8 A mixture of 1503 parts of mirleral oil and 1~20 parts (2 equiYa-lents) of a substituted succinic acylat~ng ~gent prepared as in Example 1 is heated to 110C whereupon 120 parts ~3 equivalents) of a commerclal mixture of ethylene polyamines of the type used in Example A-1 are added over a period of about 5U minutes. The reaction mixture is stirred an additional 30 minutes at110C, and the ~emperature is then rais~d to and maintained at about 151C Por 4 hours. A filter aid is added and the mixture is filtered. The filtrate is an oil solution of the desired product (53.2% oil) containing 1.44% rlitrogen (theory, 1.4g).
Example A-~
A mixture of 3111 parts of rnineral oil and ~44 parss ~21 equiva-lents~ of a con~nercial mixture of ethylene polyamine as used in Example A-l is heated to 140C whereupon 3885 parts (7.0 equivalents) of a substituted succinicacylating agent prepared as in Example 1 are added over a period of about 1.75 hours as the temperature increases to about 1 50C. While blowing with nitrogen,the mixture is maintained at 150-155C for a period of about 6 hours and thereafter filtered with a filter aid at 130C. The filtrate is an oil solution of the desired product (40% oil) eontaining 3.5% nitrogen (theory, 3.78).

WO 93/2350~ PCr/~lS92/0~73 Example A-10 A mixture is prepared by the addition of 18.2 parts (0.433 equivalent) of a commercial mixture of ethylene pnlyamines having from about 3 tv 10 rlltrogen atosns per molecule to 392 parts of mineral oll and 348 parts (0.52 equlvalent) of ~he substltuted succinlc a~ylating agent prepared in Example 2 at 140CC. Th~ reaction mixtur~ i5 heated to 150C in 1.8 hollrs and stripped by blowing with nitrogen. The reac~ion mixture Is filtered to yield the filtrateas an oil solution (55% oil) of the desired product.
Exampl~ A-1 1 110 An appropria~c size flask fit~ed with a stirrer, nitrogen inlet tube, addl~ion funnel and Dean-Stark trap/condenser is charged with a mixture of 2483 parts acylating agent (4.2 equivalents) as described in Fxample 3, and 1104 r~ar~s oi}. This mixture :s heated to 710C while nitrogen was slowly bubbled through the mixture. Ethylene polyamine bottorrls (134 parts, 3.14 equivalents) are slowly lS added sver about one hour at this temperature. The temperature is maintained a~ about 210C for 3 hours and then 3688 parts oil is added to decrease the temperature to 125C:. Af~er s~orage at 138C for 17.5 hours, the mixt:ure is filtered through diatomaceous earth to provide a 65% oil solution of the desiredacylated amine bottoms.
Example A-12 A mixture of 3660 parts (6 equivalents) of a substituted succinic acylating agent prepared as in Example 1 in 4664 parts of diluent oil is prepared and heated at about l l O'C whereupon nitrogen îs blown through the rnixture. Tothis mixture there are then added 210 parts: ~5.25 equivalents) of a cornmercialmixture of ethylene polyamines containing from about 3 to about 10 nitrogen atoms per molecule over a period of one hour and the mixture is maintained at 110C for an additional 0.5 hour. After~heating for 6 hours at 155C while removing water, a filtrate is added and the reaction mixture is filtered at about 150~. The filtrate is the oil solu~ion~ o~ the desired product.

WC~ 93/23S05 P~/US92/08737 X.~

Example A-13 The general procedure uf Example A-12 is repeated with the excepti~n tha~ 0.8 equi-ralent of a substltuted succinic acylating agent as prepared in E~sample 1 is reac~ed with 0,67 equivalent of the commercial mixtureof ethylene polyamines. The product obtained in thls manner is an oil solutlon of the product c~ntaining 5S% diluent oil.
Example A-14 The general procedure of E:xampl~ A-12 is repeated except that the polyamirle u~sed in thls example is an equivalerlt amount of an allcylene polyamine mixture comprising 80~ of ethylene polyamine bottoms from Union Carbide and 20% of a commercial mixture of ethylene polyamines corresponding in emplrical formula to diethylene triamine. l`hls polyamine mixture is charac~erized as having an equivalent weight of about 43.3.
Example A-15 Th~ general procedure of ExaTnple A-12 is repe~ted except that the polyamine utilized In this example comprises a mixture of 80 parts by weight of ethylene polyamine bottoms available from Dow and 20 parts by weight of diethylenetriamine. This ~Ixture of amines has an equivalent weight of ab~lt 41.3.
.
Example A-16 A mixture of: 444 parts (0.7 equivalent) of a substltuted succinic acylating agent prepared as in Example 1 and 563 parts of mineral oil is prepared and heated to 140C whereupon 22.2 parts of an ethylene polyamine mixture corresponding in empirical formula to triethylene tetramine (0.58 equivalent) are added oYer a period of one:hour as the temperature is maintained at 140C. The mixtllre ~is blown with nitrogen as it is heated to 15ûC and maintained at thistemperature for 4 hours while remo~ring water. The mixture then is filtered through a filter aid at about 135C,~ and the filtrate is an oil solution of thedesired product comprising about 55% of mineral oil.

WC) 93/2350s PCI /US~/0~737 2 i ~

Example A-17 A,mixture of 422 parts (0.7 equivalent) of a substituted succinic acylati~g agent prepared as in Example 1 and 188 parts of mineral oil is prepared and heated to 210C whereupon 22.1 parts (0.53 equivalent) of a cosnmercial mixture of ethylene polya~nine bottorns from Dow are added over a period of one hour blowing with nltrogen. The temperat~Lre then is increased to about 210-216C and maintained at this temperature for 3 hours. Mineral oil (625 parts) is ~dded and the mixture is malntained at 135C for about 17 hours whereupon the mixture is filtered and the filtrate is an ail solution of the desired product (65% oil).
Exa~nple A-18 The gen~ral procedure of Example A-17 is repeated except that the polyamine used in this example is a co~ ercial mixture of ethylene polyamines havlng from about 3 to 10 nltrogen atoms per molecule (equivslent weight of 42).Ex~nple A-19 A mi~ture is prepared of 414 parts (0.71 equivalent) of a substitut-ed succinic acylating agent prepared as in Exarnple 1 and 183 parts of mineral oil. This mixture is heated ~o ~10C whereupon 20.5 parts (0.49 equivalent),of a commercial mixture of ethylene polyamilles having from about 3 to 10 nitrogen atoms per molecule are added o~er ~ period of about one hour as the tempera-ture ls inreased to 210-217~C. The reaction mixture is maintained at this temperature for 3 hours while blowing with nitrogen, and 612 parts of mineral oil are added. The mixture is maintained at 145-135C for about one hour, and at 135C: for 17 hours. The mixture is filtered while hot, and the filtrate is an ; ~ i ! j , oil solution of the de~ired product (65% oil~.
Example A-20 A mixture of 414 parts (0.71 equivalent~ of a substituted succinic ~; : acylating agent prepared as in Example 1 and 184 parts of mineral oil is prepared and heated to about 80C whereupon 22.4 parts (0.534 equivalent) of melamine are added. The mixture is heated tO 160C over a period of about 2 hours and WO 93/2350~ PCr/U~g2/08737 ;) f~ J

maintained at this temperature for 5 hours. After cooling overnight, the mixtureis heated to 170C over 2.5 hours snd to 215C over a period of 1.5 hours. The mixture is maintained at abou~ 215C for about 4 hours and at about 220C for 6 hours. After cooling overnight~ the reaction mixture i5 filtered at 150C:
through a fllter aid. The filtra~e i5 an oll solution of the desired product (30%
mineral oil).
Example A-21 A mixture of 414 parts (0.71 equivalent) of a substituted acylating agent prepared as ln E~ample 1 and 184 parts of mineral oil is heated to 21aC
whereupon 21 parts (0.53 equivalent) of a commercîal mixture of ethylene polyamine corresponding in empirical formula to tetraethylene pentamine are added o~rer a period of 0.5 hour as the temperature is maintained at about 21~217C. Vpon completion of the addition of the polyamin~, the mixture is maintained at 217C for 3 hours while blowing with nitrogen. Mineral oil is added (613 parts) and the mixture is maintained at about 135C for 17 hours and filtered. The flltrate is an oil solution of the desired product (65% mineral oil), Example A-22 A mixture of 414 parts (0.71 equivalent) of a substituted acylati~lg agent prepared as in E:xample 1 and 183 parts of mineral oil is prepared and heated to 210C whereupon 18.3 parts (0.44 equivalent) of ethylene amine botto ns (Dow) are added o~er a period of one hour while blowing with nitrogen.
The mixture is heated to about 210-217C in about 15 minutes and maintained at this ~emperature for 3 bours. An addltional 608 parts of mineral oil are added ~ and the mixlture is maintained a~ about 135C for 17 hours. The mixture is filtered at 135C through a filter aid, and the filtrate is an oil solution of the desired product (65% oil).

.

WO ~3/23505 PCI /US92/08737 ~2 I Q ? ~

F,xample A-23 The general procedure of Example A-22 is repeated except ~hat the ethylene arnine bot~oms are replaced by an equivalent amour~t of a corr~nercial mixture of ethylene polyamines having frum about 3 to 10 nitrogen atoms per molecule.
E:xample A-~4 A mlxture of 422 parts ~0~70 equivalent) of a substituted acylatlng agent prepared as in l~ample 1 and l90 p~ s of mineral oil is heated to 210C
whereupon 26.75 parts (0.636 equi~ralent) ~f ethylene a-nine bvttoms ~Dow) are added over one hour while blowing with rli~rogen. After all of the ethylene amine ls added, the mixture is maintained at ~10-21S~C for about 4 hours, and 632 parts of mineral oil are added with stirring. This m~x~ure is maintained for17 hours at 135C ~nd filtered ~hrough a filter aid. The filtrate i5 an oil solu~ion of the desired product ~65% oil)~
Example A-25 A mlxture of 468 parl:s (û.8 eqllivalent) of a substltuted succinic acylating agent prepared as in E~xample 1 and 908.1 parts of mlneral oil ls heated to 142C whereupon 28.63 parts ~0.7 equivalent) of ethylene amine bottoms (Do,w)are added o~rer a period of 1.5-2 hours. The mixture was stilTed an additional 4hours at about 142C and filtered. The filtrate is an oil solution of the desired product ~65% oil).
Example A-26 A mixture af 2653 parts of a substituted acylating agent prepared as in Exarnple 1 and 1186 parts of mineral oil is heated to 210C whereupon 154 parts of ethylene amine bottoms (Dow~ are added over a period of 1.5 hours as the temperature is maintained between 210-~15C. The mixture is maintained at 215-220C for a period oî about 6 hours. Mineral oil (3953 parts) is added at210C and the mixture is s~irred fur 17 hours with nitrogen blowing at 135-128C.
The mixture is filtered hot through a filter aid, and the filtrate is an oil solution of the desired product (65% oil).

Wo 93/23505 PC~US92/08737 ? ' ?

Example A-27 To a mixture of 5ûO parts (1 equivalent) of the polyisubutenyl succinic anhydride prepared ln Example 4, and to 160 parts of toluene, there areadded at room temperature, 35 par~s (1 equivalent) of diethylene triamine. The addition is made portionwise through a period of 15 minutes, and an initial exothermic reaction caus~s the temperature to r~e to about 50C. The mlxture is heated and a water-toluene azeo~rope Is distilled from the mixture. YVhen no additional water distills, the mixture is he~ed to 150C at reduced pressure to remove the toluene. The residue is dlluted with 300 parts of mineral oil, and this solution is found to have a nitrogen content of 1.6~.
Example A-28 To a mixture of 300 parts by weight of the polyisobutenyl succinic anhydride prepared ln Example 5, and 16û parts by weight of miner~l oil, there is added at 6S-95C, an equivalent amount ~25 parts by weight) of Polyamin~ H
wh~ch is an ethylene~nine mixture having an average composition corresponding to that of tetraethylene pentamine. The mixture is then heated to 150C to distill water formed in the reaction. Nitrogen is bubbled through the mixture atthis temperature to insure removal of the last tr~ces of water. The residue, is diluted with 79 parts by weight of mineral oil, and this oil solution is found to have a nitrogen content of 1.6%.
Example A-29 To 710 parts (0.51 equivalent) of the substituted succinic anhydride prep~ed in E:xample 6, and 500 parts of toluene there are added portionwise 22 parts (0.51 equivalentj of Polyamine H. The mixture is heated at reflux temperature for 3 hours to remove water formed during the reaction by azeotropic distillation. The mixture then is heated to 150C/20 mm. to remove the toluene. The residue contains l.l% by weight of nitrogen.
(B) Alkali Metal Overbased Salts of HydrocarbYI-Substituted Carboxylic Acids.
The lubricating oll compositions of the present invention also contain (8) an alkali metal overbased salt of a carboxylic acid or a mixture of WO 93/2350~ PCr/US~2/0873?

-3~-a carboxylic acid and an organic sulfonic acid provided that the carboxylic acidin the mlx~ure comprises more than 5Q% of the acid equivalents of the mixture.
The carboxylic acids are generally hydrocarbyl-substituted carboxylic acids wherein the hydrocarbyl substituent generally contains at least about 8 carbon atoms, and preferably contains at le~st 50 carbon atoms.
The amount of the alkali metal overbased salt of ~he hydrocarbyl-substituted carboxylic acid or r~ixlture of carboxylic acid and sulfonic scid included in the }ubricating oil compositions vf the present invention is an amount sufflcient to provide at least about 0.002 equiva1ent of alkali metal per 100 grams of lubricating oil composition. ïn other embodiments, sufficient alkali metal overbased salt is included in the lubricating oil composition to provide at least about 0.003 snd even at least about O.OOS equivalent of alkali metal per I00 grams of the lubricating oil composition.
The alkali metal overbased salts (B) are characterized by a metal content in excess of that which would be present according to the stoichiome~ry of the metal and the particular hydrocarbyl-substituted carboxylic acid reacted with the metal. The amount of excess metal is commonly expressed in terms of metal ratio which is the ratio of the total equivalen~s of the metal to the equivalents of the acidic organic compound. For example, a salt having 4.5 timesas much metal as present în a nonnal salt is characterized as having a metal ratio of 4~5. In the present invention, the alkali metal overbased salts have a metal ratio of greater than 1, preferably at least about 1.5 or at least about 2or 3 up to about 30 or even up to about 40. In yet another embodiment the metal ratis:~ is at least about 6.5.
The alkali metal overbased compositions are prepared by reacting an acidic material which is typically~ carbon dloxide with a mixture comprising the carboxylic aci~ or mixture of carboxylic and sulfonic acids, of an alkali metal :: compound, typically a nnetal oxide or hydroxide, a promoter and at least one inert organic diluent ~or the carboxylic acid compound.

)93/23505 PCI/US92/08737 .~','; S ~ Jl The carboxylic ~cids from ~rhich useful al~ali metal o~erbased salts can be prepared include aliphatic, cycloaliphatic and aromatic mono- and polybasic carboxylic acids. The aliphatlc acids generally will contain at least about 8 carbon a~oms and preferably contain at least abou~ 12 carbon atoms. I
one embodiment, the ~liphatic acids contaln from 8 to about 50 carbon atoms and prefer~bly from about 12 to about 25 carbon atoms. The aliphatic mono- and polycarboxylic acids are preferred, and they may be saturated or unsat~Lrated.
The allphatic carbox~lic acids include fatty ~clds wherein there are present at lcast about 12 carbon a$oms such~ or ~x~nple, palmitic, stearic, myristlc, olelc, linolelc aclds, etc. Exa~nples of allpha~ic-substituted aromatic acids include stearyl-benzoic acid, mono- or polywax-substituted benzoic or napthoic acids wherein the wax group contains at leas~ about l8 carban atosns, cetyl bydroxy benzoic acids, etc. xamples of c3~cloaliphatlc carbox~ylic acids include hydrocarbyl-substituted cyclopenta~oic acids, hydrocarbyl-substituted cyclohex-l 5 anoic acids, etc~
A preferred type of carboxylic acid usefu1 in preparing the alkali metal overbased salts (B) is prepared by reacting an olefin polymer or halogenat-ed alefin polymer with an a,J~-unsa~urated ~cid or its anhydride such as acryl~c, methacrylic, maleic or fumarlc scid, or maleic anhydride to form the corre-sponding hydrocarbyl-substituted acid or deri~ative thereof. Thus the hydro-carbyl groups of ~he hydrocarbyl-substituted carboxylic acids and hydrocarbyl-subst~tut:ed sulfonic acids may be derived from polyalkenes. The molecular weight of ~he polyalkenes may vary wlthin broad limits such as from 100 to about50,000 or even higher. Polyalkenes having molecular weights of from about 250 to about 5000 are especially useful. In one preferred embodiment, the polya}kenes may be chara~terized ~as containing at least about 50 carbon atoms up to about 300 or 400 carbon atoms. In one embodiment, the polyalkene is characteri~ed by an ~In value of at least about 9ûO or 1000 up to about 2500 or even up to about 5000.

Wo 93/23505 PCr/US92/OB737 2 1 1~ 3 The polyalkenes from which the hydrocarbyl subs~ituent of the acld is derived include homopolymers nnd interpolymers of polyrnerizable olefin monomers of from ~ to abou~ 16 carbon atoms, usually from 2 to about 6 carbon atoms, and preferably from 2 to about 4 ca-bon atcrns. The olefins may be monoolefisls such as ethylen~, propylerle, 1-butex~e, Isobutene and l-octene or a polyolefinlc rnonorner, preferably diolefi~lic monomer such as 1,3-butadiene andisoprene. The polyalkenes are prepared by conventional procedures. Additional examples of polyalkenes from which the hydrocarbyl substituen~ of the succinic and sulfonic acids can be derlved Include any oî the polyalkenes described abovewith regard to the preparation of th2 acylating agen~ ~A-1), and that portion ofthe specification describing such polyalkenes is here~n irlcurporated by reference.
When preparing the hydrocarbyl-subs~ituted carboxylic acids useful in preparing the ~Ikali metal salts utilized in the present invention, one or more of the above-described polyalkenes ls reacted with one or mor~ a,~-unsaturated mono- or dicarboxylic acid reagents by techniques known ln ~he art. Fa)r example, a halogenated hydrocarbon such as can be obtained from polylsobutene and a halogenating agent can be reacted with an a"B-unsatura~ed carboxylic acid reagent by mixing the reactants at a suitable temperature such as 8ûC ,or higher. The reactlon can be caITied out in the presence of an inert solvent or diluent.
The ~ unssturated monocarboxylic acid reagent may be ~he acid, ~ter, amide, imide, ~onh~m salt, or halide. It preferably contains less than about 12 carbon atoms. Exampl:es of such monocarboxylic acids include, for e~Yslnple, acrylic acid, m ethacrylie acid (i.e., a- m ethylacrylic acid), crotonic 2~ acid, cinnamic acid9 cL-ethylacr~lic acid, ~-phenylacrylic acid, a-octylacrylic :
acid, ~-propylacrylic acid, ~-octylacrylic acid9 ~-cyclohexylacrylic acid, u-cyclopentylacrylic acid, ~-decylacrylic acid, a-meth~l-,B-pentylacrylic acid1 -propyl-~-phenylacrylic acid, -chloroacrylic acid, a-bromoacrylic acid, ~-chloroacrylic acid, -chlorocrotonic acid, isocrotonic acid, a-methylcrotonic acid, a-methylisocrotonic acid, ~,~-dichloroacrylic acid, etc .

