CA2201778A1 - Lubricating oil dispersants derived from hydroxy aromatic succinimide mannich base condensates of heavy polyamine - Google Patents

Abstract

The present invention is directed to lubricating oil and fuel dispersants comprising hydroxy aromatic succinimide Mannich Base condensates of heavy polyamine. A heavy polyamine is a mixture of polyalkylenepolyamines comprising small amounts of lower polyamine oligomers such as tetraethylene pentamine and pentahexamine but primarily oligomers with 7 or more nitrogens, 2 or more primary amines per molecule, and more extensive branching than conventional polyamine mixtures.

Description

LUBRICATING OIL DISPERSANTS
DERIVED FROM HYDROXY AROMATIC SUCCINIMIDE
MANNICH BASE CONDENSATES OF HEAVY POLYAMrNE

FIELD OF THE INVENTION

The invention relates to hydroxy aromatic s-lcçinimide Mannich base 10 dispel~ar.l additives prepaled from the condensation of "heavy polyamines". "Heavy polyamine" as lefel-ed to herein includes mixtures of higher oligomers of polyalkylene, e.g. polyethylene, amines cont~ining, e.g., essenti~lly no tetraethylene pe~ ..;..P, small ~mol~nts of pentaethyleneheY~mine but primarily oligomers with 7 or more nitrogens, 2 or more primary amines per molecule and more br~nrlling than 15 conventional polyarnine mixtures. Use of heavy polyamine allows for incorporation of greater amounts of nitrogen into the dispersant molecule than prior art amines and thusly, superior sludge dispersancy properties are obtained. The hydroxy aromatic sucrinimide Mannich base dispersants disclosed herein are useful as additives in fuel and lubricating oils.
BACKGROUND OF THE rNVENTION

USSN 273294 entitled "Lubricating Oil Succinimide Dispersants Derived from Heavy Polyarnine", filed July 11, 1994, discloses imidi7~tion of function~li7ed 25 hydrocarbons or polyrners with heavy polyamine and is incorporated by reference herein.

USSN 261554 entitled "Lubricating Oil Dispersants Derived from Heavy Polyamine", filed June 17, 1994, discloses arnidation (derivatization) of polymers 30 fimr,tion~li7ed by the Koch reaction with heavy polyamine and is incollJo~a~ed by ererence herein.

USSN 261507, entitled "Amidation of Ester Functionalized Hydrocarbon Polymers", filed June 17, 1994, discloses a prefelled amid~tion process for polymers 35 functionalized by the Koch reaction and use of heavy polyarnine therein and is incorporated by reference herein.

USSN 322715 entitle~, "Lubricating Oil Mannich Base Dispersants Derived from Heavy Polyamine", filed October 12, 1994, discloses an oil-soluble lubricating oil additive useful as a dispersant, comprising Mannich Base con~enc~tes of an alkyl substituted hydroxy aromatic compound with an aldehyde and a heavy polyamine andis incorporated by reference herein.

Mannich Base condçn.c~tion products are used as dispersants in lubricating oil applications. They are typically prepared by reacting an alkyl substituted phenol, forrnaldehyde and a polyalkylene polyamine.

US-A-5017299 and the divisional thereof, US-A-5186851, disclose dispersants comprising Mannich Base con~enC~tes of an alkyl substituted hydroxy aromatic compound with formaldehyde and an amine, wherein the alkyl moiety of the aromatic compound is derived from at least one ethylene alpha-olefin copolymer of 300 to 10,000 number average molecular weight, wherein at least about 30 percentof the polymer's chains contain tenninal ethenylidene unsaturation, and are incorporated by reference herein.

US-A-3442808 discloses lubricating oil additives prepared by reacting an alkenyl succinic anhydride with a Mannich condenc~tion product pre?aled by cond~ncing alkyl substituted phenol, formaldehyde and polyalkylene polyamine.
US-A-4354950 discloses a lubricating oil additive prepared by reacting a hydrocarbyl substituted succinic anhydride with an amino phenol to produce an inlcl...rrli~te N-(hydroxyaryl) hydrocarbyl succinimide. This intermediate is then reacted with an alkylene di~mine or polyalkylene polyamine and an aldehyde in a 25 Mannich Base reaction.

US-A-5219480, US-A-5128056, and US-A-5043084 disclose lubricating additives comprising Mannich Base condenc~tes of polymers, an optionally alkyl-substituted N-hydroxyaryl compound, an aldehyde, and an amine, and are 30 incorporated by lererence.

US-A-5259968 and the divisional thereof, US-A-5306313 disclose dispersant additives cG~ g the reaction product of a Mannich condenc~tion product forrned by con~lenci~ a long chain hydrocarbyl substituted hydrox~arolllatic compound with 35 an aldehyde and polyamine and reacting with a polyanhydride.

US-A-5102570 discloses a process for preparing a lubricating oil additive comprising the steps of reacting an amine with an alkenyl succinic acid anhydride to W O 96/20992 PC~rAUS95/16778 forrn a mono- and/or bis-alkenyl succinimide; adding a hydroxyaromatic amine and an excess of formaldehyde to form a Mannich hydroxy aromatic amine coupled mono-and/or bis-alkenyl succinimide; and acylating with an acylating agent.

Polyalkenyl sucrinimides are a widely used class of dispersants for lubricant and fuels applications. They are prepared by the reaction of, for example, polyisobutylene with maleic anhydride to forrn polyisobutenylsuccinic anhydride, and a subsequent condenc~tion reaction with polyethylene amines.

EP-A 0 475 609 Al discloses the use of "heavy polyamine" which is ~icrl~sed to be a mixture of polyethyleneamines sold by Union Carbide Co. under the ~esiEr ~fion Polyamine ~A-X.

US-A-5230714 discloses the use of"polyamine bottoms" derived from an alkylene polyamine mixture. "Polyamine bottoms" are characterized as having lessthan 2, usually less than 1% by weight of material boiling below about 200C. In the case of ethylene polyamine bottoms, the bottoms were disclosed to contain less than about 2% by weight total diethylene triamine (DETA) or triethylene tetraamine (TETA). A typical sample of such ethylene polyamine from Dow ChPmic~l CGIIIPallY, dPci~n~tp~l as "E-100" was tlicrl~sed to have a percent nitrogen by weight of 33.15 and gas chro..,atography analysis showed it to contain about 0.93% "Light Ends" (I)ETA), 0.72% TETA, 21.74% tetraethylene pe~ n.;.-e and 76.61%
pentaethylene heY~mine and higher (by weight).

US-A-4938881 similarly discl~ses the use of "polyamine bottoms".

US-A-5164101 discloses the polybutenyl~ucrinimide of polyamines, WLel~.;
the polyamine has a specific formula.

US-A-5114435 disclQses a polyalkylenesucçinimide p,~i)ared from a polyalkylenPsucçinic acid or anhydride reacted with a polyalkylene polya".ine of a specific formula. ~eY~Pthylene heptamine is disclosed to be a suitable amine.

US-A-4927551 discloses a polybutenyl succinic anhydride reacted with Dow E-100 heavy polyamine (average Mw = 303 available from Dow ChPrn;~
Company).

US-A-S241003 discloses succinimides derived from amines of a specific formula. Various suitable low cost polyethylene polyamine mixtures are disclosed to be available under various trade desi~n~tions such as "Polyamine H", "Polyamine 400", Dow Polyamine E-100" and "Dow S-1107".
S

US-A-4152499 discloses isobutene polymer reacted with maleic anhydride and this adduct then converted into a lubricating oil additive by reaction with polyamines of a specific formula. Diethylenetriamine and triethylenet~ e are disclosed to be suitable amines.
US-A-5053152 and the divisional thereof, US-A-5160648, disclose con-1Pn~ses produced by the acid catalyzed conden~tion of an amine reactant with a hydroxy alkyl or hydroxy aryl reactant. The amine reactant is disclosed to be a high molecular weight extended polyamine.
US-A-5171466 discloses dispersants formed by reacting an aliphatic hydrocarbyl substituted succinic acylating agent in which the hydrocarbyl substituPnt conlains an average of at least 40 carbon atoms with a mixture conci~tin~ ec~çnti~lly of hydrocarbyl polyamines cont~inil-~ from 10 to 50 weight percent acyclic alkylene 20 polyamines and 50 to 90 weight percent cyclic alkylene polyamines.

SUMMARY OF THE INVENTION

Most commercial dispersants are based on the reaction of a call,o~ylic acid 25 moiety with a polyamine or a hydroxyaromatic compound with formaldehyde and apolyamine, such as tetraethylene pe~ e (TEPA) with 5 nitrogens per molecule.
The hydroxy aromatic s~lccinimides useful in the prepa- ~lion of the materials of this invention include those succinimides derived from the reaction of a hydrocarbyl substituted succinic anhydride or diacid moiety with an aminophenol compound 30 producing an interrne~ te N-(hydroxyaryl, i.e. aromatic) hydrocarbyl s~lccinimide, which is then reacted with a heavy polyamine and an aldehyde (e.g. formaldehyde) in a Mannich base reaction.

The condenc~tion product of a phenol, formaldehyde and a reactive amine is 35 known as a Mannich corldetlc~tion product. The present invention is directed to a lubricating oil dispersant additive which comprises a condensation product obtained by the reaction of at least one oil soluble hydrocarbon grafted with an ethylenically unsaturated carboxylic acid material having I to 2 dicarboxylic acid groups or W 096/20992 PCTrUS95/16778 anhydride group; at least one N-hydroxyaryl amine compound; at least one aldehyde re~ct~nt; and a heavy polyamine.

