WO1997018281A1 - Carbonyl containing compound derivatives as multi-functional fuel and lube additives - Google Patents

Abstract

The present invention relates to dispersants for lubricating oils comprising the reaction product of a functionalized polymer and a polyamine metaborate. The functionalized polymer is prepared using reactions selected from the group consisting of halogen assisted, thermal ene, free radical grafting using a catalyst, phenol alkylation and carbonylation via Koch. Polyamine metaborate is the reaction product of a polyamine and boric acid.

Description

CARBONYL CONTAINING COMPOUND DERIVATIVES AS MULTI-FUNCTIONAL FUEL AND LUBE ADDITIVES

FIELD OF THE INVENTION This invention relates to carbonyl containing compound derivatives as additives useful in oleaginous compositions such as fuels, lubricants, power transmission fluids, and the like.

BACKGROUND OF THE INVENTION

Oleaginous substances have found wide industrial use Unfortunately, many oleaginous compositions contain additives which contain chlorine which is environmentally undesirable Also, many of today's high performance applications for oleaginous compositions require multifunctional additives.

Organic compounds containing two or more carbonyl groups in a row are generally referred to as vicinal polycarbonyl (VP) monomers The reactions of VP monomers with unsaturated hydrocarbons, including unsaturated hydrocarbon polymers, will produce carbonyl containing adducts as disclosed in US-A-5057564 and USSN 935604 These adducts are referred to herein as ene adducts More recently, various hydrocarbons, and especially saturated hydrocarbons, and saturated hydrocarbon polymers, have been found to react with VP monomers in the presence of a free radical initiator These compounds are disclosed, for example, in US-A- 5288811 and 5274051, and are referred to herein as radical adducts

Related case USSN 242,750 discloses a product formed by reacting (a) an adduct of a hydrocarbon and a vicinal polycarbonyl compound, the adduct having a value of n greater than 1, wherein n is the average number of vicinal polycarbonyl compounds incorporated per adduct chain, with (b) a reagent selected from the group consisting of nucleophiles, electrophiles, metal salts and metal complexes

The present invention provides improved oleaginous compositions such as fuels, lube oils, and the like, by incorporating into these compositions additives prepared from the reaction product of a functionalized polymer and a polyamine metaborate (herein referred to as PMB) These products have multifunctional properties. SUMMARY OF THE INVENTION

USSN-242,750 relates to an adduct of a hydrocarbon and a vicinal polycarbonyl compound, the adduct having a value of n greater than 1, wherein n is the average number of vicinal polycarbonyl compounds incoφorated per adduct chain. The hydrocarbon is typically a saturated or unsaturated hydrocarbon or hydrocarbon polymer with an Mn value ranging from about 200 to about 10 million The hydrocarbon optionally contains polar substituents. The VP compound (alternatively referred to herein as "VP monomer") is cyclic or acyclic. The adduct is an ene adduct or a radical adduct. The adduct can be further reacted with a reagent to obtain a product, wherein the reagent is selected from the group consisting of nucleophiles, electrophiles, metal salts and metal complexes. The reagent can be selected from (i) nucleophiles selected from the group consisting of amines, hydrazines, hydrazine derivatives, alcohols. water, polyamines. polyols, amino alcohols, amino thiols- (ii) electrophiles selected from the group consisting of carboxy anhydrides, carboxy esters, borate esters, phosphate and phosphate esters; (iii) metal salts containing metal ions selected from the group consisting of alkali metals, alkaline earth metals, and transition metals and (iv) metal complexes containing metal ions selected from the group consisting of alkali metals, alkaline earth metals, and transition metals. The product obtained from the above-described adduct can be post-treated with an electrophilic reagent such as a borating, acylating or thio acid reagent or a metal ion, to obtain a post-product.

The present invention relates to functionalized polymers, wherein a post product is prepared by derivatizing said functionalized polymer with a polyamine metaborate. It has been surprisingly found that this process, hereinafter referred to as Bor-Amination, provides the following advantages. Conventional derivatization (e.g. amination) and post treatment (e.g. boration) requires two steps. The present invention requires only one step. The final product of the present invention contains less sediment than the product from separate amination and boration steps. This is believed to be due to a more complete reaction between the polyamine and boric acid than between the conventional functionalized polymer-polyamine adduct which is post treated with boric acid in a separate step.

Another advantage of preparing the PMB is that the reaction between the polyamine and boric acid can occur at ambient temperatures (e.g. 20 to 30°C), although it is preferable to heat the mixture to 80 to 130°C to complete the reaction. The present invention further relates to oleaginous compositions comprising a major amount of an oleaginous substance selected from fuels and oils and a minor amount ofthe post-product.

GENERAL DESCRIPTION

The present invention relates to lubricating oil compositions comprising a lubricating oil and a dispersant .wherein said dispersant comprises the reaction product of a functionalized polymer and a polyamine metaborate. The dispersant is prepared from a polymer functionalized using a reaction selected from the group consisting of halogen assisted, thermal ene, free radical grafting using a catalyst, phenol alkylation and carbonylation via Koch. The dispersant can be derived from polymer functionalized by groups ofthe formula -CO-Y-R³, wherein Y is O or S, and either R³ is H, hydrocarbyl, aryl, substituted aryl and at least 50 mole % of the functionalized groups are attached to a tertiary carbon atom of the copolymer. The functionalized polymer is derived from polymers selected from the group consisting of poly-n-butene, polyisobutylene, and ethylene alpha olefin copolymers. The alpha olefin comprises butene. The polymer number average molecular weight is about 500 to about 20,000. The polymers can be functionalized with a carboxylic acid moiety including maleic anhydride. The polyamine metaborate is prepared by a process comprising, heating a mixture of polyamine and boric acid comprising about three moles of boric acid per each amino group of the polyamine for a time and a temperature sufficient to form a clear liquid. The preferred polyamine is heavy polyamine.

The present invention even further relates to a process for preparing a low sediment dispersant prepared by reacting a functionalized polymer with a polyamine metaborate, wherein the polyamine metaborate is prepared by reacting polyamine and boric acid at a temperature of from about 80°C to about 130°C for from about a half hour to about 120 hours. The polyamine and boric acid can also be mixed at ambient temperature (e.g. 20 to 30°C) and if necessary heated to higher temperatures (e.g. 80 to 130°C) to complete the reaction. Carbonyl containing compounds include consisting of (a) ene and radical adducts having one or more VP monomers per adduct, (b) products derived from said ene and radical adducts, and (c) post-products derived from said products, which are useful in oleaginous compositions, especially as multifunctional additives, dispersants, and dispersant viscosity modifiers. The adducts are prepared via the ene and radical addition of VP monomers to unsaturated and saturated hydrocarbons and polymers respectively, with Mn values ranging from about 200 to about 10 million. The hydrocarbon and polymer reactants may contain one or more polar substituents, provided that the polar substituents are compatible with the ene and radical chemistry involved in the functionalization with VP monomers. The adducts can be further reacted with a variety of nucleophiles, electrophiles, and metal ions to form products which in turn can be reacted with borating reagents, thio acids, and metal ions to form post-products Oleaginous compositions containing the adduces, produces, and post- products are encompassed within this invention. Oleaginous substances include fuels, oils, and other lubricants such as greases.

