Patent Publication Number: US-4925579-A

Title: Lubricating oil containing hydroperoxidized ethylene copolymers and terpolymers as dispersants and V.I. improvers

Description:
This is a continuation of application Ser. No. 505,661, filed June 20, 1983. 
    
    
     BACKGROUND OF THE INVENTION 
     1. Field of the Invention 
     The present invention relates to lubricating oil compositions which contain oil soluble hydroperoxidized polymeric additives which improve the sludge and varnish dispersancy as well as improving the viscosity index characteristics of the lubricating oil. 
     2. Description of the Prior Art 
     An important property of a lubricant composition is the rate at which its viscosity changes as a function of temperature. The relationship between the viscosity and temperature is commonly expressed in terms of the viscosity index (V.I.). Lubricant compositions which change little in viscosity with variations in temperature have greater viscosity index than do compositions whose viscosity is materially affected by changes in temperature. It is readily apparent, therefore, that one of the major requirements of lubricating oils or other hydrocarbon oil products is their satisfactory viscosity-temperature characteristics. These characteristics are necessary in order that the oil&#39;s viscosity will not become too low but will show an equally good performance within a relatively wide temperature range to which it may be exposed in service. The wider the possible temperature variations, the smaller should be the change in viscosity with temperature. Hence, the viscosity-temperature characteristics of a lubricant which is used in applications where wide variations in temperature are encountered are of great importance and lubricant compositions having high viscosity indices are highly desirable. 
     Also, lubricants for modern, high compression, piston-type internal combustion engines must necessarily have high detergency properties, i.e., they must have efficient sludge and varnish dispersant action and chemical and thermal stability in order to free the engines from deposits of varnish, sludge and coke-like materials. Generally, a heavy duty detergent type lubricating oil is employed in such engines in order to maintain the desired high degree of engine cleanliness and thereby promote longer engine life. 
     A variety of polymeric or high molecular weight materials have been described as viscosity index improvers for lubricants. For example: U.S. Pat. Nos. 3,551,336 and 3,691,078 teach the preparation of ethylene copolymers which act as viscosity index improvers for lubricants. 
     U.S. Pat. No. 3,417,020 teaches a process for preparing viscosity index improvers by reacting an olefinic polymer with ozone and reduction of the resulting ozonolysis product until carbonyl groups are formed thereon. 
     U.S. Pat. No. 3,388,067 teaches lubricating oil compositions of improved viscosities containing degraded ethylene-alpha-olefin polymers wherein the degraded polymers have been hydroxylated. The hydroxylated degraded polymers are prepared by hydroperoxidizing the polymer with subsequent reduction of the hydroperoxide groups to yield degraded products containing hydroxyl groups and minor amounts of carboxyl, keto and aldehyde groups. 
     U.S. Pat. No. 3,756,954 teaches the preparation of viscosity index improvers prepared by air oxidation of interpolymers of ethylene and propylene in the presence of an aliphatic amine. 
     British Pat. No. 2,040,296A teaches the preparation of a viscosity index improver additive by oxidatively and mechanically degrading an ethylene copolymer containing as one of its components from 0.05 to 3% of 2,5-norbornadiene. 
     Also, a variety of compositions comprising polymeric or high molecular weight materials which incorporate nitrogen have been described as dispersants and as viscosity index improvers for lubricants. For example: 
     U.S. Pat. No. 3,316,177 teaches reaction of polyamine with the reaction product of maleic anhydride with an oxidized interpolymer of ethylene and propylene, as a sludge dispersant in lubricant and fuel compositions. 
     U.S. Pat. No. 3,404,091 describes the preparation of nitrogen containing polymers, useful as sludge dispersants and viscosity index improvers, by grafting polar monomers such as acrylonitrile onto hydroperoxidized ethylene-propylene copolymers. 
     U.S. Pat. No. 3,404,092 describes the preparation of polymeric viscosity index improvers containing urethane groups by the reaction of hydroxylated ethylene-propylene copolymers with isocyanates. 
     U.S. Pat. No. 3,687,849 describes the preparation of viscosity index improvers, pour point depressants and dispersants, for fuels and lubricants, by grafting various unsaturated monomers onto a degraded, oxidized, interpolymer of ethylene and propylene. 
     U.S. Pat. No. 3,687,905 describes the preparation of additives for fuels and lubricants by the reaction of an unsaturated acid, such as maleic acid or anhydride, with an oxidized, degraded interpolymer of ethylene and propylene, followed by reaction with a polyamine. 
     British Pat. No. 983,040 describes the preparation of detergent additives for lubricants by the reaction of a polyamine with a long chain monocarboxylic acid prepared by oxidation of an olefin polymer. 
     British Pat. No. 1,027,410 describes the preparation of ashless detergents for lubricating oils by the reaction of a polyhydroxyamine with a polymeric monocarboxylic acid. 
     British Pat. No. 1,172,818 describes the preparation of additives for lube oils by the condensation of an amine with an ozonized polymer. 
     U.S. Pat. No. 3,769,216 discloses the preparation of lube oil additives by the condensation of an amine with an oxidized ethylene-propylene copolymer, prepared by air blowing in the presence of a peroxide (also see U.S. Pat. No. 3,785,980), or by mastication of the polymer in the presence of oxygen. 
     We have now found, however, that dispersant-viscosity index improvers for lubricating oils may be prepared from hydroperoxidized ethylene copolymers and terpolymers which additives contain an excess of carboxylic acid groups over hydroxyl groups, and, further, that functionalization with amines is not required. 
     SUMMARY OF THE INVENTION 
     The present invention advantageously provides an effective oil composition with an ash-free detergent type inhibitor and dispersant and further, the hydroperoxidized polymeric additives used in the lubricating oil composition of this invention are very effective in markedly improving the viscosity index of the lubricating oil compositions to which they are added while concomitantly having excellent thickening power and shear stability. 