~1VO 93/~3505 P~T/VS~2/0~737 n l 1 ~ r~ CJ 'J ~

Esters of such a,~-unsaturated carboxylic acids especially those in which the ester group is derived from a lower alkanol ~i.e., having less than about ~ carbon atoms) likewise are useful in the invention. Specific examples of such esters include methyl acrylate, methyl methaerylate~ ethyl acryl~te, cyclohexyl acrylate, cyclopentylmethacrylate) neopentyl a~-phenyloacrylate, hexyl a-propyl-~-propylacrylate, octyl ~-de- ylacrylate and the like. Other esters such as thase derived from other alcohols (e.g., decyl alcohol, epichlorohydrin"~-chloroethanol, dodecyl alcohol, and 4-bromo-1-decanol) are also contemplated. 5tlll other esters which ~re useful in the invention ~re eJcempllfied by those deri~red fromphenolic compounds including phenol, naphthol, cresol, o-butylphenol, m-heptylphenol, p-tertiary butylpbenol, o,p-diisopropylphenol, a-decyl-~-naphthol,p-dodecylphenol, and other alkyl phen~ls and alkyl naph~hols in whlch the alky1 substituent preferably has less than about 12 carbon a~osns.
The halides of ~he e~,~-unsaturated monocarboxylic acids are principally the chlorides and bromides. They are illustrated by acrylyl chloride, methacrylyl brom~de, a-phenylacrylyl chloride, ,B-decylacrylyl chloride as well as the chlorides and bromides of the above-lllustrated acids. The amides and theammonia salts of ~ unsaturated monocarboxylic acids include principally tho,se derived from a~nmonia or a monoamine such as an aliphatic ~nine or an aryl amine. Such amlnes may be mono-, di- or trialkyl or aryl amirJes sucb as methylamine, d~methy!arnine, trimethyIamine, diethylamine, aniline, toluidine, cyclohexylamineg dicyclohexylamine, triethylamine, melamine, piperazine, pyridine, N-methyloctylamine, N9N-dlethylcyclohexylamine, o-butylaniline, p-decylaniline, etc. ~ Again the unsaturated acids from which the am~des and ammoniurn salts of:~he above amines may be those illustrated previously. Imides of such acids derived from ammonia or a primary amine likewise are useful in the invention and the Imides are forrned by the replacemen~ of 2 hydrogen atoms of ammonia or a primary amine with the carboxy radicals of the a"B-unsaturated .
monocarboxylic acid. Likewise useful are the anhydrides of such monocarboxylic acids such as are: formed by molecular dehydration of the acid. It should be :

WO 93~23~0~ P~r/~JS~2~08737 ~ 3 ~ 2 ~ 42-noted that the above-noted aclds and derivatives are capable of yielding the a"B-unsatursted monocarboxylic acld and, for the sake of convenience, they are described by the generic expressions "a,~-unsaturated monocarboxylic acid reagent" or "a7~ saturated monoearbo~Yylic acid-produclng compound".
Procedures for preparing hydrocarbon-substi~uted monocarboxylic acid reagents useful in preparing the alkali metal overbased sal~s (B) are described in, for example, U.S. Patent 3,454,607 ~LeSuer et al), and tbe description of such procedure~ and ~dditlonal examples of such reagents are hereby incorporated by reference.
The following examples Illustrate such procedures and reagents.
Example 7 A chlorinated polyisobutene having a molecular weight of 1000 ~nd a chlnrine content of 4.5% ~6300 granu~ 8 equivalen~s of chlorine) is mixed wlthacrylic acid (940 grams, 13 equi1ralents) and the mixture is heated to 235C while hydrogen chloride is evoled. It is then heated at 130-182C/6 mm. and then filtered. The filtrate is an acid having a chlorine content of 0.62'Yo and an acid number of 63.
EXaITlpl~ 8 A mixture of ac~ylic acid (720 grams, 10 equivalents) and a chlori~ated polylsobutene having a molecular w~ight of 1000 and ~ chlorine content of 4.3% (6536 grams, 8 equivalents of chlorine) is heated at 170-225C
fnr 12 hours and then at 200C/10 mm. The residue is filtered at 140C and the filtrate is the desired acid having a chlorine content of 0.36% and an acid " I nwnber of 60.
Example 9 The procedure of Example 7 is repeated except that the chlorinated isobutene is replaced on a halogen equivalerlt basis with a brominated copolymerof isobutene (98% by weight) and isoprene (2% by weight) ha~ing a rnolecular weight of 5000 and a bromine content of 2.5 and that the acrylic acid used i replaced on a chemical equivalent basis with phenyl acrylate.

Wo 93/23s0s Pc~ Js92/~737 Example 10 A mixture of crotonic acid (2 equivalents) and a chlorinated polypropene having a nnolecular weight of 2500 and a chlorine content of 5~ ~0.5equivalent of chlorln~3 is hea~ed at 1%0-~2ûC for 5 hours and then at 200C/l mm. The resldue ls filtered and the flltrate is the desired acid.
Exampl~ 11 ~ methyl ester of a high molecular weight monocarboxylic acid is prepared by heating an equlmolar mixture of a chlorinated polyisogutene havng a molecular welght of 1000 and a chlorln~ content of 4.7% by weight and methylmethacrylate at 140-220C.
When preparing the hydrocarbyl-substituted dicarboxylic acids useful in prepar~ng the alkali metal salts used in ~he presen~ in~ention, one ormore of the above polyalkenes (or halogenated polyalken~) is reacted with one or more acldic reagents selected from the group consisting of maleic or furnaricreactants of the general formula X~O)C:-CH=CH-C(O)X' ~CII) wherein X and X' ~r~ the same or diff~rent provided that at least one of X and X' are each îndependently OH, O-lower hydrocarbyl, O-M, Cl, Br or together, X
and X' can be -O- so as to form the anhydride. Ordinarily/ the maleic or fumaricreactants will be maleic acid, furnaric acid, maleic anhydride~ or a mixture of two or rnore of these. The maleic reactants are usually preferred over the fumaric reactants because the former are more readily available and are, in general, mnre readily reacted with the polyalkenes to prepare the desired hydrocarbyl-substi~uted succinic acids.
2$ The hydrocarbyl-substituted succinic acid reagents used to prepare ~he alkali metal overbased salts (B) are similar to the hydrocarbyl-substituted succinic acids used as the acylating agents (A-l) described above where the hydrocarbyl-substituted succinic acids contain at least about one succinic group WO 93/23505 Pcr/us92~o873? ~

2 i ;3 2 ~ I j r ~
-4~-for each equivalent weight of substituent group~ Thus, in one embodiment the hydrocarbyl-substituted succinic acids are prepared by reacting about one mole (or 1 equivalent) of a polyalkene with one mole (or 2 equivalents) of the maleicor fumaric acid reactant~
Procedures for prep~ring hydr~carbyl-substituted dicarboxylic acid reagents useful in preparing the alkali metal overbased salts are described in, for example, U.S. Patents 3,087,936 (LeSuer~ and 3,219,666 (Norman), the disclosuresof which are hereby incorporated by reference. Examples of hydrocarbyl-substituted succinic acid reagents useful in preparing the alkali metal salts (B) include the succinic acylating agents exemplified above in Examples 1-~.
In one embodiment, the carboxylic acids are aromatic carboxylic acids. A group of useful aromatic carboxylic acids are those of the formula 1 5 ~C-XH)b (R1)a Ar \

(XH)C
.
wherein E~l is an aliphatic hydrocarbyl group prefer~bly derived from the above-described polyalkenes, a is a number in the range of 1 to about 4, usually 1 or 2, Ar is an aromatic group, each X is independently sulfur or oxygen, preferably oxygen, b is a number in the range of from 1 to abou~ 4, usually 1 or 2, c is a nwnber in the` range of zero to about 4, usually 1 ~o 2, with the proviso that the swn of a, b and c does not exceed the number of valences of Ar. Examples oî
aromatic carboxylic acids inclùde substituted benzoic~ phthalic and salicylic acids.
The Rl group is a hydrocarbyl group that is directly bonded to the aromatic group Ar. Examples of Rl groups include substituents derived from polyrnerized olefins such as polyethylenes, polypropylenes, polybutylenes, ethyl-W~ 93/23505 P~r/USs~/0~737 ene-propylene copolymers, chlorinated olefinpolymers and oxidized ethylene-pro-pylene copolymers.
The aromatic group Ar may have the same structure as any of the aromatic groups Ar discussed below. Ex~mples of the arorrIatlc groups that are usefu11 herein include the polyvalent aromatic groups derived from benzene, naph-thale~e, 2nthracene, etc., preferably benzene. Specific examples of Ar groups Include phenylenes and naphthylene, e.g., methylphenylenes, ethoxyphenylenes, isopropylphenylenes, hydroxyphenylenes, dlpropoxyn~phthylenes, etc.
Within th~s group of ~romatic acids, a wsefu} class of carboxylic acids are those of the fo~nula "(COOH)b ~, ' ~Rl)at O l ., ~
(OH)C
: `
wherein Rl is deflned above, a is a number in the range o~ from 1 ~o about,4, preferably 1 to about 3; b is a number in the range of 1 to about 4, preferably 1 to about 29 C is a number in the range of zero to about 4, preferably 1 to about 2, and more preferably 1; with the proviso that the sum of a, b and c does not exceed 6~ Preferably, b and c are cach one and the carboxylic acid is a salicylic acid.
Overbased salts prepared from salicylic acids wherein the aliphatic hydrocarbon substituents (R1) are derived from the above-described polyalkenes, particularly polymerized lower l-mono-olefins such as polyethylene, polypro-pylene, polyisobutylene, ethylenelpropylene copolymers and the like and having average carbon contents of about 50 to about 400 carbon atoms are particularly useful.

WO 93/23505 l~cr/us92/o8737 ..~ .

~la2~9'3 -46-The above aromatic carboxylic acids are well known or can be prepared according to procedures known in the art. Carboxylic acids of the type illustrated by these formulae and processes for preparing the}r neutral and b~sic metal salts are well known and di~closed, for exarnple, ln U~S. Patents 2,197,832;
2,197,835; 2,2527662; 2,252,664; 2,714,0~2; 3,410,798; and 3,595,791. These references are 1ncorporated by reference for disclosure of carboxylic acid, their basic salt and processes of making the xame.
As noted pre~iously7 the ~Ikall metal overbased hydrocarbyl-substltuted carboxylic acid may be derived from a mixture of carboxylic acid (preferably a hydrocarbyl-substltuted carboxylic acid) and hydrocarbyl-substitut-ed sulfonic acld. The hydrocarbyl-substituted carboxyli~ acid In the mixture generally will contE~in at le~st ~bout 50 carbon atoms in the hydrocarbyl substituent, and the hydrocarbyl substituent may also be characterized as havlnga number a~erage molecular weight of a~ least about gao. The sulfonlc acids useful in the mixtures include the sulfonic and thiosulfonic acids. Generally they are salts of sulfotlic acids. The sulfonic acids include the mono- or polynuclear aromatic or cycloaliphatic compounds, The oil-soluble sulfonic acids can be repre~ented for the most parc by one of the following formu1ae: Rz-T-(SO3)aH
and R3-(S03)bH, whereln T is a Qclic nucleus such as, for example, benzene, naphthalene, anthracene, diphenylene o~ide, diphenylene sulfide, petrolewn naph-thenes, etc. R2 and R3 are generally a hydrocarbon an essentially hydrocarbon group, preferably free of ~setyloenic unsaturation, and containing abou~ 4 to about 60 or more aliphati~ carbon atoms, preferably an aliphatic hydrocarbon group such as alkyl or alkenyl. When R3 is aliphatic it usually contains at least about 15 carbo~s; when it is an aliphatic-substituted cycloallphatic grQUp, the aliphatic substituents usualloy contain a total of at least about 12 carbon atoms.
Specific ~asnpl~s f R2 and R3 are groups derived from petrolatum, satura~ed and unsaturated paraffin wax, and the above-described polyalkenes. The groups T, R2, and R3 in the:above formulae can also contain other inorganic or organic substituents in addition to those enumerated above such as, for example, ~'0 ~3/~35~ Pcr/US92/~)8737 ... . .
;, .,, ,', ji -~7-hydroxy, mercapto, halogen, nitro, amino, nltroso, sulflde, disulfide, etc. In the ~bove Forsnulae, a and b are at least 1.
Speciflc ex~mples of such sulfonic ~clds include mahogany sulfonic acids, bright stock sulfonic acids, petrala~um sulfonic acids, mono ~ and polywax-substltuted naphthalene sulfonic acids, cetylchlorobenzene sulfonic acids, cetylpherlol sulfonic a~ , cetylphenol dlsulfide sulfonlc aclds, cetoxycapry}
benzene sulfonic acids~ dlcetyl thianlthrene sulfonlc acids, dilauryl beta-naphthol sulfonic acids, dicapryl nitronaphthalene sulfonic aclds, saturated paraffin waxsulfoDic acids, unssturated p~Taffin wax sulfonic aclds, hydroxy-subs~ituted iO paraffin wax sulfonic acids, tetraisobutylene sulfonic acids, tetraalxlylelle - sulfonic acids, chlorine substituted paraffln wax suifonic acids, nitroso subs~ituted paraffin wax sulfonic acids, petroleum naphthene sulfonic aclds, cetylcyclopentyl sulfonic acids, lauryl cycl~hexyl sulfonic acids, mono- and polywax substituted cyclohexyl sulfonic aclds, dodecylbenzene sulfonic acids, "dirner alkylatei' sulfonic acids, and the like.
Alkyl-subst~tu~ed benzene sulfonlc acids wherein the alkyl group contains at least 8 carbon atoms including dodecyl benzene "bottorns" sulfonic 8cld~; are particularly useful. The latter a2-?e acids derived from benzene wh~h- has beein alkylated wlth propylene tetramers or isobutene trimers to introduce 1, 2, 3~ or more branched-chain C12 ~ubstituents on the lbenzene ring. Dodecyl benzelle bottoms, principally mixtures of mono- and di-dodecyl benzenes, are available as by products from the manufacture of household detergents. Similar products obtained from ~Ikylation bottoms fo~ned during manufacture of linear slkyl sulfonates (LAS) are also useful in making the sulfonates used in this inven~ion.
Illustrative examples ~f these sulfonic acîds include polybu~ene or polypropylene substituted naphthalene sulfonic acids, sulfonic acids derived by the trea~nent of pclybutenes having a number average molecular weight ll~n) in the range of 700 to 5000, preferably 700 to 1200, more preferably about 1500 with ehlorosulfonic acids, paraffin wax sulfonic acids, polyethylene (Mn equals WO 93/23505 Pcr/us~/os737~

2 ~ ~J ~, ', ~, abou~ 900-2000, preferably about 900-1500, more preferably 900 l200 or 1300) sulfonic acids, etc. Preferred sulfonic acids are mono-, di-, and tri-alkylated benze~e (including hydrogenated forrn~ thereof) sulfonic acids.
The promoters, that is~ the rnater~als whlch facilltste the incorporstlon of exces~ metal Into the overbased ~aterial lmprove contact between the acidlc material and the ciarboxylic ~cid or mixture of carboxyllc acid and sulfonic acid ~overb~sing substrate). Generally, the promoter is a material which ~s sllghtly acldic and able ~o form a salt wlth the basic metal compound. The promoter musi~ also be an acid weak enough to be displaced by the acidlc material, usually carbon dloxide. Generally, the promoter hasi a pKa in the range from about 7 to about 10. A particularly compreher~siYe discussion cf suitable promoters ls found ln II.S. Patents 2,777,874, 2,69579}0, 2,616,904,3,384,586 snd 3,492,23l. These p~tents ~re 1ncorporated by reference for their disclosure of promoters. Promotersi may Include phenolic substances such as phenols and naphthols; amines such as aniline, phenylenediamine~ dodecylamlne;
e~c. In one embodiment, the preferred promoters are the phenolic promoters.
Phenolic promoters include a varlety of hydroxy-substituted benzenes and naphthalenes. A particularly useful class of phenolsi are the alkylated phenols of the type listed In U.S. Patent 2,777,874, e.g., heptylphenols, octylphenols, nonyl-phenols, and tetrapr~penyl-substituted phenols. Mixtures of various promoters are sometimes used.
The inorganic or lower carboxylic acid}c materials, which are reacted with the mixture of promoter, basic metal compourld, reaction mediurn and the hydrocarbyl-substituted csrboxylic acid are disclosed in the above citedpatents, for example, U.S. Patent 2,616,904. Included within the known group of useful acidic materials are lower carboxylic acids, having from 1 to about 8,preferably 1 to about 4 carbon atoms. Examples of these acids include formic acid, ace~ic acid, propanoic acid, etc., preferably acetic acid. Useful inorganic acidic compounds include HCI, S02, 5O3, C02, H~S, N203, etc., are ordinarily , ~VO 93/235~5 PCr/US92/08737 employed as the acidic materials. Prefzrred acidic materials are carbon dioxide and acetic acid, more preferably carbon dioxide.
The al~ali metals present in the alkali metal overbased salts include prlncipally lithiwn, sodlum and pota~slu~n, with sodlum being preferred. 1'he overbased metal salts are prepared using a basic alkali metal compound. Illus-tratire of ~asic alkali metal campounds are hydroxides, oxides, alkoxides (typically those in whieh the slkoxy group contains up to 10 and preferably up to 7 carbon atoms), hydrides and amides of alkall metals. Thus, useful basic alkalirnetal compounds include sodiurn oxide, potassiwn oxide, llthium oxide, sodium hydroxide, potassium hydroxide, l~thium hydroxide, sodium propoxide, lithium methoxide, potassium ethoxide, sodiw~ butoxlde, lithiwn hydride, sodiuzn hydr~de, potassiwn hydride, lithiuzn amide, sodium amide and potassium amide. Especially pre~erred are sodium hydroxide and the sodium lower alkoxides (l~e., those con~aining up to 7 carbon atoms).
The alkali metal oYerbased materials useful in the present inventian may be prepared by msthods known to ~hose in the ~rt. The methods generally involve adding acidic material to a re~rtion mixture oompris~ng ~he hydrocarbyl-substituted carboxylic acid or mixture of carboxylic acid and sulfonic acid, thepromoter and a b~sic alkali metal compwnd. These processes are described in the following U.S. Patent Nos.: 2,616,904; 2,616,905; 2,616,906; 3,242,080;
3,250,710; 3,256,186; 3,274,135; 3,492,231; and 4,230,586. These pat~nts are inco2porated herein by reference for these disclosuuesO
In the present invention, the preferred hydro~arbyl-substituted carboxyllc acids have~ relatively high molecular weights. Higher temperatures ` 25 sre generally used to promote contact between the acidio material, the succinic acid and the basic alksll metal compound. The higher temperatures also promote formation of the salt of the weakly acidic promoter by removal of at leat sorne of the wa~er. ln preparing the overbased metal salts useful in the present inven-tion, water must be removed from the reaction.
.

WO 93/23s0s PCr/US9~/0$737 'f., ~ , o Ç ~ ~

The reaction generally proceeds at temperatures from about 100C
up to the decomposition temperature of the reaction mixture or the individual components of the reaction. The reaction may proceed at temperatures lower than 100C, such as B0C or above, if ~ vacuum is applied. Generally, the reactlon ocs at a temper~ture from about 110C to ~bout 200C, preferably 120C to about 175C and more preferably about 130C to about 150C.
Preferably, the reaction i8 p~rformed in the presence of a reaction mediurn whlch includes naphtha, miner~l oil, xylenes, toluenes and the }ike. In the present inventlon w~ter may be removed by applying ~ vacuL~n, by blowing the reaction mixture wlth a gas such 8S nitrogen or by removlng water as an azeotrope, such as a xylene-wate~ azeotrope. C;enerally, ln ~he present inven-~on, the acidic materlsl is provided as a gas, usually carbon dioxlde. The carbon dioxlde, whlle participating in the overbasing process, also removes wster if the carbon dloxlde ls added at a rate which exceeds the rate carbon dloxide is consumed ln the reaction.
The alkali metal overbased metal sal~s used in the present inventlon may be prepared incrementally ~batch) or by continuous processes. One incre~nental process involves the following s~eps: ~A) adding a basic alkali metal compound to a reaction mixture comprising the hydrocar~byl-substituted carboxylic ~cid ~or mixture of carboxylic arld sulfonic acids) and promoter, andremo~ing free water from the reactioll mixture to form an alkali metal salt of the acidic organic compound; ~B) adding more basic alkali metal compound to the reaction mixture and removing free wster frorn the reaction mixture; and (C) :
introducing the acidic material to the reaction mixture whlle removing water.
Steps (B) and (C) are repeated until a product of the desired metal ratio is obtained.
Another method of preparing the alkali metal overbased salts is a semi-continuous process for preparing the alkali metal overbased salts. The process involves (A) adding at least one basic alkali metal compound to a reaction mixture comprising an alkali metal salt of hydrocarbyl-substituted WO 93/235û5 PCr/USg2/08737 ,.;, .,~. . , ~. , . ;
Ir~ " ~

carboxylic acid (or mixt~re of carboxylic acid and sulfonic acid) and removing free water from the reaction mixture; and (B) concurrently thereafter, (1) adding basic alkali metal compound to the reactio~ mixture; (2) ~dding an inorganic or lower carboxyllc acldic materi~l to the resction mixture; and (3) removing waterfrom the reaction mixture~ The addition of basic alkall metal compounds together wi~h the inorganic or lower carboxylic acidlc material where the addition is done continuously along wlth the removal of water results in a - shortened processing time for the reaction.
The term l'free water" refers to the amount of water readlly removed from the reaction mixture. This water is typlcally removed by azeotropic distillation. The water which remains In the reaction mixture is beXieved to be coordinated, associated, or solv~ted. ~he water may be in the fo~n of water of hydration. Some basic alkali metal compounds may be delivered to the reaction mixture as aqueous solutions. The excess water added~
or free water, with the basic alkali metsl ~ompound is usually then removed by azeotropic distillation, or vacuum stripping.
Any water generated during the overbasing process is desirably removed as it is fo~ned t~ minimlze or eliminate formation of oil-insolu41e metal carbonate~. During the overbasing process above, the amount of water present prior to addition of the inorganic or lower carboxylic acidic material (steps (B) and (B-l) abo~e) i~ less than about 30% by weight of the reaction mixture, preferably~less than 20%, more preferably less than 10%. Generally, the amount of water present after addition of the inorganic or lower carboxylic acidic material is up to about 4% by~ weight of the reaction mixtu~e, more preferably up to about 2%.
In another embodiment, the alkali metal overbased salts are :~ :
borated alkali metal overbased salts. Borated overbased metal salts are preparedby reacting a boran compound with the basic alkali metal salt. Boron compounds include boron oxide, boron oxide hydrate, boron trioxide, boron trifluoride, boron tribromide, boron trichloride, boron acid such as boronic acid, boric acid, WO g3/2350~ P~r/llJs92/0873,~.