Unsaturated Substrates In general, the olefinic hydrocarbons and polymers with which VP monomers can be reacted are well known in the art. These oil soluble olefinic compounds comprise substantially saturated hydrocarbon backbones, yet they have a minor amount of ethylenic unsaturation which is available for adduct formation by means of the thermal ene addition process. Olefins which form useful ene adducts with VP monomers will typically be long chain, straight, and/or branched alkenes consisting of about 10 or more carbon atoms suitable so as to provide oil solubility. Useful alkenes include C12 to C30 olefins, such as dodecene-1, 2-propylnonene-l, 2-hexyloctene-l, pentadecene-1, octadecene-1, octadecene-9, docosene-1, and pentatriacontene-17 and diolefins such as hexadecadiene- 1, 1 5, eicosadiene- 1, 19, 2, 19-dimethyl-eicosadiene- 1, 19, and octahydrosqualene. Oligomers of C3, to Cj2 olefins, preferably of C3 to Cg olefins, both alpha-olefins and internal olefins are also useful. These preferably include from 2 to 8 repeating units, as typified by pentaisobutylene and octapropylene, and trimers of alpha-olefins such as 1-decene. Other useful unsaturated substrates can incorporate one or more polar groups

In this instance, the optimal number and type of polar groups attached to the alkene depends upon the oil solubility of the adducts with VP monomers, as well as their effectiveness as additives. Useful olefins containing one or more polar groups include unsaturated alcohols such as 7-dodecen-l-ol, oleyl alcohol and cholesterol; ethers; carboxylic acids, esters and amides such as undecenylic acid, 2-dodecenyl succinic acid. N-methyl-2-dodecenyl-succinimide, and N-ethyl-2-octadecenylsuccinimide, sulfides, sulfur oxygen and phosphorus compounds, alkene-substituted aromatics, and hetero aromatics.

An especially useful group of unsaturated reagents amenable to the ene process of the present invention is cited in "McCutcheon's Emuisifiers and Detergents", 1986 North American Edition, McCutcheon Division, MC Publishing Co., Glen Rock, New Jersey. A variety of unsaturated anionic, nonionic, cationic, and amphotheric emulsifiers and detergents having a range of HLB values from 0 8 to about 42.0 can be functionalized with the ene reactive VP monomers of the present invention to produce useful additives for fuels and lubes

Oil soluble olefinic polymers which form useful ene adducts will generally have a number average molecular weight Mn) of about 500 to about 20K when the ene adducts are used for dispersant and detergent applications, and from about 10K to about one million, and most generally from about 20K to about 200K for dispersant- viscosity improver applications. Preferred V.I. improver polymers will generally have a narrow range of molecular weight, as determined by the ratio of weight average molecular weight (Mw) to number average molecular weight (Mn) Polymers having a Mw/Mn of less than about 10, for example from about 1 to about 4 are most desirable

The olefinic polymers useful in this invention may be essentially amorphous in character, including those with up to about 25 percent by weight of crystalline segments as determined by x-ray or differential scanning calorimetry. Additionally, the polymers may be of any of the tapered or block copolymers known in the prior art or the copolymers of alpha-olefins comprised of chains of intra-molecularly heterogenous and inter-molecularly homogenous monomer units, such as those prepared by the process of US-A-4540753.

Suitable hydrocarbon polymers include homopolymers and copolymers of one or more monomers of C2 to C30, e.g., C2 to Cg olefins, including both alphaolefins and internal olefins, which may be straight or branched, aliphatic, aromatic, alkylaromatic, and cycloaliphatic. In one preferred embodiment, these will be polymers of ethylene with C3 to C30 olefins, preferably copolymers of ethylene and propylene, and more preferably, copolymers of ethylene and butene Examples of polymers of other olefins include polymers of ethylene or polymers of propylene which contain nonconjugated diolefins, such as 1,4-hexadiene. Also included are polymers of butene, isobutylene, polymers and copolymers of C and higher alphaolefins, particularly useful examples being polybutenes, polyisobutylenes, copolymers of propylene and isobutylene. copolymers of isobutylene and butadiene, and the like. Other suitable hydrocarbon polymers containing, olefinic unsaturation well known in the art include hydrogenated or partially hydrogenated homopolymers, and random, tapered or block polymers (copolymers including teφolymers and tetrapolymers) of conjugated dienes and or monovinyl aromatic compounds with, optionally, alpha-olefins or lower alkenes e.g., C3 to Cig alpha-olefins or lower alkenes. The conjugated dienes include isoprene, butadiene, 2,3-dimethylbutadiene, piperylene and/or mixtures thereof The monovinyl aromatic compounds are preferably monovinyl monoaromatic compounds, such as styrene or alkylated styrenes substituted at the alpha-carbon atoms of the styrene, such as alphamethylstyrene, or at ring carbons, such as methylstyrene, ethylstyrene, propylstyrene, isopropyl-styrene, butyl- styrene, isobutylstyrene, and tert-butylstyrene.

The present invention also includes star polymers as disclosed in patents such as US-A-371 1406, 4108945, 41 16917, 5049294 and 5070131.

The term copolymer as used herein, unless otherwise indicated, is thus meant to include teφolymers, and tetrapolymers of ethylene, C3 to C2 alphaolefins, non- conjugated diolefins, and mixtures of such diolefϊns, and of isobutylene with C4 to C _j g non-conjugated diolefins, and mixtures of such diolefins. The amount of non- conjugated diolefin will generally range from about 0.5 to 20 wt percent, and preferably from about 1 to about 10 wt percent, based on the total amount of ethylene and alpha-olefin present.

Representative examples of non-conjugated dienes that may be used in forming adducts targeted for use as dispersant viscosity modifiers (VM's), include acyclic dienes such as 1,4-hexadiene; alicyclic dienes such as 1 ,4-cyclo-hexadiene, 4- vinylcyclohexene and 4-aIlylcyclohexene, and alicyclic fused and bridged ring dienes such as tetrahydroindene, dicyclo-pentadiene, bicyclo[2.2. l]hepta-2,5-diene, 5- methylene-6-methyl-2-norbornene, 5-propenyl-2-norbornene, 5-( 1 -cyclopentenyl)-2- norbornene, and most preferably, 5-ethylidene-2-norbornene. Polymers derived from butadiene and isoprene, such as polybutadiene and polyisoprene, having Mn ranging from about 50K to about 10 million, including natural rubber, are also useful.

Ene Adduct Formation The ene adducts can be prepared by various processes in which the unsaturated hydrocarbon or polymer and the VP monomers are intimately intermixed and reacted at a temperature at which thermal ene addition occurs without appreciable decomposition. Generally, reaction temperatures within the range of from about 20°C to about 200°C are useful. The reaction temperature will vary depending upon the particular unsaturated hydrocarbon or polymer and VP monomer that are employed. Effective mixing of the olefinic polymer and the VP monomer can be achieved by combining these reactants together with a solvent or neat.

