Lactone modified viscosity modifiers useful in oleaginous compositions

Abstract: Oil soluble viscosity index improving additives comprising ethylene copolymers such as copolymers of ethylene and propylene; and ethylene, propylene and diolefin; etc. reacted or grafted with ethylenically unsaturated carboxylic acid moieties, preferably maleic anhydride moieties, and reacted with amines having two or more primary amine groups or at least one primary amine group and at least one secondary amine group preferably alkylene polyamine and with alkenyl succinic anhydride such as polyisobutenyl succinic anhydride, are improved by being further reacted with a lactone, preferably a lactone having at least 6 atoms in the lactone ring. The resulting lactone modified products are useful per se as oil soluble V.I. additives in fuel and lubricating compositions including concentrates containing the additives.

Description: This invention relates to polymeric viscosity index (V.I.) improvers useful as additives in petroleum oils, particularly lubricating oils, to concentrates containing said additives, and to methods for their manufacture and use. The present V.I. improver additives comprise a generally known class of V.I. improvers which have been post-treated by reaction with a lactone, preferably a C₅-C₉ polymerizable lactone. The V.I. improvers which are to be lactone modified in accordance with the present invention comprise, for example, a copolymer of ethylene with one or more C₃ to C₂₈ alpha-olefins, which has been grafted with acid moieties, e.g. maleic anhydride, and then reacted with a mixture of an acid component, and a polyamine having two or more primary amine groups. In the alternative, the acid component may be prereacted with the polyamine to form salts, amides, imides, etc. and are then reacted with the grafted olefin polymer. The concept of derivatizing V.I. improving high molecular weight ethylene copolymers with acid moieties such as maleic anhydride, followed by reaction with an amine to form a V.I. dispersant oil additive is known in the art. The concept of polymerizing lactones having 6 to 10 atoms in their ring structure is also well known. For example, it is known that polymers of valerolactone or E-caprolactone can be prepared by reacting the lactone monomer with a hydroxyl or amine initiator. When reacting E-caprolactone, for example, the polymerization reaction may be illustrated by the following equations: The reactions are known to be catalyzed by various esterification catalysts such as stannous octanoate, and a variety of different molecular weight products are feasible depending upon the ratio of lactone to initiator. Molecular weights on the order of from a few hundred up to about 5,000 are reproducably achievable. Caprolactone can also be polymerized to a very high molecular weight, e.g., on the order of 100,000 or more. Typically such high molecular weight polymers do not employ initiators and preservation of functionality is not a requirement. It is also known to react a lactone such as E-caprolactone with a polyol to form polyesters having terminal hydroxyl groups which are useful as plasticizers. US-A-4 362 635 describes fully esterified reaction products of inter alia 6-9 membered lactones of C₅₋₁₂ hydroxycarboxylic acids with alcohols as being useful as high temperature synthetic oils and as viscosity improving adducts for mineral oils. GB-A-1 054 370 describes detergents for lubricating oils which comprise the reaction product of alkenyl substituted succinic anhydride of molecular weight 600-3,000 and the reaction product of a polyamine having two primary amino groups and gamma-butyro or gamma-valero lactone. It is known to produce viscosity index improving adducts by grafting ethylene polymers such as ethylene/propylene copolymers with dicarboxylic acids such as maleic acid so as to produce polymer-substituted succinic acid or anhydride. Such grafted copolymers may be post-reacted to provide additional functionality. Thus, US-A- 4 517 104 and 4 632 769 describe viscosity index improving adducts for e.g. lubricants formed by grafting ethylene polymers with e.g. maleic anhydride, and reacting the product with a polyamine and with a second carboxylic acid component such as polyisobutenyl succinic anhydride. The presence of the polyamine component provides dispersant properties not present in the grafted copolymer, and the additives perform well in sludge removal and varnish inhibition tests. It has now been discovered that further reaction with a lactone unexpectedly improves the dispersant properties of the viscosity index improvers. The present invention provides a process for producing a reaction product useful as a viscosity improver and dispersant additive for lubricating oil compositions comprising: grafting an oil soluble ethylene copolymer comprising from 15 to 90 wt% ethylene and from 10 to 85 wt% of one or more C₃₋₂₈ alpha-olefins, and having a number average molecular weight of 15,000 to 500,000 with ethylenically unsaturated C₄₋₁₀ mono- or dicarboxylic acid or anhydride wherein the carboxylic acid or anhydride groups are located on vicinal carbon atoms, to produce a grafted copolymer (a); reacting the grafted copolymer (a) with (b) an amine having at least two primary amine groups or having at least one primary amine group and at least one secondary amine group, and (c) an acid component selected from (i) a C₁₂₋₄₉ hydrocarbyl substituted succinic anhydride or acid; (ii) a C₂₅₋₄₀₀ hydrocarbyl substituted succinic anhydride or acid; and (iii) a C₂₅₋₄₀₀ hydrocarbyl substituted monocarboxylic acid; and (d) a lactone; wherein (a), (b) and (c) are first reacted and then (d) is reacted. The lactone may be a non-polymerisable lactone such as gamma-butyrolactone (which does not undergo ring opening) or a polymerisable C₅₋₉ lactone such as E-caprolactone. The invention also includes viscosity index improving additives having improved dispersant properties obtainable by the above process and lubricating oil compositions and oil concentrates containing such additives. The reaction with the lactone component can be illustrated as follows by reference to the reaction of E-caprolactone with the product of ethylene-propylene grafted maleic anhydride, a polyamine having two primary and at least one secondary amine group, and polyisobutenyl succinic anhydride. where R represents ethylene-propylene copolymer (hereinafter EP) having a number average molecular weight (M n ) of from 15,000 to 500,000 and R' represents polyisobutylene having a M n of from 350 to 5,000, and m has an average value of from 0.2 to 100. The novel lactone modified V.I. improvers adducts of this invention are useful per se as an additive, e.g., a V.I. improver additive, for example, in the same manner as disclosed in U.S. Patent 4,517,104 where prior art ethylene copolymer viscosity index improvers are used as viscosity improver-dispersant/additives in oil compositions, especially lubricants intended for use in the crankcase of internal combustion engines, gears, and power transmitting units. Accordingly, one or more objects of this invention are achieved by providing lubricating oil compositions, e.g., automatic transmission fluids, heavy duty oils suitable for use in the crankcases of gasoline and diesel engines, etc. containing the novel lactone modified viscosity index improvers of this invention. Such lubricating oil compositions may contain additional additives such as dispersants, antioxidants, corrosion inhibitors, detergents, pour depressants, antiwear agents, etc. The invention includes concentrate compositions comprising from 50 to 90 weight % of a normally liquid, substantially inert, organic solvent/diluent, e.g., mineral lubricating oil, or other suitable solvent/diluent, and from 10 to 50 weight % of a lactone modified viscosity index improver, as mentioned above and described in more detail hereinafter. DESCRIPTION OF THE PREFERRED EMBODIMENTS ETHYLENE COPOLYMER Oil soluble ethylene copolymers used in the invention generally will have a number average molecular weight (M n ) of from 15,000 to 500,000; preferably 15,000 to 200,000 and optimally from 20,000 to 100,000. In general, polymers useful as V.I. improvers will be used. These