Patent Publication Number: US-2012042856-A1

Title: Egr equipped diesel engines and lubricating oil compositions

Description:
FIELD OF THE INVENTION 
     The present invention relates to diesel engines, particularly passenger car (PCD) and heavy duty diesel (HDD) engines, provided with exhaust gas recirculation (EGR) systems, and lubricating oil compositions providing improved performance in such engines. More particularly, the present invention relates to compression-ignited internal combustion engines equipped with EGR systems lubricated with a lubricating oil composition containing alkylated phenothiazine soot dispersants. 
     BACKGROUND OF THE INVENTION 
     Environmental concerns have led to continued efforts to reduce NO x  emissions of compression-ignited (diesel) internal combustion engines. The latest technology being used to reduce the NO x  emissions of heavy duty diesel engines is known as exhaust gas recirculation or EGR. EGR reduces NO x  emissions by introducing non-combustible components (exhaust gas) into the incoming air-fuel charge introduced into the engine combustion chamber. This reduces peak flame temperature and NO x  generation. In addition to the simple dilution effect of the EGR, an even greater reduction in NO x  emission is achieved by cooling the exhaust gas before it is returned to the engine. The cooler intake charge allows better filling of the cylinder, and thus, improved power generation. In addition, because the EGR components have higher specific heat values than the incoming air and fuel mixture, the EGR gas further cools the combustion mixture leading to greater power generation and better fuel economy at a fixed NO x  generation level. 
     Diesel fuel conventionally contains 300 to 400 ppm of sulfur, or more. Even the most recently contemplated “low-sulfur” diesel fuel will contain up to 50 ppm of sulfur (e.g. 10 to 50 ppm). When the fuel is burned in the engine, this sulfur is converted to SO x . In addition, one of the major by-products of the combustion of a hydrocarbon fuel is water vapor. Therefore, the exhaust stream contains some level of NO x , SO x  and water vapor. In the past, the presence of these substances has not been problematic because the exhaust gases remained extremely hot, and these components were exhausted in a disassociated, gaseous state. However, when the engine is equipped with an EGR system, particularly an EGR system in which the EGR stream is cooled before it is returned to the engine, the NO x , SO x , water vapor mixture is cooled below the dew point, causing the water vapor to condense. This water reacts with the NO x  and SO x  components to form a mist of nitric and sulfuric acids in the EGR stream. 
     In the presence of these acids, it has been found that soot levels in lubricating oil compositions build rapidly, and that under said conditions, the kinematic viscosity (kv) of lubricating oil compositions increase to unacceptable levels, even in the presence of relatively small levels of soot (e.g. 3 wt, % soot). Because increased lubricant viscosity adversely affects performance, and can even cause engine failure, the use of an EGR system, particularly an EGR system that operates in a condensing mode during at least a portion of the operating time, requires frequent lubricant replacement. API-CI-4 oils developed specifically for EGR-equipped HOD engines that operate in a condensing mode have been found to be unable to address this problem. It has also been found that simply adding additional dispersant is ineffective. 
     Therefore, it would be advantageous to identify lubricating oil compositions that perform better in passenger car and heavy duty diesel engines equipped with EGR systems, particularly EGR systems that operate in a condensing mode. 
     EP-A-1 741 772 (&#39;772) describes the addition of phenylenediamine (PDA) compounds to lubricating oil compositions for diesel engines, particularly heavy duty diesel engines equipped with EGR systems, particularly EGR systems operating in a condensing mode, to ameliorate soot-induced kinematic viscosity increase of the compositions. &#39;772 mentions possible drawbacks in the use of PDA&#39;s, particularly apparent with PDA&#39;s having higher nitrogen contents, noting that PDA&#39;s have two nitrogen atoms per molecule. Also, &#39;772 describes comparative tests of compounds containing one nitrogen atom per molecule, namely alkylated diphenylamines (ADPA&#39;s) and finds that they perform poorly in soot-dispersancy tests. 
     SUMMARY OF THE INVENTION 
     The present invention solves the problem in &#39;772 by providing compounds, namely alkylated phenothiazines that have one nitrogen atom per molecule and that are found to possess excellent soot-dispersancy properties in the above environment in spite of their close structural similarity to the poorly-performing ADPA&#39;s. 
     In accordance with a first aspect of the invention, there is provided a passenger car or heavy duty diesel engine provided with an exhaust gas recirculation system, the engine being lubricated with a lubricating oil composition comprising a major amount of oil of lubricating viscosity, and a minor amount of one or more oil-soluble or oil-dispersible alkylated phenothiazines. 
     An embodiment of the first aspect of the invention provides an engine, as described in the first aspect, in which intake air and/or exhaust gas recirculation streams are cooled to below the dew point for at least a portion of the time (such as at least 10% of the time) the engine is in operation. 
     In accordance with a second aspect of the invention, there is provided a method of operating a passenger car or heavy duty diesel engine provided with an exhaust gas recirculation system which method comprises lubricating the engine with a lubricating oil composition as described in the first aspect. 
     An embodiment of the second aspect of the invention provides a method, as described in the second aspect, in which the engine is a passenger car diesel engine and is operated for at least 6,000 miles without a change of lubricating oil. 
     A further embodiment of the second aspect of the invention provides a method, as described in the second aspect, in which the engine is a heavy duty diesel engine and is operated for at least 15,000 miles without a change of lubricating oil. 
     A further aspect of the invention is directed to the use of the above alkylated phenothiazines to ameliorate soot viscosity increase in lubricating oil compositions for the lubrication of the crankcase of internal combustion engines, particularly passenger car or heavy duty diesel engines provided with an exhaust gas recirculation system, more particularly an exhaust gas recirculation system in which intake air and/or exhaust gas recirculation streams are cooled to below the dew point for at least 10% of the time said engine is in operation. 
     Other and further objects, advantages and features of the present invention will be understood by reference to the following specification. 
    
