Dispersant anti-oxidant viscosity index improver and lubricating oil composition containing same

Abstract: A multi-functional lubricant additive havingt dispers­ ant, anti-oxidant and VI-improving properties can be prepared by reacting a polymer comprising from 15 to 80 mole percent of ethylene, from 20 to 85 mole percent of at least one C₃ -C₁₀ alpha-monoolefin, and from 0 to 15 mole percent of a non-conjugated diene or triene, and having an average molecular weight from 5,000 to 500,000, with a nitrosodi­ phenylamine compound having the formula: in which R and R′ which may be the same or different, each represents hydrogen or an alkyl , alkenyl or alkoxyl radical having from 1 to 10 carbon atoms, and which may contain oxygen, nitrogen or sulfur.

Description: This invention relates to a novel multi-functional lubricant additive, which is a dispersant, anti-oxidant and a V.I. improver when employed in a lubricating oil composition. The art contains many teachings on the use of polymer additives in lubricating oil compositions. Ethylene propylene copolymers and ethylene alpha olefin non-conjugated diene terpolymers, which have been further derivatized to provide bifunctional properties in lubricating oil compositions, illustrate this type of oil additive. US-A-3522180 discloses a method for the preparation of an ethylene-propylene copolymer substrate effective as a viscosity index improver for lubricating oils. US-A-4089794 discloses ethylene copolymers derived from ethylene and one or more C₃ to C₂₈ alpha olefins, solution grafted with an ethylenically-unsaturated carboxylic acid material, followed by a reaction with a polyfunctional material reactive with carboxyl groups, such as a polyamine, a polyol, or a hydroxyamine. The reaction product is useful as a sludge- and varnish-control additive in lubricating oils. US-A-4137185 discloses a stabilized imide graft of an ethylene copolymer additive for lubricants. US-A-4146489 discloses a graft copolymer where the backbone polymer is an oil-soluble ethylene-propylene copolymer, or an ethylene-propylene-diene modified terpolymer, with a graft monomer of C-vinylpyridine or N-vinylpyrrolidone. This is a dispersant VI improver for lubricating oils. US-A-4320019 discloses a multipurpose lubricating additive prepared by the reaction of an interpolymer of ethylene and a C₃ - C₈ alpha-monoolefin with an olefinic carboxylic acid acylating agent to form an acylating reaction intermediate, which is then reacted with an amine. US-A-4340689 discloses a process for grafting a functional organic group onto an ethylene copolymer or an ethylene-propylene-diene terpolymer. US-A-4357250 discloses a reaction product of a copolymer and an olefin carboxylic acid via the "ene" reaction, followed by a reaction with a monoamine-polyamine mixture. US-A-4382007 discloses a dispersant - VI improver prepared by reacting a polyamine-derived dispersant with an oxidized ethylene-propylene polymer or an ethylene-propylene diene terpolymer. US-A-4144181 discloses polymer additives for fuels and lubricants comprising a grafted ethylene copolymer reacted with a polyamine, polyol or hydroxyamine, and finally reacted with an alkaryl sulfonic acid. This invention is concerned with the problem of providing a process for preparing a derivatized copolymer without the need for an acylating graft reaction, and to provide a multi-functional lubricant additive effective for imparting viscosity index, dispersancy and anti-oxidant properties to a lubricating oil composition. In one embodiment, this invention provides a lubricant additive composition prepared by reacting a polymer comprising from 15 to 80 mole percent of ethylene, from 20 to 85 mole percent of at least one C₃ - C₁₀ alpha-monoolefin, and from 0 to 15 mole percent of a polyene selected from non-conjugated dienes and trienes, and having an average molecular weight from 5,000 to 500,000 with a nitrosodiphenylamine compound having the formula: in which R and R' which may be the same or different, each represents hydrogen or an alkyl, alkenyl or alkoxyl radical having from 1 to 10 carbon atoms, and which may contain oxygen nitrogen or sulfur. Another embodiment provides a lubricating oil