The ene adducts can be prepared in solution, in which case the unsaturated hydrocarbon or polymer substrate is dissolved in a solvent such as toluene, xylene, synthetic oil, mineral oil or other suitable solvents, and mixtures thereof and the VP monomer is added as is, or as a solution, to the dissolved hydrocarbon The mixture can then be reacted at temperatures of about 50°C to about 200°C for several hours (reaction is monitored by IR analysis) in the substantial absence of air, preferably under a blanket of inert gas, such as nitrogen until ene adduction is complete Optionally, a trace of an antioxidant such as BHT (butylated hydroxy toluene) can be used.

Typically, the ene adducts are separated from the reaction mixture by stripping off the solvent, and further diluted with appropriate lubricating oil packages for desired intermediate or end use purposes. Ene and radical adducts formed in mineral or synthetic oils can be used directly in product forming reactions, or a specific ene use.

The proportions of the reactants vary according to the particular olefinic hydrocarbon employed, but normally will range between about 0.01 and 3, and preferably between about 0.1 and 2 moles of the VP monomer per mole of ethylenic unsaturation in the polymer. The degree of ethylenic unsaturation of the polymer is measured by several methods which are known to those of ordinary skill in this art, including nuclear magnetic resonance (NMR), calibrated infrared spectroscopy, refractive index comparisons (particularly for ethylene-propylene-norbornene teφolymers), and calibrated iodine titration measurements.

The polyfunctional adducts with n ranging from about 1.1 to about 1.8 (average number of functional groups per chain) prepared from mono-unsaturated polymers afford highly useful additives and additive precursors, owing to their outstanding V.I. properties. Usually, n will be dictated by the number of C=C bonds present in the unsaturated reactant and the reactant ratio. Thus, a high VP monomer/olefin ratio usually affords high n values owing to multiple ene reactions on each reactive olefinic site. With terpolymers containing about 20-40 olefinic sites, n values of about 20-40 or greater can be obtained.

When the mixture of hydrocarbon and VP monomer has sufficiently iow melt viscosity for effective mixing, they may be reacted without a solvent in a stirred mixer or in a masticator. In a typical stirred mixer experiment, a neat polyolefin such as ethylene butene- 1 copolymer (Mn of approximately 2K, and about 55 wt% ethylene) and an equimolar amount of VP monomer, such as IT or AX, are combined in a nitrogen-purged reactor and stirred at about 160°C for about 6 hours, or until infrared analysis indicates complete reaction. Ene adduct formation is usually quick and quantitative, and multiple ene adductions can be achieved by using an excess ofthe VP monomer.

Useful free radical initiators, I, essential to the formation of the radical adducts of this invention include dialkyl peroxides such as di-teitiary-butyl peroxide,2,5- dimethyl-2,5-di-tertiary-butyl-peroxy-hexane, di-cumyl peroxide; alkyl peroxides such as tertiary-butyl hydroperoxide. tertiary-octyl hydroperoxide, cumene hydroperoxide, aroyl peroxides such as benzoyl peroxide; peroxyl esters such as tertiary-butyl peroxypivalate, tertiary-butyl perbenzoate, and azo compounds such as azo-bis- isobutyronitrile. Any free radical initiator with a suitable half life at the reaction temperatures between about 80°C and 200°C can be used, as well as ionizing radiation The radical-initiated reaction of VP monomers can be applied to a wide spectrum of hydrocarbons (R_ZH) selected from the group consisting of (a) normal alkanes such as decane, hexadecane, octadecane, tricosane, and paraffins having about 10 to about 40 carbons; branched alkanes such as trimethyldecane, tetramethylpentadecane (pristane), squalane, white oils, Nujols, mineral oils, hydrogenated oligomers and co-oligomers of ethylene, propylene, butylene and higher molecular weight olefin oligomers having 10 to about 40 carbons, (b) substituted hydrocarbons consisting of normal and branched alkanes with about 10 to about 40 carbons may feature one or more functional groups such as ORf, O(CH2CH2θ)xH wherein x is an integer ranging from about 1-10, CN, COORf, C(=O)R_g, aryl, and ethylenically unsaturated groups, useful substituted hydrocarbons comprise decanol, octadecanol, ethoxylated octadecanol, stearic acid, ethyl stearate, methyl decyl ketone, tetrapropylbenzene, and polyesters, (c) polymers derived from one or more of the following monomers ethylene, propylene, butenes, higher alpha-olefins, styrene, allyl esters, vinyl esters such as vinyl acetate, acrylic acid, acrylonitrile, and the like Polymers can be linear or branched, with Mn values ranging from about 500 to about 10 million. Homopolymers of ethylene such as high and low density polyethylene, atactic or crystalline polypropylene, polybutene, polyisobutylene homopolymers and copolymers of higher alpha-olefins, copolymers of ethylene with propylene EPR, which may also contain unconjugated dieries (EPDM), copolymers of ethylene with buteries or higher alpha-olefins, copolymers of propylene with buteries, and higher alpha-olefins. When dienes such as butadiene and isoprene are used in copolymer formation, the resulting polymers are preferably hydrogenated to saturate substantially all of the ethylenic unsaturation Useful polymers include hydrogenated poly-alpha- olefins. styrene butadiene and/or isoprene block, and tapered copolymers, hydrogenated styrene isoprene block, and hydrogenated star branched polyisoprene polymers. Since polymers containing excess ethylenic unsaturation are prone to crosslinking reactions during radical grafting, polymers containing only residual levels of ethylenic unsaturation are preferred The polymers described above for ene adductions leading to la, 2a, and 3a are useful, per se; however, the hydrogenated versions of these polymers, are most preferred Radical Adduct Formation

The radical-induced reactions of VP monomers with hydrocarbon and/or polymer substrates can occur in the neat state, in a melt, or in solution, bulk modifications can be effected in polymer processing equipment such as a rubber mill, an extruder, and a Brabender or Banbury mixer.

Radical grafting of high molecular weight polymers may also be conducted without a solvent, as in a melt, and is a preferred route to multifunctional viscosity improvers (MFVI) Polymer processing equipment such as a rubber mill, an extruder, a Banbury mixer, Brabender mixer, and the like are used. Reaction temperatures ranging from about 90°C to about 220°C, and reaction times ranging from about 1 minute to about 1 hour are employed Reaction times will vary with the nature and amount of polymer, the VP monomer, the reactant ratio and melt reaction conditions, and accordingly, IR analysis for example, is used to ascertain complete reaction

Typically, when grafting in solution, the polymer is dissolved in a suitable solvent, such as chlorobenzene, dichlorobenzene, or mineral oil, and heated to temperatures ranging from about 90°C to about 180°C depending upon the radical initiator used The VP monomer is added and heated for a suitable period to free any radical-reactive carbonyl groups which may be tied up as a hydrate, alcoholate, or polar solvate At this point, the radical initiator is added in one dose, or dropwise over a suitable time span, usually from about 5 to 60 minutes Another option is to add a mixture of compatible monomer and peroxide in a suitable solvent to the hydrocarbon or polymer solution at an addition rate and suitable reaction temperature consistent with the half life of the radical initiator The reaction mixture is heated, with stirring, until visual color changes infrared analysis, and/or NMR analysis indicate that the radical addition of the VP monomer to the hydrocarbon is complete In the case of puφle-colored IT, the visible color change from lavender to amber that occurs during radical grafting, provide a convenient method for monitoring the reaction Depending on the temperature and concentration, reaction times of about 0 05 to about 12 hours are usually sufficient to achieve high conversions to the radical adducts In general, the amount of VP monomer employed is dictated by the level of functionality desired in radical adducts while still maintaining sufficient oil solubility Levels of radical grafting onto hydrocarbons and polymers ranging from about 1 to 2 VP monomers per each hydrocarbon chain or a polymer chain segment containing about 20 to about 100 carbons, are useful Functionality levels leading to desirable chain extension are preferred when designing dispersants and multifunctional additives The amount of free radical initiator used is generally between 1 and 100 wt % based on the weight of VP monomer, and often depends upon the nature of the free radical initiator, and hydrocarbon or polymer substrate being grafted. The susceptibility, of certain polymers to undergo crosslinking and/or chain scission necessitates careful discretion regarding reagent concentrations, time, temperature, and process conditions since these parameters are all dependent variables in the grafting process.