    
     DETAILED DESCRIPTION OF THE INVENTION 
     In the operation of an EGR-equipped heavy duty diesel engine, a portion of the exhaust gas is directed from the exhaust manifold of the engine to an EGR mixer in which the portion of the exhaust gas routed to the EGR system is mixed with combustion air provided through an air inlet to form an air/exhaust gas mixture. Preferably, the portion of exhaust gas and the combustion air are cooled in an EGR cooler and aftercooler, respectively, before being mixed. Most preferably, the portion of the exhaust gas routed to the EGR system and/or the intake air is cooled such that the air/exhaust gas mixture exiting the EGR mixer is below the dew point for at least 10% of the time the engine is operated. The air/exhaust gas mixture is fed to the intake manifold of the engine, mixed with fuel and combusted. Exhaust gas not routed to the EGR system is exhausted through an exhaust outlet. 
     When the engine is a passenger car diesel engine and is lubricated with a lubricating oil composition of the present invention, it is preferable that such an engine can be operated over at least 6,000, preferably at least 8,000, more preferably from 8,000 to 12,000, miles without a required lubricating oil change. When the engine is a heavy duty diesel engine and is lubricated with a lubricating oil composition of the present invention, it is preferable that such an engine can be operated over at least 15,000, preferably at least 20,000, more preferably from 20,000 to 40,000, miles without a required lubricating oil change. 
     Lubricating oil compositions useful in the practice of the present invention comprise a major amount of oil of lubricating viscosity, and a minor amount of at least one alkylated phenothiazine compound. 
     Oils of lubricating viscosity useful in the context of the present invention may be selected from natural lubricating oils, synthetic lubricating oils and mixtures thereof. The lubricating oil may range in viscosity from light distillate mineral oils to heavy lubricating oils such as gasoline engine oils, mineral lubricating oils and heavy duty diesel oils. Generally, the viscosity of the oil ranges from 2 to 40, especially from 4 to 20, mm 2 s −1 , as measured at 100° C. 
     Natural oils include animal oils and vegetable oils (e.g., castor oil, lard oil); liquid petroleum oils and hydrorefined, solvent-treated or acid-treated mineral oils of the paraffinic, naphthenic and mixed paraffinic-naphthenic types. Oils of lubricating viscosity derived from coal or shale also serve as useful base oils. 
     Synthetic lubricating oils include hydrocarbon oils and halo-substituted hydrocarbon oils such as polymerized and interpolymerized olefins (e.g., polybutylenes, polypropylenes, propylene-isobutylene copolymers, chlorinated polybutylenes, poly(1-hexenes), poly(1-octenes), poly(1-decenes)); alkylbenzenes (e.g., dodecylbenzenes, tetradecylbenzenes, dinonylbenzenes, di(2-ethylhexyl)benzenes); polyphenyls (e.g., biphenyls, terphenyls, alkylated polyphenols); and alkylated diphenyl ethers and alkylated diphenyl sulfides and derivative, analogues and homologues thereof. Also useful are synthetic oils derived from a gas to liquid process from Fischer-Tropsch synthesized hydrocarbons, which are commonly referred to as gas to liquid, or “GTL”, base oils. 
     Alkylene oxide polymers and interpolymers and derivatives thereof where the terminal hydroxyl groups have been modified such as by esterification or etherification, constitute another class of known synthetic lubricating oils. These are exemplified by polyoxyalkylene polymers prepared by polymerization of ethylene oxide or propylene oxide, and the alkyl and aryl ethers of polyoxyalkylene polymers (e.g., methyl-polyiso-propylene glycol ether having a molecular weight of 1000 or diphenyl ether of poly-ethylene glycol having a molecular weight of 1000 to 1500); and mono- and polycarboxylic esters thereof, for example, the acetic acid esters, mixed C 3 -C 8  fatty acid esters and C 13  oxo acid diester of tetraethylene glycol. 