,~ 3 i~

tetraboric acid and metaboric acid, boron hydrides, boron amides and various esters of boron acîds. The boron esters are preferably lower alkyl (1-7 carbon atoms) esters of boric acid. Preferably, the boron compounds are boric acid.
Generally, the overbased metal salt is reacted with a boron ~ompound at about S 50C ta about 250~, prefer~bly 100C to about 200C. The reaction may be aceomplished in th~ presence of a solvent such a~ mineral oll, naphtha, kerosene, toluene or xylene. The overba~sesl metal salt is reacted with a boron cornpound in amounts to provlde at least about 0.5q~, preferably about 1~ up to about 5%, preferably about 4%, more preferably about 3% by weight boron to the composition.
The followitlg examples illustrate the ~Ikali metal overbased salts (B) useful in the present invention ~nd methods of making the same.
Example B-l A reaction vessel is charged with 1122 grarns (2 equivalents) of a polybutenyl-substituted succinic anhydcride derived from a polybutene (Mn=10001 1:1 ratio of polybu~ne to maleic acid), 105 grams (0.4 equivalent) of tetrapro-penyl phenol, 1122 grams of xylene and 1000 grams of 100 neutral mineral oil.
The mixture is stirred and heated to 80C under nitrogen, and 580 grams of a 5û% aquevus solution of sodium hydroxide are added to the vessel over 10 minutes. The mixture is heated from 80C to 120C over 1.3 hours. Water is removed by azeotropic reflux and the temperature rises to 150C over 6 hours while 300 grams of water is collected. (1) The reaction mixture is cooled to about 80C whereupon 540 grams of a 50% aqueous solution of sodium hydroxide are added to the vessel7 (2) The reaction mixture is beated to 140C over 1.7 hours and water is removed at reflux conditions. (3) The reaction mixture is carbonated at 1 standard cubic foot per hour (scfh) while removing water for 5 hours. Steps (1)-(3) are repeated using 560 grams of an aqueous sodium hydroxidesolution. Steps ~ (3) are repeated using 640 grams of an aqueous sodium hydroxide solution. Steps (1)-(3) are then repeated with another 640 grarns of a50% aqueous sodium hydroxide solution. ~he reaction mixture is cooled and 1 000 WO 93/~C3505 PCT/US92/087~7 grams of 100 neutral mineral oil are added to the reaction mixture. The reactionmixture is vacuum stripped to 115C at abou~ 30 millimeters of mercury. The residue is ~iltered through diatomaceous earth. The filtrate has a total base number of 361, 43.4% sulfated ash, 16.0% sodium, 39.4% oil, a specific gravity of 1.11, and the overbased metal salt has a metal ratio of about 13.
~cample ES-2 The overbased salt obta~ned in Example E~l is diluted with mineral oil to provide a composition containlng 13.75 sodium, a total base nwnber of about 320, and 45~6 oil.
F~arnple B-3 A reaction vessel is charged with 700 grams of a 100 neutral mineral oil, 700 grams (1.25 equiYalents) of the succinic anhydride of Examp1e B-l and 200 grams (2.5 equi-ralen~s) of a 50% aqueous solution of sodium hydroxide. The reaction mixture is stirred and heated to 80C~ whereupon 66 lS grsms (0.25 equivalent) of ~etrapropenyl phenol are added tu tbe reaction vessel.
The reaction m~xture is heated from 80C to 140~C over 2.5 hours while blowing of nitrogen and removing 40 gra~r~ of water. Carbon dioxide ~28 grarns, 1.25 equivalents) is added over 2.25 hours at a ~emperatlLre from 140-165C. T~e reaction mixture is blown with nitrogen at 2 stand~rd cubic foot per hour (scfh)and a total of 112 grams of water is removed. The reaction temperature is decseased to 115C and the reaction mixture is filtered through diatomaceous earth. The filtrate has 4.06~ sodium, a total base number of 89t a specific gravity of 0.948, 44.596 oil, and the overbased salt has a metal ratio of about 2.
Example B-4 ~ f ` I
A reaction vessel is charged with 281 grarns ~0.5 equi~alent) of the succinic anhydride of Example B-l, 281 grams of xylene, 26 grams of tetrapro-penyl substituted phenol and 250 grams of lO0 neutral mineral oil. The mixture is heated to 80C: and 272 grams (3.4 equivalents) of an aqueous sodiurn hydroxide solution are added to the reaction mixture. The mixture is blown with n;trogen at 1 scfh, and the reaction ~emperature is increased to 148C. The reaction :

WO ~3/23505 PCr/US92/0~73?~

r r7l ~J ,~ j ~

mixture is then blown with carbon dioxide at 1 scfh for one hour and 25 minutes while 150 grams of water are collected~ The reaction mixture is cooled to ~0C
whereupon 272 grams (3.4 equivalents) of the above sodium hydroxide solution are added to the reaction mixture, snd the mixture Is blown with nitrogen at 1 scfh. The reaction temperature is in~eased to 140C whereupon the reactlon mixture is blown with carbon dioxlde at 1 scfh for 1 hour and 25 mlrlutes while 150 grams of water are collected. The reaction temperature is decreased to 100C, and 272 grams (3.4 equiYalents) of the above sodiwn hydroxid¢ solution are added while blowing the mix~ure with nitrogen a~ 1 scfh. The reaction temperature is increased to 148C, and the reaction mlxture i5 blown with carbondioxide at 1 scfh for 1 hour snd 40 minu~es while 160 grams of water are collect-ed. The reaction mixture is cooled to 90C and 250 grams of 100 neutral ~nineraloil are added to the reaction mixt1~re. The reaction mixture is vaculun strippedat 70C and the residue is filtered through diatomaceous earth. The filtrate contairls 50.0% sodium sulfate ash by AS~TM D-874, total base number of 408, a specific gravity of 1.18, 37.1% oil, and the salt has a metal ratio of about 15.8.
Example B-5 A reaction vessel is charged with 700 grams of the product of Example B-4. The reaction mixture is heated to 75C whereupon 340 grams (5.5 equivalents) of boric acid are added over 30 minutes. The reaction mix~ure is heated to 110C over 45 minutes, and the reaction temperature is maintained for 2 hours. A 100 neutral mineral oil (8Q grams) is added to the reaction mixture.
The reaction mixture is blown with nitro~en at 1 scfh at 160C for 30 minutes while 95 grams of water are collected. Xylene (200 grams) is added to the 2~ reaction mixture and the reaction temperature is maintained at 130-140C for 3 hours. The reaction m~xture is vacuum stripped at 150C and 20 millimeters of mereury. The residue is filtered throu~h diatomaceous earth. The filtrate contains 5.84~ boron and 33.1% oil. The residue has a total base nurnber of 309.

WO 93/2350~ P~/US92~ 737 ,, ~ ,~ ., . . ,.;,; . .. ....
~' b ~ s Example ~6 A reaction vessel is charged wi~h 224 grams (0.4 equivalents) of the succinic anhydride of Example B-1, 21 grarns ~0.08 equivalent) of a tetrapropenyl phenol, 224 grams of xylene and 224 grams of 100 neutral mineral oil. The mixture is heated, and 212 grams ~2.65 e~uivalents~ of a 509~ aqueous sodium hydroxide s~luti~n are added to the reaction vessel. The re~ction temperature increases to 13(1C and 41 grams of water ure removed by ni~rogen blowing at 1 scfh. The reaction mixture is then blown with c:arbon dioxide at 1 scfh for 1.25hours. ~dditional sodium hydroxide solution ~43~ grams, 5.4 equivalents) is added over four hours while blowing with carbon dio:~ide at 0.5 scfh at 130C. During the addition, 301 grams of water are removed from the reactian Yessel. The reaction te~lperature is increased to 15ûC and the rate of carbon dioxide blowing is increased to 1.5 scfh and malntained ~or 1 hour and 15 mlnutes. The reaction mixture is cooled to 150C and b1Own wlth nitrogerl at 1 scfh while 176grams of oll are added to the reaction mixture. The reaction mixture is blown with nitrogen at 1.~ scfh for 2.5 hours, and the mixture is then filtered through diatomaceous earth. The filtrate contains 15.7% sodium and 39% oil. The filtrate has a total base number of 380, and a metal ratio of about 14.5.
Example B-7 A reaction vessel is charged with 561 grams (1 equivalent) of the succinic anhydride of Example ~1, 52.S grams ~0.2 equivalent) of a tetrapro-penylphenol, 561 grams xylene and 500 grams of a 100 neutral mineral oil. The mixture is heated tc 50C under nitrogen, and 373.8 grams (6.8 equivalents) of potassiurn hydroxide and 299 grams of water are added to the mixture. The reac~ion mixture Is heated to 135C while 145 grams of water are removed. The azeotropic distillate is clear. Carbon dioxide is added to the reaction mixture at 1 scfh for two hours while 195 grams of water are removed azeotropically.
The reactinn mixture is cooled to 75C whereupon a second portion of 373.8 grams of potassium hydroxide and 150 grams of water are added to the reaction vessel. The reaction mixture is heated to 150C with azeotropic removal of 70 WO 93/23~0~ PCI`/US92/08737 2 J~L ~ 2 ~ ~, 3 grams of water. Carbon dioxide ~1 sc~) is added for 2.5 hours while 115 gr~ns Df water is removed azeotropically. The re~ction is cooled to 100C where a third portion of 373.8 grams of pota~sium hydroxlde and 150 grams of wa~er is added to the Yessel. The reaction mixture is heated to 150C while 70 grams of water ar¢ removed. The reaction mixture is blown wlth carbon dioxide at 1 scfh for one hour while 30 grams of water are removcd. The reaction temperature is decreased to 70C. The reaction mixture }s rehes~ed to 1 50C~ under nitrogen.
----At 150C the reaction mixture is blown wlth carbon dioxide at 1 scfh for twohours while 80 grams of water is removed. The carbon dioxide is replaced wlth a nitrogen purge, and 60 granns of water is removed. The reactlon is then blown wlth c~rbDn dioxide at 1 scfh far three hours with removal of ff4 grarns of water.
The reaction mixture is caoled to 75C where 500 grarns of 100 neutral mineral are added to the reaction mixtu~e. The resction is vacuurn stripped to 11 5C and 25 millimeters of mercury. The residue is filtered through diatomaceous earth.
The filtrate contains 35% oil, has a base number of about 3~2, and a metal ratioof about 13.6.
Example ~8 An overbased sodi~n sulfonate/suecinate mixsure is prepared by the process described in Example ~1 using 562 grams (1 equivalent) of the succinic anhydride of Example B-1 and 720 grams (0.8 equivalent) of a polybut-enyl-substituted sulfonic acid derived from a polybutene (Mn=800) and 1632 grams (20.4 equivalents) of a 50% aqueous solution of sodium hydroxide.
Example B-9 A sodium overbased monocarboxylic acid salt is prepared by the general process of Example B-l by reacting 1 equivalent of the high molecular weight monocarboxylic acid of Example 8 with a total of 15 equivalents of sodium hydroxide.

WO 93/235(~ PCI /US92/08737 , 3 ~57- -Example B 10 A sodium overbased succinic acid sal~ is prepared by the general process of ~;xample ~1 by reacting one equivalent of the hydrocarbt~l-substituted succinic re~gent prepared in Example 4 with a total of 12 equivalents of sodium hydroxide.
The lubricating ~il cvmpositions of the present inventiorl contain a major amount of an oil of lubricating vlscosity, at lea~t 1% by weight of the carboxylic derivative compos~tions (A) described above, and an arnount of ~t least one alkali metal overb~sed salt ~B) of a carboxylic acid or mixture of carboxylic and sulfonic acids as described ab~ve. More of'ten~ the lubrica~ing composltions of this invention will contain at least 70~ or 8~h of oil. The amount of carboxylic derivative (A) included in the lubricating oil compositi~nsof the invention may vary over a wide range provlded that the o~l composition contains at least about 1% by weight ~on a chemical, oil-free basis) of th~
carboxylic derivatlve composition (A~. In other ~mbodiments, the oil composi-tions of the present invention may contai~ at least about 2h or 2.5% by weight or even at least about 3% by weight of the carboxylic deriYative composition (A).
The carboxylic derivative composition ~A) provides ~he lubr~cating oil compos,-tions of the present in~ention with desirable Vl and dispersant properties.
As noted above, the lubricating oil compositions of the present invention also conta1n at least about 0.002 cquivalent of alkali metal per 100 grams of lubric~ting oll composition. In other embodimen~, the lubricating oil compositions will contain at least about 0.003 or at least about 0.005 equivalent of alkali metal per 100 grams of lubricating oil composition. The maximum arnount of alk~li metal presen~ in the lubricating oil compositions may vary over a wide range depending upon the nature of the other components of the lubricating oil compositiorl and the intended use of the lubricating oil composi-tion. Generally, however, the lubricating oil compositions of the present invention will contain up to about 0.008 or even 0.01 equivalent of alkali metalper 100 grams of lubricating oil composltion.

WO 93/2350~ PCI /US92/OB737 2~i ~?2~l'3f-~ ' (C) Ma~nesium or Calcium Overbased Salt.
The lubricating oil compositions of the present invention contain at least one magnesium or at least one calcium overbased salt of an acidic organic compound. ln particul~r, the lubricatlng oil compositions of the present inYention contain either (C-1) at least orle magnesium overbassd salt of an acidic organic compound prcvided that the lubrlcat~ng oll composition is free of calcium overbased salts of acidic arganic compourlds; or (C-2) at least one calcium overbased salt of an acidic crganic compound provided that the luhricating oll compositlon is free of magneslum overbased salts of acidic organic compounds.
The amount of magnesium or calciusn overbased salt in~luded in the lubric~nts of the present lnvention may be varied over a wide rsnge, and useful amounts in any par~icular lubricating oil composition can be readily determined by one skilled in the art. The magnesium and calcium salts function as awciliaryor supplementary detergents. The amount vf the calcium or rxlagnesium salt contained in a lubricant of the invention may vary fram about 0.01 up to about 5% or more. Generally, the magnesium or ~he c~lcium overbased salt is presen,t in an amount of from about 0.1 to about 2% by weight.
The use of the terrn "free of" in this application and claims refers to compositions which are substan~ially free of the indicated compositions. Someof the indicated metal may be present in the lubrican~s as a contaminant.
The acidîc organlc compnund from which the magnesiurrl and calciurn salts may be prepared may be at least one sulfur acid, carboxylic acid,phosphorus acid, phenol, or mixtures thereof.
The salts which are useful as component (C) are overbased or basic.
The overbased or basic salts contain an excess of the magnesium or calcium cation. The basic or overbased salts will have metal ratios (MR) of up to about 40 and more particularly from about 1.5 or ~ up to about 30 or 40.

W~ 93/2350:. PCr/US92/n8737 2 ~ v, , A commonly employed method for preparing the basic (or overbased) salts comprises heating a mineral uil solution of the acid with a stoichiometric excess of a metal neutralizing agent, e.g., a metal oxide, hydrox-ide, carbon~te, bicarbonate, sulfide, etc., at temperatures above ab~ut 50(::. In S addition, various promoters may be used in the neutralizing process to aid In the incorporaticn of the largc excess of metal. These promoters Include such compounds as the phenollc substances, e.g~, phenol ~nd naphthol; alcohols such ~s methanol, 2-propanolj octyl alcohol and Cellosol~e carbitol, amInes such as aniline, phenylenediamine, and dodecyl amine, etc.
As mentioned above, the acldic organic compound from which the salt of component (C) is derived may be at least one sulfur acid7 carbo%ylic acid, phosphorus acid, or phenol or mixture~ thereof. The sulfur aclds lnclude sulfonic acids, thiosulfonic, sulfinic, sulfenic, partial ester sulfuric, sulfurous and thiosul-furic acids.
The sulfonic acids which are useful in preparing component (C) include those represen~ed by the fo~nulae R~CTlSO3~1)y ~XIll) and R~(SO3~)r (XlV) In these formulae, R' is an aliphatic or aliphatic-substituted cycloaliphatic hydrocarbon or cssentially hydrncarbon group free from acetylenic unsaturation and containing up eo about 60 carbon al:orns. When R' is aliphatic, it usually contains at lcast about 15 carbon atoms, when it is an aliphatic-substituted c~cloaliphatic group, the aliphatic substituents usually contain a total of at least abou~ 12 carbon atoms. Example~s of R' are alkyl, alkenyl and alkoxyalkyl radicals, and aliphatic-substituted cycloaliphatic groups wherein the aliphatic WO 93/2350 ~ PCr/US92/0873 'iL~ '< '''~

substituents are alkyl, alkenyl, alkoxy, alkoxyalk$~1, carboxyalkyl and ~he like.
Gener~lly7 the cycloaliphatic nucleus is derived frorrl a cycloalkane or a cycloalkene such as cyclopen~ane, cyclohexane, cyclohexene or cyclopentene.
Specific examples of R' are cetylcyclohexyl, laurylcyclohexyl, cetyloxyethyl, actadecenyl, and ~roups deriYed from petr~leum, saturated and unsaturased paraffin wax, and olefin polymers including polymerized monuolefins containing about 2-8 carbon atoms per olefinlc monomer unlt and diolefins containing 4 to 8 c~rbon atoms per monomer unit. R' can aJso contain other ~ubstituents such as phenyl, cycloal~;yl, hydroxy, mercapto, halo, nitro, amlno, nltroso, lower alkoxy, lower alkyimercapto, carboxy, carbalkoxy, oxo or thio, or interrup~ing groups such as -I~IH-, -O- or -S-, as long as ~he essentially hydrocarborl character i~ not destroyed.
~ in Fo~nula X~C is generally a hydrocarbon or essentially hydrocarbon group free from acetylenic unsaturation and contsining from about 4 to about 60 aliphatic carbon atorns, preferably an aliphatic hydrocarbon groupsuch as alkyl or alkenyl. It may also, however, contain substituents or interrupting groups such as those enurn~rated above provided the essential}y hydrocarbon character thereof is retained. In general, any non-carbon atoms present in R' or R do not acc~unt for more than 10~ of the total weight thereof.T ~s a cyclic nucleLls which may be derived from an aromatic hydrocarbon such as benzene, naphthalene, anthracene or biphenyl, or from a heterocyclic compolmd such as pyridine, indole or isoindole~ Ordinarily, T is anaromatic hydrocarbon nucleus, especially a benzene or naphthalene nucleus The subscript x is at least 1 and is generally 1-3. The subscripts r and y have an average value of about 1-2 per molecule and are generally also 1.
The sulfonic acids are generally petroleum sulfonic acids or synthetically prepared alkaryl sulfonic acids. A~nong the petroleum sulfonic acids, the most useful products are those prepared by the sulfonation of suitable pe~oleum fractions with a subsequent removal of acid sludge, and purification.

WO ~3/2350~ P~/US92/OB737 Synthetic alkaryl sulfonic acids are prepared usually from alkylated benzenes such as the Friedel-Crafts reac~ion products of benzene and polymers such as polypropylene. The following are specific examples of sulfonic acids useful in preparing the salts ~C)~ It is to be understood ~hat such examples serve also toillustrate ~he salts of such sulfonic acids useful as component (C). In other words, for every sulfonic acld enumerated, i~ is lntended that the correspondingbasic metal salts thereof are also unders~ood to be Illustrated. (The same applies to the lists of osher acid materials listed below.) Such sulfonic aclds include mahog~ny sulfonic acids, bright stock sulfonic aclds, petrolatum sulfonic acîds,mono- and polywax-substituted naphthalene sulfonic acids, cetylchlorobenzene sulfonic acids, cetylphenol sulfonic acids, cetylphenol disulfide sulfonic acids, cetoxycapryl benzene sulfonic acids, dicetyl thianthrene sulfonic acids, dilauryl beta-naphthol sulfonic acids, dicapryl nitronaphthalene sulfonic scids, saturated paraffin wax sulfonic acids, unsaturated paraffin wax sulfonic acids, hydroxy-sub-stituted paraffin walc sulfonic acids, tetraisobutylene sulfonic acids, tetraamyl-ene sulfonic acids, chlorine substituted paraffir wax sulfonic acids, nitroso substituted paraffin wax sulfonic acids, petroleurrl naphthene sulfonic acids, cetylcyclopentyl sulfonic acids, lauryl cyclohexyl sulfonic acids, mono- and polywa~ substitu~ed cyclohexyl sulfonic acids, dodecylbenzene sulfonic acids, "dimer alkylate" sulfonic acids~ and the like.
~lkyl-substituted benzene sulfonic acids wherein the alkyl group contains at least B carbon atoms including dodecyl benzene "bottoms" sulfonic acids are particularly useful. The latter are acids derived from benzene which has been alkylated with propy1ene tetralTIers cr isobutene trimers to introduce l, 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. Simllar .

produc~ 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 slcilled in the art.
See, for exar;nple, the article "Sulfonates" in Kirk-Othrner ~Encyclopedia of Chemicai Technol~gy", Second Edition, Vol. 19, pp. 291 et seq. published by .1ohn Wiley & Sonst N.Y. ~1969).
Other descrip~ions of basic magnesiurn or calci~n sulfonate sal~
which can be incorporated into the lubrica~ing oil compositlons of this invention as component (C), snd techniques for making them can be found in the following U.S. Patents: 2,174,110; 2,202,781; ~,239,974; 2,319,121; 2,337,55~; 3,488,284;
3,595,790; and 3,798,012. These are hereby incorporated by reference for their disclosures in this regard.
Suitable carboxylic acids from which useful alkaline earth metal salts (C) can be prepared include aliphatic, cycloaliphatic and aromatic mono-and polybasic csrboxylic acids including naphthenic acids, alkyl- or alkenyl-sub-stituted cyc}opentanoic acids, alkyl- or alkenyl-substitu~ed cyclohexanoic acids, and alkyl- or alkcnyl-substituted aromatic carboxylic acids. The aliphatic acidsgenerally contain from about 8 to about 50, and preferably from about 12 to about 25 carbon atosns. The cycloaliphatic and aliphatic carboxylic acids are preferred, and they can be saturated or unsatur~ted. Specific exarnples include 2-ethylhexanoic acid, linolenic acid, propylene tetramer-substituted rnaleic acid, behenic acid, isostearic acid, pelargonic acid, capric acid, palmitoleic acid, linoleic acid, lauric acid, oleic acid, ricinoleic acid, undecyclîc acid, dioctyl-cyclopentanecarboxylic acid, myristic acid, dilauryldecahydronaphthalene-carbox-ylic acid, stearyl-octahydroindenecarboxylic acid, palmitic acid, alkyl- and 2~ alkenylsuccinic acids, acids formed by oxidation of petrolaturn or of hydrocarbon waxes, and commercially available mixtures of two or more carboxylic acids such as tall oil acids, rosin acids, and the like.
The equivalent ~weight o~ the acidic organic compound is its molecular weight divided by the number of acidic groups (i.e., sulfonic acid or ` 30 carboxy groups) pr~sent per molecule.
:
~: :

WO g3/23505 PCr/~S92~0g737 I

i~ ~ tJ t,J 'J ~J

The pentavalent phosphorusi acids u~ciéful in the preparation of component (C) may be an organophosphoric, phosphonic~ or phosphinic acid, or a thio analog of any of these.
Component (C) may also be prepared from phenols; that is, compoundsi containing a hydroxy group ~ound directly to an aromat~c ring. The term "phenol" as used hereiTI includes cnmpounds having more than one hydroxy group bound to an aromatic ring, such as catechol, resorcinol and hydroquinone.
It also includesi alkylphenols such as th~ cresols and ethylphenols, snd alkenyl-phenols. Preferred are phenols containing at least one alkyl substituent 10 containing about 3-100 and especlally about 6-50 carbon atomx, such as heptylpheool, octylphenol, dodecylphenol, tetrapr~pene-~lkylated phenol, octadecylphenol and polybutenylphenols. Phenols containing more than one alkyl substltuent may also be usied, but the monoalkylphenols are preferred because oftheir availabili~y and ease of production.
Also useful are condensiation products of the above-described phenols with at least one lower aldehyd¢ or ketone, the term "lower" denoting aldehydes and ketones containing not more than 7 carbon atoms. Suitable aldehydes include formialdehyde, acet~ldehyde, propionaldehyde, etc.
The equivalent weight of the acidic organic compound is itsi 20 molecular weight divided by the numiber of acidic groups ~i.e., sulfonic acid or carboxy groups) present per molecule.
The following examples illustrate the preparation of the overbased magnesium and calcium salts useful as component (C).
Example C:-1 A mixture of ~06 grams of an oil solution of an alkyl phenyl sulfonic acid (having an averagè molecular weight of 450, vapor phase osmome-try)~ 564 grams mineral oii, 600 grams toluene, 98~7 grams magnesium oxide and 120 grams water is blown with carbon dioxide at a tempera~ure of 78-85C for 7 hours at a rate of about 3 cubic feet of carbon dioxide per hour. The reaction30 mixture is constantly~ agitated throughout the carbonation. After carbonation, .