Product Formation

The products of this invention are prepared by reacting a wide assortment of ene and radical adducts with selected nucleophiles, electrophiles and metal ions according to the following protocol:

Adducts of hydrocarbons and polymers derived from:

[i] vicinal polyketones such as indantrione (IT), naphthalene 1,2,3,4- tetrone, rhodizonic acid, triquinoyl, croconic acid, leuconic acid, dimethyl triketone, and diphenyl triketone; [ii] vicinal polycarbonyl containing amides such as alloxan (AX), 1,3- dimethylalloxan, quinoline-2,3,4 -trione, and

[iii] vicinal polycarbonyl containing esters, and lactones, such as isopropylidene ketomalonate, furan-2,3,4-trione, benzopyran-2.3,4-trione, dehydroascorbic acid and its derivatives, and diethyl ketomalonate (KM); when reacted with:

[a] nucleophiles such as amines, hydrazines, alcohols, water, polyamines, polyols, amino alcohols, amino thiols, and dithiols;

[b] electrophiles such as acylating agents like carboxy anhydrides and esters, borate esters, phosphate and phosphate esters; and [c] metal salts and metal complexes; produce a wide assortment of products consisting of antioxidants, antioxidant dispersants, dispersant viscosity modifiers, detergents, and multifunctional additives for fuels and lubes.

The structure and yield of products derived from the chemistry, outlined above are a sensitive function of reactant structure and reaction parameters. The strictures depicted for the characterized products illustrate in part, the multiple reaction pathways involved in product formation. When polyfunctional adducts are used in the foregoing reactions, related products, some of which can be chain extended in nature and not easily defined, will often be present. Accordingly, the products derived from lc, 2c, and 3c via reaction with the nucleophiles, electrophiles, and metal salts and metal complexes, can be complex mixtures which are highly useful as fuel and lube additives. Typically the reactions are conducted by contacting, e.g., mixing, the adduct with the nucleophile, electrophile, or metal reagent as the case may be, neat or in a suitable solvent at a temperature, and time sufficient to form the product. The precise conditions for carrying out the reactions are not critical. Electrophilic reactions will usually involve the hydroxyl group attached to the ene or radical adduct. Useful electrophiles for reacting with adducts to from products include carboxylic acids, anhydrides, and esters, phosphates, phosphates, boric acid, and borate esters Useful metals that react with adducts include alkali metals such as lithium, sodium, potassium, alkaline earth metals such as calcium, magnesium, barium; and transition metals such as copper, nickel, and cobalt. Useful carriers (counter ions) for the alkali and alkaline earth metals include acetate, carbonate, bicarbonate, and counter ions; carriers for the transition metals include acetate ion, and oxygen-containing ligands such as acetylacetone (2,4-pentanedione) Useful nucleophiles include mono-reactive nucleophiles, such as monoamine, hydrazine, and monohydric alcohol reagents, and poly-reactive nucleophiles such as polyamine, amino alcohol, and polyol reagents.

Useful amines feature a NH2 or NH group capable of reacting with the adducts of the present invention. The NH2 or NH functional group can be attached to linear and/or branched alkanes having from about I to 100 carbons. The NH2, NH, or aminoalkyl groups can also be attached to homocyclic rings such as a cycloalkane having from 3) to about 18 members, aromatic rings, or fused aromatic by benzene and naphthalene, respectively- heterocyclic rings, or fused heterocyclic rings having 5 or 6 members consisting of carbon, nitrogen, oxygen and sulfur. All of the above described amines can contain substituents including ethers, polyethers, thioethers and polythioethers, carboxyl, carboxamide and nitrile groups, sulfur-oxygen substituents; and phosphorus-oxygen substituents. The presence of these substituents in amine containing alkanes, homocycles, and heterocycles imparts new and useful properties to the additive products. Reaction of the above amines with adducts lc, 2c and 3c, depending on reaction conditions, produces a wide assortment of useful amide imide and imine derivatives. The reduction ofthe imines with boranes affords useful amine products

Hydrazines useful in the present invention include hydrazine groups attached to alkanes, homocyclics, and heterocyclics as described above. Reaction of the above hvdrazines with adducts lc, 2c and 3c of the present invention affords useful hydrazide and hydrazone products Reduction of certain hydrazones with borohydride. for example, gives useful substituted hydrazine derivatives Monohydric alcohols useful in the present invention include hydroxy alkanes, hydroxy and hydroxyalkyl containing homocycles, and heterocycles as well as their substituted derivatives by analogy with the amines described above.

In a highly preferred embodiment of the present invention, polyamines, amino alcohols, and polyhydric alcohols are reacted with the ene and radical adducts to give a wide variety of useful products. An important feature of polyreactive nucleophiles is their ability to couple two or more adducts together thereby chain extending the product, and oftimes enhancing the viscometric properties of the product Moreover, the presence of multiple functionality in the radical and ene adducts leads to even more pronounced Mn increases, and enhanced V.I. performance owing to the ability of polyamines to induce chain extension via reaction with multiple functional groups attached to the adducts

Useful polyamines and substituted polyamines feature two or more amino groups selected from NH2 and/or NH radicals which are capable of reacting with the adducts of the present invention. By analogy with monoamines, the amine groups can be attached to alkanes, homocycles, and heterocycles, in addition, the polyamine derivatives may also contain one or more substituents.

Useful polyamines feature two or more amino radicals such as NH2 and/or NH, and are attached to alkanes or branched alkanes containing from about 2 to about ten thousand carbons. Other useful polyamines are those where the amino or aminoalkyl groups are attached to a homocycle, a heterocycle, or. wherein the NH groups ofthe polyamine are members ofa heterocyclic ring having from about 6 to about 30 members The cyclic polyamines may contain other heteroatoms such as oxygen and sulfur. Examples of polyamines bearing alkane and substituted alkane groups include. ethylenediamine (EDA), l,3-propane-diamine(PDA), 1,2-propanediamine, 1,4- butanediamine, diethylenetriamine (DETA), N-2-aminoethyl-l,3-propane-diamine, tri- ethylenetetramine (TETA), tetraethylenepentamine (TEPA), and pentaethyienehexamine (PEHA). The most preferred polyamines are the alkylene polyamines as typified by EDA,

DETA, TEPA, PEHA, their higher molecular weight polyamine homologs, and commercial polyethylene polyamines such as "Polyamine H, Polyamine 400, and Dow Polyamine E-100."