     Another suitable class of synthetic lubricating oils comprises the esters of dicarboxylic acids (e.g., phthalic acid, succinic acid, alkyl succinic acids and alkenyl succinic acids, maleic acid, azelaic acid, subecic acid, sebacic acid, fumaric acid, adipic acid, linoleic acid dimer, malonic acid, alkylmalonic acids, alkenyl malonic acids) with a variety of alcohols (e.g., butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, ethylene glycol, diethylene glycol monoether, propylene glycol). Specific examples of such esters includes dibutyl adipate, di(2-ethylhexyl) sebacate, di-n-hexyl fumarate, dioctyl sebacate, diisooctyl azelate, diisodecyl azelate, dioctyl phthalate, didecyl phthalate, dieicosyl sebacate, the 2-ethylhexyl diester of linoleic acid dimer, and the complex ester formed by reacting one mole of sebacic acid with two moles of tetraethylene glycol and two moles of 2-ethylhexanoic acid. 
     Esters useful as synthetic oils also include those made from C 5  to C 12  monocarboxylic acids and polyols and polyol esters such as neopentyl glycol, trimethylolpropane, pentaerythritol, dipentaerythritol and tripentaerythritol. 
     Silicon-based oils such as the polyalkyl-, polyaryl-, polyalkoxy- or polyaryloxysilicone oils and silicate oils comprise another useful class of synthetic lubricants; such oils include tetraethyl silicate, tetraisopropyl silicate, tetra-(2-ethylhexyl)silicate, tetra-(4-methyl-2-ethylhexyl)silicate, tetra-(p-tert-butyl-phenyl) silicate, hexa-(4-methyl-2-ethylhexyl)disiloxane, poly(methyl)siloxanes and poly(methylphenyl)siloxanes. Other synthetic lubricating oils include liquid esters of phosphorus-containing acids (e.g., tricresyl phosphate, trioctyl phosphate, diethyl ester of decylphosphonic acid) and polymeric tetrahydrofurans. 
     The oil of lubricating viscosity may comprise a Group I, Group II or Group III, base stock or base oil blends of the aforementioned base stocks. Preferably, the oil of lubricating viscosity is a Group II or Group III base stock, or a mixture thereof, or a mixture of a Group I base stock and one or more a Group II and Group III. Preferably, a major amount of the oil of lubricating viscosity is a Group II, Group III, Group IV or Group V base stock, or a mixture thereof. The base stock, or base stock blend preferably has a saturate content of at least 65%, more preferably at least 75%, such as at least 85%. Most preferably, the base stock, or base stock blend, has a saturate content of greater than 90%. Preferably, the oil or oil blend has a sulfur content of less than 1%, preferably less than 0.6%, most preferably less than 0.4%, by weight. 
     Preferably the volatility of the oil or oil blend, as measured by the Noack volatility test (ASTM D5880), is less than or equal to 30%, preferably less than or equal to 25%, more preferably less than or equal to 20%, most preferably less than or equal 16%. Preferably, the viscosity index (VI) of the oil or oil blend is at least 85, preferably at least 100, most preferably from 105 to 140. 
     Definitions for the base stocks and base oils in this invention are the same as those found in the American Petroleum Institute (API) publication “Engine Oil Licensing and Certification System”, Industry Services Department, Fourteenth Edition, December 1996, Addendum 1, December 1998. This publication categorizes base stocks as follows:
     a) Group I base stocks contain less than 90 percent saturates and/or greater than 0.03 percent sulfur and have a viscosity index greater than or equal to 80 and less than 120 using the test methods specified in Table 1.   b) Group II base stocks contain greater than or equal to 90 percent saturates and less than or equal to 0.03 percent sulfur and have a viscosity index greater than or equal to 80 and less than 120 using the test methods specified in Table 1.   c) Group III base stocks contain greater than or equal to 90 percent saturates and less than or equal to 0.03 percent sulfur and have a viscosity index greater than or equal to 120 using the test methods specified in Table 1.   d) Group IV base stocks are polyalphaolefins (PAO).   e) Group V base stocks include all other base stocks not included in Group I, II, III, or IV.   