     More specifically, the present invention is concerned with a lubricating oil composition comprising an oil of lubricating viscosity and from about 0.05 to 2% by weight of a dispersancy and viscosity index improving hydroperoxidized copolymer of ethylene with one or more alpha-olefins or terpolymer of ethylene, one or more alpha-olefins and one or more non-conjugated diolefins wherein said copolymer and terpolymer has an excess of carboxylic acid to hydroxy groups. The polymeric additive is prepared by dissolving in a solvent a copolymer of ethylene and a C 3  -C 18  alpha-olefin or a terpolymer of ethylene, a C 3  -C 18  alpha-olefin and a C 5  -C 12  non-conjugated diolefin, having a molecular weight in the range of 20,000 to 1,000,000, reacting the copolymer or terpolymer with oxygen in the presence of a free radical initiator, the reaction being carried out at a temperature of from about 60° to 250° C. under a pressure of from 0 to 1000 psig. 
     Another embodiment of this invention is a method of lubricating the crankcase of an internal combustion engine by contacting the surface of the engine with the oil composition containing the hydroperoxidized polymer additive. 
     DETAILED DESCRIPTION OF THE INVENTION 
     The term &#34;copolymer of ethylene with one or more alpha-olefins&#34; as used herein and in the appended claims, refers to essentially amorphous copolymers derived from essentially ethylene and alpha-olefins containing from 3 to 18 carbon atoms. The alpha-olefins have the structure R--CH═CH 2 , where R is C 1  to C 16 , preferably, C 1  to C 8  alkyl radical and preferably C 1  alkyl. 
     Representative examples of the alpha-olefins include: propylene; 1-butene; 4-methyl-1-pentene; 1-pentene; 1-hexene; 1-heptene; 1-octene; 1-nonene; 1-decene; 5-methyl-1-nonene; 5,5-dimethyl-1-octene; 4-methyl-1-hexene; 4,4-dimethyl-1-pentene; 5-methyl-1-hexene; 4-methyl-1-heptene; 5-methyl-1-heptene; 1-heptadecene, etc. Propylene is the most preferred alpha-olefin. 
     These copolymers can be prepared using Ziegler-type catalysts. These reactions are well known and are conventionally employed. Accordingly, the present invention is not predicated upon the particular catalyst system employed in preparing the copolymer starting materials. 
     Additionally, terpolymers may be employed for producing the dispersant-viscosity index improvers herein contemplated. The terpolymers contain ethylene, the same alpha-olefins described above, but in addition small mole percentages, such as from 0.1 to 15%, and preferably, from 1 to 10% of a third unsaturated monomer, viz., a non-conjugated diolefin is employed. These terpolymers are also prepared by conventional processes using Ziegler-type catalysts and forms no part of the invention so far as the production of the terpolymers is concerned. Examples of such third monomers are C 5  to C 12  acyclic or alicyclic non-conjugated diolefins, such as 1,4-hexadiene, 1,4-pentadiene, 2-methyl-1,5-hexadiene, 1,7-octadiene, 5-methylene-2-norbornene, 1,4-cyclohexadiene, etc. 
     Methods of preparation of the copolymers and terpolymers are well known; such methods as described in many U.S. patents, such as, among others, U.S. Pat. Nos. 2,700,663; 2,726,231; 2,933,480; 3,000,866; 3,063,973; 3,083,621; 2,799,668; 2,975,159 and others. 
     The ethylene monomer unit concentration in the polymers of the present invention ranges in general from about 30 mol percent to about 80 mol percent, with about 20 mol percent to about 70 mol percent of the higher alpha-olefin, and 0 to about 15 mol percent of the diolefin. Preferably, the ethylene-higher alpha-olefin copolymers and terpolymers have viscosity average molecular weights ranging from about 20,000 to 1,000,000, preferably, about 40,000 to 500,000. 
     In accordance with the present invention, the heretofore mentioned copolymers and terpolymers are employed as starting materials in a controlled hydroperoxidation reaction using molecular oxygen in the presence of a free radical initiator or mixture of free radical initiators. More specifically, the hydroperoxidized ethylene copolymers and terpolymers which are used in the compositions of this invention are prepared by dissolving the polymer in an inert solvent at a temperature in the range of from about 60° C. to 250° C. using agitation. A free radical initiator is added and oxygen, preferably in the form of air, is added to the reaction medium under a pressure of from 0 to 1,000 psig for a period of from about 0.05 to 20 hours. The introduction of oxygen into the reaction medium may also be initiated prior to the addition of the free radical initiator. The products of the reaction obtained have an excess of carboxylic acid as compared to hydroxy groups. This can occur by the further reaction of initially formed hydroperoxide groups or their decomposition products with the oxidizing agent. 
     The final polymeric product may be recovered from solution by evaporation of the solvent or by precipitation with a non-solvent or by any other suitable method. Alternatively, prior to removal of the inert solvent, a lubricating oil may be added directly to the reaction mixture and the inert solvent removed by vacuum distillation. 
     The additives can be made in batch or continuous operation. In batch operation, the individual components are added to a suitable reaction vessel together or in discrete portions and dissolved in an inert solvent. In continuous operation the reactant or reactants are added continuously to a horizontal or vertical reaction zone at appropriate feed rates in diluent or neat at temperatures to promote easy handling, reaction and solubility. 
     The hydroperoxidation is carried out in solvents relatively inert to the reaction conditions. Solvents such as toluene, xylene, or mineral neutral oils can be used. Preferred solvents are benzene, chlorobenzene, t-butylbenzene and the like. 
     The free radical initiators which may be peroxides, hydroperoxides and azo compounds, which may be used alone or as mixtures thereof, include, for example, cumene hydroperoxide, dicumyl peroxide, benzoyl peroxide, azo-bis(isobutyronitrile), tertiary butyl hydroperoxide, and the like. Preferably the free radical initiator is cumene hydroperoxide, dicumyl peroxide, and mixtures thereof. These free radical initiators have been conventionally employed in effecting hydroperoxidation of polymers and copolymers. 
     It has been found that the more vigorous the oxidation conditions and the longer the length of time maintaining such conditions, the greater the number of carboxyl groups introduced into the starting material. It is sufficient, however, that on an average at least one carboxyl is introduced into each molecule of the starting material. 