composition comprising a major amount of an oil of lubricating viscosity and a minor amount of an additive composition as defined above. A further embodiment provides a concentrate for a lubricating oil comprising a diluent oil of lubricant (VI improver), viscosity and from 1 to 50 weight percent of the additive composition defined above, based on tne total weight of the concentrate. The polymer or copolymer substrate employed in the novel additive of the invention may be prepared from ethylene and propylene or it may be prepared from ethylene and a higher olefin within the range of C₃ to C₁₀ alpha-monoolefins. It may employ a polymer prepared from isoprene or hydrogenated isoprene, as well as their copolymers with styrene. More complex polymer substrates often designated as interpolymers, may be prepared using a third component. The third component generally used to prepare an interpolymer substrate is a polyene monomer selected from non-conjugated dienes and trienes. The non-conjugated diene component has preferably from 5 to 14 carbon atoms in the chain. Preferably the diene monomer has a vinyl group in its structure and can include cyclic and bi-cyclo compounds. Representative dienes include 1,4-hexadiene, 1,4-cyclohexadiene, dicyclopentadiene, 5-ethylidene-2-norbornene, 5-methylene-2-norborene, 1,5-heptadiene, and 1,6-octadiene. A mixture of more than one diene can be used in the preparation or tne interpolymer. A preferred non-conjugated diene for preparing a terpolymer or interpolymer substrate is 5-ethylidene-2-norbornene. The triene component will have at least two non-conjugated double bonds, and generally up to 30 carbon atoms in the chain. Typical trienes useful in preparing the interpolymer tetrahydroindene, 1-isopropylidenedicyclopentadiene, dehydrooiso-dicyclopentadiene, and 2-(2-methylene-4-methyl-3-pentenyl) [2.2.1] bicyclo-5-heptene. Polymers and copolymers prepared from the above-mentioned monomers, and having short and long branches or star shape structures, may also be employed. The polymerization reaction to form the polymer substrate is generally carried out in the presence of a catalyst in a solvent. The polymerization solvent may be any suitable inert organic solvent that is liquid under reaction conditions for solution polymerization of monoolefins, which is generally conducted in the presence of a Ziegler type catalyst. Examples of satisfactory hydrocarbon solvents include straight chain paraffins having from 5-8 carbon atoms, with hexane being preferred. Aromatic hydrocarbons, preferably aromatic hydrocarbon having a single benzene nucleus, such as benzene, toluene and the like; and saturated cyclic hydrocarbons having boiling point ranges approximating those of the straight chain paraffinic hydrocarbons and aromatic hydrocarbons described above, are particularly suitable. The solvent selected may be a mixture of one or more of the foregoing hydrocarbons. It is desirable that the solvent be free of substances that will interfere with a Ziegler polymerization reaction. In a typical preparation of a polymer substrate, hexane is first introduced into a reactor and the temperature in the reactor is raised moderately to about 30°C. Dry propylene is fed to the reactor until the pressure reaches 135 to 155 KPa. The pressure is then increased to about 205 KPa, and dry ethylene and 5-ethylidene-2-norbornene are fed to the reactor. The monomer feeds are stopped and aluminum sesquichloride and vanadium oxytrichloride are added to initiate the polymerization reaction. Completion of the polymerization reaction is evidenced by a drop in the pressure in the reactor. Ethylene-propylene or higher alpha monoolefin copolymers from 15 to 80 mole percent of ethylene and from 20 to 85 mole percent of propylene or higher monoolefin, with the preferred mole ratios being from about 25 to 60 mole percent of ethylene and from 40 to 75 mole percent of a C₃ to C₁₀ alpha monoolefin. Most preferred are ratios from 25-85 mole percent of ethylene and from 15 - 75 mole percent of a C₃ to C₈ alpha-monoolefin. Terpolymer variations of the foregoing polymers may, for instance, contain from 0.1 to 10 mole percent of a non-conjugated diene or triene. The polymer