Note: Descriptions are shown in the official language in which they were submitted.
?CA 02263959 l999-02- 19W0 93/03517 PCT /US97Il2l25-1-POLAR MONOMER CONTAINING COPOLYMERS DERIVED FROM OLEFINSUSEFUL AS LUBRICANT AND FUEL OIL ADDITIVES, PROCESSES FORPREPARATION OF SUCH COPOLYMERS AND ADDITIVES AND USETHEREOFFT TINThe invention relates to copolymers derived from polar monomers suchas alkyl acrylates and olefinic monomers such as ethylene, C3-C20 aâolefins,and mixtures thereof, which possess a specific combination of chemical andphysical properties rendering the copolymers particularly suitable as "polymer(or copolymerl backbones" for the preparation of fuel and lubricating oiladditives, particularly dispersants, viscosity modifiers and flow improvers.The invention also relates to improved oilâso|uble dispersant additives preparedfrom the copolymers and useful in fuel and lubricating oil compositions, and toconcentrates containing the oil-soluble dispersant additives. Furthermore, theinvention relates to a continuous process for the copolymerization of at leastone alkyl acrylate and at least one of ethylene, on-olefins and mixtures ofethylene and or-olefins using a lateâtransition-metal catalyst system, andwhere an on-olefin monomer is used, using it in the form of a highly diluted 0:-olefin feed, preferably obtained from a refinery or steam cracker feedstream.N INV NT NHydrocarbon oil and fuel oil compositions typically include additives toenhance performance. For example, such oils typically comprise a mixture ofat least one hydrocarbon base oil and one or more additives, e.g., dispersant,viscosity modifier, wax crystal modifier (e.g., pour point depressant),detergent, antioxidant, etc. additives, where each additive is employed for thepurpose of improving the performance and properties of the base oil in itsintended application; e.g., as a lubricating oil, heating oil, diesel oil, middledistillate fuel oil, power transmission fluid and so forth.Dispersants are typically polymeric materials with an oleophiliccharacteristic providing oil solubility and a polar characteristic providingdispersancy. The number average molecular weight of a polymer âbackboneâused as a vehicle for synthesizing a dispersant is generally 10,000 or less.Viscosity modifiers also are typically polymeric materials that can beused neat or with suitable functionalization and/or derivatization be used as?CA 02263959 2004-09-20-2-multifunctional viscosity modifiers. When used as viscosity modifiers the.polymer or copolymer backbone generally has a number average molecularweight of greater than about 15,000.Dispersants used in lubricating oils typically are hydrocarbon polymersor copolymers modified to contain nitrogen- and ester-based groups.Polyisobutylene is commonly used in the preparation of dispersants, althoughother hydrocarbon polymers, such as ethylene-oi-olefin copolymers, can beemployed as well. lt is the primary function of a dispersants to maintain insuspension in the oil those insoluble materials formed by oxidation, etc. duringuse, thereby preventing sludge flocculation and precipitation. The amount ofdispersant employed is dictated by the effectiveness of the particular materialin achieving its dispersant function. Dispersants can have additionalfunctions, such as viscosity modifying properties and antioxidancy, dependingon their chemical and structural characteristics.Nitrogen- and ester-based dispersants can be prepared by firstfunctionalizing a long-chain hydrocarbon polymer, e.g., polyisobutylene, andethylene or-olefin (EAO) copolymers with maleic anhydride to form thecorresponding polymer substituted with succinic anhydride groups, and thenderivatizing the succinic anhydride-substituted polymer with an amine or analcohol or the like. Polyisobutylene generally contains residual unsaturation inamounts of about one ethylenic double bond per polymer chain, positionedalong the chain, whereas the more recently developed EAO copolymers (basedon metallocene catalyst systems) contain a substantial amount of terminalvinylidene unsaturation (see, e.g. WO 94/19436, published Sept. 1, 1994). Theethylenic double bonds serve as sites for functionalization by, for example,the thermal "ene" reaction (i.e., by direct reaction with maleic anhydride orone or more other dicarboxylic acid moieties).Polyisobutylene (PlBl polymers employed in conventional dispersantsare sometimes limited by viscosity effects associated with the polymer aswell as limited reactivity. EAO copolymers offer improvements, since theseproducts are primarily terminated with vinylidene type unsaturation, but thereare additional efficiencies which can be realized with further improvements inreactivity for functionalization and derivatization: also such copolymers requirethe use of multiple monomer feed streams to produce a copolymer.The use of highly diluted, purified refinery monomer feedstreams forethylene and oi-olefin polymerization using a metallocene catalyst system to?CA 02263959 2004-09-20- eproduce an ethylene a-ole?n copolymer lS known. As a consequencof using a Ziegler-Natta catalystgenerally, or a metallocene based catalyst system specifically, there arenecessary concerns about the purity of the feedstreams since such catalystsystems are particularly sensitive to moisture as well as nitrogen, sulfur andoxygen compounds which can deactivate the catalyst (see, e.g.,W093/24539, page 13, published Dec. 9, 1993).Johnson, L. K. et al., in J. Am Chem Soc., 1995, 117, 6414, describe theuse of Ni and Pd complexes using various activators (including MAO and alkylaluminum chloride) for the solution homopolymerization of ethylene, propylene,and 1-hexene. Polymers varying in molecular weight, branch length andcrystallinity are disclosed.Johnson, L. K. et al., in J. Am Chem Soc., 1996, 118, 267, describe thesolution copolymerization of ethylene with acrylate comonomers, including methylacrylate, tert-butyl acrylate, per?uorinated octyl acrylate, and methyl vinyl ketoneand propylene with methyl acrylate and perfluorinated octyl acrylate, using a Pdcatalyst. The copolymers are disclosed as random, amorphous, and branched (itis stated that ethylene copolymers have approximately 100 branches/1000 Catoms) with functional groups located predominantly at branch ends.Brookhart, M. S. et al., in published patent application EP 0 454 231 A2(1991) describe a catalyst for the polymerization of ethylene, aâolefins, diole?ns.functionalized ole?ns, and alkynes. The general description of the catalystbroadly includes Group Vlllb metals (Groups 8, 9, 10); cobalt and nickel areexemplified in solution polymerizations to produce oligomers and polymers oflimited molecular weight.Brookhart, M. et al. in J. Am. Chem. Soc, 1994, 116, 3641 and 1992, 114,5894 describe the use of Pd(Il) catalysts to produce alternating olefin/COcopolymers. (Subsequently, it is noted in J. Am Chem Soc., 1995, 117, 6414 thatthe complexes used in the 1992 reference only dimerize ethylene.)Keim, W. et al. in Angew. Chem, Int. Ed. Engl., 1981, 20, 116 describe theuse of an aminobis(imino)phosphorane complex of Ni to polymerize ethyleneunder pressure in a toluene solution. The polymer is said to contain short chainbranches.Mohring, V. M. et al. in Angew. Chem., Int. Ed. Engl., 1985, 24, 1001describe the use of the catalyst system aminobis(imino)phosphorane complex ofNi to polymerize C3 to C20 linear on-ole?ns and singly branched aâolefins. Ole?ns?CA 02263959 1999-02-19WO 98/03617 PCT/US97/12125- 4 -containing quaternary carbons, vinylene, or vinylidene groups did polymerize, butcopolymers of ocâo|e?ns could be obtained. Polymerization of linear or-olefinsproduced polymers containing methyl branches evenly spaced corresponding tothe length of the ole?n chain. (A âchain running" mechanism proposed as anexplanation for the branched polymer structure is also described by L.K. Johnsonin J. Am Chem Soc., 1995, 117, 6414, above.)Peuckert, M. et al. in Organometallics, 1983, 2, 594 describe a Ni catalystfor the oligomerization of ethylene in toluene. The catalysts are said to containthe chelating phosphino-acetate ligand used in SHOP catalysts. The C4 to C24oligomers are >99% linear and >93% on-ole?n. An ethylene/hexene co-oligomerization produced product with no detectable branches.A component described as useful in lubricating oil flow improversdescribed in U.S. 4,839,074 includes polymers and interpolymers of sidechain unsaturated monoesters which are unsaturated esters, generally acrylateor 2-alkylacrylate monoesters represented by a defined formula.It has been found in the present invention, that further improvementscan be achieved in the performance of fuel and lubricant additives, particularlyincluding ashless dispersants and wax crystal modifiers, based on the use ofcopolymers derived from polar and olefinic monomers; also, significantimprovements in the economics of producing and using such additives can beachieved by selective use of late-transition-metal catalysts and polymerizationprocesses which use highly dilute refinery or steam cracker olefin feedstreamsto produce a copolymer having a unique combination of properties forsubsequent functionalization and derivatization.RY HE I NTI NHydrocarbon copolymers derived from polar and olefinic monomerswhich are suitable for use as a fuel or lubricant additives, e.g., polarmonomers including alkyl acrylates and olefinic monomers including ethyleneand ocâolefins such as propylene, 1-butene, etc. (such copolymers referred to,for convenience, as âpo|arâo|efin hydrocarbonâ copolymers or POHcopolymers), characterized by a complex set of properties: (a) an averageethylene sequence length, ESL, of from about 1.0 to less than about 3.0; (b)an average of at least 5 branches per 100 carbon atoms of the copolymerchains comprising said copolymer; (cl at least about 50% of such branchesbeing methyl and/or ethyl branches; (d) at least about 30% of the copolymer? CA 02263959 l999-02- l9wo 98/03617 PCT/US97/12125_ 5 -chains terminated with a vinyl or vinylene group: (e) a number averagemolecular weight, Mn of from about 300 to about 10,000 for dispersant usesand from about 15,000 to about 500,000 for viscosity modifier uses; and (flsubstantial solubility of the copolymer in hydrocarbon and/or synthetic baseoil.This combination of properties yields POH copolymers of the inventionespecially suitable for use as polymer/copolymer backbones in the preparationof lubricating and fuel oil additives, particularly dispersant additives, as well asfor use as wax crystal modifiers and viscosity modifiers. When used as adispersant backbone, the limited range of number average molecular weightcharacterizing the POH copolymers of the present invention ensures thatdispersants produced therefrom are substantially soluble in lubricating baseoils, and, simultaneously, avoids or reduces handling problems due to highviscosity levels and wax crystal interactions. Furthermore, the definedcopolymer properties also result in products which have the desired level ofwax interaction for their use as wax crystal modifiers and the solutionviscosity/temperature properties for use as viscosity modifiers. Because ofthe relatively high level of terminal vinyl and vinylene unsaturation in theinventive POH copolymers, the dispersant additives produced therefrom havehigh active ingredient concentrations, thereby providing enhanced lubricatingoil dispersancy, including enhanced sludge and varnish control properties.The copolymers of the present invention are preferably produced usinga process which employs as the monomerlsl highly dilute refinery or steamcracker feedstreamlsl based on C3, C4 or C5 sources with or without addedethylene. The process is particularly advantageous in that the monomerfeedstream need not be totally free of materials which would otherwise bepoisons for ZieglerâNatta or metallocene based catalyst systems.Furthermore, the copolymers of the present invention and thedispersant additives produced therefrom, will possess enhanced pour pointperformance in lubricating oil compositions to which they are added,particularly in compositions which also contain conventional lubricating oilflow improvers (LOFl's). This beneficial pour point behavior of the dispersantsis believed to be attributable in part to the unique copolymer chain structureachievable with the late-transition-metal catalyst system.A further aspect of this invention relates to the POH copolymerfunctionalized with reactive groups, such as by substitution with mono- ordicarboxylic acid materials (i.e., acid, anhydride or acid ester) produced by ?CA 02263959 2004-09-20-5-reacting (e.g., by the "ene" reaction) the POH copolymers of the inventionwith mono-unsaturated carboxylic reactants. The monocarboxylic acid andthe dicarboxylic acid or anhydride substituted POH copolymers are useful perse as additives to lubricating oils, and, in another aspect of this invention, canalso be reacted with nucleophilic reagents, such as amines, alcohols, aminoalcohols and metal compounds, to form derivative products which are alsouseful as lubricating oil additives, e.g., as dispersants.In still another aspect of this invention, lubricating oil additives areproduced by functionalizing the POH copolymers of the invention usingreactants other than the mono-unsaturated carboxylic reactants describedabove. Accordingly, the copolymer can be functionalized by reaction with ahydroxy aromatic compound in the presence of a catalytically effectiveamount of at least one acidic alkylation catalyst. Subsequently, the alkylatedhydroxyaromatic compound can be reacted by Mannich Base condensationwith an aldehyde and an amine reagent to provide a derivatized copolymer.Lubricating oil additives within the scope of this invention are alsoproduced by oxidation of the POH copolymer of the invention, such asoxidation with a gas containing oxygen and/or ozone. The copolymer can alsobe functionalized by hydroformylation and by epoxidation, The POHcopolymers can also be functionalized by contacting the copolymers underKoch reaction conditions with carbon monoxide in the presence of an acidiccatalyst and a nucleophilic trapping agent such as water or a hydroxy-containing compound or a thiol-containing compound to form carboxyl groupson the copolymer. Functionalization can also be accomplished using âl'-ieppeâreaction chemistry (as described in U.S. Patent No. 5,773,567). Furthermore, theaforesaid functionalized copolymers formed by oxidation, hydroformylation,epoxidation, and Koch reaction can be derivatized by reaction with at leastone derivatizing compound to form derivatized copolymers.S lPTl TlWhen used in the disclosure and claims, the terms "polymer" and"copolymer" are used interchangeably unless the terms are otherwisespecifically distinguished. The present invention relates to copolymers derivedfrom polar monomers such as alkyl acrylates and olefinic monomers such as?CA 02263959 l999-02- 19W0 98I03617 PCT/US97/12125-7-ethylene, propylene and 1-butene characterized by a certain combination ofchemical and physical properties which makes the copolymers especiallysuitable for use as the backbone of dispersant additives. More particularly,the polar-olefinic hydrocarbon (POH) copolymers of the invention possess arelatively high degree of terminal vinyl and/or vinylene unsaturation, a numberaverage molecular weight within defined ranges, controlled ethylene sequencelength within copolymer chains, and the ability to form mineral and/orsynthetic oil solutions. Each of these properties contributes in one or morerespects to the utility of the copolymer as a dispersant backbone.'nfhP- " r rPolarâolefinic hydrocarbon (âPOHâ) copolymers of the present inventionhaving a relatively high degree of terminal vinyl and/or vinylene unsaturation,for example, at least about 30% of the copolymer chains, can be prepared bypolymerizing at least one olefinic monomer selected from the group consistingof la) ethylene, ( b) one or more on-olefins or (c) mixtures of la) and (b) andoptionally, an additional polyene, in the presence of a late-transitionâmeta|catalyst system described below. The POH copolymer chain structure can becontrolled through the selection of the late-transition-metal catalyst systemand by controlling the relative proportions of the ethylene and/or other oc-olefins. One preferred method for preparing the POH copolymers is describedin more detail below; it is based on the use of one or more highly dilutedmonomer feedstreams originating in a refinery or steam cracker.The polymerization catalyst useful for this invention can be derived fromthe late-transition-metal compounds of formula:LMX,wherein M is a Group 9, 10, or 11 metal. preferably a de, d8 or d1°metal, most preferably d8 (wherein "Group" refers to the identifiedgroup of the Periodic Table of Elements, comprehensivelypresented in "Advanced Inorganic Chemistry," F.A. Cotton, G.Wilkinson, Fifth Edition, 1988, John Wiley & Sons);L is a bidentate ligand that stabilizes a square planar geometry andcharge balances the oxidation state of MX,;.,,. _._..........................................-.........,.._.,., . . . .. .. z.,,._ .. . .. , ..?W0 98/0361 7CA 02263959 l999-02- 19PCT/US97I12125_ 3 _each X is, independently, a hydride radical, a hydrocarbyl radical, asubstituted hydrocarbyl radical, a halocarbyl radical, a substitutedhalocarbyl radical, and hydrocarbyl- and halocarbyl-substitutedorganometalloid radicals; or two X's are joined and bound to themetal atom to form a metallacycle ring containing from about 3 toabout 20 carbon atoms; or one or more X can be a neutralhydrocarbyl containing donor ligand, eg, an olefin, diolefin, aryneligand; and r = 0, 1, 2, or 3. When Lewis-acid activators, such asmethylalumoxane, aluminum alkyls or alkylaluminum halides, whichare capable of donating an X ligand as described above to thetransition metal component, are used , one or more X mayadditionally be independently selected from the group consisting ofa halogen, alkoxide, aryloxide, amide, phosphide or other univalentanionic ligand or two such Xâs joined to form an anionic chelatingligand; or one or more neutral nonâhydrocarbyl atom containingdonor ligand. e.g., phosphine, amine, nitrile or CO ligand.in a preferred embodiment of the invention, the bidentate ligand, L, is defined bythe following formula:R?