V.I. improvers will generally have a narrow range of molecular weight, as determined by the ratio of weight average molecular weight (M w ) to number average molecular weight (M n ). Polymers having a M w /M n of less than 10, preferably less than 7, and more preferably 4 or less are most desirable. As used herein M n and M w are measured by the well known techniques of vapor phase osmometry (VPO), membrane osmometry and gel permeation chromatography. In general polymers having a narrow range of molecular weight may be obtained by a choice of synthesis conditions such as choice of principal catalyst and cocatalyst combination and addition of hydrogen during the synthesis. Post synthesis treatment such as extrusion at elevated temperature and under high shear through small orifices, mastication under elevated temperatures, thermal degradation, and fractional precipitation from solution may also be used to obtain narrow ranges of desired molecular weights and to break down higher molecular weight polymer to different molecular weight grades for V.I. use. The polymers are prepared from ethylene and ethylenically unsaturated hydrocarbons, including cyclic, alicyclic and acyclic hydrocarbons containing from 3 to 28 carbons, e.g. 2 to 18 carbons. These ethylene copolymers may contain from 15 to 90 wt. % ethylene, preferably 30 to 80 wt. % of ethylene, and 10 to 85 wt. %, preferably 20 to 70 wt. %, of one or more C₃ to C₂₈, preferably C₃ to C₁₈, more preferably C₃ to C₈, alpha olefins. While not essential, such copolymers preferably have a degree of crystallinity of less than 25 wt. % as determined by x-ray and differential scanning calorimetry. Copolymers of ethylene and propylene are most preferred. Other alpha-olefins suitable in place of propylene to form the copolymer, or to be used in combination with ethylene and propylene to form a terpolymer or tetrapolymer include 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, and 1-decene, ; also branched chain alpha-olefins, such as 4-methyl-1-pentene, 4 methyl-hexene, 5-methylpentene-1, 4,4-dimethyl-pentene, and 6-methylheptene-1, and mixtures thereof. The term copolymer as used herein, unless otherwise indicated, includes terpolymers and tetrapolymers of ethylene, said C₃₋₂₈ alpha-olefin and/or a non-conjugated diolefin or mixtures of such diolefins which nay also be used. The amount of the non-conjugated diolefin will generally range from about 0.5 to 20 mole percent, preferably about 1 to about 7 mole percent, based on the total amount of ethylene and alpha-olefin present. Representative examples of non-conjugated dienes that nay be used as the third monomer in the terpolymer include: a. Straight chain acyclic dienes such as: 1,4-hexadiene; 1,5-heptadiene; 1,6-octadiene. b. Branched chain acyclic dienes such as 5-methyl-1,4-hexadiene; 3,7-dimethyl 1,6-octadiene; 3,7-dimethyl 1,7-octadiene; and the mixed isomers of dihydro-myrcene and dihydro-cymene. c. Single ring alicyclic dienes such as: 1,4-cyclohexadiene; 1,5 cyclooctadiene; 1,5 cyclo-dodecadiene; 4-vinylcyclohexene; 1-allyl, 4-isopropylidene cyclohexane; 3-allyl-cyclopentene; 4-ally cyclohexene and 1-iospropenyl-4-(4-butenyl)cyclohexane. d. Multi-single ring alicyclic dienes such as: 4,4'-dicyclopentenyl and 4,4'-dicyclohexenyl dienes. e. Multi-ring alicyclic fused and bridged ring dienes such as: tetrahydroindene; methyl tetrahydroindene; dicyclopentadiene; bicyclo(2.2.1)hepta 2,5-diene; alkyl, alkenyl, alkylidene, cycloalkenyl and cycloalkylidene norbornenes such as: ethylidine norbornene; 5-methylene-6-methyl-2-norbornene; 5-methylene-6, 6-dimethyl-2-norbornene; 5-propenyl-2-norbornene; 5-(3-cyclopen-tenyl)-2-norbornene, 5-cyclohexyldene-2-norbornene; and norbonadiene. ETHYLENICALLY UNSATURATED CARBOXYLIC ACID MATERIAL These materials which are grafted (attached) onto the ethylene copolymer contain at least one ethylenic bond and at least one, and preferably two, carboxylic acid groups, or anhydride groups, or polar groups which are convertible into said carboxyl groups by oxidation or hydrolysis. The carboxylic acid material comprises a C₄-C₁₀ monocarboxylic acid or a C₄-C₁₀ dicarboxylic acid wherein the carboxyl groups are located on vicinal carbon atoms. Maleic anhydride or a derivative thereof is preferred since it does not appear to homopolymerize appreciably, but rather grafts onto the ethylene copolymer to give two carboxylic acid functionalities. Such preferred materials have the generic formula wherein R₁ and R₂ are hydrogen or a halogen. Suitable examples additionally include chloro-maleic anhydride, itaconic anhydride, or the corresponding dicarboxylic acids, such as maleic acid or fumaric acid or their mono-esters. As taught by U.S. Pat. No. 4,160,739 and U.S. Pat. No. 4,161,452 various unsaturated comonomers may be grafted on the olefin copolymer together with the unsaturated acid component, e.g. maleic anhydride. Such graft monomer systems may comprise one or a mixture of comonomers different from the unsaturated acid component and which contain only one copolymerizable double bond and are copolymerizable with said unsaturated acid component. Typically, such comonomers do not contain free carboxylic acid groups and are esters containing alpha, beta-ethylenic unsaturation in the acid or alcohol portion; hydrocarbons, both aliphatic and aromatic, containing alpha, beta-ethylenic unsaturation, such as the C₄-C₁₂ alpha olefins, for example isobutylene hexene, nonene, and dodecene.; styrenes, for example styrene, a methyl styrene, p-methyl styrene, and p-sec. butyl styrene; and vinyl monomers, for example vinyl acetate, vinyl chloride, vinyl ketones such as methyl and ethyl vinyl ketone. Comonomers containing functional groups which may cause cross linking, gelation or other interfering reactions should be avoided, although minor amounts of such comonomers (up to about 10% by weight of the comonomer system) often can be tolerated. Specific useful copolymerizable comonomers include the following: (A) Esters of saturated acids and unsaturated alcohols wherein the saturated acids may be monobasic or polybasic acids containing up to 40 carbon atoms such as the following: acetic, propionic, butyric, valeric, caproic, stearic, oxalic, malonic, succinic, glutaric, adipic, pimelic, suberic, azelaic, sebacic, phthalic, isophthalic, terephthalic, hemimellitic, trimellitic, and trimesic including mixtures. The unsaturated alcohols may be monohydroxy or polyhydroxy alcohols and may contain up to about 40 carbon atoms, such as the following: allyl, methallyl, crotyl, 1-chloroallyl, 2-chloroallyl, cinnamyl, vinyl, methyl vinyl, 1-phenallyl, butyenyl, propargyl, 1-cyclohexene-3-ol, and oleyl, including mixtures. (B) Esters of unsaturated monocarboxylic acids containing up to 12 carbon atoms such as acrylic, methacrylic and crotonic acid, and an esterifying agent containing up to 50 carbon atoms, selected from saturated alcohols and alcohol epoxides. The saturated alcohols may preferably contain up to 40 carbon atoms and include monohydroxy compounds such as methanol, ethanol, propanol, butanol, 2-ethylhexanol, octanol, dodecanol, cyclohexanol, cyclopentanol, neopentyl alcohol, and benzyl alcohol; and alcohol ethers such as the monomethyl or monobutyl ethers of ethylene or propylene glycol, including mixtures. The alcohol epoxides include fatty alcohol epoxides, glycidol, and various derivatives of alklene oxides, and epichlorohydrin, including mixtures. The components of the graft copolymerizable system are preferably used in a ratio of unsaturated acid monomor component to comonomer component of 1:4 to 4:1, more preferably 1:2 to 2:1 by weight. GRAFTING OF THE ETHYLENE COPOLYMER The grafting of the ethylene copolymer with the carboxylic acid material may be accomplished by any suitable method, such as thermally by the "ene" reaction, using copolymers containing unsaturation, such as ethylene-propylene-diene polymers either chlorinated or unchlorinated; or more preferably, the grafting may be accomplished by free radical induced grafting in bulk or in a solvent such as benzene or toluene, and preferably in a mineral lubricating oil solvent. The radical grafting is preferably carried out using free radical initiators such as peroxides, hydroperoxides, and