     
       
         
           
               
             
               
                 TABLE I 
               
             
            
               
                   
               
               
                 Analytical Methods for Base Stock 
               
            
           
           
               
               
               
            
               
                   
                 Property 
                 Test Method 
               
               
                   
                   
               
               
                   
                 Saturates 
                 ASTM D 2007 
               
               
                   
                 Viscosity Index 
                 ASTM D 2270 
               
               
                   
                 Sulfur 
                 ASTM D 2622 
               
               
                   
                   
                 ASTM D 4294 
               
               
                   
                   
                 ASTM D 4927 
               
               
                   
                   
                 ASTM D 3120 
               
               
                   
                   
               
            
           
         
       
     
     Alkylated phenothiazine compounds useful in the practice of the invention include compounds of the formula: 
     
       
         
         
             
             
         
       
     
     wherein R 1  is a linear or branched radical having from 4 to 24, such as 4 to 10, carbon atoms and being an alkyl, heteroalkyl or alkylaryl radical; and R 2  is, independently of R 1 , a linear or branched radical having from 4 to 24, such as 4 to 10 carbon atoms and being an alkyl, heteroalkyl or alkylenyl radical, or is a hydrogen atom. 
     As an example of the above formula R 1  is a nonyl group and R 2  is a hydrogen atom or a nonyl group. 
     The alkylated phenothiazines of the invention preferably comprise mixtures of mono- and dialkylated phenothiazines, for example where 15 to 85 mass % of the mixture is monalkylated. 
     Alkylated phenothiazines are known in the art and may be prepared by methods known in the art. For example, phenothiazine may be alkylated in the prescence of an acid catalyst by reaction with a C 1  to C 10  olefin or mixture thereof, suitable such olefins including alpha olefins and internal olefins, for example isobutylene, dilsobutylene, nonene and 1-decease. 
     Preferably, the phenothiazine compound(s) are present in the lubricating oil composition in an amount of from 0.04 to 4.5, preferably from 0.05 to 2, more preferably from 0.08 to 0.8, mass %, wherein all mass percentages are based on the total mass of the lubricating oil composition. 
     Additional additives may be incorporated in the compositions of the invention to enable them to meet particular requirements. Examples of additives, different from the above-mentioned alkylated phenothiazines, which may be included in the lubricating oil compositions are dispersants, detergents, metal rust inhibitors, viscosity index improvers, corrosion inhibitors, oxidation inhibitors, friction modifiers, other dispersants, anti-foaming agents, anti-wear agents and pour point depressants. Some are discussed in further detail below. 
     Lubricating oil compositions of the present invention may further contain one or more ashless dispersants, which effectively reduce formation of deposits upon use in gasoline and diesel engines when added to lubricating oils. Ashless dispersants useful in the compositions of the present invention comprise an oil-soluble polymeric long chain backbone having functional groups capable of associating with particles to be dispersed. Typically, such dispersants comprise amine, alcohol, amide or ester polar moieties attached to the polymer backbone, often via a bridging group. The ashless dispersant may be, for example, selected from oil-soluble salts, esters, amino-esters, amides, imides and oxazolines of long chain hydrocarbon-substituted mono- and polycarboxylic acids or anhydrides thereof; thiocarboxylate derivatives of long chain hydrocarbons; long chain aliphatic hydrocarbons having polyamine moieties attached directly thereto; and Mannich condensation products formed by condensing a long chain substituted phenol with formaldehyde and polyalkylene polyamine. 
     Preferred dispersants include polyamine-derivatized poly α-olefin dispersants, particularly ethylene/butene alpha-olefin and polyisobutylene-based dispersants. Particularly preferred are ashless dispersants derived from polyisobutylene substituted with succinic anhydride groups and reacted with polyethylene amines, e.g., polyethylene diamine, tetraethylene pentamine; or a polyoxyalkylene polyamine, e.g., polyoxypropylene diamine, trimethylolaminomethane; a hydroxy compound, e.g., pentaerythritol; and combinations thereof. One particularly preferred dispersant combination is a combination of (A) polyisobutylene substituted with succinic anhydride groups and reacted with (B) a hydroxy compound, e.g., pentaerythritol; (C) a polyoxyalkylene polyamine, e.g., polyoxypropylene diamine, or (D) a polyalkylene diamine, e.g., polyethylene diamine and tetraethylene pentamine using about 0.3 to about 2 moles of (B), (C) and/or (D) per mole of (A). Another preferred dispersant combination comprises a combination of (A) polyisobutenyl succinic anhydride with (B) a polyalkylene polyamine, e.g., tetraethylene pentamine, and (C) a polyhydric alcohol or polyhydroxy-substituted aliphatic primary amine, e.g., pentaerythritol or trismethylolaminomethane, as described in U.S. Pat. No. 3,632,511. 
     Another class of ashless dispersants comprises Mannich base condensation products. Generally, these products are prepared by condensing one mole of an alkyl-substituted mono- or polyhydroxy benzene with 1 to 2.5 moles of carbonyl compound(s) (e.g., formaldehyde and paraformaldehyde) and 0.5 to 2 moles of polyalkylene polyamine, as disclosed, for example, in U.S. Pat. No. 3,442,808, Such Mannich base condensation products may include a polymer product of a metallocene-catalyzed polymerization as a substituent on the benzene group, or may be reacted with a compound containing such a polymer substituted on a succinic anhydride in a manner similar to that described in U.S. Pat. No. 3,442,808. Examples of functionalized and/or derivatized olefin polymers synthesized using metallocene catalyst systems are described in the publications identified supra. 