WO 93/23505 PCT/l~Sg2/08737 2 ~

the reaction mixture i5 stripped to 165C/20 torr and the residue filtered. The filtrate is an oil solution (34~ oil) of the desired overbased magnesium sulfonate having a metal ratio of about 3.
Exampl~ C-2 A mix~ure of 160 grams of blend o~l, 111 grams of polyisobutenyl - (number average Mw_950~ succinlc ~nhydride, 52 grams of n-butyl alcohol, 11 grams of water, 1.98 grarrl.s of Peladow ~a product of Dow Chemical identlfied as corltaining 94-~7% CaC12J and 90 grams of hydrated lime are mixed together.
Additional hydrated lime is added to neutralize thc sub~equently added sulfonic acid, the amount of said additional lime being deperldent upon the acid nwnber of the sulfonic acid. An oil solution (1078 grams, 58~ by weight of oil) of a straight chsin dialkyl benzene sulfonic acid ~Mw=430) 3s added with the tempera~ure of the reaction mixture not exceedlng 79~C. The temperature is adjusted to 60C. Tbe reaction product of hep~yl phenol, lime and formaldehyde . ~64.5 grams), and 217 grams of me~hyl alcohol are added. The re~ction mixture is blown with carbon dioxide to a base number ~bromophenol blue) of 20-30.
Hydrated lime ~112 grams) is added to the reaction mLxture, and the mixture is blown with carbon dioxide to a base nurnber (bromophenol blue) of 45-60, whi!e maintaining the temperature of the reaction mixture at 46-52C. The latter step of hydra~ed lime addition followed by carbon dioxide blowing is repeated three more times with the excep~ion with the last repetition the reaction mixture is carbonated to a base number (bromophenol blue) of 45-55. The reaction mixture is flash dried at 93-104~C, kettle dried at 149-160C, filtered and adjusted with oil to a 12.0% Ca level. The product is an overbased calcium sulfonate having 2~ a base number ~bromophenol blue) of 300, a metal content of 12.0~ by weight, a metal ratio of I2, a sulfate ash content of 40.7% by weight, and a sulfur .
content of l.S% by weight. The oil content is 53% by weight.
Example C-3 A reaction mixture comprisin~ 135 grams rnineral oil, 330 grams xylene, 200 grams ~0.235 equivalent) of a mineral oil solution of an alky~phenyl-WO ~3/23505 P~/U~92/08737 sulfonic acid (average molecular weight 425), 19 grams (0.068 equivalent) of tall oil acids, 60 grams (about 2.75 equivalents) of magnesium oxide, 83 grams methanol, and 62 grams water is carbonated at a rate of 15 grams of carbon dioxide per hour for about two hours at the methanol reflux temperature. The carbon dioxide inlet rate is then reduçed to abou~ 7 grams per hour, and the methanol is removed by raising the t~nperature to about 98C over a three hour perlod. Water (47 grams) is added ~nd carbonation i8 con~inued for an additional3.5 hours at a temperaturç~ of about 95C. Th~: carbonated mixture is then stripped by hea~ing IO a temperature of 140-145C over a 2.5 hour period. ~his results in an oil solution of a basic magnesium sal~ characterized by a metal ratio of about 10.
The carbonated mixture is cooled to about 60-65C, and 20~ grarns xylene, 60 grsms m~gnesiurn oxide, 83 ~r~ns methanol and 6~ grams water are added thereto. Carbonation is resumed at a ra~e of 15 graTns per hour for two hours at the methanol reflux temperature. The carbon dioxide addition rate is reduced to 7 grams per hour and ~he methanol is removed by raising the temperature to about 95C over a three hour period. An additional 41.5 grams of water are added and carbonation ïs continued at 7 grams per hour at a temperature of about 90-95~C for 3.5 hours. The carbonated mass is then heated to about 150-160C over a 3.5 hour period and then further stripped by reducing the pressure to 20 mm. (Hg.) at this temperature. The carbona~ed reaction product is filtered, and the~filtrate is an oil-solution of the desired basic magnesium salt characterized by a metal ratio of 20.
E;xample C-4 A mixture of 835 grams of 100 neutral mineral oil, 118 grams of -a polybutenyl ~Mw-950)-substituted succînic anhydride, 140 grams of a 65:35 molar mixture of isobutyl alcohol and amyl alcohol, 43.2 grams of a 15% calcium chloride aqueous solution and 86.4 grams of lime is prepared. Wbile maintaining the temperature below 80C, 1000 grams of an 85b solution of a primary bright stock mono-alkyl benzene sulfonate, having a molecular weight of about 480, a WO 93/23~ PCl/US92/08737 neutralizatior~ acid number of 110; and 15% by weight of ~n organlc diluent is added to the mixture. The mix~ure is dried at 150C to about 0.7% water. The mixture is cooled to 46-52C where 127 grams of the isobutyl-amyl alcohol mixture described above, 277 grams of methanol and 87.6 grams of a 31%
solution of calciwn overbased, formaldehyde-coupled, heptylphenol having a metal ratio of 8 and 2.2% calcium are added to the mix~;ure. Three increments of 171 grams of lime are added separately and carbonated to a neutralization base number in the range of 50-60. A fourth lime incremen~ of 171 grams is added and carbonated to a neu~ral~zation base number of 45-55. Approximately 331 grams of carbon dioxide are used. The mixture is dried at 150C to approximately 0.5% water. The reaction mixture is filtered and the filtrate is the desired product. The product con~ains 41% oil, 12% ca}cium and has a metal ratio of 11.
(D) Metal Dih~vdr~arb~Yl Dithio~hosDhate.
In addition to the c~rboxylic dispersant ~A), the alkali metal oYerbased metal salt (B) and either tbe magnesium sal., ~C-1) or the calcium salt ~C-2), the lubricating oil compositions of the present invention may contain andgenerally do contain other additive components including antiwear agents such as metal sal~s of dihydrocarbyl dithiophosphates.
The metal dihydrocarbyl dithiophosphate which may be included in the oil compositions are characterized by the formula R1 O\ ~
R20/ / ~XV) ~: :
wherein Rl and R2 are each ir dependently hydrocarhyl groups containing from 3 to about 13 carbon atoms, M is a metal, and n is an integer equal to the valence of M.

WO 93/23505 Pcr/US~2/0~737 J

~7-Generally, the oil compositions of the present invention will contain varying amounts of one or more of the abvve-id~ntified metal dithiophosphates such as from about 0.01 up to about ~% or to 5% by weight, and more general1y from about 0~01 to about 1% by weigbt based orl the we1ght of the total oil S composition. The me~al dlthicphosphates are added ~o the lubricating oil compositions of the Invention to improve the ~ntl~wear and antioxidant proper~les of the ail compositions.
The hydrocarbyl groups Rl and R2 in the dithiophosphate may be alkyl, cy~loalkyl, aralkyl or alkaryl groups, or a substantially hydrocarbon group of simil~r structure. 13y "substantially hydrocarbon" i8 meant hydrocarbons which contain substltuent groups such as f~ther, ester, nitroJ or halogen which do notmaterially affect the hydrocarbon chara~er of the group.
IllustratiYe alkyl groups include isopropyl, isobutyl, n-butyl, sec-butyl, the various amyl groups, n-hexyl, methylisobutyl carbinyl, heptyl, 2-ethylhexyl, diisobutyl, isooctyl, nonyl, behenyl, decyl, dodecyl, tridecyl, etc.
Illustrative lower alkylphenyl groups includebutylphenyl, amylphenyl, heptylphen-yl, etc. Cycloalkyl groups likewise are useful and ~hese include chiefly cyclohexyl and the lower alkyl-cyclohexyl radicals. Many substituted hydrocarbon grou~s may also be used, e.g., chloropentyl, dichlorophenyl, and dichlorodecyl.
In another embodiment, at least one of Rl and R2 in Formula XV
is an isopropyl or secondary butyl ~roup. In yet another embodiment, both and R2 are secondary alkyl groups.
The phosphorodithioic acids fram which the metal salts useful in this invention are prepared are well known. Examples of dihydrocarbyl phosphorodithioic acids and metal saltst and processes for preparing such acids - and salts are found in, for exarnple, U.S. Patents 4,263,150; 4,289,635; 4,308,154;
and 4,4t7,990. These patents are hereby incorporated by reference for such disclosures.
The phosphorodithioic acids are prepared by the reaction of phosphorus pentasulfide with an alcohol br phenol or mixtures of alcohols. The WO 93/~35~)s PCI /U~92/0~737 2 ~ ~J~

reaction invol~es four moles of the alcohol or phenol per ml~le oî phosphorus pentasulfide, and may be carrled out within the temperature rangç from about 50C to about 200C. Thus the preparation of O,O~di-n-bexyl phosphorodithioic acid involves the reac~ion of phosphorus pentssulfide with four moles of n-hexylalcohol a~ sbou~ 100C for about two hours. Hydrogen sulfide is liberated and the residue is the defined acid. The preparation of the metal salt of this acid may be effected by reaction with metal ~xide. Simply mlxing and heating these two reactants is sufficient to cause the reactioll ~o take place and the resulting product is sufficientl~ pure for the purposes of this invention.
The metal salts of dihydrocarbyl dithiophosphates which are useful in this invention include thosei salts containing Group I metals, Group 11 metals, aluminurn, lead, tin, molybdenum, mang~nese, cobalt, and nlckel. The Group Il metals, aluminum, tin, Iron, cohalt, lead, mollrbdenum, mang~nese, nickel and copper are among the preferred metals. Zlnc and copper are especially useful metals. In one embodi~ent, the lubric~nt compositions of the invention contain exampleis of metal compounds which may be reacted with the acid include lithiurn oxide, litbium hydroxide, sodiurn hydroxide, sodiurn carbonate, potassiurn hydroxide, potassium carborlate, silver oxide, magnesiurn oxide, magnesiu~
hydroxide, calcium ~xide, zinc hydroxide, strontium hydroxide, cadmium oxide, cadmium hydroxide, barium oxide, alluninum oxide, iron carbonate, copper hydroxide, lead hydroxide, tin butylate, cobalt hydroxide, nickel hydroxide, nickel carbonate, etc.
In some instances, the incorporation of certain ingredien~s such as ~; small amounts of the metal scetate or ~cetic acid in conjunction wiSh the metal reactant will facilitate the reaction and result in an improved product. For example, ~he use of up to about 5% of zinc acetate in combination with the required amount of zinc oxide facilitates the formation of a zinc phosphorodi-thioate.

WO 93/~3505 PCr/US92/08737 3 ~1 3 ln one preferred embodiment, ~he ~Ikyl groups Rl and R2 are derived from secondary alcohols such as isopropyl alcohol, secondar~ butyl alcohol, 2-pentanol, 2-methyl-4-pent~nol, 2-hexanol, 3~hexanol, etc.
Especially useful metal phosphorotllthioates can be prepared from phosphorodithioic acidls which in turn are prepared ~ the reaction of phosphoruspentasulfide with mixtures of alcohols. In addition, the use of such mixtures enables the utllization of cheaper alcohols which in ~hemselves may not yield oil-solublc phosphorodithiolc acids.
Useful ~ixture~ of metal saltg of dihydrocarbyl dithlophosphoric acid are obtained by reacting phosphcrus pentasulfide with a mixture of (a) i~opropyl or secondary butylo alcohol, and (b~ an alcohol containing at least 5 carbon atoms wherein at least 10 mole percent, preferably 20 or 25 mole percent, of the alconol in the mlxture isoprowl alcohol, sec~ndary butyl alcoholor a mixture thereof.
Thus a mixture of isopFopyl and hexyl alcohols can be used to produce a very effecti-re, oil-solu~le metal phosphorodithioa~e. For the same reason mixtures of ~phosphorodithioic acids can be reacted with the metal compounds to form less expensi-te, oil-soluble salts.
The mixtures of ~lcohols may be mixtur~s of different primary alcohols, mixtures of different secondary a!cohols or mixtures of primary and secondary alcohols. Examples of useful mlxtures include: n-butanol and n-oc-tsnol; n-pentanol and 2-ethyl-1-hexanol; isobutanol and n-hexano}; isobutanol and isoamyl alcohol;~ isoprupanoi and 2-methyl-4-pentanol; isopropanol and sec-butylalcohol; isoprnpanol ~and isooctyl alcohol; etc. Particularly useful alcohol mixtures are mixtures of secondary alcohols containing at least about 20 mole percent of isopropyl alcohol, and in a preferred embodiment, at least 40 mole percent of isopropyl alcohol. ~ ~
The î ollowing examples illustrate the preparation of metal phosphorodithioates prepared from mlxtures of alcohols.
~ Exampl~ D-I

: : ' : : ~

W(~ 93J23505 I~Cr/US92/08737 f 3 _7~

A phosphorodithioic acid is prepared by reacting a mixture of alcohols comprising 6 moles of 4-methyl-2-pentanol and 4 moles of isopropyl alcohol with phosphorus pentasulfide. The phosphorodithioic acid then is reactedwith an oil slurry of zinc oxide. The arnowlt of zinc oxide in the slurry is about 1.08 times the theoretical amount required to completely neutralize the phos-phorodithioic acid. The oil solution of the zinc phoæphorodlthioate obtained in this manner (103h oit) contains 9.59~ phosphorus, 20.0~ sulfur and 10.5% zinc.
Example D-2 A phosphorodithioic acld is prepared by reacting finely powdered phosphorus pentasulfide with an alcohol mixt~Lre c~ntaining 11.53 moles (692 parts by weight) of isopropyl slcohol and 7.69 moles tlO00 parts by weight) of isooctanol. The phosphorodithioic acid obtained in this manner has an acid number of about 17~-186 and contains 10.0% phosphorus and 21.0% sulfur, This phosphorodithioic acid is then reacted with an oil slurr~ of zlnc oxide. The quantity of zinc oxide included in the oil slurry is 1.10 times the theoretical equivalent of the ac~d number of the phosphorodithioic acid. The oil solution ofthe zinc salt prepared in this manner contains 12% oil, 8.~% phosphorus, 18.5%
sulfur and 9.5% zinc.
Example D-3 A phosphorodithioic ucid is prepared by reacting a mixture of 1560 parts tl2 moles~ of isooctyl alcohol and 180 parts (3 moles) of isopropyl alcohol with 756 parts (3.4 moles) of phosphorus pentasulfide. The reaction is conductedby heating the aicohol mlxture to about 55C and thereafter adding the phosphorus pentasulfide over a period of 1.5 hours while maintaining the reaction temperature at about 60-75C. After all of the phosphorus pentasulfide is added,the mixture is heated and stirred for an additional hour at 70-75`C,and there-after filtered through a filter aid.
Zinc oxide (282 parts, 6.87 moies~ is charged to a reactor with 278 parts of mineral oil. The above-prepared phosphorudithioic acid t2305 parts, 6.28 moles) is charged to the zinc oxide slurry over a period of 30 minutes with an WO ~3/2350~ PCI /US~2/08737 ~ ~ ?~ 2 ~ 3 exo~herm to 60C. The mixture then ~s heateid to 80C and maintained at this temperature for 3 hours. After stripping to 100''C and 6 mm.Hg., the mixture is filtered twice through a fllter ~id, and the filtrate is the desired oil solution of the zinc salt containing 10% oil, 7.979~ zinc (theory 7.40); 7.21% phosphorus(theory 7.06); and 15.649~ sulfur ~theory 14.57).
Ex~nple D-4 1sopropyl alcohol (396 parts, 6.6 moles) and 1287 par~s (9.~ moles) of isooctyl alcobol are charged to a reactur and hea~ed with stirrirlg to 59C.
Phosphorus pentasulfide (833 parts, 3.75 moles) is then added under a nitrogen sweep. 1 he addition of the phosphorus pentasulfide is completed in abo~t 2 hours at a reaction temperature between 59-63C. The mixture ~hen is s~irred at 45-63C for about 1.45 hours and filtered. The filtrate is the desired phosphorodi-thioic acid.
A reactor is charged with 312 parts ~7.7 equivalerlts) of zinc oxide and 580 parts of mineral oil. While stirring at room temperature, the abo~e-pre-pared phosphorodithioic acid (2287 parts, 6.97 e~uiYalents) is~ added o~er a period of about 1.26 hours with an exotherm to 54C. The mixture is heated to 78C
and maintained at 78-85C for 3 hours. The reaction mixture is vacuum stripped to 100C at 19 mm.Hg. The residue is filtered through a filter aid, and the filtrate is an oil solution (19.2% oil) of the desired zinc salt containing 7.86%
zinc, 7.76% phosphorus and 14.8% sulfur.
Example D-5 The general procedure of Example D-4 is repeated except that the mole ratio of isopropyl alcohol to isooctyl alcohol is 1:1. The product obtained .
in this manner is an oil solution ( 10~ oil) of the zinc phosphorodithioate containing 8.96% zinc, 8.49% phosphorus and 18.05% sulfur.
Example D-6 A phosphorodithioic acid is prepared in accordance with the general procedure of Example D-4 utilizing an alcohol mixture containing 520 parts ~4 moles) of isooctyl alcohol and 360 parts ~6 moles) of isopropyl alcohol with 504 WO S33/23~05 PCr/US92/087~?~."

7 ~

parts ~2.27 moles) of phosphorus pentasulfide. The zinc salt is prepared by reacSing an oil slurry of 116.3 parts of mineral oil and 141.5 parts (3.44 moles) of zinc oxide with 950.8 parts (3.20 mol~) of the above-prepared phosphorodi-thioic acid. The product prepared in this manner is an oil solution (109~ mineral oil) of the desired zinc sslt, and the oil solution contains 9.36% zinc, 8.81%
phosphorLts and 18.659~ sulfur.
Example D-7 A mixture of S20 parts (4 moles) of isooctyl alcohol and 559.8 parts (9.33 moles) of isopropyl alcohol is prepared and heated to ffOC at which time 672.5 parts (3.03 moles) of phosphorus pentasulfide are added ln portions while stirring. The reaction then is malntained at 60-65C for about one hour and filtered. The filtrate is the desired phosphorodithioic acid.
An oil slurry of 188.6 parts ~4 moles) of zinc oxide and 144.2 parts of mineral oil is prepared, and 1145 parts of the above-prepared phosphorodi-thioic acid are added in portions while maintaining the mixture at about 70C.
After all of the a~id is charged, the mixture is heated at 80C for 3 hours. Thereaction mixture then is stripped of water to 110C. The residue is filtered through a filter aid, and thc filtrate is an oil solution ~10% mineral oil) of th,e desired product containing 9.99% zinc, 19.55% sulfur and 9.33% phosphorus.
~0 E :xample D-8 A phosphorodithi~ic acid is prepared by the general procedure of Example D-4 utilizing 260 parts ~2 moles) of isooctyl alcohol, 480 parts ~8 moles) of isopropyl alcohol, and 504 parts (2.27 moles) of phosphorus pentasulfide. Thephosphorodithioic acid (1094 parts, 3.84 moles~ is added to an oil slu~y containing 181 parts (4.41 moles) of zinc oxide and 135 parts of mineral oil over a period of 30 minutes. The mixture is heated to 80C and maintained at this temperature for 3 hours. After stripping to 100C and 19 rmn.Hg.9 the mixture is fil~ered twice through a filter aid, and the filtrate is an oil solution ~10%mineral oil) of the zinc salt containing 10.06% zinc, 9.04% phosphorus~ and 19.2%
sulfur.