Post Products

Another aspect of the present invention involves the post-treatment of the products Id, 2d, and 3d to further enhance their properties as fuel and lube additives. Thus, the post-treatment, or "capping" of polyamine and polyol derivatives of Id, 2d, and 3d, with electrophilic reagents can endow these products with enhanced seal compatibility properties; enhanced product stability; antioxidant properties and improved chelating, complexing, and aggregation properties. These attributes translate into improved dispersancy viscometrics and fluoroelastomer seal compatibility properties for the additives ofthe present invention.

Useful "capping" reagents for the post-treatment of products Id, 2d, and 3d include: boron-oxygen compounds, alkane carboxylic acids, anhydrides, and esters; 5- ,6-, and 7-membered lactones; alpha, beta-unsaturated acids and esters; diketones, and 1.3-keto esters, oxiranes, and thiranes, aldehydes, and ketones, isocyanates, and isothiocyanates, sulfur and sulfur-oxygen reagents; and phosphorus-oxygen and phosphorus-sulfur reagents.

Post-products containing boron can be formed via the addition of boric acid, ester or metaborate ester to the aminated adducts ofthe present invention. A preferred method of the present invention involves the direct treatment of adducts with a soluble form of boron which is prepared by combining a mixture of a polyamine and boric acid, and heating the mixture at about 130°C until a clear liquid polyamine metaborate (PMB) salt is obtained as shown below wherein T is selected from the group consisting of ethylene, propylene, trimethylene, and (CH2CH2NH)_XCH2CH2, and x is a numerical value ranging from about 1 to about 10. Addition of the PMB to an adduct of the present invention at about 120°C to about 180°C, appears to "bor-aminate" the adduct, and produces a borated polyamine dispersant in one step.

Polyalkenyl (e.g. polybutene) succinimides are a widely used class of dispersant for lubricant and fuels applications. They are prepared by the reaction of, for example, polyisobutylene with maleic anhydride to form polyisobutenyl-succinic anhydride, and then subsequently undergo a condensation reaction with ethylene amines The dispersants of the present invention include this class of functionalized polymers but which undergo a condensation reaction with PMB. The preferred dispersants of the present invention are based on the ethylene alpha-olefin polymers as disclosed in USSN 992, 192 and incoφorated herein by reference. The preferred ethylene alpha-olefin copoiymer is ethylene butene The preferred ethylene content is about 30 weight percent to about 50 weight percent Even more preferred is about 35 weight percent to about 45 weight percent. Most preferred is about 39 weight percent ethylene. The ethylene content on a molar basis is preferably about 40 percent to about 67 percent. More preferred is about 45 to about 60 mole % ethylene. These polymers can be functionalized using a variety of means including halogen assisted functionalization (e g , chlorination), the thermal "ene" reaction, free radical grafting using a catalyst (e g , peroxide) with a carboxylic acid material such as maleic anhydride, and phenol alkylation These reactions are well known to those skilled in the art Polyalkenes (e g poly-n-butenes and polyisobutylene) can also be functionalized using these reactions Carbonylation via the Koch reaction is also useful to practice the present invention The Koch reaction is disclosed in USSN 992,402 and is incoφorated herein by reference USSN 992,403 discloses amidation of ethylene alpha-olefin polymers functionalized by the Koch reaction and derivatized with amine and is incoφorated by reference herein in its entirety for all purposes USSN 261,554 discloses ethylene alpha-olefin polymers functionalized by the Koch reaction but derivatized with "heavy polyamine" USSN 261,554 is incoφorated by reference herein in its entirety for all puφoses

The preferred polymers are polymers of ethylene and at least one alpha-olefin having the formula H2C=CH^ wherein R^ is straight chain or branched chain alkyl radical comprising 1 to 18 carbon atoms and wherein the polymer contains a high degree of terminal ethenylidene unsaturation. Preferably R^ in the above formula is alkyl of from 1 to 8 carbon atoms and more preferably is alkyl of from 1 to 2 carbon atoms Therefore, useful comonomers with ethylene in this invention include propylene, 1-butene, hexene-1, octene-1, etc., and mixtures thereof (e g mixtures of propylene and 1 -butene, and the like) Preferred polymers are copolymers of ethylene and propylene and ethylene and butene- 1 Most preferred are copolymers of ethylene and butene- 1

Preferred ranges of number average molecular weights (Mn) for the copolymer are from 500 to 20,000, preferably from 1,000 to 8,000, even more preferably from 2,000 to 6,000 Most preferred are about 2,500 A convenient method for such determination is by size exclusion chromatography (also known as gel permeation chromatography (GPC) which additionally provides molecular weight distribution information Such polymers generally possess an intπnsic viscosity (as measured in tetralin at 135°C) of between 0 025 and 0 6 dl/g, preferably between 0 05 and 0 5 dl/g, most preferably between 0 075 and 0 4 dl g These polymers preferably exhibit a degree of crystallinity such that, when functionalized, they are essentially amoφhous

The preferred ethylene alpha-olefin polymers are further characterized in that up to about 95% and more of the polymer chains possess terminal vinylidene-type unsaturation Thus, one end of such polymers will be of the formula POLY-C(R¹ 1) = CH2 wherein R^ is C_j to C_jg alkyl, preferably C \ to Cg alkyl, and more preferably methyl or ethyl and wherein POLY represents the polymer chain A minor amount of the polymer chains can contain terminal ethenyl unsaturation, i e POLY-CH=CH2, and a portion of the polymers can contain internal monounsaturation, e g POLY- CHKΗC ^{1 ]}), wherein R^{1 1} is as defined above.

The preferred ethylene alpha-olefin polymer comprises polymer chains, at least about 30% of which possess terminal vinylidene unsaturation. Preferably at least about 50%, more preferably at least about 60%, and most preferably at least about 75% (e.g. 75 to 98%), of such polymer chains exhibit terminal vinylidene unsaturation The percentage of polymer chains exhibiting terminal vinylidene unsaturation may be determined by FTLR spectroscopic analysis, titration, HNMR, or C13NMR.

The polymers can be prepared by polymerizing monomer mixtures comprising ethylene with other monomers such as alpha-olefins, preferably from 3 to 4 carbon atoms in the presence of a metallocene catalyst system comprising at least one metallocene (e.g. a cyclopentadienyl-transition metal compound) and an activator, e.g alumoxane compound The comonomer content can be controlled through selection of the metallocene catalyst component and by controlling partial pressure of the monomers.