azo compounds and preferably those which have a boiling point greater than 100°C. and which decompose thermally within the grafting temperature range to provide said free radicals. Representative of these free-radical initiators are azobutyro-nitrile, 2,5-dimethyl-hex-3-yne-2,5 bis-tertiary-butyl peroxide (sold as Lupersol 130) or its hexane analogue, di-tertiary butyl peroxide and dicumyl peroxide. The initiator is generally used at a level of between 0.005% and 1%, based on the total weight of the polymer solution, and temperatures of 150°C to 200°C. The ethylenically unsaturated carboxylic acid material, preferably maleic anhydride, will be used generally in an amount ranging from 0.01% to 10%, preferably 0.1 to 2.0%, based on weight of the initial total solution. The aforesaid carboxylic acid material and free radical initiator are generally used in a weight percent ratio range of 11:1 to 30:1, preferably 3.0:1 to 10:1. The initiator grafting is preferably carried out in an inert atmosphere, such as that obtained by nitrogen blanketing. While the grafting can be carried out in the presence of air, the yield of the desired graft polymer is generally thereby decreased as compared to grafting under an inert atmosphere substantially free of oxygen. The grafting time will usually range from 0.1 to 12 hours, preferably from 0.5 to 6 hours, more preferably 0.5 to 3 hours. The graft reaction usually will be carried out to at least approximately 4 times, preferably at least 6 times the half-life of the free-radical initiator at the reaction temperature employed, e.g. with 2,5-dimethyl hex-3-yne-2, 5-bis(t-butyl peroxide) 2 hours at 160°C, and one hour at 170°C. In the grafting process, usually the copolymer solution is first heated to grafting temperature and thereafter the unsaturated carboxylic acid material and initiator are added with agitation, although they could have been added prior to heating. When the reaction is complete, the excess acid material can be eliminated by an inert gas surge, e.g. nitrogen sparging. Preferably the carboxylic acid material that is added is kept below its solubility limit in the polymer solution, e.g., below 1 wt.%, preferably below 0.4 wt.% or less, of free maleic anhydride based on the total weight of polymer-solvent solution e.g. ethylene copolymer-mineral lubricating oil solution. Continuous or periodic addition of the carboxylic acid material along with an appropriate portion of initiator, during the course of the reaction, can be utilized to maintain the carboxylic acid below its solubility limits, while still obtaining the desired degree of total grafting. In the initiator grafting step, the maleic anhydride or other carboxylic acid material used will be grafted onto both the polymer and the solvent for the reaction. Many solvents such as dichlorobenzene are relatively inert and may be only slightly grafted, while mineral oil will tend to be more grafted. The exact split of graft between the substrate present depends upon the polymer and its reactivity, the reactivity and type of oil, the concentration of the polymer in the oil, the maintenance of the carboxylic acid material in solution during the course of the reaction and the minimization of dispersed, but undissolved acid, e.g. the maleic anhydride, since undissolved acid material appears to have a greater tendency to react and form oil insoluble materials than does dissolved acid material. The split between grafted oil and grafted polymer may be measured empirically from the infrared analysis of the product dialyzed into oil and polymer fractions. The grafting preferably is carried out in a mineral lubricating oil which need not be removed after the grafting step, since the oil can be used as the solvent in the subsequent reaction of the graft polymer with the amine material and as a solvent for the end product to form the lubricating additive concentrate. The oil, having attached or grafted carboxyl groups, will also be converted to the corresponding derivatives when reacted with the amino material. The solution grafting step, when carried out in the presence of a high temperature decomposable peroxide, can be accomplished without substantial degradation of the chain length (molecular weight) of the ethylene-containing polymer. This can be an advantage as opposed to high temperature thermal reactions which depend on degradation to apparently form free radical reactive sites. Measurement of molecular weights and degradation can be evaluated by determination of the thickening efficiency (T.E.) of the polymer as described hereinafter. THE AMINES The amino component will have at least one and generally two or more primary amino groups, wherein the primary amino groups may be unreacted or wherein one of the amine groups may already be reacted. In cases where the amino contains only one primary amino group, the amine component must also contain at least one and preferably at least two secondary amino groups. Preferred amino compounds have the following formulas: A) aliphatic saturated amines: where R, R', R'', R''' are independently selected from the group consisting of hydrogen; C₁ to C₂₅ straight or branched chain alkyl radicals; C₁ to C₁₂ alkoxy C₂ to C₆ alkylene radicals; C₁ to C₁₂ alkylamino C₂ to C₆ alkylene radicals; and wherein R''' can additionally comprise a moiety of the formula: wherein R' is as defined above, and wherein s and s' can be the same or a different number from 2 to 6, preferably 2 to 4; and t and t' can be the same or different and are numbers from 0 to 10, preferably 2 to 7, and most preferably about 3 to 7, with the proviso that the sum of t and t' is not greater than 15, and further provided that R, R', R'', R''', s, s', t, and t' are selected in such a manner as to provide the above compounds with at least two primary amine groups or at least one primary and at least one secondary amine group, preferably at least two primary and at least one secondary amine groups. The most preferred amines contain at least two primary amine groups and at least one, preferably at least three secondary amine groups, e.g. as represented by formula IIIa: H₂N-[-alkylene-NH-] x -H IIIa where x is 1 to 10 and alkylene is ethylene or propylene. (B) polyoxyalkylene polyamines: NH₂-alkylene ( O-alkylene ) m NH₂ (V) wherein m has a value of about 3 to 70 and preferably 10 to 35; and R ( alkylene ( O-alkylene ) n NH₂)3-6 (VI) wherein n has a value of 1 to 40 with the provision that the sum of all the n's is from 3 to 70 and preferably from 6 to 35 and R is a polyvalent saturated hydrocarbon radical of up to ten carbon atoms having a valence of 3 to 6. The alkylene groups in either formula (V) or (VI) say be straight or branched chains containing 2 to 7, and preferably 2 to 4 carbon atoms. Other useful amine compounds include: alicyclic diamines such as 1,4-di(aminomethyl) cyclohexane, and heterocyclic nitrogen compounds such as imidazolines, and N-aminoalkyl peperazines of the general formula VII: wherein P1 and P2 are the same or different and are each integers of from 1 to 4, and n₁, n₂ and n₃ are the same or different and are each integers of from 1 to 3. Non-limiting examples of such amines include 2-pentadecyl imidazoline and N-(2-aminoethyl) piperazine. Non-limiting examples of suitable aliphatic saturated amine compounds include: 1,2-diaminoethane; 1,3-diaminopropane; 1,4-diaminobutane; 1,6-diaminohexane; polyethylene amines such as diethylene triamine; triethylene tetramine; tetraethylene pentamine; polypropylene amines such as 1,2-propylene diamine; di-(1,2-propylene)triamine; di-(1,3-propylene) triamine; N,N-dimethyl-1,3-diamino-propane; N,N-di(2-aminoethyl) ethylene diamine; N,N-di(2-hydroxyethyl)-1,3-propylene diamine; 3-dodecyloxypropylamine; N-dodecyl-1,3-propane diamine; tris hydroxymethylaminomethane (THAM); diisopropanol amine; diethanol amine; triethanol amine; mono-, di-, and tri-tallow amines; amino morpholines such as N-(3-amino-propyl)morpholine; and mixtures thereof. Commercial mixtures of amine compounds may advantageously be used. For example, one process for preparing alkylene amines involves the reaction of an alkylene dihalide (such as ethylene dichloride or propylene dichloride) with ammonia, which results