WO '33/23505 PCr/US92/08737 J ~ "

Additional specific examples of metal phosphorodithioates useful as ~omponent ~D3 in the lubricatirlg oils of the present invention are listed in the following table. E:xamples D-9 to D-14 are prepared from single alcohols, and Examples D-15 to D-lg are prepared from alcohol mixtures following thc general 5procedure of Example D-1.
TABLE
Component D: Metal Phosphorodithioates R1O ~
/PS~S~

Exam~le Rl R2 M n D-9 n-nonyl n-nonyl Ba 2 D-10 cyclohexyl cyclohexyl Zn 2 D-l 1 isobutyl isobutyl Zn 2 lS D-12 hexyl hexyl Ca 2 D-13 n-decyl n~decyl Zn 2, D-14 4-methyl-2-pentyl 4-methyl-2-pentyl Cu D-15 ~n-butyl ~ dodecyl) ~l:l)w Zn 2 D-16 (isopropyl I isooctyl) (l:l)w Ba 2 D-17 (isopropyl ~ 4-methyl-2 pentyl) (40:60)m Cu 2 D-18 (isobutyl ~ isoamyl) ~65:35)m Zn 2 D-19 (isopropyl'sec-butyl) ~40:60tm Z n 2 Another class of the phosphorodithioa~e additives contemplated for use in the lubricating composition of this invention comprises the adducts of the metal phosphorodithioates described above with an epoxide. The metal phosphorodithioates useful in preparing such adducts are for the most parl: the zinc phosphorodithioates. The epoxides may be alkylene oxides or arylalkylene W~ g3/2350:~ PCr/US92/0873~

2 ~ .3 oxides. The arylalkylene oxides ~re exemplified by styrene oxide, p-ethylstyreneoxide, alpha-methylstyreneoxide, 3-beta-naphthy1-1,1,3-butyleneoxide, m-dode-cylstyrene oxide, and p-chlorostyrene oxide. The alkylene oxides include principally the lower alkylene oxides in which the a~kylene radical contains 8 or less carbon atoms. Exarnples cf such lower alkylene oxldes are ethylene oxide, propylene oxide, 1,2-butene oxide, trlmethylene oxlde, tetramethylene o~cide, ~utadiene monoepoxide, 1,2-hexene oxide, ~nd epichlorohydrin. Other epoxides useful herein include, for example, butyl 9,10-epoxy stearate, epoxidized soya bean oil, epoxidized tung oll, and epoxidized copolymer of styrene wlth butadiene.
The adduct may be obtained by simply mixing the metal phosphoro-dithioate and the epoxide. The reaction is usus11y exothermic and may be carriedout within wide temperature limits from about 0C to about 300C~ Because the reaction is exotherrnic, it is best carrled out by adding on reactant, usually ~he epoxide, in small increments to the other reactant in order to obtain conversient control of the temperature of the reaction. The reaction may be carried out in a solvent such as benzene, mineral oil, naphtha, or n-hexene.
The chemical structure of the adduct is not known. For the purpose of this invention adducts obtained by the reaction of one mole of the phosphorodithioate~ with from about 0.25 mole to 5 molesl usually up to about 0.75 mole or about 0.5 mole of a lower alkylene oxide, particularly ethylene oxide and propylene oxide, have been found to be especially useful and thereforeare preferred.
The preparation of such adducts is more speclfically illustrated by the following example.
Example D-20 A reactor is charged with 2365 parts (3.33 moles) of the zinc phosphorodithioate prepared in Example D-2, and while stirring at room temperature, 38.6 parts (0.67 mole) of propylene oxide are added with an exotherm of frorn 24-31~C. The mixture is maintained at 80-90C for 3 hours : ~:

.

WO 93/235~)~ PCJ/USg2/08737 .,. ~ .., .., , ~ .

and then vacuurn stripped to 101C at 7 mm. Hg. The resiciue is filtered using a filter aid, and the filtrate Is an oil solution ~11.8% oil) of the desired salt containing 17~1% sulfur, 8.17~6 zinc and 7.449~ phosphorus.
In one embodiment, the metal dihydros~srbyl dithiophospha~es which are utilized as component (D~ ln ~e lubricating oil compositlons of th~3 presentinvention will be characterized as havlng at least one of the hydrucarbyl groups(R1 or R2) attached to the oxygen atoms through ~ secondar~ carbon atom. In one preferred embodlmen~, both of the hydrocarbyl groups R1 and R2 are attached to the oxygen atoms of the dithiophosphate through s~condary carbon atoms. In a further embodiment, the dihydrocarbyl dithiophosphoric acids used in the preparation of the metal salts are obtalned by reacting phosphorus pentasulfide with a mixture of aliphatic alcohols wherein at 1east 20 mole percent of the mix~ure is isopropyl al~ohol. More generally, such mixtures will contain at least 40 mole percent of isopropyl alcohol. The other alcohols in themixtures may be either primary or secondary alcohols. In some applications, such as in passenger car crankcase oils, metals phosphorodithloates derived frnma mixture of isopropyl and another secondary alcohol ~e.g., 2-methyl-4-pentanol)appear to provide improved results. For oils designed for use in both compressi~n and spark-ignited engines, improYed results ~re obtained when the phosphorodi-thîoic acid is prepared from a mixture of isopropyl alcohol and a primary alcohol such as isooctyl alcohoi.
Another class of the phosphorodithioate additives (D~ contemplated as useful in the lubricating compositions of tbe invention comprises mixed metalsalts of (a) at least one phosphorodithioic acid as defined and exemplified above, , I i ~
2~ and (b) at least one aliphatic or alicyclic carboxylic acid. The carboxylic acid may be 8 monocarboxylic or polycarboxylic acid, usually containing from 1 to about 3 carboxy groups and preferably only 1. It may contain from about 2 to about 40, preferably from about 2 to about 20 carbon atoms, and advantageously about 5 to about 20 carbon atoms. The preferred carboxylic acids are those 3V having the formula R3CooH,~ wherein R3 is~ an aliphatic or alicyclic hydrocar~

WO 93/2350~ P~/~JS92108737 2 ~ (i .3 ~

bon-based radical preferably free from ace~ylenic unsaturation. Suitable ~cids include the butanoic, pentanoic, hexanoic, octanoic, nonanoic, decanoic, dodecanoic, octadecarloic and eicosanoic acids, as well as olefinic acids such as oleic, linoleic, and linolenic acids and linoleic acid dimer. For the most part, R3 is a saturated aliphatic group and especially a branched alkyl group such as theisopropyl or 3-heptyl group. Illustrative polycarboxylic acids ~re succlnic, alkyl-and alkenylsuccinic~ adipic, sebaci~ and citric aclds.
The mixed metal sal~s may be prepared by merely blending a metal salt of a phosphorodithioic acid with a metal salt of a carb~xylic acid in the desired ratio. The ratio of equivalents of phosphorodithioic to carboxylic acid salts is between about 0.5:1 to about 400:1. Preferably, the ratio is between about 0.5:1 and about 200:1. Advantageously, the ratio can be from ~bout 0.5:1 to about 100:1, preferab1y from abou~ 0.5:1 to about 50:1, and more preferably from about 0.5:1 to about 20:1. Further, the ratio can be from about 0.5:1 to about 4.5:1, preferably about 2.5:1 to about 4.25:1. For this purpose, the equivalent weight of a phosphorodithioic acid is its molecular weight divided bythe number of -PSSH groups therein, and that of a carboxylic acid is Its molecular weight divided by the ntLmber of carboxy groups therein.
A second and preferred method for preparing the mixed metal salts useful in this invention is to prepare 8 mixture of the acids in the desired ratio and to react the acid mixture with a suitable metal base. When this method of preparation is used, it is frequently possible to prepare a salt containing an excess of metal with respect to the number of equivalents of acid present; thus,mixed me~al salts containing as many as 2 equivalents and especially up to about1.5 equivalents of metal per equivalent of acid may be prepared. l`he equivalentof a metal for this purpose is its a~omic weight divided by its valence.
Variants o~ the above-described methods may also be used to prepare the mixed metal salts useful in this invention. For exannple, a metal salt of either acid may be blended with an acid of the other, and the resulting blendreacted with additional metal base.

WV ~3/23505 PCI/USg2/~8737 . p , t,i ~ J' ~77-Suitable metal bases for the preparation of the mLl~ed metal salts include tbe free metals prevlously enumerated and their oxides, hydroxides, alkoxides and basic salts. Examples are sodium bydroxide, potassium hydroxide, magnesium oxide, calcium hydroxide, zinc oxide, lead oxide, nickel oxide and the5like.
The temperature at which the mixed metal s~lts are prepared is generally between about 30~C and about 150C, preferably up to about 125C.
If the mixed salts are prepared by neutrallzation of a mixture of acids with a metal base, it is preferred to employ temperstures above about 50C and especially above about 75C. It is frequently ad~antageous to conduct the react~on in the presence of a substantlally i2~ert, norrnally liquid organic~diluent such as naphtha, benzene, xylene, mineral oil or the like. If the diluent is mineral oil or is physically and chemically similar tu miner~1 oil, it frequently need not be removed before using the mixed metal sal~ as an additlve for lubricants or funGtional fluids.
U.S. Patents 4,308,154 and 4,417,970 describe procedures for preparing these mixed metal salts and disclose a number of examples of such mixed salts. Such disclosures of these patents are hereby incorporated by reference.
The preparation of the mixed salts is illustrated by the following example.
Example D-21 A mixture of 67 parts (1.63 equhralents) of zinc oxide and 48 parts of mineral oil is stirred at room temperature and a mixture of 401 parts (1 equivalent) of di-~2-ethylhexyl) phospharodithioic acid and 36 parts (0.25 equi~ralen~) of 2-ethylhexanoic~ acid is~ added over 10 minutes. The temperatureincreases to 40C during the addition. W~len addition is complete, the tempera-ture is increased to 80Ç for 3 hours. The mixture is tnen vacuurn stripped at 100C to yield the desired mixed metal salt as a 91% solution in mineral oil.
(E) A_tioxidant.

WO ~3/~3505 Pcr/us92/o873?

3 /'J lJ '~ 78-The lubricating oil compositions of the present invention also may include an antioxidant ~E), with the proviso that (E) the antioxidant and ~D) the metal dithiophosphalte are not the same. ~or instance, (D) and ~E~ may both be metal dithiophosphateis provided that the me~al of (D) is not the sarne as the metal of ~E)~ In one embodiment, the antioxidants are selected from the group consisting of: sulfur-containing composltlons, allcylated aromatic amlnes, phe-nols, and oîl-soluble transition metal containing compounds When present, the lu~rica~ing oil compositions may cantaln from about 0.01 to about 2~ or even $%
of at least one antioxidant.
The antioxidant may be one or more sulfur-containing compositions.
Materials which may be sulfurized to form the sulfurized organic compositions of the present invention include oils, fatty acids or esters, olefins or polyolefins made thereof or Diels-Alder adducts.
Oils which m~y be sulfurized are natur21 or synthetic oils including mineral oils, lard oll, carboxyli~ acid esters derived from aliphatic alcohols and fatty acids or aliphatic carboxylic acids (e.g., myristyl oleate and oleyl olea~e) sperm whale oil, synthetic sperm whale oil substitutes and synthetic unsaturatedesters or glycerides.
Fatty acids generally contain from about 8 to about 30 carbon atoms. The unsaturated fatty acids generally contained in the naturally occurring vegetable or animal fats and such acids inc}ude palmitoleic acid, oleic acid, linoleic acid, linolenic acid, and erucic acidO The fatty acids may comprise mixtureis of acids, such as those obtained from naturally occurring animal and vegetable oi!s, including beef tallow, depot fat, lard oil, tall oil, peanut oil, corn oil, safflower oil, sesame oil, poppy-seed oil, soybean oil, cottonseed oil, sunîlower seed oil, or wheat germ oil. Ta!l oil is a mixture of rosin acids, mainly abietic acid, and unsaturated fatty acids, mainly oleic and linoleic acids. Talloil is a by-product of the sulfate process for the manufacture of wood pulp.
The fatty acid esters also may be prepared from aliphatic olefinic ~0 acids of the type described above by reaction with arly of the above-described .

WO ~3/23505 P~r/US92/08737 !-, .L ~ ' .; ' , , , ~J

s~lcohols and polyols. Examples of aliphatic alcohols include monohydr ic alcohols such as methanol) ethanol; n- or isopropanol; n-, iso-, sec-, or tertbutanol, etc.;
and polyhydric alcohols including ethylene glycol, propylene glycol, trimethylene gly~ol, neopentyl glycol, glycerol, etc.
The olefinic compounds which may be sulfurized are diverse in nature. They contsi~ at least one olefinic dauble bond, whicb is defined as a non-aromatic double bond; that is, one connec~ing two aliphatic carbon atoms.
- In its broadest sense, the olef~n may be defined by the formula R lR 2C=CR 3-R 4, wherein each of R 1, R Z, R 3 and R 4 is hydroKen or an organic group. In general, the R groups in the above formula which are not hydrogen may be satisfied by such groups as -C~R 5)3,-CooR 5~-CoN(R 5)2,-CooN(R 5)4, -COOM, -CN, -X, -YR S or -~r, wherein:
each R 5 is independently hydrogen, alkyl, alkcnyl, ~ryl, substituted alkyl, substituted alkenyl or substituted 81-yl, with the proYiso that any two R 5 groups can be alkyl~ne or substituted alkylene whereby ~ ring of up to about 12 carbon atoms is formed;
M is one equivalent of a metal cation (preferably Group I or 11, e.g~, sodium, po~assium, barium, calciwn);
X is halogen (e.g., chloro, bromo, or iodo);
Y is oxygen or divslent sulfur;
Ar is an a~yl or substituted aryl group of up to about 12 carbon atoms.
Any ~wo of R l, R 2, R 3 and R 4 may also together forrn an al~cylene or substituted alkylene group; i.e., the olefinic compound may be sli~yclic.
The olefinic compound is usually one in which each R group which is not hydrogen is independently alkyl, alkenyl or arS~I group. Monoolefinic anddiolefinic compoùnds, particularly the :forrner, are preferred, and especially terminal monoolefinic hydrocarbons;:that is, those cornpounds in which R 3 and R 4 are hydrogen and R 1 and R 2 are alkyl or aryl, especially alkyl ~that is, the WO 93/2350-, PCI /US92tO8737 ~

.
~J~ai~t~ J~

olefin is aliphatic) having 1 to about 30, preferably 1 to about 16, more preferably 1 to about 8, and more preferably 1 to about 4 c:arbon atoms. Olefinic compounds having about 3 to 30 and especlally about 3 to 1~ ~most often less than g) carbon aton~C~ are particul~rly desirable.
Isobutene, propylene and thelr dimers, trimers ~nd tetramers, and mixtures thereof are especially preferred oleflnic compounds. Of these compounds? isobutylene and di~sobutylene are particularly de~irable because of their availability and the particularly high sulfur containing compositions whlch can be prepared therefrom.
In another embodiment, the sulfurized organic compound is a - sulfurized terpene compound. The term "terpene compoundl' as used in the specification and claims is i2ltended to include the various isomeric terpene hydrocarbons having the empirlcal formula CloH16, such as c~ntairled in turpentine, pine oil and dipentenes, and the variou~ synthetic and naturally occurring oxygen-containing derivatives. Mixtures of these various compounds generally will bei utilized, especially when natural products such as pine oil and turpentine are used. Pine oll, for example, comprises a mixture of alpha-terpineol, beta-~erpineol, alpha-fenchol, camphor, borneol/isoborneol, fenchonç,estragole, dihydrn alpha-terpineol, anethole, and other mono-terpene hydrocar-bons. The specific ratios and amounts of the various components in a given pine oil will depend upon the particular source and the degree of purification. A
group of pine oil-derived produc~s are available corrunercially from Hercules Incorporated. It has been found that the pine oil products generally known as terpene alcohols available from Hercules Incorporated are particularly useful in, ,: I , , ;
~he preparation of th sulfurized products of the inYention. Pine oil products are available from Hercules under such designations as alpha-Terpineol, Terpineol 318 Prime, Yarmor 302, Her~o pine oll, Ya~nor 302W, Yarmor F and Yarmor 60.
In another embodiment, the sulfurized organic composition is at leaist one sulfur-containing material which comprises the reaction product of a sulfur source and at least onei Diels-Aldeir adduct. GenerallY, the molar ratio of WO 93/23s05 PCI/lJS92/08737 ~s~ i '.f sulfur source to Diels-Alder adduct is in a range of from about 0.75 to about 4.û, preferably about 1 to about 2.5, more preferably about 1 to sbout 1.8. In one embodiment the molar ratio of sulfur to adduct is from about 0.8:1 to 1.2:1.
The Diels-Alder adducts are a well-known, art-recognized class of compounds prepared by the diene syrl~hesis or Diels-Alder reac~lon. A sun-mary of the prlor art relating to this class of compounds is found in the Ru~sian monograph, ~, Izdatelstwo Akadem~ Nauk 5SSR, 1963 by A.S.
Onischenko. (Translated into the English language by L. Mandel as A.S.
Onischenko, Diene S~esist N.Y., Daniel Davey and Co., Inc., 1964.) This monograph and references cited therein are incorporated by reference into the present specificatlon.
Basically, the diene synthesis (Dlels-A1d~r resction] invol~res the reaction of at least one con3ugated dienc with at least one ethylenically or acetylenlcally unsaturated campound, these latter compounds being known as dienophiles. Piperylerle, isoprene, methylisoprene, chloroprene, and 1 ,3-butadiene are among the preferred dienes for use in preparing the Diels-Alder adducts.
Examples of cyclic dienes are the cyclopentadienes, fulvenes, 1,3-cyclohexa-dienes, 1 ,3-cycloheptadienes, 1 ,3,5-cyclaeptatrienes, cyclooctatetraene, and 1 ,3,5-cyclononatrienes.
2Q A preferred class of dienophiles are those having at least one electron-acceptiDg groups selected frorn groups such as formyL cyano, ni~ro, carboxy, carbohydrocarbyloxy, etc. Usually the hydrocarbyl and substituted hydrocarbyl groups, if not present, will not contain more than 10 carbon atoms each~ ~
~5 Qne preferred class of dienophiles are those wherein at least one carboxylic ester group represented by -C~O)O-Ro where Ro is the residue of a saturated aliphatic alcohol of up to about 40 carbon atoms, the aliphatic alcohol from which -Ro is derived can be any of the above-described mono or polyhydric alcohols. Preferably the alcohol is a lower aliphatic alcohol, more preferably 3 0 metbanol, ethanol, propanol~ or butanol.

WO 93/23505 PCr/US9~/0~737 ln additiorl to the ethylenically unsaturated dienophiles, there are rnany useful acetylenically utlsaturated dienophiles such as propiolaldehyde, rnethyl-ethynylketone, propylethynylketone, propenylethynylketone, propiolic acid, propiolic acid nitrlle, ethyl-propiolate9 tet;rolic ~c}d, pr~pargylaldehyde, acetylene-dicarboxylic acid, the d~nethyl ester of ~cetylenedicarboxylic acid, dibenzoylace~ylene, and the like.
Normally, the adducts involve the reaction of equirnolar arnounts of diene and dienophile. However, if ~be dienophlle has more than one ethylenic linkage, it is possible for additional diene to react if present In the reactionmixtura It is frequently 2dvantageous ~o incorporate materials useful as sulfurization promoters in the reaction mixture. These materials may be acldic, basic or neutral. Useful neutral and acldic materials include acidified clays such 8S "Super Filtrol" ~sulfuric acid treated diatornaceous earth), p-toluenesulfonic acid, phosphorus-containing reagents such as phosphorus acids (e~g, dialkyl-pho~-phorodithioic acids, phosphorus acid esters (e.g., triphenyl phosphate), phosphorus sulfides such as phosphorus pentasulfide and surface active agents such as lecithin.
The preferred promo~ers are basic materials. These may be inorganic oxides and salts such as sodium hydroxide, calciwn oxide and sodium sulfide. The most desirsble b~:sic promoters, however, are nitrogen bases including ammonia and amines. ~
The amount of promoter material used is generally about 0.0005-2.0% of the combined weight of the teF~ene and olefinic compounds. In the case of the preferred ammonia and amine catalysts, about 0.0005-0.5 mole per mole of the combined weight is preferred, aod about 0.001-0.1 i5 especially desirable.
Water is also present in the reaction mixture either as a promoter or as a diluent for one or more of the promoters recited hereinabove. The amount of water, when present, is usually about 1-25% by weight of the olefinic compound. The presence of wa~er i5, however, not essential and when certain WO 93/2350~ P(~r/us92/0~737 types of reaction equipmen~ are used it may be advantageous to conduct the reaction under substantially anhydrous conditions.
When promoters are incorporated into ~le reaction mixture as described hereinabove, It is generally obser red that the reaction can be conducted at lowel ternperatures9 and the product generally is lighter in color.The sulfur source or reagent used for preparing any of the sulfur-con~ainlnz materials OI thls inventlon may be, for example, sulfur, a sulfur halide such as sulfur monochloride or sulfur dichlorlde, a mixture of hydrogen sulfide and sulfur or sulfur dioxide; or the like. Sulfur) or mixtures of sulfur and hydrogen sulfide often are preferred. Ho~verer, lt ~will be understood that other sulfurization reagents may, when apprc)priste, be substitu~ed therefor.
Commercial sc~urces of all ~he sulfurizing reagen~s ar~ normally used for the purpose of this invention, and impurities no~nally ~ssociated with these commer-cial products may be presen~ without adverse results.
When the sulfurization reaction is effected by the use of sulfur alone, the reaction is effected by merely heating the reagents wlth the sulfur at temperatures of from about 50 to 250C, usually, from about 150 to about 210C.
The weight ratio of the materials to be sulfur~zed to sulfur is between about 5~1 and about 15:1, generally between about 5:1 and~ abou~ 10:1. The sulfurization reaction is conducted with efficient agitation and generally in an inert atmosphere (e.g., nitrogen~. If any of the components or reagents are apprecia-bly volatile at the reaction temperature, the reaction vessel may be sealed and maintained ur~der pressure. It is frequently advantageous to add the sulfur p~rtionwise to the mixture of the oeher components.
When mixtures of sulfur and hydrogen sulfide are utilized in the process of the invention, the amounts of sulfur and hydrogen sulfide per mole ofcomponent(s~ to be sulfurized are, respectively, usually about 0.3 to about 3 gram-atoms and about 0.1 to about 1.5 moles. A preferred range is from about 0.5 to about 2.0 grarn-atoms and about 0.4 to about 1.25 moles, respectively, and the most desirable ranges are about 0.8 to about 1.8 gram-atoms, and about 0.4 WO 93/235~5 P~r/US92/087?s7 -~4-to about 0.8 mole, respectively. In reaction mixture operations, ~he components are introduced at levels to provide these ranges. In semi-continuous oper~tions, 3 they may be admixed at any ratio, but on a mass balance basis, they are present so as to be consumed irl amounts within ~hese ratios. Thus, fDr example, if the reaction vessel is initially charged wlth sulfur alone, the terpene and/or olefirlic compound and hydrogen sulfide are added incrementally at a rate such that the desired ratio is obtained.
When mixtures of sulfur and hydrogen sulfide are utilized in the sulfurization reaction, the temperature range of the sulfurization reactio~ is ~enerally from about 50 to about 350C. The preferred range is about 100 to about 200C wi~h about 120 to about 180C being especlally suitable. The reaction often is conducted under super atmospheric pressure which may be and usually is autogenous pressure ~i.e~, pressure which rlatural~y developed during the course of the reaction), but may also be externally applied pressurs. The exact pressure developed during the reaction Is dependent upon such fac~ors as design and operation of the system, the resction temperature, and the vapor pressure of the reactants and products, and it may vary during the course of the reac~ion~
While i~ is preferred generally that the reaction mixture consis,ts entirely of the components and reagents described above, the reaction also may be effected in the presence of an iner~ solven~ (e.gO~ an alcohol, ether, ester,aliphatic hyd;ocarbon, halogenated aromatic hydrocarbon, etc.) which is liquid within the temperature range employed. When the reaction temperature is relatively high, for ex~nple, at about 200C, there may be some evolution of sulfur from the prod~t which is avoided Is a lower reaction temperature such as from about 150-170C is used.
In some instalaces, it may be desirable to treat the sulfurized product obtained in accordance with the procedures described herein to reduce active sulfur. The term "aetive sulfur" Includes sulfur in a form which can cause staining of copper and similar materials, and standard te~ts are available to determine sulfur activity. As an alternative to the trea~nent tO reduce active .