The dispersants of the present invention can be prepared by derivatization, using PMB, of polymers functionalized by the Koch reaction, wherein the polymer backbone has Mn>500, and functionalization is by groups ofthe formula

-CO-Y-R³

wherein Y is O or S, and either R³ is H, hydrocarbyl and at least 50 mole % of the functional groups are attached to a tertiary carbon atom of the polymer backbone or R³ is aryl, substituted aryl or substituted hydrocarbyl Thus, the functionalized polymer may be depicted by the formula

POL Y— {CR ! R²)— CO- Y-R3 )_n

wherein POLY is a hydrocarbon polymer backbone having a number average molecular weight of at least 500, n is a number greater than 0 and represents the functionality or average number of functional group per polymer chain R¹, R² and R³ may be the same or different and are each H, hydrocarbyl with the proviso that either Rl and R² are selected such that at least 50 mole % of the CR*R² groups wherein both R* and R² are not H, or R³ is aryl, substituted aryl or substituted hydrocarbyl.

The Koch reaction permits controlled functionalization of unsaturated polymers. When a carbon of the carbon-carbon double bond is substituted with hydrogen, it will result in an "iso" functional group, i.e. one of R^ or R² is H; or when a carbon ofthe double bond is fully substituted with hydrocarbyl groups it will result in a "neo" functional group, i.e. both Rl or R² are non-hydrogen groups.

Polymers produced by processes which result in terminally unsaturated polymer chain can be functionalized to a relatively high yield in accordance with the Koch reaction. It has been found that the neo acid functionalized polymer can be derivatized to a relatively high yield.

The Koch process also makes use of relatively inexpensive materials, i.e. carbon monoxide at relatively low temperatures and pressures. Also the leaving group -YR³ can be removed and recycled upon derivatizing the Koch functionalized polymer with amine.

The process for preparing the functionalized polymer of the present invention comprises the steps of catalytically reacting in admixture:

(a) at least one hydrocarbon polymer having a number average molecular weight of at least about 500 and an average of at least one ethylenic double bond per polymer chain;

(b) carbon monoxide;

(c) at least one acid catalyst; and

(d) a nucleophilic trapping agent selected from the group consisting of water, hydroxy-containing compounds and thiol-containing compounds, the reaction being conducted a) in the absence of reliance on transition metal as a catalyst; or b) with at least one acid catalyst having a Hammett acidity of less than 7; or c) wherein functional groups are formed at least 40 mole % of the ethylenic double bonds; or d) wherein the nucleophilic trapping agent has a pKa of less than 12. The polymers having at least one ethylenic double bond are reacted via a Koch mechanism to form carbonyl or thio carbonyl group-containing compounds, which may subsequently be derivatized. The polymers react with carbon monoxide in the presence of an acid catalyst or a catalyst preferably complexed with the nucleophilic trapping agent. A preferred catalyst is BF3 and preferred catalyst complexes include BF3Η2O and BF3 complexed with 2,4-dichlorophenol. The starting polymer reacts with carbon monoxide at points of unsaturation to form either iso- or neo- acyl groups with the nucleophilic trapping agent, e.g. with water, alcohol (preferably a substituted phenol) or thiol to form respectively a carboxylic acid, carboxylic ester group, or thio ester. In a preferred process, at least one polymer having at least one carbon-carbon double bond is contacted with an acid catalyst or catalyst complex having a Hammet Scale acidity value of less than -7, preferably from -8.0 to -1 1.5 and most preferably from -10 to -1 1 5 Without wishing to be bound by any particular theory, it is believed that a carbenium ion may form at the site of one of carbon-carbon double bonds The carbenium ion may then react with carbon monoxide to form an acylium cation The acylium cation may react with at least one nucleophilic trapping agent as defined herein.

At least 40 mole %, preferably at least 50 mole %, more preferably at least 80 mole %, and most preferably 90 mole % of the polymer double bonds will react to form acyl groups wherein the non-carboxyl portion of the acyl group is determined by the identity ofthe nucleophilic trapping agent, i.e. water forms acid, alcohol forms acid ester and thiol forms thio ester. The polymer functionalized by the recited process of the present invention can be isolated using fluoride salts The fluoride salt can be selected from the group consisting of ammonium fluoride and sodium fluoride

Preferred nucleophilic trapping agents are selected from the group consisting of water, monohydric alcohols, polyhydric alcohols hydroxyl-containing aromatic compounds and hetero substituted phenolic compounds The catalyst and nucleophilic trapping agent can be added separately or combined to form a catalytic complex

Following reaction with CO, the reaction mixture is further reacted with water or another nucleophilic trapping agent such as an alcohol or phenolic or thiol compound The use of water releases the catalyst to form an acid. The use of hydroxy trapping agents releases the catalyst to form an ester, the use of a thiol releases the catalyst to form a thio ester.

Koch product, also referred to herein as functionalized polymer, typically will be derivatized as described hereinafter Deπvatization reactions involving ester functionalized polymer will typically have to displace the alcohol derived moiety therefrom Consequently, the alcohol derived portion of the Koch functionalized polymer is sometimes referred to herein as a leaving group The ease with which a leaving group is displaced during derivatization will depend on its acidity, i e. the higher the acidity the more easily it will be displaced. The acidity, in turn, of the alcohol is expressed in terms of its pKa The pKa value is determined from the corresponding acidic species in water at room temperature

Preferred nucleophilic trapping agents include water and hydroxy group containing compounds. Useful hydroxy trapping agents include aliphatic compounds such as monohydric and polyhydric alcohols or aromatic compounds such as phenols and naphthols The aromatic hydroxy compounds from which the esters of this invention may be derived are illustrated by the following specific examples phenol, naphthol, cresol, resorcinol, catechoi, 2-chlorophenol Particularly preferred is 2,4- dichlorophenol The polymer added to the reactant system can be in a liquid phase Optionally, the polymer can be dissolved in an inert solvent

Preferably, the polymer, catalyst, nucleophilic trapping agent and CO are fed to the reactor in a single step The reactor contents are then held for a desired amount of time under the pressure of the carbon monoxide The reaction time can range up to 5 hours and typically 0 5 to 4 and more typically from 1 to 2 hours The reactor contents can then be discharged and the product which is a Koch functionalized polymer comprising either a carboxylic acid or carboxylic ester or thiol ester functional groups separated Upon discharge, any unreacted CO can be vented off Nitrogen can be used to flush the reactor and the vessel to receive the polymer

Depending on the particular reactants employed, the functionalized polymer containing reaction mixture may be a single phase, a combination of a partitionable polymer and acid phase or an emulsion with either the polymer phase or acid phase being the continuous phase Upon completion of the reaction, the functionalized polymer is recovered by suitable means

The functionalized polymer, whether prepared by halogenation, "ene" reaction, free radical grafting, phenol alkylation, or the Koch reaction is then derivatized with the PMB to make the dispersant of the present invention Polyalkylene amines (e g polyethylene amines) are suitable for use in the present invention to react with the boric acid prepare the PMB The preferred amines are "heavy polyamines "

The heavy polyamine as the term is used herein refers to polyamines containing more than six nitrogens per molecule, but preferably polyamine oligomers containing 7 or more nitrogens per molecule and with 2 or more primary amines per molecule The heavy polyamine comprises more than 28 wt % (e g >32 wt %) total nitrogen and an equivalent weight of pπmary amme groups of 120-160 grams per equivalent Commercial dispersants are based on the reaction of carboxylic acid moieties with a polyamine such as tetraethylenepentamine (TEPA) with five nitrogens per molecule Commercial TEPA is a distillation cut and contains oligomers with three and four nitrogens as well Other commercial polyamines known generically as PAM, contain a mixture of ethylene amines where TEPA and pentaethylene hexamine (PEHA) are the major part of the polyamine, usually less than about 80% Typical PAM is commercially available from suppliers such as the Dow Chemical Company under the trade name E-100 or from the Union Carbide Company as HPA-X This mixture typically consists of less than 1 0 wt % low molecular weight amine, 10-15 wt % TEPA, 40-50 wt % PEHA and the balance hexaethyleneheptamine (HEHA) and higher oligomers Typically PAM has 8 7 - 8 9 milliequivalents of primary amine per gram (an equivalent weight of 1 15 to 1 12 grams per equivalent of primary amine) and a total nitrogen content of about 33-34 wt. %.