in a complex mixture of alkylene amines wherein pairs of nitrogens are joined by alkylene groups, forming such compounds as diethylene triamine, triethylenetetramine, tetraethylene pentamine and isomeric piperazines. Low cost poly(ethyleneamines) compounds averaging 5 to 7 nitrogen atoms per molecule are available commercially under trade marks such as "Dow Polyamine E-100". The ethylene amines, which are particularly useful aliphatic saturated amines, are described, for example, in the Encyclopedia of Chemical Technology under the heading "Ethylene Amines" (Kirk and Othmer), Volume 5 pgs. 898-905; Interscience Publishers, New York (1950). These compounds are prepared by the reaction of an alkylene chloride with ammonia. This results in the production of a complex mixture of alkylene amines, including cyclic condensation products such as piperazines. While mixtures of these amines may be used for purposes of this invention, it is obvious that pure alkylene amines may be used with complete satisfaction. The polyoxyalkylene polyamines of formulas V and VI above, preferably polyoxyalkylene diamines and polyoxyalkylene triamines, may have average molecular weights ranging from 200 to 4,000 and preferable from 400 to 2,000. The preferred polyoxyalkylene polyamines include the polyoxyethylene and polyoxypropylene diamines and the polyoxypropylene triamines having average molecular weights ranging from 200 to 2,000. The polyoxyalkylene polyamines are commercially available and may be obtained, for example, from the Jefferson Chemical Company, Inc. under the trade name "Jeffamines D-230, D-400, D-1000, D-2000 and T-403. THE ACID COMPOUNDS The acid component includes hydrocarbyl substituted succinic anhydride or acid having 12 to 49 carbons, (e.g. dodecyl, tetradodecyl, octadecyl, octadodecenyl, etc.) preferably 16 to 49 carbons in said hydrocarbyl group; long chain monocarboxylic acid of the formula RCOOH where R is hydrocarbyl group of 25 to 400 carbons; and long chain hydrocarbyl substituted succinic anhydride or acid having 25 to 400 carbons in said hydrocarbyl groups. The hydrocarbyl groups are essentially aliphatic and include alkenyl and alkyl groups. The long chain acids and anhydrides are preferred, particularly when the grafting reaction is carried out in lubricating oil because of ability to impart dispersancy to reacted oil molecules as well as their greater solubilizing effect. Primarily because of its ready availability and low cost, the long chain hydrocarbyl portion, e.g. long chain alkenyl groups of the carboxylic acid or anhydride preferably is derived from a polymer of a C₂-C₅ monoolefin, said polymer generally having a molecular weight of 350 to 5,000 e.g., 700 to 5,000, most preferably 700 to 3,000. Particularly preferred is polyisobutylene. PRE-REACTED AMINE-ACID COMPONENT The aforesaid amine and acid components may be pre-reacted, with the acid being generally attached to the amine linkages so that a primary amine group of the polyamine is still available for reaction with the acid moieties of the grafted polymer. A convenient source of these prereacted materials are the well-known lubricating oil dispersants provided they retain primary amine groups capable of further reaction with the grafted polymer. Usually, these dispersants are made by condensing a hydrocarbyl substituted monocarboxylic acid or a dicarboxylic acid, having 25 to 400 carbons in the hydrocarbyl substituent, as described above under the "The Acid Component", preferably a succinic acid producing material such as alkenyl succinic anhydride, with an amine or polyamine, including those described above under "The Amines". Monocarboxylic acid dispersants can be prepared by reacting a polyamine with a high molecular weight monocarboxylic acid derived from a polyolefin, such as polyisobutylene, by oxidation with nitric acid or oxygen; or by addition of halogen to the polyolefin followed by hydrolysis and oxidation; etc. Monocarboxylic acid dispersants can be prepared by halogenating, e.g. chlorinating a polyolefin, such as the polymers of C₂ to C₅ monoolefin, e.g. polypropylene or polyisobutylene, and then condensing the halogenated polyolefin with an alpha, beta-unsaturated, monocarboxylic acid of from 3 to 8, preferably 3 to 4, carbon atoms, e.g. acrylic acid, alpha-methyl-acrylic acid, ie., 2-methyl propanoic acid, and crotonic acid,. and then reacting the resulting product with polyamime. Formation of dicarboxylic acid dispersants by reaction of an amine with alkenyl succinic anhydride prepared from the reaction of a polyolefin or chlorinated polyolefin and maleic anhydride is well known in the art, as seen, for example, in U.S. Patent 3,272,746. Most preferred are the lubricating oil dispersants made by reaction of the aforesaid "aliphatic saturated amines" previously described, with alkenyl succinic anhydride. Reaction, preferably amination and/or imidation of the carboxylic acid material is usually done as a solution reaction with the acid material, usually polyisobutenylsuccinic anhydride, dissolved in a solvent such as mineral oil, to which the other reactant is added. The formation of the dispersants in high yield can be effected by adding from 0.5-3.3:1, preferably 0.7 to 1.3:1, and most preferably 1:1 molar proportions of aliphatic saturated amine: alkenyl succinic anhydride to said solution and heating the mixture of 140°C to 165°C or higher until the appropriate amount of water of reaction is evolved. Typically the mineral oil solvent is adjusted so that it constitutes about 50% by weight of the final acyl nitrogen compound solution. REACTION OF GRAFTED COPOLYMER WITH AMINE AND ACID COMPONENT The grafted polymer, preferably in solution generally equal to 5 to 30 wt.%, preferably 10 to 20 wt. % polymer, can be reacted readily with a mixture of amine and acid components, or with prereacted amine and acid, by being mixed with said grafted polymer and heated at a temperature of from 100°C to 150°C preferably from 170°C to 230°C, for from 1 to 10 hours, usually 2 to 6 hours. The heating is preferably carried out to favor formation of imides rather than amides and salts. This imide formation will give a lower viscosity of the reaction mixture than amide formation, and considerably lower than salt formation. This lower viscosity permits the utilization of a higher concentration of grafted ethylene copolymer in the reaction mixture. Removal of water assures completion of the imidation reaction. Reaction ratios can vary considerably depending upon the reactants, amounts of excess, type of bonds formed, etc. Generally from 1 to 2, preferably 1 mole of said bi-primary amine, and 1 to 4, preferably from 1.5 to 3, most preferably 2 mole equivalent of said acid component (e.g. 2 moles of monocarboxylic or 1 mole of dicarboxylic acid component), is used, per mole of the grafted dicarboxylic acid moiety content, e.g. grafted maleic anhydride content. Alternatively, if pre-reacted amine and acid component is used, such as a dispersant, sufficient dispersant is used to give 1 to 2 primary amine groups per dicarboxylic acid moiety in the grafted polymer, depending on whether primarily imides or amides are formed. Usually 1 to 2 moles of said dispersant is used per molar amount of said dicarboxylic acid moieties in the grafted polymer. For example, for making imides with an ethylene-propylene copolymer of about 40,000 M n i.e. a thickening efficiency of 2.1 and averaging 4 maleic anhydride groups per molecule, 4 moles of amine with two primary groups and 4 moles of alkenyl succinic anhydride preferably would be used per mole of grafted copolymer. THE LACTONE COMPONENT The lactone component which is reacted with the above-described grafted ethylene copolymer/amine/acid component reaction products include lactones which are capable of undergoing a ring opening addition reaction using a secondary amine group on the grafted ethylene copolymer/amine/acid reaction products as the ring opening initiator. The lactones may be substituted or unsubstituted and the substituents, if any, may comprise, for example, alkyl, aryl, aralkyl, cycloalkyl, alkoxy or other groups which would not interfere with the ring opening reaction and adduct formation. The preferred lactones generally have