     The dispersant can be further post treated by a variety of conventional post-treatments such as boration, as generally taught in U.S. Pat. Nos. 3,087,936 and 3,254,025. Boration of the dispersant is readily accomplished by treating an acyl nitrogen-containing dispersant with a boron compound such as boron oxide, boron halide boron acids, and esters of boron acids, in an amount sufficient to provide from 0.1 to 20 atomic proportions of boron for each mole of acylated nitrogen composition. Useful dispersants contain from 0.05 to 2.0, e.g., from 0.05 to 0.7, mass % boron. The boron, which appears in the product as dehydrated boric acid polymers (primarily (HBO 2 ) 3 ), is believed to attach to the dispersant imides and diimides as amine salts, e.g., the metaborate salt of the diimide. Boration can be carried out by adding from 0.5 to 4, e.g., from 1 to 3, mass % (based on the mass of acyl nitrogen compound) of a boron compound, preferably boric acid, usually as a slurry, to the acyl nitrogen compound and heating with stirring at from 135 to 190° C., e.g., 140 to 170° C., for from 1 to 5 hours, followed by nitrogen stripping. Alternatively, the boron treatment can be conducted by adding boric acid to a hot reaction mixture of the dicarboxylic acid material and amine, while removing water. Other post-reaction processes commonly known in the art can also be applied. 
     The dispersant may also be further post treated by reaction with a so-called “capping agent”. Conventionally, nitrogen-containing dispersants have been “capped” to reduce the adverse effect such dispersants have on the fluoroelastomer engine seals. Numerous capping agents and methods are known. Of the known “capping agents”, those that convert basic dispersant amino groups to non-basic moieties (e.g., amido or imido groups) are most suitable. The reaction of a nitrogen-containing dispersant and alkyl acetoacetate (e.g., ethyl acetoacetate (EAA)) is described, for example, in U.S. Pat. Nos. 4,839,071; 4,839,072 and 4,579,675. The reaction of a nitrogen-containing dispersant and formic acid is described, for example, in U.S. Pat. No. 3,185,704. The reaction product of a nitrogen-containing dispersant and other suitable capping agents are described in U.S. Pat. Nos. 4,663,064 (glycolic acid); 4,612,132; 5,334,321; 5,356,552; 5,716,912; 5,849,676; 5,861,363 (alkyl and alkylene carbonates, e.g., ethylene carbonate); 5,328,622 (mono-epoxide); 5,026,495; 5,085,788; 5,259,906; 5,407,591 (poly (e.g., bis)-epoxides) and 4,686,054 (maleic anhydride or succinic anhydride). The foregoing list is not exhaustive and other methods of capping nitrogen-containing dispersants are known to those skilled in the art. 
     For adequate piston deposit control, a nitrogen-containing dispersant can be added in an amount providing the lubricating oil composition with from 0.03 to 0.15, preferably from 0.07 to 0.12, mass % of nitrogen. 
     Metal-containing or ash-forming detergents function both as detergents to reduce or remove deposits and as acid neutralizers or rust inhibitors, thereby reducing wear and corrosion and extending engine life. Detergents generally comprise a polar head with a long hydrophobic tail, with the polar head comprising a metal salt of an acidic organic compound. The salts may contain a substantially stoichiometric amount of the metal in which case they are usually described as normal or neutral salts, and would typically have a total base number or TBN (as can be measured by ASTM D2896) of from 0 to 80. A large amount of a metal base may be incorporated by reacting excess metal compound (e.g., an oxide or hydroxide) with an acidic gas (e.g., carbon dioxide). The resulting overbased detergent comprises neutralized detergent as the outer layer of a metal base (e.g. carbonate) micelle, Such overbased detergents may have a TBN of 150 or greater, and typically have a TBN of from 250 to 450 or more. 
     Detergents that may be used include oil-soluble neutral and overbased sulfonates, phenates, sulfurized phenates, thiophosphonates, salicylates, and naphthenates and other oil-soluble carboxylates of a metal, particularly the alkali or alkaline earth metals, e.g., sodium, potassium, lithium, calcium, and magnesium. The most commonly used metals are calcium and magnesium, which may both be present in detergents used in a lubricant, and mixtures of calcium and/or magnesium with sodium. Particularly convenient metal detergents are neutral and overbased calcium sulfonates having TBN of from 20 to 450 TBN, and neutral and overbased calcium phenates and sulfurized phenates having TBN of from 50 to 450. Combinations of detergents, whether overbased or neutral or both, may be used. 
     Sulfonates may be prepared from sulfonic acids which are typically obtained by the sulfonation of alkyl-substituted aromatic hydrocarbons such as those obtained from the fractionation of petroleum or by the alkylation of aromatic hydrocarbons. Examples included those obtained by alkylating benzene, toluene, xylene, naphthalene, diphenyl or their halogen derivatives such as chlorobenzene, chlorotoluene and chloronaphthalene. The alkylation may be carried out in the presence of a catalyst with alkylating agents having from 3 to more than 70 carbon atoms. The alkaryl sulfonates usually contain from 9 to 80 or more, preferably from 16 to 60, carbon atoms per alkyl substituted aromatic moiety. 
     The oil-soluble sulfonates or alkaryl sulfonic acids may be neutralized with oxides, hydroxides, alkoxides, carbonates, carboxylate, sulfides, hydrosulfides, nitrates, borates and ethers of the metal. The amount of metal compound is chosen having regard to the desired TBN of the final product but typically ranges from about 100 to 220 mass % (preferably at least 125 mass %) of that stoichiometrically required. 
     Metal salts of phenols and sulfurized phenols are prepared by reaction with an appropriate metal compound such as an oxide or hydroxide and neutral or overbased products may be obtained by methods known in the art. Sulfurized phenols may be prepared by reacting a phenol with sulfur or a sulfur-containing compound such as hydrogen sulfide, sulfur monohalide or sulfur dihalide, to form products which are generally mixtures of compounds in which 2 or more phenols are bridged by sulfur-containing bridges. 
     Dihydrocarbyl dithiophosphate metal salts are frequently used as antiwear and antioxidant agents. The metal may be an alkali or alkaline earth metal, or zinc, aluminum, lead, tin, molybdenum, manganese, nickel or copper. The zinc salts are most commonly used in lubricating oil in amounts of 0.1 to 10, preferably 0.2 to 2, wt. % based upon the total weight of the lubricating oil composition. They may be prepared in accordance with known techniques by first forming a dihydrocarbyl dithiophosphoric acid (DDPA), usually by reaction of one or more alcohol or a phenol with P 2 S 5 , and then neutralizing the formed DDPA with a zinc compound. For example, a dithiophosphoric acid may be made by reacting mixtures of primary and secondary alcohols. Alternatively, multiple dithiophosphoric acids can be prepared where the hydrocarbyl groups on one are entirely secondary in character and the hydrocarbyl groups on the others are entirely primary in character. To make the zinc salt, any basic or neutral zinc compound could be used but the oxides, hydroxides and carbonates are most generally employed. Commercial additives frequently contain an excess of zinc due to the use of an excess of the basic zinc compound in the neutralization reaction. 
     The preferred zinc dihydrocarbyl dithiophosphates are oil-soluble salts of dihydrocarbyl dithiophosphoric acids and may be represented by the following formula: 
     