The present invention is even further directed to a process for producing a 5 Mannich base di~.t.~alll condensation composition useful as a fuel additive orlubricating oil additive comprising the steps of: providing at least one hydroxyaryl polymeric suc,cinimide; providing at least one aldehyde reactant; and contacting a heavy polyamine with said succinimide and aldehyde for a time and under conditions sufficient to form said Mannich base condensation dispersant additive.
The present invention is an oil soluble dispersant comprising a functionalized hydrocarbon reacted with a nitrogen containing hydroxyaromatic compound, then analdehyde and a heavy polyamine. The present invention is also a process for producing dispersant comprising the steps of functionalizing by halogen~ting ene15 reacting, or free radical grafting a backbone selected from the group concicsing of hydrocarbon, polymer, copolymer and olefinic polymers with a carboxylic acid or anhydride agent; and then reacting with said N-hydroxyalolllalic compound, aldehyde and heavy polyamine to form a hydroxyaromatic s~lccinimide Mannich base con~enc~te. Heavy polyamine comprises an average of at least about 7 nitrogens per 20 molecule, a p.i.na~.~r amine content of at least about 6.3 to about 8.5 milliequivalents of primary amine per gram and a total nitrogen content of at least about 32 wt. %.
Heavy polyamine comprises subst~nti~lly no oxygen.

DETAILED DESCRIPTION OF THE INVENTION
The present invention relates to Mannich base dispersant additives plepared from functionalized hydrocarbons or polymers reacted with an N-hydroxy aromatic amine and then reacted with an aldehyde and with "heavy polyamines". "Heavy polyamine" as referred to herein includes a mixture of higher oligomers of 30 polyalkylene, e.g. polyethylene, amines col,lail--"g, e.g., ecc~nti~lly no tetraethylenep~ ..ine, at most small amounts of pentaethylen~lleY~mine, but primarily oligomers with more than 6 nitrogens and more bl anching than conventional polyamine mixtures. The Mannich base s~lccinimide di~c~a-~
disclosed herein are useful as additives in fuel and lubricating oils.
The hydrocarbons or polymers are functionalized (e.g. gra~ed) using a variety of means in-ln~ing halogen ~csicted functionalization (e.g. chlorination), the thermal "ene" reaction, and free radical grafting using a catalyst (e.g. peroxide) and then are W O 96/20992 PC~rrUS9S/16778 reacted with an N-hydroxyaryl compound and subsequently reacted Mannich base with an aldehyde and a heavy polyamine.

As used hereinafter the terms functionaliz~ng or grafting means at~t~ç~ling to 5 the polymer compound, e.g. an ethylenically unsaturated carboxylic acid moiety, preferably a maleic anhydride moiety.

The heavy polyamine as the term is used herein contains more than six nitrogens per molecule, but preferably polyamine oligomers cont~ining 7 or more 10 nitrogens per molecule and with 2 or more primary amines per molecule. The heavy polyamine cG"lp,ises more than 28 wt. % (e.g. > 32 wt. %) total nitrogen and an equivalent weight of primary amine groups of 120-160 grams per equivalent (e.g.
125-140 grams per equivalent of primary amine). Commercial dispersants are basedon the reaction of carboxylic acid moieties with a polyamine or a hydroxy aromatic 15 compound with formaldehyde and a polyamine such as tetraethylenepe..~ e (TEPA) with five nitrogens per molecule. Comrnercial TEPA is a distill~tiQn cut and cor~lAi.~c oligomers with three and four nitrogens as well. Other commercial polyamines known generically as PAM, contain a mixture of ethylene amines where TEPA and pentaethylene h~ e (PEHA) are the major part of the polyamine, 20 usually less than about 80%. Typical PAM is col"",ercially available from suppliers such as the Dow Chemical Company under the trade name E-100 or from the Union Carbide CGIIIPall.~ as HPA-X. This mixture typically consists of less than 1.0 wt. %
low molecular weight amine, 10-15 wt. % TEPA 40-50 wt.% PEHA and the balance hPY~ethyleneh~ a",ine (HEHA) and higher oligomers. Typically PAM has 8.7 - 8.9 25 milliequivalents of primary amine per gram (an equivalent weight of 115 to 112 grams per equivalent of primary amine) and a total nitrogen content of about 33-34 wt. %.

It has been discovered that heavier cuts of PAM oligomers with practically no 30 TEPA and only very small ~m ountc of PEHA but cont~ining primarily oligomers with more than 6 nitrogens and more extensive branching produce dis~ e,~-Ls with improved disluu~ancy when compared to products derived from regular cG"""~rc;al PAM under similar conditions with the same polymer backbones. An ~ ...ple of oneof these heavy polyamine compositions is co~ er~;ially available from the Dow 35 Ch~mic~l Company under the trade name of Polyamine HA-2.

HA-2 is p,epared by ~lictillin~ out the lower boiling polyethylene amine oligo",~ ,~ (light ends) inrl~ in~ TEPA. The TEPA content is less than 1 wt. %.

W O 96/20992 PC~rrUS95/16778 Only a small amount of PEHA, less than 25 wt. %, usually 5 - 15 wt. %, remains in the mixture. The balance is higher nitrogen content oligomers usually with a greater degree of br~nching The heavy polyamine preferably comprises essenti~lly no oxygen.

Typical analysis of HA-2 gives primary nitrogen values of about 7.8 milliequivalents (meq) (e.g. 7.7 - 7.8) of primary amine per gram of polyamine. This c~lc~ es to be about an equivalent weight (EW) of 128 grams per equivalent (g/eq).
The total nitrogen content is about 32.0 - 33.0 wt. %. Commercial PAM analyzes for 8.7 - 8.9 meq of primary amine per gram of PAM and a nitrogen content of about 33 to about 34 wt. %.

The dispersants of the present invention are an improvement over other Mannich base dispersants because of their effectiveness and their ability to provide 15 enh~nced lubricating oil dispersancy, as exhibited by their enh~nced sludge control propel ~ies.

For example, as the molecular weight of a dispersant backbone is increased, the polar segment of the molecule becomes the limiting factor in dispel ~ar,cy 20 pe.ru....ance with polyamine systems ofthe prior art such as triethylenetelran..ne and tetraethyle.-epe~ .. ne. Increasing the stoichiometric ratio of amine to polymerraises the nitrogen content, but results in significant levels of free unreactedpolyamine which is detrimental to diesel engine and elastomer seal pel~l...ance.
The present invention relates to a condPn~tion reaction (via Mannich base reaction) using a heavy polyamine, of filnction~li7~d hydrocarbons or polymers wL~ in the polymer backbones have a number average molecular weight (Mn) of greater than 300. Preferably 800 to 7500. Most preferably 1000 to 3000. The prefe,led number average molecular weight depends on the proi)ellies ofthe particular backbone. For example, for ethylene alpha olefin copolymers the p-t;f~lled molecular weight is 900 to S000 (e.g. 200.0 - 4000). For polybutenes the pl~felled molec~ r weight is 900 to 2500 (e.g. 2200). A typical example of function~li7ed polymer is polyisobutenyl succinic anhydride (PIBSA) which is a reaction product of polyisobutene and maleic anhydride. This reaction can occur via halogen-assistedfunctionalization (e.g. chlorination), the thermal "ene" reaction, or free radical a~ tion using a catalyst (e.g. a peroxide). These reactions are well know in the art.
In the present invention the functionalized backbones are subsequently reacted with N-hydroxyaryl amine. In the case of PIBSA, the reaction with the N-hydlo~y~uyl W 096/20992 PCTrUS9~/16778 amine yields a hydroxyaromatic polybutenyl succinimide which is converted to a Mannich base product with heavy polyamine and an aldehyde.

Dis~.ela~ s made from backbones less than 300 Mn are useful in 2-cycle 5 engine oils. The present invention inchldes dispersants useful for this application.

Suitable Hydroca~l,ons and Pol,vmers The prere,led hydrocarbons or polyrners employed in this invention include 10 homopolymers, interpolymers (e.g. copolymers, etc.) or lower molecular weighthydrocarbons. The prefel.ed polymers comprise at least one C3 to C28 alpha-olefin having the formula H2C=CH~l wherein Rl is straight or branched chain alkyl radical comprising 1 to 26 carbon atoms and wherein the polymer contains carbon-to-carbon unsaturation, preferably a high degree of terminal ethenylidene unsaturation.
15 Preferably, the polymers employed in this invention comprise interpolyrners of ethylene and at least one alpha-olefin of the above formula, wherein Rl is alkyl of from 1 to 18 carbon atoms, and more preferably is alkyl of from 1 to 8 carbon atoms, and more pref~,.ably still 1 to 2 carbon atoms. Therefore, useful alpha-olefin monomçrs and comonomers include~ for example, propylene, butene-l, he,~e,le-l, 20 octene-l, 4-methylpentene-l, decene-l, dodecene-l, tridecene-l, tetr~rlecene pe-nt^dec~ne-1, h~y~dece-le-l, hept~decPne-l, oct~decene-1, n~n~decene-1, and mixtures thereof (e.g., mixtures of propylene and butene-1, and the like). F~e...pl5. y of such polymers are propylene homopolymers, butene-1 homopolymers, ethylene-propylene copolymers, ethylene-butene- 1 copolymers and the like, wherein the 2S polymer contains at least some terminal andlor internal unsaturation. ~lefel.t;d polymers are unsaturated copolymers of ethylene and propylene and ethylene and butene-1. The interpolyrners ofthis invention may contain a minor amount, e.g. 0.5 to 5 mole % of a C4 to Cl 8 non-conjugated diolefin comonomer. However, it is prefelled that the polymers ofthis invention comprise only alpha-olefin 30 homopolymers, interpolymers of alpha-olefin comonomers and interpolyrners of ethylene and alpha-olefin COIllOl-Olllel~. The molar ethylene content ofthe polymers employed in this invention is preferably in the range of 20 to 80 %, and more preferably 30 to 70 %. When propylene and/or butene-1 are employed as colllonoll,e,(s) with ethylene, the ethylene content of such copolymers is most 35 preferably between 45 and 65 %, although higher or lower ethylene contents may be present.