-E\E""â Rnwherein A is a bridging group containing a Group 13-15 element;each E is independently a Group 15 or 16 element bonded to M;each R is independently a C1-C30 containing radical group which is ahydrocarbyl, substituted-hydrocarbyl, halocarbyl, substituted-halocarbyl; hydrocarbylâsubstituted organometalloid, halocarbyl-substituted organometalloid;m and n are independently 1 or 2, depending on the valency of E;andp is the charge on the bidentate ligand such that the valency of MX,is satisfied.In the most preferred embodiment of the invention, the bridging group, A, isdefined by the following formulas:?CA 02263959 l999-02- 19WO 98/03617 PCT/US97/12125- 9 -\Gâ-G/R. R\Gâ-G-:::R R'D-T:--E3â G:â=LRR\G:G/R' 1;â G)/ X / Aâ2 / A-3 \ z A 4 \ /A 5\âG "3 \0-G/ \0ââcin- \ âG::R'/A-6\ /A-7\ [ ,A,.3 \ [ A_9 [Râ Râ R' R. R.Râ R, R- Râ R'\ Râ RâRâ R» /it %i% WA-ll A-l2 A-13 A-l4wherein G is Group 14 element especially C, Si, and Ge;Q is a Group 13 element especially B, and AI; andRâ are independently hydride radicals, C1 - C30 hydrocarbyl radicals,substituted hydrocarbyl radicals, halocarbyl radicals, substitutedhalocarbyl radicals, and hydrocarbyl- and halocarbyl-,substitutedorganometalloid radicals, and optionally two or more adjacent Râmay form one or more C4 to C40 ring to give a saturated orunsaturated cyclic or polycyclic ring.Also in the most preferred embodiment of the invention, R is a bulkyC1-C30 containing radical group which is a hydrocarbyl, substituted-hydrocarbyl, halocarbyl, substituted-halocarbyl, hydrocarbyl~substitutedorganometalloid, halocarbyl-substituted organometalloid. Bulky radical groupsinclude phenyls, substituted phenyls, alkyls and substituted alkyls, especiallythose bonded to E through a tertiary carbon atom, alicyclics andpolyaclicyclics containing hydrocarbyls, especially those bonded to E througha tertiary carbon and the like.In the definitions above, the term "substituted" is as defined or refersto C,-C30 containing radicals which are to be essentially hydrocarbyl, but mayinclude one or more non-hydrocarbyl atoms (such as Si, Ge, 0, S, N, P,halogen, etc.) in place of one or more carbon atoms.?CA 02263959 2004-09-20-10-In the very most preferred embodiment of this invention, M is a group10 metal, E is a group 15 element, especially nitrogen, with m and n beingone and p being zero, the bridge is as drawn in A-1, and R is a substitutedphenyl group preferably substituted in at least the 2 and 6 positions with Râgroups. The use of Pd is particularly preferred for copolymerization of polarmonomers such as or, B unsaturated carbonyl compounds such as alkylacrylates and methyl vinyl ketone, as defined hereinafter.Various forms of the catalyst system of the lateâtransitionâmetal typemay be used in the polymerization process of this invention. Severaldisclosures in the art which include such catalysts are discussed aboveithese publications teach the structure of various late-transition-metal catalystsand include alumoxane as a cocatalyst. There are a variety of methods forpreparing alumoxane, one of which is described in US. Patent 4,665,208, andit is also available commercially.For the purposes of this patent specification, the terms "cocatalysts oractivators" are used interchangeably and are defined to be any compound orcomponent which can activate a bulky ligand transition metal compound. Thelate-transition-metal catalyst compounds according to the invention may beactivated for polymerization catalysis in any manner suf?cient to allowcoordination polymerization. This can be achieved, for example, when one Xligand can be abstracted and the other X will either allow insertion of theunsaturated monomers or will be similarly abstractable for replacement with an Xthat allows insertion of the unsaturated monomer. The traditional activators ofmetallocene polymerization art are suitable activators; those typically includeLewis acids such as alumoxane compounds, and ionizing, anion pre-cursorcompounds that abstract one X so as to ionize the transition metal center into acation and provide a counterbalancing, compatible, noncoordlnating anion.Alkylalumoxanes and modi?ed alkylalumoxanes are suitable as catalystactivators. The alumoxane component useful as catalyst activator typically is anoligomeric aluminum compound represented by the general fonnula (R"-Al-O),,,which is a cyclic compound, or R"(R"-Al-O),,AlR"2, which is a linear compound. Inthe general alumoxane formula Râ is independently a C1 to C10 alkyl radical, forexample, methyl, ethyl, propyl, butyl or pentyl and "n" is an integer from 1 to about50. Râ may also be, independently, halogen, including fluorine, chlorine andiodine, and other nonâhydrocarbyl monovalent ligands such as amide, alkoxideand the like, provided that not more than 25% of R" is methyl and ânâ is at least 4.?CA 02263959 2004-09-20-11-Alumoxanes can be prepared by various procedures known in the art. Forexample, an aluminum alkyl may be treated with water dissolved in an inertorganic solvent, or it may be contacted with a hydrated salt, such as hydratedcopper sulfate suspended in an inert organic solvent, to yield an alumoxane.Generally, however prepared, the reaction of an aluminum alkyl with a limitedamount of water yields a mixture of the linear and cyclic species of thealumoxane. Methylalumoxane and modi?ed methylalumoxanes are preferred.For further descriptions see, U.S. Patent Nos. 4,665,208, 4,952,540, 5,041,584,5,091,352, 5,206,199, 5,204,419, 4,874,734, 4,924,018, 4,908,463, 4,968,827,5,329,032, 5,248,801, 5,235,081, 5,157,137, 5,103,031 and EP 0 561 476 Al, EP0 279 586131, EP 0 516 476 A, EP 0 594 218 Aland WO 94/10180.When the activator is an alumoxane, the preferred transition metalcompound to activator molar ratio is from 1:10000 to 10:1 ,. more preferably fromabout 125000 to 10:1, even more preferably from about 121000 to 1:1.The term "noncoordinating anion" as used for the ionizing, anion preâcursorcompounds is recognized to mean an anion which either does not coordinate tosaid transition metal cation or which is only weakly coordinated to said cationthereby remaining suf?ciently labile to be displaced by a neutral Lewis base."Compatible" noncoordinating anions are those which are not degraded toneutrality when the initially fonned complex between the late-transition-metalcatalyst compounds and the ionizing, anion preâcursor compounds» decomposes.Further, the anion will not transfer an anionic substituent or fragment to the cationso as to cause it to form a neutral four coordinate metal compound and a neutralby-product from the anion. Noncoordinating anions useful in accordance with thisinvention are those which are compatible, stabilize the late-transition-metal cationin the sense of balancing its ionic charge in a +1 state, yet retain suf?cient labilityto permit displacement by an ole?nically unsaturated monomer duringpolymerization. Additionally, the anions. useful in this inventionwillbe large orbulky in the sense of sufficient molecular size to partially inhibit or help to preventneutralization of the late-transition-metal cation by Lewis bases other than thepolymerizable monomers that may be present in the polymerization process.Descriptions of ionic catalysts, those comprising a transition metal cation(based on metallocenes) and anon-coordinating anion, suitable for coordinationpolymerization appear in U.S. patents 5,064,802, 5,132,380, 5,198,401,5,278,119, 5,321,106, 5,347,024, 5,408,017, WO 92/00333 and.WO 93/14132.These references teach a preferred method of preparation wherein metallocenes?CA 02263959 2004-09-20-12-are protonated by an anion precursor such that an alkyl/hydride group isabstracted from a transition metal to make it both cationic and chargeâbalancedby the non-coordinating anion. These teachings may be useful to those skilled inthe art for the late-transition-metal catalysts of the present invention.The use of ionizing ionic compounds not containing an active proton butcapable of producing both the active metal cation and an noncoordinating anion isalso known. See, EPâA-0 426 637, EP-A-0 573 403 and U.S. patent 5,387,568.Reactive cations other than the Bronsted acids include ferrocenium, silver,tropylium, triphenylcarbenium and triethylsilylium, or alkali metal or alkaline earthmetal cations such as sodium, magnesium or lithium cations. A further class ofnoncoordinating anion precursors suitable in accordance with this invention arehydrated salts comprising the alkali metal or alkaline earth metal cations and anon-coordinating anion as described above. The hydrated salts can be preparedby reaction of the metal cationânon-coordinating anion salt with water, forexample, by hydrolysis of the commercially available or readily synthesizedLiB(pfp)., which yields [Li-xH20] [B(pfp)4], where (pfp) is pentafluorophenyl orperfluorophenyl.Any metal or metalloid capable of forming a coordination complex which isresistant to degradation by water (or other Bronsted or Lewis Acids) may be usedor contained in the anion. Suitable metals include, but are not limited to,aluminum, gold, platinum and the like. Suitable metalloids include, but are notlimited to. boron, phosphorus, silicon and the like.An additional method of making the ionic catalysts uses ionizing anionprecursors which are initially neutral Lewis acids but form the cation and anionupon ionizing reaction with the late-transition-metal compounds, for exampletris(penta?uorophenyl) boron acts to abstract a hydrocarbyl, hydride or silyl ligandto yield a late-transition-metal cation and stabilizing non-coordinating anion; seeEP-A-O 427 697 and EP-A-0 520 732 which are directed to metallocene catalystsystems. ionic catalysts for coordination polymerization can also be prepared byoxidation of the metal centers of transition metal compounds by anionicprecursors containing metallic oxidizing groups along with the anion groups, seeEP-A-O 495 375.?CA 02263959 2004-09-20-13-When the cation portion of an ionic non-coordinating precursor is aBronsted acid such as protons or protonated Lewis bases (excluding water), or areducible Lewis acid such as ferricinium or silver cations. or alkaline metal oralkaline earth metal cations such as those of sodium, magnesium or lithiumcations, the transition metal to activator molar ratio may be any ratio. butpreferably from about 10:1 to 1:10; more preferably from about 5:1 to 1:5; evenmore preferably from about 2:1 to 1:2; and most preferably from about 1.2:1 to1:1.2 with the ratio of about 121 being the most preferred.A further useful method of activating the late-transition-metal catalyst is toemploy a Ziegler cocatalyst. Such cocatalysts will typically be organometalliccompounds of a metal of Groups 1, 2, 12, or 13 of the Periodic Table selectedfrom the group consisting of aluminum alkyl, aluminum alkyl halide and aluminumhalide. These can be represented by the formulas:Al (R)m(R'),, X3-,,,_,, wherein Râ and R are independently hydrocarbyl,including C1 to C10 aliphatic. alicyclic or aromatichydrocarbon radicals which may be the same ordifferent; X is a halogen such as chlorine, bromine oriodine; m and n are integers from 0 to 3 and the sumof (m+n) s 3; andAl2R3X3 which are hydrocarbylaluminum sesquihalides, suchas Al2Et3Cl3 and Al2(iBu)3Cl3; wherein Et is ethyl andiBu is isobutyl.Examples include triethyl aluminum, diethyl aluminum chloride, Al2Et3Cl3 andAl2(iBu)3Cl3. As is generally recognized in the art. these Ziegler cocatalystcompounds will not effectively activate metallocene catalyst compounds. In apreferred method this activator is reacted with the late-transitionâmetal catalystprior to addition of the activated catalyst system to the polymerization reactor.Further useful late-transitionâmetal catalysts include those which are knownas supported catalysts. Useful catalyst systems of this type are disclosed in theU.S. patent application titled âSupported Late Transition Metal Catalyst Systemsâ(G.A. Vaughan et al.. W097/48736).When using ionic catalysts of the late-transition-metals comprising cationsand non-coordinating anions, the total catalyst system can additionally compriseone. or more scavenging compounds. The term "scavenging compounds" ismeant to include those compounds effective for removing polar impurities fromthe reaction environment. Impurities can be inadvertently introduced with any of?CA 02263959 l999-02- 19WO 98/03617 PCT/US97ll2l25-14-the polymerization reaction components, particularly with solvent, monomer andcatalyst feed, and adversely affect catalyst activity and stability. impurities canresult in decreased, variable or even elimination of catalytic activity, particularlywhen a late-transition-metal cation-noncoordinating anion pair is the catalystsystem. The polar impurities, or catalyst poisons include water, oxygen, metalimpurities, etc. While the late-transition-metal catalysts of the present inventioncan be less sensitive to impurities than those of the prior art, e.g., metallocenecatalyst systems, reduction or elimination of poisons is a desirable objective.Preferably steps are taken before provision of such into the reaction vessel, forexample by chemical treatment or careful separation techniques after or duringthe synthesis or preparation of the various components; some minor amounts ofscavenging compound can still normally be used in the polymerization processitself.Typically the scavenging compound will be an organometallic compoundsuch as the Group 13 organometallic compounds of U.S. patents 5,153,157,5,241,025 and WO-A-91/09882, W0-A-94/03506, WO-A-93/14132, and that ofWO 95/07941. Exemplary compounds include triethyl aluminum, triethyl borane,triisobutyl aluminum, methylalumoxane, isobutyl aluminoxane, and nâoctylaluminum. Those scavenging compounds having bulky or C3âC20 linearhydrocarbyl substituents covalently bound to the metal or metalloid center beingpreferred to minimize adverse interaction with the active catalyst. Whenalumoxane is used as activator, any excess over the amount of late-transition-metal present will act as scavenger compounds and additional scavengingcompounds may not be necessary. The amount of scavenging agent to be usedwith late-transition-metal cation-non-coordinating anion pairs is minimized duringpolymerization reactions to that amount effective to enhance activity.E I . . EGenerally, the polymerization process is preferably conducted in acontinuous manner by simultaneously feeding a polymerizable polar monomerfeedstream, one or more refinery or steam cracker feedstream containing theolefinic monomerlsl, or separate streams of reaction diluent (if employed),monomers, catalyst and cocatalyst to a reactor and withdrawing solvent,unreacted monomer and copolymer from the reactor, allowing sufficientresidence time to form copolymer of the desired molecular weight, andsubsequently separating the copolymer from the reaction mixture. If desired,the monomers can be premixed prior to introducing them into the reactor.?W0 98/0361 7CA 02263959 l999-02- 19PCT/US97/12125-15..The preferred process for producing the POH copolymer is a continuousprocess using a highly diluted, refinery or steam cracker monomer feedstreamin combination with a late-transition-metal catalyst system. Severaladvantages result from such a process:(1) the use of dilute monomer feeds results in a lowerconcentration gradient at the point of monomer introduction into the reactorand, consequently, less time is required to achieve uniform monomer mixingand less time is available for higher molecular weight species formation at theinput port;(2) the use of dilute feeds enables the process to operate athigh conversion rates without the attendant buildup of mass transferresistance attributable to copolymer formation in pure feed systems;(3) in a preferred embodiment of the process of the presentinvention employing a boiling reactor and dilute feed, monomer in the vaporspace and in the liquid reaction mixture are in equilibrium, particularly whenethylene is used as a comonomer. This is achievable because of the ease ofattaining uniform mixing resulting in a reaction mixture having essentially nomass transfer resistance at the liquid/vapor interface;(4) still further improvements are possible [where two or moremonomers are polymerized] by the presence of a high concentration of diluentin the olefin feed, such that the major constituents of the diluent boil at aboutthe same temperature as the oLâolefin(s) to be polymerized or, whereapplicable, copolymerized with, e.g., ethylene. Accordingly, wherecopolymerization with ethylene is involved, ethylene content in the vaporspace is further diluted by the oLâolefin feed constituents, a major portion ofwhich is diluent. Thus, evaporative cooling does not depend on recycle ofhigh amounts of ethylene in the vapor, ethylene buildup in the reflux is furtherminimized, and mass transfer resistance to ethylene mixing is further reduced;(5) a boiling reactor allows the polymerization reaction to beaccomplished in a highly isothermal manner because the heat of reaction iseasily removed by boiling unreacted monomer and diluents out of the reactionmedia at nearly constant temperatures, resulting in a narrower molecularweight distribution POH copolymer;(6) where a copolymer is produced, uniformity of thecopolymer is greatly enhanced without the need for manipulation of thecondensed vapor to alter its compositional distribution;?CA 02263959 l999-02- l9wo 93/03517 PCT/US97/12125-15-(7)facilitates removal of catalyst (deashing) residue and quenching of thethe combined use of dilute feed and high conversioncopolymer/catalyst mixture since it is easier to mix the copolymer withdeashing and quench media;(8)allows for a significant improvement in the overall economics of the processuse of dilute oc-olefin containing feeds and high conversionbecause such dilute feeds can be readily obtained at very low cost as by-product or waste streams derived from other commercial sources, forexample, refinery or steam cracker feed streams containing C3, C4 or C5olefins. _Copolymers produced in accordance with the process of the presentinvention are copolymers comprising monomer units derived from at least oneolefin such as ethylene and on-olefins. Such monomers are characterized bythe presence within their structure of at least one ethylenically unsaturatedgroup of the structure >C =CH2 and are highly reactive at low catalystconcentrations. Lateâtransitionâmeta| catalyzed polymerizations areparticularly adaptable for use with ethylene and oz-olefin monomers; otherolefinically unsaturated monomers may be less reactive. Therefore, variouscomponents in suitable refinery or steam cracker streams such as a Raffinateâ2 stream (e.g., components such as 2âbutenes, and isobutylene), may havelimited reactivity in the presence of a late-transition-metal catalyst system.Such components may be considered diluents in the present process and neednot be separated from the polymerizable componentlsl of the feedstream.Other constituents which may be undesirable, such as butadiene, are madenon-reactive or nonâpoisonous to the catalyst by preâsaturating the doublebonds with hydrogen.Accordingly, suitable oLâolefin monomers include those represented bythe structural formula H2C =CHR1 wherein R1 is straight chain or branchedchain alkyl radical comprising 1 to 18 carbon atoms and wherein thecopolymer formed therefrom contains a high degree of terminal vinyl andvinylene unsaturation. Preferably R1 in the above formula is alkyl of from 1 to16 carbon atoms, more preferably alkyl of from 1 to 12 carbon atoms,particularly for use as wax crystal modifiers. Those monomers suitable forpreparing copolymers intended for use as dispersant backbones are typicallythose where R1 in the above formula is alkyl of from 1 to 8 carbon atoms,preferably alkyl of from 1 to 6 carbon atoms. Therefore, useful monomersinclude ethylene, propylene, buteneâ1 , pentene-1, 4-methylpentene-1, hexeneâ?CA 02263959 l999-02- 19WO 98103617 PCT/US97ll2l25-17-1, octeneâ1 , decene-1, dodecene-1, tridecene-1, tetradecene-1, pentadeceneâ1, hexadecene-1, heptadeceneâ1, octadecene-1, nonadecene-1 and mixturesthereof (e.g., mixtures of ethylene and butene-1, ethylene and propylene,propylene and buteneâ1, octeneâ1 and tetradecene-1 and the like).After polymerization and, optionally, deactivation of the catalyst (e.g.,by conventional techniques such as contacting the polymerization reactionmedium with an excess of water or an alcohol, such as methanol, propanol,isopropanol, etc., or cooling or flashing the medium to terminate thepolymerization reaction), the product copolymer can be recovered byprocesses well known in the art. Any excess reactants may be flashed offfrom the copolymer.The polymerizable polar monomer useful in the present invention is anon, [3 unsaturated carbonyl compound selected from the group represented bythe formula:CH2 = C - COXIRxwherein X is hydrogen (H), NH2, RV or ORV ; R, is H or a C1-C5 straight orbranched alkyl group and Ry is H or a C1 to C20 straight or branched alkylgroup; for short chain unsaturated ester monomers, Ry is preferably a C1-C5alkyl group and for long chain monomers, preferably a C10 to C13 alkyl group.Representative acrylate monomers suitable for use in the present inventioninclude methyl acrylate, methyl methacrylate, ethyl acrylate, propylmethacrylate, propyl ethacrylate, butyl acrylate, tertâbutyl acrylate, octylpropacrylate, decyl butacrylate, dodecyl pentacryalate, hexyl methacrylate,octyl ethacrylate, decyl methacrylate, dodecyl methacrylate, tetradecylmethacrylate, hexadecyl methacrylate, octadecyl methacrylate, tridecylacrylate, tetradecyl methacrylate, pentadecyl acrylate, hexadecyl acrylate andoctadecyl acrylate. A preferred aldehyde is acrolein (CH2 =CHCHO), apreferred ketone is methyl vinyl ketone (CH2=CHCOCH3) and a preferredcompound wherein X is NH2 is acrylamide (CH2 =CHCONH2).The minimum number of carbon atoms of the RV substituent is typicallyselected to avoid insolubility of the copolymer in the fuel or lubricating oil andthe maximum number of carbon atoms is selected to avoid crystallization ofthe copolymer out of the fuel or lubricating oil at low temperatures.?CA 02263959 1999-02-19WO 98/03617 PCT/US97l12125_ 13 _The concentration of polar moiety in the copolymer resulting fromcopolymerization of the polar monomer described above can range from about1 to about 6 per chain, preferably from about 1 to about 2 per chain wheresuch copolymer is used to produce dispersants using polyamines incombination with chainâstopping agents (as described later) in order to avoidthe formation of gel or oil insoluble dispersant product. The concentration ofpolar moiety can preferably range from about 2 to about 6 per chain wherethe amine used to produce the dispersant is a "1-armedâ amine (as describedlater). Generally the polar moiety can be present in said copolymer used toproduce dispersants at an average concentration of from about one polarmoiety for each 5,000 Mn segment of polymer backbone, including branches,to about one polar moiety for each 1,000 Mn segment.The polymerization is preferably conducted employing as the reactionmedium, a highly diluted monomer feedstream obtained from a refinery orsteam cracker. In such a medium there is present a hydrocarbon inert to thepolymerization such as butane, isobutane, pentane, isopentane, hexane,isooctane, decane, toluene, xylene, and the like. Alternatively, thepolymerization may be conducted using substantially pure monomers, e.g.,ethylene and/or propylene. In a process which uses a refinery or steamcracker feedstream, the feedstream containing the olefinic monomer to bepolymerized, e.g., 1-butene, typically contains certain amounts of other C4hydrocarbons. More particularly, the feedstream can comprise less than 5weight percent isobutylene, at least 12 weight percent total nâbutenes (i.e.,1-butene and 2-butene), and less than 1 weight percent butadiene, togetherwith nâbutane and isobutane. When used to prepare the POH copolymer, apreferred C4 feed stream comprises spent C4 streams produced as by-productin the manufacture of polyisobutylene, wherein the C4 feedstream (oftenreferred to as Raffinate ll) contains less than 5 weight percent isobutylene, 10to 70 weight percent saturated butanes and 15 to 85 weight percent 1-butene and 2-butene. The saturated butanes function as a diluent or solventin the reaction mixture. Typically the C4 feedstream is maintained at asufficient pressure to be in the liquid form both at the reactor inlet and in thereaction mixture itself at the reaction temperature. In addition to the olefinicfeedstream component there is required a polar monomer feed component asdefined above. The polar monomer can be diluted, used neat and,alternatively, can be fed as a separate feedstream or mixed with the olefinfeedstream. The amount of polar monomer fed to the reactor will depend on?W0 98/03617CA 02263959 l999-02- l9PCT/US97/12125- 19 -the efficiency of polar monomer incorporation in the copolymer for theparticular catalyst system employed and the level of polar monomer desired inthe copolymer. These aspects can be readily determined by one skilled inpolymerization art.The preferred reaction process of the present invention is continuous,employs a dilute feed, and is operated to achieve a high level of monomerconversion. For purposes of this invention "continuous" means that a feedstream containing the olefinic monomer is continuously introduced into thereaction zone and resultant POH copolymer product is continuouslywithdrawn.The advantages of employing a highly diluted monomer feed aredescribed above. For the purposes of the present invention, the diluent canbe any non-reactive (under the conditions employed) material which preferablyis capable of: (i) being liquefied under reaction conditions; (ii) dissolving atleast the or-olefin monomer where one is employed; and (iii) dissolving or atleast suspending the copolymer product under reaction conditions such thatviscosity buildup is sufficiently minimized to the extent that the mass transferrate of the olefin, and ethylene in particular, needed to homogeneouslydistribute olefin throughout the reaction zone is at least equal to andpreferably is greater than, the reaction rate at which olefin is consumed in thepolymerization reaction. Suitable but less preferred diluents include suchsolvents as alkanes, aromatic hydrocarbons, and nonreactive alkenes. It iscontemplated that the non-reactive diluents comprise typically at least 30,preferably at least 40, and most preferably at least 50 weight % of the Ol-olefin feed stream and the diluent can range typically from 30 to 90 (forexample from 35 to 75 weight %l preferably from 40 percent to 80, andmost preferably from 50 to 60 weight % of the otâolefin feed stream (whereethylene is used as a comonomer, the recited levels refer to concentrationsbefore admixture with ethylene).It is a particular advantage of the present invention that the preferredmonomer feedstream comprises preferred diluents which are present invarious refinery or steam cracker streams containing aâo|efin monomerreactants; to be useful such streams must contain at least one oLâo|efin as thereactive constituent. However, these streams typically will contain nonâreactive constituents which have a similar carbon number to the on-olefin. Thesimilarity in carbon number causes the non-reactive constituents to havesimilar boiling points to the or-olefin. Consequently, the non-reactive?CA 02263959 l999-02- 19WO 98103617 PCTIU S97/ 12125-20-constituents will vaporize together with the oLâolefin and not only dilute the on-olefin in the vapor space, but also, where used, ethylene comonomer. Thisdilution effect decreases the mass transfer resistance of the reactivemonomers in the vapor space, particularly ethylene.Accordingly, a preferred diluent will contain components comprisingtypically at least 50, preferably at least 75, and most preferably at least 95weight %, and typically from 50 to 100, preferably from 75 to 100, and mostpreferably from 95 to 100 weight % thereof, having a boiling point at thereaction conditions of typically within :20°C, preferably within : 15°C, andmost preferably within : 10°C of the average boiling point of the or-olefinconstituents of the feed. Representative of such refinery or steam crackerstreams are those which contain buteneâ1 , propylene or C5 on-olefin. Preferredbuteneâ1 containing streams are referred to herein as Raffinate-2 streams.Such streams typically have isobutylene content significantly lowered inrelation to the stream from which they are derived. Raffinate-2 is typicallyderived from either butane/butene catalytic cracking or refinery streams (BB-streams) or Raffinate-1 which, in turn, is derived from butadiene crudeproduced by steam cracking plants. The composition of Raffinate-2 can varywidely, depending upon the source, e.g., (weight °/o):Crude Raff-2 Raffâ2 I Bmas?erm ELO_DJ_C_lâ_l.ld_Q 5.8 F. ro__m BB. f-1Butadiene 43.5:20 0 â 5 0.3:.15 0.4:0.2 0.1 :.OSlsobutylene 25.2:1O 0 - 5 12.6:6 O.2:0.1 44.6:2OButeneâ1 15.5:8 49.5:25 13.6:6 15.4:7 27.4:15cis-Buteneâ2 2.0:1 6.4:3 9.0:4 10.2:5 3.5: 1.5trans-Butene-2 6.2:3 19.6: 10 13.8:6 15.6:7 10.9:5nâButane 4.6:2â 14.729-.7 10.5:5 12.0:6 8.1 :4lsobutane 2.9:1.5a) 9.4:4 36.7: 1(5)) 42.1 :20 5.2:2.5Other* 0.1:0.5 O.2:O.1 0.2:0.1 3.5:1.54.1 :2*Other: (a) includes propane, propene, pentanes, pentenes, water, traceother hydrocarbons.(b) Raffinate-2 derived from MTBE production (using BBâstream orRaffinate-1) will include traces of MTBE, methanol, diâmethylether, and tert-butyl alcohol.?WO 98/03617CA 02263959 l999-02- l9PC'Iâ/US97/ 12125-21-Typical commercially available buteneâ1 concentrations in Flaffinate-2range from about 15 to about 55 weight %. The above buteneâ1âcontainingrefinery or steam cracker streams are preferred for making POH homopolymeror copolymers containing, e.g., ethylene. The instant invention may alsomake use of BB streams and Raffinate-1 directly, since isobutylene is almostentirely unreactive in the presence of the late-transition-metal catalystsystems. Hence, depending upon shipping costs, convenience, or whateverother factors may affect the decision-making process, one skilled in the arthas the option of either acquiring Raffinate-2 and running it through theprocess of the instant invention or first acquiring either Raffinate-1 or a BBstream, running it through the process, and then shipping the resultantisobutylene-enriched stream to an MTBE plant or other end use. The use ofRaffinate-2 is preferred. The use of crude butadiene streams directly is notdesired since it would waste butadiene which is hydrogenated prior topolymerization. While it is preferred, It is not required that refinery or steamcracker streams be used and, in fact, it is contemplated that dilute oc-olefincontaining streams can be prepared by separately combining pure ocâolefin andone or more pure diluents, e.g. pure isobutane, such as those typically foundin the above refinery or steam cracker streams. If the latter approach isfollowed, the level of diluent should be based on the teachings herein in orderto achieve the advantages of the process disclosed.It will also be seen that this invention is useful in the production ofseveral POH copolymers and copolymers and may therefore be used in theprocessing of other dilute refinery or steam cracker streams, such as dilutepropene and pentene streams common in the industry. Dilute refinery orsteam cracker propene streams, known in the industry as "C3 streamsâ, anddilute refinery or steam cracker pentene streams, known as "C5 streams", arealso derived from steam and catalytic cracking and generally can berepresented to comprise the following components (ranges, weight %): ForC3 streams: Propylene = 55 1 20; Propane = 34 1- 15; Ethylene = 2 i 1;Ethane = 8 i 4; and Other = 1 :.5 (Other includes methane, acetylenes,propadiene, trace C4âs and C5's, and trace polar compounds such as water,carbonyl sulfide, methyl mercaptan, and hydrogen sulfide). For C5 streamscomposition is more complex than that of C3 and C4 streams:?CA 02263959 l999-02- 19WO 98/03617 PCT/US97/12125- 22 -C_o.m.o_o_nen1 Baug9_lw_t._%1 Qgmopnent Banga_lmLt._âZQ12-methyl-Butene-1 9.0 1- 4 n-Pentane 5.5 : 23-methyl-Butene-1 1.6 i 1 Cyclopentane 0.6 1*: .3Pentene-1 5.1 i 2 Cyclopentene 1.5 i .752âmethylâButene-2 14.9 1 7 Piperylene 0.9 :1: .4Penteneâ2 15.4 1 7 C6 Olefins 1.5 1 .75lsoprene 0.7 i .3 C5 Alkyls 3.5 : 1.5lsopentane 36.2 i 15 C7âs and C3âs 2.0 i 1Others* 1.6 -l_- 1*Others include benzene and polar compounds.Pentene-1 and cyclopentene are the most reactive components of a C5stream in the presence of a late-transitionâmetal catalyst system and arereadily separated from each other by distillation and concentrated.Whether a constituent, e.g. of the refinery or steam cracker stream,qualifies as a diluent under reaction conditions depends on whether it is non-reactive which in turn depends on the specific catalyst and type ofpretreatment to which the feed is subjected. "Non-reactive" when used inconjunction with diluent is meant that less than 5 wt.%, preferably less than3 wt.%, and most preferably less than 1 wt.% of the constituent present inthe feed is incorporated into the copolymer product and the constituent doesnot totally deactivate the late-transitionâmetal catalyst system. Typically, anysaturated hydrocarbon constituent will qualify as diluent as well asunsaturated constituents such as butene-2 and isobutylene which are highlyunreactive in the presence of a late-transitionâmetal catalyst system.Materials such as butadiene tend to deactivate the catalyst. Hence, it ispreferred that they be removed or at least partially saturated byhydrogenation. Once saturated, the butadiene becomes part of the diluent asbutane, butene-2, or a polymerizable oc-olefin, butene-1.The process of the invention is controlled to achieve high ethylene and0L-olefin conversion. Conversion is directly proportional to monomerconcentration, catalyst concentration and residence time. Accordingly, theseparameters are controlled to achieve an ethylene conversion of typically atleast 70%, preferably at least 80%, and most preferably at least 90% andcan range typically from 70% to 100%, preferably from 80% to 100% andmost preferably from 90% to 100% (e.g., 90-95%). The oi-olefin conversion?CA 02263959 l999-02- 19WO 98/03517 PCT /US97I 12125-23-is controlled to be typically at least 30%, e.g., at least 40%, preferably atleast 50%, and most preferably at least 60% and can range typically from30% to 95%, preferably from 40% to 90% and most preferably from 50% to90%. Monomer conversion (%) can be determined by either of the followingequations:= x 1oowt/hr of monomer in feed ;or_â_ m x 100wt/hr monomer in feedWhere a mixed olefin feed is used, e.g., and ocâolefin incombination with ethylene, the particular on-olefin conversion employeddepends in part on the apparent ethylene content sought to be imparted to thecopolymer and hence on the ethylene concentration in the mixed feed. Forexample, at low ethylene content the ot-olefin conversion typically will belower than for high ethylene content feeds. While high conversion can beachieved by any combination of process conditions affecting conversion, it ispreferred to maintain a low catalyst concentration and low monomerconcentration and attain high conversion with a long residence time. Whereethylene is used as a comonomer, preferably the ethylene conversion iscontrolled in a manner such that the ratio of the weight % of ethylene in thevapor phase to the weight % of ethylene in the reactant feed stream istypically not greater than 1.2:1, preferably less than 1:1 and most preferablyfrom 0.1 :1 to 0.7:1 (e.g., 0.1 :1 to 0.5:1). The monomer in the reactionmixture is kept low through the use of the diluent in the feed and operating athigh conversions.The catalyst concentration is typically held just above the poison leveldue to cost of the catalyst. Preferably the feed is treated to remove most ifnot all catalyst poisons, but this can vary depending on the sensitivity of theparticular catalyst system to the presence of poisons. Minor poisoncontamination can be accommodated by increasing the catalyst systemconcentration with the excess used to remove the poison by reactiontherewith. Accordingly, while any effective catalyst concentration can beemployed, it is contemplated that such effective amounts will be sufficient toachieve a weight ratio of late-transition-metal catalyst system to copolymerproduct of typically from 1 x 10521 to 1 x 10'1 :1.?CA 02263959 1999-02-19wo 93/03617 PCTIUS97/12125- 24 _The residence time is determined from the following equation:total true volume of liquid in reactorResidence timetotal volume/time of liquid exiting reactorwherein gas bubble volume in the liquid is subtracted from apparent volume ofliquid in reactor to obtain true volume. Accordingly, residence times can varyfrom typically, about 0.1 to about 5 hrs.; preferably from about 0.5 to about4 hrs.; and more preferably from about 1 to about 3 hrs.Reaction temperature and pressure are preferably controlled to liquefythe diluent and on-olefin. However, when ethylene is present, the reactiontemperature is typically selected to be above the critical temperature ofethylene but below the critical temperature of the 0câo|efin feed and/or diluent.Accordingly, while any effective temperature can be employed in order toproduce the POH copolymer of the desired Mn in an efficient manner, it iscontemplated that polymerization will generally be conducted at temperaturesof from about 0 °C to about 300 °C; preferably from about 10 °C to about200 °C; for a feed containing butene-1 such effective temperatures will rangetypically from about 10 °C to about 150 °C, preferably from about 15 °C toabout 120 °C, and most preferably from 25 °C to about 110°C. For thedilute refinery or steam cracker streams of propylene having propane as themajor diluent, the critical temperature of propylene and propane are 92.42°C(198.36°F) and 96.7°C (206.06°F) respectively, so the typical range ofreaction temperatures would be 10 to 96, and preferably from 25 to 92°C.The critical temperature of the feed components in the reactor places anupper limit on temperature when using a boiling reactor since the refluxmechanism becomes useless if nearly all or all of the feed flashes into thereactor vessel and there remains no liquid phase to reflux. In less preferredembodiments, the operation above the critical temperature of the majorreactor constituents must be compensated for by assisting or eliminating thereflux mechanism altogether and relying on alternative cooling means, such asjacketed reactor cooling or internal reactor cooling coils. Neither of thesesolutions is as effective nor as efficient as reflux cooling in maintaininghomogeneity of temperature throughout the reaction solution. As indicatedabove, the boiling reactor represents the preferred method for temperaturecontrol. Variations on the boiling reactor configuration include internal reflux,e.g. using cooling coils inserted into the vapor space or an external system?W0 98/03617CA 02263959 l999-02- l9PCT/US97I12l25-25-wherein vapor is removed from the vapor space and introduced to an externalreflux apparatus, the vapor condensed and the condensate returned to thereactor and/or feed. Alternative non-reflux temperature control means includepumparound cooling where liquid is removed from the reactor, cooled, andthen returned to the reactor. Pumparound cooling offers the added advantageof being able to return cooled liquid to the reactor using high pressure pumpsto also provide mixing of reactor contents with high speed jets.Reactor pressures are typically controlled to maintain the diluent and oc~olefin in liquid form at the selected temperature. In boiling reactors thepressure is selected to obtain boiling of the diluent/oLâo|efin reactorconstituents at the reaction temperature. Accordingly while any effectivepressure can be employed it is contemplated that where, e.g., a feedstreamcontaining butene-1 is used, such effective pressures will range typically fromabout 2.4 to about 39 atm., preferably from about 4.4 to about 28 atm., andmost preferably from about 5.6 to about 23.5 atm.The reaction mixture is preferably vigorously mixed by any suitablemeans such as impeller, jet pump, or vigorous boiling or combinations thereof.Baffles and strategic placement of feed input can be employed to furtherfacilitate mixing. While conducting the polymerization, there is preferablysufficient mixing in the reactor in order to provide substantial homogeneityand where more than one monomer is used, e.g., ethylene and an ocâo|efin,sufficient mixing to avoid the production of homopolymer of one or both ofthe monomers, or a compositionally nonuniform copolymer. More particularly,when two or more monomers are used, it is preferred that the monomerstogether enter a turbulent zone inside the reactor. This can be accomplishedin a stirred reactor, for example, by placing all of the all monomer feed inletsnear to each other and near the impeller blade. As described herein, mixing isalso facilitated by the use of a dilute pre-mixed feed stream from a refinery orsteam cracker. Sufficient mixing in the reactor promotes the randomincorporation of each monomer unit in a growing copolymer chain, resulting incopolymers of relatively homogeneous composition (both interâchain and intra-chain) and relatively short sequences of any one monomer, e.g., ethylene (i.e.,low ESL values), compared to analogous copolymers produced without suchmixing. Analogously, sufficient mixing provides an opportunity to randomizethe structure of the POH copolymer even where a single olefinic monomer isused by facilitating mass and heat transfer involving both the catalystcomponents and the monomers. Effective mixing is especially important to?CA 02263959 l999-02- 19wo 93/03517 PCT/US97/12125_ 25 -the production of copolymers of the invention having a high concentration ofone monomer in a multiâmonomer polymerization process (i.e., above 35weight percent), because, without such mixing, the resulting copolymer couldhave sufficient monomer sequences to increase the probability of crystallinity,e.g., ethylenic crystallinity in an ethylene copolymer derived from ethylene oranother oLâolefin, in combination with a polar monomer, e.g., as manifested byESL values above 2.50.When carrying out the polymerization in a batch-type fashion, thereaction diluent (if any), and themonomers are charged at appropriateconcentration and ratios to a suitable reactor. Care should be taken that allingredients are dry, with the reactants typically being passed throughmolecular sieves or other drying means prior to their introduction into thereactor. Although certain of the lateâtransitionâmetal catalysts of thisinvention may be less susceptible to moisture and other poisons thancatalysts such as ZieglerâNatta and metallocenes, it is preferred that thecatalyst system be of uniform composition and quality in order to reducevariations in the process and the resulting POH copolymer, e.g., its molecularweight and/or MWD. Subsequently, either the catalyst and then thecocatalyst, or first the cocatalyst and then the catalyst are introduced whileagitating the reaction mixture, thereby causing polymerization to commence.Alternatively, the catalyst and cocatalyst may be premixed in a solvent andthen charged to the reactor. As copolymer is being formed, additionalmonomers may be added to the reactor. Upon completion of the reaction,unreacted monomer and solvent are either flashed or distilled off, if necessaryby vacuum, and the copolymer of suitable molecular weight withdrawn fromthe reactor.: :| ..Employing a late-transition-metal catalyst system in accordance withthe procedures and under the conditions as described herein results in a POHcopolymer having a high degree of terminal unsaturation, e.g., vinyl and/orvinylene group terminating at least about 30% of the copolymer chains. Incontrast, prior art polymers or copolymers produced using a metallocenecatalyst system were generally incapable of copolymerizing a significantamount of polar monomer and also resulted in terminally unsaturated olefinicpolymers exhibiting a high concentration of vinylidene type unsaturation?CA 02263959 l999-02- 19WO 98103617 PCT/US97l12l25_ 27 -relative to vinyl type unsaturation, e.g., at least 3.5 to 1; this translates toabout 22% vinyl. (see WO 90/1 ,503) The POH copolymer chains can berepresented by the formula POLY-CH =CH2 or POLY-CH =CH-R wherein POLYrepresents the copolymer chain (including the incorporated polar monomermoiety which is generally present at the terminal position of a branch), âCH =CH2 represents a vinyl group terminating one end of the chain and -CRâ =CH-R represents a vinylene group, terminating one end of the chain,wherein R represents an alkyl group such as methyl, ethyl, etc., and