       
         
         
             
             
         
       
     
     wherein R and R′ may be the same or different hydrocarbyl radicals containing from 1 to 18, preferably 2 to 12, carbon atoms and including radicals such as alkyl, alkenyl, aryl, arylalkyl, alkaryl and cycloaliphatic radicals. Particularly preferred as R and R′ groups are alkyl groups of 2 to 8 carbon atoms. Thus, the radicals may, for example, be ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, amyl, n-hexyl, i-hexyl, n-octyl, decyl, dodecyl, octadecyl, 2-ethylhexyl, phenyl, butylphenyl, cyclohexyl, methylcyclopentyl, propenyl, butenyl. In order to obtain oil solubility, the total number of carbon atoms (i.e. R and R′) in the dithiophosphoric acid is generally 5 or greater. The zinc dihydrocarbyl dithiophosphate can therefore comprise zinc dialkyl dithiophosphates. The present invention may be particularly useful when used with passenger car diesel engine lubricant compositions containing phosphorus levels of from 0.02 to 0.12, such as from 0.03 to 0.10, or from 0.05 to 0.08, mass %, based on the total mass of the composition, and with heavy duty diesel engine lubricant compositions containing phosphorus levels of from 0.02 to 0.16, such as from 0.05 to 0.14, or from 0.08 to 0.12, mass %, based on the total mass of the composition. In one preferred embodiment, lubricating oil compositions of the present invention contain zinc dialkyl dithiophosphate derived predominantly (e.g., over 50 mol. %, such as over 60 mol. %) from secondary alcohols. 
     Oxidation inhibitors or antioxidants reduce the tendency of mineral oils to deteriorate in service. Oxidative deterioration can be evidenced by sludge in the lubricant, varnish-like deposits on the metal surfaces, and by viscosity growth. Such oxidation inhibitors include hindered phenols, alkaline earth metal salts of alkylphenolthioesters having preferably C 5  to C 12  alkyl side chains, calcium nonylphenol sulfide, oil soluble phenates and sulfurized phenates, phosphosulfurized or sulfurized hydrocarbons, phosphorus esters, metal thiocarbamates, oil-soluble copper compounds as described in U.S. Pat. No. 4,867,890, and molybdenum-containing compounds. 
     Typical oil soluble aromatic amines having at least two aromatic groups attached directly to one amine nitrogen contain from 6 to 16 carbon atoms. The amines may contain more than two aromatic groups. Compounds having a total of at least three aromatic groups in which two aromatic groups are linked by a covalent bond or by an atom or group (e.g., an oxygen or sulfur atom, or a —CO—, —SO 2 — or alkylene group) and two are directly attached to one amine nitrogen are also considered aromatic amines having at least two aromatic groups attached directly to the nitrogen. The aromatic rings are typically substituted by one or more substituents selected from alkyl, cycloalkyl, alkoxy, aryloxy, acyl, acylamino, hydroxy, and nitro groups. 
     Multiple antioxidants are commonly employed in combination. In one preferred embodiment, lubricating oil compositions of the present invention, in addition to the alkylated phenothiazine(s) compound(s) added to ameliorate soot-induced viscosity increase, contain from 0.1 to 1.2 mass % of aminic antioxidant and from 0.1 to 3 mass % of phenolic antioxidant. In another preferred embodiment, lubricating oil compositions of the present invention contain from 0.1 to 1.2 mass % of aminic antioxidant, from 0.1 to 3 mass % of phenolic antioxidant and a molybdenum compound in an amount providing the lubricating oil composition from about 10 to about 1000 ppm of molybdenum. Preferably, lubricating oil compositions useful in the practice of the present invention, particularly lubricating oil compositions useful in the practice of the present invention that are required to contain no greater than 1200 ppm of phosphorus, contain ashless antioxidants other than the alkylated phenothiazine(s), in an amount of from 0.1 to 5, preferably from 0.3 to 4, more preferably from 0.5 to 3, mass %. Where the phosphorus-content is required to be lower, the amount of ashless antioxidant other than the alkylated phenothiazine(s) is preferably increased accordingly. 
     Representative examples of suitable viscosity modifiers are polyisobutylene, copolymers of ethylene and propylene, polymethacrylates, methacrylate copolymers, copolymers of an unsaturated dicarboxylic acid and a vinyl compound, interpolymers of styrene and acrylic esters, and partially hydrogenated copolymers of styrene/isoprene, styrene/butadiene, and isoprene/butadiene, as well as the partially hydrogenated homopolymers of butadiene and isoprene. 
     A viscosity index improver dispersant functions both as a viscosity index improver and as a dispersant. Examples of viscosity index improver dispersants include reaction products of amines, for example polyamines, with a hydrocarbyl-substituted mono- or dicarboxylic acid in which the hydrocarbyl substituent comprises a chain of sufficient length to impart viscosity index improving properties to the compounds. In general, the viscosity index improver dispersant may be, for example, a polymer of a C 4  to C 24  unsaturated ester of vinyl alcohol or a C 3  to C 10  unsaturated mono-carboxylic acid or a C 4  to C 10  di-carboxylic acid with an unsaturated nitrogen-containing monomer having 4 to 20 carbon atoms; a polymer of a C 1  to C 20  olefin with an unsaturated C 3  to C 10  mono- or di-carboxylic acid neutralised with an amine, hydroxyamine or an alcohol; or a polymer of ethylene with a C 3  to C 20  olefin further reacted either by grafting a C 4  to C 20  unsaturated nitrogen-containing monomer thereon or by grafting an unsaturated acid onto the polymer backbone and then reacting carboxylic acid groups of the grafted acid with an amine, hydroxy amine or alcohol. 