WO 96/20992 PCI~/US95/16778 The polymers employed in this invention generally possess a Mn of 300 to 10,000, preferably 800 to 7,500; more preferably 1,000 to 3,000 (e.g., 1,500 to 2,500). The Mn for such polymers can be determined by several known techniques such as size exclusion chromatography (also known as gel permeation chromatography (GPC)) which also provides molecular weight distribution il~ollnation.

Suitable polymers will typically have a narrow molecular weight distribution (MWD) also referred to as polydispersity, as determined by the ratio of weight average molecular weight (Mw) to (Mn). Polymers having a Mw/Mn of less than 5, preferably less than 4, are most desirable. Suitable polymers have a polydispe~ y of, for example, 1 to 5. Consequently, such polymers generally possess an intrinsic viscosity (as measured in tetralin at 135C) of 0.025 to 0.9 dVg, preferably 0.05 to 0.5 dUg, most preferably 0.075 to 0.4 dl/g. The polymers employed in this invention preferably exhibit a degree of crystallinity such that, when grafted, they are ess~nti~lly amorphous.

Low molecular weight polymers are polymers having Mn less than 20,000, preferably 500 to 20,000 (e.g. 1,000 to 20,000), more prefe~bly 1,500 to 10,000 (e.g. 2,000 to 8,000) and most preferably from 1,500 to 5,000. The number average molecular weights are measured by vapor phase osmometry or GPC as tlicc~cced above. Low molecnl~r weight polymers are useful in forming dispersants for lubricant additives.

High molecular weight polymers Mn's ranging from 20,000 to about 250,000, preferably 25,000 to 100,000; and more preferably, from 25,000 to 80,000 are useful for viscosity modifiers for lubricating oil compositions.

Specific examples of terminal and internal olefin monomers which can be used to plepare the polymers ofthe present invention according to conv~ntion~l well-known polylll~ alion techniques include ethylene; propylene; butene-l; butene-2;isobutene; pentene-l; etc.; propylene-tetramer; diisobutylene; isobutylene trimer;
~lltA liene-1,2; but~Aiene-1~3; pentadiene-1,2; pe~t~iiene-1~3; etc.

Useful polymers include alpha-olefin homopolyrners and interpolymers, and ethylene alpha-olefin copolymers and terpolymers. Specific examples of polyalkenes include polypropylenes, polybutenes, ethylene-propylene copolymers, ethylene-butene copolymers, propylene-butene copolymers, styrene-isobutene copolymers, isobutene-b~lt~ ne-1,3 copolymers, etc., and terpolymers of isobutene, styrene and piperylene and copolymers of 80% of ethylene and 20% of propylene. A useful source of polymers are the poly(isobutene)s obtained by polymerization of C4 refinery stream having a butene content of about 35 to about 75% by wt., and an 5 isobutene content of about 30 to about 60% by wt., in the presence of a Lewis acid catalyst such as al~mim~m trichloride or boron trifluoride.

Also useful are the high molecular weight poly-n-butenes of USSN 992871 filed December 17, 1992.
A pre~c"cd source of monomer for making poly-n-butenes is petroleum feedstreams such as Rafflnate II. These feedstocks are disclosed in the art such as in US-A-4952739.

The polymers employed in this invention, which preferably are further characterized in that up to 95 % and more of the polymer chains possess terminalethenylidene-type unsaturation, may be prepared by polymerizing alpha-olefin ",onGl.ler, or mixtures of alpha-olefin monomers, or mixtures comprising ethylene and at least one C3 to C28 alpha-olefin monomer, in the presence of a catalyst system co,n~ ;ng at least one metallocene (e.g., a cyclopentadienyl-transition metal compound) and an alumoxane compound. Interpolymers of this latter type, which are prercll cd interpolymers for use in the invention, may be characterized by the formula POLY-C(R1)=CH2 wherein Rl is Cl to C26 alkyl, preferably C1 to C18 alkyl, more preferably Cl to C8 alkyl, and most preferably Cl to C2 alkyl, (e.g., methyl or ethyl) and wherein POLY rel)lese-lts the polymer chain. The chain length of the Rl alkyl group will vary depending on the comono,.-e- (s) selected for use in the polymerization. A minor amount of the polymer chains can contain terminal ethenyl, i.e., vinyl, unsaturation, i.e. POLY-CH=CH2, and a portion of the polyrners can contain internal monounsaturation, e.g. POLY-CH=CH(Rl), wherein Rl is as defined above.

In the ~ic~llcd polymers contemplated for use in this invention, at least about 30 % ofthe polymer chains possess terminal ethenylidene unsatu-alion.
Preferably at least 50 %, more preferably at least 60 %, and most preferably at least 75 % (e.g. 75-98 %), of such polymer chains exhibit terminal ethenylidene unsaturation. The pe- ce..l~ge of polymer chains exhibiting terminal ethenylidene unsaturation may be determined by FTIR spectroscopic analysis, titration, or C 13NMR.

The prefelled terminally unsaturated interpolymer to be used in this invention may be prepared by known metallocene chemistry. Preferred polymers to be used inthis invention also may be prepared as described in USSN's 992871; 992690; and 992192, all filed December 17, 1992.

The prefe, l ed interpolymers can be prepared by polymerizing monomer i~ules comprising ethylene in combination with other monomers such as alpha-olefins having from 3 to 28 carbon atoms (and preferably from 3 to 4 carbon atoms, 10 i.e., propylene, butene-1, and mixtures thereof) in the presence of a catalyst system comprising at least one metallocene (e.g., a cyclopentadienyl-transition metal compound) and an alumoxane compound. The comonomer content can be controlled through the selection of the metallocene catalyst component and by controlling the partial pressure of the various monomers. Most preferably, the polymers used in this 15 invention are subsf~nti~lly free of ethylene homopolymer.

The catalyst is preferably a bulky ligand transition metal compound. The bulky ligand may contain a multiplicity of bonded atoms, preferably carbon atoms, forrning a group which may be cyclic with one or more optional heteroatoms. The 20 bulky ligand may be a cyclopentadienyl derivative which can be mono- or polynuclear. One or more bulky ligands may be bonded to the tr~nei~ion metal ("Group" refers to an identified group ofthe Periodic Table of Flçments~
coll,plehcnsively presented in "Advanced Inorganic Chemistry", F.A. Cotton, G.
Wilkin.con, Fifth Edition, 1988, John Wiley & Sons). Other ligands may be bonded to 25 the transition metal, preferably det~c~ble by a cocatalyst such as a hydrocarbyl or halogen leaving group. The catalyst is derivable from a compound of the formula [L]m M[X]n wherein L is the bulky ligand, X is the leaving group, M is the transition metal and m and n are such that the total ligand valency corresponds to the transition metal valency. ~efe~bly the catalyst is four coordinate such that the compound is 30 ionizable to a 1+ valency state.

- The ligands L and X may be bridged to each other and if two ligands L and/or X are present, they may be bridged. The metallocenes may be full-sandwich compounds having two ligands L which are cyclopentadienyl groups or half-sandwich compounds having one ligand L only which is a cyclopentadienyl group.

For the purposes of this patent specification the term "metallocene" is defined to contain one or more cyclopentadienyl moiety in combination with a transition WO 96t20992 PCI/US95/16778 metal of the Periodic Table of Elements. In one embodiment the metallocene catalyst component is represented by the general formula (Cp)mMRnR~p wherein Cp is a substituted or unsubstituted cyclopentadienyl ring; M is a Group IV, V or VI
transition metal; R and R' are independently selected halogen, hydrocarbyl group, or hydrocarboxyl groups having 1-20 carbon atoms; m = 1-3, n = 0-3, p = 0-3, and the sum of m + n + p equals the oxidation state of M. In another embodiment the metallocene catalyst is I e~.l esenled by the formulas:

(CsR~m)pR~S(c5R m)MeQ3-p-x and R"S(C5R'm)2MeQ

wherein Me is a Group IV, V, or VI transition metal CsR'm is a substituted cyclopentadienyl each R', which can be the same or different is hydrogen, alkenyl aryl alkaryl or arylalkyl radical having from I to 20 carbon atoms or two carbon atoms 15 joined together to form a part of a C4 to C6 ring, R" is one or more of or a cG,l,bh1alion of a carbon, a germanium, a silicon, a phosphorous or a nitrogen atom co..~ ;ng radical substituting on and bridging two CsR'm rings or bridging one CsR'm ring back to Me, when p = 0 and x = 1 otherwise x is always equal to 0, each Q which can be the same or diffel e"l is an aryl alkyl, alkenyl, alkaryl, or arylalkyl 20 radical having from 1 to 20 carbon atoms or halogen, Q' is an alkylidene radical having from 1 to 20 carbon atoms, s is 0 or 1 and when s is 0, m is 5 and p is 0, 1 or 2andwhensisl,mis4andpisl.

Various forms of the catalyst system of the metallocene type may be used in 25 the poly",~,i,AIion process of this invention. Exemplary of the development of metallocene catalysts in the art for the polymerization of ethylene is the disclosure of US-A-4871705 to Hoel, US-A-4937299 to Ewen et al., and EP-A-0 129 368 published July 26, 1989, and US-A-5017714 and S120867 to Welborn, Jr. These publications teach the structure of the metallocene catalysts and include ~l~lmolC~n~ as 30 the cocatalyst. There are a variety of methods for prepa~ ing alumoxane, one of which is described in US-A-4665208.