     The product produced by the hydroperoxidation reaction is an oil-soluble product of lower molecular weight than the starting material. The molecular weight depends upon the extent and conditions employed during the oxidation reaction. Ultimately, the intermediate hydroperoxidized polymers are converted by further oxidation reactions to fragmented or degraded polymer materials containing an excess of carboxylic acid groups over hydroxyls and wherein the carboxylated polymer materials have viscosity average molecular weight of from about one-half to about one-tenth of the molecular weight of the original material. The acid group content of the carboxylated polymers is in the range of from 1 to 50 mmole/100 g polymer, and preferably from 1 to 10 mmole/100 g, and most preferably from 2 to 6 mmole/100 g polymer. 
     When the carboxylic acid content and hydroxy content are given in terms of mmoles per 100 g of polymer, then the ratio of carboxy to hydroxy is greater than 1, preferably greater than 5 and most preferably greater than 10. The procedure for the determination of the acid group content and hydroxy group content and definition of the terms used therein is given in Example 1. 
     The copolymers or terpolymers of this invention are employed as additives in concentrations of from about 0.05 to 2 percent, preferably from between about 0.5 to 2 percent based on the lubricating oil composition being treated. Higher concentrations of up to 10% by weight and more may be used, however, the major beneficial effects are found in the ranges described. 
     The compositions of this invention have a thickening power in the range of 7-40 cSt or more. &#34;Thickening power&#34; as used herein is defined as the viscosity at 100° C. of a neutral oil having a viscosity at 40° C. of 28.6 cSt and at 100° C. of 4.7 cSt, containing 2.8 weight percent of the dry polymeric composition. Thickening power is thus measured as an actual viscosity of the oil due to incorporation of the polymer. Thickening power is directly related to the molecular weight of the polymer, but is used instead of molecular weight because the ease of measurement and greater practical significance of data. While the thickening power of the compositions of this invention may be broadly defined as being in the range of 7-40 cSt, thickening power is more usually in the range of 15-35 cSt and, preferably, in the range of 15-25 cSt. 
     The carboxylated copolymers and terpolymers used in the compositions of this invention have an infrared spectrum having distinguishing absorbance peaks at frequencies of 1,370-1,380 cm -1 , 1,460-1,470 cm -1 , 1,700-1,750 cm -1 , and 2,800-3,000 cm -1 . Other peaks have been observed at 715-725 cm -1  and 1,150-1,160 cm -1 . 
     More specifically, the copolymers and terpolymers used in the compositions and method of this invention are the intermediate reactants described in U.S. Pat. Nos. 3,785,980 and 4,132,661, which intermediate polymers in each of these patents are subsequently reacted with an amine to form amidated polymers useful as viscosity index improvers and dispersants. 
     The base lubricating oil used in the compositions of the invention are oils of lubricating viscosity, and particularly of the type useful in internal combustion engines and can be predominantly paraffinic, 1-naphthenic or it can be a mixture of both types of mineral oils, as well as synthetic oils which include polymers of various olefins, generally of from 10 carbon atoms or higher, alkylated aromatic hydrocarbons, etc. In general, the base oil will be a relatively highly refined mineral oil of predominantly a paraffinic nature and will have a viscosity in the range of from 2 to about 20 cSt at 100° C. 
     The lubricating oil compositions of this invention are particularly useful in lubricating an internal combustion engine and may be used in both compression and spark ignition engines. Thus, they may be used to lubricate both automobile and railroad engines. 
     Preferred additives which may be present in the lubricating oil compositions of this invention in order to obtain a proper balance of properties and which are particularly useful in lubricating an internal combustion engine include an alkali or alkaline earth metal sulfonate or phenate or combinations thereof, an alkenyl succinimide or succinate or mixtures thereof and a Group II metal salt of a dihydrocarbyl dithiophosphoric acid. In railroad oil formulations the metal salt dihydrocarbyl dithiophosphate is generally omitted because of the adverse effect of these salts on silver bearings which are present in railroad engines. For railroad oil applications it is advantageous to include as an anti-wear agent from 0.01% to 1% and preferably 0.02% to 0.2% by weight of a sulfurized fatty acid ester. 
     The alkali or alkaline earth metal hydrocarbyl sulfonates may be either petroleum sulfonate, synthetically alkylated aromatic sulfonates, or aliphatic sulfonates such as those derived from polyisobutylene. One of the more important functions of the sulfonates is to act as a detergent and dispersant. These sulfonates are well known in the art. The hydrocarbyl group must have a sufficient number of carbon atoms to render the sulfonate molecule oil soluble. Preferably, the hydrocarbyl portion has at least 20 carbon atoms and may be aromatic or aliphatic, but is usually alkylaromatic. Most preferred for use are calcium, magnesium or barium sulfonates which are aromatic in character. 
     Certain sulfonates are typically prepared by sulfonating a petroleum fraction having aromatic groups, usually mono- or dialkylbenzene groups, and then forming the metal salt of the sulfonic acid material. Other feedstocks used for preparing these sulfonates include synthetically alkylated benzenes and aliphatic hydrocarbons prepared by polymerizing a mono- or diolefin, for example, a polyisobutenyl group prepared by polymerizing isobutene. The metallic salts are formed directly or by metathesis using well-known procedures. 
     The sulfonates may be neutral or overbased having base numbers up to about 400 or more. Carbon dioxide is the most commonly used material to produce the basic or overbased sulfonates. Mixtures of neutral and overbased sulfonates may be used. The sulfonates are ordinarily used so as to provide from 0.3% to 10% by weight of the total composition. Preferably, the neutral sulfonates are present from 0.4% to 5% by weight of the total composition and the overbased sulfonates are present from 0.3% to 3% by weight of the total composition. 
     The phenates for use in this invention are those conventional products which are the alkali or alkaline earth metal salts of alkylated phenols. One of the functions of the phenates is to act as a detergent and dispersant. Among other things, it prevents the deposit of contaminants formed during high temperature operation of the engine. The phenols may be mono- or polyalkylated. 