substrate, that is the ethylene copolymer or terpolymer, is an oil-soluble, substantially linear, rubbery material having an average molecular weight from 5,000 to 500,000, with a preferred molecular weight range of 25,000 to 250,000, and a most preferred range from 50,000 to 150,000. The terms polymer and copolymer are used generically to encompass ethylene copolymers, terpolymers or interpolymers. These materials may contain minor amounts of other olefinic monomers so long as their basic characteristics are not materially changed. The ethylene copolymer backbase is reacted with a nitrosodiphenylamine compound represented by the formula: in which R and R' each represents hydrogen or an alkyl, alkenyl or alkoxyl radical having from 1 to 10 carbon atoms, which may contain nitrogen, oxygen or sulfur atoms. A preferred nitrosodiphenylamine compound is one in which R and R' each represent hydrogen or an aliphatic hydrocarbon radical having from 1 to 5 carbon atoms. Examples of suitable nitrosodiphenylamine compounds include 4-nitrosodiphenylamine, 3-nitrosodiphenylamine, and 4-nitroso-2,3'-dimethyl-diphenylamine. A preferred ratio is 0.2 to 60 parts of nitrosodiphenylamine per 100 parts of polymer. The nitrosodiphenylamine compound may be reacted with the polymer backbone in a number of ways. It may be reacted in a thermal process known as the "ene" process or by a reaction in solution or in solid form using a radical initiator. The free-radical induced reaction of materials in solvents, such as mineral oil is a preferred method. It is generally carried out at an elevated temperature of 100°C to 250°C, preferably 120° to 190°C, and more preferably at 150° to 180°C, e.g. above 160°C, in a solvent, preferably a mineral lubricating oil solution containing, for instance, 1 to 50, preferably 5 to 30 wt.%, based on the initial total oil solution, of the ethylene polymer and preferably under an inert environment. The free-radical initiators which may be used are peroxides, hydroperoxides, and azo compounds and preferably those which have a boiling point greater than 100°C and decompose thermally within the prescribed temperature range to provide free radicals. Representative of these free-radical initiatgors are dicumyl peroxide (DICUP), 2,2'-azobis-(2-methyl-N-[1,1-bis(hydroxymethyl)ethyl]-propionamide, di-tert-butylperoxide, azobisisobutyronitrile, diacetylperoxide, and diisopropylperoxidicarbonate. The initiator is generally used in an amount between 0.001% and 30% by weight, based on the weight of the polymer. The reaction is preferably carried out in an inert atmosphere, such as under nitrogen blanketing. The polymers used herein are substantially linear, hydrocarbon polymers. Typical are the oil soluble ethylene-propylene based copolymers, saturated and unsaturated containing 35 to 80 mole % ethylene units. This includes ethylenepropylene-copolymer (EPM) or diene terpolymers (EPDM) such as an ethylene propylene-1,4-hexadiene terpolymer or an 5-ethylene-2-norbornene terpolymer. Polymer substrates or interpolymers are available commercially. Particularly useful are those containing from 40 to 80 mole percent of ethylene units, and 60 to 20 mole percent of propylene units. Examples are "Ortholeum 2052" and "PL-1256" available from E.I. duPont deNemours and Co. The former is a terpolymer containing 48 mole percent of ethylene units, 48 mole percent of propylene units and 4 mole percent of 1,4-hexadiene units, having an inherent viscosity of 1.35. The latter is a similar polymer with an inherent viscosity of 1.95. The viscosity average molecular weights of the two are of the order of 200,000 and 280,000 respectively. The process can be carried out in the following manners: 1. In the presence of free radical initiator in solution. A solution containing 10 to 30 parts of EPM or EPDM and 90 to 70 parts of solvent such as mineral oil or n-hexane is stirred and heated at 80 to 165°C under nitrogen to form a homogeneous solution. 0.06 to 6 parts of 4-nitrosodiphenylamine (NDPA) and 0.03 to 6 parts of free radical initiator are charged. The mixture is heated with stirring above the decomposition temperature of the initiator (under nitrogen) for 0.5 to 5 hours. Typically 20 parts of EPM, 80 parts of mineral low sulfur oil, 0.8 parts of NDPA and 0.16 parts of dicumyl peroxide are used. The reaction mixture is maintained at 155±5°C for 2 hours. 