For the purposes of this patent specification, the terms "cocatalysts or activators" are used interchangeably and are defined to by any compound or 35 component which can activate a bulky ligand transition metal compound. In oneembodiment the activators generally contain a metal of Group II and III of the Periodic Table of Elements. In the prefe~, ~d embodiment, the bulky transition metal compound are metallocenes, which are activated by trialkyl~ mimlm compounds, W 096/20992 PCTrUS95/16778 alumoxanes both linear and cyclic, or ionizing ionic activators or compounds such as tri (n-butyl) a.l."loluum tetra (pPnt~fluorophenyl) boron, which ionize the neutral mPt~llocPne compound. Such ionizing compounds may contain an active proton, or some other cation associated with but not coordin~ted or only loosely coordinated to 5 the rç~ ;ng ion ofthe ionizing ionic compound. Such compounds are described inEP-A-0520732, EP-A-0277003 and EP-A-0277004 published August 3, 1988, and US-A-5153157; 5198401; and 5241025. Further, the metallocene catalyst co,..l)onent can be a monocyclopentadienyl heteroatom cont~ining compound. This heteroatom is activated by either an alumoxane or an ionic activator to form an active 10 polymerization catalyst system to produce polymers useful in this invention. These types of catalyst systems are described in, for example, PCT International Publication 3 published January 9, 1992, US-A-5057475; 5096867; 5055438 and 5227440 and EP-A-0420436, WO 91/04257. In addition, the metallocene catalysts useful in this invention can include non-cyclopentadienyl catalyst components, or 15 ancillary ligands such as boroles or carbollides in combination with a transition metal.
Additionally, it is not beyond the scope of this invention that the catalysts and catalyst systems may be those described in U.S.-A-5064802 and PCT public~tio~ WO
93/08221 and WO 93/08199 published April 29, 1993. All the catalyst systems of the invention may be, optionally, prepolymerized or used in conjunction with an 20 additive or scavenging component to enh~nce catalytic productivity.

Illustrative examples of the metallocenes are dialkyl metallocenes such as bis(cyclopent~ienyl)tit~nillm di-methyl, bis(cyclopent~dienyl)h~fnium di",cll"~l, bis(cyclopentadienyl)~-lcon;llm di-neopel.lyl, etc. Other ~ ..ples of metallocenes 25 which can be usefully employed are monocyclopent~-lienyl titanocenes such as,pe~ ...cthyl-cyclopentadienyl tit~nium trichloride, substituted bis(Cp)Ti(IV) compounds such as bis(indenyl) tit~nium diphenyl etc. Illustrative PY~mples of the zirconocenes which can be usefully employed are, pent~methylcyclop~nt~dienyl zirconium tri-chloride, etc. Mixed cyclopentadienyl metallocene compounds such as 30 cyclopçnt~dienyl (pen~...tlhyl cyclopPnt~içnyl)-zirconium dichloride, can be employed. Bis(cyclopent~dienyl)h~fni..m dichloride, is illustrative of other metallocenes. Some pl~ ed metallocenes are bis(cyclopent~iPnyl)~lcoluum dimethyl; and the recemic and/or meso isomer of 1, 2-ethylene-bridged bis-(4, 5, 6, 7 -tetra-hydroindenyl) zirconium dichloride.
The alumoxane compounds useful in the polymerization process may be cyclic or linear. Cyclic alumoxanes may be represented by the general formula (R-AI-)nwhile linear alumoxanes may be I epl ese,~ed by the general formula R(R-AI-WO 96t20992 PCItUS9S/16778 )n'AlR2. In the general formula R is a C 1 -Cs alkyl group such as, for example, methyl, ethyl, propyl, butyl and pentyl, n is an integer of from 3 to 20, and n' is an integer from l to 20. Preferably, R is methyl and n and n' are 4-18. Generally, in the pl ~pala~ion of alumoxanes from, for example, ~ min~lm trimethyl and water, a 5 mixture of the linear and cyclic compounds is obtained. Preferably, they are p, ~I)ared by cont~ing water with a solution of ~ minum trialkyl, such as ~hlminllm trimethyl in a suitable organic solvent such as toluene or an aliphatic hydrocarbon. The mole ratio of aluminum in the alumoxane to total metal in the metallocenes which can be usefully employed can be in the range of 0.5:1 to 1000:1, and desirably 1:1 to 100:1.
Preferably, the mole ratio will be in the range of 50:1 to about 5:1 and most preferably 20:1 to 5:1. The solvents used in the preparation ofthe catalyst system are inert hydrocarbons, in particular a hydrocarbon that is inert with respect to the catalyst system. Such solvents include isobutane, butane, pentane, etc.

Polyrnerization is generally conducted at temperatures ranging between 20 and 300C, preferably between 30 and 200C. Reaction time is not critical and may vary from several hours or more to several minlltes or less, depending upon factors such as reaction tem;)e. a~lre~ the monomers to be copolymerized, and the like. The skilled artisan may readily obtain the optimum reaction time for a given set of 20 reaction pal~ Lers by routine expel;..~ on. The catalyst systems described herein are suitable for the polylllel i~alion of olefins in solution over a wide range of pressures. Preferably, the polymerization will be completed at a pressure of 10 to 3,000 bar, and generally at a pressure within the range of 40 bar to 2,000 bar, and most preferably, the polymerization will be completed at a pressure within the range from 50 bar to 1,500 bar. A~er polymerization and, optionally, deactivation ofthe catalyst (e.g., by conventional techniques such as cont~cting the polyllltli~lion reaction me-lium with water or an alcohol, such as meth~nol, propanol, isopropanol, etc., or cooling or fl~chin~ the me~ m to terminate the polyrnerization reaction), the product polymer can be recovered by known processes. Excess re~ct~nts may be flashed off. The polylll~.izalion may be cond~lcted employing liquid monomer, such as liquid propylene or mixtures of liquid monollltl ~ (such as mixtures of liquid propylene and l-butene as the reaction medium. Alternatively, polymeli~lion may be ~ccomplished in the pl ~sence of a hydrocarbon inert to the polymerization such as butane, pentane, isopenlal1e, hexane, isooctane, decane, toluene, xylene, and the lilce.
In those situations wherein the molecular weight of the polymer product that would be produced at a given set of operating conditions is higher than desired, any of the techniques known in the art for control of molecular weight, such as the use of hydrogen and/or polyrnerization temperature control, may be used in the process of WO 96/20992 PCI`IUS95/16778 this invention. If so desired, the polymerization may be carried out in the presence of hydrogen to lower the polymer molecular weight. Care should be taken, however, to assure that terminal ethenylidene unsaturation is not reduced below the prefelled level of at least 30 % ofthe polymer chains.

However, since the prefel, ed polymers are reactive polymers possesci~
ethenylidene-type terrninal unsaturation, it is pl eÇe" ed to prepare the polymers in the substantial absence of added H2 gas, that is, the absence of H2 gas added in ~mol~nts effective to subst~nti~lly reduce the polymer molecular weight. More preferably, the 10 polymerizations will be conducted employing less than 5 wppm, and more preferably less than 1 wppm, of added H2 gas, based on the moles of the ethylene monomer charged to the polymerization zone.

When carrying out the polymerization in a batch-type fashion, the reaction 15 diluent (if any), and the ethylene and alpha-olefin comonomer(s) are charged at approl)~iate ratios to a suitable reactor.

The polyl"e,i~lion may be cond~lcted in a continuous manner by si nult~lleQusly feeding the reaction diluent (if employed), mono.,ler~, catalyst and 20 cocatalyst to a reactor and withdrawing solvent, unreacted monomer and polymer from the reactor so as to allow a residence time of ingredients long enough for forming polymer of the desired molecular weight and separating the polymer from the reaction mixture.

Polyisobutylene is a most plefelled backbone ofthe present invention because it is readily available by cationic pol~",e,i~ation from butene streams (e.g., using AIC13 catalysts). Such polyisobutylenes generally contain residual unsaturation in ~mollnt~ of about one ethylenic double bond per polymer chain, positioned along the chain.
The polyisobutylene polymers employed are generally based on a hydrocarbon chain of from about 900 to 2500. Polyisobutylene having an Mn of less than about300 tends to give poor pelro""ance when employed as dispersant because the molecular weight is in~ufficient to keep the dispel sant molecule fully solubilized in lubricating oils. Methods for making polyisobutylene are known. Polyisobutylene can be functionalized by halogenation (e.g. chlorination), the thermal "ene" reaction, or by free radical grafting using a catalyst (e.g. peroxide) as described below.

Other polymers, such as ethylene-alpha-olefin interpolyrners having a number average molecular weight above 10,000 (e.g. 20,000 to 250,000) (e.g., ethylene-propylene copolymers and terpolymers cont~ining non-conjugated dienes) are suitable polymers for the preparation of dispersants or mllltifilnctional viscosity 5 modifiers of the present invention. However, ethylene-alpha-olefin interpolymers of the above molecular weights could be produced using Ziegler-Natta catalysts only in cG~lbh~alion with H2 as molecular weight control in order to terminate the glowillg copolymer chains within this molecular weight range. Without use of H2 or other conventional, so-called "chain-stoppers", the interpolymers produced with Ziegler-10 Natta catalysts would tend to have molecular weights greatly in excess of the aboverange. (Such higher copolymers, for example, are widely employed in ungrafted form as viscosity index improvers, and when functionalized and then Mannich base reacted with heavy polyamine, as described below, can be employed as dispersant-viscosity index improver polymers. (e.g. multifunctional viscosity modifiers)) The use of H2 15 as a chain stopper has the disadvantage of causing the saturation of the olefinic double bond content of the copolymer. Thus, while lower molecular weight copolymers were theoretically possible to prepare, their low unsaturation content (and the accompanying low graft copolymer yields) would have made their further functionalization by a thermal "ene" reaction, e.g., with dicarboxylic acid moie~ies in 20 prepa~ing dispelsallts, highly unattractive.