     The alkyl portion of the alkylphenate is present to lend oil solubility to the phenate. The alkyl portion can be obtained from naturally occurring or synthetic sources. Naturally occurring sources include petroleum hydrocarbons such as white oil and wax. Being derived from petroleum, the hydrocarbon moiety is a mixture of different hydrocarbyl groups, the specific composition of which depends upon the particular oil stock which was used as a starting material. Suitable synthetic sources include various commercially available alkenes and alkane derivatives which, when reacted with the phenol, yield an alkylphenol. Suitable radicals obtained include butyl, hexyl, octyl, decyl, dodecyl, hexadecyl, eicosyl, tricontyl, and the like. Other suitable synthetic sources of the alkyl radical include olefin polymers such as polypropylene, polybutylene, polyisobutylene and the like. 
     The alkyl group can be straight-chained or branch-chained, saturated or unsaturated (if unsaturated, preferably containing not more than 2 and generally not more than 1 site of olefinic unsaturation). The alkyl radicals will generally contain from 4 to 30 carbon atoms. Generally when the phenol is monoalkyl-substituted, the alkyl radical should contain at least 8 carbon atoms. The phenate may be sulfurized if desired. It may be either neutral or overbased and if overbased will have a base number of up to 200 to 300 or more. Mixtures of neutral and overbased phenates may be used. 
     The phenates are ordinarily present in the oil to provide from 0.2% to 27% by weight of the total composition. Preferably, the neutral phenates are present from 0.2% to 9% by weight of the total composition and the overbased phenates are present from 0.2 to 13% by weight of the total composition. Most preferably, the overbased phenates are present from 0.2% to 5% by weight of the total composition. Preferred metals are calcium, magnesium, strontium or barium. 
     The sulfurized alkaline earth metal alkylphenates are preferred. These salts are obtained by a variety of processes such as treating the neutralization product of an alkaline earth metal base and an alkylphenol with sulfur. Conveniently the sulfur, in elemental form, is added to the neutralization product and reacted at elevated temperatures to produce the sulfurized alkaline earth metal alkylphenate. 
     If more alkaline earth metal base were added during the neutralization reaction than was necessary to neutralize the phenol, a basic sulfurized alkaline earth metal alkylphenate is obtained. See, for example, the process of Walker et al, U.S. Pat. No. 2,680,096. Additional basicity can be obtained by adding carbon dioxide to the basic sulfurized alkaline earth metal alkylphenate. The excess alkaline earth metal base can be added subsequent to the sulfurization step but is conveniently added at the same time as the alkaline earth metal base is added to neutralize the phenol. 
     Carbon dioxide is the most commonly used material to produce the basic or &#34;overbased&#34; phenates. A process wherein basic sulfurized alkaline earth metal alkylphenates are produced by adding carbon dioxide is shown in Hanneman, U.S. Pat. No. 3,178,368. 
     The Group II metal salts of dihydrocarbyl dithiophosphoric acids exhibit wear, antioxidant and thermal stability properties. Group II metal salts of phosphorodithioic acids have been described previously. See, for example, U.S. Pat. No. 3,390,080, columns 6 and 7,  wherein these compounds and their preparation are described generally. Suitably, the Group II metal salts of the dihydrocarbyl dithiophosphoric acids useful in the lubricating oil composition of this invention contain from about 4 to about 12 carbon atoms in each of the hydrocarbyl radicals and may be the same or different and may be aromatic, alkyl or cycloalkyl. Preferred hydrocarbyl groups are alkyl groups containing from 4 to 8 carbon atoms and are represented by butyl, isobutyl, sec.-butyl, hexyl, isohexyl, octyl, 2-ethylhexyl and the like. The metals suitable for forming these salts include barium, calcium, strontium, zinc and cadmium, of which zinc is preferred. 
     Preferably, the Group II metal salt of a dihydrocarbyl dithiophosphoric acid has the following formula: ##STR1## wherein: R 2  and R 3  each independently represent hydrocarbyl radicals as described above, and 
     M 1  represents a Group II metal cation as described above. 
     The dithiophosphoric acid salt is present in the lubricating oil compositions of this invention in an amount effective to inhibit wear and oxidation of the lubricating oil. The amount ranges from about 0.01 to about 4 percent by weight of the total composition, preferably the salt is present in an amount ranging from about 0.1 to about 2.5 percent by weight of the total lubricating oil composition. For example, for railroad oil applications it is preferable that the lubricating oil contain none or very little metal dihydrocarbyl dithiophosphoric acid salt since these compounds have an adverse effect on silver bearings which are present in railroad engines. 
     The alkenyl succinimide or succinate or mixtures thereof are present to, among other things, act as a dispersant and prevent formation of deposits formed during operation of the engine. The alkenyl succinimides and succinates are well known in the art. The alkenyl succinimides are the reaction product of a polyolefin polymer-substituted succinic anhydride with an amine, preferably a polyalkylene polyamine, and the alkenyl succinates are the reaction product of a polyolefin polymer-substituted succinic anhydride with monohydric and polyhydric alcohols, phenols and naphthols, preferably a polyhydric alcohol containing at least three hydroxy radicals. The polyolefin polymer-substituted succinic anhydrides are obtained by reaction of a polyolefin polymer or a derivative thereof with maleic anhydride. The succinic anhydride thus obtained is reacted with the amine or hydroxy compound. The preparation of the alkenyl succinimides has been described many times in the art. See, for example, U.S. Pat. Nos. 3,390,082, 3,219,666 and 3,172,892, the disclosure of which are incorporated herein by reference. The preparation of the alkenyl succinates has also been described in the art. See, for example, U.S. Pat. Nos. 3,381,022 and 3,522,179, the disclosures of which are incorporated by reference. 
     Particularly good results are obtained with the lubricating oil compositions of this invention when the alkenyl succinimide or succinate is a polyisobutene-substituted succinic anhydride of a polyalkylene polyamine or polyhydric alcohol, respectively. 