2. Without free radical initiator in solution. A solution containing 10 to 30 parts of EPDM and 90 to 70 parts of solvent, such as mineral oil or n-hexane, is stirred and heated at 150 to 300°C under nitrogen to form a homogeneous solution. 0.06 to 6 parts of 4-nitrosodiphenylamine (NDPA) is charged. The mixture is stirred at 150 to 300°C (under nitrogen) for 0.5 to hours. Typically, 20 parts of EPDM, 80 parts of mineral low sulfur oil, and 0.8 parts of NDPA are used. The reaction mixture is maintained at 255±5°C for 2 hours. 3. Using a Bramley-Beken Mixer (masticated rubber without initiator). 20 to 200 g of EPDM is charged to the Bramley-Baken Mixer. The rubber is ground at room temperature and then heated with stirring at 140 to 190°C under nitrogen. 0.1 to 60 parts of NDPA is charged and the mixture is stirred at the above temperature for 0.5 to 4 hours. To the product prepared by methods 1, 2 or 3, enough mineral oil is added to obtain a fluid concentrate at room temperature (6 to 14 wt% polymer solution). The fluid solution (a lubricant additive) is used for further testing. The so-prepared graft polymers may find use in lubricating oils as dispersant/antioxidant and viscosity index improvers when present in effective amount of 0.4 to 5 wt%, preferably 0.6 to 3 wt%, say 0.9 wt% (2 to 20 wt% of polymer concentrate, VI improver, preferably 8 to 15 wt%), most preferably in amount of 0.1 to 10 weight percent based on the total weight of oil composition. Lubricating oils in which the dispersant/antioxidant index improvers of this invention may find use may include automotive, aircraft, marine, railway, oils; oils used in spark ignition or compression ignition; summer or winter oils; . Typically the lubricating oils may be characterised by an initial boiling point (ibp) of 300 to 350°C, say 320°C; an end point (ep) of 400 to 650°C, say 550°C; and a specific gravity of 0.87 to 0.90, say 0.885. A typical lubricating oil in which the VI improver of this invention may be present may be a standard SAE 5W-30 hydrocarbon motor oil formulation having the following composition: Use of the additive of this invention makes it possible to increase the viscosity index by 25-40 units, say 35 units, and to obtain improved ratings on the tests measuring the dispersancy of the system. The viscosity index is determined by ASTM Test D-445. Antioxidancy is measured by the Bench Oxidation Test (BOT). The sample is heated while air is passed through the mixture. Samples are withdrawn periodically and analyzed by Differential Infrared Analysis (DIR) to observe changes In the intensity of the carbonyl group vibration at 1710/cm⁻¹. A higher intensity indicates lower thermal oxidation stability. The Oxidation Index (OI) is reported as the change in intensity after 144 hours. Dispersancy is determined by the Bench VC Test (BVCT). In this test, the turbidity of an oil containing an additive is measured after heating the test oil to which has been added a standard blow-by. The result correlates with dispersany and is compared to three standards (Good, Fair and Poor) tested simultaneously with the test sample. The numerical rating decreases with an increase in dispersant effectiveness. Results above 90 indicate that the additive does not provide dispersant activity. Grafting yield of grafted monomer is determined by IR-analysis of isolated rubber. Changes in the aromatic band at 1600 cm-1 compared to the ungrafted rubber band at 722 cm-1 are examined. The rubber is isolated from solution by multiple solution/precipation, using cyclohexane as a solvent and acetone as precipitator. Then the rubber is dried in vacuum at 60°C for 36 hours. The product of invention is evaluated in the Sequence VE Engine Test. The Sequence VE test procedure is designed to evaluate the propensity of crankcase motor oils to prevent sludge and varnish deposits and engine wear. The test utilizes a Ford 2.3 liter in line four cylinder engine. This engine has an overhead camshaft, electronic fuel injection, hydraulic valve clearance adjustment, and