~epa~lion of Functionalized (Halo~en Assisted. "Ene" Reacted or Free-Radically Grafted) Backbone The polymer or hydrocarbon may be function~li7erl for example, with carboxylic acid producing moieties (preferably acid or anhydride) by reacting the polymer or hydrocarbon under conditions that result in the addition (e.g. ~ttaç~mPnt) offunctional moieties or agents, i.e., acid, anhydride, ester moietiPs~ etc., onto the polymer or hydrocarbon chains primarily at sites of carbon-to-carbon unsaturation (also referred to as ethylenic or olefinic unsaturation) using the halogen acsicted functionalization (e.g. chlorination) process or the thermal "ene" reaction. When using the free radical grafting process using a catalyst (e.g. peroxide), the fimction~ tion is randomly effected along the polymer chain. In one embodiTnpnt~this selective functionalization can be accomplished by halogen~ting, e.g., chlorinating or bromin~ting the unsaturated a-olefin polymer to about 1 to 8 wt. %, preferably 3 to 7 wt. % chlorine, or bromine, based on the weight of polymer or hydrocarbon, by passing the chlorine or bromine through the polymer at a te~ el~ re of 60 to 250C, preferably 110 to 160C, e.g., 120 to 140C, for about 0.5 to 10, preferably 1 to 7 hours. The halogenated polymer or hydrocarbon (hereinafter backbones) is then reacted with suff~cient monounsaturated reactantcapable of adding fimctional moieties to the backbone, e.g., monounsaturated carboxylic reactant, at 100 to 250C, usually about 180C to 235C, for about 0.5 to 5 10, e.g., 3 to 8 hours, such that the product obtained will contain the desired number of moles of the monounsaturated carboxylic reactant per mole of the halogenated backbones. Alternatively, the backbone and the monounsaturated carboxylic reactant are mixed and heated while adding chlorine to the hot material.

In accordance with this invention, the hydrocarbon or polymer backbone can be functionalized, e.g., with carboxylic acid producing moieties (prefel ably acid or anhydride moieties) selectively at sites of carbon-to-carbon unsaturation on thepolymer or hydrocarbon chains, or randomly along chains using the three processes mentioned above or combinations thereof in any sequence.
The prerel.ed monounsaturated react~nts that are used to functionalize the backbone comprise mono- and dicarboxylic acid material, i.e., acid, anhydride, or acid ester material, including (i) monounsaturated C4 to Clo dicarboxylic acid wl,erein (a) the carboxyl groups are vicinyl, (i.e., located on adjacent carbon atoms) 20 and (b) at least one, preferably both, of said ~dj~cent carbon atoms are part of said mono unsaturation; (ii) derivatives of (i) such as anhydrides or C 1 to Cs alcohol derived mono- or diesters of (i); (iii) monounsaturated C3 to Clo monocarboxylicacid wherein the carbon-carbon double bond is conjugated with the carboxy group,i.e., ofthe structure -C=C-CO-; and (iv) derivatives of(iii) such as C1 to Cs alcohol 25 derived mono- or diesters of (iii). Mixtures of monounsaturated carboxylic materials (i) - (iv) also may be used. Upon reaction with the backbone, the monounsaturation of the monol-nc~n-rated carboxylic reactant becomes saturated. Thus, for example, maleic anhydride becomes backbone-substituted sucçiniç anhydride, and acrylic acid becornPs backbone-substihlted propionic acid. Exemplary of such mono~msalurated 30 carboxylic re~ct~ntc are fumaric acid, itaconic acid, maleic acid, maleic anhydride, chloromaleic acid, chloromaleic anhydride, acrylic acid, methacrylic acid, crotonic acid, cinn~mic acid, and lower alkyl (e.g., Cl to C4 alkyl) acid esters ofthe folegoing, e.g., methyl maleate, ethyl fumarate, and methyl fumarate. The monounsaturated carboxylic re~ct~nt, preferably maleic anhydride, typically will be 35 used in an amount ranging from about 0.01 to about 20 wt. %, preferably 0.5 to 10 wt. %, based on the weight of the polymer or hydrocarbon.

While chlorination normally helps increase the reactivity of starting olefin polymers with monounsaturated function~li7ing react~nt it is not nPcess~ry with the polymers or hydrocarbons contennrl~ted for use in the present invention, particularly those prere,led polymers or hydrocarbons which possess a high terminal bond 5 content and reactivity. Preferably, therefore, the backbone and the mono.lnc~tllrated functionality react~nt, e.g., carboxylic re~ct~nt, are contacted at elevated telllpelalllre to cause an initial thermal "ene" reaction to take place. Ene reactions are known.

High molecular weight ethylene/propylene copolymer and ethylene/
10 propyleneJdiene terpolymers, having number average molecular weights of from 20,000 to 250,000, are generally produced employing Ziegler catalysts, generallyVC14 or VOC13 with a halide source, such as organo~ r~irl~lrn halides and/or hydrogen halides. Such high molecular weight EP and EPDM polymers find use as viscosity modifiers.
These high molecular weight ethylene/propylene interpolymers can be functionalized by random ~tt~chment of functional moieties along the polymer chains by a variety of methods For example, the polymer, in solution or in solid form, may be grafted with the monounsaturated carboxylic re~ct~nt, as described above, in the 20 presence of a free-radical initiator. When p~,.ro,...cd in solution, the ~,~ni"g takes place at an elevated te...pe,~ re in the range of about 100 to 260C, preferably 120 to 240C. Plertlably, free-radical initi~ted g~aL~g would be accomplished in a mineral lublicdling oil solution conl~in;ng~ e.g., 1 to 50 wt.%, preferably 5 to 30 wt.
% polymer based on the initial total oil solution.
The free-radical initiators which may be used are peroxides, hyd,opero~ides, and azo compounds, preferably those which have a boiling point greater than about 100C and decompose therrnally within the g,~ling temperature range to provide free-radicals. Rep,c;se,.lali~e ofthese free-radical initiators are azobutyronitrile, 2,5-30 dimethylhex-3-ene-2,5-bis-tertiary-butyl peroxide and dic~lnnene peroxide. The initiator, when used, typically is used in an amount of between 0.005% and 1% byweight based on the weight of the reaction mixture solution. Typically, the aforesaid monoune~turated carboxylic reactant material and free-radical initiator are used in a weight ratio range offrom about 1.0:1 to 30:1. preferably 3:1 to 6:1. The grafting is 35 ~l~rwably carried out in an inert atmosphere, such as under nitrogen b!~n~ n~ The res..lting graf'led polymer is characterized by having carboxylic acid (or ester or anhydride) moieties randomly att~hed along the polyrner chains: it being understood, of course, that some of the polymer chains remain ungrafted. The free radical W O 96/20992 PCTrUS95/16778 grafting described above can be used for the other polymers and hydrocarbons of the present invention.

Once functionalized the hydrocarbon or polymer then may be reacted with the 5 N-hydroxy amine compound.

The pre~"ed functionalized polymer is a 2,200 number average molecular weight polybutenyl succinic anhydride.

10 The N-Hydroxyaryl Amine Material The N-hydroxyaryl amines employed in this invention can comprise any aromatic compound having at least one hydroxy group and at least one amine-co.~ g group substituted on at least one ring of the aromatic compound. The N-15 hydroxyaryl amines which are prerell ed in this invention comprise N-hydroxyaryl mono-primary amines of the formula (I):

H2N-Ar-OH
20 wL~.~hl Ar represe,.ls ~-r or and wherein r is 1 or 2, and alkyl- and halide-substituted derivatives thereof, wherein 30 from 1 to 3 ring carbon atoms are substituted by a hydrocarbyl group or halide atom.
Illustrative of such Ar groups are phenylene, biphenylene, 5 naphthylene, and the like. The Ar group may be substituted with to 3, preferably 1 to 2, 10 hydrocarbyl groups, e.g., alkyl groups containing 1 to 20 carbon atoms, or with 1 to 3 halogen radicals, e.g., chloro-, bromo-, or iodo-.

Preferred N-hydroxyaryl amine re~ct~ntc are amino phenols of the formula H2N~OH

in which T is hydrogen, an alkyl radical having from 1 to 3 carbon atoms or a halogen radical such as the chloride or bromide radical.
Suitable aminophenols include 2-aminophenol, 3-aminophenol, 4-aminophenol, 4-amino-3-methylphenol, 4-amino-3-chlorophenol, 4-amino-2-~lolnophenol and 4-amino-3-ethylphenol. The p. ~re- ed N-hydroxyal ol~lalic amine to practice the present invention is 4-aminophenol.
Suitable amino-substituted polyhydroxyaryls are the aminoc~te~hols, the amino lesol~ih~ols, and the aminohydroquinones, e.g., 4-amino-1,2-dil~yd~ o~el~ene, 3 -amino- 1 ,2-dihydroxyben_ene, 5-amino- 1,3 -dihydroxyben7~n.o, 4-amino- 1 ,3-dihydroxyben_ene, 2-amino- 1 ,4-dihydroxyben_ene, 3 -amino- 1,4-30 dihydroxybenzene and the like.

Suitable aminonaphthols include l-amino-5-hydroxynaphth~lene, 1-amino-3-h~dlo~y..~r.h~ lene and the like.

W 096/20992 PCTÇUS95/16778 The Aldehyde Material The aldehyde reactants will generally comprise formaldehyde or 5 p~arc,~ aldehyde, although it will be understood that other aldehyde-group cQl-t~ compounds, such as C2 to Clo hydrocarbyl aldehydes (e.g., butyraldehyde, acet~ldehyde, propionaldehyde, and the like) can also be employed. A
plc;re,led group of aldehyde materials are compounds ofthe formula:

RCHO

whereil1 R is H or aliphatic hydrocarbon radical having from 1 to 4 carbon atoms.
The p,efelled aldehyde to practice the present invention is formaldehyde.