Wo 93~23505 PCl /US92/0~737 ~ ~ J. `~i i. J ' `; j _~

-8~-sulfur, metal deactivators can be used with the lubricants containing sulfurizedcompositions.
The following examples relate to sulfurized compositions useful in the present inven~ion, E.x~mple 1~
A reactlon vessel i5 charged with 780 par~s isopropyl alcohol, 752 par~s water7 35 parts of a 50% by w~}ght aqueous solution of sodium hydroxide, 60 psr~s of sulfuric acid treated di~tomaceous earth ~Super Filtrol available from Engelhard Corporation, Menlo Park~ New Jer~ey) and 239 parts of sodium sulfide.
The mixture is stirred and heated to 77-80C. The reaction temperaturc is main-tained for two hours. The mixture is cooled to 71C whereupon 1000 parts of the sulfurized olefin prepared by reacting 337 parts of sulf~ rnorlochloride with 1000 par~s of a mix~ure of 733 parts of 1-dodecene ~nd lOûO parts of Neodene 1618, a C16_1golefin mixture avaiiable from Shell Chemical, are added to the mixtur~.
The reacticn mixture i5 heated to 77-80C and the temperature is maintained until the chlorine content is a ~aximurn of 0.5. The reaction mixture is vacuum stripped to 80C and 20 millimeters of mercury. The residue is filtered through dia~omaceous earth. The filtrate has 19.0~ sulfur an(i a specific gravity of 0.95.
Exa~mple E-2 A mixture of lO0 parts of soybean oil and 50 parts of coIT~nercial C~6 -olefins is heat~d to I7~C. under nitrogen and 17.4 parts of sulfur are added gradually, whereupon an exothermic reaction causes the temperature to rise to 20SC. The mixture ls heated at lB8-200C. for S hours, allowed t~ coolgradually to 90C. and filtered to yield the desired product containing 10.13%
sulfur.
Example E-3 A mixture of 100 parts of soybean oil, 3.7 parts of ~all oil acid and 4603 par~s of commercial C15 18 a~olefirls is~heated to 165C. under nitrogen and 17.4 parts of sulfur are added. The temperature of the mixture rises to 191C.

WO 93/23~ PCI/US9~/98737 2~ flf~ 3 lt is maintained at 165-200C. for 7 hours and is then cooled to 90C. and filtered. The product contains 10.139~ sulfur.
Example E-4 A mixture of 93 parts (0.5 equivalen~ of pine oil and 48 par~s (1.5 equivalerlts) of sulfur is charged to a reaction vessel e~uipped with condenser,thermometer and stirrer. The mix~ is heated to about 140C with nitrogen blowing and malntained at thls ~empera~ure for about 28 hours. After cooling, 111 parts of a C16 alpha-olefin (available from Gulf Oil Chemicals Company under the general trade name Gulftene 16) are added thrsugh an addltion funnel, and after addition is complete, the addition funnel is replaced wlth a nitrogen tube. The re~ction mixture is heated to 170C wlth nitrogen blowing and maintained at the temperature for about 5 hours. The mixture is cooled and fil~ered through a filter aid. The filtrate is the desired product having a sulfur content of 19.01% (theory 19.04%3.
Example E-5 (a) A mixture comprising 400 grams of toluene ~nd 66.7 grams of aluminum chloride is charged to a two- liter flaslc fitted with a stirrer, nitrogen inlet tube, and a solid carbon dioxide-cooled reî lux condenser. A second mixture comprîsing 640 grams (5 moles) of butyla~rylate and 240.B grams of toluene is added to the AlCl3 slurry over a 0.25 hour period while maintaining the temperature within the range of 37-58C:. Thereafter, 313 grams ~5.8 moles) of butadiene are ad~ed to the slu~ over a 2.75-hour period while maintaining the temperature of che reaction mass at 60 61C by means of external cooling.
The reaction mass is blown with nitrogen f~r about 0.33-hour and then trans-j,, I . , ferred to a four-liter separatory funnel and washed with a solution of 150 gramsof concentrated hydrochloric acid in 1100 grams of water. Thereafter, the product is subjected to two additional water washings using 1000 ml of water foreach wash. The washed reaction product is subsequently distilled to remove unreacted butylac~late and toluene. The residue of this first distillation step is subjected to further distillation at a pressure of 9-10 millimeters of mercury WO g3J~350~ Pcr/uS92/08737 j, , ,-~ t .' ~ :

whereupon 785 grams of the desired adduct are collected over the ternperature ~f 105-115C.
(b) The above-prepared butad~erle-butylacrylate Diels-Alder adduct ~4550 grams, 25 moles) and lB00 gr~ns ~50 moles) of sulfur flowers are S cha~ged to a 12 liter flask, fitted with st~rer, reflux conden.ser, and nitrogen inlet tube~ The reaction mixture Is heated at a tennperature wlthlll the range of 150-155C for 7 hours whi1~: passing nitrogen ~herethrough at a rate of about 0.5 cubi~ feet per hour. After heating, the mass is permitted to cool to room temperature and filtered, the sulfur-con~aitJlng product being the filtrate.
The antioxidant (E) may als~ be an alkylatecl aron~atic amlne.
Alkylated aromatic amines include compounds represented by the formula ~6 Ar3-N-A} 4 ..
wherein Ar3 and Ar4 are independen~ly mononuclear or polynuclear, substituted or wlsubstltuted aromatic groups; and R6 is hydr~gen, halogen, OH, NH2, SH, N02 or a hydrocarbyl group of from 1 to about 50 carbon a~oms. Ar3 and A~4 msy be any of the above-described aromatic grcups. When Ar3 and/or ~r4 are substituted aromatic groups, the Ilumber of substituents on Ar3 andior Ar4 rangeindependently up to the number of positions available on Ar3 and/or Ar4 for substitution. These substituents are independently selected from the group consisting of halogen ~e~g., chlorine, bromine, etc.), OH, NH2, SH, N02 or hydrocarbyl groups of from 1 to about 50 carbon atoms.
In a preferred embodiment, antioxidant (E~ is represented by the formula , WO 93/2351)5 PCl /US92~08737 2 ~ Q ~ ~
-$~-~ R~

R7--~ <~ (XVI) wherein R7 and R8 are independently hydrogen or hydroearbyl groups of from 1 to about 50 car~on ~toms, preferably hydrocarbyl groups of from about 4 to about 20 carbon atoms. Examples of aromatic ~nines include p,p'-dioctyldi-phenylam~ne,octylphenyl-be~a-naphthylamine~,oetylphenyl-~lpba-naphthylamine, phenyl-alpha-naphthylamine; phenyl-beta-naph~hylamine; p-octylphenyl-alpha naphthylarnine a~d 4-octylphenyl-1-octyl-beta-naphthylaITline and di(nonyl-phenyl)aminc, with dl(nonylphenyl)amine preferred.
U.5. Patents 2,558,285; 3,601,632; 3,368,~75; and 3,S05,225 disclose diarylamines wlthin the scope of component ~E). These patents are inco2~0rated herein by reference.
The an~ioxidants (E) used in ~he present invention ma~r be one or more of several types of phenolic compoun~s which may be metal-free phenolic compounds.
ln one embodiment, the antioxidant of the present invention include~ at least one metal-free hindered phenol. ~Ikylene coupled derivatives ofsaid hindered phenols also can be used. Hindered phenols are defined (in the specification and claims) as those containing a sterically hindered hydroxyl group, and these; include those de~ivatives of dihydroxy aryl compounds wherein the hydroxyl groups are in the o- or p-position to each other.
The metal-free hindered phenols may be represented by the following Formulae XVII, XVIII and XlX.

W0~3/23505 , ~ 9 . PCr/US92tO8737 OH

OH OH
R9-( ~^ R9 (XVIII) Ri0 OH C)H
R9~C~R12)~ ~R9 (XI~C) :

wherein each R9 ~s independently an alkyl group containing from 3 to about 9 carbon atoms, each R10 is hydrogen or an alkyl group, Rl1 is hydrogen or an alkyl group containing from 1 to about 9 carbon atoms, and each R12,is ~`; lndependently hydrogen or a methyl group. ln the preferred embodiment, R10 is -an alkyl group containing from abo~t 3 to about 50 carbon a~oms, preferably :: 15 about 6 tc about 20, more preferably:;from about 6 to about 12. ~ a nples of such groups inclllde hexyl, heptyl, oct l,~de~yl, dodecyl~ ~ripropenyl, ~etrapropen-yl, etc. Exa~nples~ of R9, R10 and Rl~ groups lnclude propyl, isopropyl, butyl, `` ~ secondary butyl, tertiar~r butyl, heptyl, octyl, and nonyl. Preferæbly, each R9 and Rll are:tertiary groups such as tertia~r butyl~ tertiary amylg etc. The phenolic2 Q: ~ compounds of the:type represented by For~slula XV may be prepared by various :techniques, and in one embodiment, such~phenols are prepared in stepwise marmer::by first preparing the para-substitu~ed alkyl phenol, and thereafter alkylatl~ng~ the para-substitùted phenol in~ the 2- asld/or 6-position as desired.
When it is desired to prep~re coupled phenols of the type represented by WO 93/2350~ PCr/US92/08737 2 1 ~ f ;~
_90_ Formulae ~CVI and XVII~ the second step alkylation is conducted under conditions which result in the alkylation of only one of the positions ortho to the hydroxyl group.
Exa}nples of useful phenolic materials of the type represented by S Formula X~ include: ~-t-butyl-4-heptyl phenol; 2-t-butyl-4-octyl phenol;
2-t-bu~yl-4-dodecyl phenol; 2,6-dl-t-butyl-~butylphenol; 2,6-di-t-butyl-4-heptylphenol; 2,ff-di-~-butyl-~dodecyl phenol; 2-methyl-6-dl-t-btltyl-4-heptyl phenol;2,4-dimethyl-6-t-butyl phenol; 2,6-t-butyl-4-ethyl phenol; 4-t-butyl catechol; 2,4-di-t-butyl-p-cresol; 2,6-di-t-but~rl-4-methyl phenol; and 2-me~hyl-6-di-t-butyl-~dodecyl phenol.
Examples of the ortho caupled phenols of the type represerlted by Forrnula XVI lnclude: 2,7'-bis(6-t-butyl~4-heptyl phenol); 2,2'~bis16-t-butyl-4-octyl phenol~; 2,6-bis-(1'-metbylcyclohexyl)-4-methyl phenol; and 2,2'-bis(6-t-butyl-4-dodecyl phenol).
Alkylene-c~upled pheoolic compounds of the type represented by Formula XVII can be prepared from the phenols represented by Formula }CV
wherein Rl 1 is hydrogen by reaction of the phenolic compound with an aldehyde such as formaldehyd~, acetaldehyde, etc~ or a ketone such as aceton,e.
Proc~dures for coupling of phenolic compounds with aldehydes and ketones are : 20 well known in the srt, ~nd the procedures do not need to be described in detail herein. To illustrat2 the process, a phenolic compound of the type represented by Formula ~CV wherein Rll ~s hydrogen is heated with a base or an acid, such as sulfuric acid, in: a diluent such as toluene or xylene, and this mixture is then contacted with an aldehyde or ketone while heating the mixture to reflux and removing water as the reaction progresses.
Examiples of phenolie compounds of the type represented by , Formiula XVII include 2,2'-methylene-bis(6-t-butyl-4-heptyl phenol~; 2,2'-methyl-ene-bis(~t-butyl~octyl phenol); 2,2'-methylene-bis-(4-dodecyl-6-t-butyl phenol);
2,2'-methylen~bis-~4-octyl~-t-butyl~pheinol); 2,2'-methylene-bis-(4-octyl phenol~;
2,2'-methylene-bis-(4-dodecylphenol);2,2'-methylene-bis-(4-heptylphenol);2,2'-WO 93/~3sO5 P~/US92/0~737 " ~
j " "~ .,J~ ' methylene-bis(6-t-butyl-4~dadecyl phenol); 2,2'-me~lylene-bis~6-t-butyl-4-~etrapropenyl phenol); and ~,2'methylene-bis~6-t-butyl-4-butyl phenol).
The alkylene-coupled phenols may be obtained by reacting a phenol ~2 equiv~lents) with 1 equivalel t of an aldehyde or ketone. Lower molecular weight aldehydes are preferred and particularly preferred examples s~f useful aldehydes include formaldehyde, a reversible polymer thereof such as paraform-aldehyde, ~rioxane, ace~aldehyde) e~c. As used in this speclfication and claims,the word "formaldehyde" shall be deemed to include such reversible polymers.
The alkylene-coupled phenols can be deriYed ~om phenol ar substltuted al~l phenols, and substituted alkyl phenols are preferred. The phenol must ha~e an ortho or para position available for reaction with the aldehyde.
In one embodiment, ~he phenol will contain one or more 21kyl groups which may or may not resul~ in a sterically hindered lrydroxyl group.
Examples of hindered phenols which ~an be used in the formation of the alkylene-l S coupled phenols inelude: 2,4-dimethylphenol; 2,4-di-t-butyl phenol, 2,6-di-t-butyl phenol; 4-octyl-6-t-butyl phenol; etc.
In one preferred embodimeslt, the phenol ~om which the alkylene-coupled phellols are prepared are phenols substituted in the para position with aliphatic groups containing at least 6 carbon atoms as described above.
Generally, the alkyl groups contain from 6 to 12 carbon atoms. Preferred alkyl groups are derived from polymers of ethylene, propyleneJ 1-~utene and isobutene,preferably propylene tetramer or trimer.
The reaction between the phenol and the aldehyde, polysner thereof or ketone is usually carried out between room temperature and about 150Ç, , preferably about 50-125C. The reaction preferably is carried out in the presence of an acidic or basic material such as hydrochloric acid, acetic acid, sulfuric acid, ammonium hydroxide, sodium hydroxide or potassium hydroxide.
The relathre amounts of the reagents used are not critical, but it is generally convenient to use about 0.3 to about 2.0 moles o~ phenol per equivalent of formaldehyde or other aldehyde.

WO 93/2350~i P~/US9l/~873?

r/~ ~J YJ ~

The following examples illus~rate the preparation of p~nolic compounds of the type represented by Formulae XVII and XLX.
Example E-6 A re~ction vessel is charged with 3192 parts (î2 moles~ of a 4-tetrapropenyl phenol. The phenol is hested to 80C ln 30 minutes an~ 21 parts (0.2 mole~ of a 93~ sulfurlc acid solutlon ~re added to the vessel. The mixttlreis heated to 85C and 1344 parts ~24 rnoles) of {sobu~ylene zre added ~rer 6 hours. Th¢ temperat;lre i~ maintalned between 85-gl~C. After introduction of the isobutylene, the reaction is blown with nitrogesl a~ Z standard cub{c feet per hour for 30 mlnutes at 85C. Calclum hydroxide ~6 parts, 0.2 mole) along with 12 p~rts of water are added to the reaction Yessel. The mixt~re is he~d to 130C under n{trogen for 1.5 hours~ The reaction is vacuum stripped ~t 13~C
and 2û mill{meter~ of merc~y for 30 minutes. The residue i5 caoled to 90C and the res{due is flltered through dlatomaceous ear~h to ~ive the desired product.
Th~i desired product filtrate ha~ a specific gravity of 0.901 and ~ percent hydroxyl ~Grignard~ equals 4.25 (theoretical 4.4g).
Example E-7 A reaction vessel is charged with 798 parts (3 moles) of 4-tetrapropenyl phenol~ The phenol Is heated to 95-100C whereupon 5 parts of a 93% solution of sulfuric acid are added to the Yessel. Isobutylene (168 parts, 3moles) is added to the vessel over 1.7 hours at 100C. After introductiorl of the isobutylene the reaction is blown with natrogen at 2 standard cubic feet per hour for one-half hour at 100C. All additlonal 8gO parts of the above-described ~henol (2.98 moles) are added to a: reaction vessel and heated to 34-40~ A 37%
aqueous formaldehyde solution ~137 gr~ns, 1.7 moles) is added ~o ~he vessel. The~: ~ mixture is heated to~ 135C with remova! of water. Nitroget~ blowing at 1.5 scfh begins at 105-110C. The reaction mixture is held at 120C for 3 hours under nitrogen~ and cooled to 83C whereupon 4 parts: (0.05 mole) of a 50% aqueous sodium hydroxide solution are ~dded to the vessel. The reaction mix~ure is heated to 135C under nitrogen.~ The reaction mixture is vacuum stripped to :

W(~ 93/2350~ ~ s ,~ PCI /US~2/0~737 ,,~, ,. i ,~ ,,, ..,. ,,i -g3-135C and 20 millirneters of mercury for 10 minutes, cooled to 95~C, and the residue is filtered through di~tomaceol~ earth. The product has a percent hydroxyl (~rignard) of 5.47 (theoretical 5.5) and a molecular weight (Yapor phase osmometry) of 682 ttheoretical 667).
Ex~ple E-8 The general procedure o~ Examp1e E-6 is repeated except th~t the 4-heptyl phenol is replaced by an equi ralent amount of trl-propylene phenol. The subs~ituted phenol obtained in this manner contalns 5 9D,% hydroxyl.
Exarrlple E 9 The general procedure of Exsmple E-7 is repeated except that the phenol of Exarnpl~ E-6 is replaced by the phenol of Example E-8. The methylene coupled phenol prepared in this manner contsins 5O749~ hydroxyl.
In another embodiment, ~he lubricant compositions of the present invention may contairl a metal-free (or 2shless) alkyl phenol sulfide. The alkylphenols from which the sulfides are prepared also may comprise phenols of the type discussed above arld represented by Formula XV wherein Rl 1 is hydrogen.
For example, the allcyl phenols which can be converted to alkyl phenol sulfides include: 2-t-butyl-4-heptyl phenol; 2-t-butyl-4~octyl phenol; and 2-t-butyl-4-do-decyl phenol.
The term "alkylphenol sulfides" is meant to include di-(alkylphenol) -monosulfides, disulfldes, polysulfides, and ather prsducts obtained by the reaction of the alkylphenol with sulfur monochloride, sulfur dichloride or elemental sulfur.
One mole of phenol is reacted with about 0.5-1.5 mole, or higher, or sulfur compound. For example, the alkyl phenol sulfides are readily obtained by mixing,one mole of an alkylphenol and 0.5-1.0 mole of sulfur diehloride. The reaction mixture is usually maintained at about 150-160F for about 2-5 hours, after which time the resulting sulfide is dried and flltered. When elemental sulfur isused~ one mole of alkyl phenol is reacted with 0.5 to 2.0 moles of elemental sulfur, and temperatures of about 150-250C or higher are typically used. It is WO 93/235û~ r/US92/OX737 f~ ~ 3 ~ '~ g~j~

alsQ desirable that the drying operation be conducted under nitrogen or a similar inert gas.
Suitable basic alkyl pheno} sulfides are disclosed, for example, in U.S. Paten~s 3,372tll6; 3,410,798; and 4,021,41g, which are hereby incorporated by reference.
These sulfur-containing phenolic compositions described in U.S.
Patent 4,021,419 are obtained by sulfurlzing a substituted phenol with sulfur ora sulfur hallde and thereafter reacting the sulfurized phenol with ~ormaldehyde or a reverslble polymer thereof. Al~ernatlvely ~he substituted phen~l can be first reacted with forrnaldehyde and thereafter reacted with sulfur or a ~ulfur halideto produce the desired ~lkyl phenol æulfide. The disclosure of U.S. Patent 4,021,419 is hereby incorporated by reference for its disclosure of such compounds, and methods for preparing such compounds. A synthetic oil of the type described below is used In place Or sny mineral or natural oils used in thepreparation of the sal~s for use in this invention.
In another embodiment, the antioxldant ~E) may be phenothiazine, substituted phenothiazines, or derivatives such as represented by Formula XX

3S(o)aRl4 ~,", ~ ~ (XX) (R~5)b ~`SIO~--.
wherein R14 is selected from the group consisting of higher alkyl groups, or an j, ! \q alkenyl, alyl, alkaryl or aralkyl group and mixtures thereof; R13 is an alkylene, alkenylene or an aralky!ene group, or mixt~Lres thereof; each Rl 5 is independently alkyl, alkienyl, aryl, alkaryl, arylalkyl, halo8en~ hydroxyl, alkoxy, alkylthio,arylthio, or fused aromatic rings, ~ or mixtures thereof; a and b are each independently 0 or greater.