a high compression, fast burn combustion chamber design. The engine fuel led with Phillips "J" Fuel, a non-detergent, unleaded reference gasoline. The test comprises three distinct stages. Together, the three stages comprise one cycle. Each cycle last four hours (240 minutes) and is repeated 72 times, for a total of 288 hours. During Stage I, the engine is operated at moderate speed and load, and moderate oil and water temperatures, for 120 minutes. During Stage II, the engine is operated for 75 minutes at the same slightly "leaner" (excess air) than stoichiometric in Stages I and II. During Stage III, the engine is operated for 45 minutes at low speed and load and low oil and water temperatures. The air-fuel ratio is "richer" (excess fuel) than stoichiometric in Stage III. The test has been set up to provide repeatable, relatively fast accumulation of deposits and wear. To accelerate wear and deposit formation, the engine is not operated in the same manner as in an automobile. As an example, the combustion blowby into the crankcase and NOx (oxides of nitrogen) concentration in the exhaust are operated at significantly elevated levels. In addition, the environment under the rocker arm cover is controlled by circulating coolant through a jacket surrounding the rocket arm cover. Along with the temperatures and air-fuel ratios noted above, these items promote the formation of sludge and varnish deposits and engine wear. At the conclusion of the test, the engine is completely disassembled to determine the levels of sludge and varnish deposits and engine wear that have accumulated. The following Examples illustrate the preparation of the novel additive of the invention. All parts and percentages are by weight, unless otherwise indicated. Control examples are designated by an asterisk. Example 1 4-nitrosodiphenylamine was grafted onto EPM containing around 0.3 mole % of 5-ethylidene-2-norbornene (extruded EPsyn 4106) in the presence of a free radical initiator, (dicumyl peroxide). EPM (Mn = 80,000 as measured by SEC) containing approximately 60 mol % of ethylene is used. 100 parts of EPM dissolved in 400 parts of mineral grafting oil (SUN-148) was heated to 155°C (with stirring under nitrogen). 4.0 parts by weight of NDPA dissolved in 4.0 parts of toluene was added followed by 0.8 parts of dicumyl peroxide dissolved in 2.4 parts of oil. The mixture was stirred under these conditions for 2 hours, allowing toluene to be evaporated. Solvent neutral oil (SNO-100) was added to give an oil solution containing 12.5% of polymer. Example 2 The procedure of Example 1 was followed, except that 2,2'-azobis(2-methyl-N-[1,1-bis(hydroxymethyl)ethyl] propionamide, was used as a free radical initiator. Example 3 The procedure of Example 1 was followed, except that a lower polymer concentration (12.5 instead of 20%), in a mixture of grafting oil and SNO-100, and no free radical were used. Example 4 The procedure of Example 1 was used except that EPDM (Ortholeum 2055) was used instead of EPM (extruded EPsyn 4106). Example 5 The procedure of Example 4 was followed, except that no free radical initiator was charged. Example 6 The procedure of Example 5 was followed, except for using a lower polymer concentration (9.0% instead of 20%) in a mixture of grafting oil and SNO-100, and 2 parts of NDPA dissolved in 2.0 parts of toluene. Example 7 The reaction was performed in laboratory Bramley-Beken Mixer. 100 parts of EPDM (Ortholeum 2052) was charged to the mixer. The rubber is ground for 30 minutes and heated with stirring under nitrogen to about 160°C. Two parts of NDPA were charged and the mixture was stirred at 160°C under air for 60 minutes. Then the mixture was cooled to room temperature under nitrogen and discharged from the mixer. Solvent neutral oil (SNO-100) was added to give a final product as described in the Example 1. Example 8 The procedure of Example 4 was followed, except for using EPM (Mn = 130,000 as measured by SEC). Example 9 The procedure of Example 1 was followed, except that no free radical initiator was charged. Example 10* 12.5 EPM solution in mineral oil was prepared. 