     The polyisobutene from which the polyisobutene-substituted succinic anhydride is obtained by polymerizing isobutene and can vary widely in its compositions. The average number of carbon atoms can range from 30 or less to 250 or more, with a resulting number average molecular weight of about 400 or less to 3,000 or more. Preferably, the average number of carbon atoms per polyisobutene molecule will range from about 50 to about 100 with the polyisobutenes having a number average molecular weight of about 600 to about 1,500. More preferably, the average number of carbon atoms per polyisobutene molecule ranges from about 60 to about 90, and the number average molecular weight ranges from about 800 to 1,300. The polyisobutene is reacted with maleic anhydride according to well-known procedures to yield the polyisobutene-substituted succinic anhydride. 
     In preparing the alkenyl succinimide, the substituted succinic anhydride is reacted with a polyalkylene polyamine to yield the corresponding succinimide. Each alkylene radical of the polyalkylene polyamine usually has up to about 8 carbon atoms. The number of alkylene radicals can range up to about 8. The alkylene radical is exemplified by ethylene, propylene, butylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, octamethylene, etc. The number of amino groups generally, but not necessarily, is one greater than the number of alkylene radicals present in the amine, i.e., if a polyalkylene polyamine contains 3 alkylene radicals, it will usually contain 4 amino radicals. The number of amino radicals can range up to about 9. Preferably, the alkylene radical contains from about 2 to about 4 carbon atoms and all amine groups are primary or secondary. In this case, the number of amine groups exceeds the number of alkylene groups by 1. Preferably the polyalkylene polyamine contains from 3 to 5 amine groups. Specific examples of the polyalkylene polyamines include ethylenediamine, diethylenetriamine, triethylenetetramine, propylenediamine, tripropylenetetramine, tetraethylenepentamine, trimethylenediamine, pentaethylenehexamine, di-(trimethylene)triamine, tri(hexamethylene)tetramine, etc. 
     Other amines suitable for preparing the alkenyl succinimide useful in this invention include the cyclic amines such as piperizine, morpholine and dipiperizines. 
     Preferably the alkenyl succinimides used in the compositions of this invention have the following formula: ##STR2## wherein: a. R 1  represents an alkenyl group, preferably a substantially saturated hydrocarbon prepared by polymerizing aliphatic monoolefins. Preferably R 1  is prepared from isobutene and has an average number of carbon atoms and a number average molecular weight as described above; 
     b. the &#34;Alkylene&#34; radical represents a substantially hydrocarbyl group containing up to about 8 carbon atoms and preferably containing from about 2 to 4 carbon atoms as described hereinabove; 
     c. A represents a hydrocarbyl group, an amine-substituted hydrocarbyl group, or hydrogen. The hydrocarbyl group and the amine-substituted hydrocarbyl groups are generally the alkyl and amino-substituted alkyl analogs of the alkylene radicals described above. Preferably A represents hydrogen; 
     d. n represents an integer of from about 1 to 10, and preferably from about 3 to 5. 
     The alkenyl succinimide can be reacted with boric acid or a similar boron-containing compound to form borated dispersants having utility in this invention. The borated succinimides are intended to be included within the scope of the term &#34;alkenyl succinimide&#34;. 
     The alkenyl succinates are those of the above-described succinic anhydride with hydroxy compounds which may be aliphatic compounds such as monohydric and polyhydric alcohols or aromatic compounds such as phenols and naphthols. The aromatic hydroxy compounds from which the esters may be derived are illustrated by the following specific examples: phenol, beta-naphthol, alpha-naphthol, cresol, resorcinol, catechol, p,p&#39;-dihydroxybiphenyl, 2-chlorophenol, 2,4-dibutylphenol, propene tetramer-substituted phenol, didodecylphenol, 4,4&#39;-methylene-bisphenol, alpha-decyl-beta-naphthol, polyisobutene(molecular weight of 1000)-substituted phenol, the condensation product of heptylphenol with 0.5 mole of formaldehyde, the condensation product of octylphenol with acetone, di(hydroxyphenyl)oxide, di(hydroxyphenyl)sulfide, di(hydroxyphenyl)disulfide, and 4-cyclohexylphenol. Phenol and alkylated phenols having up to three alkyl substituents are preferred. Each of the alkyl substituents may contain 100 or more carbon atoms. 
     The alcohols from which the esters may be derived preferably contain up to about 40 aliphatic carbon atoms. They may be monohydric alcohols such as methanol, ethanol, isooctanol, dodecanol, cyclohexanol, cyclopentanol, behenyl alcohol, hexatriacontanol, neopentyl alcohol, isobutyl alcohol, benzyl alcohol, betaphenylethyl alcohol, 2-methylcyclohexanol, beta-chloroethanol, monomethyl ether of ethylene glycol, monobutyl ether of ethylene glycol, monopropyl ether of diethylene glycol, monododecyl ether of triethylene glycol, monooleate of ethylene glycol, monostearate of diethylene glycol, sec-pentyl alcohol, tert-butyl alcohol, 5-bromo-dodecanol, nitro-octadecanol and dioleate of glycerol. The polyhydric alcohols preferably contain from 2 to about 10 hydroxy radicals. They are illustrated by, for example, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, dibutylene glycol, tributylene glycol, and other alkylene glycols in which the alkylene radical contains from 2 to about 8 carbon atoms. Other useful polyhydric alcohols include glycerol, monooleate of glycerol, monomethyl ether of glycerol, pentraerythritol, 9,10-dihydroxy stearic acid, methyl ester of 9,10-dihydroxy stearic acid, 1,2-butanediol, 2,3-hexanediol, 2,4-hexanediol, pinacol, erythritol, arabitol, sorbitol, mannitol, 1,2-cyclohexanediol, and xylene glycol. Carbohydrates such as sugars, starches, celluloses, etc., likewise may yield esters. The carbohydrates may be exemplified by a glucose, fructose, sucrose, rhamnose, mannose, glyceraldehyde, and galactose. 
     An especially preferred class of polyhydric alcohols are those having at least three hydroxy radicals, some of which have been esterified with a monocarboxylic acid having from about 8 to about 30 carbon atoms such as octanoic acid, oleic acid, stearic acid, linoleic acid, dodecanoic acid, or tall oil acid. Examples of such partially esterified polyhydric alcohols are the monooleate of sorbitol, distearate of sorbitol, monooleate of glycerol, monostearate of glycerol, di-dodecanoate of erythritol. 