::

:

WO 93/23505 P~/US9~/08737 g5 In another embodiment, the phenothiazine derivatives may b~
repres~nted by Formula X~I

"S(~ ~ (RlS) (R )b~N~J b ~13 5l(~)a (X~CI) ~o ~t ~ J ~Rls)b wherein R13, R14, Rt5, a and b are as defined with respect to Forrnula XX.
The above-described phenothiazine derivati~res, and methods for their preparation are described ~n U.S~ Patent 4,7859095, and the disclosure,of this patent is hereby incorporated by reference for Its teachings of such methods and compounds. In one embodiment, a dialkyldlphenylamine is treated with sulfur at an elevated temperature such as in the range of 145C to 205C for a sufficient time to complete the reaction. A catalyst sucb as iodine may be utilized to establish the sulfur bridge.
Phenothiazine and its various derivatives can be converted to compounds of ~ormula XX by contacting the phenothiazine compound containing the free NH group with a thio alcohol of the formula R14SR130Hwhere R14 and R13 are defined wi~h respect to Fo~nula XVlil. The thio alc~hol may be obtained by the reaction of a mercaptan R14SH with an ~lkylene oxide under basic conditions. Alternatively, ~he thio alcohol may be obtained by reacting a terminal oiefin with mercaptoethanol under free radical conditions. The reaction WO 93/235~5 PCI /US92/0~737 .
~ ~ ~3 ~

between the thio alcohol and the phenothiazine compound generally is c~nducted in the presence of an inert solvent such as toluene, benzene~ el:c. A strong acid catalyst such as sulfuric acid or para~toluene sulfonic acid at about 1 part to about 50 parts of catalyst per 1000 parts of phenothiazlne is preferred. The reaction is conducted generally 8'C reflux tempera~ure w5th remov~l of wa~er as it is formed. Conveniently, the reaction temperature may be rnaintained between 80C and 170~C
Whcn it is desired to prepare compounds of the type represented by Formulae XX and XXI wherein x is 1 or 2, i.e., sulfones or sulfoxides, the derivatives prepared by the react~on with the thio alcohols described above are oxidized with an oxidizing ~gent such as hydrogen peroxide in a solvent such a~
glacial acetic acid or ethanol ~ulder ~n inert g~s blaDke~. The partial oxldation takes place conveniently at from about 20~C to about 150~C. The followirlg examples illus~rate the preparatlon of phenothiazines which may be utilized as the non-phenolic antioxidant (E) in the lubricants of the present invention.
ple E-1 0 One mole of phenothlazine is placed in a one- liter, round bottom flask with 300 ml. of toluene. A nitrogen blanket is maintained in the re~cto,r.To the mixture of phenothiazine and toluene is added 0O05 mole of sulfuric acid catalyst. The mixture is then heated to reflux ternperature and 1.1 moles of n-dodecylthioethanol is added dropwise over a period of approximately 90 minutes. Water is continuously removed as it is formed in the reaction process.
The reaction mixture is continuously stirred under reflux until substantially no further water is evolved. The reactiorl mixture is then allowedto coo} to 90C. The sulfllric acid catalyst is neutralized with sodiurn hydroxide.
The solvent is then removed under a vacuum of 2 KPa at 110C. The residue is filtered giving a 95% yield of the desired product.
In another cmbodiment, the antioxidant ~E) is a transition metal-containing composition. The transition metal-containing antioxidant is oil s~luble. The compositions generally contain at least ~ne transition metal WO 93/23505 ~ b ~ PCI /US92/08737 selected from titaniurn, manganese7 cobalt, nickel, copper, and zinc, preferablymanganese, copper, and zinc, more preferably copper. The mel;als may be in the form of nitrates, nitrites, halides, oxyhalides, carboxylatès, borates, phosphates, phosphites, sulfates, sulfites, carbonates and oxides. The ~ransi~ion metal-containing composltlon is generally in the farm of a metal-orga~lic compound complex. The organic compounds include carboxylic aclds and esters, mono- and dithiophosphoric acids, dithiocarbamic a~ids and dispers~n~s. Generally, the transition metal-containing compositlons contain at least about 5 carbon atoms to render the composltions oil-soluble.
In one embodiment, the organic compound is a carboxylic acid. The carboxylic acid m~y be a mono or polycarboxyl~c acid contais~ing from 1 to about 10 carboxylic groups nnd ~ to about 75 carbon atoms, preferably 2 to about30, mcre prefersbly 2 to about 24. Ex~x~ples of monocarboxylic acids ~nclude 2-ethylhexanoic acid, octanolc acid, decanoic acid, olelc acid, linolcic acid, stearic acid and gluconic acid. Examples of polyc~ xylic acids include succinic, malonic, citraconic acidls as well as substituted Yersions of these acids. The carboxylic acid may be one of the above-described hydrocarbyl-substituted carboxylic acylating agents.
In another embodiment, the organic compound is a mono- or dithiophosphoric acid. The dithiophosphoric scids may be any of the above-described phosphoric acids (see dihydrocarbyl ditbiophosphate). A monothiophos-phoric acid is prepared by treating a dithiophosphoric acid with steam or water.In anotber embodiment, the organic compound is a mono- or d~thiocarbamic acid. Mono- or dithiocarbamic acids are prepared by reacting carbon disulfide or carbon oxyslllfide with a primary or secondary arnine. The amines may be any of the amines described above.
In another embodiment, the organic compound may be any of the phenols, aromatic amines,~ or di~persants described above. In a preferred embodiment, the trans~tion metai-containing composition ~s a lower carboxylic ~; 30 acid-transition m~tal-dispersant cornplex. The lower alkyl carboxylic acids :

WO ~3/23505 PCI /1 IS92/0~737 -g8-contain from 1 to about 7 carbon atoms and in~lude formic acid, acetic, propionic, butanoic, 2-ethylhexanoic, benzoic scid, and salicylic acid. The dispersant rnay be any of the dispersants described above, preferably the dispersant is a nitrogen-containing carboxylic dispersant. The trans~tion metal complex is prepared by blending a lower carboxylic acid salt of a transition metal with a dispersant at a temperature from about 25C up to the decomposition temperature of the reaction mixture, usually from ~bout 25C up to about 100C.
A solvent such a xylene, toluene1 naph~ha or mineral oil may be used.
Example E~ll The metal complex is obtained by heating at 160C for 32 hours 50 parts oï copper diacetate monohydrate, 283 parts of lOa neutral mineral oil, 250rnilliliters of xylene and 507 parts of an acylated nitrogen intermediate prep~red by reacting 4,392 parts of a polybutene-substltuted succinic anhydride (preparedby the reaction of a chlorinated p~lybutene having a number average malecular weight of 1000 and a chlorine con~ent of 4.3% and 20~ molar excess of maleic anhydride) with 540 parts of an alkylene arnine polyamine mlxture of 3 parts by weight of triethylene tetramine and I part by weight of diethylene triamine, and3240 parts of 100 neutral minsral oil at 130C-240C for 3.5 hours. The reactionis vacuum stripped to tlOC and 5 millimeters of mercury. The reaction is filtered through diatomaceous earth to yield a filtrate which has 59% by weight oil, 0.3% by weight copper and 1.2% by weight nitrogen.
Example E-12 (aj A mixture of 420 parts (7 moles) of isopropyl alcohol and 518 parts (7 moles) of n-butyl alcohol is prepared and heated to 60C under a :, i I ` , 2~ nitrogen atrnosphere. Phosphorus pentasulfide ~647 parts, 2.91 moles) Is added over a period of one hour while maintaining the temperatLlre at 65-77C. The mixture is stirred an additional hour while cooling. The material is filtered ~hrough a fil~er aid, and the filtrate is the desired phosphorodithioic acid.
(b) A mixture of 69 parts (0.97 equivalent) of cuprous oxide and 38 parts of mineral oil is prepared, and 239 parts (0.88 equivalent) of the WO 93/23505 ~ r, PClr/US92/08737 _9~_ phosphorordithioic acid prepared in (a) are added over a period of about ~ hours.
The reaction is slightly exothermic during the addition, the m~xture is thereafter stirred for an addltional 3 hours while ma~ntaining the temperature at about 70C. The mixture is stripped to 105C/10 mrn.Hlg. and filtered. The fll~rate isa dark-green liquid containing 17.39~ copper.
Example E-13 A mixture of 285 parts of 100 neutral mineral oil and 260 parts (1.8 e~uivalents) of coppeir (I) oxide is prepared and heated to 93C. Isopropyl, methylarnyldithiophosphoric acid (1000 parts, 3.3 equivalents), prepared from phosphorus pen~asulfide and a 60:40 molar mixture of methylamyl alcohol and isopropyl alcohol, is added over 3 hours to the mixture, while the temperature is maintained at 95-95C. The reac~ion mixture is stearn blown at 105-110C for 3 hours. The reaction mixture is then nitrogen blown at 82-88C~ for one hour.
The residue is filtered through diatomaceous ~arth. The filtrate is the desired 1~ produc~ and contains 20% oil and 15.35~ copper.
(F) Friction_Modifiers.
The lubrica~ing oil compositions of the present invention also m~y contain friction modifiers which provide the lubricating oil with addition,al desirable frictional characteristics. Generally from about 0.01 to about 2 or 3~by weight of the friction modifiers is sufficient to provide improved perfor-mance. Various amides and amines, particularly tertiary amines are effective friction modifiers. Exarnples of tertiary amine friction modifiers include N-fatty alkyl-N,N-diethanol amines, N-fatty alkyl-N,N diethoxy ethanol amines, etc.
Such tertiary amines can be prepared by reacting a fatty alkyl amine with an appropriate number of moles of ethylene oxide. Ter~iary amines derived from naturally occu~Ting substances such as coconut oil and oleoamine are a~ailable from Armour Chemical Company under the trade designation "Ethomeen".
Particular examples are the Ethomeen-C and the Ethomeen-O series. Amides include fatty acid amides wherein the fatty acid contains from 8 to 22 carbon atoms. Examples include oleylamides, stearylamides, laurylamides, etc.

.

WO 93/23505 P~r/US92/08737 , ;"3 -1~0-Partial fatty acid esters sf polyhydric alcohols also are useful as friction modifiers~ The fatty acids gener~lly contain from about 8 to about 22 carbon ato~ns, and the esters may be obtained by reaction with dihydric or polyhydric alcohols containing 2 to about 8 or 10 hydroxyl groups. Suitable fatty acid esters include sorbitan monooleate, sorb}tan dioleate, glycerol monooleate,glycerol dioleate, and mixtures ~hereof Including commercial mixtures such as Emerest 2421 (Emery Industries Inc.), etc. 5:)ther exarnples of partial fatty acid esters of polyhyd~ic alcohols may be found in K.S. Markley, Ed., "Fatty Acids", second edition, par~ nd V, Interscience Publishers ~lg68).
Sulfur containing compounds such as sulfurized C12_24 fats, alkyl sulfides and polysulfides wherein th0 alkyl groups contain from 1 to ~ carbon atoms" and sulfurized polyolef~ns also may function as frictlon modlfa~rs in thelubricating oil compusitions of the invention.
The lubricating compositions of the present invention may include other additives such as supplementary dispersants, antiwear agents, extreme pressure agents, emulsifiers, demulsifiers, ~ntirust ~gents, corrosion inhibitors, viscosity improvers, pour point depressants, dyes, and foam Inhibitors. These additives may be present in various amounts depending on the needs of the final produc~.
The supplementary dispersants may be selected from the group consisting of: ~a) arnine dispersants other than the carboxylic derlvatives (A) described above, (b~ ester dispersants, (c) Mannich dlspersants, (d) dispersant viscosity improvers and (e) mixtures thereof. In one embodiment, the dispersantsmay be post-treated with such reagents as urea, thiourea, carbon disulfide, alde-hydes, ketones, carboxylic acids,~ hydrocarbon-substituted succinic anhydrides, ni-triles, epoxides, boron compounds, phosphorus compounds, etc.
Amine dispersants are hydrocarbyl-substituted amirles. These hydrocarbyl-substituted amines are well known to those skilled in the art. Theseamines are disclosed in U.S. patents 3,~75,554; 3,438,757; 3,454,555; 3,565,804;

WO 93/23505 PCr/~JS~2/08737 "

3,755,433; and 3,~22,289. These patents ~re hereby incorporated by reference for their disclosure of hydrocarbyl amines and methods of rnaking the same.
Typically, amine dispersants are prepared by reacting olefins and olefin polymers (polyalkenes) wl~h ~nlnes ~mono- or poly~nines). The polyalkene may be any of the polyalkenes described above. The amines nay be any of the amines described above. E:xa~T~ples of amine dispersants include poly(prop~l-ene)~nine; N,N-dimethyl-N-poly(ethylene/propylene)amine, ~50:50 mole ratio of monomers); polybutene amine; ~ N-di(hydroxyethyl)-N-polybutene amine; N-(2-hydroxypropyl)-N-polybutenealmine,N-polybutene-anilin¢;N-polybutenemorphol-ine; N-poly(butene)ethylenediamineJ N-poly~(propylene)~rimethylenediamine; N-poly(butene)diethylenetriamlne;N',N'-poly~butene)tetraethylenepen~amine;N71~-dimethyl-N'-poly(propylene)-1,3-propylenediamine and the like.
In another embodiment, the supplementary dispersar~t may be an ester dispersant. The ester dispersant is prepared by reacting at least one of the hydrocarbyl-substituted carboxylic acylating agents described above as (A-1) with at least one organic hydroxy ~mpound and optionally an amlne. In another embodiment, the ester dispersant is prepared by reacting the acylating agent with at least one of the above-deseribed hydroxy amine.
The organic hydroxy compound includes compounds of the general 2Q formula R"(OH)m wherein R" is a mono~alent or poly~alent organic group joined to ths -OH groups through a carbon bond, and m is an integer of ~om } to about 10 wherein the hydrocarbyl group contains at least about 8 aliphatic carbon atoms. The hydroxy compounds may be aliphatic compounds such as monohydric and polyhydric alcohols, or aroznatic cornpounds such as phenols and naphthols.
The aromatic hydroxy compounds from which the esters may be derived are illustrased by the following specific examples: ~henol, beta-naphthol, alpha-naphthol, cresol, resorcinol, catechol, p,p'-dihydroxybiphenyl, 2-chlorophenol, 2,4-dibutylphenol, etc.
The alcohols from which the esters may be derived preferably contain up to about 40 aliphatic carbon atoms, preferably from 2 to about 30, W~93/23505 PCI/US9~/08737 S ? ~3 more preferably 2 to about 10. They may be monohydric alcohols such as methano}, ethanol, isooctanol, dodecanol, cyclohexanol, etc. In one embodimerlt,the hydroxy compounds are polyhydric alcohols, such as alkylene polyols.
Preferably, the polyhydric alcchols contain from 2 to about 40 carbon atoms, more preferably 2 to about 20; and preferably from 2 to about 10 hydroxyl groups, mo~e preferably 2 to about 6. Polyhydric alcohols include ethylene glycols, including di-, trl- and tetraethylene glycols; propylene glycols, Including di-, tri- and tetrapropylene glycols; glycerol; bu~ane diol; bexane diol; sorbitol;
arabitol; mannitol; sucrose; fructose; glucose; cyclohexane diol; erythritol; and - pentaerythritols, including di- and tripentaerythritol; preferably, diethyleneglycol, triethylene glycol, glycerol, sorbitol, pentaerythritol and dipentaeryth-ritol.
The polyhydric alcohols may be esterlfied with monocarboxyllc acids having from 2 to about 30 carbotl atoms, preferably abou~ 8 to about 18, provided that at least one hydroxyl group remains unesterified. Examples of monocarboxylic acids include acetic, propionic, butyric and fatty carboxylic acids. The fatty monocarboxylic acids have from about 8 to about 30 carbon atoms and include octanoic, oleic, stearic, linoleic, dodecanoic and tall oil acids.
Specific examples of these esterified polyhydric alcohols include sorbitol oleate, including mono- and dioleate, sorbitol stearate, including mono- and distearate,glycerol oleate, including glycerol mono-, di- and trioleate and erythritol octano-ate.
The carboxylic ester dispersants may be prepared by any of several known methods. The method which is preferred because of comenience and the superior proper~ies of the esters it produces, involves the reaction of a the carboxylic acylating agents described above with one or more alcohols or phenolsin ratios of from about 0.5 equivalent to about ~ equivalents of hydroxy compound per e~uivalent of acylating agent. The esterification is usually carried out at a temperature above about 100C, preferably between 150C and 300C.
The water formed as a by-product is removed by distillation as the esterification , W~ 93/2350~ PCI`/US9~/087~s7 - 1 ~3-proceeds. The preparation of useful c:arboxylic ester dispersant is described inU.S. Patents 3~522,179 and 4,234,435.
The carboxylic ester dispersants may be further reacted with at least one of the above described arnines and preferably at le~st one of the above S described polyamines. The ~nine is added In an a~mour~t sufficient to neu~ralize any nonesterifed carboxyl groups. In one preferred embodiment, ~he nitrogen-containing carboxylic ester dispersants arf~ prepared by reacting about 1.0 to 2.0 equivalents, preferably about 1.0 to 1.8 equivalen~s of hydroxy compounds, and up to about 0.3 equivalent, preferably about 0.02 to about 025 equivalent of polyamine per equiYalent of acylating ageint.
In another embodiment, the carboxylic acid acylating agent may be reacted simultaneously wIth ~oth the alcohol and the amine. There is generally at least about 0 01 equivalent of the alcohol and at least 0.01 equivalent of the amine although the total amount of equivalents of the combination should be at least about 0.5 equivalent per equivalent vf acylating agent. These nitrogen-containing carboxylic ester dispersant compositions are known in the art, and the preparation of a number of these derivatives ls de~scribed in, for example, U.S. Patents 3,g57,854 and 4,~34,435 whish ha~e be&nincorporated by reference previously.
The carboxylic ester dispersants and methods of making the same are known in the art and are disclosed in U.S. Patents 3,219,666; 3,381,022;
3,522,179; and 4,234,435 which are hereby incorporated by re~erence for their disclosur~ of the preparation of carboxylic ester dispersants.
The following example~s illustrate the ester dispersants and the processe~s for preparing such esters. ~
Example SD-I
A substantially hydrocarbon-substituted ~uccinic anhydride is prepared by chlorinating a polybutene having a number aYerage rnolecular weight of 1000 to a chlorine content of 4.5% and then heating the chlorinated poly-butene with I.2 molar proportions Or maleic anhydride at a temperature of `:
' WO 93/z350~ P~/USg2/~)87~

; 2 ~i fi 3 150-2~0C, A mixture of 874 grarns (1 mole3 of the succinic anhydride and 104 grams (1 mole) of neopentyl glycol is maintained at ~40-250C/30 mm for 12 hours. The residue is a mixture of the esters resul~ing frsm the e~terification of one and both hydroxy groups of the glycol.
Example SD-2 A mixture of 3225 parts ~5.0 equlvalents) of the polybutene-substJ-tuted succinic acylating agent prepared in Example II, 289 parts (8.5 e~uivalen~s) of pentaerythritol and 5Z04 parts of mineral oil is heated at 22~-235C for 5.5 hours. The reaction mixture ls fil~ered a~ 130C to yield an oil solution of the desired product.
The carboxylic ester derivatives which are described above resulting from the reaction of an acylating ~gent with a h~droxy-containing compound such as an slcohol or a phenol may be further reacted with any of the above-described amines, and particulsrly polyam~nes in the tnanner describ~d previously for the nitrogen-contaioing disper~ants.
In another embodiment, the carboxylic acid acylatlng agent may be reacted simultaneously with both the alcohol and the amîne. There is generally at least about 0.01 equivalent of the alcohol and at least 0;01 equivalent of the amine although the total arnount of equivalents of the combination should be at least about 0.5 equivalent per equivalent of acylating agent. These carboxylic es~er derivative compositivns are known irl the art~ andthe preparation of a nurnber of these derivatives is described in, for example, U.S. Patents 3??9~7,854 and 4,234,435 which are hereby incorporated by reference.
The following specific example illustrates the preparation of the esters wherein, both an alcohol and an amine are reacted with the acylating agen~.
Example SD-3 A mixture of 1000 parts of polybutene having a n~nber average molecular weight of about 1000 and 108 parts (l.l moles) of maleic anhydride is heated to about 190C and 100 parts (1.43 moles~ of chlorine are added beneath the surface over a period of about 4 hours while maintaining the temperature at W~ 93/ 23505 ~ 2 i ~ / US92/û873 7 about 185-190C The mixture then is blown with nitrogen at this temperature for several hours, and the residue is the desired polybutenyl-~ubstituted succinic acylating agent.
A solution of 100~ parts of the above-prepared acylating agent in 857 parts of mineral oil i5 heated to about 150C wlth stlrring, ~nd 109 parts ~3.2 equivalents) of pentaerythritol are added with stirring. The mixture is blown witb nitrogen and heated to ~bout 200C over a perlod of abaut 14 hours to form an oil solution of the desired carboxylic es~er intermediate. To the intermediate, there are added 19.25 parts (.46 equiv~lent) of a commercial mlxture of ethylelle poiyamines having an average of about 3 to about 10 ni~rogen atorns per molecule. The reaction mixture is stripped by heating at 205C with nitrogen blowing for 3 hours and filtered. The filtrate is an oil solution ~45% 100 neu~ral mineral oil) of the desired ~nine-modified carboxylic ester which contains 0.35 nitrogen.
The supplementary dispersant may also be a Mannich dispersant.
Mannich dispersants are generally formed by the reaction of at least one aldehyde, at least one of the above described amine and at least one alkyl substituted hydrcxyaromatic compound. The reaction may occur from ro4m temperature to 225C, usually from 50 to about 200C (75C-150C most preferred), with the amounts of the reagents being such that the molar ratio of hydroxyaromatic compound to formaldehyde to amine is in the range from about 1) to about (1:3:3).
The first reagent is an alkyl substituted hydroxyaromatic compound. This tezm includes phenols (which are preferred), carbon-, oxygen-, sulfur- ar;d nitrogen-bridged phenols and the like as well as phenols directly linked through cova!ent bonds (e.g. 4,4'-bis(bydroxy)biphenyl), h~roxy compoundsderived from fused-ring hydrocarbon (e.g., naphthols and the like); and polyhydroxy compounds such as catechol, resorcinol and hydroquinone. Mixtures of one or more hydroxyaromatic compounds can be used as the first reagent.
.