100 parts of EPM which is used in the Example 1 was added to 400 parts of SUN-148 and 300 parts of SNO-100. The mixture was heated at 155°C with stirring and under nitrogen for 3 hours until the rubber completely dissolved. Example 11* Four parts of NDPA per 100 parts of rubber is mixed with a solution containing 8.6 parts of sample 10* in SNO-130. The sample was tested by the Bench Oxidation Test without additional dilution. Example 12* The procedure of Example 10* was followed except that Ortholeum 2052 was used instead of EPM, and 611 parts instead of 300 parts of SNO-100 was added. Example 13* The procedure of Example 11* was followed, except that the sample of Example 12* was used instead of that of Example 10*. V. RESULTS The evaluation data for the samples of Examples 1-13 are listed in Tables 1 and 2. The sample numbers are related to the Example numbers. As seen in Tables 1 and 2, samples of Examples 1-8 containing rubber grafted with 4-nitrosodiphenylamine (IR spectra show large bands at 1600 cm-1) show dispersant and anti-oxidant activity. The sample of Example 9, where EPM not containing any unsaturation and no free radical initiator are used, shows very low grafting level of NDPA, and provides antioxidant activity only. The reference samples of Examples and 12 containing unmodified rubber show neither dispersant nor antioxidant activity. Samples 11* and 13* containing a mixture of rubber and nitrosoamine show antioxidant activity but do not provide any dispersancy. Sample 1, showed significantly better performance in Seq. V-E Engine Test than a commercial DOCP VI improver or competitive additives. The above data indicate that when EPM or EPDM polymers are grafted with 4-nitrosodiphenylamine; multifunctional VI improvers exhibiting dispersant and antioxidant activity are produced.

Claims: A lubricant additive composition prepared by reacting a polymer comprising from 15 to 80 mole percent of ethylene, from 20 to 85 mole percent of at least one C₃-C₁₀ alpha-monoolefin, and from 0 to 15 mole percent of a polyene selected from non-conjugated dienes and trienes, and having an average molecular weight from 5,000 to 500,000 with a nitrosodiphenylamine compound having the formula: in which R and R' which may be the same or different, each represents hydrogen or an alkyl, alkenyl or alkoxyl radical having from 1 to 10 carbon atoms, and which may contain oxygen, nitrogen or sulfur. A composition according to Claim 1 characterized in that R and R' each represent hydrogen or an aliphatic hydrocarbon radical having from 1 to 5 carbon atoms. A composition according to Claim 1 or 2 characterized in that the nitrosodiphenylamine compound is 4-nitrosodiphenylamine, 3-nitrosodiphenylamine or 4-nitroso-2,3'-dimethyl diphenylamine. A composition according to any one of Claims 1 to 3 characterized in that nitrosodiphenylamine is reacted with the polymer in the ratio of 0.2 to 60 parts of nitrosodiphenylamine per 100 parts of said polymer. A composition according to any one of Claims 1 to 4 characterized in that the polymer has a number average molecular weight from 25,000 to 250,000. A composition according to any one of Claims 1 to 5 characterized in that the polymer comprises from 25 to 85 mole percent of ethylene and from 15 to 75 mole percent of a C₃ to C₈ alpha-monoolefin. A lubricating oil composition comprising a major amount of oil of lubricating viscosity and a minor amount of an additive composition according to any one of Claims 1 to 6. A lubricating oil composition according to Claim 7 characterized by from 0.1 to 10 weight percent of the additive composition, based on the total weight of oil composition. A concentrate for a lubricating oil comprising a diluent oil of lubricant (VI improver) viscosity and from 1 to 50 weight percent of the additive composition according to any one of Claims 1 to 6, based on the total weight of the concentrate.

Inventors: BIGGS ROBERT THOMAS, CHAFETZ HARRY, KAPUSCINSKI MARIA MAGDALENA, LIEU CHRISTOPHER SOUNDANG, NALESNIK THEODORE-EUGENE, BIGGS, ROBERT THOMAS, CHAFETZ, HARRY, KAPUSCINSKI, MARIA MAGDALENA, LIEU, CHRISTOPHER SOUNDANG, NALESNIK, THEODORE-EUGENE
Applicants: TEXACO DEVELOPMENT CORP, TEXACO DEVELOPMENT CORPORATION
Application year: 1990
Main classification: C08F8
IPC codes: C08F8, C10M133, C10M143