15 ~lepalalion ofthe Dispersant Heavy Amines The novel dis~el~ants ofthe present invention are based on, for eY~mple, the polyolefins as disclosed in USSN 992192, filed Decelllber 17, 1992, which are 20 illCOl ~oraled herein by l ~re~ ence for all purposes. These polymers can be functionalized (e.g. grafted) using halogen assisted function~li7~tion (e.g.
chlorination), the thermal "ene" reaction, or via free radical grafting using a catalyst (e.g. peroxide). Once the grafted polymers have been reacted with the N-hydroxyarolnàtic amine they are reacted with a heavy polyamine. It has been found 2S that the amine segment of the dis~ el san~ is very critical both to product pelrul Illance of the diSpel~àfilS and that disp.,. sa-lls made from heavy polyamine are superior to dispersants made from conventional polyamine mi-xtures (PAM).

For example, as the molecular weight of a iispe. ~alll backbone is increased, 30 the polar se~ ." ofthe molecule becomes the limiting factor in dispelsan~iy p~,.rOl ll,ance with polyamine systems of the prior art such as triethylenetetramine and tetraethylenep~nt~mine Increasing the stoichiometric ratio of amine to polymer raises the nitrogen content, but results in significant levels of free unreactedpolyamine which is detrimental to diesel engine and elastomer seal pelrullllallce~
Using amines higher than heavy polyamines of the present invention is dell;,.,e..lal because higher amines are insoluble or only partially soluble in oils and result in a hazy product in a lubricating oil composition. Amines higher than heavy WO 96/20992 PCI`/US95/16778 polyamine comprise less than about 6.0 milliequivalents of primary amine per gram (alternatively an equivalent weight of primary amine greater than about 160 grams per equivalent) and greater than about 12 nitrogens per molecule.

Typical dieslosures of polyamine react~nts for the prepal~lion of lubricant dispersants teach a range of nitrogens per molecule of from 1-12, a variety of spacing groups between the nitrogens, and a range of substitution patterns on the amine groups. We have discovered that dispersants derived from the prefelled compositions described below exhibit surprisingly enh~nced dispersancy relative to the prior art while ret~ining superior solubility in oil.

Specifically, one embodiment of this invention comprises oil-soluble derivatized compositions of C2-C1 g a-olefin polymers, copolymers, homopolymers or hydrocarbons, functionalized with carboxylic acid or anhydride moieties then reacted with a N-hydroxyaromatic amine, and further reacted with an aldehyde andheavy polyalkylene polyamines which contain ~28% N, more preferably >30% N, e.g. >32% N, and an equivalent weight of primary amine groups of between 120-160g/eq, more prere-~bly 120-150 g/eq, e.g. 12S-140 g/eq. Best results are oblainedwhen the polyamines contain more than 6 nitrogen atoms per molecule on the average (more preferably 7 or more, e.g. >8 nitrogen atoms per molecule), and more than two primary amines per molecule on the average (preferably >2.2, e.g. >2.4).
Good results are obtained when the spacing~ between the nitrogens are C2-C3. Theheavy polyamine preferably comprises essenti~lly no oxygen.

Polyamines with these characteristics are commercially available and can be produced by di~tilling out the tetraethylenepent~mine and most of the pent~ethylenf~hf .;~..;..e fractions from standard polyethylf.~ ..;ne mixtures.
Alternatively, they could be synthesi7ed by cyanoethylation ofthe l,lhl,al~ amine groups of polyethylene or polypropylene pe~-t~..;nes or h~ ~...;nes followed by 30 hydrogenation.

Reaction of the Functionalized Polyrner with the N-hydroxyaryl Amine and Heavy Polyamine Component In the process ofthe invention, the reaction between the functionalized backbone (e.g. hydrocarbon or polymer) and the N-hydroxyaromatic amine compound is carried out for a time and under conditions sllfflrient to form imide W O 96/20992 PC~rrUS95/16778 groups on the functionalized polymer with the concomitant release of water. The progress of this reaction can be followed by infrared analysis.

The functionalized polymer, preferably in solution generally equal to about 5 S to 30 wt. %, prefelably 10 to 20 wt. % polymer, can be readily reacted with the N-hydroxyaryl amine by admixture together with said functionalized polymer and heating at a temperature offrom about 100C. to 250C., preferably from 150 to 200C., for from about 0.1 to 10 hours, usually about 0.1 to about 2 hours. The heating is preferably carried out to favor formation of imides rather than amides and 10 salts. Thus, imide formation will give a lower viscosity of the reaction mixture than amide formation and particularly lower than salt formation. This lower viscositypermits the utilization of a higher concentration of functionalized polymer in the reaction mixture. Removal of water assures completion of the imidation reaction.Reaction ratios can vary considerably, depending upon the react~nt~ amounts of 15 excess, type of bonds formed, etc. Generally from about 1 to 2 molar equivalents, preferably about 1 molar equivalents, of said N-hydroxyaryl amine is preferably used, per mole of the functionalized polymer. For example, with an ethylene-propylene copolymer of about 40,000 (Mn)~ and averaging 4 maleic anhydride groups per molecule, and making imides, about 4 moles of N-hydroxyaryl amine with one 20 primary group would preferably be used per mole of grafted ethylene copolymer.
With a polybutene of about 950 (Mn) and averaging one maleic anhydride group permolecule, and making imides, about one mole of N-hydroxyaryl amine with one primary group would preferably be used per mole of gra~ed polybutene.

In one p- efel I ed aspect of this invention, the novel dispersants of this invention are prepared by reacting the functionalized polymer with the N-hydro~y~yl amine material to form a carbonyl-amino material cont~ ing at least one group having a carbonyl group bonded to a secondary or a tertiary nitrogen atom. In the amide form, the carbonyl-amino material can contain 1 or 2 -C(O)-NH- groups, andin the imide form the carbonyl-amino material will contain -C(O)-N-C(O)- groups.The carbonyl-amino material can therefore comprise N-(hydro~y~uyl) polymer-substituted dicarboxylic acid di~mide, N-(hydroxyaryl) polymer-substihlted dicarboxylic acid imide, N-(hydroxyaryl) polymer substituted-monocarboxylic acidmono~mide, N-(hydroxyaryl) polymer-substituted dicarboxylic acid mono~mide or a mixture thereof.

In general, equimolar amounts of the functionalized polymer (such as polybutene succinic anhydride or ethylene-propylene copolymer substituted with W O 96/20992 PC~rrUS9S/16778 sucçinic anhydride groups), and of the N-hydroxyaryl amine (such as 4-aminophenol), are dissolved in an inert solvent (i.e., a hydrocarbon solvent such as toluçn~, xylene, or isooctane) and reacted at a moderately elevated temperature up to the reflux temperature of the solvent used, for sufficient time to complete the 5 formation ofthe intermedi~te N-(hydroxyaryl) hydrocarbyl amide or imide.
Thereafter, the solvent is removed under vacuum at an elevated tel,lpel~Lure, generally, at approxilllately 1 60C (l mm). The reaction can similarly take place in a mineral oil.

Alternatively, the intermedi~te is prepared by combining equimolar ~mollntc of the functionalized polymer and the N-(hydroxyaryl) amine and heating the resulting mixture at elevated temperature under a nitrogen purge in the absence of solvent.

The resultin~ N-(hydroxyaryl) polymer substituted imides can be illustrated by the suc~inimides of the formula (III):

C~2-C ~OH
O T

20 wherein T is as defined above, and wherein Poly repl esents the polymer substituent group (e.g., polybutene or ethylene-propylene or ethylene butene copolymer, etc.).

In the second step ofthis invention, the carbonyl-amino inte~...e.~i~te is reacted with at least one heavy polyamine together with an aldehyde (eg., 25 formaldehyde) in the Mannich base reaction. In general, the re~ct~nts are ? lmil~çd and reacted at an elevated telllpel~l~re until the reaction is conlplete. This reaction may be condllcted in the presence of a solvent such as a mineral oil which is aneffective solvent for the carbonyl-amino intermediate and for the finished Mannich base dispersant material. This second step can be illustrated by the Mannich base 30 reaction between the above N-(hydroxyaryl) polymer sucçinimide interme~ t~, p~o"l-aldehyde and heavy amine in accordance with the following equation:

W 096/20992 PCTrUS95/16778 CH~--C ~ + CH O + heavy polyamine o /f Poly C~ C ~ ~
/N ~ ~ CH2 heavypolyamine CH2--~ \rOH
T

S Wherein Poly and T are as defined above.

In one prefe" ed embodiment of the invention, a gra~ed polybutene polymer, which has been prepared by first grafting succinic anhydride moieties onto a polybutene polymer using maleic anhydride, is reacted with an aminophenol to form 10 an interrnP~ te succinimide product, which is then reacted with formaldehyde and a heavy polyamine in the Mannich base reaction as outlined above to form the improved dispersants of this invention.

The amount of the reaGt~ntC employed is not critical and can vary over a wide 15 range. It is, however, prefe"ed to react the N-hydroxyaromatic s~lccinimide inte,...P,.l;~lP~ aldehyde reactant and heavy polyamine in the especli~e molar ratio of about 1~ 8:1 1. An excess of aldehyde reactant may be used. The reactions are exothermic, but it is desirable to heat the reaction to a temperature above about 50C, preferably in the range of from about 50 - 140C. This additional 20 heating drives the reaction to completion and removes water from the res~llt~nt condPnc~tion reaction product.

The reactions of grafted polybutene polymer with the N-hydroxyar,vl amine materials and subsequent amination is preferably carried out in the subst~nti~ sP-nce 25 of oxygen, e.g., under an inert atmosphere such as under a nitrogen blanket.