     The esters may also be derived from unsaturated alcohols such as allyl alcohol, cinnamyl alcohol, propargyl alcohol, 1-cyclohexene-3-ol, an oleyl alcohol. Still other classes of the alcohols capable of yielding the esters of this invention comprises the ether-alcohols and amino-alcohols including, for example, the oxy-alkylene-, oxy-arylene-, amino-alkylene-, and amino-arylene-substituted alcohols having one or more oxy-alkylene, amino-alkylene or amino-arylene oxy-arylene radicals. They are exemplified by Cellosolve, carbitol, phenoxy-ethanol, heptylphenyl-(oxypropylene) 6  -H, octyl(oxyethylene) 30  -H, phenyl(oxyoctylene) 2  -H, mono(hepty-phenyl-oxypropylene)-substituted glycerol, poly(styrene oxide), amino-ethanol, 3-amino ethyl-pentanol, di(hydroxyethyl)amine, p-aminophenol, tri(hydroxypropyl)amine, N-hydroxyethyl ethylene diamine, N,N,N&#39;,N&#39;-tetrahydroxytrimethylene diamine, and the like. For the most part, the ether-alcohols having up to about 150 oxy-alkylene radicals in which the alkylene radical contains from 1 to about 8 carbon atoms are preferred. 
     The esters may be di-esters of succinic acids or acidic esters, i.e., partially esterified succinic acids, as well as partially esterified polyhydric alcohols or phenols, i.e., esters having free alcoholic or phenolic hydroxyl radicals. Mixtures of the above-illustrated esters likewise are contemplated within the scope of the invention. 
     The alkenyl succinates can be reacted with boric acid or a similar boron-containing compound to form borated dispersants having utility in this invention. Such borated succinates are described in U.S. Pat. No. 3,533,945, the disclosure of which is incorporated herein by reference. The borated succinates are intended to be included within the scope of the term &#34;alkenyl succinate.&#34; 
     The alkenyl succinimide and succinates are present in the lubricating oil compositions of the invention in an amount effective to act as a dispersant and prevent the deposit of contaminants formed in the oil during operation of the engine. The amount of alkenyl succinimide and succinates can range from about 1 percent to about 20 percent weight of the total lubricating oil composition. Preferably the amount of alkenyl succinimide or succinate present in the lubricating oil composition of the invention ranges from about 1 to about 10 percent by weight of the total composition. 
     The sulfurized fatty acid esters which act as anti-wear agents are present from 0% to 1% and for railroad oil applications are present in the range of from 0.01% to 1% by weight. The esters are prepared by reacting sulfur, sulfur monochloride, and/or sulfur dichloride with an unsaturated fatty ester under elevated temperatures. Typical esters include C 1  -C 20  alkyl esters of C 8  -C 24  unsaturated fatty acids, such as palmitoleic, oleic, ricinoleic, petroselinic, vaccenic, linoleic, linolenic, oleostearic, licanic, paranaric, tariric, gadoleic, arachidonic, cetoleic, etc. Particularly good results have been obtained with mixed unsaturated fatty acid esters, such as are obtained from animal fats and vegetable oils, such as tall oil, linseed oil, olive oil, caster oil, peanut oil, rape oil, fish oil, sperm oil, and so forth. 
     Exemplary fatty esters include lauryl tallate, methyl oleate, ethyl oleate, lauryl oleate, cetyl oleate, cetyl linoleate, lauryl ricinoleate, oleyl linoleate, oleyl stearate, and alkyl glycerides. 
     Cross-sulfurized ester olefins, such as a sulfurized mixture of C 10  -C 25  olefins with fatty acid esters of C 10  -C 25  fatty acids and C 1  - 25  alkyl or alkenyl alcohols, wherein the fatty acid and/or the alcohol is unsaturated may also be used. 
     Sulfurized olefins are prepared by the reaction of the C 3  -C 6  olefin or a low-molecular-weight polyolefin derived therefrom with a sulfur-containing compound such as sulfur, sulfur monochloride, and/or sulfur dichloride. 
     Other additives, such as the detergents, rust and corrosion inhibitors, pour point depressants, metal deactivators, anti-oxidants, anti-wear agents, foam inhibitors, etc., may also be present in the finished lubricant. These other additives will be present in conventional concentrations. 
     The invention is further illustrated by the following examples, which are given without any intention that the invention be limited thereto. 
    
    
     EXAMPLE 1 
     A solution containing 8% by weight of an ethylene/propylene/1,4-hexadiene terpolymer (a product manufactured by Du Pont Company, Wilmington, Del. and sold under the trade name Ortholeum 2038, which is a terpolymer having about 60 mole percent ethylene groups, 39 mole percent propylene groups and 1 mole percent 1,4-hexadiene groups and having a molecular weight of about 250,000) in chlorobenzene was prepared and heated to 100° C. To this solution was continuously added at an appropriate rate in order to supply 4.2% by weight based on the weight of polymer of dicumyl peroxide and 1.8% by weight based on the weight of polymer of cumene hydroperoxide. The reaction mixture was continuously passed through a three-quarter inch stainless steel tubular reactor such that the residence time in the reactor was 2.75 minutes at a reaction temperature of 190° C. and a pressure of 200 psig. Air was continuously passed into the reactor tube at 0.35 cm 2  /gm polymer at 200 psig. Sufficient 100 Neutral Oil was added to yield a 15% by weight of product in solution when the chlorobenzene solvent was removed. The chlorobenzene solvent was removed by distillation at reduced pressure. The viscosity or thickening power of the polymer product (viscosity at 100° C., 2.8% polymer in RPM 130N) was 17.8 cSt. The acid content was 4.8 mmole COOH/100 g polymer and the hydroxyl content was 0.28 mmole OH/100 g polymer as calculated below. 