It has been discovered that heavier cuts of PAM oligomers with practically no TEPA and only very small amounts of PEHA but containing primarily oligomers with more than 6 nitrogens and more extensive branching, produce dispersants with improved dispersancy when compared to products derived from regular commercial PAM under similar conditions with the same polymer backbones. An example of one of these heavy polyamine compositions is commercially available from the Dow Chemical Company under the trade name of Polyamine HA-2. HA-2 is prepared by distilling out the lower boiling polyethylene amine oligomers (light ends) including TEPA. The TEPA content is less than 1 wt. %. Oniy a small amount of PEHA, less than 25 wt. %, usually 5 - 15 wt. %, remains in the mixture. The balance is higher nitrogen content oligomers usually with a greater degree of branching. The heavy polyamine preferably comprises essentially no oxygen. Typical analysis of HA-2 gives primary nitrogen values of about 7.8 milliequivalents (meq) (e.g. 7.7 - 7.8) of primary amine per gram of polyamine. This calculates to be about an equivalent weight (EW) of 128 grams per equivalent (g/eq). The total nitrogen content is about 32.0 - 33.0 wt. %. Commercial PAM analyzes for 8.7 - 8.9 meq of primary amine per gram of PAM and has a nitrogen content of about 33 to about 34 wt. %.

Bor-Amination

Post-products containing boron can be formed via the addition of boric acid, ester or metaborate ester to aminated adducts of functionalized polymers including aminated polyalkenyl-succinic anhydrides, carboxylic acids, and esters.

A new, and preferred method for producing said post-products containing boron involves contacting adducts such as polyalkenyl succinic anhydrides, carboxylic acids, and esters with a soluble form of boron which is prepared by combining a mixture of a polyamine and boric acid, and heating the mixture at about 1 10°C to about 130°C until a clear liquid polyamine metaborate (PMB) salt is obtained as shown below wherein T is selected from the group consisting of ethylene, propylene, trimethylene, and (CH2CH2NH)_XCH2CH2; and x is a numerical value ranging from about 1 to about 10.

Addition of the PMB to said adduct at about 1 10°C to about 180°C, "bor- aminates" the adduct, and produces a borated polyamine dispersant in one step Products prepared in this way are expected to have lower sediment levels

Electrophiles such as ethyl acetate, acetic anhydride, ethyl ortho-acetate, ethyl acetoacetate, and 2,4-pentandione react with polyamine-modified additives, thereby passivating their basic properties, and as a consequence, enhancing their seal compatibility properties. Similarly, the addition of thioacids such as sulfanes (di-, tri- and tetrasulfane), thiosulfuric acid, and thiophosphoric acid to polyamine-treated adducts produces salt derivatives with enhanced seal compatibility properties as well as antioxidant properties.

The adducts, products, and post-products have been found to be especially useful as fuel and lube additives.

When the additive compositions of this invention are used in fuels, such as middle distillates boiling from about 65°C to about 425°C, including kerosene, diesel fuels, home heating fuel oil, and jet fuels, a concentration of the additive in the fuel in the range of typically from about 0.001 wts to about 0.5 wt.%, preferably about 0 005 wt.% to about 0.2 wt.% based on the total weight of the composition, will usually be employed. The adducts, products and post-products of this invention are useful additives for fuels in the gasoline boiling range, for preventing or reducing deposits in the combustion chamber, and adjacent surfaces such as valves, ports, and spark plugs, and thereby reducing octane requirements. The additives (i.e., the adducts, products and post-products) of this invention, and particularly the polymer analogs, find their primary utility in lubricating oil compositions, which employ a base oil in which the additives are dissolved or dispersed. Such base oils may be natural or synthetic and include those conventionally employed as crankcase lubricating oils for spark-ignited and compression-Ignited internal combustion engines, such as automobile and truck engines, marine and railroad diesel engines, and the like.

While any effective amount of these additives can be incoφorated into a fully formulated lubricating oil composition, it is contemplated that the composition contain from about 0.01 to about 10 wt %, e.g., and preferably from about 0.1 to about 6 wt.%, based on the weight of said composition.

The additives of the present invention can be incoφorated into the lubricating oil in any convenient way. Thus, they can be added directly to the oil by dispersing, or dissolving the same in the oil at the desired level of concentration, typically with the aid of a suitable solvent such as toluene, cyclohexane, or tetrahydrofuran. Such blending can occur at room temperature or elevated temperatures. Alternatively, these additives may be blended with a suitable oil soluble solvent or base oil to form a concentrate, which may then be blended with a lubricating oil base stock to obtain the final formulation. Concentrates will typically contain from about 2 to about 80 wt.%, and preferably from about 5 to about 40 wt.% based on the weight ofthe additive.

Advantageous results are also achieved by employing the additives of the present invention in base oils conventionally employed in and/or adapted for use as power transmitting fluids such as automatic transmission fluids, tractor fluids, universal tractor fluids and hydraulic fluids, heavy duty hydraulic fluids, power steering fluids and the like. Gear lubricants, industrial oils, pump oils and other lubricating oil compositions can also benefit from the incoφoration therein of the additives of the present invention.

Substantial benefits can also be realized by employing low molecular weight

(Mn ranging from about 400 to about 2K) products and post-products of polyarnine- treated adducts especially RpAX, RpIT, and RpKM adducts, in two cycle engine oils.

Suitable polyamines include: EDA, PDA, DETA, TETA, TEPA, Polyamine-H, and o- phenylene diamine.

When employed in a lubricating oil composition, the additive of the present enhanced dispersancy and/or V.I. improvement. Conventional additives as well as additives of the present invention can be used to meet the particular requirements of a lubricating oil composition.

The lubricating oil base stock for the additives of the present invention typically is adapted to perform a selected, function by the incorporation of additives therein to form lubricating oil compositions (i.e., formulations). Representative additives typically present In such formulations (which can be selected from the adducts, products and post-products of the present invention) include viscosity modifiers, corrosion inhibitors, oxidation inhibitors, friction modifiers, other dispersants. anti- foaming assents, anti-wear agents, pour point depressants, detergents, rust inhibitors and the like.

Compositions containing the above additives are typically blended into the base oil in amounts which are effective to provide their normal attendant function. Representative effective amounts of such additives are illustrated as follows:

Additive Wt.% a.i. (Broad) Wt.% a.i. (Preferred .