Rârepresents H or an alkyl group such as methyl, ethyl, etc. The POHcopolymers typically have vinyl and/or vinylene groups terminating at leastabout 30 percent of the copolymer chains (although typically, the oppositeends of the same copolymer chain do not each contain an unsaturatedstructure); preferably, at least about 50 percent, more preferably about 75percent, still more preferably at least about 80 percent, and most preferablyat least about 90 percent of the copolymer chains; typically from about 30 toabout 95 percent, preferably from about 50 to about 90 percent, morepreferably from about 75 to about 90 percent of the copolymer chains beingso terminated. In addition, the copolymers typically have vinylidene groupsli.e., POLY-Cl-CHZCH3) =CH2, where -C(CH2CH3) == CH2 is ethylvinylidene),terminating no more than 15 percent of the chains; e.g., from about 0 toabout 15 percent; preferably from about 2 to about 10 percent.Trisubstituted olefinic groups can also be present in minor amounts, forexample, no more than 15 percent of the chains; e.g., from about 0 to about15 percent; preferably from about 0 to about 10 percent. The predominanceof vinyl and vinylene terminal olefinic structures differs significantly from thepredominantly terminal vinylidene structures resulting from metallocenecatalyzed polymerizations of ethylene on-olefin copolymers. The percentage ofcopolymer chains exhibiting terminal vinyl, vinylene, vinylidene, etc.unsaturation, may be determined by C13 NMR. It will be understood that achange in the type of late-transition-metal catalyst and/or co-catalyst oractivator used to prepare the copolymer can shift the above described doublebond distribution to some extent. Because of the relatively high level ofterminal vinyl and vinylene unsaturation in the POH copolymers, thedispersant additives produced therefrom have particularly high activeingredient concentrations, thereby providing enhanced lubricating oildispersancy, which can be exhibited as enhanced sludge and varnish controlproperties.?CA 02263959 1999-02-19wo 98/03617 PCT/US97/12125-23-The copolymers of this invention, particularly those intended for use indispersant applications, typically have a number average molecular weight(Mn) of from about 300 to about 10,000; preferably from about 700 to about5,000 (e.g., 1,000-5,000), more preferably from about 700 to about 2,500(e.g., 1,500 to 2,500) and most preferably from about 750 to about 2,500.When lower molecular weight copolymers are used in wax crystal modifierapplications their Mn is up to about 15,000, e.g., from about 500 to about15,000. Higher molecular weight copolymers of the invention that are oilsoluble also find utility in lube oil flow improver and viscosity modifierapplications, as well as wax crystal modifiers. For example, useful highermolecular weight copolymers and copolymers have Mn of from about 15,000to about 500,000; preferably from about 30,000 to about 300,000; morepreferably from about 45,000 to about 250,000 e.g., from about 50,000 toabout 150,000. Typically, selection of molecular weight in viscosity modifierapplications is controlled by shear stability requirements of the contemporarymarketplace.The POH copolymers of this invention preferably exhibit a degree ofcrystallinity such that they are essentially, and substantially, amorphous.The nature of the catalyst system employed in this invention can resultin a phenomenon referred to as âchain straightening," producing copolymerchains having monomer sequences which appear to have been derived fromethylene monomer (for the sake of convenience, sometimes referred to hereinas âapparentâ ethylene content), even in those circumstances in whichethylene monomer is not, in fact, employed in the polymerization.Conversely, the use of ethylene monomer alone in the presence of the recitedcatalyst system results in chain branching, thus giving the appearance of theuse of a higher alkyl comonomer, e.g., propylene, even when none is used.(In comparison, the polymerization of ethylene using a Ziegler-Natta ormetallocene catalyst system typically results in less than one branch perhundred carbon atoms as a result of âdefective" monomer insertion.)Similarly, in the present invention, polymerization of 1âbutene leads tosubstantial incorporation of linear methylene sequences and a distribution ofamorphous chain branches; polymerization of the olefins described leads tobranch lengths preferably of from C1âC,,, where n is typically 1 to 4.The on-olefin that is polymerized and the extent and type of branchingshould be controlled for copolymers intended for use in lubricant and fuelapplications. For dispersant and lower molecular weight applications, the?WO 98/03617CA 02263959 l999-02- l9PCT/US97/12125-29-olefin is preferably at least one selected from C2-C8 monomers (i.e., ethyleneand C3"C3 oLâo|efins); more preferably C2-C5; most preferably C2-C4 olefinicmonomers. Very long chain branching should be avoided because dispersancyin, e.g., gasoline engine applications is related to the hydrodynamic volume ofthe copolymer chain. Incorporating most of the molecular weight of thecopolymer into the backbone is preferred; hence typically at least about 50%of the branches should be methyl and/or ethyl (C1 or C2) and at least about80% of the branches should be C1-C4; preferably at least about 75% shouldbe C1-C2 and 85% should be C1-C4; more preferably at least about 90%should be C1-C2 and 95% should be C1-C4; most preferably at least about95% of the branches are C1-C4 branches.The POH copolymers of the present invention provide a uniquelystructured backbone for producing the additives of interest. Prior art polymersand copolymers produced using Ziegler-Natta or metallocene catalyst systemstypically contained branches whose length was essentially determined by themonomer which was polymerized; e.g., polymerization of propylene resultedin a copolymer containing almost exclusively methyl branches (the exceptionsbeing introduced by incorporation âerrorsâ during polymerization). in contrast,as noted above, the POH copolymers of the present invention contain adistribution of branch lengths which typically result from the polymerization ofeach monomer or combination of monomers. The distribution of branchlengths results in copolymers whose solution properties, response totemperature and wax interaction/cocrystallization response differs from theprior art. These characteristics can be tuned in order to achieve a balance notpreviously available. Generally, catalyst and process features are selected inorder to reduce long ethylene sequences in the copolymer backbone and"introduce additional branches. This is preferably accomplished by using a Ni-based catalyst and conducting the polymerization at a lower temperature.Conversely, too little chain branching can lead to insolubility in oil andpotential problems with pour point properties. Sufficient chain branching isrequired so that long, uninterrupted methylene sequences, which are capableof crystallizing at low temperatures and interfering with oil solubility areavoided. Controlled branching and controlled co-crystallization isadvantageous in order to modify wax crystal growth in fuel oils so as tooptimize such performance in that application. Typically, there should be, onaverage, at least about 5 branches per 100 carbon atoms, i.e., from about 10to about 33, for example from about 15 to about 30 branches per 100 carbon?CA 02263959 l999-02- l9wo 93/03517 PCT/US97/12125-30-atoms of copolymer. In various applications the number of branches ispreferably from about 11 to about 25 per 1OQ carbon atoms; more preferablyfrom about 12 to about 20; most preferably from about 13 to about 16; forexample, useful copolymers are produced having from about 10 to about 12.5branches per 100 carbon atoms present in the copolymer chains. in thepresent invention additional control means are available at the 'âcopolymerdesignâ level to control the copolymer structure so that it best suits theparticular application. For example, in those applications where the extent ofbranching would be too great using an oLâo|efin monomer as the onlypolymerizable olefin, ethylene can be employed as a comonomer. In thismanner additional straight chain segments or methylene sequences can beintroduced but, since ethylene polymerized using the catalyst system hereinalso introduces branches, its use would not introduce, e.g., pour pointproblems.For the purposes of the present invention in dispersant applications, thePOH copolymer will typically contain not greater than 50 weight percentmonomer triad sequences which appear to be ethylene-monomer centered,based upon the total copolymer weight; preferably not greater than 45; andmost preferably not greater than 40 weight percent of such apparent ethylenemonomer sequences based upon the total copolymer weight. Thus, theapparent ethylene content can range typically from 1 to 50 (e.g., from 5 to50) weight percent, preferably from 5 to 45 (e.g., 5 to 40) weight percent,and most preferably from 10 to 40 (e.g., 10 to 35) weight percent. One canreadily calculate the equivalent mole % values for recited ranges based on theparticular or-olefin that is used during the polymerization, either alone or incombination with ethylene, for dispersant applications which preferablyemploy a C3-C3 ocâolefin. For example, 50 weight % ethylene in the presenceof C3 monomer sequences converts to 60 mole % ethylene, but in thepresence of C8 monomer sequences converts to 80 mole %. Similarly, thecorresponding values can be calculated for other monomer combinations. Forthe use of the POH copolymers of the invention as wax crystal modifiers formiddle distillate fuels such as diesel fuels and oils such as heating oils, typicalethylene content would be from about 70 to about 90 mole %; preferablyfrom about 74 mole % to about 84 mole %. When used as a viscositymodifier, the copolymer can be produced using ethylene, C3-C20 or-olefins andmixtures thereof. Copolymers of suitable molecular weight typically containfrom about 50 mole % apparent ethylene derived sequences to about 78 mole?CA 02263959 l999-02- 19W0 93/03517 PCT/US97/ 12125-31-percent for a copolymer containing apparent C3 derived sequences and fromabout 87 mole % to about 96 mole percent ethylene for a C20 derivedcopolymer. (These ranges correspond to 40 to 70 weight %; a more preferredrange is from about 45 to about 60 weight percent apparent ethylenesequencesJThe copolymers of this invention may optionally contain small amounts,e.g., typically up to 10, preferably up to 5 weight percent, of units derivedfrom other or-olefins and C4 to C22 diolefins. For example, introduction ofsmall amounts of C4 olefins other than butene-1 can result during thepreparation of the POH copolymers through the use of 1-butene monomerfeed streams which also contain limited amounts of 2âbutene, isobutene,and/or butadiene; similarly, limited amounts of polymerizable monomers maybe present in refinery or steam cracker-derived C3 and C5 streams.The POH copolymers of the invention typically also have an averageethylene sequence length (ESL) of from about 1.0 to less than about 3.0;preferably from about 1.0 to about 2.5; more preferably from about 1.0 toabout 2.0; for example from about 1.0 to about 1.5. ESL is the ratio of thetotal number of ethylene units in the copolymer chains to the total number ofdiscrete ethylene sequences in the copolymer chains, as given by thefollowing equation:ESL = lXEEE + XREE+EER + XRERWXRER + 0-5*XREE+EER)wherein XEEE is the mole fraction of ethy|ene-ethylene-ethylene triadsequences in the copolymer; XREE + EER is the mole fraction of higher alkyl,R, such as butene, e.g., butene-ethylene-ethylene and ethylene-ethylene-butene triad sequences; and XRER is the mole fraction of the higher alkyl, R,such as butene-ethylene-butene triad sequences. The ethylene sequences canbe present as a result of the copolymerization of ethylene with an on-olefin or,as a result of the use of the late-transitionâmetal catalyst, âchainstraightening" which occurs when polymerizing one or more ocâolefins,resulting in the presence of a higher alkyl, R, in the copolymer chain. The ESLvalue is an index reflecting the distribution of the units derived from ethyleneor resulting in ethylene sequences (and therefore apparently derived fromethylene) in the POH copolymer chains. As the value for ESL increases for agiven POH copolymer of fixed ethylene content (actual or apparent), thenumber of isolated ethylene units in the chains declines, and, concomitantly,?CA 02263959 1999-02-19W0 98/03617 PCT/US97/12125_ 32 _the number of ethylene units per ethylene sequence increases. Naturally, asthe ethylene content increases in an POH copolymer containing even arandom distribution of ethylene units, the general tendency is to obtainincreased ESL values. As per the above equation, the ESL value of acopolymer can be calculated from XEEE, XREE.,_EER, and XRER, where R is,for example, butene, which values are determined from the copo|ymer's C-13NMR spectrum, using the methods described in, for example, Randall, JamesC., Journal of Macromolecular Science - Reviews of MacromolecularChemistry and Physics, 923, 201-317 (1989). Alternatively, and as anapproximation, one can use the integral of the âpo|ymethyleneâ peak at29.9ppm and compare the value obtained to the total aliphatic or methylintegral.The POH copolymers of this invention preferably also have a molecularweight distribution (MWD), defined as the ratio of the weight averagemolecular weight lMw) to the number average molecular weight (i.e., MWDMw/Mn), of less than about 5, preferably less than about 4, and mostpreferably less than about 3. More specifically, the copolymers have amolecular weight distribution of from about 1.0 to about 3.5, and mostpreferably from about 1.1 to about 3. It will be appreciated by one skilled in Athe art that the MWD of the copolymer is broadened by variations oftemperature, monomer concentration, and catalyst concentration and thespecific level will be affected by the specific process conditions selected andthe specific catalyst system employed. Both Mn and Mw can be determinedby the technique of gel permeation chromatography (GPC) with a suitablecalibration curve, from which MWD can be readily obtained. Mn and MWDfor ethyleneâaâo|efin copolymers, for example, can be obtained usingI calibration curves based upon polydisperse ethylene-on-olefin copolymershaving ethylene contents similar to that of the samples under test. For adescription of the determination of Mn and MWD using GPC (also known assize exclusion chromatography), see W. W. Yau, J. J. Kirkland and D. D. Bly,"Modern Size Exclusion Liquid Chromatography", John Wiley and Sons, NewYork, 1979. Mn can alternatively be determined for certain copolymers suchas ethylene-on-olefin copolymers from either their protonâ or carbon-13 NMRspectra obtained in solution, using conventional analytical techniques knownto those skilled in the art. See, for example, "C13-NMR in PolymerQuantitative Analyses," J. C. Randall and E. T. Hiseh, in: [\_lM_l3,??CA 02263959 l999-02- 19W0 93/03517 PCT /US97/12125-33- ACSSymposium Series No. 247, 131-151 (American Chemical Society, 1984).E.|..|E...[I:!rThe copolymers produced in accordance with the present invention canbe considered to be functionalized as a consequence of the presence of thepolar moiety, i.e., having at least one functional group present within itsstructure, which functional group is capable of: (1) undergoing furtherchemical reaction (e.g. derivatizationl with other material/or (bl impartingdesirable properties, not otherwise possessed by an olefinic homopolymer orcopolymer alone, absent the presence of a polar moiety. However, thecopolymer of the present invention also has olefinic unsaturation present in itsstructure, preferably in the form of a terminal vinyl group, and suchunsaturation is capable of being further modified or further functionalized.Additionally, the functional group can be incorporated into the backbone ofthe copolymer, or can be attached as a pendant group from the copolymer. backbone. The functional group typically will be polar and contain heteroatoms such as P, O, S, N, halogen and/or boron. It can be attached to thesaturated hydrocarbon part of the copolymer via substitution reactions or toan olefinic portion via addition or cycloaddition reactions. Alternatively, thefunctional group can be incorporated into the copolymer by oxidation orcleavage of a small portion of the end of the copolymer (e.g. as in ozonolysis).The function of dispersants is to maintain materials which are insoluble inoil (and which result from oil use) in suspension in the fluid thus preventing sludge?occulation and precipitation. Suitable dispersants include, for example,dispersants of the ash-producing (also known as detergents) and ashless type,the latter type being preferred. The derivatized copolymer compositions of thepresent invention, can be used as ashless dispersants and multifunctionalviscosity index improvers in lubricant and fuel compositions. Generally, acopolymer containing a reactive moiety, with or without further functionalization. ismixed with at least one amine to form dispersant additives.The copolymer of the invention polymer can be used as a dispersant ormultifunctional viscosity modifier if the latter also contains a group capable ofperforming the requisite dispersancy function. The copolymer as synthesizedcontains ethylenic functionality as well as a residue or moiety from the polarcomonomer. In addition, the copolymer can be modified to introduce other?WO 98/03617CA 02263959 1999-02-19PCT/US97/12125_ 34 -functional groups to enable the copolymer to participate in a variety of derivatizingchemical reactions. These derivatized copolymers can have the requisiteproperties for a variety of uses including use as dispersants and viscositymodifiers. For the purposes of this disclosure a derivatized copolymer is onewhich has been chemically modi?ed to perform one or more functions in asigni?cantly improved way relative to the unfunctionalized copolymer and/or thefunctionalized copolymer. Representative of such functions, are dispersancyand/or viscosity modification in lubricating oil compositions.The derivatizing compound typically contains at least one reactivederivatizing group selected to react with the reactive_ or functional groups of thecopolymer by various reactions. Representative of such reactions arenucleophilic substitution, transesteri?cation, salt formation, and the like. Thederivatizing compound preferably also contains at least one additional groupsuitable for imparting the desired properties to the derivatized polymer, e.g., polargroups. Thus, such derivatizing compounds typically will contain one or moregroups including amine, hydroxy, ester, amide, imide, thio, thioamido, oxazoline,or carboxylate groups or form such groups at the completion of the derivatizationreaction. Additionally, the functionalized copolymer can be reacted with basicmetal salts to form metal salts of the polymer; preferred metals are Ca, Mg, Cu,Zn, Mo, and the like.Suitable properties sought to be imparted to the derivatized copolymerinclude one or more of dispersancy, multifunctional viscosity modification,antioxidancy, friction modification, antiwear, antirust. seal swell, and the like. Thepreferred properties sought to be imparted to the derivatized copolymer includedispersancy (both mono- and multifunctional) and viscosity modification, primarilywith attendant secondary dispersancy properties. A multifunctional dispersanttypically will function primarily as a dispersant with attendant secondary viscositymodification.While the techniques for derivatization and further functionalization forpreparing multifunctional viscosity modifiers (also referred to herein asmultifunctional viscosity index improvers or MFVI) are the same as for ashlessdispersants (see below), the functionality of a functionalized copolymer intendedfor derivatization and eventual use as an MFVI will be controlled to be higher thanfunctionalized copolymer intended for eventual use as a dispersant. This stemsfrom the difference in Mn of the MFVI copolymer backbone vs. the Mn of thedispersant copolymer backbone. Accordingly, it is contemplated that an MFVI willbe derived from functionalized copolymer having typically up to about one and at?CA 02263959 2004-09-20-35-least about 0.5 functional groups, for each 20,000, preferably for each 10,000.most preferably for each 5,000 for each 1,000 Mn molecular weight segment inthe backbone polymer.The derivatized copolymers include the reaction product of the POHcopolymer with an amine reactant to form oil soluble amides.E e i . I. I E . ; IUseful amine compounds for derivatizing the POH copolymers of theinvention, with or without further functionalization of the copolymer itself, compriseat least one amine and can comprise one or more additional amine or other" reactive or polar groups. Where the functional group is a carboxylic acid,carboxylic ester or thiol ester, it reacts