     The acid and hydroxyl content was determined as follows: 
     A Determination of Acid Group Content 
     40.0 g of a solution of oxidized polymer intermediate in 100 neutral mineral oil (containing about 5-6 g of polymer) was dissolved in 100 ml of xylenes. 10.0 ml of 0.0999M NaOH solution was added, and the mixture was refluxed for 30 minutes. 75 ml of isopropyl alcohol was added followed by 1 ml of phenolphthalein indicator (0.1% in ethyl alcohol). The mixture was titrated to the phenolphthalein end point with 0.100N HCl. The acid functionality per 100 g of polymer is calculated using the formula below. ##EQU1## 
     A Determination of Hydroxyl Number 
     Description of Method 
     The dibutyl tin dilaurate-catalyzed reaction between alcohols and isocyanates was used to measure the hydroxyl content of the oxidized polymer. Using the reaction conditions described below, acid groups are not reactive, only hydroxyl functional groups are consumed. The difference in the concentration of isocyanate before and after reaction (as measured by infrared spectroscopy) indicates the amount of hydroxyl groups in the polymer. 
     Procedure 
     A solution of 1.00 g phenylisocyanate in 50 ml dry toluene was prepared. Several dilutions of the stock isocyanate solution were made and an infrared absorbance versus concentration curve was obtained using the IR absorbance at 2265 cm -1  divided by the IR cell path length (in cm). The slope of this line gave a concentration factor of 0.118 mmole isocyanate/absorbance unit cm -1 . 
     100 g of a solution of oxidized polymer intermediate in chlorobenzene (containing about 12-15 g polymer) was treated with 2.0 ml of the isocyanate stock solution and 2 drops of dibutyl tin dilaurate catalyst. The mixture was stirred and heated at 80° C. for 100 min. A blank consisting of 100 g of chlorobenzene was run under the same conditions. An infrared spectrum of each solution was recorded in a 0.0171 cm path length NaCl cell. The hydroxyl group content was calculated from the isocyanate consumption by the polymer solution, correcting for subtracting the blank, using the formula below. ##EQU2## where 2265 poly=IR absorbance for polymer solution 
     2265 blank=IR absorbance for blank solution 
     ICF=isocyanate concentration factor ##EQU3## PL=IR cell path length (cm) WP=Weight of polymer ##EQU4## Thus the product of Example 1 had a COOH:OH ratio of 4.9:0.28 or about 19:1. 
     EXAMPLE 2 
     A solution containing 8% by weight of the ethylene/propylene/1,4-hexadiene terpolymer of Example 1 in chlorobenzene was prepared and heated to 100° C. To this solution was continuously added at an appropriate rate in order to supply 0.2% by weight based on the weight of polymer of dicumyl peroxide. The reaction mixture was continuously passed through a three-quarter inch stainless steel tubular reactor such that the residence time in the reactor was 2.75 minutes at a reaction temperature of 190° C. and a pressure of 200 psig. Air was continuously passed into the reactor tube at 1.7 cm 2  /gm polymer at 200 psig. Sufficient 100 neutral oil was added to yield a 15.7% by weight of product in solution when the chlorobenzene solvent was removed. The chlorobenzene solvent was removed by distillation at reduced pressure. The viscosity or thickening power of the polymer product (viscosity at 100° C., 2.8% polymer in RPM 130N) was 17.8 cSt, the acid content was 4.3 mmole COOH/100 g polymer and the hydroxyl content was 0.06 mmole OH/100 g polymer giving a ratio of 4.3 to 0.06 or about 72:1 acid to hydroxyl. Multi-grade lubricating oils with good dispersancy characteristics may be prepared using the product of this example. 
     EXAMPLE 3 
     Thirty parts of the commercial ethylene/propylene/1,4-hexadiene terpolymer of Example 1 was dissolved in 365 parts of xylene at 200° F. over a period of about 16 hours with stirring. The temperature was raised to 250° F. and 0.118 parts dicumyl peroxide was added to the polymer solution. An air sparge of 1 ft 3  /min was used to introduce oxygen into the polymer solution over a period of about 6 hours. Sufficient 100 Neutral Oil was added to yield a 12% by weight of product in solution when the xylene solvent was removed. The xylene solvent was removed by distillation at reduced pressure. The viscosity or thickening power of the polymer product (viscosity at 100° C., 2.8% dry polymer in RPM 130N) was 16 cSt. 
     EXAMPLE 4 
     Thirty pounds of an ethylene/propylene copolymer rubber (a product manufactured by B. F. Goodrich and sold under the trade name EPCAR 405 which is an ethylene/propylene copolymer having about 60 mole percent ethylene and 40 mole percent propylene and having a Mooney viscosity of 60) was dissolved in 345 pounds of chlorobenzene at 210° F. over a period of about five hours. The temperature was raised to 250° F. and 270 ml of a 10% by weight dicumyl peroxide was added to the polymer solution. An air sparge of 0.5 ft 3  /min was used to introduce oxygen into the solution over a period of about 5 hours. An additional 25 ml of 10 percent by weight dicumyl peroxide was added every 30 minutes over the 5-hour reaction period. After a nitrogen sparge for 30 minutes, sufficient 100 neutral oil was added to yield a 12% by weight of product in solution when the chlorobenzene was removed. The chlorobenzene solvent was removed by distillation at reduced pressure. The viscosity or thickening power of the polymer product (viscosity at 100° C., 2.8% dry polymer in RPM 130N) was 17 cSt. The acid content was 5.8 mmoles COOH/100 g polymer and the hydroxyl content was 0.23 mmoles OH/100 g polymer giving a ratio of 5.8:0.23 or about 25:1 acid to hydroxyl. 
     Multi-grade lubricating oil with good dispersancy characteristics may be prepared using the product of this Example. 
     EXAMPLE 5 
     The lubricating oil compositions of this invention were evaluated in the standard Sequence V-D automotive engine test and the 1-G2 caterpillar engine test. In the Sequence V-D and 1-G2 engine tests, lubricants containing the experimental additives are charged respectively to a standard internal combustion engine and to a diesel engine. The engines are operated at an assigned load and temperature, and at the end of a prescribed time the engines are disassembled and examined for deposits and wear. These engine tests are standard methods well known in the industry. 