W 096/20992 PCTrUS95/16778 The dispersant-forrning reaction can be conducted in a polar or non-polar solvent (e.g., xylene, toluene, benzene and the like), and is preferably con~ucted in the presence of a mineral or synthetic lubricating oil.

US-A-5219480, US-A-5128056 and US-A-5043084 disclose such reactions of a grafted polymer reacted with an N-hydroxyaryl amine and then condenced withan aldehyde and an amine to form a Mannich base dispersant and are incorporated by reference herein in their entirety for all purposes.
Dispersants Dispersants m~int~in oil insolubles, resulting from oil use, in suspension in the fluid thus preventing sludge flocculation and precipitation. Suitable dispersants 15 incl~ldç, for example, dispersants ofthe ash-producing (also known as detergents) and ashless type, the latter type being pre~l ~ ed. The compositions of the present invention, can be used as dispersants and mllltifilnctional viscosity index improvers in lubricant and fuel compositions.

20 Post Trealmenl The hydrox~al o,llalic succinimide Mannich base condenc~tes of heavy polyamine, herein after "derivatized polymers". may be post-treated. The processes for post-ll ea~ g the derivatized polymer or hydrocarbon are analogous to the post-25 lleâling processes used with respect to conventional dispersants and MFVM's of theprior art. Accordingly, the same reaction conditions, ratio of re~ct~nts and the like can be used. Accordillgly, derivatized polymer or hydrocarbon can be post-treated with such reagents as urea, thiourea, carbon dic~lfidç, aldehydes, ketones, carboxylic acids, hydrocarbon-substituted succinic anhydrides, nitriles, epoxides, boron 30 compounds, phosphorus compounds, or the like.

The amine derivatized polymers or hydrocarbons of the present invention as described above can be post-treated, particularly for use as dispersants and viscosity modifiers by cont~cting said polymers or hydrocarbons with one ore more post-35 ~reàlillg reagents such as boron compounds, nitrogen compounds, phosphoruscompounds, oxygen compounds, succiniC acids and anhydrides (e.g., succinic anhydride, dodecyl succinic anhydride, and Cl to C30 hydrocarbyl substituted sucçinic anhydride), other acids and anhydrides such as maleic and fumaric acids and anhydrides, and esters of the foregoing e.g., methyl maleate. The amine derivatized polymers or hydrocarbons are preferably treated with boron oxide, boron halides,boron acid esters or boron ester in an amount to provide from 0.1 - 20.0 atomic proportions of boron per mole of nitrogen composition. Borated derivatized polymer useful as dispersants can contain from 0.05 to 2.0 wt. %, e.g. 0.05 to 0.7 wt. %boron based on the total weight of said borated rlitrogen-cor,~ g disp~
compound.

Treating is readily carried out by adding said boron compound, pr~.ably boric acid usuâlly as â slurry, to said nitrogen compound and heating with stirring at from about 135 to 190C, e.g. 140 to 170C, for from 1 to S hours.

The derivatized polymers or hydrocarbons of the present invention can also be treated with polymerizable lactones (such as epsilon-caprolactone) to form dispersant ~dduct~

Lubricating Compositions The additives of the invention may be used by incorporation into an alea~nol~s material such as fuels and lubricating oils. Fuels include normally liquid petroleum fuels such as middle tiictill~te boiling from 65 to 430C, inrlu(lin~
lcelosene, diesel fuels, home heating fuel oil, jet fuels, etc. A conc~ntration ofthe additives in the fuel is in the range oftypically from 0.001 to 0.5 wt.%, and preferably 0.005 to 0.15 wt. %, based on the total weight of the composition, will usually be employed.

The additives of the present invention may be used in lubricating oil compositiQn~ which employ a base oil in which the additives are dissolved or d,~t,~ed therein. Such base oils may be natural or synthetic. Base oils suitable for use in pre~aling the lubricating oil compositions of the present invention include those conventionally employed as crankcase lubricating oils for spark-ignited and colll~lession-ignited intemal combustion engineC, such as automobile and truck ~ngin~s, marine and railroad diesel engines, and the like. Advantageous results are also achieved by employing the additive mixtures of the present invention in base oils conventionally employed in and/or adapted for use as power llan~ fluids, universal tractor fluids and hydraulic fluids, heavy duty hydraulic fluids, power steering fluids and the like. Gear lubricants, industrial oils, pump oils and other WO 96/20992 PCI~/US95/16778 lubricating oil compositions can also benefit from the incorporation therein of the additives of the present invention.

Natural oils include animal oils and vegetable oils (e.g., castor, lard oil) liquid 5 petroleum oils and hydrorerlt-ed, solvent-treated or acid-treated mineral lubricating oils of the pararrl"-c, naphthenic and mixed paraffinic-naphthenic types. Oils of lubricating viscosity derived from coal or shale are also useful base oils.

Synthetic lubricating oils include hydrocarbon oils and halosubstituted 10 hydrocarbon oils such as polymerized and interpolymerized olefins (e.g., polybutylenes, polypropylenes, propylene-isobutylene copolymers, chlorinated polybutylenes, etc. Alkylene oxide polymers and interpolymers and derivatives thereof where the terrninal hydroxyl groups have been modified by esterification, etherification, etc., constitute another class of known synthetic lubricating oils.
15 Another suitable class of synthetic lubricating oils comprises the esters of dicarboxylic acids. Esters useful as synthetic oils also include those made from Cs to C12 monocarboxylic acids and polyols and polyol ethers such as neopc.,lyl glycol, etc. Silicon-based oils such as the polyalkyl-, polyaryl-, polyalkoxy-, or polyaryloxysiloxane oils and silicate oils comprise another useful class of synthetic 20 lubricants. Unrefined, refined and rerefined oils can be used in the lubricants of the present invention.

The additives of the present invention, particularly those adapted for use as di~,e-~a,lls or viscosity modifiers, can be incorporated into a lubricating oil in any 25 convenient way. Thus, they can be added directly to the oil by dia~Jel~;ng ordissolving the same in the oil. Such blending into the additional lube oil can occur at room temperature or elevated temperatures. Altematively, the additives may be first formed into concentrates, which are in turn blended into the oil. Such dis~e.~
concentrates will typically contain as active ingredient (A.I.), from 10 to 80 wt. %, 30 typically 20 to 60 wt. %, and preferably from 40 to 50 wt. %, additive, (based on the collc~ late weight) in base oil. MFVI concentrates typically will contain from 5 to 50wt. %AI.

The additives of the invention may be mixed with other additives selected to 35 pt~Çul~" at least one desired function. Typical of such additional additives are delel~;e,,ls~ viscosity modifiers, wear inhibitors, oxidation inhibitors, co--us;on inhibitors, friction modifiers, foam inhibitors, rust inhibitors, dem~lcifier ~ntioxi~nts~ lube oil flow improvers, and seal swell control agents.

Compositions, when containing these additives, typically are blended into the base oil in amounts which are effective to provide their normal ~tt~nd~nt function.
R~,"resel-tali~e effective amounts of such additives are illustrated as follows:

(Broad) (Pre~elled) Compositions Wt. % Wt. %
V.I. Improver 1-12 1-4 Corrosion Inhibitor 0.01-3 0.01-1.5 Oxidation Inhibitor 0.01-5 0.01-1.5 Dispc.~alll 0.1-10 0.1-5 Lube Oil Flow Improver 0.01-2 0.01-1.5 Detergents and Rust 0.01-6 0.01-3 Inhibitors Pour Point D~ e~san~ 0.01-1.5 0.01-1.5 Anti-Foaming Agents 0.001-0.1 0.001-0.01 Antiwear Agents 0.001-5 0.001-1.5 Seal Swellant 0.1-8 0.1~
Friction Modifiers 0.01-3 0.01-1.5 Lubricating Base Oil Balance R~l~nce When other additives are employed, it may be desirable, although not l ecç~c~ ~, to prepare additive concentrates or packages comprising conce.-l-aled 25 solutions or dispersions of the subject additives of this invention together with one or more of said other additives. Dissolution of the additive concentrate into the lubricating oil may be f~rilitated by solvents and by mixing accG...~ ied with mild he~tine, but this is not essenti~l The final forrnulations may employ typically 2 to 20 wt. %, e.g. about 10 wt. %, of the additive package with the rçm~in-lçr being base 30 oil.

All of said weight percents e~yl essed herein (unless otherwise indic~ted) are based on active ingredient (A.I.) content of the individual additives, and the total weight of the additive p~cL ~ee or formulation, which will include the weight of total 35 oil or diluent.

EXA~fPLES

The following examples are representative of hydroxy aromatic sucrinim:1e 40 M~nni~h base co~den~te dispersants prepared from heavy polyamine. In the following examples the number average molecular weight (Mn) was detell..h~ed by Gel P~,l..e&~ion Chromatography (GPC).

WO 96/20992 PCI`/US95tl6778 Example 1 - P~epa~lion of Hydroxy Aromatic Succinimide 1000 grams (0.35 mol, Sap=39.4, and AI=71.5) of an oil diluted polyisobutenyl succinic anhydride (PIBSA) derived from the reaction of a S polyisobutylene(Mn=2200) and maleic anhydride using known techniques, was mixed with 38.3 grams(O.3S mol) of 4-aminophenol, comm~rcially available from Aldrich Chçmic~l Supply Company, 300 grams of xylene and 213 grams of Exxon Solvent lSO Neutral base oil. The reaction mixture was heated to reflux(lSO-160C) while~iictilling offthe water of reaction. Af~er four hours, the h~,~red analysis in~ qted 10 the reaction was completed. The xylene was distilled offand the residue was aLIipped at lSOC with a nitrogen stream for about two hours.