with the amine to form an amide. Preferredamines are aliphatic saturated amines. Non-limiting examples of suitable aminecompounds include: 1,2-diaminoethane; 1,3-diaminopropane; 1,4-diaminobutane; 1.6-diaminohexane; polyethylene amines such as diethylenetriamine; triethylene tetramine; tetraethylene pentamine; etc. (Aminederivatization of POH polymers and production of dispersants and lubricantadditives therefrom can be carried out according to the general teachings inWO 95/35329, published 28 December 1995).Other useful amine compounds include: alicyclic diamines such as 1,4-di(aminomethyl) cyclohexane, and heterocyclic nitrogen compounds such asimidazolines. Mixturesof amine compounds may advantageously be used.Useful amines also include polyoxyalkylene polyamines. A particularly usefulclass of amines are the polyamido and related amines.For the preferred polyamine dispersant of this invention, the novelpreferred compositions allow the benefit of using higher molecular weightbackbones without the limitation of low nitrogen content and the debit of highviscosities.Polyamines containing one primary amino group and 1-10 secondary ortertiary amino groups are particularly useful (Referred to herein as âType l"amines). For lubricant applications, polyamines with 3-8 secondary or tertiaryamino groups are preferred. For fuel applications polyamines with 1-3 secondaryor tertiary amino groups are preferred. These polyamines may optionally containoxygen and sulfur atoms as part of the molecule. The amino groups and theoxygen and sulfur are generally separated from each other by hydrocarbylenew?CA 02263959 1999-02-19WO 98103617 PCT/US97/12125-36-groups containing from 1-6 carbons. The polyamines could contain heterocyclesas part of their structure.The preferred polyamines contain only one primary amine per molecule;they are also referred to hereinafter as âone armed polyamines". However, as thenumber of nitrogen atoms in the polyamines increases, some branching couldoccur giving mixtures of polyamines containing primarily one amino group withsome molecules containing more than one primary amino group. To minimize theviscosity of the final product and maximize the nitrogen content, polyamines withthe least amount of branching are particularly preferred.In general, these one armed polyamines belong to two groups: (1 )nonvolatile and (2) volatile amines. Volatile one armed polyamines areconsidered those polyamines that can be distilled during a stripping step of theprocess if any remain unreacted as free amine. Volatile amines can be used inlarge excess to facilitate the completion of the reaction in the shortest possibletime since the unreacted amines can be recovered and reused. Thestoichiometry of the nonvolatile amine is limited to about one primary amino groupper carbonyl group to avoid residual unreacted polyamine in the dispersantmixture.One type of one armed polyamine can be represented by the formula:H2N(-Rl-NH-)2-(-Râ-A-)y-R5"Wherein:R5 and Râ are hydrocarbyl groups of from one to six carbons;Rm is a hydrocarbyl group containing from one to 40 carbons or a heterocyclicstructure containing N, and/or S, and/or 0;A is oxygen or sulfur;z = 1 to 10; andy = O to 1.As used herein the term "hydrocarbyl" denotes a group having a carbonatom directly attached to the remainder of the molecule and having predominantlyhydrocarbon character within the context of this invention and includes polymerichydrocarbyl radicals. Such radicals include the following:(1) Hydrocarbon groups; that is, aliphatic, (e.g., alkyl or alkenyl),alicyclic (e.g., cycloalkyl or cycloalkenyl), aromatic, aliphatic- and alicyclic-substituted aromatic, aromatic-substituted aliphatic and alicyclic radicals,and the like, as well as cyclic radicals wherein the ring is completed?CA 02263959 l999-02- 19W0 98/03617 PCT/US97/12125-37-through another portion of the molecule (that is, the two indicatedsubstituents may together form a cyclic radical). Such radicals are knownto those skilled in the art; examples include methyl, ethyl, butyl, hexyl,octyl, decyl, dodecyl, tetradecyl, octadecyl, eicosyl, cyclohexyl, phenyl andnaphthyl (all isomers being included).(2) Substituted hydrocarbon groups; that is, radicals containing non-hydrocarbon substituents which do not alter predominantly hydrocarboncharacter of the radical. Those skilled in the art will be aware of suitablesubstituents (e.g., halo, hydroxy, alkoxy, carbalkoxy, nitro, alkylsulfoxy).(3) Hetero groups; that is, radicals which, while predominantlyhydrocarbon in character, contain atoms other than carbon present in achain or ring otherwise composed of carbon atoms. Suitable hetero atomswill be apparent to those skilled in the art and include, for example,nitrogen, particularly non-basic nitrogen, oxygen and sulfur.In general, no more than about three substituents or hetero atoms, andpreferably no more than one, will be present for each 10 carbon atoms inthe hydrocarbon-based radical. Polymeric hydrocarbyl radicals are thosederived from hydrocarbon polymers, which may be substituted and/orcontain hetero atoms provided that they remain predominantlyhydrocarbon in character.One method to prepare these one armed polyamines consists of stepwisereaction of known alcohols, mono or polyamines with acrylonitrile followed byhydrogenation. The following is a partial list of these polyamines:CH3(CH2)16â18(NHCH2CH2CH2)3-NH2CH3(CH2)16-18-0-(NHCH2CH2CH2)3-NH2CH3(CH2)11-O-(NHCH2CH2CH2)5-NH2CH3(CH2)16-18-0-(NHCH2CH2CH2)3-NH2CH3(CH2)16-18-0-(NHCH2CH2CH2)3-NH2(CH3)2NCH2CH2CH2NHCH2CH2CH2NH2(CH3)2N(CH2CH2CH2NH)2CH2CH2CH2NH2(CH3)2N(CH2CH2CH2NH)3CH2CH2CH2NH2CH3(CH2)3CHCH2(NHCH2CH2CH2)2NH2ICHZCH3?CA 02263959 2004-09-20-33-CH3(CH2)3CHCH2(NHCH2CH2CH2)3NHgICHZCH3HN O NCH2CH2CH2NHCH2CH2CH2NH2HN O N(CH2CH2CH2NH)2CH2CH2CH2NH2HN©N(CH2CH2CH2NH)3CH2CH2CH2NH2O NCH2CH2CH2NHCH2CH2CH2NH;;_O N(CH2CH2CH2NH)2CH2CH2CH2NH2O N(CH2CH2CH2NH)3CH2CH2CH2NH2N = CRCH2/ ]\CHp_ - - CHQCHQCHQNHCH2/â |\CH2 - N - CHQCHQCHQNHCHQCHQCHQNHN = CRCH2/ |\CH3 â - (CH2CH2CH2NH)2CH2CH2CH2NHDerivatization with amines can also be conducted using amines containingmore than one primary amino group, including polyamines. in combination withthe use of chainâstopping or end-capping reactants to prevent gel formation(Referred to herein as "Type II" amines). (Amine derivatization of POH polymersusing polyamines and production of dispersants and lubricant additivestherefrom can be carried out according to the general teachings inU.S. Patent No. 5,578,237).A particularly useful class of polyamines comprise bis(pâamino cyclohexyl) methane (PACM) and oligomers and mixtures of PACMwith isomers and analogs thereof containing on average, from 2 to 6 or higher(usually 3 to 4) cyclohexyl rings per PACM oligomer molecule. The totalnitrogen content of the PACM oligomers will comprise generally from 8 to 16wt. %, and preferably from 10 to 14 wt.%. The PACM oligomers can beobtained, e.g., by fractionation, or distillation, as a heavies byâproduct or?W0 98/03617CA 02263959 l999-02- l9PCT/US97/12125-39-bottoms from the PACM-containing product produced by high pressurecatalytic hydrogenation of methyleneâdianiline.Still another useful class of Type ll amines are the poly-amido andrelated amines which comprise reaction products of a polyamine and an alpha,beta unsaturated compound. Any polyamine, whether aliphatic,cycloaliphatic, heterocyclic, etc., (but not aromatic) can be employed providedit is capable of adding across the acrylic double bond and amidifying with forexample the carbonyl group of an acrylate-type compound or with thethiocarbonyl group of a thioacrylate-type compound.The hydrocarbyl groups of the alpha, beta unsaturated compound cancomprise alkyl, cycloalkyl, or heterocyclic, which can be substituted withgroups which are substantially inert to any component of the reaction mixtureunder conditions selected for preparation of the amido-amine. Suchsubstituent groups include hydroxy, halide (e.g., Cl, Fl, l, Br), -SH andalkylthio. When one or more of the hydrocarbyl groups are alkyl, such alkylgroups can be straight or branched chain, and will generally contain from 1 to20, more usually from 1 to 10, and preferably from 1 to 4, carbon atoms.illustrative of such alkyl groups are methyl, ethyl, propyl, butyl, pentyl, hexyl,heptyl, octyl, nonyl, decyl, dodecyl, tridecyl, hexadecyl, octadecyl and thelike. When one or more are cycloalkyl, the cycloalkyl group will generallycontain from 3 to 12 carbon atoms, and preferably from 3 to 6 carbon atoms. _Illustrative of such cycloalkyl groups are cyclopropyl, cyclobutyl, cyclohexyl,cyclooctyl, and cyclododecyl. When one or more are heterocyclic, theheterocyclic group generally consists of a compound having at least one ringof 6 to 12 members in which on or more ring carbon atoms is replaced byoxygen or nitrogen. Examples of such heterocyclic groups are furyl, pyranyl,pyridyl, piperidyl, dioxanyl, tetrahydrofuryl, pyrazinyl and 1,4-oxazinyl.Examples of the alpha, beta-ethylenically unsaturated carboxylatecompounds useful for reaction with the polyamine are acrylic acid,methacrylic acid, the methyl, ethyl, isopropyl, n-butyl, and isobutyl esters ofacrylic and methacrylic acids, and 2-butenoic acid.Various types of alpha, beta ethylenically unsaturated compounds maybe employed, including:(a) carboxylate thioester compounds; examples of thesecompounds are methylmercapto 2-butenoate and ethylmercapto 2-hexenoate;(b) carboxyamide compounds; examples of these compoundsarea 2-butenamide and 2âhexenamide;?CA 02263959 1999-02-19WO 93103517 PCT/US97/12125.. 40 -(c) thiocarboxyamide compounds; examples are 2-butenthioicacid and 2-hexenthioic acid;(d) dithioic acid and acid ester compounds; examples are 2-butendithioic acid and 2-hexendithioic acid; and(e) thiocrboxyamide compounds; examples of thesecompounds are 2âbutenthioamide and 2-hexenthioamide.Preferred compounds for reaction with the polyamines in accordancewith this invention are lower alkyl esters of acrylic and (lower alkyl)substituted acrylic acid. In the preferred embodiments these compounds areacrylic and methacrylic esters such as methyl or ethyl acrylate, methyl orethyl methacrylate. When the selected alpha, beta-unsaturated compoundcontains oxygen, the resulting reaction product with the polyamine containsat least one amido linkage (-C(O)N<l and such materials are herein termed"amidoâamines." Similarly, when the selected alpha, beta unsaturatedcompound contains sulfur, the resulting reaction product with the polyaminecontains thioamide linkage(-C(S)N <) and these materials are herein termed "thioamido-amines."Generally, equimolar amounts of polyamine and alpha, beta ethylenicallyunsaturated carboxylate yields a more linear amidoâamine whereas an excessof alpha, beta unsaturated compound tends to yield an amidoâamine which iscrosslinked. Preferably, the amido-amines are not crosslinked to a substantialdegree; more preferably they are substantially linear.The reaction can be carried out at any suitable temperature, generallybelow 100 °C, for example 80-90 °C. Reaction time can vary from about 2 to30 hours; such as 5 to 25 hours; preferably 3 to 10 hours.When the post-treating reactant comprises a polyfunctional compound,i.e. a compound containing more than one reactive group, it is necessary touse sufficient chain-stopping or endâcapping reactant in combination with thepolyfunctional post-treating reactant to ensure that the derivatized productmixture will be gel-free.The chain-stopping or endâcapping reactants contemplated for use inthis aspect of the invention include monofunctional reactants which arecapable of reacting with reactive amine groups present in the polyfunctionalreactants of the Type ll amines or with the polar moiety or reactive groupswhich are grafted or otherwise attached to the POH copolymer to inhibit crosslinking and gelation and/or viscosity increase due to any further reaction ofunreacted amino groups in the aminated or modified «POH copolymer.?CA 02263959 1999- 02 - 19W0 98,03,517 PCT/US97/12125-41-Preferred chain-stopping or end-capping reactants include, for example,hydrocarbyl substituted dicarboxylic anhydride or acid, preferably succinicanhydride or acid, having from about 12 to 400 carbons in the hydrocarbylgroup; long chain monocarboxylic acid of the formula RCOOH where R is ahydrocarbyl group of 12 to 400 carbons in the hydrocarbyl group; alcoholcompounds having only a single hydroxy group per molecule; and aminecompounds having only a single reactive amine group per molecule. Thehydrocarbyl groups are essentially aliphatic and include alkenyl and alkylgroups. The longer chain acids and anhydrides are preferred, particularlywhen the grafting reaction is carried out in lubricating oil because of theirability to impart dispersancy to reacted oil molecules as well as their greatersolubilizing effect. In one preferred embodiment, the chain-stopping or end-capping reactant comprises a C12 to C49 hydrocarbyl substituted succinicanhydride, e.g. a C12 to C13 hydrocarbyl substituted succinic anhydride. Inother preferred embodiments, the hydrocarbyl substituent contains from 50 to400 carbon atoms.Primarily because of its ready availability and low cost, the hydrocarbylportion, e.g. alkenyl groups, of the carboxylic acid or anhydride is preferablyderived from a polymer of a C2 to C5 monoolefin, said polymer generallyhaving a Mn of about 140 to 6,500, e.g. 700 to 5,000, most preferably 700to 3,000. Particularly preferred polymer is polyisobutylene. Particularly- preferred chain-stopping reactants include polyisobutylene succinic anhydridewherein the Mn of the polyisobutylene portion is from 700 to 2,500.Alcohols having a single reactive hydroxy group per molecule useful aschain-stopping or end-capping reactants generally comprise from 4 to 8carbon atoms and include, for example, C4 - C3 aliphatic alcohols such asbutanol, pentanol and hexanol. The use of alcohols having less than 4 carbonatoms generally is to be avoided because of their low volatility. Alcoholshaving more than about 8 carbon atoms generally are to be avoided since it isdifficult to remove unreacted higher molecular weight alcohols from thederivatized product and since the presence of unreacted higher molecularweight alcohols in the product mixture can result in dispersant additiveshaving less favorable viscometric properties.The aforesaid post-treating, amine reactants having more than onereactive amino group and the chain-stopping or end-capping reactants may bepre-reacted with the chain-stopping or end-capping reactant generally beingattached to the post-treating reactant through salt, imide, amide amidine,?CA 02263959 1999-02-19WO 98/03617 PCT/US97/12125- 42 _ester, or other linkages so that a single reactive group of the postâtreatingreactant is still available for reaction with the reactive moieties of the POHcopolymer. A convenient source of these prereacted materials are the well-known carboxylic acid derivatives such as succinimides used as lubricating oildispersants, provided they retain reactive amine and/or hydroxy groupscapable of further reaction with the POH copolymer.The POH copolymer, with or without further functionalization, can bereacted with an individual amine reactant or such reactant and chain-stoppingor endâcapping reactant or any combination of two or more of any of thesereactants; that is, for example, one or more monoreactive amines orpolyamines, so long as sufficient monoreactive reactant is used when areactant having more than one reactive group is used to ensure a gel-freereaction.The reaction between the copolymer and the amine and/or chain-stopping or end-capping reactants is readily accomplished, for example, byheating a solution containing 5 to 95 wt. percent of the copolymer in asubstantially inert organic solvent or diluent at from 100 to 250°C, preferably125 to 175°C, generally for 1 to 10, e.g., 2 to 6 hours. Suitable diluentsinclude, for example, aliphatic, cycloaliphatic, and aromatic hydrocarbons, aswell as the corresponding halogenated hydrocarbons, particularly chlorinatedhydrocarbons. These diluents are exemplified by benzene, toluene,chlorobenzenes, hexane, heptane, or mixtures of these. Mineral oilsparticularly low viscosity mineral oils are very good diluents. Preferreddiluents are mineral oils of lubricating viscosity.Reaction ratios of copolymer to equivalents of amine reactant, andchain-stopping or end-capping reactants described herein, can varyconsiderably, depending, e.g., on the reactants and type of bonds formed.Generally, when an amine compound is reacted with a copolymer, from 0.05to 4.0, preferably from 0.5 to 2.0, e.g., 0.6 to 1.5, moles of polar moietycontent is used, per equivalent of amine reactant.A preferred group of ashless dispersants, in accordance with thepresent invention, are those derived from POH copolymer reacted withpolyethylene amines, e.g., tetraethylene pentamine, pentaethylene hexamine,polyoxyethylene or polyoxypropylene amines, e.g., polyoxypropylene diamine,and with polyisobutylene succinic anhydride chain-stopping reactant. Anotherpreferred group of ashless dispersants are those derived from POH copolymer?CA 02263959 2004-09-20-43-reacted with monofunctional heterocyclic amines, eg, N.â(.3âaminopropyl)morpholine.Supplemental or further functionalization of the copolymer withfunctional groups typically relies on ethylenic unsaturation, preferably terminalethylenic unsaturation, present in the copolymer for reaction with a functionalcompound containing or constituting the functional group. Thus, reaction ofthese functional compounds and the copolymer can occur through a variety ofmechanisms. Useful and preferred functional groups include halogen,carboxyl materials present as acids, esters, salts, or anhydrides, alcohols,amines, ketones, aldehydes and the like.Useful functionalization reactions which are generally well known tothose skilled in the art include the following. However, the unique features ofthe POH copolymers of the present invention provide significant advantagesnot previously available:(A) reaction of the copolymer at its point of unsaturation withcarbon monoxide using a Koch-type reaction wherein an acid group such asan iso acid. or neo acid is formed. Functionalization of POH copolymers bymeans of the Koch reaction and production of derivatives therefrom can becarried out according to the general teachings in WO/94/13709, published23June1994».However, use of the Koch reaction with ethylene/on-olefin copolymers and on-olefin homopolymers containing primarily vinylidene and/or trisubstituteddouble bonds (e.g., produced by means of metallocene catalyst systems fromethylene and aâolefin feed streamsl leads to derivatives containing more than50% neoacid derivatives. The steric hindrance about the on-carbon of suchneoacid derivatives makes such materials more difficult to condense withpolyamines to form dispersants. High temperatures and aryl leaving groupsare required in order to drive the reaction to completion. The POH copolymerof the present invention which contains a significant concentration of vinyland/or vinylene terminated copolymer chains results in significantly moreisoacid structures which are easier to derivatize and therefore more desirable.in particular, the chemically modified POH copolymers of the present inventiontypically contain less than 50% of neoâsubstituted carbonyl groups, preferablyless than 40%, more preferably less than 30% and most preferably less than20% neoâsubstituted carbonyl groups. For example, the modifiedâ POHcopolymers of the present invention typically will contain from about 5 to lessthan about 50% neoâsubstituted carbonyl groups; preferably from about 5 to?CA 02263959 2004-09-20-44-about 40%; more preferably from about 5 to about 30%; most preferablyfrom about 5 to about 25% of such groups;(B) hydroformylation or oxycarbonylation with cobalt orrhodium catalysts introduce a carbonyl group at the less hindered end of atrisubstituted double bond, leading to isoaldehydes and acids (see,W0/95/24431, published Sep. 14, 1995);amine derivatives useful as derivatives canbe formed by either a single step aminomethylation process or a two stephydroformylation and reductive amination process. However, vinyl olefinswhich are present at higher concentrations in the POH copolymers of thisinvention, lead to the completely unhindered primary functional group which iseasiest to derivatize. Consequently, the presence of vinyl olefins enables thecondensation of the polymeric acid with polyamines directly without thenecessity of phenols as leaving groups;(C) acyl functionalization, and in particular, the preferredmaleation reaction, which is the reaction of the copolymer at the point ofunsaturation with maleic acid or anhydride. A related reaction is thealternating copolymerization of maleic anhydride with copolymers containingvinylidene unsaturation, but the degree of polymerization in such systems islimited, e.g., from about 5-10. in contrast, the vinyl groups of the POHcopolymers of the present invention are much more amenable to radicalinitiated copolymerization leading to a significantly higher degree ofpolymerization (DP), e.g., a DP greater than about 20. The functionalizedreaction product can be further reacted with, e.g., amines to producedispersant products. When the reactant is a polyamine, polyol oraminoalcohol, the reaction is conducted in the presence of sufficient chain-stopping or end-capping co-reactant to ensure a gelâfree product (seeW0/94/13761, published June 23, 1994).Alternatively, functionalization can be . âaccomplished by reaction of the copolymer with an unsaturated functionalcompound using the "ene" reaction absent halogenation;(D) halogenation of the copolymer at the olefinic bond andsubsequent reaction of the halogenated copolymer with an ethylenicallyunsaturated functional compound or an amine;(E) reaction of the copolymer with the functional compoundby free radical addition using a free radical catalyst; and?CA 02263959 2004-09-20.45.