WO 93/2350~ P~/lJS92/0~737 r~ 3 The hydroxyaromatic compounds are those substituted with at least one, and preferably not more than two, aliphatic or slicyclic groups having at least about 6 (usually at least about 3~, more preferably at least 50) carbon atoms and up to about 400 s~arbon atoms, preferably 300, more preferably 200.
These groups may be deriv~d from the above described polyalkenes In one embodimen~, the hydroxy aromatic compound is ~ phenol substituted with an aliphatic or a}icyclic hydrocarbon-based group having an Mn of about 420 to about 10,000.
The second re~gent is a hydrocarbon-based aldehyde, preferably a lower aliphatic aldehyde. Suitable aldehydes lnclude formaldehyde, benzalde-hyde, acetaldehyde, the butyraldehydes, hydroxybutyraldehydes and heptanalst as well as aldehyde precursors which react as aldehydes under the conditions of the reaction such as paraformaldeihyde, paraldehyde, formalin and methal.
Formaldehyde and i~s precursors (e.g., paraformaldehydet trioxane) are preferred.
Mixtures of aldehydes may be used as the sel ond reagent.
The third reagent is any asnine described above. Pre~erably the amine is a polyamine as described above.
Mannnich dispersants are described in the following patents: U;S.
Patent 3,980,569; U.S. Patent 3,877,899; and U.S. Patent 4,454,059 (her~iin incorporated by reference for their disclosure to Mannich dispersants).
The~supplementary dispersant may also be a dispersant-viscosity .

improver. The dispersarlt-viscosity improvers includei pol~ner backbones which are functionalized by reacting with an amine source. A true or normal block copolyrner or a random block copolymer, or combinations of both arel utilized.
They are hydrogenated before use in this invention to remove virtually all of their olefinic double bonds. Techniques for accomplishing this hydrogenation arewell known to ~hose of skill in the art. Briefly, hydrogenation is accomplished by contacting the copolymers with hydrogen at superatmospheric pressures in the presence of a metal catalyst such as colloidal nickel, palladium supported on charcoal, etc.

wn g3/23505 ~ ,r, ~ ' PCI /US92/5)8'737 -1()7-ln general, it is preferred ~hat these block copolymers, for reasons of oxidative stabllity, contain no rnore than about 5 percen~ and preferably no more than about 0.5 percent residual olefinic uulsatura~ion on the basis of the total number of carbon-to-carbon covalent linkages within the average rnolecule.Such unsaturation can be measured by a m.unber of means well known to those of skill in the art, such as infrared, hlMR, etc. Most preferably, these copoly-mers contain no discernible unsaturation, ~s determined by the aforementioned analytical techniques.
The block copolymers ~ypicall~ have number average molecular -weights (Mn) in ~he range of about 10,000 to about 50071)00 preferably about 30,000 to about 200,000. The weight average molecular weight ~Mw) for these copolyme~s is generally in the range of about 50,000 to about 500,000, preferably about 30,0ûO to about 300,000.
The amine source may be an unsatura~ed amine compound or an unsaturated carb~xylic reagent which is capable of reacting with an amine. The unsatura~ed carboxylic reagents and amines are described above.
Examples of saturated amine compounds include N-(3,6-dioxahep-tyl)maleimide, N-(3-dimethylaminopropyl)-maleimide, and N-(2-methoxyethoxy-ethyl)maleimide. Preferred amines are ammonia and prim~ry amine containing compounds. Exemplary of such primary amine-containing compounds include amrnonia, N,N-dimethylhydraz~ne, methylamine, ethylamine, butylamine, 2-meth-oxyethylamine, N,N-dime~hyl-1,3-propanediamine, N-ethyl-N-n~ethyl-1,3-pro-panediamine, N-methyl-1,3-prop~nediamine, N-~3-aminopropyl)morpholine, 3-methoxypropylaminç, 3-isobutyoxypropylamine and 4,7-dioxyoctylamine, , I : ` :
N-(3-aminopropyl)-N-l-methylpiperazine,N-(2-aminoethyl)piperazine,(2-amino-ethyl)pyridines, aminopyridines, 2-àminoethylpyridines, 2-aminomethylfuran, 3-amirlo-2-oxotetrahydrofuran, N-(2-a~inoethyl)pyrolidine, 2 aminomethylpyTrol-idine, l-methyl-2-aminomethylpyrrolidine, l-amino-pyrrolidine, 1-(3-amino-propyl)-2-methylpiperidine, 4-arninomethylpiperidine, N-(2-aminoethyl)morpho-line, 1-ethyl-3-aminopiperidine, l-aminopiperidine, N-aminomorpholine, and the WO ~3/23~0~ PCr/US92/087 like. Of these compounds, N-(3-aminopropyl)morpholine and N-ethyl-N-methyl 1,-3-propanediamine are preferred with N,N-dimethyl-1,3-propanedi~nine being highly preferred.
Another group of primary amine-containing compounds are the variaus amine terminated polyethers. The ~nlne te~minated polyethers are available conlmerclally from Texaco Chemical Company under the general trade deslgn~tion "Jeffamine0". Specific exasnples of these materials include Jeffamine~ M-600; M-1000; M-~005; and M-2070 amines.
Exarnples of dispersaslt--viscosity improvers are given in, for example, EP 171,167; 3,687,849; 3,756,954; and 4,320fOl9, whlch are herein incorporated by reference for their disclosure to dispersant-viscosity improvers.
The above disper~ants m~y be post-trea~ed with one or more post-treating reag~nts selected from the group consisting of boron compounds ~discussed above), carbon disulfide, hydrogen sulfide, sulfur, sulfur chloride~s, alkenyl cyanides, carboxylic acid acylating agents, aldehyde~, ketones, urea, thl-ourea, guanidine, ~icyanodiamide, hydrocarbyl phosphates, hydrocarbyl phosphites, hydrocarbyl thiophosphates, hydrocarbyl thiophosphites, phosphorus sulfides, phosphorus oxides, phosphoric acid, hydrocarbyl thiocyanat~s, hydrocarbyl isocyanstes, hydrocarbyl isothiocyanates, epoxides, episulfides, formaldehyde or formaldehyde-producing compounds with phenols, and sulfur with phenols.
The following U.S. Patents are express~y incorporated herein by reference for their disclosure of post-treating processes and post-treating reagents applilcable to the carboxylic derivative compositions of this invention:
U.S. Patent Nos. 3,087,936; 3,254,025; 3,~56,185; 3,278,550; 3,282,955; 3,284,410;
3,338,832; 3,533,945; 3,639,242; 3,708,522; 3,8593318; 3,865,813; 4,234,435; etc.
U.K. Patent Nos. 1,085,903 and 1,162,436 also describe such processes.
ln one embodiment, the dispersants are post-treated with at least one boron compound. The reaction of the dispersant with the boron compounds ~ can be effected simply by mixing the reactants at the desired temperature.

~ ~3/23505 ~ S ~ ~ P~/US92/0~737 Ordinarily it is preferably between about 50C and about 250C. In some instances it may be 25C or even lower. The upper llrnit of the temperature is the decomposition point of the particu}ar reaction mixture and/or product.
The arnount of boron compound reacted with the dispersant generally is sufficien~ to pro~ide from about O.l to about lO atomic proportionsof boron for each mole of dlspersant, i.e., the atomic proportion of nitrogen orhydroxyl group contained in the dispersant. The preferred ~nounts of reactants are such as to provide from about 0.5 to about 2 atomic proportlans of boron foreach mole of dispersant. To illustrate, the amount of a boron cornpound having one boron atom per molecule to be used with one mole of an amine dispersant having five nitrogen a~oms per molecule is with~n the range from about O.l mole to about 50 moles, preferably from about 0~5 mole to about lO moles.
Corrosiorl inhibitors, extreme pressure and antiwear agents include but are not limited to metal salts of a phosphorus acid7 chlorinated aliphatic l 5 hydrocarbons; phosphorus esters includin~ dlhydrocarbyl and trihydrocarbyl phosphites; boron-containing compounds including borate esters; dimercaptothia-diazole derivatives; benzotrlazole derivatives; almino-mercaptothiadiazole derivatives; and molybdenum compourlds.
Viscosity improvers include but are not limited ~o polyisobutenes, polymethyacrylate acid esters9 polyacrylate acid esters, diene polymers, polyalkyl styrenes, alkenyl aryl conjugated diene copolymers (preferably styrene-maleic anyhydride copolysner esters), polyolefins and multifunctional viscosity improvers.
Pour point depressants are a particularly useful type of additive 25~ often included in the~lubricating oils described herein. See for example, page 8 of "Lubricant Additives" by C.Y. Smalheer and R. Kennedy Smith ~Lesius-Hiles Company Publishers, Cleveland, Ohio, l9671.
Anti-foam agents used to reduce or prevent the formation of stable foam include silicones or organic polymers. Exa~ples of these and additional :

WO 93/2350:~ ~cr/U592~08737~

anti-foam compositions are described in "Foam Con~ol Agents"7 by Henry T.
Kerner (Noyes Data Corporation, 1976), pages 125-162.
These and other additives are described in greater detail in U.S.
Patent 4,582,618 (Col. 14, lirle 52 through Col. 17, line 16, inclushe), herein incorporated by reference for its disclosure nf other additives that may be usedin combination with the present invention.
The lubricating compositions of the present invention may be prepared by blendlng componemts (A) and ~B) and either C-l or C-2 ~s described above with or without ~ddltional optional additives such as components (D)-~F~
and others described above in an oil of lubricating viscosity. More often, one or more of the chemicai components of tbe present inverltion are diluted with a substantially inert, normal1y liquid organlc diluent/solvent such as mineral oil) to form an additive concentrate. These concentrates usually comprise from about 20-90%, preferably 10-50% of component (A~, 20 to 80~h, preferably O.t to 20% of component ~B) 0.1 to 20~, by weight of either C-1 or C-2 and optionally one or more of the components ~D) through ~). Ch~mical concentra-tions such as 15%, 20%, 30~ or 509~ or higher may be employed. For example, concentrates may contain on a chemical basis, from about 10 to about 50% by weight of the carboxylic derivative composition (A) and from 0.1 to about 10%
of tB) and either C-1 or C-2. The concentrates may also contain about 0.001 to about 15% of ~1~), 0.001 to about 15% of ~E) and/or about 1 to about 20% of ~F).Blending is accomplished by mixing (usually by stirring) the ingredients from roam temperature up to the decomposition temperature of the mixture or individual components. Generally, the ingredients are blended at a temperature from about 25C up to about 250C, preferably up to about 200C, more preferably up to about 150C, still more preferably up to about 100(:.
The following examples illustrate the concentrates and lubricants of the present invention. "Bal." or "remainder" in the table represents that thebalance or remainder of the composition is oil. Unless otherwise indicated, the wr~ 93/235n~ ,4 b ~ 7~ P~/US92~0~737 amount of each component in the examples is in percent by volume and reflects the amount of the oil-containing products used in the lubricants.
Concentrate Exam~les Concentrate I
Produc~ of Example A-13 ~5 Product of Example E~1 12 Product of Ex~nple G3 Mineral C)il 38 Concentrate 11 Product of Exarnple A-28 40 Product of Exarnple ~1 15 Product of Example C-4 5 Mineral Oil 40 Concentrate 1l1 }5 Product of Example A-20 60 Product of Exarrlple ~2 15 Product of Example t:~-3 5 Produc~ of Example D-l 3 Mineral Oil 17 Concentrate lV
Product of Example A-21 40 Product of Example B-2 10 ~ :
Product of Example G3 5 Product OI Example D-2 5 Product of Example E-5 5 Mineral Oil 3~

.

WO g3/235V5 PCr/US92/0~7~7~

~..J ~ . 3 Concentrate V
Product of F,xample A-21 40 Product of Exarnple ~2 10 Product of Example C-3 Product of Example D-~ 5 Product of Example E-7 5 l~fineral Oil 35 Lubrlcant Exam~les Lubricant A
Product of Example A-13 6.0 Product of Example ~2 1.2 Product of Example C-3 0.5 100 Neutral Paraffinic Oil Remainder Lubricant B
. Product of E:xample A-13 6.2 Product oî Example ~2 1.2 Product of Example C-3 0.4 Product of Example D-l 0.S
100 Neutral Paraffinic C)il Remainder Lubricant C
Product of Example A-21: 5.8 Product of Example B-l 1.0 Product of Example C-4 0.5 Product of Example. D-2 0.5 2S Product of Example E-S 0.S
100 Neutral Paraffinic Oil Remainder VY~ 93/235~5 ~ 3 s~ PCl`/US92J08737 Lubricant D
Product of Example A-21 5.0 Product of Example ~1 0~8 Product of Example C-1 0.4 S Product of Example D-2 0.4 Produc~ nf Exarslple E-5 0.5 100 Neu~ral Paraffin~c Oil Rernainder T~@L~
Product of ~k~
Exam~le Ea Fb G H Ib Jb A-13 5.5 6.0 6.0 6.0 6.0 6.0 û.3 ------ ~-- ___ ___ __ ES 2 ~- 1.2~ 1.20 1.20 1.20 1.20 C-1 _ _ _ 0,50 ___ _ 1~ C--4 ~ ---- ------ 0~5 D-1 0.38 1~12 1.20 1.12 1.20 1~12 E-3 0.5 ~ __ ___ ___ __ - E-5 --- ~-- 0.5 --- 0.25 ---E-6 - 1.0 1.0 1.4 1.0 1.4 E-13 0.15 0.10 --'- 0.10 --- 0.10 Di(nonylphenyl)amine --- --- --- --- 0.25 0.25 Basic magnesium alkylated benzene sulfonate (32%
oil, metal ratio=15) 0.5 0.25 0.25 0.25 0.25 ---Oleyl amide 0.10 0.10 --- 0.10 QolO O~10 8% Hydrogenated styrene-~utadiene in 100 neutral mineral oil 6.0 ---. --- --- _-- __ Silicone antifoan:l agent 80ppm 80ppm 80ppm 80ppm 80ppm 80ppm 30: Oil Bal. Bal. Bal. Bal~ Bal. Bal.
-a values are in % by volumeb values are in % by weight WO 93/23505 PCr/US92/0~7~,~.q, t~ (JS ~ 114-The lubricating oil cumpositions of the present invention exhibit a reduced tendency to deteriorate us~der conditions of use and thereby reduce wear, corrosion, rust, and the formation of such undesirable deposits as varnish, sludge, carlbonaceous materlals and r~sinous materials which tend to adhere to the various engine parts and reduce the efficiency of the engines. lubricating oils also can be formulated in accordance with this invention which result in improved fuel economy when used in the crankcase of a passenger automobile.
While the invention h&Ls been explained in relation to its preferred embodimen~s, lt is to be understood that various modifications thereof wlll become apparen~ to those skilled in the art upon reading the specific~tion.
Therefore, it is to be unders~ood that the invention disclosed herein is ~ntended to cover such modlfications as fall within the scope of the appended claims.

Claims (16)

AMENDED CLAIMS
[received by the International Bureau on 26 March 1993 (26.03.93);
original claims 1-65 replaced by amended claims 1-16 (3 pages)]

1. A lubricating oil composition comprising a major amount of an oil of lubricating viscosity and (A) at least about 196 by weight of at least one carboxylic derivative composition produced by reacting (A-1) at least one substituted succinic acylating agent containing at least about 50 carbon atoms in the substituent with (A-2) from about 0.5 equivalent up to about 2 moles, per equivalent of acylating agent (A-1), of at least one amine compound characterized by the presence within its structure of at least one HN< group;
(B) an amount of at least one alkali metal overbased salt of a carboxylic acid or a mixture of a carboxylic acid and an organic sulfonic acid sufficient to provide at least about 0.002 equivalent of alkali metal per 100 grams of the lubricating oil composition provided that when the alkali metal salt comprises a mixture of overbased alkali metal salts of a hydrocarbyl-substituted carboxylic acid and a hydrocarbyl-substituted sulfonic acid, then the carboxylic acid comprises more than 50% of the acid equivalents of the mixture, and either (C-1) at least one magnesium overbased salt of an acidic organic compound provided that the lubricating composition is free of calcium overbased salts of acidic organic compounds; or (C-2) at least one calcium overbased salt of an acidic organic compound provided that the lubricating composition is free of magnesium overbased salts of acidic organic compounds, and optionally (D) at least one metal dihydrocarbyl dithiophosphate, and (E) at least one antioxidant provided that the antioxidant (E) and the dithiophosphate (D) are not the same.

2. The oil composition of claim 1 containing at least about 1.5% by weight of the carboxylic derivative composition (A).

3. The oil composition of claim 1 wherein the ?n of the substituent in (A-l) is at least about 1500.

4. The oil composition of claim 1 wherein the carboxylic derivative composition (A) is obtained by reacting from about 0.7 to about 1.5 equivalents of the amine (A-2) per equivalent of the acylating agent (A-1).

5. The oil composition of claim 1 wherein the amine (A-2) is an aliphatic, cycloaliphatic or aromatic polyamine.

6. The oil composition of claim 1 wherein the succinic acylating agent (A-1) consists of substituent groups and succinic groups wherein the substituent groups are derived from polyalkene, said polyalkene being characterized by an ?n value of 1300 to about 5000 and an ?w/?n of about 1.5 to about 4.5, and the acylating agent is characterized by the presence within its structure of at least 1.3 succinic groups for each equivalent weight of the substituent groups.

7. The oil composition of claim 1 wherein the carboxylic acid (B) is a hydrocarbyl-substituted carboxylic acid containing at least about 50 carbon atoms in the hydrocarbyl substituent.

8. The oil composition of claim 1 wherein the carboxylic acid of (B) is a hydrocarbyl-substituted succinic acid.

9. The oil composition of claim 1 wherein the alkali metal overbased salt (B) is a sodium or potassium salt of a hydrocarbyl-substituted succinic acid wherein the number average molecular weight of the hydrocarbyl substituent is from about 900 to about 5000.

10. The oil composition of claim 8 wherein the alkali metal overbased salt (B) is characterized as having a ratio of equivalents of alkali metal to equivalents of succinic acid or mixture of succinic acid and sulfonic acid of at least about 1.5.

11. The oil composition of claim 1 wherein the metal of the metal dihydrocarbyl dithiophosphate (D) is zinc, copper, or mixtures thereof.

12. The oil composition of claim 1 wherein the antioxidant (E) is at least one sulfur-containing composition, at least one alkylated aromatic amine, at least one phenol, at least one oil-soluble transition metal containing antioxidant, or mixtures thereof.

13. The oil composition of claim 1 containing (C-1) at least one magnesium overbased salt of a sulfonic or carboxylic acid and the oil composition is free of calcium overbased salts.

14. The oil composition of claim 4 wherein the carboxylic derivative composition (A) is obtained by reacting from about 0.5 up to less than 1 equivalent of the amine (A-2) per equivalent of acylating agent (A-1).

15. The oil composition of claim 13 wherein the magnesium salt is an overbased magnesium sulfonate.

16. The lubricating oil composition of claim 1 wherein the dithiophosphate (D) comprises a mixture of metal salts of dihydrocarbyl phosphorodithioic acids wherein in at least one of the dihydrocarbyl phosphorodithioic acids, one of the hydrocarbyl groups (D-1) is an isopropyl or secondary butyl group, the other hydrocarbyl group (D-2) contains at least 5 carbon atoms, and at least about 10 mole percent of all of the hydrocarbyl groups present in (D) are isopropyl groups, secondary butyl groups or mixtures thereof.