no more than two substituent groups, and the more preferred lactones are unsubstituted. The preferred lactones are polymerizable lactones having at least five or six atoms in the lactone ring, e.g, 5 or 6 to 9 or 10 atoms. Non-limiting examples of the useful lactones include gamma-butyrolactone, methyl-gamma-butyrolactone, delta-valerolactone, methyl-delta-dihexyl-E-caprolactone and methyl-caprolactone, with E-caprolactone being particularly preferred. REACTION OF LACTONE WITH GRAFTED ETHYLENE COPOLYMER/AMINE/ACID COMPONENT REACTION PRODUCT In one aspect of the invention, the novel lactone modified viscosity index improving additives are prepared by reacting the lactone component using the secondary amine functionality of the intermediates formed by reacting the grafted ethylene copolymer with the amino and acid components (hereinafter refered to as the viscosity improving intermediates or precursors) as the ring opening addition and/or polymerization initiator. The ring opening addition and/or polymerization of the lactone component may be carried out, with or with out a catalyst, simply by heating a mixture of the lactone and viscosity improving intermediate material in a reaction vessel in the absence of a solvent at a temperature of 50°C to 200°C, more preferably to a temperature of 75°C to 180°C, and most preferably at 90°C to 160°C, for a sufficient period of time to effect ring opening addition and/or polymerization. Optionally, a solvent for the lactone and/or the polymeric viscosity improving intermediate and/or the desired reaction products can be employed to control viscosity and or reaction rates. In one preferred emodiment of the invention a lactone is reacted with a viscosity improving intermediate which has been prepared by reacting an ethylene-propylene copolymer grafted with maleic anhydride moieties and reacted with an alkylene polyamine and a polyisobutenyl succinic acid or anhydride as outlined above. This reaction can be depicted generally, for example, by the equation: where R is ethylene-propylene copolymer, polyisobutylene and/or solvent, e.g. mineral oil, (when the ring opening reaction is conducted in the presence of a solvent); alkylene is an alkylene radical which is straight or branched chain and which contains from 2 to 7, preferably 2 to 4 carbon atoms; x is a number from 1 to 10, preferably from 2 to 7; y is a number from 1 to about 7, preferably from 3 to 6, and more preferably 4; and m has an average value of from 0.2 to 100, preferably from 0.2 to 50, and more preferably from 0.5 to 20. It will be appreciated that a variety of products may be formed, and that in most cases, the reaction mass will comprise a mixture viscosity index improving lactone modified products. It will be appreciated, also, that when lactones having less than about five atoms in the lactone ring, such as butyrolactone, are employed, the average value of m in the above equation cannot exceed 1 under the reaction conditions disclosed herein. Catalysts useful in the promotion of the above identified reactions, particularly in cases where the lactone component is a polymerizable lactone, are selected from the group consisting of stannous octanoate, stannous hexanoate, stannous oxalate, tetrabutyl titanate, a variety of metal organic based catalyst acid catalysts and amine catalysts, as described on page 266, and forward in a book chapter authored by R.D. Lundberg and E.F. Cox entitled, "Kinetics and Mechanisms of Polymerication: Ring Opening Polymerization"; edited by Frisch and Reegen, published by Marcel Dekker in 1969, where stannous octanoate is an especially preferred catalyst. The catalyst is added to the reaction mixture at a concentration level of 50 to 10,000 parts of catalyst per one million parts by weight of total reaction mixture. In reactions discussed above, when a polymerizable lactone component is employed, the degree of polymerization (DP) of the lactone monomer may vary depending upon the intended application. At DP's much greater than 10, e.g., greater than 50, the lactone modified viscosity index improvers can exhibit crystallinity; a characteristic which is undesirable in an oil soluble additive due to the consequent high viscosity, or even solid, oil products which can be obtained. However, at lower DP's oil soluble viscosity index improvers are obtained. Accordingly, regardless of the identity of the lactones and viscosity improving precursors, the average value of m (or the degree of polymerization (DP)) should be between 0.2 and 100, more preferably between 0.2 and 50, and most preferably 0.5 and 20. THE COMPOSITIONS The lactone modified additives of the present invention have been found to possess very good viscosity index improving and dispersant properties as measured herein in a wide variety of environments. Accordingly, the lactone modified additives are used by incorporation and dissolution into an oleaginous material such as lubricating oil or hydrocarbon fuel. When the lactone modified viscosity index improvers of this invention are used in normally liquid petroleum fuels such as middle distillates boiling from 65° to 430°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 0.001 to 0.5, and preferably 0.001 to 0.1 weight percent, based on the total weight of the composition, usually will be employed. However, the present lactone modified viscosity index improvers 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 although the natural base oils will derive a greater benefit. Thus, base oils suitable for use in preparing lubricating compositions of the present invention 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. Advantageous results are also achieved by employing the lactone modified viscosity index improving 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, and power steering fluids. Gear lubricants, industrial oils, pump oils and other lubricating oil compositions can also benefit from the incorporation therein of the additives of the present invention. Thus, the additives of the present invention may be suitably incorporated into synthetic base oils such as alkyl esters of dicarboxylic acids, polyglycols and alcohols; polyalphaolefins, alkyl benzenes, organic esters of phosphoric acids, and polysilicone oils. Natural base oils include mineral lubricating oils which may very widely as to their crude 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. More specifically, the natural lubricating oil base stocks which can be used in the compositions of this invention may be straight mineral lubricating oil or distillates derived from paraffinic, naphthenic, asphaltic, or mixed base crudes, or, if desired, various blends oils may be employed as well as residuals, particularly those from which asphaltic constituents have been removed. The oils may be refined by conventional methods using acid, alkali, and/or clay or other agents such as aluminum chloride, or they may be extracted oils produced, for example, by solvent extraction with solvents of the type of phenol, sulfur dioxide, furfural, dichlorodiethyl ether, nitrobenzene, crotonaldehyde, molecular sieves, etc. The lubricating oil base stock conveniently has a viscosity of typically about 2.5 to about 12, and preferably about 2.5 to about 9 cs. at 100°C. Thus, the lactone modified additives of the present invention can be employed in a lubricating oil composition which comprises lubricating oil, typically in a major amount, and the lactone modified additive, typically in a minor amount, which is effective to impact enhanced viscosity index improvement relative to the absence of the additive. Additional conventional additives selected to meet the particular requirements of a selected type of lubricating oil composition can be included as desired. The viscosity index improvers of this invention are oil-soluble, dissolvable in oil with the aid of a suitable solvent, or are stably dispersible materials. Oil-soluble, dissolvable, or stably dispersible, as that terminology is used herein, does not necessarily indicate that the materials are soluble, dissolvable, miscible, or capable of being suspended in oil in all proportions. It does mean, however, that the lactone modified viscosity index improving additives, for instance, are soluble or stably dispersible in oil to an extent sufficient to exert their intended effect in the environment in which the oil is employed. Moreover, the additional incorporation of other additives may also permit incorporation of higher levels of a particular lactone modified viscosity index improver, if desired. Accordingly, while any effective amount of the present viscosity index improving additives can be incorporated into the lubricating oil composition, it is contemplated that such effective amount be sufficient to provide said lube oil composition with an amount of the additive of typically from 0.1 to 10 wt.