(F) reaction of the copolymer by air oxidation methods,epoxidation, chloroamination or ozonolysis.(G) reaction of the copolymer with at least one phenol groupthus permitting derivatization in a Mannich Base-type condensation (see, forexample, U.S. patents 5,128,056 issued July 7, 1992 and U.S. 5,200,103issued April 6, 1993).Characterization of the degree to which the copolymer has beenfunctionalized is referred to herein as "functionality". Functionality refersgenerally to the average number of functional groups present within thecopolymer structure per copolymer chain. Thus, functionality can beexpressed as the average number of moles of functional groups per "mole ofcopolymer''. When said "mole of copolymer" in the functionality ratioincludes both functionalized and unfunctionalized copolymer, functionality isreferred to herein as F. When said "mole of copolymer" includes onlyfunctionalized copolymer, functionality is referred to herein as F*. Typicalanalytical techniques employed to determine F* will normally necessitateidentification of the weight fraction of functionalized copolymer, based on thetotal weight of copolymer (functionalized + unfunctionalized) in the samplebeing analyzed for functionality. This weight fraction is commonly referred toas Active Ingredient or A.l. Since the determination of A.l. is a separateanalytical step, it can be more convenient to express functionality as F ratherthan Fâ. In any event, both F and F* are alternate ways of characterizing thefunctionality.The particular functionality selected, for copolymer intended to bederivatized, will depend on the nature of the derivatization reactions and typeand number of chemical linkages established by the derivatizing compound.In most instances, one derivatizing linkage will be formed for each functionalgroup, e.g., each carboxy functional group will form one ester or amideHnkage.Accordingly, while any effective functionality can be imparted to thefunctionalized copolymer intended for subsequent derivatization, it iscontemplated that such functionalities, expressed as F*, can be, fordispersant end uses, typically not greater than 3, preferably not greater than2, and typically can range from 1 to 3, preferably from 1.5 to 2.5, and mostpreferably from 1.1 to 2 (e.g. 1.2 to 1.3). F and F* values can be related?CA 02263959 1999- 02 - 19WO 93103517 PCT/US97/12125-46-using the A.l., which for copolymers of the present invention typically are atleast .50, preferably from .65 to .99, more preferably from .75 to .99, yetmore preferably .85 to .99. However, the upper limit of A.l. is typically from0.90 to 0.99, and more typically 0.90 to 0.95. Where A.l. is 1.0, F = F*.As indicated above, a functionalized copolymer is one which ischemically modified primarily to enhance its ability to participate in a widervariety of chemical reactions than would otherwise be possible with theunfunctionalized copolymer. In contrast, a derivatized copolymer is one whichhas been chemically modified to perform one or more functions in asignificantly improved way relative to the unfunctionalized copolymer and/orthe functionalized copolymer. Representative of such functions, aredispersancy and/or viscosity modification in lubricating oil compositions.Typically, derivatization is achieved by chemical modification of thefunctionalized copolymer by reaction with at least one derivatizing compoundto form derivatized copolymers. The derivatizing compound typically containsat least one reactive derivatizing group capable of reacting with the functionalgroups of the functionalized copolymers, for example, by nucleophilicsubstitution, Mannich Base condensation, transesterification, salt formations,and the like. The derivatizing compound preferably also contains at least oneadditional group suitable for imparting the desired properties to the derivatizedcopolymer, e.g., polar groups. Thus, such derivatizing compounds typicallywill contain one or more groups including amine, hydroxy, ester, amide, imide,thio, thioamido, oxazoline or salt groups derived from reactive metal orreactive metal compounds. Thus, the derivatized copolymers can include thereaction product of the above recited functionalized copolymer with anucleophilic reactant, which includes, amines, alcohols, aminoâalcohols andmixtures thereof, to form oil soluble salts, amides, imides, oxazoline, reactivemetal compounds and esters of mono- and dicarboxylic acids, esters oranhydrides. Suitable properties sought to be imparted to the derivatizedcopolymer include especially dispersancy, but also multifunctional viscositymodification, antioxidancy, friction modification, antiwear, antirust, seal swell,andthe?ke.Ash-producing detergents can be made using the functionalizedcopolymers of the present invention as exemplified by oil-soluble neutral andbasic salts of alkali or alkaline earth metals with alkyl phenols, alkyl sulfonicacids, carboxylic acids, salicylic acids or organic phosphorus acidscharacterized by at least one direct carbonâto-phosphorus linkage such as?CA 02263959 2004-09-20-47-those prepared from the functionalized olefin copolymer of the presentinvention (e.g., functionalized copolymer having a molecular weight of 1,500)with a phosphorizing agent such as phosphorus trichloride, phosphorusheptasulfide, phosphorus pentasulfide, phosphorus trichloride and sulfur,white phosphorus and a sulfur halide, or phosphorothiolc chloride. The mostcommonly used salts of such acids are those of sodium, potassium, lithium,calcium, magnesium, strontium and barium. The alkyl groups of the aboveacids or compounds constitute the copolymer of the present invention.Preferred ash-producing detergents which can be derived from thefunctionalized copolymers of the present invention include the metal salts ofalkyl sulfonic acids, alkyl phenols, sulfurized alkyl phenols, alkyl salicylates,alkyl naphthenates and other oil soluble monoâ and dicarboxylic. acids. Highlybasic (viz., overbased) metal salts, such as highly basic alkaline earth metalalkyl sulfonates (especially Ca and Mg salts) are frequently used asdetergents.The derivatized copolymer compositions of the present invention can beused as ashless dispersants in lubricant and fuel compositions. Ashlessdispersants are referred to as being ashless despite the fact that, dependingon their constitution, the dispersants may, upon combustion, yield a non-volatile material such as boric oxide or phosphorus pentoxide. Thecompounds useful as ashless dispersants generally are characterized by a"polar" group attached to a relatively high molecular weight hydrocarbonchain supplied by the copolymer of the present invention. The "polar" groupgenerally contains one or more of the elements nitrogen, oxygen andphosphorus. The solubilizing chains are generally higher in molecular weightthan those employed with the metallic based dispersants, but in someinstances they may be quite similar. Various types of ashless dispersants canbe made by derivatizing the copolymer of the present invention and aresuitable for use in the lubricant compositions. The following are illustrative:1. Reaction products of functionalized copolymer of the presentinvention derivatized with nucleophilic reagents such as amine compounds,e.g. nitrogen-containing compounds, organic hydroxy compounds such asphenols and alcohols, and/or basic inorganic materials. More specifically,nitrogen- or ester-containing ashless dispersants comprise members selectedfrom the group consisting of oil-soluble salts, amides, imides, oxazolines and?CA 02263959 2004-09-20-48-esters, or mixtures thereof, of the copolymer of the present invention,functionalized with mono- and dicarboxylic acids or anhydride or esterderivatives thereof, said copolymer having dispersant range molecular weightsas defined hereinabove. At least one functionalized copolymer is mixed withat least one of amine, alcohol, including polyol, aminoalcohol, etc., to formthe dispersant additives. One class of particularly preferred dispersantsincludes those derived from the copolymer of the present inventionfunctionalized mono- or dicarboxylic acid material, e.g. succinic anhydride,and reacted with (i) a hydroxy compound, e.g. pentaerythritol, (ii) apolyoxyalkylene polyamine, e.g. polyoxypropylene diamine, and/or (iii) apolyalkylene polyamine, e.g., polyethylene diamine, tetraethylene pentamine("TEPAâ) or triethylene tetramine (âTETA"). Another preferred dispersantclass includes those derived from functionalized copolymer reacted with (i) apolyalkylene polyamine, e.g. tetraethylene pentamine, and/or (ii) a polyhydricalcohol or polyhydroxy-substituted aliphatic primary amine, e.g.,pentaerythritol or trismethylolaminomethane.Further enhancements in dispersancy can be achieved by the use ofmaterials known as heavy polyalkylene polyamines ("heavy PAM") tointroduce an amine as the polar segment of the dispersant (see, e.g., U.S.Ser. No. 322715 filed Oct. 12, 1994).Generally, heavy PAM is a mixture of higheroligomers of polyalkylene amines (e.g., polyethylene) containing essentially noTEPA, at most small amounts of pentaethylene hexamine (âPEHA"), butprimarily oligomers with more than 6 nitrogens and more branching thanconventional polyamine mixtures. Specifically, heavy PAM typically contains> 28% nitrogen (e.g., > 32%), an equivalent weight of primary amine groupsof between 120-160 grams per equivalent (e.g., 125-140). more than 6nitrogen atoms per molecule on the average and more than two primaryamines per molecule on the average and essentially no oxygen. Heavy PAM isavailable commercially (e.g., trade name Polyamine HA-2, Dow ChemicalCompany) and can also be synthesized from polyethylene or polypropylenepolyamine. Reduced levels of free, unreacted polyamine is beneficial to dieselengine and elastomer seal performance in vehicles.2. Reaction products of the copolymer of the present inventionfunctionalized with an aromatic hydroxy group and derivatized with aldehydes(especially formaldehyde) and amines (especially polyalkylene polyamines).?CA 02263959 l999-02- 19WO 98103617 PCT/US97/12125-49-through the Mannich reaction, which may be characterized as "Mannichdispersants".3. Reaction products of the copolymer of the present inventionwhich have been functionalized by reaction with halogen and then derivatizedby reaction with amines (e.g. direct amination), preferably polyalkylenepolyamines. These may be characterized as "amine dispersants" andexamples thereof are described, for example, in U.S. Patent Nos. 3,275,554;3,438,757; 3,454,555; 3,565,804; 3,755,433; 3,822,209 and 5,084,197.Useful amine compounds for derivatizing functionalized copolymerscomprise at least one amine and can comprise one or more additional aminesor other reactive or polar groups. Where the functional group is a carboxylicacid, ester or derivative thereof, it reacts with the amine to form an amide.Where the functional group is an epoxy it reacts with the amine to form anamino alcohol. Where the functional group is a halide the amine reacts todisplace the halide. Where the functional group is a carbonyl group it reactswith the amine to form an imine. Amine compounds useful as nucleophilicreactants for reaction with the functionalized copolymer of the presentinvention include those disclosed in U.S. Patent Nos. 3,445,441, 5,017,299and 5,102,566. Preferred amine compounds include monoâ and (preferably)polyamines, of 2 to 60, preferably 2 to 40 (e.g. 3 to 20), total carbon atomsof 1 to 12, preferably 3 to 12, and most preferably 3 to 9 nitrogen atoms inthe molecule. These amines may be hydrocarbyl amines or may behydrocarbyl amines including other groups, e.g., hydroxy groups, alkoxygroups, amide groups, nitriles, imidazoline groups, and the like. Hydroxyamines with 1 to 6 hydroxy groups, preferably 1 to 3 hydroxy groups, areparticularly useful. Preferred amines are aliphatic saturated amines.The functionalized copolymers, particularly acid functionalizedcopolymers, of the present invention can be reacted with alcohols, e.g. toform esters. The alcohols may be aliphatic compounds such as monohydricand polyhydric alcohols or aromatic compounds such as phenols andnaphthols. The esters may be prepared, for example, by reacting a suitablealcohol or phenol with the acid or anhydride (i.e., functionalized copolymersuccinic anhydride). Ester derivatives likewise may be obtained by thereaction of a acid functionalized copolymer with epoxide or a mixture of anepoxide and water. Such reaction is similar to one involving the acid oranhydride with a glycol. For instance, the product may be prepared by thereaction of functionalized copolymer with alkylene oxide to yield half-esters,?CA 02263959 1999-02-19wo 98/03617 PCT/US97/12125_ 50 -monoesters or diesters. In lieu of the acid functionalized copolymer, acopolymer functionalized with lactone acid or an acid halide may be used inthe processes illustrated above for preparing the ester derivatives of thisinvention. Such acid halides may be acid dibromides, acid dichlorides, acidmonochlorides, and acid monobromides. The derivative compositionsproduced by reacting functionalized copolymer with alcohols are estersincluding both acidic esters and neutral esters. Acidic esters are those inwhich less than all of the functional groups in functionalized copolymer areesterified, and hence possess at least one free functional group. Obviously,acid esters are easily prepared by using an amount of alcohol insufficient toesterify all of the functional groups in the functionalized copolymer.Procedures are well known for reacting high molecular weightcarboxylic acids with alcohols to produce acidic esters and neutral esters.These same techniques are applicable to preparing esters from thefunctionalized copolymer of this invention and the alcohols described above.All that is required is that the functionalized copolymers of this invention besubstituted for the high molecular weight carboxylic acids discussed in thesepatents, usually on an equivalent weight basis. The following U.S. Patentsdisclose suitable methods for reacting the functionalized copolymers of thisinvention with the alcohols described above: U.S. Patent Nos. 3,331,776;3,381,022; 3,522,179; 3,542,680; 3,697,428 and 3,755,169.The hydroxy aromatic functionalized copolymer aldehyde/aminocondensates useful as ashless dispersants in the compositions of thisinvention include those generally referred to as Mannich condensates.Generally they are made by reacting simultaneously or sequentially at leastone active hydrogen compound such as a hydrocarbon-substituted phenolle.g., hydroxy aromatic functionalized copolymer of the present invention),having at least one hydrogen atom bonded to an aromatic carbon, with atleast one aldehyde or aldehyde-producing material (typically formaldehydeprecursor) and at least one amino or polyamino compound having at least oneNH group. Preferred phenolic compounds include the hydroxy aromaticfunctionalized copolymer and useful amine compounds are well known andreferred to above. The amine compounds include primary or secondarymonoamines having hydrocarbon substituents of 1 to 30 carbon atoms orhydroxyl-substituted hydrocarbon substituents of 1 to about 30 carbonatoms. Another type of typical amine compound are the polyamines. Thematerials described in the following patents are illustrative of Mannich?CA 02263959 l999-02- 19WO 93/03517 PCT/US97Il2l25- 51 -dispersants: U.S. Patent Nos. 3,413,347; 3,697,574; 3,725,277;3,725,480; 3,726,882; 4,454,059 and 5,102,566.A useful group of Mannich Base ashless dispersants are those formedby condensing phenol functionalized copolymer with formaldehyde andpolyethylene amines, e.g., tetraethylene pentamine, pentaethylene hexamine,polyoxyethylene and polyoxypropylene amines, e.g., polyoxypropylenediamine and combinations thereof. One particularly preferred dispersantcomprises a condensation of (A) phenol functionalized copolymer, (B)formaldehyde, (C) a polyoxyalkylene polyamine, e.g., polyoxypropylenediamine, and (D) a polyalkylene polyamine, e.g. polyethylene diamine andtetraethylene pentamine, using about 2 to about 8 moles each of (B) andabout 1 to about 4 moles of (C) or (D) per mole of (A).A useful class of nitrogen-containing condensation products for use inthe present invention are those made by a "2-step process" as disclosed inU.S. Patent No. 4,273,891. Briefly, these nitrogen-containing condensatesare made by (1) reacting at least phenol functionalized copolymer of thepresent invention with a lower aliphatic C1 to C7 aldehyde or reversiblecopolymer thereof in the presence of an alkaline reagent, such as an alkalimetal hydroxide, at a temperature up to about 150°C; (2) substantiallyneutralizing the intermediate reaction mixture thus formed; and (3) reactingthe neutralized intermediate with at least one compound which contains anamino group having at least one âNH- group. These 2-step condensates canbe made from (a) phenol functionalized copolymer and (b) formaldehyde, orreversible copolymer thereof, (e.g., trioxane, paraformaldehyde) or functionalequivalent thereof, (e.g., methylol) and (c) an alkylene polyamine such asethylene polyamines having between 2 and 10 nitrogen atoms.Condensates made from sulfurâcontaining reactants also can be used inthe compositions of the present invention. Such sulfurâcontainingcondensates are described in U.S. Patent Nos. 3,368,972; 3,649,229;3,600,372; 3,649,659 and 3,741,896. These patents also disclose sulfur-containing Mannich condensates.4. Useful reactive metals or reactive metal compounds are thosewhich will form metal salts or metal-containing complexes with thefunctionalized copolymer. Metal complexes are typically achieved by reactingthe functionalized copolymers with amines and/or alcohols as discussed aboveand also with complex forming reactants either during or subsequent toamination. Reactive metal compounds for use in the formation of complexes?CA 02263959 l999-02- 19W0 98/03617 PCT/US97/12125-52-with the reaction products of functionalized copolymer and amines includethose disclosed in U.S. Patent No. 3,306,908. Complexâforming metalreactants include the nitrates, nitrites, halides, carboxylates, phosphates,phosphites, sulfates, sulfites, carbonates, borates, and oxides of cadmium aswell as metals having atomic numbers from 24 to 30 (including chromium,manganese, iron, cobalt, nickel, copper and zinc). These metals are the so-called transition or coordination metals, i.e., they are capable of formingcomplexes by means of their secondary or coordination valence.Processes are disclosed in U.S. 3,306,908 and Re. 26,433 which areapplicable to the carboxylic derivative compositions of the functionalizedcopolymer of this invention with the amines as described above bysubstituting, on an equivalent basis, the functionalized copolymer of thisinvention with the high molecular weight carboxylic acid functionalizedpolymer of U.S. Patent No. 3,306,908 and carboxylic acylating agents of Re.26,433. Similarly, the metal salts of U.S. 3,271,310 can be adapted to makethe present functionalized copolymer.1!. IEHIH |..The copolymer of this invention, having a suitable number averagemolecular weight, may be used as a synthetic base oil. The functionalizedcopolymer, in addition to acting as intermediates for dispersant manufacture,can be used as a molding release agent, molding agent, metal workinglubricant, point thickener and the like. The primary utility for the above-described materials, from copolymer all the way through and including post-treated derivatized copolymer, is as an additive for oleaginous compositions.For ease of discussion, the above-mentioned materials are collectively andindividually referred to herein as additives when used in the context of anoleaginous composition containing such "additives". Accordingly, theadditives of the present invention may be used by incorporation anddissolution into an oleaginous material such as fuels and lubricating oils.When the additives of this invention are used in normally liquid petroleumfuels such as middle distillates boiling from 65°C to 430°C, includingkerosene, diesel fuels, home heating fuel oil, jet fuels, etc., there is typicallyused a concentration of.the additives in the fuel in the range of from 0.001 to0.5, and preferably 0.005 to 0.15 wt. %, based on the total weight of the?CA 02263959 l999-02- 19WO 93103517 PCT/US97/12125.. -composition. Useful compositions and additives are disclosed in U.S. PatentNo. 