Viscosity Modifier .01 - 12 .01 - 4

Corrosion Inhibitor .01 - 5 .01 - 1.5

Oxidation Inhibitor .01 - 5 .01 - 1.5

Dispersant 1 - 20 .1 - 8

PourPoint Depressant .01 - 5 .01 - 1.5

Anti-Foaming Agents .001 - 3 .001 - 0.15

Anti-Wear Agents .001 - 5 .001 - 1.5

Friction Modifiers .01 - 5 .01 - 3

Detergents/Rust Inhibitors .01 - 10 .01 - 3

Mineral Oil Base Balance Balance

All of said weight percents expressed herein are based on active ingredient (a.i.) content of the additive, and/or upon the total weight of any additive-package, or formulation which will be the sum ofthe a.i. weight of each additive plus the weight of total oil or diluent.

This invention will be further understood by the following examples, which include preferred embodiments.

In the following examples, number average molecular weight (Mn) is determined by Gel Permeation Chromatography (GPC). The sediment level of the products is determined by variations of test method ASTM D-97 that are know to those skilled in the art. D-97 is incoφorated by reference herein in its entirety for all puφoses.

Examples

Comparative Example 1 (Conventional boration method)

Two hundred grams of polyisobutenyl succinic anhydride (PLBSA) with Mn«

1000 and a saponification value of 108, previously aminated with about 18.9 grams of tetraethylene pentamine ( TEPA )at 160°C for about 8 hours and rotoevaporated at 120°C for about 6 hours, is combined with about 6.2 grams of boric acid powder and stirred at 120°C for 24 hours Rotoevaporation ofthe reaction mixture at 120°C for 6 hours afforded borated product The sediment level ofthe product was negligible

Example 2 About a tenth mole (23.4 grams) of Polyamine-H (a commercial polyamine composed primarily of ethylene amines heavier than TEPA with the PEHA cut left in the product, and analyzing for 33 % nitrogen) was stirred at 120°C in a 250 ml beaker, while 12.4 grams of boric acid were added in gram portions over a 5 minute period. The mixture was stirred at 120°C for about an hour, or until a clear solution was obtained. The clear, amber-colored PAM metaborate (PMB) reagent analyzed for 6.05%) boron and 23.29% nitrogen

Example 3

About a tenth moie ( 18.9 grams ) of tetraethylene pentamine ( TEPA ) was stirred at 120°C in a 500 ml beaker, while 6.2 grams ( 0.1 mole ) of boric acid were added in one portion The mixture was then stirred at 120°C for about a half hour, or until a clear yellow solution of TEPA-metaborate was obtained.

Example 4 About a tenth mole ( 18.9 grams ) of tetraethylene pentamine ( TEPA ) was stirred at room temperature in a 500 ml beaker, while 6.2 grams ( 0 1 mole ) of boric acid were added in one portion The mixture was then stirred at 120°C for about a half hour, or until a clear yellow solution of TEPA-metaborate was obtained

Example 5

About twenty grams of polyisobutenyl succinic anhydride (PLBSA) with Mn* 1000 and a saponification value of 108, were stirred at about 150°C in an open beaker. Bor-amination of the PLBSA was effected by adding about 5 1 grams of the clear yellow solution of TEPA-metaborate prepared in Example 3 directly to the PLBSA reagent stirred at 150°C. Some frothing was caused by the rapid evolution of water produced during amidation, but ceased after stirring for several minutes After heating at 150°C for about 4 hours, the reaction mixture was rotoevaporated for about 2 hours at about 120°C. Infrared analysis of the residue indicated that the amidation of PLBSA by TEPA-metaborate was complete. The sediment level ofthe product was negligible. Example 6

About forty grams of polyisobutenyl succinic anhydride, PIBSA ( Mn~ 1000 and a saponification value of 108 ), were stirred at about 150°C in an open beaker. Bor-amination of the PIBSA was effected by adding about 5.0 grams of the clear yellow solution of TEPA-metaborate prepared in Example 4 directly to the PLBSA reagent stirred at 150°C. Some frothing was caused by the rapid evolution of water produced during amidation, but ceased after stirring of several minutes. After heating at 150°C for about 4 hours, the reaction mixture was rotoevaporated for about 2 hours at about 120°C. Infrared analysis ofthe residue indicated that the amidation of PLBSA by TEPA-metaborate was complete as evidenced by the absence of anhydride carbonyl absoφtion band at about 5.6 microns, and the presence of imide carbonyl absoφtion band at about 5.9 microns. The sediment level ofthe product was negligible.

The examples demonstrated that a functionalized product could be derivatized in one less step, by pre-reacting the polyamine and boric acid , prior to reacting with the functionalized polymer. The examples further show that the polyamine boric acid adduct could be prepared at a substantially lower temperature. Although the sediment levels of the examples of the present invention and the comparative example appeared to be the same, a higher level was expected in the comparative examples.

Claims

CLAIMS :

1. A composition comprising a lubricating oil and a dispersant, wherein said dispersant comprises the reaction product of a functionalized polymer and a polyamine metaborate.

2. The composition of claim 1, wherein said dispersant is prepared from a polymer functionalized using a reaction selected from the group consisting of halogen assisted, thermal ene, free radical grafting using a catalyst, phenol alkylation and carbonylation via Koch

3 The composition of claim 1, wherein said dispersant is derived from polymer functionalized by groups of the formula -CO-Y-R3 wherein Y is O or S, and either R3 is H hydrocarbyl, substituted hydrocarbyl, aryl, substituted aryl and at least

50 mole % of the functionalized groups are attached to a tertiary carbon atom of the copolymer.

4. The composition of claim 1, wherein said dispersant has a number average molecular weight of about 500 to about 20,000.

5. The composition of claim 1, wherein said dispersant is prepared from polymer functionalized with a carboxylic acid moiety

6. The composition of claim 5, wherein said carboxylic acid moiety comprises maleic anhydride

7. The composition of claim 1, wherein said dispersant is prepared from functionalized polymer derived from polymers selected from the group consisting of poly-n-butene, polyisobutylene, and ethylene alpha olefin copolymers

8 The composition of claim 7, wherein said alpha olefin comprises butene

9. The composition of claim 1, wherein said polyamine metaborate is prepared by a process comprising heating a mixture of a polyamine and boric acid comprising about one to about three moles of boric acid per each amino group of the polyamines for a time and at a temperature sufficient to form a clear liquid

10. The composition of claim 9, wherein said polyamine comprises heavy polyamine.

11. A process for preparing a bor-aminated dispersant which comprises reacting a functionalized polymer with a liquid polyamine metaborate, wherein said polyamine metaborate is prepared by heating boric acid in a mixture with polyamine.

12. A process for preparing a low sediment dispersant which comprises reacting a polyamine with boric acid to form a polyamine metaborate adduct and then reacting said adduct with a functionalized polymer.

13. The composition of claim 9, wherein said mixture is heated from about a half hour to about 120 hours.

14. The composition of claim 9, wherein said mixture is heated to a temperature in the range of about 80°C to about 130°C.

15. The composition of claim 9, wherein said polyamine and boric acid are mixed at a temperature of about 20 to about 30°C and then heated to about 80°C to about 130°C.