%, e.g., 0.3 to 8 wt.%, and preferably from 0.5 to 5 wt.%, based on the weight of the total composition. The viscosity index improving additives of the present invention can be incorporated 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 blending can occur at room temperature or elevated temperatures. Alternatively, the dispersant additives may be blended with a suitable oil-soluble solvent and/or base oil to form a concentrate, and then blending the concentrate with lubricating oil base stock to obtain the final formulation. Concentrates typically will contain from 10 wt.% to 50 wt.%, preferably 10 to 30 wt.% viscosity index improving additive, and typically from 50 to 90%, preferably from 70 to 90% by weight base oil, based on the concentrate weight. The lubricating oil base stock for the viscosity index improving 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 include dispersants, other viscosity modifiers, corrosion inhibitors, oxidation inhibitors, friction modifiers, anti-foaming agents, anti-wear agents, pour point depressants, neutral or overbased metal detergents (e.g. Ca or Mg sulfonates or phenates) and demulsifiers. Viscosity modifiers impart high and low temperature operability to the lubricating oil and permit it to remain shear stable at elevated temperatures and also exhibit acceptable viscosity or fluidity at low temperatures. Viscosity modifiers are generally high molecular weight polymers including hydrocarbon polymers and polyesters. The viscosity modifiers may also be derivatized to include other properties or functions, such as the addition of dispersancy properties. Oil soluble viscosity modifying polymers will generally have number average molecular weights of from 10³ to 10⁶, preferably 10⁴ to 10⁶, e.g., 20,000 to 250,000, as determined by gel permeation chromatography or membrane osmometry. Representative examples of suitable viscosity modifiers which may be used in combination with the lactone modified viscosity index improving additives of the present invention are any of the types known to the art including polyisobutylene, copolymers of ethylene and propylene, polymethacrylates, methacrylate copolymers, copolymers of an unsaturated dicarboxylic acid and vinyl compound and interpolymers of styrene and acrylic esters. Corrosion inhibitors, also known as anti-corrosive agents, reduce the degradation of the metallic parts contacted by the lubricating oil composition. Illustrative of corrosion inhibitors are zinc dialkyldithiophosphates, phosphosulfurized hydrocarbons and the products obtained by reaction of a phosphosulfurized hydrocarbon with an alkaline earth metal oxide or hydroxide, preferably in the presence of an alkylated phenol or of an alkylphenol thioester, and also preferably in the presence of carbon dioxide. Phosphosulfurized hydrocarbons are prepared by reacting a suitable hydrocarbon such as a terpene, a heavy petroleum fraction of a C₂ to C₆ olefin polymer such as polyisobutylene, with from 5 to 30 wt.% of a sulfide of phosphorus for 1/2 to 15 hours, at a temperature in the range of 65-315°C 150°C to 600°F. Neutralization of the phosphosulfurized hydrocarbon may be effected in the manner taught in U.S. Patent No. 1,969,324. Oxidation inhibitors reduce the tendency of mineral oils to deteriorate in service which deterioration is evidenced by the products of oxidation such as sludge and varnish-like deposits on the metal surfaces. Such oxidation inhibitors include alkaline earth metal salts of alkylphenolthioesters having preferably C₅ to C₁₂ alkyl side chains, e.g., calcium nonylphenol sulfide, barium t-octylphenyl sulfide, dioctylphenylamine, phenylalphanaphthylamine, phosphosulfurized or sulfurized hydrocarbons. Friction modifiers serve to impart the proper friction characteristics to lubricating oil compositions such as automatic transmission fluids. Representative examples of suitable friction modifiers are found in U.S. Patent No. 3,933,659 which discloses fatty acid esters and amides; U.S. Patent No. 4,176,074 which describes molybdenum complexes of polyisobutyenyl succinic anhydride-amino alkanols; U.S. Patent No. 4,105,571 which discloses glycerol esters of dimerized fatty acids; U.S. Patent No. 3,779,928 which discloses alkane phosphonic acid salts; U. S. Patent No. 3,778,375 which discloses reaction products of a phosphonate with an oleamide; U. S. Patent No. 3,852,205 which discloses S-carboxyalkylene hydrocarbyl succinimide, S-carboxyalkylene hydrocarbyl succinamic acid and mixtures thereof; U. S. Patent No. 3,879,306 which discloses N-(hydroxyalkyl)alkenyl-succinamic acids or succinimides; U. S. Patent No. 3,932,290 which discloses reaction products of di-(lower alkyl) phosphites and epoxides; and U. S. Patent No. 4,028,258 which discloses the alkylene oxide adduct of phosphosulfurized N-(hydroxyalkyl) alyenyl succinimides. The most preferred friction modifiers are succinate esters, or metal salts thereof, of hydrocarbyl substituted succinic acids or anhydrides and thiobis alkanols such as described in U.S. Patent No. 4,344,853. Dispersants maintain oil insolubles, resulting from oxidation during use, in suspension in the fluid thus preventing sludge flocculation and precipitation or deposition on metal parts. Suitable dispersants include high molecular weight alkyl succinates, the reaction product of oil-soluble polyisobutylene succinic anhydride with ethylene amines such as tetraethylene pentamine and borated salts thereof. Pour point depressants lower the temperature at which the fluid will flow or can be poured. Such depressants are well known. Typically of those additives which usefully optimize the low temperature fluidity of the fluid are C₈-C₁₈ dialkylfumarate vinyl acetate copolymers, polymethacrylates, and wax naphthalene. Foam control can be provided by an antifoamant of the polysiloxane type, e.g., silicone oil and polydimethyl siloxane. Anti-wear agents, as their name implies, reduce wear of metal parts. Representatives of conventional anti-wear agents are zinc dialkyldithiophosphates, zinc diaryldithiophosphates and magnesium sulfonate. Detergents and metal rust inhibitors include the metal salts of sulphonic acids, alkyl phenols, sulfurized alkyl phenols, alkyl salicylates, naphthenates and other oil soluble mono- and dicarboxylic acids. Highly basic (viz, overbased) metal salts, such as highly basic alkaline earth metal sulfonates (especially Ca and Mg salts) are frequently used a detergents. Representative examples of such materials, and their methods of preparation, are found in co-pending Serial No. 754,001 filed July 11, 1985. Some of these numerous additives can provide a multiplicity of effects, e.g., a dispersant-oxidation inhibitor. This approach is well known and need not be further elaborated herein. Some of these numerous additives can provide a multiplicity of effects, e.g., a dispersant-oxidation inhibition. This approach is well known and need not be elaborated upon further herein. Compositions, when containing these conventional 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: Compositions Wt.% A.I. (Preferred) Wt.