5,102,566.The additives of the present invention, particularly those adapted foruse as dispersants, can be incorporated into a lubricating oil in any convenientway. Thus, they can be blended with other additives prior to blending withthe oil or added directly to the oil by dispersing or dissolving the same in theoil at the desired level or concentration of the additive; such blending stepscan be conducted at room temperature or elevated temperatures.Alternatively, the additives can be blended with a suitable oil-soluble solventand base oil to form a concentrate, and then blending the concentrate with alubricating oil basestock to obtain the final formulation. Such dispersantconcentrates will typically contain (on an active ingredient (A.l.) basis) from10 to 80 wt. %, typically 20 to 60 wt. %, and preferably from 40 to 50 wt.%, additive, and typically from 40 to 80 wt. %, preferably from 40 to 60 wt.%, base oil, i.e., hydrocarbon oil based on the concentrate weight. Thelubricating oil basestock for the additive typically is adapted to perform aselected function by the incorporation of additional additives therein to formlubricating oil compositions (i.e., formulations). Usually concentrates may bediluted with 3 to 100, e.g., 5 to 40 parts by weight of lubricating oil, per partby weight of the additive package, in forming finished lubricants, e.g.crankcase motor oils. The purpose of concentrates, of course, is to make thehandling of the various materials less difficult and awkward as well as tofacilitate solution or dispersion in the final blend. Thus, the additives of thepresent invention and formulations containing them would usually beemployed in the form of a 40 to 50 wt. % concentrate, for example, in alubricating oil fraction.The additives of the present invention are primarily useful in lubricatingoil compositions which employ a base oil in which the additives are dissolvedor dispersed therein. Such base oils may be natural or synthetic. Naturalbase oils include mineral lubricating oils which may vary widely as to theircrude source, e.g., whether paraffinic, naphthenic, mixed paraffinic-naphthenic, and the like; as well as to their formation, e.g., distillation range,straight run or cracked, hydrofined, solvent extracted and the like. Base oilssuitable for use in preparing the lubricating oil compositions of the presentinvention include those conventionally employed as crankcase lubricating oilsfor spark-ignited and compression-ignited internal combustion engines, suchas automobile and truck engines, marine and railroad diesel engines, and the?CA 02263959 l999-02- 19W0 98/03617 PCT/US97l12l25_ 54 _like. Advantageous results are also achieved by employing the additivemixtures of the present invention in base oils conventionally employed inand/or adapted for use as power transmitting fluids, universal tractor fluidsand hydraulic fluids, heavy duty hydraulic fluids, power steering fluids and thelike. Gear lubricants, industrial oils, pump oils and other lubricating oilcompositions can also benefit from the incorporation therein of the additivesof the present invention. The additives of the present invention will begenerally used in admixture with a lube oil basestock, comprising an oil oflubricating viscosity, including natural and synthetic lubricating oils andmixtures thereof. Useful oils are described in U.S. Patent Nos. 5,017,299and 5,084,197. Natural oils include animal oils and vegetable oils (e.g.,castor, lard oil) liquid petroleum oils and hydrorefined, solvent-treated or acid-treated mineral lubricating oils of the paraffinic, naphthenic and mixedparaffinic-naphthenic types. Lubricating oils useful in the present inventionare typically based on a hydrocarbon mineral oil having a viscosity of about 2-40 centistokes (ASTM D-445) at 100 °C. Oils of lubricating viscosity derivedfrom coal or shale are also useful base oils. Lubricating oil basestockscomprised of a mixture of a hydrocarbon mineral oil and up to about 50weight % of a synthetic lubricating oil are also considered suitable. Syntheticlubricating oils include hydrocarbon oils and halosubstituted hydrocarbon oilssuch as polymerized and interpolymerized olefins, esters of dibasic acids andcomplex esters derived from monobasic acids and complex esters derivedfrom monobasic acids, polyglycols, dibasic acids and alcohols. Alkylene oxidecopolymers and interpolymers and derivatives thereof where the terminalhydroxyl groups have been modified by esterification, etherification, etc.,constitute another class of known synthetic lubricating oils. Other suitableclasses of synthetic lubricating oils comprise the esters of dicarboxylic acidsand silicon and silicate based oils. Additionally, unrefined, refined andrerefined oils can be used in the lubricants of the present invention.The POH copolymers of the present invention are useful in oilcompositions, for example fuel oil compositions, and particularly in fuel oilcompositions susceptible to wax formation at low temperatures. Heating oilsand other distillate petroleum fuels, for example, diesel fuels, contain alkanesthat at low temperatures tend to precipitate as large crystals of wax in such away as to form a gel structure which causes the fuel to lose its ability toflow. The lowest temperature at which the fuel will flow is known as thepour point.?CA 02263959 l999-02- 19W0 98/03617 PCT /US97/12125-55-As the temperature of the fuel falls and approaches the pour point,difficulties arise in transporting the fuel through lines and pumps. Further, thewax crystals tend to plug fuel lines, screens and filters at temperatures abovethe pour point. These problems are recognized in the art and various additiveshave been proposed, many of which are in commercial use, for depressing thepour point of fuel oils. Similarly, other additives have been proposed and arein commercial use for reducing the size and changing the shape of waxcrystals that do form. Smaller size crystals are desirable since they are lesslikely to clog a filter; certain additives inhibit the was from crystallizing asplatelets and cause it to adopt an acicular habit, the resulting needles beingmore likely to pass through a filter than are platelets. The additives may alsohave the effect of retaining in suspension in the fuel the crystals that haveformed, the resulting reduced settling also assisting in prevention ofblockages.Preferred POH copolymers of the invention may be further characterizedby their beneficial effect on pour point, as determined by ASTM Method No.D97. In this test, measurements are made on solutions comprising a specificconcentration of the copolymer of the invention in a standard minerallubricating oil (S15ON). The pour point of an oil composition is the lowesttemperature at which it will flow when chilled in a specific manner; here, themanner prescribed by ASTM Method No. D97; pour point characterizes thelow temperature flow or pumpability properties of fluids such as lubricatingand fuel oils. Useful additives can also be produced from the POH copolymersof the invention for use in various middle distillate fuel compositions forlowering the pour point and controlling the size of wax crystals in theseproducts; such additives are known as wax crystal modifiers (WCM). Thecopolymers of the present invention are also useful as âco-additivesâ withanother WCM of the present invention or in combination with prior art WCMadditives. Since certain wax crystal modifiers are capable of affecting thesize and number of wax crystals (e.g., affecting crystal nucleation processes)and others are capable of affecting the shape of such crystals (e.g., affectingcrystal growth processes), preferred performance may be achieved by thejudicious combination of WCM additives that are effective in these differentrespects; each having somewhat different structural characteristics toaccomplish their result. For example, copolymers of the invention useful forthe purpose of affecting nucleation can have fewer than about 10 branches?CA 02263959 l999-02- l9wo 93/03517 PCT/US97/12125- 53 -per 100 carbon atoms; useful copolymers can have fewer than 6 branches,e.g., about 5 branches per 100 carbon atoms.The general term âlubricating oil flow improver" (LOFI) is also used toidentify those additives which modify the size, number and growth rate ofwax crystals in lube oils in such a way as to impart improved low temperaturehandling, pumpability and/or vehicle operability. Copolymers or additivescontaining copolymers, which can also be in various functionalized orderivatized forms, are used for this purpose. In one type of LOFI, thecopolymer backbone methylene sequences which are randomly distributed areinterrupted by branches (and other con-crystallizable segments). It is thesequences that are believed to associate or co-crystallize with the waxcrystals and the branches which inhibit or interfere with further crystal growththat would ordinarily occur in their absence. Where the branches aremethylene side chains of increased length, such side chains can be particularlyeffective in treating lube oils containing isoparaffins and n-paraffins. Theeffectiveness of an additive bears a complex relationship to copolymerstructure and is not readily predictable.A requirement of any dispersant additive is that it not adversely affect(i.e., does not significantly increase) the pour point of the lubricating oilcomposition to which it is added. It is generally accepted that the pour pointbehavior of dispersant additives is largely determined by the pour pointbehavior of the copolymer from which they are derived. More particularly, theaddition to a lubricating oil composition of an effective amount of a dispersantadditive produced by the functionalization and/or derivatization, as hereinafterdescribed, of the POH copolymer does not negatively alter the pour point ofthe composition in a significant way.The POH copolymers of this invention are also capable of functioningas a wax crystal modifier (WCM) in fuel oil compositions. in this application,performance can be measured by a pour point test, the change in pour point,measured in degrees Centigrade, when an effective amount of the WCM ispresent in the fuel oil. Performance can also be measured by a filterabilitytest, e.g., the cold filter plugging point ("CFPPâ) test, which is known tothose skilled in the art. The extent of modification of the wax crystal and theeffectiveness of the WCM will vary depending on the structural configurationof the WCM. This, in turn, is affected by the monomer used forpolymerization, e.g., whether a C3 or a C14 is used, or a mixture of monomers.Furthermore, the extent of partial "chain straighteningâ effected by the?CA 02263959 l999-02- 19W0 93/03517 PCT/US97/12125- 57 -particular catalyst employed (as explained elsewhere), will vary theperformance of the POH copolymer as a wax crystal modifier. Selection ofmonomer, catalyst and polymerization conditions can be made in order tomaximize performance of the resulting POH copolymer in this application.Among other factors affecting pour point and/or CFPP performance,besides the extent of branching, are the apparent ethylene content and thenumber average molecular weight of the copolymer. Since higher copolymermolecular weight generally increases the viscosity of the oil in which it isdissolved, the choice of copolymer molecular weight should be made withconsideration of how it will affect the flow properties of the resultingcomposition. Similarly, higher levels of apparent ethylene sequences resultsin the potential for greater participation in the crystallization process andsolubility in the oil. The extent and nature of branching can serve as a finetuning variable to âbalanceâ the extent of crystallinity of the WCM itself sothat it remains soluble in the oil and still functions to interact with the wax asrequired.Lubricating oil formulations containing the additives of the presentinvention conventionally contain other types of additives that contribute othercharacteristics that are required in the formulation. Typical of such otheradditives are detergent/inhibitors, viscosity modifiers, wear inhibitors,oxidation inhibitors, corrosion inhibitors, friction modifiers, foam inhibitors,rust inhibitors, demulsifiers, lube oil flow improvers, and seal swell controlagents, etc. Some of the additives can provide multiple effects e.g., adispersant oxidation inhibitor. Compositions, when containing theseadditives, typically are blended into the base oil in amounts which areeffective to provide their normal attendant function. Representative effectiveamounts of such additives are illustrated as follows:?CA 02263959 l999-02- 19WO 93/03517 PCT/US97ll2l25- 53 _RanceBroad Preferredcompositions _V_V1_% W1 °@Viscosity Index lmprover 1-12 1-4Corrosion Inhibitor 0.01-3 0.01-1.5Oxidation Inhibitor 0.01 -5 0.01-1.5Dispersant 0.1- 0 0.1-Lube Oil Flow lmprover 0.01-2 0.01-1.5Detergents and Rust 0.01-6 0.01-3InhibitorsPour Point Depressant 0.01-1.5 0.01-1.5Anti-Foaming Agents 0.001-0.1 0.001-0.01Antiwear Agents 0.001 -5 0.001 -1 .5Seal Swellant 0.1-8 0.1-4Friction Modifiers 0.01â3 0.01-1.5Lubricating Base Oil Balance BalanceWhen the copolymers of this invention are employed in lubricating oilsas viscosity index (Vl) improvers or viscosity modifiers their concentration canvary broadly from about 0.001 to 49 wt.%. The proportions giving thepreferred results will vary somewhat according to the nature of the lubricatingoil basestock and the specific purpose for which the lubricant is to serve in aparticular application. When used as lubricating oils for diesel or gasolineengine crankcase lubricants, the copolymer concentrations are within therange of about 0.1 to 15.0 wt.% of the total composition which are amountseffective to provide viscosity modification and/or VI improvement.When other additives are employed, it may be desirable, although notnecessary, to prepare additive concentrates comprising concentrated solutionsor dispersions of the subject additives of this invention (in concentrateamounts hereinabovedescribed), together with one or more of said otheradditives (said concentrate when constituting an additive mixture beingreferred to herein as an additiveâpackage) whereby several additives can beadded simultaneously to the base oil to form the lubricating oil composition.Dissolution of the additive concentrate into the lubricating oil may befacilitated by solvents and by mixing accompanied with mild heating, but thisis not essential. The concentrate or additive-package will typically beformulated to contain the additives in proper amounts to provide the desiredconcentration in the final formulation when the additive-package is combinedwith a predetermined amount of base lubricant. Thus, the subject additives ofthe present invention can be added to small amounts of base oil or othercompatible solvents along with other desirable additives to form additive-?CA 02263959 l999-02- 19WO 98/03617 PCT/US97ll2l25-59-packages containing active ingredients in collective amounts of typically from2.5 to 90%, and preferably from 15 to 75%, and most preferably from 25 to60% by weight additives in the appropriate proportions with the remainderbeing base oil. The final formulations may employ typically 10 wt. % of theadditiveâpackage with the remainder being base oil. (All weight percentsexpressed herein, unless otherwise indicated, are based on active ingredient(A.l.) content of the additive, and/or upon the total weight of any additive-package, or formulation which will be the sum of the A.l. weight of eachadditive plus the weight of total oil or diluent).EXAMELESThe following examples are given as illustrations of the claimed invention. Itshould be understood, however, that the invention is not limited to thespecific details set forth in the examples. All parts and percentages in theexamples are by weight unless otherwise specified.EXAMELE__âl_Ethylene (E), propylene (P) or butene-1 (B) is copolymerized with methylacrylate (MA), tert-butyl acrylate (tBuA) or methyl vinyl ketone (MVK) atambient pressure or elevated pressure, as described below. The catalystsystem is prepared according to the disclosure in J.Am.ChemSoc. 1996, 1 18,267-268 (including supporting information); the catalyst structure is shown inA, below. Comonomer concentration (moles) is varied from 0.5 to 6ØAmbient pressure polymerization: A Schlenk flask containing thecatalyst precursor is cooled to -78 °C, evacuated, and placed under the on-olefin atmosphere (e.g., ethylene, propylene or butene-1). Methylene chlorideand the acrylate are added to the cold flask via syringe. The solution isallowed to warm to room temperature with stirring. Following polymerizationfor the desired reaction time, the reaction mixture is added to approx. 600 mLor methanol to precipitate the polymer. The methanol is decanted and thepolymer is dissolved in approx. 600 mL of Et2O or petroleum ether. Thesolution is filtered through a plug of celite and/or neutral alumina, the solventis removed and the polymer is dried in vacuo for several days. Thecopolymers are isolated as viscous oils.Elevated pressure polymerization: A mechanically stirred, 300mL Parr® reactor is used which is equipped with an electric heating mantle?CA 02263959 l999-02- l9wo 93/03517 PCT/US97/12125-50-controlled by a thermocouple dipping into the reaction mixture. A solution of0.1 mmol of catalyst precursor in methylene chloride, containing thecomonomer (5-50 mL, total volume of the liquid phase: 100 mL), istransferred via cannula to the reactor under a nitrogen atmosphere. Afterrepeatedly flushing with ethylene or propylene, constant pressure is applied bycontinuously feeding the gaseous olefin and the contents of the reactor arevigorously stirred. After polymerization, the gas is vented. Volatiles areremoved from the reaction mixture in vacuo, and the polymer is dried undervacuum overnight. Residual comonomer is removed by precipitating thepolymer from methylene chloride solution with methanol.Catalyst structure A:1â +Me N H?