     Friction modifiers and fuel economy agents that are compatible with the other ingredients of the final oil may also be included. Examples of such materials include glyceryl monoesters of higher fatty acids, for example, glyceryl mono-oleate; esters of long chain polycarboxylic acids with dials, for example, the butane diol ester of a dimerized unsaturated fatty acid; oxazoline compounds; and alkoxylated alkyl-substituted mono-amines, diamines and alkyl ether amines, for example, ethoxylated tallow amine and ethoxylated tallow ether amine. 
     Other known friction modifiers comprise oil-soluble organo-molybdenum compounds. Such organo-molybdenum friction modifiers also provide antioxidant and antiwear credits to a lubricating oil composition. Examples of such oil-soluble organo-molybdenum compounds include dithiocarbamates, dithiophosphates, dithiophosphinates, xanthates, and thioxanthates, sulfides, and mixtures thereof. Particularly preferred are molybdenum dithiocarbamates, dialkyldithiophosphates, alkyl xanthates and alkylthioxanthates. 
     Additionally, the molybdenum compound may be an acidic molybdenum compound. These compounds react with a basic nitrogen compound as measured by ASTM test D-664 or D-2896 titration procedure and are typically hexavalent. Included are molybdic acid, ammonium molybdate, sodium molybdate, potassium molybdate, and other alkaline metal molybdates and other molybdenum salts, e.g., hydrogen sodium molybdate, MoOCl 4 , MoO 2 Br 2 , Mo 2 O 3 Cl 6 , molybdenum trioxide or similar acidic molybdenum compounds. 
     Among the molybdenum compounds useful in the compositions of this invention are organo-molybdenum compounds of the formula: 
       Mo(ROCS 2 ) 4  and 
       Mo(RSCS 2 ) 4    
     wherein R is an organo group selected from the group consisting of alkyl, aryl, aralkyl and alkoxyalkyl, generally of from 1 to 30 carbon atoms, and preferably 2 to 12 carbon atoms and most preferably alkyl of 2 to 12 carbon atoms. Especially preferred are the dialkyldithiocarbamates of molybdenum. 
     Another group of organo-molybdenum compounds useful in the lubricating compositions of this invention are trinuclear molybdenum compounds, especially those of the formula Mo 3 S k L n Q z  and mixtures thereof wherein the L are independently selected ligands having organo groups with a sufficient number of carbon atoms to render the compound soluble or dispersible in the oil, n is from 1 to 4, k varies from 4 through 7, Q is selected from the group of neutral electron donating compounds such as water, amines, alcohols, phosphines, and ethers, and z ranges from 0 to 5 and includes non-stoichiometric values. At least 21 total carbon atoms should be present among all the ligand organo groups, such as at least 25, at least 30, or at least 35 carbon atoms. 
     Pour point depressants, otherwise known as lube oil flow improvers (LOFI), lower the minimum temperature at which the fluid will flow or can be poured. Such additives are known. Typical of those additives that improve the low temperature fluidity of the fluid are C 8  to C 18  dialkyl fumarate/vinyl acetate copolymers, and polymethacrylates. Foam control can be provided by an antifoamant of the polysiloxane type, for example, silicone oil or polydimethyl siloxane. 
     Some of the above-mentioned additives can provide a multiplicity of effects; thus for example, a single additive may act as a dispersant-oxidation inhibitor. This approach is well known and need not be further elaborated herein. 
     In the present invention it may be necessary to include an additive which maintains the stability of the viscosity of the blend. Thus, although polar group-containing additives achieve a suitably low viscosity in the pre-blending stage it has been observed that some compositions increase in viscosity when stored for prolonged periods. Additives which are effective in controlling this viscosity increase include the long chain hydrocarbons functionalized by reaction with mono- or dicarboxylic acids or anhydrides which are used in the preparation of the ashless dispersants as hereinbefore disclosed. 
     When lubricating compositions contain one or more of the above-mentioned additives, each additive is typically blended into the base oil in an amount that enables the additive to provide its desired function. 
     When lubricating compositions contain one or more of the above-mentioned additives, each additive is typically blended into the base oil in an amount that enables the additive to provide its desired function. Representative effect amounts of such additives, when used in crankcase lubricants, are listed below. All the values listed are stated as mass percent active ingredient. 
     