% A.I. (Broad) Viscosity Modifier .01-4 0.01-12 Detergents 0.01-3 0.01-20 Corrosion Inhibitor 0.01-1.5 .01-5 Oxidation Inhibitor 0.01-1.5 .01-5 Dispersant 0.1-8 .1-20 Pour Point Depressant 0.01-1.5 .01-5 Anti-Foaming Agents 0.001-0.15 .001-3 Anti-Wear Agents 0.001-1.5 .001-5 Friction Modifiere 0.01-1.5 .01-5 Mineral oil Base Balance Balance When other additives are employed, it may be desirable, although not necessary, to prepare additive concentrates comprising concentrated solutions or dispersions of the other additives, i.e., other than the present viscosity index improvers, (said concentrate when constituting an additive mixture being referred to herein as an additive-package) whereby several additives can be added simultaneously to the base oil to form a lubricating oil composition which lacks only the viscosity index improvers. Dissolution of the additive concentrate into the lubricating oil may be facilitated by solvents and by mixing accompanied with mild heating, but this is not essential. The concentrate or additive-package typically will be formulated to contain the additives in proper amounts to provide the desired concentration in the final formulation when the additive-package is combined with a predetermined amount of base lubricant. Thus, the desired additives, other than the viscosity index improver of the present invention, can be added to small amounts of base oil or other compatible solvents to form additive-packages containing active ingredients in collective amounts of typically from 2.5 to 90%, and preferably from 5 to 75%, and most preferably from 8 to 50% by weight additives in the appropriate proportions with the remainder being base oil. The final formulations may employ typically 10 wt.% of the additive-package with the remainder being base oil. 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 of the A.I. weight of each additive plus the weight of total oil or diluent. This invention will be further understood by reference to the following examples, wherein all parts are parts by weight and all molecular weights are number average molecular weights unless otherwise noted, and which include preferred embodiments of the invention. EXAMPLE 1 Ethylene-propylene copolymer grafted with maleic anhydride (EPSA) in an oil solution was prepared in a reaction flask equipped with a stirrer, thermometer, dropping funnel, nitrogen inlet so as to maintain a nitrogen blanket, an overhead condenser and water trap. The preparation was carried out by dissolving 200 grams of ethylene-propylene copolymer in 800 grams of Solvent 100 Neutral oil (SN), which is a mineral lubricating oil having a viscosity of 22 cm²/sec x 10² (100 SUS) at 37.8°C in said reactor by warming to 100°C under a nitrogen blanket. Then 8.4 grams of maleic anhydride and 2.1 grams of ditertiary butyl peroxide as a free radical initiator were added and the reaction mixture was further heated with stirring to 190°C and maintained at this temperature for one-half hour, followed by nitrogen stripping for another one-half hour to remove volatiles and then followed by cooling to give the oil solution of the grafted polymer. The resulting oil solution analyzed for 0.10 meq. of anhydride per gram of solution. The ethylene-propylene copolymer consisted of 44 wt.% ethylene and 56 wt.% propylene and had a T.E. (thickening efficiency) of 1.25 which represents a number average molecular weight of approximately 20,000. Thickening efficiency (T.E.) is defined as the ratio of the weight percent of a polyisobutylene (sold as an oil solution by Exxon Chemical Co. as Paratone N), having a Staudinger Molecular Weight of 20,000, required to thicken a solvent-extracted neutral mineral lubricating oil, having a viscosity of 150 and an ASTM pour point of -18°C (0°F) (Solvent 150 Neutral) to a viscosity of 12.4 centistokes at 98.9°C to the weight percent of a test copolymer required to thicken the same oil to the same viscosity at the same temperature. T.E. is related to M n and is a convenient, useful measurement for formulation of lubricating oils of various grades. EXAMPLE 2 A polyisobutenyl succinic anhydride (PIBSA) having an SA:PIB ratio of 1.04 succinic anhydride (SA) moieties per polyisobutylene (PIB) molecule of 940 M n was prepared by heating a mixture of 100 parts of polyisobutylene with 13 parts of maleic anhydride to a temperature of 220°C. When the temperature reached 120°C, chlorine addition was begun and 1.05 parts of chlorine at a constant rate were added to the hot mixture for 5 hours. The reaction mixture was then heat soaked at 220°C. for 1.5 hours and then stripped with nitrogen for 1 hour. The resulting polyisobutenyl succinic anhydride had an ASTM Saponification Number of 112 which calculates to a succinic anhydride (SA) to polyisobutylene (PIB) ratio of 1.04 based upon the starting PIB as follows: The PIBSA product was 90 wt.% active ingredient (a.i.), the remainder being primarily unreacted PIB. The SA:PIB ratio of 1.04 is based upon the total PIB charged to the reactor as starting material, i.e. both the PIB which reacts and the PIB which remains unreacted. EXAMPLE 3 Part A 2000 grams of oil concentrate containing 20 wt.% of the ethylene-propylene copolymer grafted with maleic anhydride prepared in accordance with EXAMPLE 1 having an acidity of 0.1 meq./gram, were added to a reactor together with 1300 grams of Solvent 150 Neutral oil and 100 grams of the PIBSA prepared in EXAMPLE 2 and were heated to 150°C with stirring in order to form an oil solution containing 12 wt.% of the grafted ethylene-propylene copolymer. Then, 20.6 grams of diethylene triamine were slowly added over about 30 minutes to the reactor while maintaining the temperature at about 190°C. The reaction mixture was then nitrogen stripped for 2 hours and cooled to form a final product, (EPSA-DETA-PIBSA), which analyzed for 0.34 wt.% nitrogen for the oil solution. EXAMPLE 4 The same procedure as in EXAMPLE 1 was followed except that the ethylene-propylene copolymer had a TE of 2.1 and was dissolved in S150N to make a 15 wt.% ethylene-propylene solution. The final grafted oil solution had an anhydride number of 0.14 meq. of anhydride per gram of solution. EXAMPLE 5 500 grams of the EPSA-DETA-PIBSA product prepared in EXAMPLE 3 were mixed with 4.62 grams of E-caprolactone (CL) end 0.01 grams of stannous octanoate. The mixture was heated slowly heated to 160°C while stirring under a nitrogen blanket. The mixture was kept at 160°C for three hours. At the end of the third hour the resulting product (EPSA-DETA-PIBSA-CL) was nitrogen stripped at 160°C for ten minutes and collected. Infrared Analysis of the reaction mixture showed that the lactone was completely reacted within the first hour. EXAMPLE 6 The procedure of EXAMPLE 5 was repeated except that 9.24 grams of CL were reacted with the EPSA-DETA-PIBSA. EXAMPLE 7 The procedure of EXAMPLE 5 was repeated except that 500 grams of the EPSA-DETA-PIBSA product of EXAMPLE 4 were used instead of the EPSA-DETA-PIBSA product of EXAMPLE 3 EXAMPLE 8 The procedure of EXAMPLE 7 was repeated except that 9.24 grams of CL were reacted with the EPSA-DETA-PIBSA. EXAMPLE 9 The procedure of EXAMPLE 5 is repeated except that 3.5 grams of butyrolactone (BL) are used instead of the CL. Samples of the EPSA-DETA-PIBSA products of EXAMPLES 3 and 4 (controls) and the various EPSA-DETA-PIBSA-CL products were then subjected to a standard sludge inhibition bench test (SIB) and a standard varnish inhibition bench test (VIB). The SIB and VIB tests forecast the performance of a lubricant in a gasoline engine. These tests are described below: The SIB test employs a used crankcase mineral lubricating oil composition having an original viscosity of 70 cm²/sec x 10² (325 SUS) at 37.8°C that has been used in a taxicab that was driven generally for short trips only, thereby causing a buildup of a high concentration of sludge precursors. The oil used contains only a refined base mineral oil, a viscosity index improver, a pour point depressant and zinc dialkyldithiophosphate antiwear additives. The oil contains no sludge dispersants. Such oil is acquired by draining and refilling taxicab crankcases at 1610 - 3220 km (1,000-2,000 mile) intervals. The SIB test is conducted in the following manner: The used crankcase oil is freed of sludge, by centrifuging for one half hour at 382,000 m/sec² (39,000) gravities (gs). The resulting clear bright red oil is then decanted from the insoluble sludge particles. However, the supernatant oil still contains oil-soluble sludge precursors which, under the conditions employed by this test, tend to form additional oil-insoluble deposits of sludge. The sludge inhibiting properties of the additives being tested are determined by adding to portions of the used oil 0.5 wt.