Example 2 - Mannich Base Condensation With Heavy Polyamine lS 200 grams(O.OS6 mol) ofthe product of example 1 was mixed with 7.4 grams(0.056 eq. primary amine), of heavy polyamine Dow HA-2(32.8% N, 7.77 meq primary amine/g), 46 grams of Exxon S150N base oil and 100 mol oftoluene. The reaction mixture was heated to 80C and 5.5 grams(O.067 mol) of formalin was added over one half hour period. The reaction was allowed to soak at 80C for one hour, then the te"")e~al-lre was raised to 120C and kept at 120C for two hourswhile toluene refluxed and the water present was distilled off. The residue was then heated up to lSOC and stripped with nitrogen for one hour. The oil sol~-tiQn analyzed for 1.30% nitrogen and a kinem~tic viscosity of 690 cst at 100C.

2S Example 3 - (Comparative) 200 grams(O.OS6 mol) of the product of example 1 was mixed with 6.S
grams(O.OS6 eq. primary amine), of PAM (33.S % N, 8.68 meq. p.i",~ amine/g), 46 grams of Exxon SlSON base oil and 100 ml oftoluene. The reaction l~flAlule was heated to 80C and S.S grams(O.067 mol) of formalin was added over one half hourperiod. The reaction was allowed to soak at 80C for one hour, then the telllpelalllre was raised to 120C and kept at 120C for two hours while toluene refluxed and the water present was distilled off. The residue was then heated up to 150C and stripped with nitrogen for one hour. The oil solution analyzed for 1.18% nitrogen and a kin~ tic viscosity of 67S cst at 100C.

The products from Examples 2 and 3 were tested in the SIB/VIB dia~ aan~y test along with two commercially PIBSA/PAM dia~J~I aanls~

W 096/20992 PCTrUS9S/16778 SLUDGE-VARNISH BENCH TEST RESULTS

SIB (Sludge Inhibition Bench Test)/VIB (Varnish Inhibition Bench Test) The SIB and VIB tests forecast the pelro,l.,ance of a lubricant in a gasoline engine. The test is described below:

The SIB test employs a used crankcase mineral lubricating oil composition 10 having an original viscosity of about 325 SSU at 37.8C that has been used in a taxicab driven generally for short trips only thereby causing a build up of a high concentration of sludge precursors. The oil used contains only a refined base mineral oil, a viscosity index improver, a pour point depressant and a zinc dialkyldithiophosphate antiwear additive. The oil contains no sludge dispel~ants.
15 Such used oil is acquired by draining and refilling taxicab cr~nkc~ces at about 1,000 -2,000 mile intervals.

The SIB test is cond~lcted in the following manner: The used cr~n~r~se oil is freed of sludge by centrifuging for one half hour at about 39,000 gravities (gs). The 20 resvltir~g clear bright red oil is then decAntPd from the insoluble sludge particles.
However, the supel..alant oil still con~ains oil-soluble sludge precursors which, under the conditions employed by this test, will tend to form additional oil-insolubledeposits of sludge. The sludge inhibiting prop~, Lies of the additives being tested are detelll-;ned by adding to portions ofthe used oil O.S wt. %, on an active basis, ofthe 25 particular additive being tested. Ten grams of each oil sample being tested is placed in a st~inless steel centrifuge tube and is heated at 140C for 16 hrs. in the plc,sellce of air. Following the he~tin~, the tube corlh;~ the oil being tested is cooled and then centrifuged for 30 min. at about 39,000 gs. Any deposits of new sludge thatform in this step are sepa-a~ed from the oil by ~ec~ntin~ su~,e-l.atan~ oil and then 30 carefully washed with 15 ml. of pentane to remove all r~ llAinil~g oils from the sludge.
The weight, in milligrams, ofthe new solid sludge that forms in the test is detel,.,med by drying the residue and weighing it. The results are reported as milligrams ofsludge per ten grams of sludge, thus measuring differences as small as one part per ten tholls~n~ The less new sludge formed, the more effective is the additive as a 35 di~,el ~dn~. In other words, if the additive is effective, it will hold at least a portion of the new sludge that forms on heating and oxidation, stably suspended in the oil so that it does not ~-~cipi~a~e during the centrifuging period. The sludge inhibition of the di~pt;- ~a-ll is then determined by comparing the amount of sludge (in mg) formed in the blend to the amount formed by a similarly treated blank cont~ining only the oil.
SIB values are reported on a norrn~li7~d scale of 1 (high inhibition) to 10 (no inhibition).

S In the VIB test, a dispersant is admixed with the same test oil as used in the SIB test. The oil is then subjected to one or more test cycles that include heatso~king, heat cycling, and exposure to NO, SO2, and water. Varnish inhibitiQn isdetermined by visual inspection ofthe wall surfaces ofthe test flasks and co---?~ison to a blank with no additive. VIB values are reported on a scale of 1 (high inhibition) to 11 (no inhibition).

A more detailed description of the SIB and VIB tests can be found in US-A-4954572 and US-A-5219480, both of which are incorporated herein by .erelence in their entireties.
Samples of the dispersants prepared as set forth in Examples 2 and 3 and two reference dispersants were subjected to standard sludge and varnish inhibition bench tests (SIB and VIB). The samples of the dispersants were subjected to the SIB and VIB tests to provide a basis of comparison between the hydroxy aromatic 20 suc-;~.;:de Mannich base-heavy amine condenc~tçs of this invention and the cG,.~syonding prior art hydroxy aromatic succinirnide dispc,~arlls and convçntion~
PIBSA-PAM dis~,e.~ts.

Sludge-Varnish Inhibition Test Results(SIB/VIB) (Concenl~ation= 0.5% disp) Example Amine Type SlB VIB
(mg sludge/10 mg blank sludge) Ex. 2 H-PAM 1.05 3.5 Ex. 3 (CG.. l~alali~re) PAM 1.62 6 Ref. l-Comrnercial PIBSA-112/PAM 6.6 7 Re 2-CommercialPIBSA-48/PAM 5.28 5 Blank 10.0 11 The above results are the average of two runs.

The SIB and VIB results above indicate that the dispersant made from HA-2 heavy polyamine has superior sludge and varnish dispersancy properties than those made from co,,ul~crcial PAM at equivalent active ingredient for both hydroxy aromatic s~lc~inimide and PIBSA-PAM dispersants. Lower values in~ic~te better 5 dispe,~ancy performance.

Claims (21)

CLAIMS:

1. A lubricating oil dispersant additive which comprises a condensation product obtained by the reaction of:

a) at least one oil soluble hydrocarbon grafted with an ethylenically unsaturated carboxylic acid material having 1 to 2 dicarboxylic acid groups or anhydride group;
b) at least one N-hydroxyaryl amine compound;
c) at least one aldehyde reactant; and d) a heavy polyamine.

2. The product of claim 1 wherein said hydrocarbon comprises a polymer.

3. The product of claim 2 wherein said polymer comprises polybutene having a number average molecular weight of from about 300 to about 20,000.

4. The product of claim 2 wherein said polymer comprises ethylene-alpha-olefin copolymer comprising monomer units derived from ethylene and at least one alpha-olefin of the formula H2C=CHR1, wherein R1 is an alkyl group of from 1to 18 carbon atoms, and wherein said polymer has a number average molecular weight of from about 300 to about 250,000 and an average of at least about 30% of said polymer chains contain terminal ethylidene unsaturation.

5. The product of claim 4 where said ethylene-alpha-olefin copolymer comprises ethylene-propylene copolymer.

6. The product of claim 4 where said ethylene-alpha-olefin copolymer comprises ethylene-butene copolymer.

7. The product of claim 1 wherein said anhydride group comprises maleic anhydride and said aldehyde comprises formaldehyde.

8. The product of claim 1 wherein said N-hydroxyaryl amine compound comprises at least one member selected from the group consisting of compounds ofthe formula:

H2N-Ar-OH

wherein Ar represents and wherein r is 1 or 2, and derivatives thereof wherein from 1 to 3 ring carbon atoms are each substituted by an alkyl group or halogen atoms; or of the formula:

in which T is hydrogen, alkyl group having from 1 to 3 carbon atoms or halogen.

9. The product of claim 1 wherein said heavy polyamine comprises substantially no oxygen.

10. The dispersant of claim 1 wherein said heavy polyamine has an equivalent weight of about 120 - 160 grams per equivalent of primary amine and at least about 28 wt.% nitrogen.

11. The dispersant of claim 1 wherein said heavy polyamine has an average of at least about 7 nitrogens per molecule and an equivalent weight of about 125 - 140 grams per equivalent of primary amine.

12. The dispersant of claim 1 wherein said heavy polyamine comprises less than about 1 wt.% pentamines and lower polyamines and less than about 25 wt.% hexamines.

13. The product of claim 1 wherein said heavy polyamine has an average of at least about 7 nitrogens per molecule, a primary amine content of at least about 6.3 to about 8.5 milliequivalents of primary amine per gram, and a total nitrogen content of at least about 32 wt.%.

14. The use of the product of claim 1 as an additive in a fuel or lubricant.

15. An oleaginous composition comprising the product of claim 1.

16. An oleaginous composition comprising the product of claim 1 and a base oil in the form of a lubricating oil or lubricating oil additive package.

17. The use of the product of claim 1 wherein said polymer has a number average molecular weight of less than 300, as an additive in a two-cycle engine oil

18. A lubricating oil composition containing from about 0. 01 to about 20 weight percent of the product of claim 1.

19. A lubricating oil concentrate containing from about 20 to about 60 weight percent of the product of claim 1.

20. A fuel composition containing from about 0.001 to 0.5 weight percent of the product of claim 1.

21. A process for producing a Mannich base dispersant condensation composition useful as a fuel additive or lubricating oil additive comprising the steps of:
a) providing at least one hydroxyaryl polymeric succinimide;
b) providing at least one aldehyde reactant; and c) contacting a heavy polyamine with said succinimide and aldehyde for a time and under conditions sufficient to form said Mannich base condensation dispersant additive.