âK O/ Pdg \/ BAâ~NMe IArWhere Ar = 2,6âC6H3-(i-Pr)2 andBAF = B[3,5-C5H3-(CF3)2]4âSeveral polymerization runs are made under the following conditions toprepare the POH copolymers of the present invention:Bug hkmmmm? .B2gmm1 E/ MA Elevated2 E/tBuA Ambient3 P/MA Elevated4 B/MA Ambient5 B/MVK ElevatedThe copolymers are amorphous, terminally unsaturated, highly branchedolefinâacrylate copolymers having a relatively narrow molecular weightdistribution with the acrylate moiety present predominantly at the end of thebranches.?W0 98/03617CA 02263959 l999-02- l9PCT/US97/12125_ 51 _ I I I . I I . I I . . I I . I I.200 gms of the modified polymer of Example 1/Run 4 are placed in asuitable glass reactor equipped with adequate stirring. The reactor is purgedwith nitrogen for 30 minutes and the contents are heated to about 100°C.About 350 gms of polyisobutenyl succinic anhydride having an ASTM, Dâ64Sap. No. 1 12 which are diluted with 350 gms of solvent 100N diluent oil areadded to the polymer with stirring and the temperature is raised to about190°C. The reaction mixture is held at that temperature with nitrogenstripping for 3 hours, followed by cooling. The resulting product is a viscousliquid substantially free of gel.Example;The copolymer of Example 1/Run 4 is aminated with a polypropylenetetraamine with one end substituted with a tallow group with approximately oneprimary amine per molecule and a nitrogen content of 12.4%. The reagents aremixed at room temperature and heated to 200°C for 7 hrs. while nitrogenstripping. The reaction mixture shows conversion to the corresponding amide.About 150 g of the amide is diluted in 99 g of S150N mineral oil and heated to145°C. and 9.35 g of a 30% boric acid slurry in oil is added over one hour. Afteraddition is complete, the temperature is raised to 150°C and the reaction mixtureis nitrogen stripped for one hour. The corresponding borated, aminateddispersant derivative is produced.E2sampJe_4_The copolymer of Example 1/Run 4 is aminated with a polypropylene etherpentamine with only one end substituted with a dodecyl alkyl group withapproximately one primary amine group per molecule and a nitrogen content of12.92%. The reagents are mixed at room temperature and heated to 220°C for 4hrs. The product is stripped with nitrogen for 3 hrs. at 220°C resulting in an amidederivative. About 1,540 g of the amide are diluted with 810 g of S150N and theoil solution borated at 145°C with 105 g of a 30% boric acid slurry as previouslydescribed. A borated, aminated dispersant derivative is produced.Exa.mnle_5The POH copolymer of Example 1/Run 1 is aminated with 2-ethylhexylaminopropylaminopropylaminopropylamine with approximately one?CA 02263959 l999-02- l9wo 93/03517 PCT/US97/12125-62-primary amino group per molecule and a nitrogen content of 18.24% by heating to200°C. The reaction mixture is vacuum heated (10-20 mm Hg) for several hoursuntil the reaction shows conversion to the amide and the amide is nitrogenstripped. The product is diluted in mineral oil to make a 50% solution and boratedusing the process described in the preceding examples to yield a borated,aminated dispersant derivative.Examnle_6235 g of the POH copolymer of Example 1/Run 4 is heated to 180°C and23 g of dimethylaminopropylaminopropylamine (DMAPAPA) having approximatelyone primary amine group per molecule and a nitrogen content of 25.4% is added.The reaction mixture is heated at 180°C for several hours to convert thecopolymer to the corresponding amide and the product is nitrogen stripped at 180°C for 4 hrs. to distill off the unreacted amine.xa 7 .Polymerization according to Example 1/Run 4 is carried out except that acontinuous process is used with an olefinic feed obtained from a refinery Raf?nate2 source in combination with methyl acrylate polar comonomer andpolymerization conditions are controlled to produce a polar olefinic hydrocarboncopolymer useful as a dispersant backbone, with a Mn of about 1,000.Various aspects of the invention and their relationship to one anothercan be represented as follows:1. Hydrocarbon copolymer derived from at least one polymerizable"polar monomer and at least one polymerizable olefinic monomer, saidcopolymer suitable for use as a fuel or lubricant additive, said copolymerhaving the following characteristics:la) an average ethylene sequence length, ESL, of from about1.0 to less than about 3.0;(b) an average of at least 5 branches per 100 carbon atoms ofthe copolymer chains comprising said copolymer;(c) at least about 50% of said branches being methyl and/orethyl branches;ld) substantially all of said incorporated polar monomer ispresent at the terminal position of said branches;?CA 02263959 l999-02- 19W0 93/03517 PCT IUS97Il2l25-53-(e) at least about 30% of said copolymer chains terminatedwith a vinyl or vinylene group;(f) a number average molecular weight, Mn, of from about300 to about 10,000; and(g) substantial solubility in hydrocarbon and/or synthetic baseoil.2. The copolymer of aspect 1 wherein said ESL is from about 1.0 toabout 1.5.3. The copolymer of aspect 2 having an average of from about 10to about 12.5 branches per 100 carbon atoms of said copolymer chains.4. The copolymer of aspect 3 wherein at least about 95% of saidbranches are methyl and/or ethyl branches.5. The copolymer of aspect 4 wherein at least about 95% of saidcopolymer chains are terminated with a vinyl or vinylene group.6. The copolymer of aspect 5 having a number average molecularweight, Mn, of from about 700 to about 2,500.7. The copolymer of aspect 1 wherein the incorporated polar moietyderived from said polymerizable polar monomer which is incorporated in saidcopolymer is present at an average concentration of from about one polarmoiety for each 5,000 Mn segment of polymer backbone, including branches,to about one polar moiety for each 1,000 Mn segment.8. The copolymer of aspect 7 wherein said polar monomer isselected from the group consisting of methyl acrylate, ethyl acrylate, tert-butyl acrylate, methyl methacrylate, methyl ethacrylate, ethyl methacrylate,ethyl ethacrylate and methyl vinyl ketone.9. The copolymer of aspect 8 wherein said olefinic monomer isselected from the group consisting of ethylene, propylene and butene-1.?CA 02263959 l999-02- 19W0 93/03517 PCTIUS97ll2125-54-10. A composition of matter suitable for use as a fuel or lubricantadditive consisting essentially of hydrocarbon copolymer derived from at leastone polymerizable polar monomer and at least one polymerizable olefinicmonomer; said copolymer having at least two nitrogen atoms incorporatedtherein; said polar monomer selected from (1., [3 unsaturated carbonylcompounds represented by the formula:CH2 = C - COXlRxwherein X is hydrogen (H), NH2, RV or ORV ; R, is H or a C1-C5 straight orbranched alkyl group and Ry is H or a C1 to C20 straight or branched alkylgroup; for short chain unsaturated ester monomers, Ry is preferably a C1-C5alkyl group and for long chain monomers, preferably a C10 to C18 alkyl group;said olefinic monomer selected from the group consisting of ethylene, C3 - C20on-olefins and a mixture of C3 - C20 or-olefins; said copolymer having thefollowing characteristics:(a) an average ethylene sequence length, ESL, of from about1.0 to less than about 3.0;(b) an average of at least 5 branches per 100 carbon atoms ofthe copolymer chains comprising said copolymer;(c) at least about 50% of said branches being methyl and/orethyl branches;(d) substantially all of said incorporated polar monomer ispresent at the terminal position of said branches;(e) at least about 30% of said copolymer chains terminatedwith a vinyl or vinylene group;(f) a number average molecular weight, Mn, of from about300 to about 10,000; and(g) substantial solubility in hydrocarbon and/or synthetic baseoil.1 1. The composition of matter of aspect 10 wherein the incorporatedpolar moiety derived from said polymerizable polar monomer which isincorporated in said copolymer is present at an average concentration of fromabout one polar moiety for each 5,000 Mn segment of polymer backbone,including branches, to about one polar moiety for each 1,000 Mn segment.?CA 02263959 l999-02- 19W0 98/03617 PCT/US97/12125-65-12. The composition of matter of aspect 1 1 wherein said polarmonomer is selected from the group consisting of methyl acrylate, ethylacrylate, tert-butyl acrylate, methyl methacrylate, methyl ethacrylate, ethylmethacrylate, ethyl ethacrylate, methyl vinyl ketone and acrylamide.13. The composition of matter of aspect 12 wherein said olefinicmonomer is selected from the group consisting of ethylene, propylene andbutene-1 .14. The composition of matter of aspect 10 wherein said mixture ofC3 â C20 on-olefins is selected from the group consisting of C3, C4, and C5refinery or steam cracker feedstreams and raffinate derivatives thereof.15. The composition according to aspect 10 wherein saidpolymerizable olefinic monomer is ethylene, said branches in said copolymer,element (b), are present at an average of from about 5 to about 33 branchesper 100 carbon atoms and said terminal groups of (d) are vinyl and said polarmonomer is an alkyl acrylate.15. A process for continuously producing hydrocarbon copolymerderived from at least one polymerizable polar monomer and at least onepolymerizable olefinic monomer; said copolymer suitable for use as a fuel orlubricant additive; said copolymer having the following characteristics:(a) an average ethylene sequence length, ESL, of from about1.0 to less than about 3.0;(b) an average of at least 5 branches per 100 carbon atoms ofthe copolymer chains comprising said copolymer;(c) at least about 50% of said branches being methyl and/orethyl branches;id) substantially all of said incorporated polar monomer ispresent at the terminal position of said branches;(e) at least about 30% of said copolymer chains terminatedwith a vinyl or vinylene group;(f) a number average molecular weight, Mn, of from about300 to about 10,000; and(g) substantial solubility in hydrocarbon and/or synthetic baseoil;?CA 02263959 l999-02- 19W0 98/03617 PCT/US97ll2125-36-said copolymer derived from at least one polymerizable polar monomerselected from 0(., B unsaturated carbonyl compounds represented by theformula:CH2 = C - COXIRxwherein X is hydrogen (H), NH2, Ry or ORV ; R, is H or a C1-C5 straight orbranched alkyl group and Ry is H or a C1 to C20 straight or branched alkylgroup; for short chain unsaturated ester monomers, Ry is preferably a C1-C5alkyl group and for long chain monomers, preferably a C10 to C13 alkyl group;and at least one polymerizable olefinic monomer selected from the groupconsisting of ethylene, C3 - C20 on-olefins and a mixture of C3 â C20 on-olefins;said monomers polymerized in the presence of a late-transition-metal catalystsystem in a reaction zone containing liquid phase, said process furthercomprising:(A) feeding to said reaction zone a feedstream comprising saidpolar monomer, either alone or in the presence of said olefinic monomer;(B) when at least one on-olefin monomer is selected,continuously providing said on-olefin as a dilute, liquefied oi-olefin feed streamfrom a refinery or steam cracker, said feed stream containing diluent admixedtherewith wherein the amount of diluent in said feed stream is at least 30weight percent thereof;(C) when ethylene is selected, continuously providing a feedstream comprising ethylene in liquid, vapor, or liquid/vapor form;(D) when a mixture of ethylene and an aâolefin is selected,admixing the feed streams of steps (B) and (C) to provide a reactant feedstream having an oc-olefin/ethylene weight ratio effective to yield a copolymercontaining an average ethylene sequence length, ESL, of from about 1.0 toless than about 3.0;(E) continuously introducing said feed streams derived inaccordance with steps (A), (B), (C) or (D) and late-transition-metal catalystsystem into the liquid phase of the reaction zone in a manner and underconditions sufficient to:(i) polymerize the ethylene and/or on-olefin to copolymerproduct having a number average molecular weight of notgreater than 10,000;?CA 02263959 1999-02-19wo 98/03617 PCTIUS97/12125_ 57 _(ii) obtain an or-olefin conversion, when an ocâolefin isused as a monomer, of at least 30%;(iii) obtain an ethylene conversion, where ethylene isused as a monomer, of at least 70%(F) continuously withdrawing said copolymer from the reactor.17. The process of aspect 16 wherein said olefinic monomer isselected from olefinâcontaining refinery or steam cracker feedstreams.18. The process of aspect 17 wherein said feedstream is selectedfrom the group consisting of Raffinate-2, and C3, C4 or C5 sources andmixtures thereof.19. The process of aspect 16 wherein at least 50 weight °/o of theconstituents of said diluent possess a boiling point under reaction conditionswithin i20°C of the average boiling point of the or-olefin constituents of thefeed stream.20. The process of aspect 16 or aspect 19 wherein the contents ofthe reaction zone are maintained at a temperature above the criticaltemperature of ethylene and below the critical temperature of said or-olefin, asappropriate, when ethylene and/or at least one or-olefin is present.21. The process of any of aspects 16 to 20 wherein said or-olefinmonomer comprises at least one monomer selected from the group consistingof buteneâ1 , propylene, and penteneâ1 and said diluent comprisesâsubstantially nonpolymerizable C3, C4, C5 hydrocarbons and mixtures thereof,other than said or-olefin monomer.22. The process of any of aspects 16 to 21 wherein thepolymerization reaction temperature is controlled by evaporative coolingmeans.23. The process of aspect 22 wherein in step (E) continuously thevapor above "the liquid phase is at least partially condensed and thecondensate is returned to said liquid phase.?CA 02263959 l999-02- l9wo 93/03617 PCT/US97/12125-53-24. The process of aspect 16 wherein said dilute liquefied oi-olefinfeed stream is derived from a refinery or steam cracker stream comprising atleast one or-olefin from which dienes, but not polar compounds, aresubstantially removed prior to introduction of said feed stream into saidreactor.25. A dispersant comprising a functionalized hydrocarbon copolymerderived from the copolymer of aspects 1 or 10 by reacting said copolymerwith a polyamine having one primary amino group and 1 to 10 secondary ortertiary amino groups.26. The dispersant of aspect 25 wherein said copolymer from whichit is derived initially contains an average of from about 1 to about 6 polargroups per copolymer chain.27. The gel-free composition of aspect 25 wherein the reaction toproduce said derivatized copolymer is conducted in the presence of a chain-stopping or endâcapping co-reactant.28. The composition of aspect 27 wherein said chainâstopping orendâcapping co-reactant comprises C12âC4oo hydrocarbyl substituted succinicacid or anhydride; long chain monocarboxylic acid of the formula RaCOOHwherein Ra is C12-C490 hydrocarbyl; an amine containing only a single reactiveamino group per molecule; an alcohol having only a single reactive hydroxygroup per molecule; or mixtures thereof.29. The composition of aspect 28 wherein said copolymer fromwhich it is derived initially contains an average of from about 1 to about 2polar groups per copolymer chain.30. The reaction product of the copolymer of aspect 1 with anenophile.31. The product of aspect 30 wherein said enophile is maleicanhyd?de.?CA 02263959 l999-02- 19W0 98/03617 PCT/US97/12125_ 59 -32. The reaction product of aspect 31 further reacted with a memberselected from the group consisting of amines and alcohols.33. The reaction product of aspect 30 wherein said reaction isinitiated using one or more free radical generating compound and wherein saidreaction product contains an average of at least 2 of said copolymer chainslinked to said enophile.34. The reaction product of aspect 33 further reacted with polyamineand monofunctional chain stopping agent.35. The functionalized copolymer of aspect 1, wherein the copolymeris further functionalized with at least one member selected from the groupconsisting of C3 to C10 mono-unsaturated monocarboxylic acid producingmoieties and C4 to C10 mono-unsaturated dicarboxylic acid producingmoieties.36. A functionalized copolymer comprising an oxidized copolymer,wherein said oxidized copolymer is the reaction product of the copolymer ofaspect 1 or aspect 6 and a gas selected from the group consisting of anoxygenâcontaining gas, an ozone-containing gas and mixtures thereof.37. A derivatized copolymer useful as a lubricating oil dispersantadditive, which comprises the reaction product of the functionalizedcopolymer of any of aspects 30 to 36 and a derivatizing compound.38. The derivatized copolymer of aspect 37 in which thefunctionalized copolymer is reacted with at least one nucleophilic reagentselected from amines, alcohols, metal reactants, and mixtures thereof.39. The reaction product of aspect 30 in which the functionalizedcopolymer is further reacted with a heavy polyamine.40. A derivatized copolymer comprising the reaction product of:(a) at least one alkyl-substituted hydroxyaromatic compoundformed by the alkylation of at least one hydroxy aromaticcompound with the copolymer as in aspect 1;?CA 02263959 l999-02- 19W0 93/03517 PCT/US97l12l25-70-(b) at least one aldehyde reactant; and(c) at least one nucleophilic reactant.41. The reaction product of the copolymer of aspect 1 furtherreacted with a phenol in the presence of an acid catalyst.42. The reaction product of aspect 41 further reacted with a memberselected from the group consisting of aldehyde and polyamine.43. The reaction product of aspect 42 in which said polyamine is aheavy polyamine.44. A lubricating oil composition comprising a major amount ofbasestock lubricating oil of lubricating viscosity, and an effective amount of aviscosity modifier comprising hydrocarbon copolymer derived from at leastone polymerizable polar monomer and at least one polymerizable olefinicmonomer, said copolymer suitable for use as a fuel or lubricant additive, saidcopolymer having the following characteristics:(a) an average ethylene sequence length, ESL, of from about1.0 to less than about 3.0;(b) an average of at least 5 branches per 100 carbon atoms ofthe copolymer chains comprising said copolymer;(c) at least about 50% of said branches being methyl and/orethyl branches;id) substantially all of said incorporated polar monomer ispresent at the terminal position of said branches;(e) at least about 30% of said copolymer chains terminatedwith a vinyl or vinylene group;(f) a number average molecular weight, Mn, of from about15,000 to about 500,000; and(9) substantial solubility in hydrocarbon and/or synthetic baseoil.45. A lubricating oil composition comprising a major amount of alubricating base oil, lubricating oil flow improver, and a minor amount of oilsoluble copolymer as in aspect 44.?CA 02263959 l999-02- 19W0 98/03617 PCT/US97Il2125- 71 -46. The lubricating oil composition of aspect 45, containing from0.01 to 5 weight percent of said lubricating oil flow improver and from 0.1 to20 weight percent of the said copolymer, based on the total weight of thecomposition.47. An oil additive concentrate composition comprising hydrocarbonmineral oil diluent and about 2 to 50 wt.% based on the total amount ofhydrocarbon mineral oil diluent of hydrocarbon copolymer derived from atleast one polymerizable polar monomer and at least one polymerizable olefinicmonomer, said copolymer suitable for use as a fuel or lubricant additive, saidcopolymer having the following characteristics:(a) an average ethylene sequence length, ESL, of from about1.0 to less than about 3.0;(b) an average of at least 5 branches per 100 carbon atoms ofthe copolymer chains comprising said copolymer;(c) at least about 50% of said branches being methyl and/orethyl branches;(d) substantially all of said incorporated polar monomer ispresent at the terminal position of said branches;(e) at least about 30% of said copolymer chains terminatedwith a vinyl or vinylene group; and(f) substantial solubility in hydrocarbon and/or synthetic baseoil.48. The oil additive concentrate according to aspect 47, wherein saidcopolymer has a number average molecular weight, Mn, of from about 300 toabout 10,000.49. The oil additive concentrate according to aspect 47, wherein saidcopolymer has a number average molecular weight of from about 1 1,000 toabout 500,000.50. An oil additive concentrate composition comprising hydrocarbonmineral oil diluent and about 2 to 50 wt.% based on the total amount ofhydrocarbon mineral oil diluent of a derivatized copolymer useful as alubricating oil dispersant additive, which derivatized copolymer comprises thereaction product of the functionalized copolymer of any of aspects 30 to 36.?CA 02263959 1999-02-19W0 98/03617 PCT/US97/12125-72-51. A lubricating oil composition comprising base oil and, as adispersant additive, a functionalized or derivatized copolymer as in any ofaspects 30 to 40, in the form of either:(a) a concentrate containing from 1 1 to 80 weight percent ofsaid dispersant additive; or(b) a composition containing from 0.1 to 10 weight percent ofsaid dispersant additive.52. A fuel oil composition comprising base oil and, as a dispersantadditive, a functionalized or derivatized copolymer as in any of aspects 30 to40, in the form of either:(a) a concentrate containing from 1 1 to 80 weight percent ofsaid dispersant additive; or(b) a composition containing from 0.001 to 0.1 weightpercent of said dispersant additive.53. A process for continuously producing hydrocarbon copolymersuitable for use as a fuel or lubricant additive, said copolymer derived from atleast one polymerizable polar monomer selected from on, B unsaturatedcarbonyl compounds represented by the formula:CH2 = C - COXlRxwherein X is hydrogen (H), NH2, Ry or ORV ; R, is H or a C1-C5 straight orbranched alkyl group and RV is H or a C1 to C20 straight or branched alkylgroup; for short chain unsaturated ester monomers, Ry is preferably a C1-C5alkyl group and for long chain monomers, preferably a C10 to C13 alkyl group;and at least one polymerizable olefinic monomer selected from the groupconsisting of ethylene, C3 - C20 on-olefins and a mixture of C3 - C20 on-olefinsand polymerized in the presence of a late-transition-metal catalyst system in areaction zone containing liquid phase, said process further comprising:(A) when at least one on-olefin monomer is selected,continuously providing said aâolefin as a dilute, liquefied oLâolefin feed streamfrom a refinery or steam cracker, said feed stream comprising diluent admixedtherewith wherein the amount of diluent in said feed stream is at least 30weight percent thereof;?CA 02263959 l999-02- 19W0 98,036â PCT/US97l12l25-73-(B) when ethylene is selected, continuously providing a feedstream comprising ethylene in liquid, vapor, or liquid/vapor form;(C) when a mixture of ethylene and an on-olefin is selected,admixing the feed streams of steps (A) and (B) to provide a reactant feedstream having an on-olefin/ethylene weight ratio effective to yield a copolymercontaining an average ethylene sequence length, ESL, of from about 1.0 toless than about 3.0;(D) continuously introducing said feed stream or said reactantfeed stream derived in accordance with steps (A), (B) or (C) as well as a feedstream of said polar monomer, and a late-transition-metal catalyst system intothe liquid phase of the reaction zone in a manner and under conditionssufficient to:(i) polymerize the ethylene and/or ocâo|efin to copolymerproduct having a number average molecular weightsuitable for use as a fuel or lubricant additive;(ii) obtain an on-olefin conversion, when an on-olefin isused as a monomer, of at least 30%;(iii) obtain an ethylene conversion, where ethylene isused as a monomer, of at least 70%(E) continuously withdrawing said copolymer from the reactor.