% on an active basis, of the particular additive being tested. Ten grams of each one being tested is placed in a stainless steel centrifuge tube and is heated at 140°C for 16 hours in the presence of air. Following the heating, the tube containing the oil being tested is cooled and then centrifuged for 30 minutes at 382,000 m/sec² (39,000 gs). Any deposits of new sludge that form in this step are separated from the decanting supernatant oil and then carefully washed with 15 ml. of pentane to remove all remaining oils from the sludge. The weight in milligrams of the new solid sludge that forms in the test is determined by drying the residue and weighing it. The results are reported as milligrams of sludge per ten grams of oil thus measuring differences as small as one part per ten thousand. The less new sludge formed, the more effective is the additive as a dispersant. In other words, if the additive is effective, it will hold at least a portion of the new sludge that forms on heating and oxidation, stably suspended in the oil so that it does not precipitate during the centrifuging period. In the VIB test, a test sample consisting of ten grams of lubricating oil containing 0.5 wt.%, on on active basis, of the additive being evaluated is used. The test oil is a commercial lubricating oil obtained from a taxi after 3220 km (2,000 miles) of driving with said lubricating oil. Each sample is heat soaked overnight at 140°C and thereafter centrifuged to remove the sludge. The supernatant fluid of each sample is subjected to heat cycling from 150°C to room temperature over a period of 3.5 hours at a frequency of two cycles per minute. During the heating phase, a gas containing a mixture of 0.7 volume percent SO₂, 1.4 volume percent NO and the balance air is bubbled through the test samples and during the cooling phase, water vapor was bubbled through the test samples . At the end of the test period, which testing cycle can be repeated as necessary to determine the inhibiting effect of any additive, the wall surfaces of the test flasks in which the samples are contained are. visually evaluate as to the varnish inhibition. The amount of varnish deposited on the walls is rated at values of from one to eleven with the higher number being the greater amount of varnish. It has been found that this test forecasts the varnish results obtained as a consequence of carrying out the ASTM MS-VD engine tests which is described more fully in ASTM Document for Multigrade Test Sequence for Evaluating Automotive Engine Oil, Sequence VD, Part 3 of STP 315H. Table I, which follows, summarizes the compositions tested and the test results; The data in Table I indicate that the EPSA-DETA-PIBSA-CL adducts of the present invention result in superior VIB values in all cases for comparative runs A and B. The SIB values, which are acceptale in all cases, are superior to those reported for the unmodified EPSA-DETA-PIBSA control when the amount of CL in the adduct is 1% for comparative run A, and 3% for comparative run B. Thus, the data, particularly in VIB data, suggest that the present EPSA-DETA-PIBSA-CL adducts are likely to outperform the known EPSA-DETA-PIBSA V.I. additives of otherwise corresponding structure. The present lactone modified additives, when used in low concentrations on the order of a 50 to 3000 ppm, will function as flow improvers for lubricating oils and fuels. Such flow improvers modify the size, number and growth of wax crystals in lubricating oils and fuels in a manner sufficient to improve the low temperature: handling, pumpability, and/or vehicle operability. As used herein, the term aliphatic saturated amine is meant to define the above-described amines of formulas II, III, and IV, and the term oxyalkylene amine is meant to define the above-described amines of formulas V and VI. As will be evident to those skilled in the art, various modifications on this invention can be made or followed, in light of the foregoing disclosure and illustrative examples, tables and discussion, within the scope of the invention as set forth in the following claims.

Claims: A process for producing a reaction product useful as a viscosity improver and dispersant additive for lubricating oil compositions comprising: grafting an oil soluble ethylene copolymer comprising from 15 to 90 wt% ethylene and from 10 to 85 wt% of one or more C₃₋₂₈ alpha-olefins, and having a number average molecular weight of 15,000 to 500,000 with ethylenically unsaturated C₄₋₁₀ mono- or dicarboxylic acid or anhydride wherein the carboxylic acid or anhydride groups are located on vicinal carbon atoms, to produce a grafted copolymer (a); reacting the grafted copolymer (a) with (b) an amine having at least two primary amine groups or having at least one primary amine group and at least one secondary amine group, and (c) an acid component selected from (i) a C₁₂₋₄₉ hydrocarbyl substituted succinic anhydride or acid; (ii) a C₂₅₋₄₀₀ hydrocarbyl substituted succinic anhydride or acid; and (iii) a C₂₅₋₄₀₀ hydrocarbyl substituted monocarboxylic acid; and (d) a lactone; wherein (a), (b) and (c) are first reacted and then (d) is reacted. A process according to claim 1 wherein (a), (b) and (c) are reacted simultaneously with removal of water, and (d) is reacted subsequently. A process according to claim 1 wherein (a) and (b) are first reacted, followed by reaction with (c) and then (d). A process according to any of claims 1 to 3 wherein said ethylene copolymer consists essentially of a copolymer containing from 30 to 80 wt.% ethylene and 20 to 70 wt.% propylene and a number average molecular weight from 15,000 to 200,000. A process according to claim 4 wherein said C₄₋₁₀ acid or anhydride consists essentially of maleic anhydride and wherein from 1 to 2 molar proportions of (b) and from 1 to 4 molar proportions of (c) are used per molar proportion of maleic anhydride. A process according to any of claims 1 to 5 wherein (c) is hydrocarbyl substituted succinic acid or anhydride and wherein said hydrocarbyl substituent is an alkenyl or alkyl group derived from a polymer of C₂₋₅ monoolefin. A process according to any of claims 1 to 6 wherein (d) comprises a polymerisable lactone having from 6 to 10 atoms in the lactone ring. A process according to any of claims 1 to 6 wherein (d) comprises E-caprolactone. A process according to any of claims 1 to 6 wherein (d) gamma-butyrolactone. A process according to any of claims 1 to 6 wherein said reaction product corresponds to the formula: where R is ethylene-propylene copolymer, R' is polyisobutylene, alkylene is C₂₋₇, x is 1 to 10, y is 1 to 7 and m has an average value from 0.2 to 100. A process according to claim 10 wherein m has an average value from 0.5 to 20. A process according to any preceding claim wherein (b) is a polyamine of the general formula H₂N-[-alkylene-NH-) x -H where x is 1 to 10 and alkylene is ethylene or propylene. A process according to any preceding claim wherein (c) is C₂₅₋₄₀₀ polyisobutenyl succinic anhydride. A process according to any preceding claim wherein said grafting step is conducted in a lubricating mineral oil solution. A process according to any preceding claim wherein said grafting step is conducted at a temperature from 150 to 200°C using a free radical initiator. A viscosity index improving additive having improved dispersant properties obtainable by the process according to any preceding claim. A lubricating composition comprising a viscosity index improving additive according to claim 16. A lubricating composition according to claim 17 wherein said additive is present in an amount from 0.1 to 10 wt.%. A lubricating composition according to claim 17 wherein said additive is present in an amount from 0.5 to 5 wt.%. An oil concentrate comprising a viscosity index improving additive according to claim 16. Art oil concentrate wherein said additive is present in an amount from 10 to 50 wt.%. Art oil concentrate wherein said additive is present in an amount from 10 to 30 wt.%.

Inventors: GUTIERREZ ANTONIO, LUNDBERG ROBERT DEAN, GUTIERREZ, ANTONIO, LUNDBERG, ROBERT DEAN
Applicants: EXXON CHEMICAL PATENTS INC, EXXON CHEMICAL PATENTS INC.
Application year: 1989
Main classification: C10M133
IPC codes: C10M143, C10L1, C10M159, C08G63, C10M133