       
         
           
               
               
               
             
               
                 TABLE II 
               
               
                   
               
               
                   
                 MASS % 
                 MASS % 
               
               
                 ADDITIVE 
                 (Broad) 
                 (Preferred) 
               
               
                   
               
             
            
               
                 Metal Detergents 
                 0.1-15  
                 0.2-9   
               
               
                 Corrosion Inhibitor 
                 0-5 
                 0-1.5 
               
               
                 Metal Dihydrocarbyl Dithiophosphate 
                 0.1-6   
                 0.1-4   
               
               
                 Antioxidant 
                 0-5 
                 0.01-3   
               
               
                 Pour Point Depressant 
                 0.01-5   
                 0.01-1.5   
               
               
                 Antifoaming Agent 
                 0-5 
                 0.001-0.15   
               
               
                 Supplemental Antiwear Agents 
                   0-1.0 
                 0-0.5 
               
               
                 Friction Modifier 
                 0-5 
                 0-1.5 
               
               
                 Viscosity Modifier 
                 0.01-10   
                 0.25-3   
               
               
                 Basestock 
                 Balance 
                 Balance 
               
               
                   
               
            
           
         
       
     
     Fully formulated passenger car diesel engine lubricating oil (PCDO) compositions of the present invention preferably have a sulfur content of less than 0.4, such as less than 0.35, more preferably less than 0.03, such as less than about 0.15, mass %. Preferably, the Noack volatility of the fully formulated PCDO (oil of lubricating viscosity plus all additives) is no greater than 13, such as no greater than 12, preferably no greater than 10. Fully formulated PCDOs of the present invention preferably have no greater than 1200, such as no greater than 1000, or no greater than 800, ppm of phosphorus. Fully formulated PCDOs of the present invention preferably have a sulfated ash (SASH) content of about 1.0 mass % or less. 
     Fully formulated heavy duty diesel engine (HDD) lubricating oil compositions of the present invention preferably have a sulfur content of less than 1.0, such as less than 0.6, more preferably less than about 0.4, such as less than about 0.15, mass %. Preferably, the Noack volatility of the fully formulated HDD lubricating oil composition (oil of lubricating viscosity plus all additives) is no greater than 20, such as no greater than 15, preferably no greater than 12. Fully formulated HDD to lubricating oil compositions of the present invention preferably have no greater than 1600, such as no greater than 1400, or no greater than 1200, ppm of phosphorus. Fully formulated HDD lubricating oil compositions of the present invention preferably have a sulfated ash (SASH) content of about 1.0 mass % or less. 
     It may be desirable, although not essential to prepare one or more additive concentrates comprising additives (concentrates sometimes being referred to as additive packages) whereby several additives can be added simultaneously to the oil to form the lubricating oil composition. A concentrate for the preparation of a lubricating oil composition of the present invention may, for example, contain from 0.1 to 16 mass % of alkylated phenothiazine; 10 to 40 mass % of a nitrogen-containing dispersant; 2 to 20 mass % of an aminic antioxidant and/or a phenolic antioxidant, a molybdenum compound, or a mixture thereof; 5 to 40 mass % of a detergent; and from 2 to 20 mass % of a metal dihydrocarbyl dithiophosphate. 
     The final composition may employ from 5 to 25, preferably 5 to 18, typically 10 to 15, mass % of the concentrate, the remainder being oil of lubricating viscosity and viscosity modifier. 
     All weight percents expressed herein (unless otherwise indicated) 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, unless otherwise noted. 
     EXAMPLES 
     The following example us rate the invention but are not intended to limit the scope of the claims thereof. 
     Preparation of Alkylated Phenothiazine 
     Phenothiazine (55 g) and nonenes (139 g) were heated to 80° C. in a 500 mL baffled reactor fitted with a condenser, nitrogen blanket (100 ml min −1 ), mechanical stirrer (400 rpm) and a controlled mantle. A solid acid-clay catalyst (K5, ex Sud-Chemie, 9.9 g) was added and the reaction mixture heated to 146° C. over 20 minutes. After 14 hours, the reaction mixture was cooled. Thin layer chromatography (TLC) showed that a small quantity of unreacted phenothiazine was present; major spots at R f =0.52 and 0.42 were assumed to be di- and monoalkylated phenothiazine respectively. 
     The reaction mixture was filtered through celite and concentrated in vacuo to give a crude product (ca. 50 g). Part thereof (30 g) was purified by column chromatography and 20 fractions (each 250 ml) collected. Fractions 16-20, containing a mixture of di- and monoalkylated phenothiazine, were combined and the solvent extracted to give a final alkylated phenothiazine product (14:35 g). 
     The product obtained consisted of a mixture of mono- and di-nonylated phenothiazine in the ratio of 15:85 (area:area) by gas chromatography (GC). 
     Formulations 
     Three PC-10 heavy duty diesel (HDD) lubricant formulations were prepared as follows, where figures are mass %: 
     
       
         
           
               
               
               
               
               
             
               
                   
               
               
                   
                 Additive 
                   
                   
                   
               
               
                 OIL 
                 Package 
                 Viscosity Modifier 
                 Amine Antioxidant 
                 Base Oil 
               
               
                   
               
             
            
               
                   
               
            
           
           
               
               
               
               
               
            
               
                 A 
                 13.00 
                 7 
                 — 
                 80 
               
               
                 B 
                 13.00 
                 7 
                 DPA (0.6) 
                 79.40 
               
               
                 1 
                 13.00 
                 7 
                 Alkylated 
                 79.40 
               
               
                   
                   
                   
                 phenothiazine (0.6) 
               
               
                   
               
            
           
         
       
         
         
           
             Oil A was a reference oil that contained no amine antioxidant compound. 
             Oil B was a comparison oil containing DPA, a commercially available alkylated diphenylamine containing 16% mono, 74% di- and 9% tri-alkylated material. 
             Oil 1 was an oil of the invention, containing the alkylated phenothiazine prepared as above. 
           
         
       
    
     Except as indicated, Oils A, B and 1 were identical. 
     Tests &amp; Results 
     To mimic oil aging experienced in an engine, each oil was aged using the industry standard CEC L-48B test at 160° C. for 96 hours and then tested for carbon black dispersancy. CABOT “Vulcan XC-72R” carbon black was weighed at 8 mass % with the test oil in a container, which was shaken overnight at 100° C. and the oil viscosity measured. The procedure was carried out in the “Bohlin Gemini II” rheometer at 100° C.: the rheometer increases the shear rate from 0 to 300 s −1  and back down to 0 s −1 , and measures viscosity. The viscosity at shear rate 100 s −1  (VISC 100) is calculated. A high value indicates an oil with poorly dispersed soot and a low value indicates an oil with well dispersed soot. 
     The results are shown below: 
     
       
         
           
               
               
               
             
               
                   
                   
               
               
                   
                 OIL 
                 VISC 100 (average) 
               
               
                   
                   
               
             
            
               
                   
               
            
           
           
               
               
               
            
               
                   
                 A (reference) 
                 379 
               
               
                   
                 B (comparison 
                 417 
               
               
                   
                 1 (invention) 
                 49 
               
               
                   
                   
               
            
           
         
       
     
     As expected, Oil B performs less effectively than the reference oil (Oil A). This is because Oil B contained DPA which is known to have an adverse effect on soot dispersancy. However, the oil of the invention (Oil 1) was surprisingly and significantly better than the comparison oil and the reference oil.