     Also, viscosity measurements at 100° C., 40° C. and 0° C. show acceptable viscosity measurements and with the use of pour point depressants, acceptable viscosity measurements at -32° C. are obtained. 
     A. Standard Sequence V-D Engine Test 
     Formulated 10W-40 oils containing the additives shown in Table I were prepared and tested in a Sequence V-D Test method phase 9-2 (according to candidate test for ASTM) as shown in Table II. This procedure utilizes a Ford 2.3-liter four-cylinder engine. The test method simulates a type of severe field test service characterized by a combination of low speed, low temperature &#34;stop and go&#34; city driving and moderate turnpike operation. The effectiveness of the additives in the oil is measured in terms of the protection provided against deposits and valve train wear. 
     
                                           TABLE I                                 
__________________________________________________________________________
Test Oil Formulations (mmoles/kg except where noted)                      
                   A.sup.1                                                
                       B.sup.2                                            
                           C.sup.2                                        
                               D.sup.5                                    
                                  E.sup.5                                 
                                     F.sup.2,3                            
                                         G.sup.2,4                        
__________________________________________________________________________
Product of Example 1                                                      
                   1.73%                                                  
                       --  1.73%                                          
                               -- -- --  --                               
Product of Example 3                                                      
                   --  1.65%                                              
                           --  -- -- --  --                               
Amine functionalized olefin terpolymer                                    
                   --  --  --  -- -- 1.70%                                
                                         --                               
Olefin copolymer   --  --  --  -- -- --  0.55%                            
Calcium phenate    20  20  20  20 20 20  20                               
Zinc dialkyl phosphate                                                    
                   22.5                                                   
                       22.5                                               
                           22.5                                           
                               22.5                                       
                                  22.5                                    
                                     22.5                                 
                                         22.5                             
Overbased calcium sulfonate                                               
                   30  --  30  30 30 30  30                               
Polyisobutenyl succinimide                                                
                   --  1.5%                                               
                           6%  -- 6% --  --                               
(50% concentrate in oil)                                                  
Overbased magnesium sulfonate                                             
                   --  30  --  -- -- --  --                               
__________________________________________________________________________
 .sup.1 Exxon 150N Oil formulated to 10W40                                
 .sup.2 Sun 148N Oil formulated to 10W40                                  
 .sup.3 V.I. improver prepared by the condensation of an alkylene polyamin
 with a hydroperoxidized ethylenepropylene-1,4 hexadiene terpolymer as    
 described in U.S. Pat. No. 3,785,980.                                    
 .sup.4 Paratone 716, a nondispersant, nonhydroperoxidized olefin copolyme
 V.I. improver commercially available from Exxon Chemicals.               
 .sup.5 Exxon 150N Oil.                                                   
 
    
     The data in Table II demonstrate that formulations A, B and C containing the hydroperoxidized polymers of this invention have dispersant properties better than an ethylene copolymer V.I. improver and comparable to an amine functionalized hydroperoxidized ethylene terpolymer of the prior art. 
     
                       TABLE II                                                    
______________________________________                                    
Sequence V-D Performance                                                  
                              Com Lobe Wear                               
Average     Piston   Average  × 10.sup.-3 -Inch                     
Test Oil                                                                  
       Sludge    Varnish Varnish                                          
                                Average                                   
                                       Maximum                            
______________________________________                                    
A      7.2      6.6      6.6    0.5    0.9                                
B      9.7      6.7      5.0    0.5    0.9                                
C      9.7      7.2      7.0    0.5    0.8                                
D      6.4      6.4      6.3    2.7    8.3                                
E      9.6      6.8      6.8    0.4    0.5                                
F      5.9      6.6      7.1    0.4    0.6                                
G      6.5      5.6      5.1    0.6    0.7                                
______________________________________                                    
 
    
     The compositions of this invention were tested in a Caterpillar 1-G2 test in which a single-cylinder diesel engine having a 51/8&#34; bore by 61/2&#34; stroke is operated under the following conditions: timing, degrees BTDC, 8; brake mean effective pressure, psi 141; brake horsepower 42; Btu&#39;s per minute 5850; speed 1800 RPM; air boost, 53&#34; Hg absolute, air temperature in, 255° F.; water temperature out, 190° F.; and sulfur in fuel, 0.4% w. At the end of each 12 hours of operation, sufficient oil is drained from the crankcase to allow addition of 1 quart of new oil. In the test on the lubricating oil compositions of this invention, the 1-G2 test is run for 60 and 120 hours. At the end of the noted time period, the engine is dismantled and rated for cleanliness. The Institute of Petroleum Test Number 247/69 merit rating system for engine wear and cleanliness, accepted by ASTM, API and SAE, is the rating system used to evaluate the engine. The over-all cleanliness is noted as WTD, which is the summation of the above numbers. Lower values represent cleaner engines. 
     The base oil used in this test is a Sun Tulsa 148N/250N base oil formulated with sufficient viscosity index-dispersant (about 12% by weight) to prepare a 15W-40 oil containing 3% of a 50% concentrate in oil of an isobutenyl succinimide, 10 mmoles/kg calcium sulfonate, 20 mmoles/kg overbased calcium phenate, 45 mmoles/kg overbased magnesium sulfonate; 18 mmoles zinc dialkyl dithiophosphate, 1% combination of cracked wax olefin and sulfurized calcium phenate. Formulation H in Table III contains the viscosity index-dispersant of Example 1, and formulation I contains the amine functionalized olefin terpolymer used in formulation F in Table 1. 
     
                       TABLE III                                                   
______________________________________                                    
Caterpillar 1-G2 Test                                                     
Formu- Time-                     Top Grove                                
lation Hrs.     Groves    Lands  Fill %  WTD                              
______________________________________                                    
H       60      59-94-8-0 40-9-7 58      216                              
       120      73-115-3-5                                                
                          57-7-9 73      268                              
I      120      90-171-3-6                                                
                          76-14-29                                        
                                 89      388                              
______________________________________